Inertial and viscoelastic forces on rigid colloids in microfluidic channels.

PubMed

Howard, Michael P; Panagiotopoulos, Athanassios Z; Nikoubashman, Arash

2015-06-14

We perform hybrid molecular dynamics simulations to study the flow behavior of rigid colloids dispersed in a dilute polymer solution. The underlying Newtonian solvent and the ensuing hydrodynamic interactions are incorporated through multiparticle collision dynamics, while the constituent polymers are modeled as bead-spring chains, maintaining a description consistent with the colloidal nature of our system. We study the cross-stream migration of the solute particles in slit-like channels for various polymer lengths and colloid sizes and find a distinct focusing onto the channel center under specific solvent and flow conditions. To better understand this phenomenon, we systematically measure the effective forces exerted on the colloids. We find that the migration originates from a competition between viscoelastic forces from the polymer solution and hydrodynamically induced inertial forces. Our simulations reveal a significantly stronger fluctuation of the lateral colloid position than expected from thermal motion alone, which originates from the complex interplay between the colloid and polymer chains.

A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

NASA Astrophysics Data System (ADS)

Durham, Olivia Z.

This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension polymerization was attempted. This project was further expanded through an extensive evaluation of stabilizers in thiol-ene suspension polymerizations. The scope of stabilizers used included synthetic surfactants (ionic and nonionic), natural gums, and colloidal silica (Pickering stabilization). Suspension polymerizations were further expanded to include thiol-yne chemistry for the evaluation of polymer composition and thermal properties. In addition, polymer particles with excess ene, yne, or thiol functionality were successfully developed to demonstrate the potential for further functionalization. The self-limiting behavior of thiol-ene/yne reactions allows for successful synthesis of functional polymer colloids using off-stoichiometric amounts of monomers. This capacity to control functionality is illustrated through the creation of fluorescent polymer particles using both an in situ thiol-ene polymerization reaction with a vinyl chromophore as well as through post-polymerization modification of thiol-ene and thiol-yne polymers with excess thiol functionality via thiol-isocyanate chemistry. To produce smaller polymer particles without the need for intense homogenization energy or high stabilizer concentrations, an emulsion polymerization system was implemented using a water soluble-thermal initiator. It was found that unlike thiol-ene suspensions, which are limited to crosslinked systems, thiol-ene emulsion polymerizations allowed for the production of polymer particles comprised of either crosslinked or linear polymer networks. For the crosslinked systems, various anionic SDS surfactant concentrations were examined to observe the influence on particle size. In linear polymer systems, variations in polymer composition were examined. Preliminary studies performed with a monomer with an ethylene glycol-like structure indicated that the synthesis of polymer particles with narrower size distributions compared to any of the other emulsion compositions was possible. Finally, thiol-ene chemistry was also employed toward the synthesis of degradable polyanhydride polymer particles. Unlike the aforementioned studies, the approach to particle synthesis was conducted by using a premade thiol-ene polymer. Various linear thiol-ene polyanhydrides were emulsified in water or buffered solutions via sonication. Polymer latex was obtained upon solvent evaporation of the dichloromethane (DCM) solvent used to solubilize the polymer. In this work, variation of polymer composition as well as degradation was examined. Additional experiments included a study of the release of Rhodamine B dye, functionalization of the linear polymers, and studies involving the delay of degradation through the incorporation of crosslinking in the polymer particles. The projects presented herein provide an innovative approach to the synthesis of polymer colloids using thiol-ene and thiol-yne 'click' chemistry in both heterogeneous polymerizations as well as through solvent evaporation of premade polymer solutions. Polymer colloids prove to be an area of great interest for numerous applications that encompass various areas involving biomedical and industrial technologies including paints and coatings, cosmetics, diagnostics, and drug delivery. Improvements in methods of chemical synthesis as well as advances in the tailoring of material properties are of utmost importance for the ever increasing demands of new technologies and educational enlightenment.

Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions.

PubMed

Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D

2018-03-01

Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

Studies of Particle Sedimentation by Novel Scattering Techniques

NASA Technical Reports Server (NTRS)

Tong, Penger

2000-01-01

The four-year grant began May 1, 1996 (5-1-96 to 4-30-00, $100,000/year). We have finished 4 major research projects and published 10 papers during this grant period. An important aspect of this research has been the education of students at graduate and undergraduate levels. They have been fully involved in the research described below: 1. Polymer-induced depletion interaction in colloid-polymer mixtures. 2. Colloidal sedimentation in polymer solutions. 3. Velocity fluctuations in particle sedimentation. New laser light scattering techniques for velocity difference measurements.

Colloid-polymer mixtures under slit confinement.

PubMed

Pérez-Ramírez, Allan; Figueroa-Gerstenmaier, Susana; Odriozola, Gerardo

2017-03-14

We report a NVT molecular dynamic study of colloid-polymer mixtures under slit confinement. For this purpose, we are employing the Asakura-Oosawa model for studying colloidal particles, polymer coils, and hard walls as the external confining field. The colloid-polymer size ratio, q, is varied in the range 1⩾q⩾0.4 and the confinement distance, H, in 10σ c ⩾H⩾3σ c , σ c being the colloidal diameter. Vapor-liquid coexistence properties are assessed, from which phase diagrams are built. The obtained data fulfill the corresponding states law for a constant H when q is varied. The shift of the polymer and colloidal chemical potentials of coexistence follows a linear relationship with (H-σ c ) -1 for H≳4σ c . The confined vapor-liquid interfaces can be fitted with a semicircular line of curvature (H-σ c ) -1 , from which the contact angle can be obtained. We observe complete wetting of the confining walls for reservoir polymer concentrations above and close to the critical value, and partial wetting for reservoir polymer concentrations above and far from it.

Colloid-polymer mixtures under slit confinement

NASA Astrophysics Data System (ADS)

Pérez-Ramírez, Allan; Figueroa-Gerstenmaier, Susana; Odriozola, Gerardo

2017-03-01

We report a NVT molecular dynamic study of colloid-polymer mixtures under slit confinement. For this purpose, we are employing the Asakura-Oosawa model for studying colloidal particles, polymer coils, and hard walls as the external confining field. The colloid-polymer size ratio, q, is varied in the range 1 ⩾q ⩾0.4 and the confinement distance, H, in 10 σc ⩾H ⩾3 σc , σc being the colloidal diameter. Vapor-liquid coexistence properties are assessed, from which phase diagrams are built. The obtained data fulfill the corresponding states law for a constant H when q is varied. The shift of the polymer and colloidal chemical potentials of coexistence follows a linear relationship with (H-σc ) -1 for H ≳4 σc . The confined vapor-liquid interfaces can be fitted with a semicircular line of curvature (H-σc ) -1, from which the contact angle can be obtained. We observe complete wetting of the confining walls for reservoir polymer concentrations above and close to the critical value, and partial wetting for reservoir polymer concentrations above and far from it.

Surface patterning of nanoparticles with polymer patches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties.more » At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.« less

Surface patterning of nanoparticles with polymer patches

DOE PAGES

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse; ...

2016-08-24

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties.more » At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.« less

Surface patterning of nanoparticles with polymer patches

NASA Astrophysics Data System (ADS)

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse; Klinkova, Anna; Larin, Egor M.; Querejeta-Fernández, Ana; Han, Lili; Xin, Huolin L.; Gang, Oleg; Zhulina, Ekaterina B.; Rubinstein, Michael; Kumacheva, Eugenia

2016-10-01

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules, serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient, but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles, and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. Here we demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. These patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.

Programming the composition of polymer blend particles for controlled immunity towards individual protein antigens.

PubMed

Zhan, Xi; Shen, Hong

2015-05-28

In order for a more precise control over the quality and quantity of immune responses stimulated by synthetic particle-based vaccines, it is critical to control the colloidal stability of particles and the release of protein antigens in both extracellular space and intracellular compartments. Different proteins exhibit different sizes, charges and solubilities. This study focused on modulating the release and colloidal stability of proteins with varied isoelectric points. A polymer particle delivery platform made from the blend of three polymers, poly(lactic-co-glycolic acid) (PLGA) and two random pH-sensitive copolymers, were developed. Our study demonstrated its programmability with respective to individual proteins. We showed the colloidal stability of particles at neutral environment and the release of each individual protein at different pH environments were dependent on the ratio of two charge polymers. Subsequently, two antigenic proteins, ovalbumin (OVA) and Type 2 Herpes Simplex Virus (HSV-2) glycoprotein D (gD) protein, were incorporated into particles with systematically varied compositions. We demonstrated that the level of in vitro CD8(+) T cell and in vivo immune responses were dependent on the ratio of two charged polymers, which correlated well with the release of proteins. This study provided a promising design framework of pH-responsive synthetic vaccines for protein antigens of interest. Copyright © 2015 Elsevier Ltd. All rights reserved.

Linear and ring polymers in confined geometries

NASA Astrophysics Data System (ADS)

Usatenko, Zoryana; Kuterba, Piotr; Chamati, Hassan; Romeis, Dirk

2017-03-01

A short overview of the theoretical and experimental works on the polymer-colloid mixtures is given. The behaviour of a dilute solution of linear and ring polymers in confined geometries like slit of two parallel walls or in the solution of mesoscopic colloidal particles of big size with different adsorbing or repelling properties in respect to polymers is discussed. Besides, we consider the massive field theory approach in fixed space dimensions d = 3 for the investigation of the interaction between long flexible polymers and mesoscopic colloidal particles of big size and for the calculation of the correspondent depletion interaction potentials and the depletion forces between confining walls. The presented results indicate the interesting and nontrivial behavior of linear and ring polymers in confined geometries and give possibility better to understand the complexity of physical effects arising from confinement and chain topology which plays a significant role in the shaping of individual chromosomes and in the process of their segregation, especially in the case of elongated bacterial cells. The possibility of using linear and ring polymers for production of new types of nano- and micro-electromechanical devices is analyzed.

Colloidal polymers with controlled sequence and branching constructed from magnetic field assembled nanoparticles.

PubMed

Bannwarth, Markus B; Utech, Stefanie; Ebert, Sandro; Weitz, David A; Crespy, Daniel; Landfester, Katharina

2015-03-24

The assembly of nanoparticles into polymer-like architectures is challenging and usually requires highly defined colloidal building blocks. Here, we show that the broad size-distribution of a simple dispersion of magnetic nanocolloids can be exploited to obtain various polymer-like architectures. The particles are assembled under an external magnetic field and permanently linked by thermal sintering. The remarkable variety of polymer-analogue architectures that arises from this simple process ranges from statistical and block copolymer-like sequencing to branched chains and networks. This library of architectures can be realized by controlling the sequencing of the particles and the junction points via a size-dependent self-assembly of the single building blocks.

Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

PubMed Central

Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto

2017-01-01

In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels. PMID:28100492

Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

NASA Astrophysics Data System (ADS)

Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto; Barker, Thomas H.

2017-01-01

In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels.

Highly temperature responsive core-shell magnetic particles: synthesis, characterization and colloidal properties.

PubMed

Rahman, Md Mahbubor; Chehimi, Mohamed M; Fessi, Hatem; Elaissari, Abdelhamid

2011-08-15

Temperature responsive magnetic polymer submicron particles were prepared by two step seed emulsion polymerization process. First, magnetic seed polymer particles were obtained by emulsion polymerization of styrene using potassium persulfate (KPS) as an initiator and divinylbenzne (DVB) as a cross-linker in the presence of oil-in-water magnetic emulsion (organic ferrofluid droplets). Thereafter, DVB cross-linked magnetic polymer particles were used as seed in the precipitation polymerization of N-isopropylacrylamide (NIPAM) to induce thermosensitive PNIPAM shell onto the hydrophobic polymer surface of the cross-linked magnetic polymer particles. To impart cationic functional groups in the thermosensitive PNIPAM backbone, the functional monomer aminoethylmethacrylate hydrochloride (AEMH) was used to polymerize with NIPAM while N,N'-methylenebisacrylamide (MBA) and 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (V-50) were used as a cross-linker and as an initiator respectively. The effect of seed to monomer (w/w) ratio along with seed nature on the final particle morphology was investigated. Dynamic light scattering (DLS) results demonstrated particles swelling at below volume phase transition temperature (VPTT) and deswelling above the VPTT. The perfect core (magnetic) shell (polymer) structure of the particles prepared was confirmed by Transmission Electron Microscopy (TEM). The chemical composition of the particles were determined by thermogravimetric analysis (TGA). The effect of temperature, pH, ionic strength on the colloidal properties such as size and zeta potential of the micron sized thermo-sensitive magnetic particles were also studied. In addition, a short mechanistic discussion on the formation of core-shell morphology of magnetic polymer particles has also been discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

Thermomechanical Properties and Glass Dynamics of Polymer-Tethered Colloidal Particles and Films

PubMed Central

2017-01-01

Polymer-tethered colloidal particles (aka “particle brush materials”) have attracted interest as a platform for innovative material technologies and as a model system to elucidate glass formation in complex structured media. In this contribution, Brillouin light scattering is used to sequentially evaluate the role of brush architecture on the dynamical properties of brush particles in both the individual and assembled (film) state. In the former state, the analysis reveals that brush–brush interactions as well as global chain relaxation sensitively depend on grafting density; i.e., more polymer-like behavior is observed in sparse brush systems. This is interpreted to be a consequence of more extensive chain entanglement. In contrast, the local relaxation of films does not depend on grafting density. The results highlight that relaxation processes in particle brush-based materials span a wider range of time and length scales as compared to linear chain polymers. Differentiation between relaxation on local and global scale is necessary to reveal the influence of molecular structure and connectivity on the aging behavior of these complex systems. PMID:29755139

Thermomechanical Properties and Glass Dynamics of Polymer-Tethered Colloidal Particles and Films.

PubMed

Cang, Yu; Reuss, Anna N; Lee, Jaejun; Yan, Jiajun; Zhang, Jianan; Alonso-Redondo, Elena; Sainidou, Rebecca; Rembert, Pascal; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Fytas, George

2017-11-14

Polymer-tethered colloidal particles (aka "particle brush materials") have attracted interest as a platform for innovative material technologies and as a model system to elucidate glass formation in complex structured media. In this contribution, Brillouin light scattering is used to sequentially evaluate the role of brush architecture on the dynamical properties of brush particles in both the individual and assembled (film) state. In the former state, the analysis reveals that brush-brush interactions as well as global chain relaxation sensitively depend on grafting density; i.e., more polymer-like behavior is observed in sparse brush systems. This is interpreted to be a consequence of more extensive chain entanglement. In contrast, the local relaxation of films does not depend on grafting density. The results highlight that relaxation processes in particle brush-based materials span a wider range of time and length scales as compared to linear chain polymers. Differentiation between relaxation on local and global scale is necessary to reveal the influence of molecular structure and connectivity on the aging behavior of these complex systems.

Relating structure and flow of soft colloids

NASA Astrophysics Data System (ADS)

Kundu, S. K.; Gupta, S.; Stellbrink, J.; Willner, L.; Richter, D.

2013-11-01

To relate the complex macroscopic flow of soft colloids to details of its microscopic equilibrium and non-equilibrium structure is still one big challenge in soft matter science. We investigated several well-defined colloidal model systems like star polymers or diblock copolymer micelles by linear/non-linear rheology, static/dynamic light scattering (SLS/DLS) and small angle neutron scattering (SANS). In addition, in-situ SANS experiments during shear (Rheo-SANS) revealed directly shear induced structural changes on a microscopic level. Varying the molecular architecture of the individual colloidal particle as well as particle-particle interactions and covering at the same time a broad concentration range from the very dilute to highly concentrated, glassy regime, we could separate contributions from intra- and inter-particle softness. Both can be precisely "tuned" by varying systematically the functionality, 6 ≤ f≤ 64, for star polymers or aggregation number, 30 ≤ N agg ≤ 1000 for diblock copolymer micelles, as well as the degree of polymerization of the individual polymer arm 100 ≤ D p ≤ 3000. In dilute solutions, the characteristic shear rate at which deformation of the soft colloid is observed can be related to the Zimm time of the polymeric corona. In concentrated solutions, we validated a generalized Stokes-Einstein approach to describe the increase in macroscopic viscosity and mesoscopic self diffusion coefficient on approaching the glassy regime. Both can be explained in terms of an ultra-soft interaction potential. Moreover, non-equilibrium structure factors are obtained by Rheo-SANS. All experimental results are in excellent quantitative agreement with recent theoretical predictions.

Bond rupture between colloidal particles with a depletion interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whitaker, Kathryn A.; Furst, Eric M., E-mail: furst@udel.edu

The force required to break the bonds of a depletion gel is measured by dynamically loading pairs of colloidal particles suspended in a solution of a nonadsorbing polymer. Sterically stabilized poly(methyl methacrylate) colloids that are 2.7 μm diameter are brought into contact in a solvent mixture of cyclohexane-cyclohexyl bromide and polystyrene polymer depletant. The particle pairs are subject to a tensile load at a constant loading rate over many approach-retraction cycles. The stochastic nature of the thermal rupture events results in a distribution of bond rupture forces with an average magnitude and variance that increases with increasing depletant concentration. The measuredmore » force distribution is described by the flux of particle pairs sampling the energy barrier of the bond interaction potential based on the Asakura–Oosawa depletion model. A transition state model demonstrates the significance of lubrication hydrodynamic interactions and the effect of the applied loading rate on the rupture force of bonds in a depletion gel.« less

The Use of Polymer Design in Resorbable Colloids

NASA Astrophysics Data System (ADS)

Finne-Wistrand, Anna; Albertsson, Ann-Christine

2006-08-01

During the past decade, researchers in the field of polymer chemistry have developed a wide range of very powerful procedures for constructing ever-more-sophisticated polymers. These methods subsequently have been used in suitable systems to solve specific medical problems. This is complicated, and many key factors such as mechanical properties, biocompatibility, biodegradation, stability, and degradation profile must be considered. Colloid particle systems can be used to solve many biomedical- and pharmaceutical-related problems, and it is expected that nanotechnology can be used to develop these materials, devices, and systems even further. For example, an injectible scaffold system with a defined release and degradation profile has huge potential for the repair and regeneration of damaged tissues. This short, nonexhaustive review presents examples of polymer architecture in resorbable particles that have been compared and tested in biomedical applications. We also discuss the design of polymers for core-shell structures.

Design of latex-layered double hydroxide composites by tuning the aggregation in suspensions.

PubMed

Pavlovic, Marko; Rouster, Paul; Bourgeat-Lami, Elodie; Prevot, Vanessa; Szilagyi, Istvan

2017-01-25

Colloidal stability of polymeric latex particles was studied in the presence of oppositely charged layered double hydroxide (LDH) platelets of different interlayer anions. Adsorption of the LDH particles led to charge neutralization and to overcharging of the latex at appropriate concentrations. Mixing stable colloidal suspensions of individual particles results in rapid aggregation once the LDH adsorption neutralizes the negative charges of the polymer spheres, while stable suspensions were observed at high and low LDH doses. The governing interparticle interactions included repulsive electrical double layer forces as well as van der Waals and patch-charge attractions, whose strength depended on the amount of LDH particles adsorbed on the latex surface. The type of the LDH interlayer anions did not affect the colloidal stability of the samples. Structural investigation of the obtained latex-LDH composites revealed that the polymer spheres were completely coated with the inorganic platelets once their concentration was sufficiently high. These results are especially important for designing synthetic routes for hybrid systems in suspensions, where stable colloids are required for uniform film-formation and for the homogeneous distribution of the inorganic filler within the composite materials.

Crystalline Colloidal Arrays in Polymer Matrices

NASA Technical Reports Server (NTRS)

Sunkara, Hari B.; Penn, B. G.; Frazier, D. O.; Ramachandran, N.

1997-01-01

Crystalline Colloidal Arrays (CCA, also known as colloidal crystals), composed of aqueous or nonaqueous dispersions of self-assembled nanosized polymer colloidal spheres, are emerging toward the development of advanced optical devices for technological applications. The spontaneous self assembly of polymer spheres in a dielectric medium results from the electrostatic repulsive interaction between particles of uniform size and charge distribution. In a way similar to atomic crystals that diffract X-rays, CCA dispersions in thin quartz cells selectively and efficiently Bragg diffract the incident visible light. The reason for this diffraction is because the lattice (body or face centered cubic) spacing is on the order of the wavelength of visible light. Unlike the atomic crystals that diffract a fixed wavelength, colloidal crystals in principle, depending on the particle size, particle number and charge density, can diffract W, Vis or IR light. Therefore, the CCA dispersions can be used as laser filters. Besides, the diffraction intensity depends on the refractive index mismatch between polymer spheres and dielectric medium; therefore, it is possible to modulate incident light intensities by manipulating the index of either the spheres or the medium. Our interest in CCA is in the fabrication of all-optical devices such as optical switches, limiters, and spatial light modulators for optical signal processing. The two major requirements from a materials standpoint are the incorporation of suitable nonlinear optical materials (NLO) into polymer spheres which will allow us to alter the refractive index of the spheres by intense laser radiation, and preparation of solid CCA filters which can resist laser damage. The fabrication of solid composite filters not only has the advantage that the films are easier to handle, but also the arrays in solid films are more robust than in liquid media. In this paper, we report the photopolymerization process used to trap CCA in polymer matrices, the factors which affect the optical diffraction qualities of resulting polymer films, and methods to improve the efficiencies of solid optical filters. Before this, we also present the experimental demonstration, of controlling the optical diffraction intensities from aqueous CCA dispersions by varying the temperature, which establishes the feasibility of fabricating all-optical switching devices with nonlinear periodic array structures.

Reentrant equilibrium disordering in nanoparticle–polymer mixtures

DOE PAGES

Meng, Dong; Kumar, Sanat K.; Grest, Gary S.; ...

2017-01-31

A large body of experimental work has established that athermal colloid/polymer mixtures undergo a sequence of transitions from a disordered fluid state to a colloidal crystal to a second disordered phase with increasing polymer concentration. These transitions are driven by polymer-mediated interparticle attraction, which is a function of both the polymer density and size. It has been posited that the disordered state at high polymer density is a consequence of strong interparticle attractions that kinetically inhibit the formation of the colloidal crystal, i.e., the formation of a non-equilibrium gel phase interferes with crystallization. Here we use molecular dynamics simulations andmore » density functional theory on polymers and nanoparticles (NPs) of comparable size and show that the crystal-disordered phase coexistence at high polymer density for sufficiently long chains corresponds to an equilibrium thermodynamic phase transition. While the crystal is, indeed, stabilized at intermediate polymer density by polymer-induced intercolloid attractions, it is destabilized at higher densities because long chains lose significant configurational entropy when they are forced to occupy all of the crystal voids. Finally, our results are in quantitative agreement with existing experimental data and show that, at least in the nanoparticle limit of sufficiently small colloidal particles, the crystal phase only has a modest range of thermodynamic stability.« less

Tunable photonic crystals with partial bandgaps from blue phase colloidal crystals and dielectric-doped blue phases.

PubMed

Stimulak, Mitja; Ravnik, Miha

2014-09-07

Blue phase colloidal crystals and dielectric nanoparticle/polymer doped blue phases are demonstrated to combine multiple components with different symmetries in one photonic material, creating a photonic crystal with variable and micro-controllable photonic band structure. In this composite photonic material, one contribution to the band structure is determined by the 3D periodic birefringent orientational profile of the blue phases, whereas the second contribution emerges from the regular array of the colloidal particles or from the dielectric/nanoparticle-doped defect network. Using the planewave expansion method, optical photonic bands of the blue phase I and II colloidal crystals and related nanoparticle/polymer doped blue phases are calculated, and then compared to blue phases with no particles and to face-centred-cubic and body-centred-cubic colloidal crystals in isotropic background. We find opening of local band gaps at particular points of Brillouin zone for blue phase colloidal crystals, where there were none in blue phases without particles or dopants. Particle size and filling fraction of the blue phase defect network are demonstrated as parameters that can directly tune the optical bands and local band gaps. In the blue phase I colloidal crystal with an additionally doped defect network, interestingly, we find an indirect total band gap (with the exception of one point) at the entire edge of SC irreducible zone. Finally, this work demonstrates the role of combining multiple - by symmetry - differently organised components in one photonic crystal material, which offers a novel approach towards tunable soft matter photonic materials.

Binodal Colloidal Aggregation Test - 4: Polydispersion

NASA Technical Reports Server (NTRS)

Chaikin, Paul M.

2008-01-01

Binodal Colloidal Aggregation Test - 4: Polydispersion (BCAT-4-Poly) will use model hard-spheres to explore seeded colloidal crystal nucleation and the effects of polydispersity, providing insight into how nature brings order out of disorder. Crewmembers photograph samples of polymer and colloidal particles (tiny nanoscale spheres suspended in liquid) that model liquid/gas phase changes. Results will help scientists develop fundamental physics concepts previously cloaked by the effects of gravity.

2D mesoscale colloidal crystal patterns on polymer substrates

NASA Astrophysics Data System (ADS)

Bredikhin, Vladimir; Bityurin, Nikita

2018-05-01

The development of nanosphere lithography relies on the ability of depositing 2D colloidal crystals comprising micro- and nano-size elements on substrates of different materials. One of the most difficult problems here is deposition of coatings on hydrophobic substrates, e.g. polymers, from aqueous colloidal solutions. We use UV photooxidation for substrate hydrophilization. We demonstrate a new method of producing a two-dimensional ordered array of polymer microparticles (polystyrene microspheres ∼1 μm in diameter) on a polymer substrate (PMMA). We show that implementation of the new deposition technique for directed self-assembly of microspheres on an UV irradiated surface provides an opportunity to obtain coatings on a hydrophilized PMMA surface of large area (∼5 cm2). UV irradiation of the surface through masks allows creating 2D patterns consisting of mesoscale elements formed by the deposited self-assembled microparticles owing to the fact that the colloidal particles are deposited only on the irradiated area leaving the non-irradiated sections intact.

The Use of Clay-Polymer Nanocomposites in Wastewater Pretreatment

PubMed Central

Rytwo, Giora

2012-01-01

Some agricultural effluents are unsuitable for discharge into standard sewage-treatment plants: their pretreatment is necessary to avoid clogging of the filtering devices by colloidal matter. The colloidal stability of the effluents is mainly due to mutual repulsive forces that keep charged particles in suspension. Pretreatment processes are based on two separate stages: (a) neutralization of the charges (“coagulation”) and (b) bridging between several small particles to form larger aggregates that sink, leaving clarified effluent (“flocculation”). The consequent destabilization of the colloidal suspension lowers total suspended solids (TSSs), turbidity, and other environmental quality parameters, making the treatments that follow more efficient. Clay-based materials have been widely used for effluent pretreatment and pollutant removal. This study presents the use of nanocomposites, comprised of an anchoring particle and a polymer, as “coagoflocculants” for the efficient and rapid reduction of TSS and turbidity in wastewater with a high organic load. The use of such particles combines the advantages of coagulant and flocculant by neutralizing the charge of the suspended particles while bridging between them and anchoring them to a denser particle (the clay mineral), enhancing their precipitation. Very rapid and efficient pretreatment is achieved in one single treatment step. PMID:22454607

Einstein's osmotic equilibrium of colloidal suspensions in conservative force fields

NASA Astrophysics Data System (ADS)

Fu, Jinxin; Ou-Yang, H. Daniel

2014-09-01

Predicted by Einstein in his 1905 paper on Brownian motion, colloidal particles in suspension reach osmotic equilibrium under gravity. The idea was demonstrated by J.B. Perrin to win Nobel Prize in Physics in 1926. We show Einstein's equation for osmotic equilibrium can be applied to colloids in a conservative force field generated by optical gradient forces. We measure the osmotic equation of state of 100nm Polystyrene latex particles in the presence of KCl salt and PEG polymer. We also obtain the osmotic compressibility, which is important for determining colloidal stability and the internal chemical potential, which is useful for predicting the phase transition of colloidal systems. This generalization allows for the use of any conservative force fields for systems ranging from colloidal systems to macromolecular solutions.

Redox active polymers and colloidal particles for flow batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin

The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPsmore » is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.« less

Physics of Colloids in Space (PCS): Microgravity Experiment Completed Operations on the International Space Station

NASA Technical Reports Server (NTRS)

Doherty, Michael P.; Sankaran, Subramanian

2003-01-01

Immediately after mixing, the two-phase-like colloid-polymer critical point sample begins to phase separate, or de-mix, into two phases-one that resembles a gas and one that resembles a liquid, except that the particles are colloids and not atoms. The colloid-poor black regions (colloidal gas) grow bigger, and the colloid-rich white regions (colloidal liquid) become whiter as the domains further coarsen. Finally, complete phase separation is achieved, that is, just one region of each colloid-rich (white) and colloid-poor (black) phase. This process was studied over four decades of length scale, from 1 micrometer to 1 centimeter.

Responsive polymer-based colloids for drug delivery and bioconversion

NASA Astrophysics Data System (ADS)

Kudina, Olena

Responsive polymer-based colloids (RPBC) are the colloidal structures containing responsive polymeric component which is able to adapt its physico-chemical properties to the environment by undergoing chemical and/or conformational changes. The goal of the dissertation is to develop and characterize several groups of RPBC with different morphological complexity and explore their potential in drug delivery and bioconversion. The role of RPBC morphology for these specific applications is discussed in details. Three groups of RPBC were fabricated: i. polymeric micelles; ii. mixed polymeric micelles; iii. hybrid polymer-inorganic particles. All fabricated RPBCs contain polymeric component in their structure. The dissertation investigates how the changes of the responsive polymeric component properties are reflected in morphologies of RPBC. The first group of RPBC, polymeric micelles, was formed by the self-assembly of amphiphilic invertible polymers (AIPs) synthesized in our group. AIPs self-assemble into invertible micellar assemblies (IMAs) in solvents of different polarity. In this work, IMAs ability to invert the structure as a response to the change in solvent polarity was demonstrated using 1H NMR spectroscopy and SANS. It was shown that the IMAs incorporate hydrophobic cargo either in the core or in the shell, depending on the chemical structure of cargo molecules. Following in vitro study demonstrates that loaded with drug (curcumin) IMAs are cytotoxic to osteosarcoma cells. Mixed polymeric micelles represent another, more complex, RPBC morphologies studied in the dissertation. Mixed micelles were fabricated from AIPs and amphiphilic oligomers synthesized from pyromellitic dianhydride, polyethylene glycol methyl ethers, and alkanols/cholesterol. The combination of selected AIP and oligomers based on cholesterol results in mixed micelles with an increased drug-loading capacity (from 10% w/w loaded curcumin in single component IMAs to 26%w/w in mixed micelles). Even more complex colloids are hybrid polymer-inorganic particles, the third RPBC group studied in dissertation. Material was designed as core--shell particles with superparamagnetic core engulfed by grafted polymer brushes. These particles were loaded with enzymes (cellulases), thus, are turned into enzymogels for cellulose bioconversion. The study demonstrates that such RPBCs can be used multiple times during hydrolysis and provide an about four-fold increase in glucose production in comparison to free enzymes.

Weak correlations between local density and dynamics near the glass transition.

PubMed

Conrad, J C; Starr, F W; Weitz, D A

2005-11-17

We perform experiments on two different dense colloidal suspensions with confocal microscopy to probe the relationship between local structure and dynamics near the glass transition. We calculate the Voronoi volume for our particles and show that this quantity is not a universal probe of glassy structure for all colloidal suspensions. We correlate the Voronoi volume to displacement and find that these quantities are only weakly correlated. We observe qualitatively similar results in a simulation of a polymer melt. These results suggest that the Voronoi volume does not predict dynamical behavior in experimental colloidal suspensions; a purely structural approach based on local single particle volume likely cannot describe the colloidal glass transition.

Super-resolution optical microscopy resolves network morphology of smart colloidal microgels.

PubMed

Bergmann, Stephan; Wrede, Oliver; Huser, Thomas; Hellweg, Thomas

2018-02-14

We present a new method to resolve the network morphology of colloidal particles in an aqueous environment via super-resolution microscopy. By localization of freely diffusing fluorophores inside the particle network we can resolve the three dimensional structure of one species of colloidal particles (thermoresponsive microgels) without altering their chemical composition through copolymerization with fluorescent monomers. Our approach utilizes the interaction of the fluorescent dye rhodamine 6G with the polymer network to achieve an indirect labeling. We calculate the 3D structure from the 2D images and compare the structure to previously published models for the microgel morphology, e.g. the fuzzy sphere model. To describe the differences in the data an extension of this model is suggested. Our method enables the tailor-made fabrication of colloidal particles which are used in various applications, such as paints or cosmetics, and are promising candidates for drug delivery, smart surface coatings, and nanocatalysis. With the precise knowledge of the particle morphology an understanding of the underlying structure-property relationships for various colloidal systems is possible.

Thin Films from Solvated Metal Atoms and Metal-Metal Bonded Compounds

DTIC Science & Technology

1988-07-01

University 1596 Manhattan, Kansas 66506 1 1 . CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE July 1988 13. NUMBER OF PAGES 14. MONITORING AGENCY...these colloidal particles are of interest: ( 1 ) the particles appear to scavenge electrons to become negatively charged, and (2) strong salvation...of metal doped polymers. C. A Listing of Technical Reports Submitted 1 . S. T. Lin, M. T. Franklin, and K. J. Klabunde, "Non-Aqueous Colloidal Gold

A comparison of tackified, miniemulsion core-shell acrylic latex films with corresponding particle-blend films: structure-property relationships.

PubMed

Canetta, Elisabetta; Marchal, Jeanne; Lei, Chun-Hong; Deplace, Fanny; König, Alexander M; Creton, Costantino; Ouzineb, Keltoum; Keddie, Joseph L

2009-09-15

Tackifying resins (TRs) are often added to pressure-sensitive adhesive films to increase their peel strength and adhesion energy. In waterborne adhesives, the TR is dispersed in water using surfactants and then blended with colloidal polymers in water (i.e., latex). In such waterborne systems, there are problems with the colloidal stability and difficulty in applying coatings of the particle blends; the films are often hydrophilic and subject to water uptake. Here, an alternative method of making waterborne, tackified adhesives is demonstrated. The TR is incorporated within the core of colloidal polymer particles via miniemulsion polymerization. Atomic force microscopy (AFM) combined with force spectroscopy analysis reveals there is heterogeneity in the distribution of the TR in films made from particle blends and also in films made from miniemulsion polymers. Two populations, corresponding to TR-rich and acrylic-rich components, were identified through analysis of the AFM force-displacement curves. The nanoscale maximum adhesion force and adhesion energy were found to be higher in a miniemulsion film containing 12 wt % tackifying resin in comparison to an equivalent blended film. The macroscale tack and viscoelasticity are interpreted by consideration of the nanoscale structure and properties. The incorporation of tackifying resin through a miniemulsion polymerization process not only offers clear benefits in the processing of the adhesive, but it also leads to enhanced adhesion properties.

Binary Colloidal Alloy Test-3 and 4: Critical Point

NASA Technical Reports Server (NTRS)

Weitz, David A.; Lu, Peter J.

2007-01-01

Binary Colloidal Alloy Test - 3 and 4: Critical Point (BCAT-3-4-CP) will determine phase separation rates and add needed points to the phase diagram of a model critical fluid system. Crewmembers photograph samples of polymer and colloidal particles (tiny nanoscale spheres suspended in liquid) that model liquid/gas phase changes. Results will help scientists develop fundamental physics concepts previously cloaked by the effects of gravity.

Aqueous Colloid + Polymer Depletion System for Confocal Microscopy and Rheology

NASA Astrophysics Data System (ADS)

Park, Nayoung; Umanzor, Esmeralda J.; Conrad, Jacinta C.

2018-05-01

We developed a model depletion system with colloidal particles that were refractive index- and density-matched to 80 (w/w)% glycerol in water, and characterized the effect of interparticle interactions on the structure and dynamics of non-equilibrium phases. 2,2,2-trifluoroethyl methacrylate-co-tert-butyl methacrylate copolymer particles were synthesized following Kodger et al. (Sci. Rep. 5, 14635 (2015)). Particles were dispersed in glycerol/water solutions to generate colloidal suspensions with good control over electrostatic interactions and a moderately high background viscosity of 55 mPa-s. To probe the effects of charge screening and depletion attractions on the suspension phase behavior, we added NaCl and polyacrylamide (M_w = 186 kDa) at various concentrations to particle suspensions formulated at volume fractions of phi = 0.05 and 0.3 and imaged the suspensions using confocal microscopy. The particles were nearly hard spheres at a NaCl concentration of 20 mM, but aggregated when the concentration of NaCl was further increased. Changes in the particle structure and dynamics with increasing concentration of the depletant polyacrylamide followed the trends expected from earlier experiments on depletion-driven gelation. Additionally, we measured the viscosity and corrected first normal stress difference of suspensions formulated at phi = 0.4 with and without added polymer. The solvent viscosity was suitable for rheology measurements without the onset of instabilities such as secondary flows or edge fracture. These results validate this system as an alternative to one common model system, suspensions of poly(methyl methacrylate) particles and polystyrene depletants in organic solvents, for investigating phase behavior and flow properties in attractive colloidal suspensions.

From the depletion attraction to the bridging attraction: the effect of solvent molecules on the effective colloidal interactions.

PubMed

Chen, Jie; Kline, Steven R; Liu, Yun

2015-02-28

Depletion attraction induced by non-adsorbing polymers or small particles in colloidal solutions has been widely used as a model colloidal interaction to understand aggregation behavior and phase diagrams, such as glass transitions and gelation. However, much less attention has been paid to study the effective colloidal interaction when small particles/molecules can be reversibly attracted to large colloidal particles. At the strong attraction limit, small particles can introduce bridging attraction as it can simultaneously attach to neighbouring large colloidal particles. We use Baxter's multi-component method for sticky hard sphere systems with the Percus-Yevick approximation to study the bridging attraction and its consequence to phase diagrams, which are controlled by the concentration of small particles and their interaction with large particles. When the concentration of small particles is very low, the bridging attraction strength increases very fast with the increase of small particle concentration. The attraction strength eventually reaches a maximum bridging attraction (MBA). Adding more small particles after the MBA concentration keeps decreasing the attraction strength until reaching a concentration above which the net effect of small particles only introduces an effective repulsion between large colloidal particles. These behaviors are qualitatively different from the concentration dependence of the depletion attraction on small particles and make phase diagrams very rich for bridging attraction systems. We calculate the spinodal and binodal regions, the percolation lines, the MBA lines, and the equivalent hard sphere interaction line for bridging attraction systems and have proposed a simple analytic solution to calculate the effective attraction strength using the concentrations of large and small particles. Our theoretical results are found to be consistent with experimental results reported recently.

Adhesion of bacterial pathogens to soil colloidal particles: influences of cell type, natural organic matter, and solution chemistry.

PubMed

Zhao, Wenqiang; Walker, Sharon L; Huang, Qiaoyun; Cai, Peng

2014-04-15

Bacterial adhesion to granular soil particles is well studied; however, pathogen interactions with naturally occurring colloidal particles (<2 μm) in soil has not been investigated. This study was developed to identify the interaction mechanisms between model bacterial pathogens and soil colloids as a function of cell type, natural organic matter (NOM), and solution chemistry. Specifically, batch adhesion experiments were conducted using NOM-present, NOM-stripped soil colloids, Streptococcus suis SC05 and Escherichia coli WH09 over a wide range of solution pH (4.0-9.0) and ionic strength (IS, 1-100 mM KCl). Cell characterization techniques, Freundlich isotherm, and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory (sphere-sphere model) were utilized to quantitatively determine the interactions between cells and colloids. The adhesion coefficients (Kf) of S. suis SC05 to NOM-present and NOM-stripped soil colloids were significantly higher than E. coli WH09, respectively. Similarly, Kf values of S. suis SC05 and E. coli WH09 adhesion to NOM-stripped soil colloids were greater than those colloids with NOM-present, respectively, suggesting NOM inhibits bacterial adhesion. Cell adhesion to soil colloids declined with increasing pH and enhanced with rising IS (1-50 mM). Interaction energy calculations indicate these adhesion trends can be explained by DLVO-type forces, with S. suis SC05 and E. coli WH09 being weakly adhered in shallow secondary energy minima via polymer bridging and charge heterogeneity. S. suis SC05 adhesion decreased at higher IS 100 mM, which is attributed to the change of hydrophobic effect and steric repulsion resulted from the greater presence of extracellular polymeric substances (EPS) on S. suis SC05 surface as compared to E. coli WH09. Hence, pathogen adhesion to the colloidal material is determined by a combination of DLVO, charge heterogeneity, hydrophobic and polymer interactions as a function of solution chemistry. Copyright © 2014 Elsevier Ltd. All rights reserved.

Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control

NASA Astrophysics Data System (ADS)

Zou, Hua; Wu, Di; Sun, Hao; Chen, Suwu; Wang, Xia

2018-04-01

Synthesis of conducting polymer-silica colloidal nanocomposites has been recognized as an effective method to overcome the poor processability of heterocyclic conducting polymers prepared by chemical oxidative method. However, the morphology control of such conducting polymer-silica nanocomposites was seldomly reported in the literature. Novel poly(2-aminothiazole)(PAT)-silica nanocomposite particles can be conveniently prepared by chemical oxidative polymerization of 2-aminothiazole using CuCl2 oxidant in the presence of ∼20 nm silica nanoparticles. The effects of varying the oxidant/monomer ratio and silica sol concentration on the morphology and size of the resulting PAT-silica nanocmposites have been studied. Optimization of the oxidant/monomer molar ratio and initial silica sol concentration allows relatively round spherical particles of 150-350 nm in diameter to be achieved. The nanocomposite particles have a well-defined raspberry-like morphology with a silica-rich surface, but a significant fraction of PAT component still exists on the surface and, which is beneficial for its applications. Furthermore, the surface compositions of the colloidal nanocomposites could be regulated to some extent. Based on the above results, a possible formation mechanism of the spherical nanocomposite particles is proposed.

Out-of-Equilibrium Dynamics of Colloidal Particles at Interfaces

NASA Astrophysics Data System (ADS)

Wang, Anna

It is widely assumed that when colloidal particles adsorb to a fluid-fluid interface, they reach equilibrium rapidly. Recently, however, Kaz et al. [Nature Materials, 11, 138-142 (2012)] found that a variety of functionalised latex microspheres breaching an aqueous phase-oil interface relax logarithmically with time toward equilibrium. The relaxation is so slow that the time projected for the particles to reach the equilibrium contact angle of 110° is months--far longer than typical experimental timescales. In this thesis, we seek to understand the out-of-equilibrium behaviour of particles near interfaces. Because contact line pinning is likely an extra source of dissipation at interfaces, we start with experiments to elucidate the origins of contact-line pinning and find that polymer hairs on aqueous dispersed polymer particles strongly pin the contact-line. For particles without polymer hairs, nanoscale surface roughness can also pin the contact-line, though with a lower energy. We then extend our digital holography capabilities to track non-spherical particles. We demonstrate that we can track the centre-of-mass of a colloidal spherocylinder to a precision of 35 nm in all three dimensions and its orientation to a precision of 1.5°. Furthermore, the measured translational and rotational diffusion coefficients for the spherocylinders agree with hydrodynamic predictions to within 0.3%. This new functionality enables us to track colloidal ellipsoids and spherocylinders as they breach interfaces. By comparing the adsorption trajectories of the non-spherical particles to what is predicted from energy minimisation, we learn that contact-line pinning affects not just the timescales of breaching, but also the pathway to equilibrium. In fact, a particle's path to equilibrium can have complications even before the particle breaches the interface. Some particles are attracted to the interface, but stay within a few nanometers without ever breaching. We refer to this binding-mode as 'non-capillary binding', and we investigate when this binding mode is present, what causes it, and how interparticle interactions depend on the binding mode. The last few chapters in this thesis are extensions of ideas developed in the first part. We track the run and tumble of E.coli to demonstrate the potential of digital holographic microscopy as an imaging tool for active particles. Taking all of the particle-interface literature into account, we also outline some simple design principles for making particle-stabilised Pickering emulsions.

A new class of tunable hypersonic phononic crystals based on polymer-tethered colloids.

PubMed

Alonso-Redondo, E; Schmitt, M; Urbach, Z; Hui, C M; Sainidou, R; Rembert, P; Matyjaszewski, K; Bockstaller, M R; Fytas, G

2015-09-22

The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to 'manufacturability'. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the 'anisotropic elasticity' across the particle-polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies.

Interfacial properties of hydrosoluble polymers. Final report, June 15, 1993--June 15, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-12-31

During this period, the authors treated a myriad of problems associated with the interfacial properties of macromolecules. Many of them concerned indirect interactions between surfaces engendered by intervening species. The issues ranged from colloidal forces to membrane induced coupling between embedded macromolecules (membrane-bound proteins). This report presents summaries of the following papers published as a result of this study: membrane interactions with polymers and colloids; escape transitions and force laws for compressed polymer mushrooms; interaction between finite-sized particles and end grafted polymers; one long chain among shorter chains--the Flory approach revisited; conformation of star polymers in high molecular weight solvents;more » membrane-induced interactions between inclusions; filled polymer brushes--a hydrodynamic analogy; polymer adsorption at liquid/air interfaces under lateral pressure; flow induced instability of the interface between a fluid and a gel at low Reynolds number; and fluctuation-induced forces in stacked fluid membranes.« less

Synthetic control of the size, shape, and polydispersity of anisotropic silica colloids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murphy, Ryan P.; Hong, Kunlun; Wagner, Norman J.

The particle size and shape determine the microstructure and rheological properties of colloidal suspensions. This work aims to further control the size, shape, and polydispersity of anisotropic silica colloids, to reduce particle size, and to provide additional mechanistic insights on a prevalent, water-in-oil emulsion synthesis method. Key findings show that the dimensions of anisotropic silica particles can be systematically varied by approximately fivefold, with a limiting minimum particle size (D ≈ 60 nm, L ≈ 300 nm) obtained from emulsions with excess polyvinylpyrrolidone (PVP) and sodium citrate. The synthesis conditions are identified and discussed for which the emulsion composition, temperature,more » sonication, polymer entanglements, mixing, and other perturbations may induce or mitigate emulsion instabilities, citrate precipitation, a competing mechanism of templated growth, termination of anisotropic growth, irregular silica structures, and fiber formation. An improved mechanistic understanding will expand the roadmap for rational design and synthetic control of anisotropic colloids using sol-gel silica chemistry confined within water-in-oil emulsions.« less

Synthetic control of the size, shape, and polydispersity of anisotropic silica colloids

DOE PAGES

Murphy, Ryan P.; Hong, Kunlun; Wagner, Norman J.

2017-09-01

The particle size and shape determine the microstructure and rheological properties of colloidal suspensions. This work aims to further control the size, shape, and polydispersity of anisotropic silica colloids, to reduce particle size, and to provide additional mechanistic insights on a prevalent, water-in-oil emulsion synthesis method. Key findings show that the dimensions of anisotropic silica particles can be systematically varied by approximately fivefold, with a limiting minimum particle size (D ≈ 60 nm, L ≈ 300 nm) obtained from emulsions with excess polyvinylpyrrolidone (PVP) and sodium citrate. The synthesis conditions are identified and discussed for which the emulsion composition, temperature,more » sonication, polymer entanglements, mixing, and other perturbations may induce or mitigate emulsion instabilities, citrate precipitation, a competing mechanism of templated growth, termination of anisotropic growth, irregular silica structures, and fiber formation. An improved mechanistic understanding will expand the roadmap for rational design and synthetic control of anisotropic colloids using sol-gel silica chemistry confined within water-in-oil emulsions.« less

Two-Dimensional Nucleation on the Terrace of Colloidal Crystals with Added Polymers.

PubMed

Nozawa, Jun; Uda, Satoshi; Guo, Suxia; Hu, Sumeng; Toyotama, Akiko; Yamanaka, Junpei; Okada, Junpei; Koizumi, Haruhiko

2017-04-04

Understanding nucleation dynamics is important both fundamentally and technologically in materials science and other scientific fields. Two-dimensional (2D) nucleation is the predominant growth mechanism in colloidal crystallization, in which the particle interaction is attractive, and has recently been regarded as a promising method to fabricate varieties of complex nanostructures possessing innovative functionality. Here, polymers are added to a colloidal suspension to generate a depletion attractive force, and the detailed 2D nucleation process on the terrace of the colloidal crystals is investigated. In the system, we first measured the nucleation rate at various area fractions of particles on the terrace, ϕ area . In situ observations at single-particle resolution revealed that nucleation behavior follows the framework of classical nucleation theory (CNT), such as single-step nucleation pathway and existence of critical size. Characteristic nucleation behavior is observed in that the nucleation and growth stage are clearly differentiated. When many nuclei form in a small area of the terrace, a high density of kink sites of once formed islands makes growth more likely to occur than further nucleation because nucleation has a higher energy barrier than growth. The steady-state homogeneous 2D nucleation rate, J, and the critical size of nuclei, r*, are measured by in situ observations based on the CNT, which enable us to obtain the step free energy, γ, which is an important parameter for characterizing the nucleation process. The γ value is found to change according to the strength of attraction, which is tuned by the concentration of the polymer as a depletant.

Surface morphology control of cross-linked polymer particles via dispersion polymerization.

PubMed

Peng, Bo; Imhof, Arnout

2015-05-14

Cross-linked polymer colloids (poly(methyl methacrylate) and polystyrene) with diverse shapes were prepared in polar solvents (ethanol, methanol and water) via dispersion polymerization, in which a linear addition of the cross-linker was used during reaction. Apart from spherical particles we found dented spheres or particles covered with nodules, or a combination of both. A comprehensive investigation was carried out, mainly concentrating on the effect of the experimental conditions (e.g., the addition start time and total addition time, cross-linker density and the solvency of the solvents) on particle morphologies. Consequently, we suggest a number of effective ways for the synthesis of regular (spherical) colloidal particles through maintaining a relatively low concentration of the cross-linker during the entire reaction, or forcing the co-polymerization (of monomer and cross-linker) locus to the continuous medium, or using a high quality or quantity of the stabilizer. Moreover, the size of the particles was also precisely manipulated by varying the polarity of the solvents, the concentration of the cross-linker, and the amount and average molecular weight of the stabilizer. In addition, the formation of the heavily dented particles with a very rough surface prepared under a pure or oxygen-'contaminated' nitrogen environment was monitored over time. The results accumulated in this article are of use for a better understanding of the mechanism of the polymerization and control over the structure and property of polymer particles.

Large-scale assembly of colloidal particles

NASA Astrophysics Data System (ADS)

Yang, Hongta

This study reports a simple, roll-to-roll compatible coating technology for producing three-dimensional highly ordered colloidal crystal-polymer composites, colloidal crystals, and macroporous polymer membranes. A vertically beveled doctor blade is utilized to shear align silica microsphere-monomer suspensions to form large-area composites in a single step. The polymer matrix and the silica microspheres can be selectively removed to create colloidal crystals and self-standing macroporous polymer membranes. The thickness of the shear-aligned crystal is correlated with the viscosity of the colloidal suspension and the coating speed, and the correlations can be qualitatively explained by adapting the mechanisms developed for conventional doctor blade coating. Five important research topics related to the application of large-scale three-dimensional highly ordered macroporous films by doctor blade coating are covered in this study. The first topic describes the invention in large area and low cost color reflective displays. This invention is inspired by the heat pipe technology. The self-standing macroporous polymer films exhibit brilliant colors which originate from the Bragg diffractive of visible light form the three-dimensional highly ordered air cavities. The colors can be easily changed by tuning the size of the air cavities to cover the whole visible spectrum. When the air cavities are filled with a solvent which has the same refractive index as that of the polymer, the macroporous polymer films become completely transparent due to the index matching. When the solvent trapped in the cavities is evaporated by in-situ heating, the sample color changes back to brilliant color. This process is highly reversible and reproducible for thousands of cycles. The second topic reports the achievement of rapid and reversible vapor detection by using 3-D macroporous photonic crystals. Capillary condensation of a condensable vapor in the interconnected macropores leads to the increase of the effective refractive index of the diffractive medium, resulting in the red-shift of the optical stop bands. The wavelength shift is linearly proportional to the vapor partial pressure for a spectrum of vapors. Optical simulation and theoretical prediction based on Kelvin equation suggest that a liquid film is formed on the walls of the macropores during vapor condensation. The third topic describes introducing doctor blade coating fabricated large area and low cost macroporous films for thermochromic smart windows, which are useful for energy control in glazed buildings. The fabricated macroporous polymer films exhibit brilliant colors and are capable of reflecting solar radiation when in-situ heated, and become transparent as cavities are filled with a solvent which has the same refractive index as that of the polymer when cooled to building temperature. The fourth topic reports the roll-to roll fabricated excellent water-repelling and self-cleaning macroporous polymer films. The size of the voids can be easily controlled by tuning the duration of an oxygen reactive-ion etching process prior to the removal of the templating silica spheres from silica colloidal-polymer composites. After surface functionalization with fluorosilane, superhydrophobic surface with large apparent water contact angle and small sliding angle can be obtained. The self-cleaning functionality can be achieved on superhydrophobic macroporous coatings by preventing bacterial contamination is further demonstrated. The fifth topic presented is that the template macroporous polymer films with interconnected voids and uniform interconnecting nanopores can be directly used as filtration membranes to achieve size-exclusive separation of particles. The results also demonstrate that more than 85% of small sized particles are recovered after filtration. The results also demonstrate that Escherichia coli can be filtrated by the from macroporous polymer films aqueous solution.

A computational investigation of the thermodynamics and structure in colloid and polymer mixtures

NASA Astrophysics Data System (ADS)

Mahynski, Nathan Alexander

In this dissertation I use computational tools to study the structure and thermodynamics of colloid-polymer mixtures. I show that fluid-fluid phase separation in mixtures of colloids and linear polymers cannot be universally reduced using polymer-based scaling principles since these assume the binodals exist in a single scaling regime, whereas accurate simulations clearly demonstrate otherwise. I show that rethinking these solutions in terms of multiple length scales is necessary to properly explain the thermodynamic stability and structure of these fluid phases, and produce phase diagrams in nearly quantitative agreement with experimental results. I then extend this work to encompass more geometrically complex "star" polymers revealing how the phase behavior for many of these binary mixtures may be mapped onto that of mixtures containing only linear polymers. I further consider the depletion-driven crystallization of athermal colloidal hard spheres induced by polymers. I demonstrate how the partitioning of a finite amount of polymer into the colloidal crystal phase implies that the polymer's architecture can be tailored to interact with the internal void structure of different crystal polymorphs uniquely, thus providing a direct route to thermodynamically stabilizing one arbitrarily chosen structure over another, e.g., the hexagonal close-packed crystal over the face-centered cubic. I then begin to generalize this result by considering the consequences of thermal interactions and complex polymer architectures. These principles lay the groundwork for intelligently engineering co-solute additives in crystallizing colloidal suspensions that can be used to thermodynamically isolate single crystal morphologies. Finally, I examine the competition between self-assembly and phase separation in polymer-grafted nanoparticle systems by comparing and contrasting the validity of two different models for grafted nanoparticles: "nanoparticle amphiphiles" versus "patchy particles." The latter suggests these systems have some utility in forming novel "equilibrium gel" phases, however, I find that considering grafted nanoparticles as amphiphiles provides a qualitatively accurate description of their thermodynamics revealing either first-order phase separation into two isotropic phases or continuous self-assembly. I find no signs of empty liquid formation, suggesting that these nanoparticles do not provide a route to such phases.

Precise colloids with tunable interactions for confocal microscopy

PubMed Central

Kodger, Thomas E.; Guerra, Rodrigo E.; Sprakel, Joris

2015-01-01

Model colloidal systems studied with confocal microscopy have led to numerous insights into the physics of condensed matter. Though confocal microscopy is an extremely powerful tool, it requires a careful choice and preparation of the colloid. Uncontrolled or unknown variations in the size, density, and composition of the individual particles and interactions between particles, often influenced by the synthetic route taken to form them, lead to difficulties in interpreting the behavior of the dispersion. Here we describe the straightforward synthesis of copolymer particles which can be refractive index- and density-matched simultaneously to a non-plasticizing mixture of high dielectric solvents. The interactions between particles are accurately tuned by surface grafting of polymer brushes using Atom Transfer Radical Polymerization (ATRP), from hard-sphere-like to long-ranged electrostatic repulsion or mixed charge attraction. We also modify the buoyant density of the particles by altering the copolymer ratio while maintaining their refractive index match to the suspending solution resulting in well controlled sedimentation. The tunability of the inter-particle interactions, the low volatility of the solvents, and the capacity to simultaneously match both the refractive index and density of the particles to the fluid opens up new possibilities for exploring the physics of colloidal systems. PMID:26420044

Fundamental Physics

NASA Image and Video Library

2003-01-22

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Colloidal Dispersions in Polymeric Media: Interparticle Forces, Microstructure and Rheology

NASA Astrophysics Data System (ADS)

Ndong, Rose Seynabou

To enhance properties of the ultimate materials, melt processed polymers are commonly filled with colloidal particles, such as inorganic oxides. Dispersing such particles in a melt is generally difficult due to the strong van der Waals attractions. These attractive forces can be modulated through surface modifications such as polymer adsorption and grafting. Indeed, the relative viscosity of 430 nm Al2O3particles stabilized by end-tethered poly(dimethylsiloxane) (PDMS) in PDMS melts decreases with increasing graft density and molecular weight as expected, but also with increasing molecular weight of the melt, contrary to well established theories. The relative steady shear viscosity exhibits neither a low shear limit nor a yield stress, but follows a power law characterized by relative high shear viscosity (eta infinity/mu) and a structural relaxation time (tau). The measured structural time can be correlated reasonably well with a characteristic relaxation time, tauo, estimated by equating the viscous resistance with the maximum attractive force. We further explored the significance of this power law with TiO2 nanoparticles in PDMS melts with a reduction in size and an increase in Hamaker constant. Bare, octadecyl-coated, and 9k-PDMS grafted TiO2 particles dispersed in neat and binary PDMS melts revealed behavior similar to that of the large alumina particles, as the increased strength of van der Waals forces offset the reduction in size. To complete the study ZrO2 nanoparticles were dispersed in solution of associative polymers and characterized by small amplitude oscillatory shear. The data exhibits two relaxation modes: Maxwellian behavior at high frequency imparted by the associating polymers and a power law spectrum at low frequency from the particles. The timescales and volume fraction dependence reflect the attractions between particles with adsorbed polymer layers dispersed in a percolated network of associative polymers. Together these studies demonstrate the range and origin of the rheology possible with particles dispersed in polymeric media.

On the computational modeling of the viscosity of colloidal dispersions and its relation with basic molecular interactions

NASA Astrophysics Data System (ADS)

Gama Goicochea, A.; Balderas Altamirano, M. A.; Lopez-Esparza, R.; Waldo-Mendoza, Miguel A.; Perez, E.

2015-09-01

The connection between fundamental interactions acting in molecules in a fluid and macroscopically measured properties, such as the viscosity between colloidal particles coated with polymers, is studied here. The role that hydrodynamic and Brownian forces play in colloidal dispersions is also discussed. It is argued that many-body systems in which all these interactions take place can be accurately solved using computational simulation tools. One of those modern tools is the technique known as dissipative particle dynamics, which incorporates Brownian and hydrodynamic forces, as well as basic conservative interactions. A case study is reported, as an example of the applications of this technique, which consists of the prediction of the viscosity and friction between two opposing parallel surfaces covered with polymer chains, under the influence of a steady flow. This work is intended to serve as an introduction to the subject of colloidal dispersions and computer simulations, for final-year undergraduate students and beginning graduate students who are interested in beginning research in soft matter systems. To that end, a computational code is included that students can use right away to study complex fluids in equilibrium.

Movie of phase separation during physics of colloids in space experiment

NASA Technical Reports Server (NTRS)

2002-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area in the video is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Phase separation during the Experiment on Physics of Colloids in Space

NASA Technical Reports Server (NTRS)

2003-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Orbitals for classical arbitrary anisotropic colloidal potentials

NASA Astrophysics Data System (ADS)

Girard, Martin; Nguyen, Trung Dac; de la Cruz, Monica Olvera

2017-11-01

Coarse-grained potentials are ubiquitous in mesoscale simulations. While various methods to compute effective interactions for spherically symmetric particles exist, anisotropic interactions are seldom used, due to their complexity. Here we describe a general formulation, based on a spatial decomposition of the density fields around the particles, akin to atomic orbitals. We show that anisotropic potentials can be efficiently computed in numerical simulations using Fourier-based methods. We validate the field formulation and characterize its computational efficiency with a system of colloids that have Gaussian surface charge distributions. We also investigate the phase behavior of charged Janus colloids immersed in screened media, with screening lengths comparable to the colloid size. The system shows rich behaviors, exhibiting vapor, liquid, gel, and crystalline morphologies, depending on temperature and screening length. The crystalline phase only appears for symmetric Janus particles. For very short screening lengths, the system undergoes a direct transition from a vapor to a crystal on cooling; while, for longer screening lengths, a vapor-liquid-crystal transition is observed. The proposed formulation can be extended to model force fields that are time or orientation dependent, such as those in systems of polymer-grafted particles and magnetic colloids.

Integration of colloids into a semi-flexible network of fibrin.

PubMed

Bharadwaj, N Ashwin K; Kang, Jin Gu; Hatzell, Marta C; Schweizer, Kenneth S; Braun, Paul V; Ewoldt, Randy H

2017-02-15

Typical colloid-polymer composites have particle diameters much larger than the polymer mesh size, but successful integration of smaller colloids into a large-mesh network could allow for the realization of new colloidal states of spatial organization and faster colloid motion which can allow the possibility of switchable re-configuration of colloids or more dramatic stimuli-responsive property changes. Experimental realization of such composites requires solving non-trivial materials selection and fabrication challenges; key questions include composition regime maps of successful composites, the resulting structure and colloidal contact network, and the mechanical properties, in particular the ability to form a network and retain strain stiffening in the presence of colloids. Here, we study these fundamental questions by formulating composites with fluorescent (though not stimuli-responsive) carboxylate modified polystyrene/latex (CML) colloidal particles (diameters 200 nm and 1000 nm) in bovine fibrin networks (a semi-flexible biopolymer network with mesh size 1-5 μm). We describe and characterize two methods of composite preparation: adding colloids before fibrinogen polymerization (Method I), and electrophoretically driving colloids into a network already formed by fibrinogen polymerization (Method II). We directly image the morphology of colloidal and fibrous components with two-color fluorescent confocal microscopy under wet conditions and SEM of fixed dry samples. Mechanical properties are studied with shear and extensional rheology. Both fabrication methods are successful, though with trade-offs. Method I retains the nonlinear strain-stiffening and extensibility of the native fibrin network, but some colloid clustering is observed and fibrin network integrity is lost above a critical colloid concentration that depends on fibrinogen and thrombin concentration. Larger colloids can be included at higher volume fractions before massive aggregation occurs, indicating surface interactions as a limiting factor. Method II results in a loss of measurable strain-stiffening, but colloids are well dispersed and template along the fibrous scaffold. The results here, with insight into both structure and rheology, form a foundational understanding for the integration of other colloids, e.g. with stimuli-responsive functionalities, into semi-flexible networks.

Surfactant-free Colloidal Particles with Specific Binding Affinity

PubMed Central

2017-01-01

Colloidal particles with specific binding affinity are essential for in vivo and in vitro biosensing, targeted drug delivery, and micrometer-scale self-assembly. Key to these techniques are surface functionalizations that provide high affinities to specific target molecules. For stabilization in physiological environments, current particle coating methods rely on adsorbed surfactants. However, spontaneous desorption of these surfactants typically has an undesirable influence on lipid membranes. To address this issue and create particles for targeting molecules in lipid membranes, we present here a surfactant-free coating method that combines high binding affinity with stability at physiological conditions. After activating charge-stabilized polystyrene microparticles with EDC/Sulfo-NHS, we first coat the particles with a specific protein and subsequently covalently attach a dense layer of poly(ethyelene) glycol. This polymer layer provides colloidal stability at physiological conditions as well as antiadhesive properties, while the protein coating provides the specific affinity to the targeted molecule. We show that NeutrAvidin-functionalized particles bind specifically to biotinylated membranes and that Concanavalin A-functionalized particles bind specifically to the glycocortex of Dictyostelium discoideum cells. The affinity of the particles changes with protein density, which can be tuned during the coating procedure. The generic and surfactant-free coating method reported here transfers the high affinity and specificity of a protein onto colloidal polystyrene microparticles. PMID:28847149

On Determination of the Equation of State of Colloidal Suspensions

NASA Astrophysics Data System (ADS)

Sirorattanakul, Krittanon; Huang, Hao; Uhl, Christopher; Ou-Yang, Daniel

Colloidal suspensions are the main ingredients for a variety of materials in our daily life, e.g., milk, salad dressing, skin lotions and paint for wall coatings. Material properties of these systems require an understanding of the equation of state of these materials. Our project aims to experimentally determine the equation of state of colloidal suspensions by microfluidics, dielectrophoresis (DEP) and optical imaging. We use fluorescent polystyrene latexes as a model system for this study. Placing semi-permeable membranes between microfluidics channels, which made from PDMS, we control the particle concentration and ionic strengths of the suspension. We use osmotic equilibrium equation to analyze the particle concentration distribution in a potential force field created by DEP. We use confocal optical imaging to measure the spatial distribution of the particle concentration. We compare the results of our experimental study with data obtained by computer simulation of osmotic equilibrium of interacting colloids. NSF DMR-0923299, Emulsion Polymer Institute, Department of Physics, Bioengineering Program of Lehigh University.

Charge Stabilized Crystalline Colloidal Arrays As Templates For Fabrication of Non-Close-Packed Inverted Photonic Crystals

PubMed Central

Bohn, Justin J.; Ben-Moshe, Matti; Tikhonov, Alexander; Qu, Dan; Lamont, Daniel N.

2010-01-01

We developed a straightforward method to form non close-packed highly ordered fcc direct and inverse opal silica photonic crystals. We utilize an electrostatically self assembled crystalline colloidal array (CCA) template formed by monodisperse, highly charged polystyrene particles. We then polymerize a hydrogel around the CCA (PCCA) and condense the silica to form a highly ordered silica impregnated (siPCCA) photonic crystal. Heating at 450 °C removes the organic polymer leaving a silica inverse opal structure. By altering the colloidal particle concentration we independently control the particle spacing and the wall thickness of the inverse opal photonic crystals. This allows us to control the optical dielectric constant modulation in order to optimize the diffraction; the dielectric constant modulation is controlled independently of the photonic crystal periodicity. These fcc photonic crystals are better ordered than typical close-packed photonic crystals because their self assembly utilizes soft electrostatic repulsive potentials. We show that colloidal particle size and charge polydispersity has modest impact on ordering, in contrast to that for close-packed crystals. PMID:20163800

Colloids with high-definition surface structures

PubMed Central

Chen, Hsien-Yeh; Rouillard, Jean-Marie; Gulari, Erdogan; Lahann, Joerg

2007-01-01

Compared with the well equipped arsenal of surface modification methods for flat surfaces, techniques that are applicable to curved, colloidal surfaces are still in their infancy. This technological gap exists because spin-coating techniques used in traditional photolithographic processes are not applicable to the curved surfaces of spherical objects. By replacing spin-coated photoresist with a vapor-deposited, photodefinable polymer coating, we have now fabricated microstructured colloids with a wide range of surface patterns, including asymmetric and chiral surface structures, that so far were typically reserved for flat substrates. This high-throughput method can yield surface-structured colloidal particles at a rate of ≈107 to 108 particles per operator per day. Equipped with spatially defined binding pockets, microstructured colloids can engage in programmable interactions, which can lead to directed self-assembly. The ability to create a wide range of colloids with both simple and complex surface patterns may contribute to the genesis of previously unknown colloidal structures and may have important technological implications in a range of different applications, including photonic and phononic materials or chemical sensors. PMID:17592149

Crowding, Entropic Forces, and Confinement: Crucial Factors for Structures and Functions in the Cell Nucleus.

PubMed

Hancock, R

2018-04-01

The view of the cell nucleus as a crowded system of colloid particles and that chromosomes are giant self-avoiding polymers is stimulating rapid advances in our understanding of its structure and activities, thanks to concepts and experimental methods from colloid, polymer, soft matter, and nano sciences and to increased computational power for simulating macromolecules and polymers. This review summarizes current understanding of some characteristics of the molecular environment in the nucleus, of how intranuclear compartments are formed, and of how the genome is highly but precisely compacted, and underlines the crucial, subtle, and sometimes unintuitive effects on structures and reactions of entropic forces caused by the high concentration of macromolecules in the nucleus.

Colloidal Particles at Fluid Interfaces and the Interface of Colloidal Fluids

NASA Astrophysics Data System (ADS)

McGorty, Ryan

Holographic microscopy is a unifying theme in the different projects discussed in this thesis. The technique allows one to observe microscopic objects, like colloids and droplets, in a three-dimensional (3D) volume. Unlike scanning 3D optical techniques, holography captures a sample's 3D information in a single image: the hologram. Therefore, one can capture 3D information at video frame rates. The price for such speed is paid in computation time. The 3D information must be extracted from the image by methods such as reconstruction or fitting the hologram to scattering calculations. Using holography, we observe a single colloidal particle approach, penetrate and then slowly equilibrate at an oil--water interface. Because the particle moves along the optical axis (z-axis) and perpendicular to the interface holography is used to determine its position. We are able to locate the particle's z-position to within a few nanometers with a time resolution below a millisecond. We find that the capillary force pulling the particle into the interface is not balanced by a hydrodynamic force. Rather, a larger-than-viscous dissipation associated with the three-phase contact-line slipping over the particle's surface results in equilibration on time scales orders of magnitude longer than the minute time scales over which our setup allows us to examine. A separate project discussed here also examines colloidal particles and fluid-fluid interfaces. But the fluids involved are composed of colloids. With a colloid and polymer water-based mixture we study the phase separation of the colloid-rich (or liquid) and colloid-poor (or gas) region. In comparison to the oil--water interface in the previously mentioned project, the interface between the colloidal liquid and gas phases has a surface tension nearly six orders of magnitude smaller. So interfacial fluctuations are observable under microscopy. We also use holographic microscopy to study this system but not to track particles with great time and spatial resolution. Rather, holography allows us to observe nucleation of the liquid phase occurring throughout our sample volume.

Structure and Dynamics of Bimodal Colloidal Dispersions in a Low-Molecular-Weight Polymer Solution

DOE PAGES

Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; ...

2017-02-24

We present an experimental study of the structural and dynamical properties of bimodal, micrometersized colloidal dispersions (size ratio ≈ 2) in an aqueous solution of low-molecular weight polymer (polyethylene glycol 2000) using synchrotron ultra-small angle X-ray scattering (USAXS) and USAXSbased X-ray photon correlation spectroscopy. We fixed the volume fraction of the large particles at 5 % and systematically increased the volume fraction of the small particles from 0 % to 5 % to evaluate its effect on the structure and dynamics. The bimodal dispersions were homogenous through the investigated parameter space. We found that the partial structure factors can bemore » satisfactorily retrieved for the bimodal colloidal dispersions using a Percus-Yevick hard sphere potential when the particle size distributions of the particles were taken into account. We also found that the partial structure factor between the large particles does not exhibit significant variation with increasing volume fraction of small particles, whereas the isothermal compressibility of the binary mixture was found to decrease with increasing volume fraction of small particles. The dynamics of single-component large particle dispersion obey the principles of de Gennes narrowing, where the wave vector dependence of the interparticle diffusion coefficient is inversely proportional to the interparticle structure factor. The dynamics of the bimodal dispersions demonstrate strong dependence on the fraction of small particles. As a result, we also made a comparison between the experimental effective dynamic viscosity of the bimodal dispersion with theoretical predictions, which suggest that the complex mutual interactions between large and small particles have a strong effect on the dynamic behaviors of bimodal dispersions.« less

Structure and Dynamics of Bimodal Colloidal Dispersions in a Low-Molecular-Weight Polymer Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.

We present an experimental study of the structural and dynamical properties of bimodal, micrometersized colloidal dispersions (size ratio ≈ 2) in an aqueous solution of low-molecular weight polymer (polyethylene glycol 2000) using synchrotron ultra-small angle X-ray scattering (USAXS) and USAXSbased X-ray photon correlation spectroscopy. We fixed the volume fraction of the large particles at 5 % and systematically increased the volume fraction of the small particles from 0 % to 5 % to evaluate its effect on the structure and dynamics. The bimodal dispersions were homogenous through the investigated parameter space. We found that the partial structure factors can bemore » satisfactorily retrieved for the bimodal colloidal dispersions using a Percus-Yevick hard sphere potential when the particle size distributions of the particles were taken into account. We also found that the partial structure factor between the large particles does not exhibit significant variation with increasing volume fraction of small particles, whereas the isothermal compressibility of the binary mixture was found to decrease with increasing volume fraction of small particles. The dynamics of single-component large particle dispersion obey the principles of de Gennes narrowing, where the wave vector dependence of the interparticle diffusion coefficient is inversely proportional to the interparticle structure factor. The dynamics of the bimodal dispersions demonstrate strong dependence on the fraction of small particles. As a result, we also made a comparison between the experimental effective dynamic viscosity of the bimodal dispersion with theoretical predictions, which suggest that the complex mutual interactions between large and small particles have a strong effect on the dynamic behaviors of bimodal dispersions.« less

Glass/Jamming Transition in Colloidal Aggregation

NASA Technical Reports Server (NTRS)

Segre, Philip N.; Prasad, Vikram; Weitz, David A.; Rose, M. Franklin (Technical Monitor)

2000-01-01

We have studied colloidal aggregation in a model colloid plus polymer system with short-range attractive interactions. By varying the colloid concentration and the strength of the attraction, we explored regions where the equilibrium phase is expected to consist of colloidal crystallites in coexistance with colloidal gas (i.e. monomers). This occurs for moderate values of the potential depth, U approximately equal to 2-5 kT. Crystallization was not always observed. Rather, over an extended sub-region two new metastable phases appear, one fluid-like and one solid-like. These were examined in detail with light scattering and microscopy techniques. Both phases consist of a near uniform distribution of small irregular shaped clusters of colloidal particles. The dynamical and structural characteristics of the ergodic-nonergodic transition between the two phases share much in common with the colloidal hard sphere glass transition.

Microdesigning of Lightweight/High Strength Ceramic Materials

DTIC Science & Technology

1989-07-31

Continue on reverse if necessary and identiy by block number) FIELD GROUP SUB- GROUP Ceramics, Composite Materials, Colloidal Processing Iii 19. ABSTRACT...to identify key processing parameters that affect the microstructure of the composite material. The second section describes experimental results in...results of the significant theoretical effort made in our group . Theoretical models of particle-particle interaction, particle-polymer interaction

Reversible gelation of rod-like viruses grafted with thermoresponsive polymers.

PubMed

Zhang, Zhenkun; Krishna, Naveen; Lettinga, M Paul; Vermant, Jan; Grelet, Eric

2009-02-17

The synthesis and selected macroscopic properties of a new model system consisting of poly(N-isopropylacrylamide) (PNIPAM)-coated rod-like fd virus particles are presented. The sticky rod-like colloids can be used to study effect of particle shape on gelation transition, the structure and viscoelasticity of isotropic and nematic gels, and to make both open isotropic as well as ordered nematic particle networks. This model system of rod-like colloids, for which the strength of attraction between the particles is tunable, is obtained by chemically grafting highly monodisperse rod-like fd virus particles with thermoresponsive polymers, e.g. PNIPAM. At room temperature, suspensions of the resulting hybrid PNIPAM-fd are fluid sols which are in isotropic or liquid crystalline phases, depending on the particle concentration and ionic strength. During heating/cooling, the suspensions change reversibly between sol and gel state near a critical temperature of approximately 32 degrees C, close to the lower critical solution temperature of free PNIPAM. The so-called nematic gel, which exhibits a cholesteric feature, can therefore be easily obtained. The gelation behavior of PNIPAM-fd system and the structure of the nematic gel have been characterized by rheology, optical microscopy and small-angle X-ray scattering.

Chemical colloids versus biological colloids: a comparative study for the elucidation of the mechanism of protein fiber formation

NASA Technical Reports Server (NTRS)

Xu, Shaohua; Wu, David; Arnsdorf, Morton; Johnson, Robert; Getz, Godfrey S.; Cabana, Veneracion G.

2005-01-01

Fiber formation from murine serum amyloid A1 (SAA) was compared to the linear aggregation and fiber formation of colloidal gold particles. Here we report the similarities of these processes. Upon incubation with acetic acid, SAA misfolds and adopts a new conformation, which we termed saa. saa apparently is less soluble than SAA in aqueous solution; it aggregates and forms nucleation units and then fibers. The fibers appear as a string of the nucleation units. Additionally, an external electric field promotes saa fiber formation. These properties of saa are reminiscent of colloidal gold formation from gold ions and one-dimensional aggregation of the gold colloids. Colloidal gold particles were also found to be capable of aggregating one-dimensionally under an electric field or in the presence of polylysine. These gold fibers resembled in structure that of saa fibers. In summary, protein aggregation and formation of fibers appear to follow the generalized principles derived in colloidal science for the aggregation of atoms and molecules, including polymers such as polypeptides. The analysis of colloidal gold formation and of one-dimensional aggregation provides a simple model system for the elucidation of some aspects of protein fiber formation.

Structure and Dynamics of Bimodal Colloidal Dispersions in a Low-Molecular-Weight Polymer Solution.

PubMed

Zhang, Fan; Allen, Andrew J; Levine, Lyle E; Tsai, De-Hao; Ilavsky, Jan

2017-03-21

We present an experimental study of the structural and dynamical properties of bimodal, micrometer-sized colloidal dispersions (size ratio ≈ 2) in an aqueous solution of low-molecular-weight polymer (polyethylene glycol 2000) using synchrotron ultra-small angle X-ray scattering (USAXS) and USAXS-based X-ray photon correlation spectroscopy. We fixed the volume fraction of the large particles at 5% and systematically increased the volume fraction of the small particles from 0 to 5% to evaluate their effects on the structure and dynamics. The bimodal dispersions were homogenous through the investigated parameter space. We found that the partial structure factors can be satisfactorily retrieved for the bimodal colloidal dispersions using a Percus-Yevick hard-sphere potential when the size distributions of the particles were taken into account. We also found that the partial structure factor between the large particles did not exhibit a significant variation with increasing volume fraction of the small particles, whereas the isothermal compressibility of the binary mixture was found to decrease with increasing volume fraction of the small particles. The dynamics of single-component large-particle dispersion obey the principles of de Gennes narrowing, where the wave vector dependence of the interparticle diffusion coefficient is inversely proportional to the interparticle structure factor. The dynamics of the bimodal dispersions demonstrate a strong dependence on the fraction of small particles. We also made a comparison between the experimental effective dynamic viscosity of the bimodal dispersion with the theoretical predictions, which suggest that the complex mutual interactions between the large and small particles have a strong effect on the dynamic behaviors of bimodal dispersions.

The self-assembly of particles with isotropic interactions: Using DNA coated colloids to create designer nanomaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, R. B.; Dion, S.; Konigslow, K. von

Self-consistent field theory equations are presented that are suitable for use as a coarse-grained model for DNA coated colloids, polymer-grafted nanoparticles and other systems with approximately isotropic interactions. The equations are generalized for arbitrary numbers of chemically distinct colloids. The advantages and limitations of such a coarse-grained approach for DNA coated colloids are discussed, as are similarities with block copolymer self-assembly. In particular, preliminary results for three species self-assembly are presented that parallel results from a two dimensional ABC triblock copolymer phase. The possibility of incorporating crystallization, dynamics, inverse statistical mechanics and multiscale modelling techniques are discussed.

Organic-Inorganic Composites of Semiconductor Nanocrystals for Efficient Excitonics.

PubMed

Guzelturk, Burak; Demir, Hilmi Volkan

2015-06-18

Nanocomposites of colloidal semiconductor nanocrystals integrated into conjugated polymers are the key to soft-material hybrid optoelectronics, combining advantages of both plastics and particles. Synergic combination of the favorable properties in the hybrids of colloidal nanocrystals and conjugated polymers offers enhanced performance and new functionalities in light-generation and light-harvesting applications, where controlling and mastering the excitonic interactions at the nanoscale are essential. In this Perspective, we highlight and critically consider the excitonic interactions in the organic-inorganic nanocomposites to achieve highly efficient exciton transfer through rational design of the nanocomposites. The use of strong excitonic interactions in optoelectronic devices can trigger efficiency breakthroughs in hybrid optoelectronics.

Nonlinear optical probe of biopolymer adsorption on colloidal particle surface: poly-L-lysine on polystyrene sulfate microspheres.

PubMed

Eckenrode, Heather M; Dai, Hai-Lung

2004-10-12

A nonlinear optical technique--second harmonic generation (SHG)--has been applied to characterize the adsorption of poly-L-lysine on micrometer size polystyrene particles, whose surface is covered with negatively charged sulfonate groups, in aqueous solutions. Adsorption behavior of the biopolymer with two chain lengths (14 and 75 amino acid units; PL14 and PL75) has been examined. Centrifugation experiments were also performed to support the adsorption measurements made using SHG. The adsorption free energies of the two polymers PL75 and PL14 are determined as -16.57 and -14.40 kcal/mol, respectively. The small difference in the adsorption free energies of the two chain lengths, however, leads to dramatic difference in the concentration needed for saturated surface coverage: nearly 50 times higher concentration is needed for the smaller polymer. Under acidic colloidal conditions, polylysine is found to adsorb in a relatively flat conformation on the surface. The surface area that each polylysine molecule occupies is nearly 1 order of magnitude larger than the size of the molecule in its extended form. The low adsorption density is likely a result from Coulombic repulsion between the positive charges on the amino acid units of PL. The measurements demonstrate the utility of SHG as an efficient and sensitive experimental approach for measuring adsorption characteristics of bio/macromolecules on colloidal particles and define surface and colloidal conditions for achieving maximum surface coverage of a widely used biopolymer. Copyright 2004 American Chemical Society

Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srivastava, Sunita; Kishore, Suhasini; Narayanan, Suresh

We present an X-ray photon correlation spectros- copy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of col- loids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the satu- ration concentration of added polymer, in which small clusters of nanoparticles form via a short-rangemore » depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily gov- erned by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion« less

Using Light Scattering to Track, Characterize and Manipulate Colloids

NASA Astrophysics Data System (ADS)

van Oostrum, P. D. J.

2011-03-01

A new technique is developed to analyze in-line Digital Holographic Microscopy images, making it possible to characterize, and track colloidal particles in three dimensions at unprecedented accuracy. We took digital snapshots of the interference pattern between the light scattered by micrometer particles and the unaltered portion of a laser beam that was used to illuminate dilute colloidal dispersions on a light microscope in transmission mode. We numerically fit Mie-theory for the light-scattering by micrometer sized particles to these experimental in-line holograms. The fit values give the position in three dimensions with an accuracy of a few nanometers in the lateral directions and several tens of nanometers in the axial direction. The individual particles radii and refractive indices could be determined to within tens of nanometers and a few hundredths respectively. By using a fast CCD camera, we can track particles with millisecond resolution in time which allows us to study dynamical properties such as the hydrodynamic radius and the sedimentation coefficient. The scattering behavior of the particles that we use to track and characterize colloidal particles makes it possible to exert pico-Newton forces on them close to a diffraction limited focus. When these effects are used to confine colloids in space, this technique is called Optical Tweezers. Both by numerical calculations and by experiments, we explore the possibilities of optical tweezers in soft condensed matter research. Using optical tweezers we placed multiple particles in interesting configurations to measure the interaction forces between them. The interaction forces were Yukawa-like screened charge repulsions. Careful timing of the blinking of time-shared optical tweezers and of the recording of holographic snapshots, we were able to measure interaction forces with femto-Newton accuracy from an analysis of (driven) Brownian motion. Forces exerted by external fields such as electric fields and gravity were measured as well. We induced electric dipoles in colloidal particles by applying radio frequency electric fields. Dipole induced strings of particles were formed and made permanent by van der Waals attractions or thermal annealing. Such colloidal strings form colloidal analogues of charged and un-charged (bio-) polymers. The diffusion and bending behavior of such strings was probed using DHM and optical tweezers.

Encapsulation of Polymer Colloids in a Sol-Gel Matrix. Direct-Writing of Coassembling Organic-Inorganic Hybrid Photonic Crystals.

PubMed

Mikosch, Annabel; Kuehne, Alexander J C

2016-03-22

The spontaneous self-assembly of polymer colloids into ordered arrangements provides a facile strategy for the creation of photonic crystals. However, these structures often suffer from defects and insufficient cohesion, which result in flaking and delamination from the substrate. A coassembly process has been developed for convective assembly, resulting in large-area encapsulated colloidal crystals. However, to generate patterns or discrete deposits in designated places, convective assembly is not suitable. Here we experimentally develop conditions for direct-writing of coassembling monodisperse dye-doped polystyrene particles with a sol-gel precursor to form solid encapsulated photonic crystals. In a simple procedure the colloids are formulated in a sol-gel precursor solution, drop-cast on a flat substrate, and dried. We here establish the optimal parameters to form reproducible highly ordered photonic crystals with good optical performance. The obtained photonic crystals interact with light in the visible spectrum with a narrow optical stop-gap.

Light-induced crosslinkable semiconducting polymer dots† †Electronic supplementary information (ESI) available: Synthesis and characterization of monomers and polymers, preparation and characterization of thin film and Pdots, optical property measurements and flow cytometry is available. See DOI: 10.1039/c4sc03959a Click here for additional data file.

PubMed Central

Zhang, Yue; Ye, Fangmao; Sun, Wei; Yu, Jiangbo; Wu, I-Che; Rong, Yu; Zhang, Yong

2015-01-01

This paper describes a synthetic approach for photocrosslinkable polyfluorene (pc-PFO) semiconducting polymer dots, and demonstrates their superior ability to crosslink and form 3-D intermolecular polymer networks. The crosslinked pc-PFO Pdots are equipped with excellent encapsulating ability of functional small molecules. Optimum conditions of light irradiation on pc-PFO Pdots were investigated and clarified by using polymer thin films as a model. By employing the optimal light irradiation conditions, we successfully crosslinked pc-PFO Pdots and studied their particle sizes, photophysical, and colloidal properties. Single-particle imaging and dynamic-light-scattering measurements were conducted to understand the behaviors of photocrosslinked Pdots. Our results indicate pc-PFO Pdots can be easily photocrosslinked and the crosslinked species have excellent colloidal stability, physical and chemical stability, fluorescence brightness, and specific binding properties for cellular labeling. Considering that optical stimulus can work remotely, cleanly, and non-invasively, this study should pave the way for a promising approach to further develop stimuli-responsive ultrabright and versatile Pdot probes for biomedical imaging. PMID:25709806

Preparation of anatase TiO2 thin film by low temperature annealing as an electron transport layer in inverted polymer solar cells

NASA Astrophysics Data System (ADS)

Noh, Hongche; Oh, Seong-Geun; Im, Seung Soon

2015-04-01

To prepare the anatase TiO2 thin films on ITO glass, amorphous TiO2 colloidal solution was synthesized through the simple sol-gel method by using titanium (IV) isopropoxide as a precursor. This amorphous TiO2 colloidal solution was spread on ITO glass by spin-coating, then treated at 450 °C to obtain anatase TiO2 film (for device A). For other TiO2 films, amorphous TiO2 colloidal solution was treated through solvothermal process at 180 °C to obtain anatase TiO2 colloidal solution. This anatase TiO2 colloidal solution was spread on ITO glass by spin coating, and then annealed at 200 °C (for device B) and 130 °C (for device C), respectively. The average particle size of amorphous TiO2 colloidal solution was about 1.0 nm and that of anatase TiO2 colloidal solution was 10 nm. The thickness of TiO2 films was about 15 nm for all cases. When inverted polymer solar cells were fabricated by using these TiO2 films as an electron transport layer, the device C showed the highest PCE (2.6%) due to the lack of defect, uniformness and high light absorbance of TiO2 films. The result of this study can be applied for the preparation of inverted polymer solar cell using TiO2 films as a buffer layer at low temperature on plastic substrate by roll-to roll process.

A pseudo-thermodynamic description of dispersion for nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Yan; Beaucage, Gregory; Vogtt, Karsten

Dispersion in polymer nanocomposites is determined by the kinetics of mixing and chemical affinity. Compounds like reinforcing filler/elastomer blends display some similarity to colloidal solutions in that the filler particles are close to randomly dispersed through processing. It is attractive to apply a pseudo-thermodynamic approach taking advantage of this analogy between the kinetics of mixing for polymer compounds and thermally driven dispersion for colloids. In order to demonstrate this pseudo-thermodynamic approach, two polybutadienes and one polyisoprene were milled with three carbon blacks and two silicas. These samples were examined using small-angle x-ray scattering as a function of filler concentration tomore » determine a pseudo-second order virial coefficient, A2, which is used as an indicator for compatibility of the filler and polymer. It is found that A2 follows the expected behavior with lower values for smaller primary particles indicating that smaller particles are less compatible and more difficult to mix. The measured values of A2 can be used to specify repulsive interaction potentials for coarse grain DPD simulations of filler/elastomer systems. In addition, new methods to quantify the filler percolation threshold and filler mesh size as a function of filler concentration are obtained. Moreover, the results represent a new approach to understanding and predicting compatibility in polymer nanocomposites based on a pseudo-thermodynamic approach.« less

A pseudo-thermodynamic description of dispersion for nanocomposites

DOE PAGES

Jin, Yan; Beaucage, Gregory; Vogtt, Karsten; ...

2017-09-18

Dispersion in polymer nanocomposites is determined by the kinetics of mixing and chemical affinity. Compounds like reinforcing filler/elastomer blends display some similarity to colloidal solutions in that the filler particles are close to randomly dispersed through processing. It is attractive to apply a pseudo-thermodynamic approach taking advantage of this analogy between the kinetics of mixing for polymer compounds and thermally driven dispersion for colloids. In order to demonstrate this pseudo-thermodynamic approach, two polybutadienes and one polyisoprene were milled with three carbon blacks and two silicas. These samples were examined using small-angle x-ray scattering as a function of filler concentration tomore » determine a pseudo-second order virial coefficient, A2, which is used as an indicator for compatibility of the filler and polymer. It is found that A2 follows the expected behavior with lower values for smaller primary particles indicating that smaller particles are less compatible and more difficult to mix. The measured values of A2 can be used to specify repulsive interaction potentials for coarse grain DPD simulations of filler/elastomer systems. In addition, new methods to quantify the filler percolation threshold and filler mesh size as a function of filler concentration are obtained. Moreover, the results represent a new approach to understanding and predicting compatibility in polymer nanocomposites based on a pseudo-thermodynamic approach.« less

Clarification of olive mill and winery wastewater by means of clay-polymer nanocomposites.

PubMed

Rytwo, Giora; Lavi, Roy; Rytwo, Yuval; Monchase, Hila; Dultz, Stefan; König, Tom N

2013-01-01

Highly polluted effluents from olive mills and wineries, among others, are unsuitable for discharge into standard sewage-treatment plants due to the large amounts of organic and suspended matter. Efficiency of all management practices for such effluents depends on an effective pretreatment that lowers the amount of suspended solids. Such pretreatments are usually based on three separate stages, taking a total of 2 to 6h: coagulation-neutralizing the colloids, flocculation-aggregating the colloids into larger particles, and separation via filtration or decanting. Previous studies have presented the concept of coagoflocculation based on the use of clay-polymer nanocomposites. This process adds a higher density clay particle to the flocs, accelerating the process to between 15 and 60 min. This study examined suitable nanocomposites based on different clays and polymers. The charge of the compounds increased proportionally to the polymer-to-clay ratio. X-ray diffraction (XRD) measurements indicated that in sepiolite-based nanocomposites there is no change in the structure of the mineral, whereas in smectite-based nanocomposites, the polymer intercalates between the clay layers and increases the spacing depending on the polymer-to-clay ratio. Efficiency of the coagoflocculation process was studied with a dispersion analyzer. Sequential addition of olive mill or winery effluents with a boosting dose of nanocomposites may yield a very efficient and rapid clarification pretreatment. Copyright © 2012 Elsevier B.V. All rights reserved.

Advances in the microrheology of complex fluids

NASA Astrophysics Data System (ADS)

Waigh, Thomas Andrew

2016-07-01

New developments in the microrheology of complex fluids are considered. Firstly the requirements for a simple modern particle tracking microrheology experiment are introduced, the error analysis methods associated with it and the mathematical techniques required to calculate the linear viscoelasticity. Progress in microrheology instrumentation is then described with respect to detectors, light sources, colloidal probes, magnetic tweezers, optical tweezers, diffusing wave spectroscopy, optical coherence tomography, fluorescence correlation spectroscopy, elastic- and quasi-elastic scattering techniques, 3D tracking, single molecule methods, modern microscopy methods and microfluidics. New theoretical techniques are also reviewed such as Bayesian analysis, oversampling, inversion techniques, alternative statistical tools for tracks (angular correlations, first passage probabilities, the kurtosis, motor protein step segmentation etc), issues in micro/macro rheological agreement and two particle methodologies. Applications where microrheology has begun to make some impact are also considered including semi-flexible polymers, gels, microorganism biofilms, intracellular methods, high frequency viscoelasticity, comb polymers, active motile fluids, blood clots, colloids, granular materials, polymers, liquid crystals and foods. Two large emergent areas of microrheology, non-linear microrheology and surface microrheology are also discussed.

Deep-Blue Fluorescent Particles via Microwave Heating of Polyacrylonitrile Dispersions.

PubMed

Go, Dennis; Jurásková, Alena; Hoffmann, Andreas; Kapiti, Gent; Kuehne, Alexander J C

2017-03-01

This study presents a new method to produce fluorescent particles. Established methods are based on the incorporation of conjugated dye molecules into dielectric polymer matrices or preparation of colloids, which are composed of fluorescent conjugated polymer. By contrast, this study presents a method where dielectric polyacrylonitrile is exposed to microwave radiation leading to an intramolecular cyclization reaction producing π-conjugated segments, which fluoresce blue. During this conversion, the particles shrink in diameter but as an ensemble they retain their monodispersity. This work investigates the optimal reaction conditions and characterizes the optical properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Particle formation in the emulsion-solvent evaporation process.

PubMed

Staff, Roland H; Schaeffel, David; Turshatov, Andrey; Donadio, Davide; Butt, Hans-Jürgen; Landfester, Katharina; Koynov, Kaloian; Crespy, Daniel

2013-10-25

The mechanism of particle formation from submicrometer emulsion droplets by solvent evaporation is revisited. A combination of dynamic light scattering, fluorescence resonance energy transfer, zeta potential measurements, and fluorescence cross-correlation spectroscopy is used to analyze the colloids during the evaporation process. It is shown that a combination of different methods yields reliable and quantitative data for describing the fate of the droplets during the process. The results indicate that coalescence plays a minor role during the process; the relatively large size distribution of the obtained polymer colloids can be explained by the droplet distribution after their formation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of polymerized crystalline colloidal array thin film modified β-cyclodextrin polymer for paraoxon-ethyl and parathion-ethyl detection.

PubMed

Bui, Minh-Phuong N; Seo, Seong S

2014-01-01

We have developed an optical chemical sensor for the detection of organophosphate (OP) compounds using a polymerized crystalline colloidal array (PCCA) thin film composed of a close-packed colloidal array of polystyrene particles. The PCCA thin film was modified with β-cyclodextrin (β-CD) polymer as a capping cavity for the selective detection of paraoxon-ethyl and parathion-ethyl chemical agents. The fabrication of the modified PCCA thin film was optimized and the structure was characterized using scanning electron microscopy (SEM). The arrangement of polystyrene particles in the PCCA follows a pattern of the fcc (111) planes with strong diffraction peak in the visible spectral region and pH dependence. The diffraction peak of the β-CD modified PCCA thin film showed a red shift according to the change of paraoxon-ethyl and parathion-ethyl concentrations at a fast response time (10 s) and high sensitivity with detection limits of 2.0 and 3.4 ppb, respectively. Furthermore, the proposed interaction mechanism of β-CD with paraoxon-ethyl and parathion-ethyl in the β-CD modified PCCA thin film were discussed.

DNA-imprinted polymer nanoparticles with monodispersity and prescribed DNA-strand patterns

NASA Astrophysics Data System (ADS)

Trinh, Tuan; Liao, Chenyi; Toader, Violeta; Barłóg, Maciej; Bazzi, Hassan S.; Li, Jianing; Sleiman, Hanadi F.

2018-02-01

As colloidal self-assembly increasingly approaches the complexity of natural systems, an ongoing challenge is to generate non-centrosymmetric structures. For example, patchy, Janus or living crystallization particles have significantly advanced the area of polymer assembly. It has remained difficult, however, to devise polymer particles that associate in a directional manner, with controlled valency and recognition motifs. Here, we present a method to transfer DNA patterns from a DNA cage to a polymeric nanoparticle encapsulated inside the cage in three dimensions. The resulting DNA-imprinted particles (DIPs), which are 'moulded' on the inside of the DNA cage, consist of a monodisperse crosslinked polymer core with a predetermined pattern of different DNA strands covalently 'printed' on their exterior, and further assemble with programmability and directionality. The number, orientation and sequence of DNA strands grafted onto the polymeric core can be controlled during the process, and the strands are addressable independently of each other.

Grafting-Density Effects, Optoelectrical Properties and Nano-Patterning of Poly(para-Phenylene) Brushes

DTIC Science & Technology

2013-01-01

NAME OF RESPONSIBLE PERSON 19b. TELEPHONE NUMBER S. Michael Kilbey Dawen Li, Jimmy W. Mays , S. Michael Kilbey II, Jihua Chen, Jose Alonzo, Xiang Yu...Dawen Li,d Jimmy W. Mays ,be Bobby G. Sumpteraf and S. Michael Kilbey II*eg Well-defined conjugated polymers in confined geometries are chal- lenging to...relationships of conned thin lms and may serve as a basis to understand polymer micelles, polymer-stabilized colloid particles, or interfaces compatibi

Cytosolic delivery of materials with endosome-disrupting colloids

DOEpatents

Helms, Brett A.; Bayles, Andrea R.

2016-03-15

A facile procedure to deliver nanocrystals to the cytosol of live cells that is both rapid and general. The technique employs a unique cationic core-shell polymer colloid that directs nanocrystals to the cytosol of living cells within a few hours of incubation. The present methods and compositions enable a host of advanced applications arising from efficient cytosolic delivery of nanocrystal imaging probes: from single particle tracking experiments to monitoring protein-protein interactions in live cells for extended periods.

Direct Visualization of Conformation and Dense Packing of DNA-Based Soft Colloids

NASA Astrophysics Data System (ADS)

Zhang, Jing; Lettinga, Paul M.; Dhont, Jan K. G.; Stiakakis, Emmanuel

2014-12-01

Soft colloids—such as polymer-coated particles, star polymers, block-copolymer micelles, microgels—constitute a broad class of materials where microscopic properties such as deformability and penetrability of the particle play a key role in tailoring their macroscopic properties which is of interest in many technological areas. The ability to access these microscopic properties is not yet demonstrated despite its great importance. Here we introduce novel DNA-coated colloids with star-shaped architecture that allows accessing the above local structural information by directly visualizing their intramolecular monomer density profile and arm's free-end locations with confocal fluorescent microscopy. Compression experiments on a two-dimensional hexagonal lattice formed by these macromolecular assemblies reveal an exceptional resistance to mutual interpenetration of their charged corona at pressures approaching the MPa range. Furthermore, we find that this lattice, in a close packing configuration, is surprisingly tolerant to particle size variation. We anticipate that these stimuli-responsive materials could aid to get deeper insight in a wide range of problems in soft matter, including the study and design of biomimetic lubricated surfaces.

Synthesis of highly monodisperse particles composed of a magnetic core and fluorescent shell.

PubMed

Nagao, Daisuke; Yokoyama, Mikio; Yamauchi, Noriko; Matsumoto, Hideki; Kobayashi, Yoshio; Konno, Mikio

2008-09-02

Highly monodisperse particles composed of a magnetic silica core and fluorescent polymer shell were synthesized with a combined technique of heterocoagulation and soap-free emulsion polymerization. Prior to heterocoagulation, monodisperse, submicrometer-sized silica particles were prepared with the Stober method, and magnetic nanoparticles were prepared with a modified Massart method in which a cationic silane coupling agent of N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride was added just after coprecipitation of Fe (2+) and Fe (3+). The silica particles with negative surface potential were heterocoagulated with the magnetic nanoparticles with positive surface potential. The magnetic silica particles obtained with the heterocoagulation were treated with sodium silicate to modify their surfaces with silica. In the formation of a fluorescent polymer shell onto the silica-coated magnetic silica cores, an amphoteric initiator of 2,2'-azobis[ N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was used to control the colloidal stability of the magnetic cores during the polymer coating. The polymerization of St in the presence of a hydrophobic fluorophore of pyrene could coat the cores with fluorescent polymer shells, resulting in monodisperse particles with a magnetic silica core and fluorescent polymer shell. Measurements of zeta potential for the composite particles in different pH values indicated that the composite particles had an amphoteric property originating from VA-057 initiator.

Multidentate-Protected Colloidal Gold Nanocrystals: pH Control of Cooperative Precipitation and Surface Layer Shedding

PubMed Central

Kairdolf, Brad A.; Nie, Shuming

2011-01-01

Colloidal gold nanocrystals with broad size tunability and unusual pH-sensitive properties have been synthesized by using multidentate polymer ligands. Containing both carboxylic functional groups and sterically hindered aliphatic chains, the multidentate ligands are able to both reduce gold precursors and to stabilize gold nanoclusters during nucleation and growth. The “as-synthesized” nanocrystals are protected by an inner coordinating layer and an outer polymer layer, and are soluble in water and polar solvents. When the solution pH is lowered by just 0.6 units (from pH 4.85 to 4.25), the particles undergo a dramatic cooperative transition from being soluble to insoluble, allowing rapid isolation, purification, and redispersion of the multidentate-protected nanocrystals. A surprise finding is that when a portion of the surface carboxylate groups is neutralized by protonation, the particles irreversibly shed their outer polymer layer and become soluble in nonpolar organic solvents. Further, the multidentate polymer coatings are permeable to small organic molecules, in contrast to tightly packed self-assembled monolayers of alkanethiols on gold. These insights are important towards the design of “smart” imaging and therapeutic nanoparticles that are activated by small pH changes in the tumor interstitial space or endocytic organelles. PMID:21510704

Analytical phase diagrams for colloids and non-adsorbing polymer.

PubMed

Fleer, Gerard J; Tuinier, Remco

2008-11-04

We review the free-volume theory (FVT) of Lekkerkerker et al. [Europhys. Lett. 20 (1992) 559] for the phase behavior of colloids in the presence of non-adsorbing polymer and we extend this theory in several aspects: (i) We take the solvent into account as a separate component and show that the natural thermodynamic parameter for the polymer properties is the insertion work Pi(v), where Pi is the osmotic pressure of the (external) polymer solution and v the volume of a colloid particle. (ii) Curvature effects are included along the lines of Aarts et al. [J. Phys.: Condens. Matt. 14 (2002) 7551] but we find accurate simple power laws which simplify the mathematical procedure considerably. (iii) We find analytical forms for the first, second, and third derivatives of the grand potential, needed for the calculation of the colloid chemical potential, the pressure, gas-liquid critical points and the critical endpoint (cep), where the (stable) critical line ends and then coincides with the triple point. This cep determines the boundary condition for a stable liquid. We first apply these modifications to the so-called colloid limit, where the size ratio q(R)=R/a between the radius of gyration R of the polymer and the particle radius a is small. In this limit the binodal polymer concentrations are below overlap: the depletion thickness delta is nearly equal to R, and Pi can be approximated by the ideal (van't Hoff) law Pi=Pi(0)=phi/N, where phi is the polymer volume fraction and N the number of segments per chain. The results are close to those of the original Lekkerkerker theory. However, our analysis enables very simple analytical expressions for the polymer and colloid concentrations in the critical and triple points and along the binodals as a function of q(R). Also the position of the cep is found analytically. In order to make the model applicable to higher size ratio's q(R) (including the so-called protein limit where q(R)>1) further extensions are needed. We introduce the size ratio q=delta/a, where the depletion thickness delta is no longer of order R. In the protein limit the binodal concentrations are above overlap. In such semidilute solutions delta approximately xi, where the De Gennes blob size (correlation length) xi scales as xi approximately phi(-gamma), with gamma=0.77 for good solvents and gamma=1 for a theta solvent. In this limit Pi=Pi(sd) approximately phi(3gamma). We now apply the following additional modifications: With these latter two modifications we obtain again a fully analytical model with simple equations for critical and triple points as a function of q(R). In the protein limit the binodal polymer concentrations scale as q(R)(1/gamma), and phase diagrams phiq(R)(-1/gamma) versus the colloid concentration eta become universal (i.e., independent of the size ratio q(R)). The predictions of this generalized free-volume theory (GFVT) are in excellent agreement with experiment and with computer simulations, not only for the colloid limit but also for the protein limit (and the crossover between these limits). The q(R)(1/gamma) scaling is accurately reproduced by both simulations and other theoretical models. The liquid window is the region between phi(c) (critical point) and phi(t) (triple point). In terms of the ratio phi(t)/phi(c) the liquid window extends from 1 in the cep (here phi(t)-phi(c)=0) to 2.2 in the protein limit. Hence, the liquid window is narrow: it covers at most a factor 2.2 in (external) polymer concentration.

Depletion interaction between colloids mediated by an athermal polymer blend

NASA Astrophysics Data System (ADS)

Chervanyov, A. I.

2018-03-01

We calculate the immersion energy of a colloid and the potential of the depletion interaction (DI) acting between colloids immersed in an athermal polymer blend. The developed theory has no limitations with respect to the polymer-to-colloid size ratios and polymer densities, covering, in particular, dense polymer blends. We demonstrate that in addition to the standard compressibility-induced mechanism of the DI there exists the mechanism relying on the correlations between compositional fluctuations specific to polymer blends. We quantitatively investigate this "compositional" mechanism of the DI and demonstrate that it causes significant contributions to the effective force acting between colloids. Further we show that relative significance of the contributions to the colloid immersion energy and the depletion potential caused by the above compositional mechanism strongly depends on the mass fractions of the polymer species and their size ratio. We find out that these contributions strongly affect the range of the DI, thus causing a significant increase in the absolute value of the second virial coefficient of the effective potential acting between colloids.

Incorporation of additives into polymers

DOEpatents

McCleskey, T. Mark; Yates, Matthew Z.

2003-07-29

There has been invented a method for incorporating additives into polymers comprising: (a) forming an aqueous or alcohol-based colloidal system of the polymer; (b) emulsifying the colloidal system with a compressed fluid; and (c) contacting the colloidal polymer with the additive in the presence of the compressed fluid. The colloidal polymer can be contacted with the additive by having the additive in the compressed fluid used for emulsification or by adding the additive to the colloidal system before or after emulsification with the compressed fluid. The invention process can be carried out either as a batch process or as a continuous on-line process.

Dynamics of nanoparticles in complex fluids

NASA Astrophysics Data System (ADS)

Omari, Rami A.

Soft matter is a subfield of condensed matter including polymers, colloidal dispersions, surfactants, and liquid crystals. These materials are familiar from our everyday life- glues, paints, soaps, and plastics are examples of soft materials. Many phenomena in these systems have the same underlying physical mechanics. Moreover, it has been recognized that combinations of these systems, like for example polymers and colloids, exhibit new properties which are not found in each system separately. These mixed systems have a higher degree of complexity than the separate systems. In order to understand their behavior, knowledge from each subfields of soft matter has to be put together. One of these complex systems is the mixture of nanoparticles with macromolecules such as polymers, proteins, etc. Understanding the interactions in these systems is essential for solving various problems in technological and medical fields, such as developing high performance polymeric materials, chromatography, and drug delivery vehicles. The author of this dissertation investigates fundemental soft matter systems, including colloid dispersions in polymer solutions and binary mixture. The diffusion of gold nanoparticles in semidilute and entangled solutions of polystyrene (PS) in toluene were studied using fluorescence correlation spectroscopy (FCS). In our experiments, the particle radius (R ≈ 2.5 nm) was much smaller compared to the radius of gyration of the chain but comparable to the average mesh size of the fluctuating polymer network. The diffusion coefficient (D) of the particles decreased monotonically with polymer concentration and it can be fitted with a stretched exponential function. At high concentration of the polymer, a clear subdiffusive motion of the particles was observed. The results were compared with the diffusion of free dyes, which showed normal diffusive behavior for all concentrations. In another polymer solution, poly ethylene glycol (PEG) in water, the diffusion of the gold nanoparticles depends on the dimentionless length scale R/zeta, where R is the radius of the nanoparticle and zeta is the average mesh size of the fluctuating polymer network. FCS were used to study the critical adsorption on curved surfaces by utilizing spherical nanoparticles immersed in a critical binary liquid mixture of 2,6 lutidine + water. The temperature dependence of the adsorbed film thickness and excess adsorption was determined from FCS measurements of the enlarged effective hydrodynamic radius of the particles. Our results indicated that the adsorbed film thickness is of the order of correlation length associated with concentration fluctuations. The excess adsorption per unit area increases following a power law in reduced temperature with an exponent of -1, which is the mean-field value for the bulk susceptibility exponent. The kinetics of adsorption of gold nanoparticles in polymer solutions on silicon substrate was studied using ellipsometry by measuring the thickness of the adsorbed layer versus time. The data showed an exponential growth with relaxation time constants, which is proportional to the diffusion of the gold nanoparticles in polymer solution.

Design colloidal particle morphology and self-assembly for coating applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Shan; Van Dyk, Antony; Maurice, Alvin

The progressive replacement of organic solvent-based coatings by waterborne latex polymer coatings has substantially renovated the coating industry, and generated huge environmental and health benefits. Today, on top of the continuing demand for higher performance and lower costs, the coating industry faces tighter regulation and higher sustainability standards. In addition, the new waterborne coatings have created unique opportunities and challenges in terms of fundamental understanding and research development. To address these challenges, polymer latex binders with diverse particle morphologies have been developed to improve coating performance. Furthermore, colloidal self-assembly has been utilized to help manufacturers make better paint with lessmore » cost. In this report, we review the recent progress in both fundamental study and industrial application in the context of developing new generation architectural coating materials. We introduce the basic concepts in coating materials and showcase several key technologies that have been implemented to improve coating performance. As a result, these technologies also represent the most important considerations in architectural coating design.« less

Design colloidal particle morphology and self-assembly for coating applications

DOE PAGES

Jiang, Shan; Van Dyk, Antony; Maurice, Alvin; ...

2017-05-04

The progressive replacement of organic solvent-based coatings by waterborne latex polymer coatings has substantially renovated the coating industry, and generated huge environmental and health benefits. Today, on top of the continuing demand for higher performance and lower costs, the coating industry faces tighter regulation and higher sustainability standards. In addition, the new waterborne coatings have created unique opportunities and challenges in terms of fundamental understanding and research development. To address these challenges, polymer latex binders with diverse particle morphologies have been developed to improve coating performance. Furthermore, colloidal self-assembly has been utilized to help manufacturers make better paint with lessmore » cost. In this report, we review the recent progress in both fundamental study and industrial application in the context of developing new generation architectural coating materials. We introduce the basic concepts in coating materials and showcase several key technologies that have been implemented to improve coating performance. As a result, these technologies also represent the most important considerations in architectural coating design.« less

The adsorption of cationic and amphoteric copolymers on glass surfaces: zeta potential measurements, adsorption isotherm determination, and FT Raman characterization.

PubMed

Tartakovsky, Alla; Drutis, Dane M; Carnali, Joseph O

2003-07-15

The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed.

Assembly of Colloidal Materials Using Bioadhesive Interactions

NASA Technical Reports Server (NTRS)

Hammer, Daniel A.; Hiddessen, Amy L.; Tohver, Valeria; Crocker, John C.; Weitz, David A.

2002-01-01

We have pursued the use of biological crosslinking molecules of several types to make colloidal materials at relatively low volume fraction of colloidal particles. The objective is to make binary alloys of colloidal particles, made of two different colloidal particles coated with complementary biological lock-and-key binding molecules, which assemble due to the biological specificity. The long-term goal is to use low affinity lock-and-key biological interactions, so that the can anneal to form crystalline states. We have used a variety of different surface chemistries in order to make colloidal materials. Our first system involved using selectin-carbohydrate (sialyl-Lewis) interactions; this chemistry is derived from immune system. This chemical interaction is of relatively low affinity, with timescales for dissociation of several seconds. Furthermore, the adhesion mediated by these molecules can be reversed by the chelation of calcium atoms; thus assembled structures can be disassembled reversibly. Our second system employed avidin-biotin chemistry. This well-studied system is of high affinity, and is generally irreversible on a laboratory time-scale. Thus, we would expect selectin-carbohydrate interactions at high molecular density and avidin-biotin interactions to give kinetically-trapped structures; however, at low densities, we would expect significant differences in the structure and dynamics of the two materials, owing to their very different release rates. We have also begun to use a third chemistry - DNA hybridization. By attaching single stranded DNA oligonucleotide chains to beads, we can drive the assembly of colloidal materials by hybridization of complementary DNA chains. It is well known that DNA adenosine-thymine (A-T) and guanine-cytosine (G-C) bases hybridize pairwise with a Gibbs free energy change of 1.7 kcal/mol per base; thus, the energy of the assembly can be modulated by altering the number of complementary bases in the DNA chains. Using these different crosslinking molecules, we have assembled colloidal materials from different-sized colloidal particles, A and B. In the first sets of experiment, we used high densities of adhesion molecules, and 0.96 micron (A) and 5.5 micron (B) diameter particles. The high density of adhesion molecules means that the structures are kinetically trapped in nonequilibrium configurations. The structure of the suspension can be varied by changing the number ratio of the two types of colloidal particles, NA and NB, where A is the smaller particle. With carbohydrate-selectin or avidin-biotin interactions, large NA/NB leads to the formation of colloidal micelles, with the large center B particle surrounded by many smaller A particles. As the ratio NA/NB decreases, the structures become more extended, approaching the formation of macro-Rouse polymers - extended linear chains where A beads are connected with intervening small B linkers.

Molecular engineering of chiral colloidal liquid crystals using DNA origami

NASA Astrophysics Data System (ADS)

Siavashpouri, Mahsa; Wachauf, Christian H.; Zakhary, Mark J.; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

2017-08-01

Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

Molecular engineering of chiral colloidal liquid crystals using DNA origami.

PubMed

Siavashpouri, Mahsa; Wachauf, Christian H; Zakhary, Mark J; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

2017-08-01

Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

Towards biocompatible vaccine delivery systems: interactions of colloidal PECs based on polysaccharides with HIV-1 p24 antigen.

PubMed

Drogoz, Alexandre; Munier, Séverine; Verrier, Bernard; David, Laurent; Domard, Alain; Delair, Thierry

2008-02-01

This work reports on the interactions of a model protein (p24, the capside protein of HIV-1 virus) with colloids obtained from polyelectrolyte complexes (PECs) involving two polysaccharides: chitosan and dextran sulfate (DS). The PECs were elaborated by a one-shot addition of default amounts of one counterpart to the polymer in excess. Depending on the nature of the excess polyelectrolyte, the submicrometric colloid was either positively or negatively charged. HIV-1 capsid p24 protein was chosen as antigen, the ultrapure form, lipopolysaccharide-free (endotoxin-, vaccine grade) was used in most experiments, as the level of purity of the protein had a great impact on the immobilization process. p24 sorption kinetics, isotherms, and loading capacities were investigated for positively and negatively charged particles of chitosans and dextran sulfates differing in degrees of polymerization (DP) or acetylation (DA). Compared with the positive particles, negatively charged colloids had higher binding capacities, faster kinetics, and a better stability of the adsorbed p24. Capacities up to 600 mg x g(-1) (protein-colloid) were obtained, suggesting that the protein interacted within the shell of the particles. Small-angle X-rays scattering experiments confirmed this hypothesis. Finally, the immunogenicity of the p24-covered particles was assessed for vaccine purposes in mice. The antibody titers obtained with immobilized p24 was dose dependent and in the same range as for Freund's adjuvant, a gold standard for humoral responses.

Passive non-linear microrheology for determining extensional viscosity

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Dinic, Jelena; Ren, Yi; Sharma, Vivek; Schroeder, Charles M.

2017-12-01

Extensional viscosity is a key property of complex fluids that greatly influences the non-equilibrium behavior and processing of polymer solutions, melts, and colloidal suspensions. In this work, we use microfluidics to determine steady extensional viscosity for polymer solutions by directly observing particle migration in planar extensional flow. Tracer particles are suspended in semi-dilute solutions of DNA and polyethylene oxide, and a Stokes trap is used to confine single particles in extensional flows of polymer solutions in a cross-slot device. Particles are observed to migrate in the direction transverse to flow due to normal stresses, and particle migration is tracked and quantified using a piezo-nanopositioning stage during the microfluidic flow experiment. Particle migration trajectories are then analyzed using a second-order fluid model that accurately predicts that migration arises due to normal stress differences. Using this analytical framework, extensional viscosities can be determined from particle migration experiments, and the results are in reasonable agreement with bulk rheological measurements of extensional viscosity based on a dripping-onto-substrate method. Overall, this work demonstrates that non-equilibrium properties of complex fluids can be determined by passive yet non-linear microrheology.

Functional Polymer Opals and Porous Materials by Shear-Induced Assembly of Tailor-Made Particles.

PubMed

Gallei, Markus

2018-02-01

Photonic band-gap materials attract enormous attention as potential candidates for a steadily increasing variety of applications. Based on the preparation of easily scalable monodisperse colloids, such optically attractive photonic materials can be prepared by an inexpensive and convenient bottom-up process. Artificial polymer opals can be prepared by shear-induced assembly of core/shell particles, yielding reversibly stretch-tunable materials with intriguing structural colors. This feature article highlights recent developments of core/shell particle design and shear-induced opal formation with focus on the combination of hard and soft materials as well as crosslinking strategies. Structure formation of opal materials relies on both the tailored core/shell architecture and the parameters for polymer processing. The emphasis of this feature article is on elucidating the particle design and incorporation of addressable moieties, i.e., stimuli-responsive polymers as well as elaborated crosslinking strategies for the preparation of smart (inverse) opal films, inorganic/organic opals, and ceramic precursors by shear-induced ordering. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measuring the equation of state for a 2D colloidal membrane: A microfluidic approach to buffer exchange

NASA Astrophysics Data System (ADS)

Balchunas, Andrew; Cabanas, Rafael; Fraden, Seth; Dogic, Zvonimir

Previous work has shown that monodisperse rod-like colloidal particles, such as a filamentous bacteriophage, self assemble into a 2D monolayer smectic in the presence of a non-adsorbing depleting polymer. These structures have the same functional form of bending rigidity and lateral compressibility as conventional lipid bi-layers, so we name the monolayer smectic a colloidal membrane. We have developed a microfluidic device such that the osmotic pressure acting on a colloidal membrane may be controlled via a full in situ buffer exchange. Rod density within individual colloidal membranes was measured as a function of osmotic pressure and a first order phase transition, from 2D fluid to 2D solid, was observed. kon and koff rates of rod to membrane binding were measured by lowering the osmotic pressure until membrane evaporation occurred.

Hexadecapolar Colloids

DOE PAGES

Senyuk, Bohdan; Puls, Owen; Tovkach, Oleh M.; ...

2016-02-11

Outermost occupied electron shells of chemical elements can have symmetries resembling that of monopoles, dipoles, quadrupoles and octupoles corresponding to filled s-, p-, d- and forbitals. Theoretically, elements with hexadecapolar outer shells could also exist, but none of the known elements have filled g-orbitals. On the other hand, the research paradigm of ‘colloidal atoms’ displays complexity of particle behaviour exceeding that of atomic counterparts, which is driven by DNA functionalization, geometric shape and topology and weak external stimuli. We describe elastic hexadecapoles formed by polymer microspheres dispersed in a liquid crystal, a nematic fluid of orientationally ordered molecular rods. Becausemore » of conically degenerate boundary conditions, the solid microspheres locally perturb the alignment of the nematic host, inducing hexadecapolar distortions that drive anisotropic colloidal interactions. We uncover physical underpinnings of formation of colloidal elastic hexadecapoles and report the ensuing bonding inaccessible to elastic dipoles, quadrupoles and other nematic colloids studied previously.« less

Amphiphilic Soft Janus Particles as Interfacial Stabilizers

NASA Astrophysics Data System (ADS)

Wang, Wenda; Niu, Sunny; Sosa, Chris; Prud'Homme, Robert; Priestley, Rodney; Priestley Polymer Group Team; Prud'homme Research Group Team

Janus particles, which incorporate two or more ``faces'' with different chemical functionality, have attracted great attention in scientific research. Amphiphilic Janus particles have two faces with distinctly different hydrophobicity. This can be thought of as colloidal surfactants. Theoretical studies on the stabilization of emulsions using Janus particles have confirmed higher efficiency. Herein we synthesize the narrow distributed amphiphilic polymeric Janus particles via Precipitation-Induced Self-Assembly (PISA). The efficiency of the amphiphilic Janus particles are tested on different oil/water systems. Biocompatible polymers can also be used on this strategy and may potentially have wide application for food emulsion, cosmetics and personal products.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions.

PubMed

Abraham, Alex; Chatterji, Apratim

2018-04-21

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions

NASA Astrophysics Data System (ADS)

Abraham, Alex; Chatterji, Apratim

2018-04-01

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

Lattice-Boltzmann-based simulations of diffusiophoresis of colloids and cells

NASA Astrophysics Data System (ADS)

Kreft Pearce, Jennifer; Castigliego, Joshua

Increasing environmental degradation due to plastic pollutants requires innovative solutions that facilitate the extraction of pollutants without harming local biota. We present results from a lattice-Boltzmann-base Brownian Dynamics simulation on diffusiophoresis and the separation of particles within the system. A gradient in viscosity that simulates a concentration gradient in a dissolved polymer allows us to separate various types of particles based on their deformability. As seen in previous experiments, simulated particles that have a higher deformability react differently to the polymer matrix than those with a lower deformability. Therefore, the particles can be separated from each other. The system described above was simulated with various concentration gradients as well as various Soret coefficients in order to optimize the separation of the particles. This simulation, in particular, was intended to model an oceanic system where the particles of interest were motile and nonmotile plankton and microplastics. The separation of plankton from the microplastics was achieved.

Rheology and microstructure of filled polymer melts

NASA Astrophysics Data System (ADS)

Anderson, Benjamin John

The states of particle dispersion in polymer nanocomposite melts are studied through rheological characterization of nanocomposite melt mechanical properties and small angle X-ray scattering measurement of the particle microstructure. The particle microstructure probed with scattering is related to bulk flow mechanics to determine the origin of slow dynamics in these complex dispersions: whether a gel or glass transition or a slowing down of dispersing phase dynamics. These studies were conducted to understand polymer mediated particle-particle interactions and potential particle-polymer phase separation. The phase behavior of the dispersion will be governed by enthalpic and entropic contributions. A variety of phases are expected: homogeneous fluid, phase separated, or non-equilibrium gel. The effects of dispersion control parameters, namely particle volume fraction, polymer molecular weight, and polymer-particle surface affinity, on the phase behavior of 44 nm silica dispersions are studied in low molecular weight polyethylene oxide (PEO), polyethylene oxide dimethylether (PEODME), and polytetrahydrofuran (PTHF). Scattering measurements of the particle second virial coefficient in PEO melts indicates repulsive particles by a value slightly greater than unity. In PEO nanocomposites, dispersion dynamics slow down witnessed by a plateau in the elastic modulus as the particle separation approaches the length scale of the polymer radius of gyration. As the polymer molecular weight is increased, the transition shifts to lower particle volume fractions. Below polymer entanglement, the slow dynamics mimics that of a colloidal glass by the appearance of two relaxation times in the viscous modulus that display power law scaling with volume fraction. Above entanglement, the slow dynamics is qualitatively different resembling the behavior of a gelled suspension yet lacking any sign of scattering from particle agglomerates. As polymer molecular weight is increased at a fixed volume fraction, two strain yielding events emerge. Further particle loading leads to the formation of a particle-polymer network and the onset of brittle mechanical behavior. The performance of PEO nanocomposites is contrasted by PEODME and PTHF nanocomposites where a change in the polymer segment-surface activity changes the slow dynamics of the nanocomposite and the microstructure of particles in the melt. Slow dynamics and the particle microstructure indicate a gelled suspension as volume fraction is raised with particles in or near contact and support the turning on of particle attractions in the melt.

Near-infrared (NIR) emitting conjugated polymers for biomedical applications (Presentation Recording)

NASA Astrophysics Data System (ADS)

Repenko, Tatjana; Kuehne, Alexander J. C.

2015-10-01

Fluorescent biomedical markers of today such as dye-infiltrated colloids, microgels and quantum dots suffer from fast bleaching, lack surface functionality (for targets or pharmaceutical agents) and potentially leach heavy metals in case of quantum dots (e.g. Cd). By contrast, conjugated polymer particles are non-cytotoxic, exhibit reduced bleaching, as the entire particle consists of fluorophore, they are hydrophobic and show high quantum yields. Consequently, conjugated polymer particles represent ideal materials for biological applications and imaging. However currently, conjugated polymer particles for biomedical imaging usually lack near-infrared (NIR) emission and are polydisperse. Fluorescent agents with emission in the NIR spectrum are interesting for biomedical applications due to their low photo-damage towards biological species and the ability of NIR radiation to penetrate deep into biological tissue.. I will present the development and synthesis of new conjugated polymers particles with fluorescence in the NIR spectral region for bio-imaging and clinical diagnosis. The particle synthesis proceeds in a one-step Pd or Ni-catalyzed dispersion polymerization of functional NIR emitters. The resulting monodisperse conjugated polymer particles are obtained as a dispersion in a non-hazardous solvent. Different sizes in the sub-micrometer range with a narrow size distribution can be produced. Furthermore biological recognition motifs can be easily attached to the conjugated polymers via thiol-yne click-chemistry providing specific tumor targeting without quenching of the fluorescence. References [1] Kuehne AJC, Gather MC, Sprakel J., Nature Commun. 2012, 3, 1088. [2] Repenko T, Fokong S, De Laporte L, Go D, Kiessling F, Lammers T, Kuehne AJC.,Chem Commun 2015, accepted.

Experimental evidence of colloids and nanoparticles presence from 25 waste leachates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hennebert, Pierre, E-mail: pierre.hennebert@ineris.fr; Avellan, Astrid; Yan, Junfang

Highlights: • This work is the first assessment of colloids in waste leachates. • Analytical methods are proposed and discussed. • All the waste have at least one element in colloidal form, and some elements are always colloidal. • Man-made nanoparticles are observed. • It can change the interpretation of leachate elemental concentration. - Abstract: The potential colloids release from a large panel of 25 solid industrial and municipal waste leachates, contaminated soil, contaminated sediments and landfill leachates was studied. Standardized leaching, cascade filtrations and measurement of element concentrations in the microfiltrate (MF) and ultrafiltrate (UF) fraction were used tomore » easily detect colloids potentially released by waste. Precautions against CO{sub 2} capture by alkaline leachates, or bacterial re-growth in leachates from wastes containing organic matter should be taken. Most of the colloidal particles were visible by transmission electron microscopy with energy dispersion spectrometry (TEM–EDS) if their elemental MF concentration is greater than 200 μg l{sup −1}. If the samples are dried during the preparation for microscopy, neoformation of particles can occur from the soluble part of the element. Size distribution analysis measured by photon correlation spectroscopy (PCS) were frequently unvalid, particularly due to polydispersity and/or too low concentrations in the leachates. A low sensitivity device is required, and further improvement is desirable in that field. For some waste leachates, particles had a zeta potential strong enough to remain in suspension. Mn, As, Co, Pb, Sn, Zn had always a colloidal form (MF concentration/UF concentration > 1.5) and total organic carbon (TOC), Fe, P, Ba, Cr, Cu, Ni are partly colloidal for more than half of the samples). Nearly all the micro-pollutants (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Sb, Sn, V and Zn) were found at least once in colloidal form greater than 100 μg l{sup −1}. In particular, the colloidal forms of Zn were always by far more concentrated than its dissolved form. The TEM–EDS method showed various particles, including manufactured nanoparticles (organic polymer, TiO{sub 2}, particles with Sr, La, Ce, Nd). All the waste had at least one element detected as colloidal. The solid waste leachates contained significant amount of colloids different in elemental composition from natural ones. The majority of the elements were in colloidal form for wastes of packaging (3), a steel slag, a sludge from hydrometallurgy, composts (2), a dredged sediment (#18), an As contaminated soil and two active landfill leachates. These results showed that cascade filtration and ICP elemental analysis seems valid methods in this field, and that electronic microscopy with elemental detection allows to identify particles. Particles can be formed from dissolved elements during TEM sample preparation and cross-checking with MF and UF composition by ICP is useful. The colloidal fraction of leachate of waste seems to be a significant source term, and should be taken into account in studies of emission and transfer of contaminants in the environment. Standardized cross-filtration method could be amended for the presence of colloids in waste leachates.« less

A new method to prepare colloids of size-controlled clusters from a matrix assembly cluster source

NASA Astrophysics Data System (ADS)

Cai, Rongsheng; Jian, Nan; Murphy, Shane; Bauer, Karl; Palmer, Richard E.

2017-05-01

A new method for the production of colloidal suspensions of physically deposited clusters is demonstrated. A cluster source has been used to deposit size-controlled clusters onto water-soluble polymer films, which are then dissolved to produce colloidal suspensions of clusters encapsulated with polymer molecules. This process has been demonstrated using different cluster materials (Au and Ag) and polymers (polyvinylpyrrolidone, polyvinyl alcohol, and polyethylene glycol). Scanning transmission electron microscopy of the clusters before and after colloidal dispersion confirms that the polymers act as stabilizing agents. We propose that this method is suitable for the production of biocompatible colloids of ultraprecise clusters.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Klimov, Victor L.; Petruska, Melissa A.

2010-05-25

The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

A new class of tunable hypersonic phononic crystals based on polymer-tethered colloids

PubMed Central

Alonso-Redondo, E.; Schmitt, M.; Urbach, Z.; Hui, C. M.; Sainidou, R.; Rembert, P.; Matyjaszewski, K.; Bockstaller, M. R.; Fytas, G.

2015-01-01

The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to ‘manufacturability'. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the ‘anisotropic elasticity' across the particle–polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies. PMID:26390851

Polymer Brushes: Synthesis, Characterization, Applications

NASA Astrophysics Data System (ADS)

Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen

2004-09-01

Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

Applications of Density Functional Theory in Soft Condensed Matter

NASA Astrophysics Data System (ADS)

Löwen, Hartmut

Applications of classical density functional theory (DFT) to soft matter systems like colloids, liquid crystals and polymer solutions are discussed with a focus on the freezing transition and on nonequilibrium Brownian dynamics. First, after a brief reminder of equilibrium density functional theory, DFT is applied to the freezing transition of liquids into crystalline lattices. In particular, spherical particles with radially symmetric pair potentials will be treated (like hard spheres, the classical one-component plasma or Gaussian-core particles). Second, the DFT will be generalized towards Brownian dynamics in order to tackle nonequilibrium problems. After a general introduction to Brownian dynamics using the complementary Smoluchowski and Langevin pictures appropriate for the dynamics of colloidal suspensions, the dynamical density functional theory (DDFT) will be derived from the Smoluchowski equation. This will be done first for spherical particles (e.g. hard spheres or Gaussian-cores) without hydrodynamic interactions. Then we show how to incorporate hydrodynamic interactions between the colloidal particles into the DDFT framework and compare to Brownian dynamics computer simulations. Third orientational degrees of freedom (rod-like particles) will be considered as well. In the latter case, the stability of intermediate liquid crystalline phases (isotropic, nematic, smectic-A, plastic crystals etc) can be predicted. Finally, the corresponding dynamical extension of density functional theory towards orientational degrees of freedom is proposed and the collective behaviour of "active" (self-propelled) Brownian particles is briefly discussed.

Hollow Mesoporous Carbon Microparticles and Micromotors with Single Holes Templated by Colloidal Silica-Assisted Gas Bubbles.

PubMed

Huang, Xiaoxi; Zhang, Tao; Asefa, Tewodros

2017-07-01

A simple, new synthetic method that produces hollow, mesoporous carbon microparticles, each with a single hole on its surface, is reported. The synthesis involves unique templates, which are composed of gaseous bubbles and colloidal silica, and poly(furfuryl alcohol) as a carbon precursor. The conditions that give these morphologically unique carbon microparticles are investigated, and the mechanisms that result in their unique structures are proposed. Notably, the amount of colloidal silica and the type of polymer are found to hugely dictate whether or not the synthesis results in hollow asymmetrical microparticles, each with a single hole. The potential application of the particles as self-propelled micromotors is demonstrated. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal tuning the reversible optical band gap of self-assembled polystyrene photonic crystals

NASA Astrophysics Data System (ADS)

Vakili Tahami, S. H.; Pourmahdian, S.; Shirkavand Hadavand, B.; Azizi, Z. S.; Tehranchi, M. M.

2016-11-01

Nano-sized polymeric colloidal particles could undergo self-organization into three-dimensional structures to produce desired optical properties. In this research, a facile emulsifier-free emulsion polymerization method was employed to synthesize highly mono-disperse sub-micron polystyrene colloids. A high quality photonic crystal (PhC) structure was prepared by colloidal polystyrene. The reversible thermal tuning effect on photonic band gap position as well as the attenuation of the band gap was investigated in detail. The position of PBG can be tuned from 420 nm to 400 nm by varying the temperature of the PhC structure, reversibly. This reversible effect provides a reconfigurable PhC structure which could be used as thermo-responsive shape memory polymers.

pH dependence of the properties of waterborne pressure-sensitive adhesives containing acrylic acid.

PubMed

Wang, Tao; Canetta, Elisabetta; Weerakkody, Tecla G; Keddie, Joseph L; Rivas, Urko

2009-03-01

Polymer colloids are often copolymerized with acrylic acid monomers in order to impart colloidal stability. Here, the effects of the pH on the nanoscale and macroscopic adhesive properties of waterborne poly(butyl acrylate-co-acrylic acid) films are reported. In films cast from acidic colloidal dispersions, hydrogen bonding between carboxylic acid groups dominates the particle-particle interactions, whereas ionic dipolar interactions are dominant in films cast from basic dispersions. Force spectroscopy using an atomic force microscope and macroscale mechanical measurements show that latex films with hydrogen-bonding interactions have lower elastic moduli and are more deformable. They yield higher adhesion energies. On the other hand, in basic latex, ionic dipolar interactions increase the moduli of the dried films. These materials are stiffer and less deformable and, consequently, exhibit lower adhesion energies. The rate of water loss from acidic latex is slower, perhaps because of hydrogen bonding with the water. Therefore, although acid latex offers greater adhesion, there is a limitation in the film formation.

Rolling and aging in temperature-ramp soft adhesion

NASA Astrophysics Data System (ADS)

Boniello, Giuseppe; Tribet, Christophe; Marie, Emmanuelle; Croquette, Vincent; Zanchi, Dražen

2018-01-01

Immediately before adsorption to a horizontal substrate, sinking polymer-coated colloids can undergo a complex sequence of landing, jumping, crawling, and rolling events. Using video tracking, we studied the soft adhesion to a horizontal flat plate of micron-size colloids coated by a controlled molar fraction f of the poly(lysine)-grafted-poly(N-isopropylacrylamide) (PLL-g-PNIPAM) which is a temperature-sensitive polymer. We ramp the temperature from below to above Tc=32 ±1∘C , at which the PNIPAM polymer undergoes a transition, triggering attractive interaction between microparticles and surface. The adsorption rate, the effective in-plane (x -y ) diffusion constant, and the average residence time distribution over z were extracted from the Brownian motion records during last seconds before immobilization. Experimental data are understood within a rate-equations-based model that includes aging effects and includes three populations: the untethered, the rolling, and the arrested colloids. We show that preadsorption dynamics casts a characteristic scaling function α (f ) proportional to the number of available PNIPAM patches met by soft contact during Brownian rolling. In particular, the increase of in-plane diffusivity with increasing f is understood: The stickiest particles have the shortest rolling regime prior to arrest, so that their motion is dominated by the untethered phase.

Multifunctional Fluorescent-Magnetic Polymeric Colloidal Particles: Preparations and Bioanalytical Applications.

PubMed

Kaewsaneha, Chariya; Tangboriboonrat, Pramuan; Polpanich, Duangporn; Elaissari, Abdelhamid

2015-10-28

Fluorescent-magnetic particles (FMPs) play important roles in modern materials, especially as nanoscale devices in the biomedical field. The interesting features of FMPs are attributed to their dual detection ability, i.e., fluorescent and magnetic modes. Functionalization of FMPs can be performed using several types of polymers, allowing their use in various applications. The synergistic potentials for unique multifunctional, multilevel targeting nanoscale devices as well as combination therapies make them particularly attractive for biomedical applications. However, the synthesis of FMPs is challenging and must be further developed. In this review article, we summarized the most recent representative works on polymer-based FMP systems that have been applied particularly in the bioanalytical field.

Preparation of novel film-forming armoured latexes using silica nanoparticles as a pickering emulsion stabiliser.

PubMed

Shiraz, Hana; Peake, Simon J; Davey, Tim; Cameron, Neil R; Tabor, Rico F

2018-05-15

Film-forming polymer latex particles of diameter <300 nm can be prepared in the complete absence of surfactants, stabilised in part by silica nanoparticles through a Pickering type emulsion polymerisation. Control of the silica wettability through modulation of reaction pH or by reaction of the nanoparticles with a hydrophobic silane results in silica-covered latex particles. The oil-in-water polymerisation process used methyl methacrylate (MMA) and n-butyl acrylate (BA) as co-monomers, potassium persulphate (KPS) as an initiator and a commercially available colloidal nano-silica (Ludox®-TM40). It was found that pH control before polymerisation using methacrylic acid (MAA) facilitated the formation of armoured latexes, and mechanistic features of this process are discussed. An alternative, more robust protocol was developed whereby addition of vinyltriethoxysilane (VTES) to control wettability resulted in latexes completely armoured in colloidal nano-silica. The latexes were characterised using SEM, cryo-TEM and AFM imaging techniques. The mechanism behind the adsorption was investigated through surface pressure and contact angle measurements to understand the factors that influence this irreversible adsorption. Results indicate that nanoparticle attachment (but intriguingly not latex size) is dependent on particle wettability, providing new insight into the formation of nanoparticle-armoured latexes, along with opportunities for further development of diversely functionalized inorganic/organic polymer composite particles. Copyright © 2018 Elsevier Inc. All rights reserved.

Magneto-optical properties of binar ferrocolloids

NASA Astrophysics Data System (ADS)

Pshenichnikov, A. F.; Lebedev, A. V.; Lakhtina, E. V.; Stepanov, G. V.

2018-03-01

In this work, a new method for increasing optical anisotropy of a ferrocolloid through introducing the coiled polymer molecules or elongated nanosized non-magnetic particles is realized. Since the dimensions of structural elements comprising such a binary colloidal solution are small compared to the wavelength, the ferrocolloid remains optically homogeneous. Type I binary ferrocolloids are obtained by introducing polybutadiene molecules into a magnetic fluid (magnetite + kerosene + oleic acid). In this case, an increase in the double refraction (DR) is due to the deformation and stretching of the polymer coils along the magnetic field. In weak fields, double amplification of the signal was detected for the concentration of polymer molecules of about 0.5 %. A further increase in the concentration of impurity molecules weakens DR due to a disturbance of the sedimentation stability of the solution and precipitation of colloidal particles. Type II binary solution is synthesized on the basis of a magnetic fluid and rod-shaped impurity nanoparticles of goethite ( αFeOOH). The transverse dimension of the impurity particles (10 ‑ 30 nm) was close to the average diameter of single-domain magnetite particles, and the longitudinal dimension was an order of magnitude larger. An increase in the DR occurs due to the orientation of long axes of impurity particles along the magnetic field caused by the difference in the ”demagnetizing” coefficients along and across the axis of the particle. The magnetic double refraction has been studied depending on the concentration of magnetite and impurity particles and the strength of the magnetic field. For the first time, an experimental substantiation of the multiple amplification of the DR signal by impurity particles was obtained. In the fields (up to 10 kA/m) and for the volume fraction of impurity particles of the order of one percent, the DR signal is amplified by more than an order of magnitude. In stronger fields, the signal gain, associated with the influence of impurity particles, reaches saturation and, with further increase in the field strength, remains practically unchanged, while the total anisotropy of the solution continues to increase due to the orientation of the magnetite particles.

Advanced Colloids Experiment (ACE) Science Overview

NASA Technical Reports Server (NTRS)

Meyer, William V.; Sicker, Ronald J.; Chiaramonte, Francis P.; Luna, Unique J.; Chaiken, Paul M.; Hollingsworth, Andrew; Secanna, Stefano; Weitz, David; Lu, Peter; Yodh, Arjun;

The rheology and processing of “edge sheared” colloidal polymer opals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wong, Hon Sum; Mackley, Malcolm, E-mail: mrm5@cam.ac.uk; Butler, Simon

This paper is concerned with the rheology and processing of solvent-free core shell “polymer opals” that consist of a soft outer shell grafted to hard colloidal polymer core particles. Strong iridescent colors can be produced by shearing the material in a certain way that causes the initially disordered spheres to rearrange into ordered crystalline structures and produce colors by diffraction and interference of multiple light scattering, similar to gemstone opals. The basic linear viscoelastic rheology of a polymer opal sample was determined as a function of temperature, and the material was found to be highly viscoelastic at all tested temperatures.more » A Cambridge multipass rheometer was specifically modified in order to make controlled mechanical measurements of initially disordered polymer opal tapes that were sandwiched between protective polyethylene terephthalate sheets. Axial extension, simple shear, and a novel “edge shearing” geometry were all evaluated, and multiple successive experiments of the edge shearing test were carried out at different temperatures. The optical development of colloidal ordering, measured as optical opalescence, was quantified by spectroscopy using visible backscattered light. The development of opalescence was found to be sensitive to the geometry of deformation and a number of process variables suggesting a complex interaction of parameters that caused the opalescence. In order to identify aspects of the deformation mechanism of the edge shearing experiment, a separate series of in situ optical experiments were carried out and this helped indicate the extent of simple shear generated with each edge shear deformation. The results show that strong ordering can be induced by successive edge shearing deformation. The results are relevant to polymer opal rheology, processing, and mechanisms relating to ordering within complex viscoelastic fluids.« less

Shape-shifting colloids via stimulated dewetting

PubMed Central

Youssef, Mena; Hueckel, Theodore; Yi, Gi-Ra; Sacanna, Stefano

2016-01-01

The ability to reconfigure elementary building blocks from one structure to another is key to many biological systems. Bringing the intrinsic adaptability of biological systems to traditional synthetic materials is currently one of the biggest scientific challenges in material engineering. Here we introduce a new design concept for the experimental realization of self-assembling systems with built-in shape-shifting elements. We demonstrate that dewetting forces between an oil phase and solid colloidal substrates can be exploited to engineer shape-shifting particles whose geometry can be changed on demand by a chemical or optical signal. We find this approach to be quite general and applicable to a broad spectrum of materials, including polymers, semiconductors and magnetic materials. This synthetic methodology can be further adopted as a new experimental platform for designing and rapidly prototyping functional colloids, such as reconfigurable micro swimmers, colloidal surfactants and switchable building blocks for self-assembly. PMID:27426418

Shape-shifting colloids via stimulated dewetting

NASA Astrophysics Data System (ADS)

Youssef, Mena; Hueckel, Theodore; Yi, Gi-Ra; Sacanna, Stefano

2016-07-01

The ability to reconfigure elementary building blocks from one structure to another is key to many biological systems. Bringing the intrinsic adaptability of biological systems to traditional synthetic materials is currently one of the biggest scientific challenges in material engineering. Here we introduce a new design concept for the experimental realization of self-assembling systems with built-in shape-shifting elements. We demonstrate that dewetting forces between an oil phase and solid colloidal substrates can be exploited to engineer shape-shifting particles whose geometry can be changed on demand by a chemical or optical signal. We find this approach to be quite general and applicable to a broad spectrum of materials, including polymers, semiconductors and magnetic materials. This synthetic methodology can be further adopted as a new experimental platform for designing and rapidly prototyping functional colloids, such as reconfigurable micro swimmers, colloidal surfactants and switchable building blocks for self-assembly.

Large-area photonic crystals

NASA Astrophysics Data System (ADS)

Ruhl, Tilmann; Spahn, Peter; Hellmann, Gotz P.; Winkler, Holger

2004-09-01

Materials with a periodically modulated refractive index, with periods on the scale of light wavelengths, are currently attracting much attention because of their unique optical properties which are caused by Bragg scattering of the visible light. In nature, 3d structures of this kind are found in the form of opals in which monodisperse silica spheres with submicron diameters form a face-centered-cubic (fcc) lattice. Artificial opals, with the same colloidal-crystalline fcc structure, have meanwhile been prepared by crystallizing spherical colloidal particles via sedimentation or drying of dispersions. In this report, colloidal crystalline films are introduced that were produced by a novel technique based on shear flow in the melts of specially designed submicroscopic silica-polymer core-shell hybrid spheres: when the melt of these spheres flows between the plates of a press, the spheres crystallize along the plates, layer by layer, and the silica cores assume the hexagonal order corresponding to the (111) plane of the fcc lattice. This process is fast and yields large-area films, thin or thick. To enhance the refractive index contrast in these films, the colloidal crystalline structure was inverted by etching out the silica cores with hydrofluoric acid. This type of an inverse opal, in which the fcc lattice is formed by mesopores, is referred to as a polymer-air photonic crystal.

Gels from soft hairy nanoparticles in polymeric matrices

NASA Astrophysics Data System (ADS)

Vlassopoulos, Dimitris

2013-03-01

Hairy particles represent a huge class of soft colloids with tunable interactions and properties. Advances in synthetic chemistry have enabled obtaining well-characterized such systems for specific needs. In this talk we present two model hairy soft particles with diameters of the order of tens of nanometers, star polymers and polymerically grafted spherical particles. In particular, we discuss design strategies for dispersing them in polymeric matrices and eventually creating and breaking gels. Control parameters are the matrix molar mass, the grafting density (or functionality) and the size of the grafts (or arms). The linear viscoelastic properties and slow time evolution of the gels are examined in view of the existing knowledge from colloidal gels consisting of micron-sized particles, and compared. In the case of stars we start from a concentrated glassy suspension in molecular solvent and add homopolymer at increasing concentration, and as a result of the induced osmotic pressure the stars shrink and a depletion gel is formed. For the grafted colloidal particles, they are added at low concentration to a polymer matrix, and it has been shown that under certain conditions the anisotropy of interactions gives rise to network formation. We then focus on the nonlinear rheological response and in particular the effect of shear flow in inducing a solid to liquid transition. Our studies show that the yielding process is gradual and shares many common features with that of flocculated colloidal suspensions, irrespectively of the shape of the building block of the gel. Whereas shear can melt such a gel, it cannot break it into its constituent blocks and hence fully disperse the hairy nanoparticles. On the other hand, the hairy particles are intrinsically hybrid. We show how this important feature is reflected on the heating of the gels. In that case, the mismatch of thermal expansion coefficients of core and shell appears to play a role on the particle response as it imposes and internal strain on the particle, which in turn changes the shell conformation and under some conditions can lead to thermal melting of the gel. These alternative avenues for manipulating the gel-to-liquid transition have potential implications in directing the properties of hairy nanoparticles and their assemblies in viscoelastic matrices. Parts of this work reflect collaboration with D. Truzzolillo (FORTH), J. F. Moll and S. K.Kumar (Columbia). R. H. Colby (Penn State), M. Gauthier (Waterloo) and B. C. Benicewicz (Univ. South Carolina).

Two-dimensional assemblies of soft repulsive colloids confined at fluid interfaces

NASA Astrophysics Data System (ADS)

Isa, L.; Buttinoni, I.; Fernandez-Rodriguez, M. A.; Vasudevan, S. A.

2017-07-01

Colloidal systems are an excellent example of a materials class for which interrogating fundamental questions leads to answers of direct applied relevance. In our group, we in particular focus on two-dimensional assemblies of micro- and nano-particles confined at the interface between two fluids, e.g., oil-water. Here, we review our work on systems interacting through soft repulsive forces of different origin, i.e., electrostatic and steric. By starting from the paradigmatic case of charged colloids at an interface, we show how they are both offering great opportunities as model systems to investigate the structural and mechanical response of materials and as versatile patterning tools for surface nanostructuring. We then move to the case of deformable particles interacting via steric contacts. We first examine microgel particles, which we also demonstrate as very promising models for structural investigations and robust elements for tunable nanolithography. We conclude by briefly discussing the case of particles comprising a hard inorganic core and a deformable polymer shell, which maintain some of the advantageous features of microgel particles, but also enable the realization of two-dimensional functional materials. This article offers our perspective on a very active field of research, where many interesting developments are expected in the near future. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

A general approach to DNA-programmable atom equivalents.

PubMed

Zhang, Chuan; Macfarlane, Robert J; Young, Kaylie L; Choi, Chung Hang J; Hao, Liangliang; Auyeung, Evelyn; Liu, Guoliang; Zhou, Xiaozhu; Mirkin, Chad A

2013-08-01

Nanoparticles can be combined with nucleic acids to programme the formation of three-dimensional colloidal crystals where the particles' size, shape, composition and position can be independently controlled. However, the diversity of the types of material that can be used is limited by the lack of a general method for preparing the basic DNA-functionalized building blocks needed to bond nanoparticles of different chemical compositions into lattices in a controllable manner. Here we show that by coating nanoparticles protected with aliphatic ligands with an azide-bearing amphiphilic polymer, followed by the coupling of DNA to the polymer using strain-promoted azide-alkyne cycloaddition (also known as copper-free azide-alkyne click chemistry), nanoparticles bearing a high-density shell of nucleic acids can be created regardless of nanoparticle composition. This method provides a route to a virtually endless class of programmable atom equivalents for DNA-based colloidal crystallization.

Mixtures of charged colloid and neutral polymer: Influence of electrostatic interactions on demixing and interfacial tension

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Schmidt, Matthias

2005-06-01

The equilibrium phase behavior of a binary mixture of charged colloids and neutral, nonadsorbing polymers is studied within free-volume theory. A model mixture of charged hard-sphere macroions and ideal, coarse-grained, effective-sphere polymers is mapped first onto a binary hard-sphere mixture with nonadditive diameters and then onto an effective Asakura-Oosawa model [S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)]. The effective model is defined by a single dimensionless parameter—the ratio of the polymer diameter to the effective colloid diameter. For high salt-to-counterion concentration ratios, a free-volume approximation for the free energy is used to compute the fluid phase diagram, which describes demixing into colloid-rich (liquid) and colloid-poor (vapor) phases. Increasing the range of electrostatic interactions shifts the demixing binodal toward higher polymer concentration, stabilizing the mixture. The enhanced stability is attributed to a weakening of polymer depletion-induced attraction between electrostatically repelling macroions. Comparison with predictions of density-functional theory reveals a corresponding increase in the liquid-vapor interfacial tension. The predicted trends in phase stability are consistent with observed behavior of protein-polysaccharide mixtures in food colloids.

Accurate coarse-grained models for mixtures of colloids and linear polymers under good-solvent conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

D’Adamo, Giuseppe, E-mail: giuseppe.dadamo@sissa.it; Pelissetto, Andrea, E-mail: andrea.pelissetto@roma1.infn.it; Pierleoni, Carlo, E-mail: carlo.pierleoni@aquila.infn.it

2014-12-28

A coarse-graining strategy, previously developed for polymer solutions, is extended here to mixtures of linear polymers and hard-sphere colloids. In this approach, groups of monomers are mapped onto a single pseudoatom (a blob) and the effective blob-blob interactions are obtained by requiring the model to reproduce some large-scale structural properties in the zero-density limit. We show that an accurate parametrization of the polymer-colloid interactions is obtained by simply introducing pair potentials between blobs and colloids. For the coarse-grained (CG) model in which polymers are modelled as four-blob chains (tetramers), the pair potentials are determined by means of the iterative Boltzmannmore » inversion scheme, taking full-monomer (FM) pair correlation functions at zero-density as targets. For a larger number n of blobs, pair potentials are determined by using a simple transferability assumption based on the polymer self-similarity. We validate the model by comparing its predictions with full-monomer results for the interfacial properties of polymer solutions in the presence of a single colloid and for thermodynamic and structural properties in the homogeneous phase at finite polymer and colloid density. The tetramer model is quite accurate for q ≲ 1 (q=R{sup ^}{sub g}/R{sub c}, where R{sup ^}{sub g} is the zero-density polymer radius of gyration and R{sub c} is the colloid radius) and reasonably good also for q = 2. For q = 2, an accurate coarse-grained description is obtained by using the n = 10 blob model. We also compare our results with those obtained by using single-blob models with state-dependent potentials.« less

A density functional approach to ferrogels

NASA Astrophysics Data System (ADS)

Cremer, P.; Heinen, M.; Menzel, A. M.; Löwen, H.

2017-07-01

Ferrogels consist of magnetic colloidal particles embedded in an elastic polymer matrix. As a consequence, their structural and rheological properties are governed by a competition between magnetic particle-particle interactions and mechanical matrix elasticity. Typically, the particles are permanently fixed within the matrix, which makes them distinguishable by their positions. Over time, particle neighbors do not change due to the fixation by the matrix. Here we present a classical density functional approach for such ferrogels. We map the elastic matrix-induced interactions between neighboring colloidal particles distinguishable by their positions onto effective pairwise interactions between indistinguishable particles similar to a ‘pairwise pseudopotential’. Using Monte-Carlo computer simulations, we demonstrate for one-dimensional dipole-spring models of ferrogels that this mapping is justified. We then use the pseudopotential as an input into classical density functional theory of inhomogeneous fluids and predict the bulk elastic modulus of the ferrogel under various conditions. In addition, we propose the use of an ‘external pseudopotential’ when one switches from the viewpoint of a one-dimensional dipole-spring object to a one-dimensional chain embedded in an infinitely extended bulk matrix. Our mapping approach paves the way to describe various inhomogeneous situations of ferrogels using classical density functional concepts of inhomogeneous fluids.

Effective Forces Between Colloidal Particles

NASA Technical Reports Server (NTRS)

Tehver, Riina; Banavar, Jayanth R.; Koplik, Joel

1999-01-01

Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nigro, Valentina, E-mail: nigro@fis.uniroma3.it; Bruni, Fabio; Ricci, Maria Antonietta

The temperature dependence of the local intra-particle structure of colloidal microgel particles, composed of interpenetrated polymer networks, has been investigated by small-angle neutron scattering at different pH and concentrations, in the range (299÷315) K, where a volume phase transition from a swollen to a shrunken state takes place. Data are well described by a theoretical model that takes into account the presence of both interpenetrated polymer networks and cross-linkers. Two different behaviors are found across the volume phase transition. At neutral pH and T ≈ 307 K, a sharp change of the local structure from a water rich open inhomogeneousmore » interpenetrated polymer network to a homogeneous porous solid-like structure after expelling water is observed. Differently, at acidic pH, the local structure changes almost continuously. These findings demonstrate that a fine control of the pH of the system allows to tune the sharpness of the volume-phase transition.« less

Cationic polymer brush-modified cellulose nanocrystals for high-affinity virus binding

NASA Astrophysics Data System (ADS)

Rosilo, Henna; McKee, Jason R.; Kontturi, Eero; Koho, Tiia; Hytönen, Vesa P.; Ikkala, Olli; Kostiainen, Mauri A.

2014-09-01

Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications.Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications. Electronic supplementary information (ESI) available: CNC surface chain fraction and degree of substitution after BriBBr modification, NMR spectra of the SI-ATRP reaction mixture at 0 and 120 min, conversion of the DMAEMA monomer during SI-ATRP, DLS size distribution profiles of CNCs and CNC-g-P(QDMAEMA), TEM images of NoV-VLPs and their complexes with CNC-g-P(QDMAEMA) at 0 mM NaCl. See DOI: 10.1039/c4nr03584d

In situ creation of reactive polymer nanoparticles and resulting polymer layers formed at the interfaces of liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kang, Shin-Woong; Kundu, Sudarshan; Park, Heung-Shik; Oh, Keun Chan; Lyu, Jae Jin

2017-02-01

We report the in situ creation of reactive polymer nanoparticles and resulting polymer networks formed at the interfaces of liquid crystals. It is known that polymerization-induced phase separation proceeds in two distinct regimes depending on the concentration of monomer. For a high monomer concentration, phase separation occurs mainly through the spinodal decomposition process, consequently resulting in interpenetrating polymer networks. For a dilute system, however, the phase separation mainly proceeds and completes in the binodal decomposition regime. The system resembles the aggregation process of colloidal particle. In this case, the reaction kinetics is limited by the reaction between in situ created polymer aggregates and hence the network morphologies are greatly influenced by the diffusion of reactive polymer particles. The thin polymer layers localized at the surface of substrate are inevitably observed and can be comprehended by the interfacial adsorption and further cross-linking reaction of reactive polymer aggregates at the interface. This process provides a direct perception on understanding polymer stabilized liquid crystals accomplished by the interfacial polymer layer. The detailed study has been performed for an extremely dilute condition (below 0.5 wt%) by employing systematic experimental approaches. Creation and growth of polymer nanoparticles have been measured by particle size analyzer. The interfacial localization of polymer aggregates and resulting interfacial layer formation with a tens of nanometer scale have been exploited at various interfaces such as liquid-solid, liquid-liquid, and liquid-gas interfaces. The resulting interfacial layers have been characterized by using fuorescent confocal microscope and field emission scanning electron microscope. The detailed processes of the polymer stabilized vertically aligned liquid crystals will be discussed in support of the reported study.

Polydispersity effects in colloid-polymer mixtures.

PubMed

Liddle, S M; Narayanan, T; Poon, W C K

2011-05-18

We study phase separation and transient gelation experimentally in a mixture consisting of polydisperse colloids (polydispersity: ≈ 6%) and non-adsorbing polymers, where the ratio of the average size of the polymer to that of the colloid is ≈ 0.062. Unlike what has been reported previously for mixtures with somewhat lower colloid polydispersity (≈ 5%), the addition of polymers does not expand the fluid-solid coexistence region. Instead, we find a region of fluid-solid coexistence which has an approximately constant width but an unexpected re-entrant shape. We detect the presence of a metastable gas-liquid binodal, which gives rise to two-stepped crystallization kinetics that can be rationalized as the effect of fractionation. Finally, we find that the separation into multiple coexisting solid phases at high colloid volume fractions predicted by equilibrium statistical mechanics is kinetically suppressed before the system reaches dynamical arrest.

Polypeptide Liquid Crystal Assisted Assembly of Cylindrically Symmetric Silica-Polypeptide Hybrid Microparticles

NASA Astrophysics Data System (ADS)

Russo, Paul; Rosu, Cornelia; Jacobeen, Shane; Park, Katherine; Yunker, Peter; Reichmanis, Elsa

Liquid crystals can organize dispersed particles into exotic structures. Matching the particle surface coating to the chemistry of the mesogenic phase permits a tight focus on factors such as extended particle shape. The colloidal particles developed for this work consist of a magnetic and fluorescent cylinder-like silica core. One end of the silica is rounded, almost hemispherical, giving the particles a bullet-like shape. These particles are functionalized with helical poly(γ-stearyl-L-glutamate) and dispersed, at different concentrations in cholesteric liquid crystals (ChLC) of the same polymer in tetrahydrofuran. Defects introduced by the particles to the director field of the bulk PSLG/THF host led to a variety of phases, including a quasi-hexagonal alignment of the particles. National Science Foundation.

Nanodesigning of Hierarchical Multifunctional Ceramics

DTIC Science & Technology

1993-09-28

transformations were determined by XRD. As in previous studies, the final particle size of BaTiO 3, obtair-0 trom either the titanium isopropoxide ...conditions by reacting nanosized titanium oxide or titanium alkoxides with a solution of barium hydroxide. The powders produced by this approach range in...optical ceramic-polymer composites using colloidal dispersion techniques. In our experiments, we used either a high purity titania sood or titanium

Mobility of Nanoscale and Microscale iron for groundwater remediation: experiments and modelling

NASA Astrophysics Data System (ADS)

Tosco, T.; Gastone, F.; Sethi, R.

2012-12-01

Colloidal suspensions of zerovalent iron micro- and nanoparticles (MZVI and NZVI) have been studied in recent years for in-situ groundwater remediation. Thanks to their small size, MZVI and NZVI can be dispersed in aqueous suspensions and directly injected into the subsurface, for a targeted treatment of contamination plumes and even sources. However, colloidal dispersions of such particles are not stable in pure water, due to fast aggregation (for NZVI) and gravitational sedimentation (for MZVI). Viscous, environmentally friendly fluids (guar gum and xanthan gum solutions), which exhibit shear thinning rheological properties, were found to be effective in improving colloidal stability, thus greatly improving handling and injectability (1-3). The present work reports laboratory tests and numerical modelling concerning the mobility of MZVI and NZVI viscous suspensions in porous media. The efficacy of xanthan and guar gum was investigated in column transport tests, performed injecting highly concentrated iron suspensions (20 g/L), dispersed in xanthan gum (3g/L) and guar gum (3-6 g/l) solutions. Particle breakthrough curves and concentration profiles were monitored by magnetic susceptibility measurements. Pressure drop at column ends was also continuously monitored. The tests proved that green polymers can greatly improve both colloidal stability and mobility of the particles. Their use is fundamental in particular for MZVI, which cannot be transported nor even dispersed in pure water. A numerical model for NZVI and NZVI transport in porous media was then developed (E-MNM1D, Enhanced Micro-and Nanoparticle transport Model in porous media in 1D geometry) (4). Due to the high concentration of the particles and to the non-Newtonian rheology of the carrier fluid, hydrodynamic parameters, fluid properties and concentration of deposed and suspended particles are mutually influenced. The rheological properties of the suspensions are accounted for through a variable viscosity, function of flow rate and on polymer and particle concentrations. The particle-porous medium interactions are modelled with a dual-site approach, accounting for straining and physico-chemical deposition/release phenomena. A general formulation for reversible deposition is also proposed, that includes all commonly applied dynamics (linear attachment, blocking, ripening). The progressive clogging of the porous medium, due to deposition and filtration of particles and aggregates, is modelled by tying porosity and permeability to deposited iron particles. E-MNM1D can be downloaded at www.polito.itgroundwatersoftware. The software is designed as a tool for inverse modelling of laboratory transport tests, and as a support in the design of field-scale applications of MZVI and NZVI-based remediation, in particular for the estimate of the radius of influence of the slurry injection. The work was partly funded by the European Union project AQUAREHAB (FP7 - Grant Agreement Nr. 226565). References 1. Tiraferri, A.; Sethi, R. Journal of Nanoparticle Research 2009, 11(3), 635-645. 2. Tiraferri, A.; Chen, K.L.; Sethi, R.; Elimelech, M. Journal of Colloid and Interface Science 2008, 324(1-2), 71-79. 3. Dalla Vecchia, E.; Luna, M.; Sethi, R. Environmental Science & Technology 2009, 43(23), 8942-8947. 4. Tosco, T.; Sethi, R. Environmental Science and Technology 2010, 44(23), 9062-9068.

Improving the engine power of a catalytic Janus-sphere micromotor by roughening its surface.

PubMed

Longbottom, Brooke W; Bon, Stefan A F

2018-03-15

Microspheres with catalytic caps have become a popular model system for studying self-propelled colloids. Existing experimental studies involve predominantly "smooth" particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces of polymer microspheres were deformed prior to depositing a layer of platinum which resulted in the formation of nanoscopic pillars of catalyst. Self-propulsion was induced upon exposure of the micromotors to hydrogen peroxide, whilst they were dispersed in water. The topological surface features were shown to boost speed (~2×) when the underlying deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their "smooth" counterparts.

Application of asymmetric flow-field flow fractionation to the characterization of colloidal dispersions undergoing aggregation.

PubMed

Lattuada, Marco; Olivo, Carlos; Gauer, Cornelius; Storti, Giuseppe; Morbidelli, Massimo

2010-05-18

The characterization of complex colloidal dispersions is a relevant and challenging problem in colloidal science. In this work, we show how asymmetric flow-field flow fractionation (AF4) coupled to static light scattering can be used for this purpose. As an example of complex colloidal dispersions, we have chosen two systems undergoing aggregation. The first one is a conventional polystyrene latex undergoing reaction-limited aggregation, which leads to the formation of fractal clusters with well-known structure. The second one is a dispersion of elastomeric colloidal particles made of a polymer with a low glass transition temperature, which undergoes coalescence upon aggregation. Samples are withdrawn during aggregation at fixed times, fractionated with AF4 using a two-angle static light scattering unit as a detector. We have shown that from the analysis of the ratio between the intensities of the scattered light at the two angles the cluster size distribution can be recovered, without any need for calibration based on standard elution times, provided that the geometry and scattering properties of particles and clusters are known. The nonfractionated samples have been characterized also by conventional static and dynamic light scattering to determine their average radius of gyration and hydrodynamic radius. The size distribution of coalescing particles has been investigated also through image analysis of cryo-scanning electron microscopy (SEM) pictures. The average radius of gyration and the average hydrodynamic radius of the nonfractionated samples have been calculated and successfully compared to the values obtained from the size distributions measured by AF4. In addition, the data obtained are also in good agreement with calculations made with population balance equations.

Polymers at interfaces and in colloidal dispersions.

PubMed

Fleer, Gerard J

2010-09-15

This review is an extended version of the Overbeek lecture 2009, given at the occasion of the 23rd Conference of ECIS (European Colloid and Interface Society) in Antalya, where I received the fifth Overbeek Gold Medal awarded by ECIS. I first summarize the basics of numerical SF-SCF: the Scheutjens-Fleer version of Self-Consistent-Field theory for inhomogeneous systems, including polymer adsorption and depletion. The conformational statistics are taken from the (non-SCF) DiMarzio-Rubin lattice model for homopolymer adsorption, which enumerates the conformational details exactly by a discrete propagator for the endpoint distribution but does not account for polymer-solvent interaction and for the volume-filling constraint. SF-SCF corrects for this by adjusting the field such that it becomes self-consistent. The model can be generalized to more complex systems: polydispersity, brushes, random and block copolymers, polyelectrolytes, branching, surfactants, micelles, membranes, vesicles, wetting, etc. On a mean-field level the results are exact; the disadvantage is that only numerical data are obtained. Extensions to excluded-volume polymers are in progress. Analytical approximations for simple systems are based upon solving the Edwards diffusion equation. This equation is the continuum variant of the lattice propagator, but ignores the finite segment size (analogous to the Poisson-Boltzmann equation without a Stern layer). By using the discrete propagator for segments next to the surface as the boundary condition in the continuum model, the finite segment size can be introduced into the continuum description, like the ion size in the Stern-Poisson-Boltzmann model. In most cases a ground-state approximation is needed to find analytical solutions. In this way realistic analytical approximations for simple cases can be found, including depletion effects that occur in mixtures of colloids plus non-adsorbing polymers. In the final part of this review I discuss a generalization of the free-volume theory (FVT) for the phase behavior of colloids and non-adsorbing polymer. In FVT the polymer is considered to be ideal: the osmotic pressure Pi follows the Van 't Hoff law, the depletion thickness delta equals the radius of gyration. This restricts the validity of FVT to the so-called colloid limit (polymer much smaller than the colloids). We have been able to find simple analytical approximations for Pi and delta which account for non-ideality and include established results for the semidilute limit. So we could generalize FVT to GFVT, and can now also describe the so-called protein limit (polymer larger than the 'protein-like' colloids), where the binodal polymer concentrations scale in a simple way with the polymer/colloid size ratio. For an intermediate case (polymer size approximately colloid size) we could give a quantitative description of careful experimental data. Copyright 2010 Elsevier B.V. All rights reserved.

Impact of the Formulation Pathway on the Colloidal State and Crystallinity of Poly-ε-caprolactone Particles Prepared by Solvent Displacement.

PubMed

Pucci, Carlotta; Cousin, Fabrice; Dole, François; Chapel, Jean-Paul; Schatz, Christophe

2018-02-20

The formulation pathway and/or the mixing method are known to be relevant in many out-of-equilibrium processes. In this work, we studied the effect of the mixing conditions on the physicochemical properties of poly-ε-caprolactone (PCL) particles prepared by solvent displacement. More specifically, water was added in one shot (fast addition) or drop by drop to PCL solution in tetrahydrofuran (THF) to study the impact of the mixing process on particle properties including size, stability, and crystallinity. Two distinct composition maps representing the Ouzo domain characteristic of the presence of metastable nanoparticles have been established for each mixing method. Polymer nanoparticles are formed in the Ouzo domain according to a nucleation and growth (or aggregation) mechanism. The fast addition promotes a larger nucleation rate, thus favoring the formation of small and uniform particles. For the drop-by-drop addition, for which the polymer solubility gradually decreases, the composition trajectories systematically cross an intermediate unstable region between the solubility limit of the polymer and the Ouzo domain. This leads to heterogeneous nucleation as shown by the formation of larger and less stable particles. Particles formed in the Ouzo domain have semi-crystalline properties. The PCL melting point is decreased with the THF fraction trapped in particles in accordance with Flory's theory for melt crystallization. On the other hand, the degree of crystallinity is constant, around 20% regardless of the THF fraction. No difference between fast and slow addition could be detected on the semi-crystalline properties of the particles which emphasize that thermodynamic rather than kinetic factors drive the polymer crystallization in particles. The recovery of bulk PCL crystallinity after the removal of THF from particles tends to confirm this hypothesis.

Velocity and displacement statistics in a stochastic model of nonlinear friction showing bounded particle speed

NASA Astrophysics Data System (ADS)

Menzel, Andreas M.

2015-11-01

Diffusion of colloidal particles in a complex environment such as polymer networks or biological cells is a topic of high complexity with significant biological and medical relevance. In such situations, the interaction between the surroundings and the particle motion has to be taken into account. We analyze a simplified diffusion model that includes some aspects of a complex environment in the framework of a nonlinear friction process: at low particle speeds, friction grows linearly with the particle velocity as for regular viscous friction; it grows more than linearly at higher particle speeds; finally, at a maximum of the possible particle speed, the friction diverges. In addition to bare diffusion, we study the influence of a constant drift force acting on the diffusing particle. While the corresponding stationary velocity distributions can be derived analytically, the displacement statistics generally must be determined numerically. However, as a benefit of our model, analytical progress can be made in one case of a special maximum particle speed. The effect of a drift force in this case is analytically determined by perturbation theory. It will be interesting in the future to compare our results to real experimental systems. One realization could be magnetic colloidal particles diffusing through a shear-thickening environment such as starch suspensions, possibly exposed to an external magnetic field gradient.

Molecular modeling the microstructure and phase behavior of bulk and inhomogeneous complex fluids

NASA Astrophysics Data System (ADS)

Bymaster, Adam

Accurate prediction of the thermodynamics and microstructure of complex fluids is contingent upon a model's ability to capture the molecular architecture and the specific intermolecular and intramolecular interactions that govern fluid behavior. This dissertation makes key contributions to improving the understanding and molecular modeling of complex bulk and inhomogeneous fluids, with an emphasis on associating and macromolecular molecules (water, hydrocarbons, polymers, surfactants, and colloids). Such developments apply broadly to fields ranging from biology and medicine, to high performance soft materials and energy. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's thermodynamic perturbation theory (TPT1), is extended to include a crossover correction that significantly improves the predicted phase behavior in the critical region. In addition, PC-SAFT is used to investigate the vapor-liquid equilibrium of sour gas mixtures, to improve the understanding of mercaptan/sulfide removal via gas treating. For inhomogeneous fluids, a density functional theory (DFT) based on TPT1 is extended to problems that exhibit radially symmetric inhomogeneities. First, the influence of model solutes on the structure and interfacial properties of water are investigated. The DFT successfully describes the hydrophobic phenomena on microscopic and macroscopic length scales, capturing structural changes as a function of solute size and temperature. The DFT is used to investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. A comprehensive study is conducted characterizing the role of polymer concentration and particle/polymer size ratio on the structure, polymer induced depletion forces, and tendency towards colloidal aggregation. The inhomogeneous form of the association functional is used, for the first time, to extend the DFT to associating polymer systems, applicable to any association scheme. Theoretical results elucidate how reversible bonding governs the structure of a fluid near a surface and in confined environments, the molecular connectivity (formation of supramolecules, star polymers, etc.) and the phase behavior of the system. Finally, the DFT is extended to predict the inter- and intramolecular correlation functions of polymeric fluids. A theory capable of providing such local structure is important to understanding how local chemistry, branching, and bond flexibility affect the thermodynamic properties of polymers.

Stereolithographic processing of ceramics: Photon diffusion in colloidal dispersion

NASA Astrophysics Data System (ADS)

Garg, Rajeev

The technique of ceramic stereolithography (CSL) has been developed for fabricating near net shape ceramic objects. In stereolithography, the three-dimensional computer design file of the object is sliced into thin layers. Each layer is physically fabricated by photocuring the surface of a liquid photo-polymerizable resin bath by raster scanning an ultra-violet laser across the surface of the resin. In CSL, the liquid resin is a high concentration colloidal dispersion in a solution of ultraviolet curable polymers. The ceramic green body fabricated by ceramic stereolithography technique is subjected to the post processing steps of drying, binder burnout and sintering to form a dense ceramic object. An aqueous alumina dispersion in photocuring polymers with particle volume fraction greater than 0.5 was formulated for CSL process. Low molecular weight solution polymers were found to be best suited for formulating ceramic resins due to their inherently low viscosity and favorable interactions with the ceramic dispersant. A hydroxyapatite ceramic resin was also developed for the use in the CSL technique. A model is developed to describe the photocuring process in concentrated ceramic dispersion. The curing profile in ceramic dispersion is governed by multiple scattering from the ceramic particles and absorption by the photocuring polymers. Diffusion theory of light transport is used to model the multiple scattering and absorption phenomena. It is found that diffusive transport adequately describes the phenomena of laser pulse propagation in highly concentrated colloidal dispersions. A model was developed to describe the absorption in highly concentrated ceramic dispersion. Various complex-shaped monolithic alumina and hydroxyapatite objects were fabricated by CSL and shown to possess uniform microstructure. The mechanical properties and sintering behavior of the parts fabricated by CSL are shown to be comparable to those fabricated by other ceramic processing technique. An application of CSL has been established for fabricating orthopedic implants. Orthopedic implants and biomedical devices of defined micro and macro architecture with controlled pore sizes and porosity were fabricated by CSL. The bone implants were also fabricated form in vivo scan of the bone. The structures were implanted in rats to understand the biocompatibility of CSL fabricated parts.

Dynamical studies of confined fluids and polymers

NASA Astrophysics Data System (ADS)

Grabowski, Christopher A.

Soft matter, a class of materials including polymers, colloids, and surfactant molecules, are ubiquitous in our everyday lives. Plastics, soaps, foods and living organisms are mostly comprised of soft materials. Research conducted to understand soft matter behavior at the molecular level is essential to create new materials with unique properties. Self-healing plastics, targeted drug delivery, and nanowire assemblies have all been further advanced by soft matter research. The author of this dissertation investigates fundamental soft matter systems, including polymer solutions and melts, colloid dispersions in polymer melts, and interfacial fluids. The dynamics of polymers and confined fluids were studied using the single-molecule sensitive technique of fluorescence correlation spectroscopy (FCS). Here, fluorescent dyes are attached to polymer coils or by introducing free dyes directly into the solution/film. Complementary experiments were also performed, utilizing atomic force microscopy (AFM) and ellipsometry. FCS and AFM experiments demonstrated the significant difference in properties of thin fluid films of the nearly spherical, nonpolar molecule TEHOS (tetrakis(2-ethylhexoxy)silane) when compared to its bulk counterpart. AFM experiments confirmed TEHOS orders in layers near a solid substrate. FCS experiments show that free dyes introduced in these thin films do not have a single diffusion coefficient, indicating that these films have heterogeneity at the molecular level. FCS experiments have been applied to study the diffusion of gold colloids. The diffusion of gold colloids in polymer melts was found to dramatically depart from the Stokes-Einstein prediction when colloid size was smaller than the surrounding polymer mesh size. This effect is explained by noting the viscosity experienced by the colloid is not equivalent to the overall bulk viscosity of the polymer melt. The conformational change of polymers immersed in a binary solvent was measured via FCS. This experiment was conducted to test a theory proposed by Brochard and de Gennes, who postulated a polymer chain undergoes a collapse and a dramatic re-swelling as the critical point of the binary mixture is approached. Measuring polymer chain diffusion as a function of temperature, this theory was confirmed. To my knowledge, this was the first experimental evidence of contraction/re-swelling for polymers in critical binary solvents.

Avidin self-associates with boric acid gel suspensions: an affinity boron carrier that might be developed for boron neutron-capture therapy.

PubMed

Bench, Bennie J; Johnson, Rebecca; Hamilton, Craig; Gooch, Joey; Wright, John R

2004-02-15

It has been shown in preliminary studies that the antibacterial protein avidin self-associates with the boric acid gel polymer, and avidin-coated gel particles in the micrometer and submicrometer size ranges are of interest for boron neutron-capture therapy (BNCT), which is neutron-induced fission of boron-10 to produce intense alpha radiation for tumor destruction. The gel particles carry large amounts of boron-10 and are theoretically able effect a meaningful tissue dosing through BNCT. A gross precipitation of gel particles occurs within 46 min of mixing when the avidin/colloid ratio is about 0.34 g avidin/g colloid. This is a minimum time if gel and avidin concentrations are in the low microgram/milliliter range, but at higher proportions of avidin the time delay to precipitation increases significantly; i.e., the colloid surface becomes blocked, inhibiting lattice formation. The avidin-coated gel particles eventually cross-link, forming a solid matrix and precipitating on a timescale measured on the order of an hour. At shorter exposure times rapid agglutination-like reactions were observed with biotinylated bovine albumin, suggesting that two-stage pretargeting of specific tissues should be possible with biotinylated antitumor antibodies. However, for BNCT to be practical, avidin's interaction with the gel needs to be strengthened, and all aryl-B(OH)(2) groups on the particle surfaces must be blocked, or else the particles will interact strongly and nonspecifically with each other and with the carbohydrate groups present on most cell surfaces. Glyceric acid delays the precipitation of the particle suspensions while most simple and complex carbohydrates accelerate it.

Controlling the Transient Interface Shape and Deposition Profile Left by Desiccation of Colloidal Droplets on Multiple Polymer Surfaces

NASA Astrophysics Data System (ADS)

Dunning, Peter David

A colloidal suspension is a small constituent of insoluble solid particles suspended in a liquid medium. Control over the wetting, evaporation, and deposition patterns left by colloidal suspensions is valuable in many biological, medical, industrial, and agricultural applications. Understanding the governing principles of wetting and evaporative phenomena of these colloidal suspensions may lead to greater control over resultant deposition patterns. Perhaps the most familiar pattern forms when an initially heterogeneous colloidal suspension leaves a dark ring pattern at the edge of a drop. This pattern is referred to as a coffee-stain and it can be seen from dried droplets of spilled coffee. This coffee-stain effect was first investigated by Deegan et. al. who discovered that these patterns occur when outward radial flows driven by evaporation at the triple contact line dominate over other effects. While the presence of coffee-stain patterns is undesirable in many printing and medical diagnostic processes, it can also be advantageous in the production of low cost transparent conductive films, the deposition of metal vapor, and the manipulation of biological structures. Controlling the interactions between the substrate, liquid, vapor, and particles can lead to control over the size and morphology of evaporative deposition patterns left by aqueous colloidal suspensions. Several methods have been developed to control the evaporation of colloidal suspensions to either suppress or enhance the coffee stain effect. Electrowetting on Dielectric (EWOD) is one promising method that has been used to control colloidal depositions by applying either an AC or DC electric field. EWOD actuation has the potential to dynamically control colloidal deposition left by desiccated droplets to either suppress or enhance the coffee stain effect. It may also allow for independent control of the fluidic interface and deposition of particles via electrowetting and electrokinetic forces. Implementation of this technique requires that the colloidal droplet be separated from the active electrode by a dielectric layer to prevent electrolysis. A variety of polymer layers have been used in EWOD devices for a variety of applications. In applications that involve desiccation of colloidal suspensions, the material for this layer should be chosen carefully as it can play an important role in the resulting deposition pattern. An experimental method to monitor the transient evolution of the shape of an evaporating colloidal droplet and optically quantify the resultant deposition pattern is presented. Unactuated colloidal suspensions will be desiccated on a variety of substrates commonly used in EWOD applications. Transient image profiles and particle deposition patterns are examined for droplets containing fluorescent micro-particles. Qualitative and quantitative comparisons of these results will be used to compare multiple different cases in an effort to provide insight into the effects of polymer selection on the drying dynamics and resultant deposition patterns of desiccated colloidal materials. It was found that the equilibrium and receding contact angles between the surface and the droplet play a key role in the evaporation dynamics and the resulting deposition patterns left by a desiccated colloidal suspension. The equilibrium contact angle controls the initial contact diameter for a droplet of a given volume. As a droplet on a surface evaporates, the evolution of the interface shape and the contact diameter can generally be described by three different regimes. The Constant Contact Radius (CCR) regime occurs when the contact line is pinned while the contact angle decreases. The Constant Contact Angle (CCA) regime occurs when the contact line recedes while the contact angle remains constant. The Mixed regime occurs when the contact radius and angle both reduce over time. The presence of the CCA regime allows the contact line to recede creating a more uniform deposition. However, not all droplets move into the CCA regime. Some remain in the CCR regime creating a coffee-stain pattern. In order to transition into the CCA regime, the dynamic contact angle of the droplet must be reduced to an angle close to the receding contact angle. Transient interface shapes and deposition patterns were examined on four surfaces: (i) Glass, (ii) Kapton HN polyimide tape, (iii) SU-8 3005, and (iv) Teflon AF. Glass has a low equilibrium contact angle and a very low receding contact angle resulting in a large uniform coffee-stain deposition. Kapton HN and SU-8 3005 have similar equilibrium contact angles that result in similar initial contact diameters. However, Kapton HN pins at that initial diameter due to a low receding contact angle producing a smaller more intense coffee-stain. SU-8 3005 has a large receding contact angle that allows for the transition into the CCA regime which results in a smaller, more uniform, and more intense spot. Teflon AF has the largest equilibrium and receding contact angle producing the smallest, most uniform, and most intense spot. Results presented here suggest that a lower receding contact angle is beneficial in areas where the coffee-stain effect needs to be enhanced while a larger receding contact angle is beneficial in areas where the coffee-stain needs to be suppressed. Preliminary results are also presented examining droplets actuated via AC electrowetting to examine the effect of electrode geometry and applied voltage on electrowetting behavior and colloidal depositions in these cases. It was found that the Young-Lippmann equation needs to be modified to satisfy the modified capacitance per unit area of a system with different electrode geometries.

Colloidal behavior of aqueous montmorillonite suspensions in the presence of non-ionic polymer

NASA Astrophysics Data System (ADS)

Gareche, M.; Azri, N.; Allal, A.; Zeraibi, N.

2015-04-01

In this paper we characterized at first, the rheological behavior of the bentonite suspensions and the aqueous solutions of polyethylene oxide (PEO), then we were investigated the influence of this polymer in a water-based drilling fluid model (6% of bentonite suspension). The objective is to exhibit how the non ionic polymer with molecular weight 6×103 g/mol. of varying concentration mass (0.7%, 1%, 2% et 3%) significantly alter the rheological properties (yield stress, viscosity, loss and elastic modulus) of the bentonite suspensions. The rheological measurements made in simple shear and in dynamic on the mixture (water-bentonite-PEO), showed rheological properties of bentonite suspensions both in the presence and absence of non-ionic polymer. The PEO presents an affinity for the bentonite particles slowing down their kinetic aggregation. The analysis by X-rays diffraction also allowed understanding the structure of this mixture. It had revealed the intercalation between of the clay platelets on one hand, and the links bridges assured by the chains of polymer between bentonite particles beyond a critical concentration in PEO on the other hand. The Herschel- Bulkley rheological model is used for the correlation of our experimental results.

Implications of the effective one-component analysis of pair correlations in colloidal fluids with polydispersity

NASA Astrophysics Data System (ADS)

Pond, Mark J.; Errington, Jeffrey R.; Truskett, Thomas M.

2011-09-01

Partial pair-correlation functions of colloidal suspensions with continuous polydispersity can be challenging to characterize from optical microscopy or computer simulation data due to inadequate sampling. As a result, it is common to adopt an effective one-component description of the structure that ignores the differences between particle types. Unfortunately, whether this kind of simplified description preserves or averages out information important for understanding the behavior of the fluid depends on the degree of polydispersity and can be difficult to assess, especially when the corresponding multicomponent description of the pair correlations is unavailable for comparison. Here, we present a computer simulation study that examines the implications of adopting an effective one-component structural description of a polydisperse fluid. The square-well model that we investigate mimics key aspects of the experimental behavior of suspended colloids with short-range, polymer-mediated attractions. To characterize the partial pair-correlation functions and thermodynamic excess entropy of this system, we introduce a Monte Carlo sampling strategy appropriate for fluids with a large number of pseudo-components. The data from our simulations at high particle concentrations, as well as exact theoretical results for dilute systems, show how qualitatively different trends between structural order and particle attractions emerge from the multicomponent and effective one-component treatments, even with systems characterized by moderate polydispersity. We examine consequences of these differences for excess-entropy based scalings of shear viscosity, and we discuss how use of the multicomponent treatment reveals similarities between the corresponding dynamic scaling behaviors of attractive colloids and liquid water that the effective one-component analysis does not capture.

Polymeric membranes: surface modification for minimizing (bio)colloidal fouling.

PubMed

Kochkodan, Victor; Johnson, Daniel J; Hilal, Nidal

2014-04-01

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London-van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized. Copyright © 2013 Elsevier B.V. All rights reserved.

Room Temperature Radiolytic Synthesized Cu@CuAlO2-Al2O3 Nanoparticles

PubMed Central

Abedini, Alam; Saion, Elias; Larki, Farhad; Zakaria, Azmi; Noroozi, Monir; Soltani, Nayereh

2012-01-01

Colloidal Cu@CuAlO2-Al2O3 bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a 60Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO2-Al2O3 nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO2-Al2O3 nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation. PMID:23109893

Room temperature radiolytic synthesized Cu@CuAlO(2)-Al(2)O(3) nanoparticles.

PubMed

Abedini, Alam; Saion, Elias; Larki, Farhad; Zakaria, Azmi; Noroozi, Monir; Soltani, Nayereh

2012-01-01

Colloidal Cu@CuAlO(2)-Al(2)O(3) bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a (60)Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO(2)-Al(2)O(3) nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO(2)-Al(2)O(3) nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation.

Measurements of Submicron Particle Adsorption and Particle Film Elasticity at Oil-Water Interfaces.

PubMed

Manga, Mohamed S; Hunter, Timothy N; Cayre, Olivier J; York, David W; Reichert, Matthew D; Anna, Shelly L; Walker, Lynn M; Williams, Richard A; Biggs, Simon R

2016-05-03

The influence of particle adsorption on liquid/liquid interfacial tension is not well understood, and much previous research has suggested conflicting behaviors. In this paper we investigate the surface activity and adsorption kinetics of charge stabilized and pH-responsive polymer stabilized colloids at oil/water interfaces using two tensiometry techniques: (i) pendant drop and (ii) microtensiometer. We found, using both techniques, that charge stabilized particles had little or no influence on the (dynamic) interfacial tension, although dense silica particles affected the "apparent" measured tension in the pendent drop, due to gravity driven elongation of the droplet profile. Nevertheless, this apparent change additionally allowed the study of adsorption kinetics, which was related qualitatively between particle systems by estimated diffusion coefficients. Significant and real interfacial tension responses were measured using ∼53 nm core-shell latex particles with a pH-responsive polymer stabilizer of poly(methyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (pMMA-b-pDMAEMA) diblock copolymer. At pH 2, where the polymer is strongly charged, behavior was similar to that of the bare charge-stabilized particles, showing little change in the interfacial tension. At pH 10, where the polymer is discharged and poorly soluble in water, a significant decrease in the measured interfacial tension commensurate with strong adsorption at the oil-water interface was seen, which was similar in magnitude to the surface activity of the free polymer. These results were both confirmed through droplet profile and microtensiometry experiments. Dilational elasticity measurements were also performed by oscillation of the droplet; again, changes in interfacial tension with droplet oscillation were only seen with the responsive particles at pH 10. Frequency sweeps were performed to ascertain the dilational elasticity modulus, with measured values being significantly higher than previously reported for nanoparticle and surfactant systems, and similar in magnitude to protein stabilized droplets.

Arrays of size and distance controlled platinum nanoparticles fabricated by a colloidal method

NASA Astrophysics Data System (ADS)

Manzke, Achim; Vogel, Nicolas; Weiss, Clemens K.; Ziener, Ulrich; Plettl, Alfred; Landfester, Katharina; Ziemann, Paul

2011-06-01

Based on emulsion polymerization in the presence of a Pt complex, polystyrene (PS) particles were prepared exhibiting a well defined average diameter with narrow size-distribution. Furthermore, the colloids contain a controlled concentration of the Pt precursor complex. Optimized coating of Si substrates with such colloids leads to extended areas of hexagonally ordered close-packed PS particles. Subsequent application of plasma etching and annealing steps allows complete removal of the PS carriers and in parallel nucleation and growth of Pt nanoparticles (NPs) which are located at the original center of the PS colloids. In this way, hexagonally arranged spherical Pt NPs are obtained with controlled size and interparticle distances demonstrating variability and precision with so far unknown parameter scalability. This control is demonstrated by the fabrication of Pt NP arrays at a fixed particle distance of 185 nm while systematically varying the diameters between 8 and 15 nm. Further progress could be achieved by seeded emulsion polymerization. Here, Pt loaded PS colloids of 130 nm were used as seeds for a subsequent additional emulsion polymerization, systematically enlarging the diameter of the PS particles. Applying the plasma and annealing steps as above, in this way hexagonally ordered arrays of 9 nm Pt NPs could be obtained at distances up to 260 nm. To demonstrate their stability, such Pt particles were used as etching masks during reactive ion etching thereby transferring their hexagonal pattern into the Si substrate resulting in corresponding arrays of nanopillars.Based on emulsion polymerization in the presence of a Pt complex, polystyrene (PS) particles were prepared exhibiting a well defined average diameter with narrow size-distribution. Furthermore, the colloids contain a controlled concentration of the Pt precursor complex. Optimized coating of Si substrates with such colloids leads to extended areas of hexagonally ordered close-packed PS particles. Subsequent application of plasma etching and annealing steps allows complete removal of the PS carriers and in parallel nucleation and growth of Pt nanoparticles (NPs) which are located at the original center of the PS colloids. In this way, hexagonally arranged spherical Pt NPs are obtained with controlled size and interparticle distances demonstrating variability and precision with so far unknown parameter scalability. This control is demonstrated by the fabrication of Pt NP arrays at a fixed particle distance of 185 nm while systematically varying the diameters between 8 and 15 nm. Further progress could be achieved by seeded emulsion polymerization. Here, Pt loaded PS colloids of 130 nm were used as seeds for a subsequent additional emulsion polymerization, systematically enlarging the diameter of the PS particles. Applying the plasma and annealing steps as above, in this way hexagonally ordered arrays of 9 nm Pt NPs could be obtained at distances up to 260 nm. To demonstrate their stability, such Pt particles were used as etching masks during reactive ion etching thereby transferring their hexagonal pattern into the Si substrate resulting in corresponding arrays of nanopillars. Electronic supplementary information (ESI) available: Detailed description of the experimental part (S1-S4) platinum concentration inside the polymer particles synthesized by a seeded polymerization from the same seed particles measured by ICP-OES (Fig. S1 and S5); SEM image of Pt complex containing PS particles after oxygen plasma treatment (Fig. S2 and S6); effect of hydrofluoric acid treatment on silicon oxide elevation under Pt NPs (Fig. S3 and S6); SEM images demonstrating the variability of Pt NP distance while keeping the diameter constant (Fig. S4 and S8); results of experimental determination of Pt content by ICP-OES (Tables S1 and S9); diameter of the particles at different fabrication states (Tables S2 and S10). See DOI: 10.1039/c1nr10169b

Generating Bulk-Scale Ordered Optical Materials Using Shear-Assembly in Viscoelastic Media.

PubMed

Finlayson, Chris E; Baumberg, Jeremy J

2017-06-22

We review recent advances in the generation of photonics materials over large areas and volumes, using the paradigm of shear-induced ordering of composite polymer nanoparticles. The hard-core/soft-shell design of these particles produces quasi-solid "gum-like" media, with a viscoelastic ensemble response to applied shear, in marked contrast to the behavior seen in colloidal and granular systems. Applying an oscillatory shearing method to sub-micron spherical nanoparticles gives elastomeric photonic crystals (or "polymer opals") with intense tunable structural color. The further engineering of this shear-ordering using a controllable "roll-to-roll" process known as Bending Induced Oscillatory Shear (BIOS), together with the interchangeable nature of the base composite particles, opens potentially transformative possibilities for mass manufacture of nano-ordered materials, including advances in optical materials, photonics, and metamaterials/plasmonics.

Generating Bulk-Scale Ordered Optical Materials Using Shear-Assembly in Viscoelastic Media

PubMed Central

Finlayson, Chris E.; Baumberg, Jeremy J.

2017-01-01

We review recent advances in the generation of photonics materials over large areas and volumes, using the paradigm of shear-induced ordering of composite polymer nanoparticles. The hard-core/soft-shell design of these particles produces quasi-solid “gum-like” media, with a viscoelastic ensemble response to applied shear, in marked contrast to the behavior seen in colloidal and granular systems. Applying an oscillatory shearing method to sub-micron spherical nanoparticles gives elastomeric photonic crystals (or “polymer opals”) with intense tunable structural color. The further engineering of this shear-ordering using a controllable “roll-to-roll” process known as Bending Induced Oscillatory Shear (BIOS), together with the interchangeable nature of the base composite particles, opens potentially transformative possibilities for mass manufacture of nano-ordered materials, including advances in optical materials, photonics, and metamaterials/plasmonics. PMID:28773044

Electrokinetic Particle Aggregation and Flow Instabilities in Non-Dilute Colloidal Suspensions

NASA Astrophysics Data System (ADS)

Navaneetham, Guru; Posner, Jonathan

2007-11-01

An experimental investigation of electrokinetic particle aggregation and flow instabilities of non-dilute colloidal suspensions in microfabricated channels is presented. The addition of charged colloidal particles can alter the solution's conductivity, permittivity as well as the average particle electrophoretic mobility. In this work, a colloid volume fraction gradient is achieved at the intersection of a Y-shaped PDMS microchannel. The solution conductivity and the particle mobility as a function of the particle (500 nm polystyrene) volume fraction are presented. The critical conditions required for particle aggregation and flow instability are given along with a scaling analysis which shows that the flow becomes unstable at a critical electric Rayleigh number for a wide range of applied electric fields and colloid volume fractions. Electrokinetic particle aggregation and instabilities of non-dilute colloidal suspensions may be important for applications such as the electrophoretic deposition of particles to form micropatterned colloidal assemblies, electrorheological devices, and on-chip, electrokinetic manipulation of colloids.

Greensilica® vectors for smart textiles.

PubMed

Matos, Joana C; Avelar, Inês; Martins, M Bárbara F; Gonçalves, M Clara

2017-01-20

The present work aims developing a versatile Greensilica ® vector/carrier, able to bind to a wide range of textile matrices of carbohydrate polymers and susceptible of being loaded with chemicals/drugs/therapeutic molecules, to create a green tailor-made (multi)functional high-tech textile. A green, eco-friendly, ammonia-free, easily scalable, time-saving sol-gel process was established for the production of those silica-based colloidal particles (SiO 2 , amine-SiO 2 , diamine-SiO 2 , and epoxy-SiO 2 ). Two different textile matrices (cotton, polyester) were functionalized, through the impregnation of Greensilica® particles. The impregnation was performed with and without cure. Diamine-SiO 2 colloidal particles exhibited the higher bonding efficiency in cured textile matrices (both cotton and polyester), while with no cure the best adherence to cotton and polyester textile matrices was achieved with diamine-SiO 2 and amine-SiO 2 , respectively. Use once and throw away and continued use applications were envisaged and screened through washing tests. The efficiency of the textiles impregnation was confirmed by SEM, and quantified by ICP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Template-directed control of crystal morphologies.

PubMed

Meldrum, Fiona C; Ludwigs, Sabine

2007-02-12

Biominerals are characterised by unique morphologies, and it is a long-term synthetic goal to reproduce these synthetically. We here apply a range of templating routes to investigate whether a fascinating category of biominerals, the single crystals with complex forms, can be produced using simple synthetic methods. Macroporous crystals with sponge-like morphologies identical to that of sea urchin skeletal plates were produced on templating with a sponge-like polymer membrane. Similarly, patterning of individual crystal faces was achieved from the micrometer to nanometer scale through crystallisation on colloidal particle monolayers and patterned polymer thin films. These experiments demonstrate the versatility of a templating approach to producing single crystals with unique morphologies.

Filamentous phages as building blocks for reconfigurable and hierarchical self-assembly

NASA Astrophysics Data System (ADS)

Gibaud, Thomas

2017-12-01

Filamentous bacteriophages such as fd-like viruses are monodisperse rod-like colloids that have well defined properties of diameter, length, rigidity, charge and chirality. Engineering these viruses leads to a library of colloidal rods, which can be used as building blocks for reconfigurable and hierarchical self-assembly. Their condensation in an aqueous solution with additive polymers, which act as depletants to induce attraction between the rods, leads to a myriad of fluid-like micronic structures ranging from isotropic/nematic droplets, colloid membranes, achiral membrane seeds, twisted ribbons, π-wall, pores, colloidal skyrmions, Möbius anchors, scallop membranes to membrane rafts. These structures, and the way that they shape-shift, not only shed light on the role of entropy, chiral frustration and topology in soft matter, but also mimic many structures encountered in different fields of science. On the one hand, filamentous phages being an experimental realization of colloidal hard rods, their condensation mediated by depletion interactions constitutes a blueprint for the self-assembly of rod-like particles and provides a fundamental foundation for bio- or material-oriented applications. On the other hand, the chiral properties of the viruses restrict the generalities of some results but vastly broaden the self-assembly possibilities.

Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

PubMed

Zheng, Yun; Geng, Hongbo; Zhang, Yufei; Chen, Libao; Li, Cheng Chao

2018-04-02

In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for the preparation of metal colloids in inverse micelles and product preferred by the method

DOEpatents

Wilcoxon, Jess P.

1992-01-01

A method is provided for preparing catalytic elemental metal colloidal particles (e.g. gold, palladium, silver, rhodium, iridium, nickel, iron, platinum, molybdenum) or colloidal alloy particles (silver/iridium or platinum/gold). A homogeneous inverse micelle solution of a metal salt is first formed in a metal-salt solvent comprised of a surfactant (e.g. a nonionic or cationic surfactant) and an organic solvent. The size and number of inverse micelles is controlled by the proportions of the surfactant and the solvent. Then, the metal salt is reduced (by chemical reduction or by a pulsed or continuous wave UV laser) to colloidal particles of elemental metal. After their formation, the colloidal metal particles can be stabilized by reaction with materials that permanently add surface stabilizing groups to the surface of the colloidal metal particles. The sizes of the colloidal elemental metal particles and their size distribution is determined by the size and number of the inverse micelles. A second salt can be added with further reduction to form the colloidal alloy particles. After the colloidal elemental metal particles are formed, the homogeneous solution distributes to two phases, one phase rich in colloidal elemental metal particles and the other phase rich in surfactant. The colloidal elemental metal particles from one phase can be dried to form a powder useful as a catalyst. Surfactant can be recovered and recycled from the phase rich in surfactant.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids

NASA Astrophysics Data System (ADS)

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K. G.

2009-05-01

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids.

PubMed

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K G

2009-05-28

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Preparation and magnetic properties of magnetic photonic crystal by using monodisperse polystyrene covered Fe3O4 nanoparticles onto glass substrate

NASA Astrophysics Data System (ADS)

Azizi, Zahra Sadat; Tehranchi, Mohammad Mehdi; Vakili, Seyed Hamed; Pourmahdian, Saeed

2018-05-01

Engineering approach towards combined photonic band gap properties and magnetic/polymer composite particles, attract considerable attention of researchers due to their unique properties. In this research, two different magnetic particles were prepared by nearly monodisperse polystyrene spheres as bead with two concentrations of Fe3O4 nanoparticles to prepare magnetic photonic crystals (MPCs). The crystal surfaces and particles morphology were investigated employing scanning electron microscopy and transmission electron microscopy. The volume fraction of magnetic material embedded into colloidal spheres and their morphology was found to be a key parameter in the optical and magneto-optical properties of transparent MPC.

Influence of Temperature on the Colloidal Stability of Polymer-Coated Gold Nanoparticles in Cell Culture Media.

PubMed

Zyuzin, Mikhail V; Honold, Tobias; Carregal-Romero, Susana; Kantner, Karsten; Karg, Matthias; Parak, Wolfgang J

2016-04-06

The temperature-dependence of the hydrodynamic diameter and colloidal stability of gold-polymer core-shell particles with temperature-sensitive (poly(N-isopropylacrylamide)) and temperature-insensitive shells (polyallylaminine hydrochloride/polystyrensulfonate, poly(isobutylene-alt-maleic anhydride)-graft-dodecyl) are investigated in various aqueous media. The data demonstrate that for all nanoparticle agglomeration, i.e., increase in effective nanoparticle size, the presence of salts or proteins in the dispersion media has to be taken into account. Poly(N-isopropylacrylamide) coated nanoparticles show a reversible temperature-dependent increase in size above the volume phase transition of the polymer shell when they are dispersed in phosphate buffered saline or in media containing protein. In contrast, the nanoparticles coated with temperature-insensitive polymers show a time-dependent increase in size in phosphate buffered saline or in medium containing protein. This is due to time-dependent agglomeration, which is particularly strong in phosphate buffered saline, and induces a time-dependent, irreversible increase in the hydrodynamic diameter of the nanoparticles. This demonstrates that one has to distinguish between temperature- and time-induced agglomerations. Since the size of nanoparticles regulates their uptake by cells, temperature-dependent uptake of thermosensitive and non-thermosensitive nanoparticles by cells lines is compared. No temperature-specific difference between both types of nanoparticles could be observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical particle coating using polymethacrylate nanoparticle agglomerates for the preparation of controlled release fine particles: The relationship between coating performance and the characteristics of various polymethacrylates.

PubMed

Kondo, Keita; Kato, Shinsuke; Niwa, Toshiyuki

2017-10-30

We aimed to understand the factors controlling mechanical particle coating using polymethacrylate. The relationship between coating performance and the characteristics of polymethacrylate powders was investigated. First, theophylline crystals were treated using a mechanical powder processor to obtain theophylline spheres (<100μm). Second, five polymethacrylate latexes were powdered by spray freeze drying to produce colloidal agglomerates. Finally, mechanical particle coating was performed by mixing theophylline spheres and polymethacrylate agglomerates using the processor. The agglomerates were broken under mechanical stress to coat the spheres effectively. The coating performance of polymethacrylate agglomerates tended to increase as their pulverization progressed. Differences in the grindability of the agglomerates were attributed to differences in particle structure, resulting from consolidation between colloidal particles. High-grindability agglomerates exhibited higher pulverization as their glass transition temperature (T g ) increased and the further pulverization promoted coating. We therefore conclude that the minimization of polymethacrylate powder by pulverization is an important factor in mechanical particle coating using polymethacrylate with low deformability. Meanwhile, when product temperature during coating approaches T g of polymer, polymethacrylate was soften to show high coating performance by plastic deformation. The effective coating by this mechanism may be accomplished by adjusting the temperature in the processor to the T g . Copyright © 2017 Elsevier B.V. All rights reserved.

Complex patchy colloids shaped from deformable seed particles through capillary interactions.

PubMed

Meester, V; Kraft, D J

2018-02-14

We investigate the mechanisms underlying the reconfiguration of random aggregates of spheres through capillary interactions, the so-called "colloidal recycling" method, to fabricate a wide variety of patchy particles. We explore the influence of capillary forces on clusters of deformable seed particles by systematically varying the crosslink density of the spherical seeds. Spheres with a poorly crosslinked polymer network strongly deform due to capillary forces and merge into large spheres. With increasing crosslink density and therefore rigidity, the shape of the spheres is increasingly preserved during reconfiguration, yielding patchy particles of well-defined shape for up to five spheres. In particular, we find that the aspect ratio between the length and width of dumbbells, L/W, increases with the crosslink density (cd) as L/W = B - A·exp(-cd/C). For clusters consisting of more than five spheres, the particle deformability furthermore determines the patch arrangement of the resulting particles. The reconfiguration pathway of clusters of six densely or poorly crosslinked seeds leads to octahedral and polytetrahedral shaped patchy particles, respectively. For seven particles several geometries were obtained with a preference for pentagonal dipyramids by the rigid spheres, while the soft spheres do rarely arrive in these structures. Even larger clusters of over 15 particles form non-uniform often aspherical shapes. We discuss that the reconfiguration pathway is largely influenced by confinement and geometric constraints. The key factor which dominates during reconfiguration depends on the deformability of the spherical seed particles.

Magnetic assembly route to colloidal responsive photonic nanostructures.

PubMed

He, Le; Wang, Mingsheng; Ge, Jianping; Yin, Yadong

2012-09-18

Responsive photonic structures can respond to external stimuli by transmitting optical signals. Because of their important technological applications such as color signage and displays, biological and chemical sensors, security devices, ink and paints, military camouflage, and various optoelectronic devices, researchers have focused on developing these functional materials. Conventionally, self-assembled colloidal crystals containing periodically arranged dielectric materials have served as the predominant starting frameworks. Stimulus-responsive materials are incorporated into the periodic structures either as the initial building blocks or as the surrounding matrix so that the photonic properties can be tuned. Although researchers have proposed various versions of responsive photonic structures, the low efficiency of fabrication through self-assembly, narrow tunability, slow responses to the external stimuli, incomplete reversibility, and the challenge of integrating them into existing photonic devices have limited their practical application. In this Account, we describe how magnetic fields can guide the assembly of superparamagnetic colloidal building blocks into periodically arranged particle arrays and how the photonic properties of the resulting structures can be reversibly tuned by manipulating the external magnetic fields. The application of the external magnetic field instantly induces a strong magnetic dipole-dipole interparticle attraction within the dispersion of superparamagnetic particles, which creates one-dimensional chains that each contains a string of particles. The balance between the magnetic attraction and the interparticle repulsions, such as the electrostatic force, defines the interparticle separation. By employing uniform superparamagnetic particles of appropriate sizes and surface charges, we can create one-dimensional periodicity, which leads to strong optical diffraction. Acting remotely over a large distance, magnetic forces drove the rapid formation of colloidal photonic arrays with a wide range of interparticle spacing. They also allowed instant tuning of the photonic properties because they manipulated the interparticle force balance, which changed the orientation of the colloidal assemblies or their periodicity. This magnetically responsive photonic system provides a new platform for chromatic applications: these colloidal particles assemble instantly into ordered arrays with widely, rapidly, and reversibly tunable structural colors, which can be easily and rapidly fixed in a curable polymer matrix. Based on these unique features, we demonstrated many applications of this system, such as structural color printing, the fabrication of anticounterfeiting devices, switchable signage, and field-responsive color displays. We also extended this idea to rapidly organize uniform nonmagnetic building blocks into photonic structures. Using a stable ferrofluid of highly charged magnetic nanoparticles, we created virtual magnetic moments inside the nonmagnetic particles. This "magnetic hole" strategy greatly broadens the scope of the magnetic assembly approach to the fabrication of tunable photonic structures from various dielectric materials.

Laser-assisted immobilization of colloid silver nanoparticles on polyethyleneterephthalate

NASA Astrophysics Data System (ADS)

Siegel, Jakub; Lyutakov, Oleksiy; Polívková, Markéta; Staszek, Marek; Hubáček, Tomáš; Švorčík, Václav

2017-10-01

Immobilization of nanoobjects on the surface of underlying material belongs to current issues of material science. Such altered materials exhibits completely exceptional properties exploitable in a broad spectrum of industrially important applications ranging from catalysts up to health-care industry. Here we present unique approach for immobilization of electrochemically synthesized silver nanoparticles on polyethyleneterephthalate (PET) foil whose essence lies in physical incorporation of particles into thin polymer surface layer induced by polarized excimer laser light. Changes in chemical composition and surface structure of polymer after particle immobilization were recorded by wide range of analytical techniques such as ARXPS, EDX, RBS, AAS, Raman, ICP-MS, DLS, UV-vis, SEM, TEM, and AFM. Thorough analysis of both nanoparticles entering the immobilization step as well as modified PET surface allowed revealing the mechanism of immobilization process itself. Silver nanoparticles were physically embedded into a thin surface layer of polymer reaching several nanometers beneath the surface rather than chemically bonded to PET macromolecules. Laser-implanted nanoparticles open up new possibilities especially in the development of the next generation cell-conform antimicrobial coatings of polymeric materials, namely due to the considerable immobilization strength which is strong enough to prevent particle release into the surrounding environment.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

PubMed

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

What Is a Colloid?

ERIC Educational Resources Information Center

Lamb, William G.

1985-01-01

Describes the properties of colloids, listing those commonly encountered (such as whipped cream, mayonnaise, and fog). Also presents several experiments using colloids and discusses "Silly Putty," a colloid with viscoelastic properties whose counterintuitive properties result from its mixture of polymers. (DH)

Plasma Synthesis and Sintering of Advanced Ceramics

DTIC Science & Technology

1990-09-15

CONTENTS Page LIST OF TABLES iv OBJECTIVES 1 COLLOIDAL PLASMA PROCESSING: CONCEPTS 1 BACKGROUND 2 Ultrafine Particles 2 Colloidal Plasma 3 Particle...colloidal plasma processing of ceramics. COLLOIDAL PLASMA PROCESSING: CONCEPTS It is well known that ultrafine particles prepared in gas plasmas agglomerate...BACKGROUND Ultrafine Particles . There are well recognized advantages to using small particles in ceramic processing. The instantaneous densification

Submicron magnetic core conducting polypyrrole polymer shell: Preparation and characterization.

PubMed

Tenório-Neto, Ernandes Taveira; Baraket, Abdoullatif; Kabbaj, Dounia; Zine, Nadia; Errachid, Abdelhamid; Fessi, Hatem; Kunita, Marcos Hiroiuqui; Elaissari, Abdelhamid

2016-04-01

Magnetic particles are of great interest in various biomedical applications, such as, sample preparation, in vitro biomedical diagnosis, and both in vivo diagnosis and therapy. For in vitro applications and especially in labs-on-a-chip, microfluidics, microsystems, or biosensors, the needed magnetic dispersion should answer various criteria, for instance, submicron size in order to avoid a rapid sedimentation rate, fast separations under an applied magnetic field, and appreciable colloidal stability (stable dispersion under shearing process). Then, the aim of this work was to prepare highly magnetic particles with a magnetic core and conducting polymer shell particles in order to be used not only as a carrier, but also for the in vitro detection step. The prepared magnetic seed dispersions were functionalized using pyrrole and pyrrole-2-carboxylic acid. The obtained core-shell particles were characterized in terms of particle size, size distribution, magnetization properties, FTIR analysis, surface morphology, chemical composition, and finally, the conducting property of those particles were evaluated by cyclic voltammetry. The obtained functional submicron highly magnetic particles are found to be conducting material bearing function carboxylic group on the surface. These promising conducting magnetic particles can be used for both transport and lab-on-a-chip detection. Copyright © 2015. Published by Elsevier B.V.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

Schmidt, Matthias; Dijkstra, Marjolein; Hansen, Jean-Pierre

2004-08-20

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.

PREFACE: The Eighth Liquid Matter Conference The Eighth Liquid Matter Conference

NASA Astrophysics Data System (ADS)

Dellago, Christoph; Kahl, Gerhard; Likos, Christos N.

2012-07-01

The Eighth Liquid Matter Conference (LMC8) was held at the Universität Wien from 6-10 September 2011. Initiated in 1990, the conferences of this series cover a broad range of highly interdisciplinary topics, ranging from simple liquids to soft matter and biophysical systems. The vast spectrum of scientific subjects presented and discussed at the LMC8 is reflected in the themes of the ten symposia: Ionic and quantum liquids, liquid metals Water, solutions and reaction dynamics Liquid crystals Polymers, polyelectrolytes, biopolymers Colloids Films, foams, surfactants, emulsions, aerosols Confined fluids, interfacial phenomena Supercooled liquids, glasses, gels Non-equilibrium systems, rheology, nanofluids Biofluids, active matter This special issue contains scientific papers, authored by participants of the LMC8, which provide a cross-section of the scientific activities in current liquid matter science, as discussed at the conference, and demonstrate the scientific as well as methodological progress made in this field over the past couple of years. The Eighth Liquid Matter Conference contents The Eighth Liquid Matter ConferenceChristoph Dellago, Gerhard Kahl and Christos N Likos Comparing light-induced colloidal quasicrystals with different rotational symmetriesMichael Schmiedeberg and Holger Stark Hydrogen bond network relaxation in aqueous polyelectrolyte solutions: the effect of temperatureS Sarti, D Truzzolillo and F Bordi Equilibrium concentration profiles and sedimentation kinetics of colloidal gels under gravitational stressS Buzzaccaro, E Secchi, G Brambilla, R Piazza and L Cipelletti The capillary interaction between two vertical cylindersHimantha Cooray, Pietro Cicuta and Dominic Vella Hydrodynamic and viscoelastic effects in polymer diffusionJ Farago, H Meyer, J Baschnagel and A N Semenov A density-functional theory study of microphase formation in binary Gaussian mixturesM Carta, D Pini, A Parola and L Reatto Microcanonical determination of the interface tension of flat and curved interfaces from Monte Carlo simulationsA Tröster and K Binder Phase diagrams of particles with dissimilar patches: X-junctions and Y-junctionsJ M Tavares and P I C Teixeira The unbearable heaviness of colloids: facts, surprises, and puzzles in sedimentationRoberto Piazza, Stefano Buzzaccaro and Eleonora Secchi Exploring water and other liquids at negative pressureFrédéric Caupin, Arnaud Arvengas, Kristina Davitt, Mouna El Mekki Azouzi, Kirill I Shmulovich, Claire Ramboz, David A Sessoms and Abraham D Stroock The configurational space of colloidal patchy polymers with heterogeneous sequencesIvan Coluzza and Christoph Dellago Repeated sorption of water in SBA-15 investigated by means of in situ small-angle x-ray scatteringM Erko, D Wallacher, G H Findenegg and O Paris Transition of the hydration state of a surfactant accompanying structural transitions of self-assembled aggregatesM Hishida and K Tanaka The effects of topology on the structural, dynamic and mechanical properties of network-forming materialsMark Wilson Surface tension of an electrolyte-air interface: a Monte Carlo studyAlexandre Diehl, Alexandre P dos Santos and Yan Levin Water and other tetrahedral liquids: order, anomalies and solvationB Shadrack Jabes, Divya Nayar, Debdas Dhabal, Valeria Molinero and Charusita Chakravarty Diffusion coefficient and shear viscosity of rigid water modelsSami Tazi, Alexandru Boţan, Mathieu Salanne, Virginie Marry, Pierre Turq and Benjamin Rotenberg Phase behaviour of colloidal assemblies on 2D corrugated substratesSamir El Shawish, Emmanuel Trizac and Jure Dobnikar Structural properties of dendrimer-colloid mixturesDominic A Lenz, Ronald Blaak and Christos N Likos Fluid-fluid demixing of off-critical colloid-polymer systems confined between parallel platesE A G Jamie, R P A Dullens and D G A L Aarts Simulations of nematic homopolymer melts using particle-based models with interactions expressed through collective variablesKostas Ch Daoulas, Victor Rühle and Kurt Kremer Smectic shellsTeresa Lopez-Leon, Alberto Fernandez-Nieves, Maurizio Nobili and Christophe Blanc Intrinsic profiles and the structure of liquid surfacesP Tarazona, E Chacón and F Bresme Competing ordered structures formed by particles with a regular tetrahedral patch decorationGünther Doppelbauer, Eva G Noya, Emanuela Bianchi and Gerhard Kahl Heterogeneous crystallization in colloids and complex plasmas: the role of binary mobilitiesH Löwen, E Allahyarov, A Ivlev and G E Morfill Isotope effects in water as investigated by neutron diffraction and path integral molecular dynamicsAnita Zeidler, Philip S Salmon, Henry E Fischer, Jörg C Neuefeind, J Mike Simonson and Thomas E Markland Confined cubic blue phases under shearO Henrich, K Stratford, D Marenduzzo, P V Coveney and M E Cates Depletion-induced biaxial nematic states of boardlike particlesS Belli, M Dijkstra and R van Roij Active Brownian motion tunable by lightIvo Buttinoni, Giovanni Volpe, Felix Kümmel, Giorgio Volpe and Clemens Bechinger Structure and stability of charged clustersMark A Miller, David A Bonhommeau, Christopher J Heard, Yuyoung Shin, Riccardo Spezia and Marie-Pierre Gaigeot Non-equilibrium relaxation and tumbling times of polymers in semidilute solutionChien-Cheng Huang, Gerhard Gompper and Roland G Winkler Thermophoresis of colloids by mesoscale simulationsDaniel Lüsebrink, Mingcheng Yang and Marisol Ripoll Computing the local pressure in molecular dynamics simulationsThomas W Lion and Rosalind J Allen Gradient-driven fluctuations in microgravityA Vailati, R Cerbino, S Mazzoni, M Giglio, C J Takacs and D S Cannell

PREFACE: Colloidal and molecular electro-optics Colloidal and molecular electro-optics

NASA Astrophysics Data System (ADS)

Palberg, Thomas; Löwen, Hartmut

2010-12-01

The Kerr effect, also known as the quadratic electro-optic effect, was discovered more than a hundred years ago by John Kerr, a Scottish physicist [1]. It describes the change in the refractive index of a material in response to an applied electric field. Around 1950 its application swayed from simple to complex fluids. A strong contribution was made through a number of seminal papers by the French polymer scientist H Benoit [2-4]. These and others initiated wide interest from researchers working on macromolecular solutions or colloidal dispersions. Experimental activities were further boosted by the advent of the laser and theoretical approaches strongly drew from growing computer power. Use of AC or pulsed field techniques, as well as of inhomogeneous fields, including laser tweezers, studies of electrophoretic, dielectrophoretic, electro-osmotic and other types of motion by advanced optical methods and combinations with other external fields have had the greatest impact on our understanding of the electric field induced optical properties of soft matter systems. Today the field has matured and its techniques are broadly employed as versatile tools with applications ranging from biological systems to electronic ink. Fundamental interest still continues but more and more side branches have evolved fruitfully. This collection of papers was, therefore, brought together to take a fresh look at this traditional field. Further, we are to celebrate 35 years of a successful conference series, ELOPTO, with the last one held at Waldthausen Castle hosted by the Johannes Gutenberg University, MainzNote1 and the DFG Collaborative Research Centre TR6 'Physics of colloidal dispersions in external fields'Note2. In this issue we have collected the articles of some of the leading experts in the area, well garnished with novel approaches and clever ideas by younger colleagues. With our selection we hope to cover a representative spectrum of the ongoing research, catch the most exciting trends and earn the interest of a good fraction of contemporary soft matter scientists. Note1 http://www.elopto2010.fb08.uni-mainz.de Note2 http://www.sfb-tr6.de References [1] Weinberger P 2008 John Kerr and his effects found in 1877 and 1878 Phil. Mag. Lett. 88 897-907 [2] Benoit H 1948 Calcul de l'écart quadratique moyen entre les extrémités de diverses chaînes moléculaires de type usuel J. Polym. Sci. 3 376-87 [3] Benoit H 1949 Sur un dispositif de mesure de l'effet Kerr par impulsions electriques isoles Comptes Rendus 228 1716-8 [4] Benoit H 1951 Contribution a l'etude de l'effet Kerr presente par les solutions diluees de macromolecules rigide Ann. Phys. 6 561-609 Colloidal and molecular electro-optics contents Electric dichroism transients of aqueous solutions of DNA J A Bertolotto, G M Corral, E M Farias de La Torre and G B Roston The role of effective charges in the electrophoresis of highly charged colloids Apratim Chatterji and Jürgen Horbach Nonlinear response of the electric birefringence of polyelectrolyte solutions J L Déjardin and J M Martinez Kerr constant of multi-subunit particles and semiflexible, wormlike chains J García de la Torre, F G Díaz Baños and H E Pérez Sánchez Self-assembling electroactive hydrogels for flexible display technology Scott L Jones, Kok Hou Wong, Pall Thordarson and François Ladouceur Electrooptical effects in colloid systems subjected to short pulses of strong electric field S A Klemeshev, M P Petrov, A A Trusov and A V Voitylov The effect of ionic strength on electrical properties of polyelectrolyte multilayers on colloidal particles V Milkova and Ts Radeva Charge transport and current in non-polar liquids Kristiaan Neyts, Filip Beunis, Filip Strubbe, Matthias Marescaux, Bart Verboven, Masoumeh Karvar and Alwin Verschueren Ionic concentration- and pH-dependent electrophoretic mobility as studied by single colloid electrophoresis I Semenov, P Papadopoulos, G Stober and F Kremer Effect of magnesium ions and temperature on the sequence-dependent curvature of DNA restriction fragments Nancy C Stellwagen and Yongjun Lu A fluorescence correlation spectroscopy study of macromolecular tracer diffusion in polymer solutions Ute Zettl, Matthias Ballauff and Ludger Harnau Polymer concentration dependence of kilohertz electric polarizability of alumina colloid particles with adsorbed carboxymethyl cellulose Alexandar M Zhivkov and Rosen P Hristov

Colloidal isopressing: A new shaping method for ceramic suspensions

NASA Astrophysics Data System (ADS)

Yu, Benjamin Christopher

Colloidal Isopressing is a new processing method for shaping compacts from particulate suspensions. The study of interparticle interactions within a suspension, and their effect on the overall slurry behavior, has led to the prior discovery of a plastic-to-brittle transition in powder compacts formed by pressure filtration. Colloidal Isopressing utilizes this pressure dependent behavior for slurries with a short-range repulsive potential to rapidly transform plastic consolidated bodies into more complex shapes. The first results are presented for aqueous alumina suspensions where electrostatic double layer repulsion is compressed to short interparticle separations by the addition of ammonium chloride. Consolidation at low pressures produces a high relative density slurry that is plastic and can be extruded into a rubber mold. The application of an hydrostatic pressure forces a small amount of liquid into a porous portion of the mold and pushes particles together into a rigid network. As the pressure is released, the newly formed powder compact will partially separate from the lower modulus rubber mold. The body can then be ejected from the mold, dried, and densified to produce the final ceramic component. Colloidal Isopressing has been successfully modeled as a special case of consolidation via pressure filtration. Theoretical analyses have accurately predicted the time required for the rapid transformation from plastic slurry to elastic powder compact. The effects of slurry composition on processing were studied. The electrolyte concentration, powder particle size, slurry pH, and polymer concentration were shown to alter the flow behavior of filter pressed and liquefied compacts. As the free volume of liquid decreased and/or the relative attraction between particles increased, the concentrated slurry became more difficult to process. Finally, drying of compacts formed by Colloidal Isopressing did not result in any shrinkage during drying, thus allowing for very rapid heating rates to be used. In fact, the drying, burnout, and densification could be combined into one step, with final densities approaching the theoretical limit.

Entropic depletion in colloidal suspensions and polymer liquids: Role of nanoparticle surface topography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Banerjee, Debapriya; Yang, Jian; Schweizer, Kenneth S.

2015-01-01

Here, we employ a hybrid Monte Carlo plus integral equation theory approach to study how dense fluids of small nanoparticles or polymer chains mediate entropic depletion interactions between topographically rough particles where all interaction potentials are hard core repulsion. The corrugated particle surfaces are composed of densely packed beads which present variable degrees of controlled topographic roughness and free volume associated with their geometric crevices. This pure entropy problem is characterized by competing ideal translational and (favorable and unfavorable) excess entropic contributions. Surface roughness generically reduces particle depletion aggregation relative to the smooth hard sphere case. However, the competition betweenmore » ideal and excess packing entropy effects in the bulk, near the particle surface and in the crevices, results in a non-monotonic variation of the particle-monomer packing correlation function as a function of the two dimensionless length scale ratios that quantify the effective surface roughness. As a result, the inter-particle potential of mean force (PMF), second virial coefficient, and spinodal miscibility volume fraction vary non-monotonically with the surface bead to monomer diameter and particle core to surface bead diameter ratios. A miscibility window is predicted corresponding to an optimum degree of surface roughness that completely destroys depletion attraction resulting in a repulsive PMF. Variation of the (dense) matrix packing fraction can enhance or suppress particle miscibility depending upon the amount of surface roughness. Connecting the monomers into polymer chains destabilizes the system via enhanced contact depletion attraction, but the non-monotonic variations with surface roughness metrics persist.« less

Engineering Multifunctional Living Paints: Thin, Convectively-Assembled Biocomposite Coatings of Live Cells and Colloidal Latex Particles Deposited by Continuous Convective-Sedimentation Assembly

NASA Astrophysics Data System (ADS)

Jenkins, Jessica Shawn

Advanced composite materials could be revolutionized by the development of methods to incorporate living cells into functional materials and devices. This could be accomplished by continuously and rapidly depositing thin ordered arrays of adhesive colloidal latex particles and live cells that maintain stability and preserve microbial reactivity. Convective assembly is one method of rapidly assembling colloidal particles into thin (<10 microm thick), ordered films with engineered compositions, thicknesses, and particle packing that offer several advantages over thicker randomly ordered composites, including enhanced cell stability and increased reactivity through minimized diffusion resistance to nutrients and reduced light scattering. This method can be used to precisely deposit live bacteria, cyanobacteria, yeast, and algae into biocomposite coatings, forming reactive biosensors, photoabsorbers, or advanced biocatalysts. This dissertation developed new continuous deposition and coating characterization methods for fabricating and characterizing <10 microm thick colloid coatings---monodispersed latex particle or cell suspensions, bimodal blends of latex particles or live cells and microspheres, and trimodal formulations of biomodal latex and live cells on substrates such as aluminum foil, glass, porous Kraft paper, polyester, and polypropylene. Continuous convective-sedimentation assembly (CSA) is introduced to enable fabrication of larger surface area and long coatings by constantly feeding coating suspension to the meniscus, thus expanding the utility of convective assembly to deposit monolayer or very thin films or multi-layer coatings composed of thin layers on a large scale. Results show thin, tunable coatings can be fabricated from diverse coating suspensions and critical coating parameters that control thickness and structure. Particle size ratio and charge influence deposition, convective mixing or demixing and relative particle locations. Substrate wettability and suspension composition influence coating microstructure by controlling suspension delivery and spreading across the substrate. Microbes behave like colloidal particles during CSA, allowing for deposition of very thin stable biocomposite coatings of latex-live cell blends. CSA of particle-cell blends result in open-packed structures (15-45% mean void space), instead of tightly packed coatings attainable with single component systems, confirming the existence of significant polymer particle-cell interactions and formation of particle aggregates that disrupt coating microstructure during deposition. Tunable process parameters, such as particle concentration, fluid sonication, and fluid density, influence coating homogeneity when the meniscus is continuously supplied. Fluid density modification and fluid sonication affect particle sedimentation and distribution in the coating growth front whereas the suspended particle concentration strongly affects coating thickness, but has almost no effect on void space. Changing the suspension delivery mode (topside versus underside CCSA) yields disparate meniscus volumes and uneven particle delivery to the drying front, which enables control of the coating microstructure by varying the total number of particles available for deposition. The judicious combination of all these parameters will enable deposition of uniform, thin, latex-cell monolayers over areas on the order of tens of square centimeters or larger. To demonstrate the utility of biocomposite coatings, this dissertation investigated photoreactive coatings (artificial leaves) from suspensions of latex particles and nitrogen-limited Rps. palustris CGA009 or sulfur-limited C. reinhardtii CC-124. These coatings demonstrated stable, sustained (>90 hours) photohydrogen production under anoxygenic conditions. Nutrient reduction slows cell division, minimizing coating outgrowth, and promotes photohydrogen generation, improving coating reactivity. Scanning electron microscopy of microstructure revealed how coating reactivity can be controlled by the size and distribution of the nanopores in the biocomposite layers. Variations in colloid microsphere size and suspension composition do not affect coating reactivity, but both parameters alter coating microstructure. Porous paper coated with thin coatings of colloidal particles and cells to enable coatings to be used in a gas-phase without dehydration may offer higher volumetric productivity for hydrogen production. Future work should focus on optimization of cell density, light intensity, media cycling, and acetate concentration.

Nanostructured magnetic particles with polystyrene and their magnetorheological applications.

PubMed

Fang, Fei Fei; Choi, Hyoung Jin

2011-03-01

Magnetorheological (MR) fluids are known to be colloidal suspensions of magnetic particles in a non-magnetic fluid, and exposure to a magnetic field transforms the fluid into a plastic-like solid in milliseconds. To improve the stability against sedimentation and uniform dispersion, two different MR candidates, soft magnetic carbonyl iron (CI) microspheres and magnetite (Fe3O4) particles were modified with polystyrene to be applied for MR fluids in this study. After modification, their unique morphology, crystalline structure and magnetic properties were examined in addition to MR performance and sedimentation characteristics. It was found that this embedded morphology not only effectively prevents direct contact of the magnetic species thus improving particle dispersion but also leads to obvious change in their density, compared with the traditional polymer coating method with a core-shell structure.

Simulation of the injection of colloidal suspensions for the remediation of contaminated aquifer systems

NASA Astrophysics Data System (ADS)

Tosco, Tiziana; Gastone, Francesca; Sethi, Rajandrea

2014-05-01

Concentrated suspensions of microscale and nanoscale zerovalent iron particles (MZVI and NZVI) have been studied in recent years for the remediation of contaminated aquifers. The suspensions are injected into the subsurface to generate a reactive zone, and consequently the prediction of the particles distribution during the injection is a key aspect in the design of a field-scale injection. Colloidal dispersions of MZVI and NZVI are not stable in pure water, and shear thinning, environmentally friendly fluids (guar gum and xanthan gum solutions) were found to be effective in improving colloidal stability, thus greatly improving handling and injectability (1 - 3). Shear thinning fluids exhibit high viscosity in static conditions, improving the colloidal stability, and lower viscosity at high flow rates enabling the injection at limited pressures. Shear thinning fluids exhibit high viscosity in static conditions, improving the colloidal stability, and lower viscosity at high flow rates enabling the injection at limited pressures. In this work, co-funded by European Union project AQUAREHAB (FP7 - Grant Agreement Nr. 226565), laboratory and pilot field tests for MZVI injection in saturated porous media are reported. MZVI was dispersed in guar gum solutions, and the transport behaviour under several polymer concentrations and injection rates was assessed in column tests (4). Based on the experimental results, a modelling approach is proposed to simulate the transport in porous media of nanoscale iron slurries, implemented in E-MNM1D (www.polito.it/groundwater/software). Colloid transport mechanisms are controlled by particle-collector and particle-particle interactions, usually modelled by a non equilibrium kinetic model accounting for deposition and release processes. The key aspects included in the E-MNM1D are clogging phenomena (i.e. reduction of porosity and permeability due to particles deposition), and the rheological properties of the carrier fluid (in this project, guar gum solution). The influence of colloid transport on porosity, permeability, and fluid viscosity is explicitly lumped into the model and the shear-thinning nature of the iron slurries is described by a modified Darcy law generalized for non Newtonian fluids. Since during the injection in wells the velocity field is not constant over the distance, E-MNM1D was modified in order to account for variable colloidal transport coefficients on flow rate thus allowing the estimation of the radius of influence during a full scale intervention. The flow and transport of MZVI slurries is solved in a radial domain for the simulation of field-scale injection, incorporating the abovementioned relevant mechanisms. The governing equations and model implementation are presented and discussed, along with examples of injection simulations. References 1. Tiraferri, A.; Sethi, R. Enhanced transport of zerovalent iron nanoparticles in saturated porous media by guar gum. J Nanopart Res 2009, 11(3), 635-645. 2. Tiraferri, A.; Chen, K.L.; Sethi, R.; Elimelech, M. Reduced aggregation and sedimentation of zero-valent iron nanoparticles in the presence of guar gum. Journal of Colloid and Interface Science 2008, 324(1-2), 71-79. 3. Dalla Vecchia, E.; Luna, M.; Sethi, R. Transport in Porous Media of Highly Concentrated Iron Micro- and Nanoparticles in the Presence of Xanthan Gum. Environmental Science & Technology 2009, 43(23), 8942-8947. 4. Tosco, T.; Gastone, F.; Sethi, R. Guar gum solutions for improved delivery of iron particles in porous media (Part 2): iron transport tests and modelling in radial geometry. Journal of Contaminant Hydrology (submitted).

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide).

PubMed

Vandorpe, J; Schacht, E; Stolnik, S; Garnett, M C; Davies, M C; Illum, L; Davis, S S

1996-10-05

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.

A modular microfluidic platform for the synthesis of biopolymeric nanoparticles entrapping organic actives

NASA Astrophysics Data System (ADS)

Chronopoulou, Laura; Sparago, Carolina; Palocci, Cleofe

2014-11-01

Using a novel and versatile capillary microfluidic flow-focusing device we fabricated monodisperse drug-loaded nanoparticles from biodegradable polymers. A model amphiphilic drug (dexamethasone) was incorporated within the biodegradable matrix of the particles. The influence of flow rate ratio, polymer concentration, and microreactor-focusing channel dimensions on nanoparticles' size and drug loading has been investigated. The microfluidic approach resulted in the production of colloidal polymeric nanoparticles with a narrow size distribution (diameters ranging between 35 and 350 nm) and useful morphological characteristics. This technique allows the fast, low cost, easy, and automated synthesis of polymeric nanoparticles, therefore it may become a useful approach in the progression from laboratory scale to pilot-line scale processes.

Flow of colloid particle solution past macroscopic bodies and drag crisis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iordanskii, S. V., E-mail: iordansk@itp.ac.ru

2013-11-15

The motion of colloid particles in a viscous fluid flow is considered. Small sizes of colloid particles as compared to the characteristic scale of the flow make it possible to calculate their velocity relative to the liquid. If the density of a colloid particle is higher than the density of the liquid, the flow splits into regions in which the velocity of colloid particles coincides with the velocity of the liquid and regions of flow stagnation in which the colloid velocity is higher than the velocity of the fluid. This effect is used to explain qualitatively the decrease in themore » drag to the flows past macroscopic bodies and flows in pipes.« less

Electrohydrodynamically patterned colloidal crystals

NASA Technical Reports Server (NTRS)

Hayward, Ryan C. (Inventor); Poon, Hak F. (Inventor); Xiao, Yi (Inventor); Saville, Dudley A. (Inventor); Aksay, Ilhan A. (Inventor)

2003-01-01

A method for assembling patterned crystalline arrays of colloidal particles using ultraviolet illumination of an optically-sensitive semiconducting anode while using the anode to apply an electronic field to the colloidal particles. The ultraviolet illumination increases current density, and consequently, the flow of the colloidal particles. As a result, colloidal particles can be caused to migrate from non-illuminated areas of the anode to illuminated areas of the anode. Selective illumination of the anode can also be used to permanently affix colloidal crystals to illuminated areas of the anode while not affixing them to non-illuminated areas of the anode.

Complex Fluids at Interfaces and Interfaces of Complex Fluids

NASA Astrophysics Data System (ADS)

Nouri, Mariam

The present thesis deals with two independent projects and is consequently divided into two parts. The first part details a computational study of the fluid structure of ring-shaped molecules and their positional and orientational molecular organizations in different degrees of confinement, while the second part concerns an experimental study of phase behavior and interfacial phenomena in confined colloid-polymer systems. In the first part, ring-shaped molecules are studied using Monte Carlo simulation techniques in one, two and three dimensions. The model used to describe ring-shaped molecules is composed of hard-spheres linked together to form planar rigid rings. For rings of various sizes and for a wide range of densities, positional and orientational orderings are reported in forms of pair distribution functions of the ring centers and correlation functions of the ring normal orientations. Special emphasis is given to understand structural formation at interfaces, i.e., the structure and orderings of these molecules when they are confined to two dimensions. In a plane but the rings themselves are free to rotate around all axes, nematic ordering is observed at sufficiently high densities. In the second part, phase equilibria of confined aqueous colloid-polymer systems are studied experimentally using fluorescence microscopy. Aqueous mixtures of fluorescent polystyrene spheres and polyacrylamide are confined between a glass slide and a coverslip. The phase diagram is determined as a function of the colloidal and polymer concentrations. Liquid-liquid phase coexistence between a colloid-rich phase and a polymer-rich phase occurs at intermediate polymer concentrations, while liquid-solid phase coexistence between a polymer-rich liquid and a colloid-rich solid is observed at high polymer concentrations. Interfacial thickness and tension of the interface between these coexisting phases are measured using image analysis techniques. It is also observed that the colloid-rich solid and liquid domains coarsen mainly by Ostwald ripening.

Micro-rheology on (polymer-grafted) colloids using optical tweezers.

PubMed

Gutsche, C; Elmahdy, M M; Kegler, K; Semenov, I; Stangner, T; Otto, O; Ueberschär, O; Keyser, U F; Krueger, M; Rauscher, M; Weeber, R; Harting, J; Kim, Y W; Lobaskin, V; Netz, R R; Kremer, F

2011-05-11

Optical tweezers are experimental tools with extraordinary resolution in positioning (± 1 nm) a micron-sized colloid and in the measurement of forces (± 50 fN) acting on it-without any mechanical contact. This enables one to carry out a multitude of novel experiments in nano- and microfluidics, of which the following will be presented in this review: (i) forces within single pairs of colloids in media of varying concentration and valency of the surrounding ionic solution, (ii) measurements of the electrophoretic mobility of single colloids in different solvents (concentration, valency of the ionic solution and pH), (iii) similar experiments as in (i) with DNA-grafted colloids, (iv) the nonlinear response of single DNA-grafted colloids in shear flow and (v) the drag force on single colloids pulled through a polymer solution. The experiments will be described in detail and their analysis discussed.

Synthesis of silica-polymer core-shell nanoparticles by reversible addition-fragmentation chain transfer polymerization.

PubMed

Moraes, John; Ohno, Kohji; Maschmeyer, Thomas; Perrier, Sébastien

2013-10-14

Hybrid nanoparticles hold great promise for a range of applications such as drug-delivery vectors or colloidal crystal self-assemblies. The challenge of preparing highly monodisperse particles for these applications has recently been overcome by using living radical polymerization techniques. In particular, the use of reversible addition-fragmentation chain transfer (RAFT), initiated from silica surfaces, yields well-defined particles from a range of precursor monomers resulting in nanoparticles of tailored sizes that are accessible via the rational selection of polymerization conditions. Furthermore, using RAFT allows post-polymerization modification to afford multifunctional, monodisperse, nanostructures under mild and non-stringent reaction conditions.

Influence of the type of electric discharge on the properties of the produced aluminium nanoparticles

NASA Astrophysics Data System (ADS)

Shiyan, L. N.; Yavorovskii, N. A.; Pustovalov, A. V.; Gryaznova, E. N.

2015-04-01

The effect of the method of aluminum nanopowder production on the aluminum products with water reaction is described. It has been established that the interaction of aluminum nanopowder prepared by the electric wire explosion, the phase composition of the reaction products mainly consists of boehmite (AlOOH) and has a fibrous structure. Therefore, that boehmite (AlOOH) can be used for modification of polymer membranes. The modified membranes can be used as water treatment from the impurity of formed true solutions according to adsorptive mechanism, and from colloidal nanometer and micron particles according to the mechanism of mechanical separation of particles depending on sizes.

Normal modes of weak colloidal gels

NASA Astrophysics Data System (ADS)

Varga, Zsigmond; Swan, James W.

2018-01-01

The normal modes and relaxation rates of weak colloidal gels are investigated in calculations using different models of the hydrodynamic interactions between suspended particles. The relaxation spectrum is computed for freely draining, Rotne-Prager-Yamakawa, and accelerated Stokesian dynamics approximations of the hydrodynamic mobility in a normal mode analysis of a harmonic network representing several colloidal gels. We find that the density of states and spatial structure of the normal modes are fundamentally altered by long-ranged hydrodynamic coupling among the particles. Short-ranged coupling due to hydrodynamic lubrication affects only the relaxation rates of short-wavelength modes. Hydrodynamic models accounting for long-ranged coupling exhibit a microscopic relaxation rate for each normal mode, λ that scales as l-2, where l is the spatial correlation length of the normal mode. For the freely draining approximation, which neglects long-ranged coupling, the microscopic relaxation rate scales as l-γ, where γ varies between three and two with increasing particle volume fraction. A simple phenomenological model of the internal elastic response to normal mode fluctuations is developed, which shows that long-ranged hydrodynamic interactions play a central role in the viscoelasticity of the gel network. Dynamic simulations of hard spheres that gel in response to short-ranged depletion attractions are used to test the applicability of the density of states predictions. For particle concentrations up to 30% by volume, the power law decay of the relaxation modulus in simulations accounting for long-ranged hydrodynamic interactions agrees with predictions generated by the density of states of the corresponding harmonic networks as well as experimental measurements. For higher volume fractions, excluded volume interactions dominate the stress response, and the prediction from the harmonic network density of states fails. Analogous to the Zimm model in polymer physics, our results indicate that long-ranged hydrodynamic interactions play a crucial role in determining the microscopic dynamics and macroscopic properties of weak colloidal gels.

Dynamics of gold nanoparticles in synthetic and biopolymer solutions

NASA Astrophysics Data System (ADS)

Kohli, Indermeet

Soft matter systems of colloidal particles, polymers, amphiphiles and liquid crystals are ubiquitous in our everyday life. Food, plastics, soap and even human body is comprised of soft materials. Research conducted to understand the behavior of these soft matter systems at molecular level is essential for many interdisciplinary fields of study as well as important for many technological applications. We used gold nanoparticles (Au NPs) to investigate the length-scale dependent dynamics in semidilute poly(ethylene glycol) (PEG)-water, bovine serum albumin (BSA)-phosphate buffer, dextran and particulate solutions. In case of PEG-water solutions, fluctuation correlation spectroscopy was used to measure the diffusion coefficients (D) of the NPs as a function of their radius, Ro (2.5-10 nm), PEG volume fraction, φ (0-0.37) and molecular weight, Mw (5 kg/mol and 35 kg/mol). Our results indicate that the radius of gyration, Rg of the polymer chain is the crossover length scale for the NPs experiencing nanoviscosity or macroviscosity. In BSA-phosphate buffer solutions, we observed a monolayer formation at the NP surface with a thickness of 3.8 nm. The thickness of the adsorbed layer was independent of NP size. Best fit was obtained by the anticooperative binding model with the Hill coefficient of n = 0.63. Dissociation constant (KD) increased with particle size indicating stronger interaction of BSA with smaller sized NPs. We also contrasted the diffusion of gold nanoparticles (AuNPs) in crowded solutions of randomly branched polymer (dextran) and rigid, spherical particles (silica) to understand the roles played by the probe size and structure of the crowding agent in determining the probe diffusion. AuNPs of two different sizes (2.5 nm & 10 nm), dextran of molecular weight 70 kDa and silica particles of radius 10 nm were used. Our results indicated that the AuNP diffusion can be described using the bulk viscosity of the matrix and hydrodynamically dextran behaved similar to soft colloid. In all situations, we observed normal diffusion except for 2.5 nm sized AuNP particles in dextran solution at higher volume fraction. This was caused by transient trapping of particles within the random branches. The results showed the importance of macromolecular architecture in determining the transport properties in intracellular matrix and in cells with spiny dendrites.

Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes.

PubMed

Nguyen, Mai; Kanaev, Andrei; Sun, Xiaonan; Lacaze, Emmanuelle; Lau-Truong, Stéphanie; Lamouri, Aazdine; Aubard, Jean; Felidj, Nordin; Mangeney, Claire

2015-11-24

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

Aggregation of montmorillonite and organic matter in aqueous media containing artificial seawater.

PubMed

Furukawa, Yoko; Watkins, Janet L; Kim, Jinwook; Curry, Kenneth J; Bennett, Richard H

2009-01-23

The dispersion-aggregation behaviors of suspended colloids in rivers and estuaries are affected by the compositions of suspended materials (i.e., clay minerals vs. organic macromolecules) and salinity. Laboratory experiments were conducted to investigate the dispersion and aggregation mechanisms of suspended particles under simulated river and estuarine conditions. The average hydrodynamic diameters of suspended particles (representing degree of aggregation) and zeta potential (representing the electrokinetic properties of suspended colloids and aggregates) were determined for systems containing suspended montmorillonite, humic acid, and/or chitin at the circumneutral pH over a range of salinity (0 - 7.2 psu). The montmorillonite-only system increased the degree of aggregation with salinity increase, as would be expected for suspended colloids whose dispersion-aggregation behavior is largely controlled by the surface electrostatic properties and van der Waals forces. When montmorillonite is combined with humic acid or chitin, the aggregation of montmorillonite was effectively inhibited. The surface interaction energy model calculations reveal that the steric repulsion, rather than the increase in electronegativity, is the primary cause for the inhibition of aggregation by the addition of humic acid or chitin. These results help explain the range of dispersion-aggregation behaviors observed in natural river and estuarine systems. It is postulated that the composition of suspended particles, specifically the availability of steric polymers such as those contained in humic acid, determine whether the river suspension is rapidly aggregated and settled or remains dispersed in suspension when it encounters increasingly saline environments of estuaries and oceans.

Hydrophobic-Sheath Segregated Macromolecular Fluorophores: Colloidal Nanoparticles of Polycaprolactone-Grafted Conjugated Polymers with Bright Far-Red/Near-Infrared Emission for Biological Imaging.

PubMed

Yang, Cangjie; Liu, Hui; Zhang, Yingdan; Xu, Zhigang; Wang, Xiaochen; Cao, Bin; Wang, Mingfeng

2016-05-09

This article describes molecular design, synthesis and characterization of colloidal nanoparticles containing polycaprolactone-grafted conjugated polymers that exhibit strong far red/near-infrared (FR/NIR) fluorescence for bioimaging. Specifically, we synthesized two kinds of conjugated polymer bottle brushes (PFTB(out)-g-PCL and PFTB(in)-g-PCL) with different positions of the hexyl groups on the thiophene rings. A synthetic amphiphilic block copolymer PCL-b-POEGMA was employed as surfactants to encapsulate PFTB-g-PCL polymers into colloidal nanoparticles (denoted as "nanoREDs") in aqueous media. The chain length of the PCL side chains in PFTB-g-PCL played a critical role in determining the fluorescence properties in both bulk solid states and the colloidal nanoparticles. Compared to semiconducting polymer dots (Pdots) composed of PFTB(out) without grafted PCL, nanoRED(out) showed at least four times higher fluorescence quantum yield (∼20%) and a broader emission band centered at 635 nm. We further demonstrated the application of this new class of nanoREDs for effective labeling of L929 cells and HeLa cancer cells with good biocompatibility. This strategy of hydrophobic-sheath segregated macromolecular fluorophores is expected to be applicable to a broad range of conjugated polymers with tunable optical properties for applications such as bioimaging.

Macromolecular Colloids of Diblock Poly(amino acids) That Bind Insulin.

PubMed

Constancis; Meyrueix; Bryson; Huille; Grosselin; Gulik-Krzywicki; Soula

1999-09-15

The diblock polymer poly(l-leucine-block-l-glutamate), bLE, was synthesized by acid hydrolysis of the ester poly(l-leucine-block-l-methyl glutamate). During the hydrolysis reaction the leucine block precipitates from the reaction mixture, forming nanosized particulate structures. These particles can be purified and further suspended in water or in 0.15 M phosphate saline buffer (PBS) to give stable, colloidal dispersions. TEM analysis shows the predominant particle form to be that of platelets with a diameter of 200 nm. Smaller cylindrical or spherical particles form a relatively minor fraction of the sample. After fractionation, analysis shows the platelets to be compositionally rich in leucine, while the spheres are glutamate-rich. (1)H NMR, CD, and X-ray diffraction indicate that the core of the platelets is composed of crystalline, helical leucine segments. The poly(l-glutamate) polyelectrolyte brush extending out from the two faces of the disk stabilizes individual particles from flocculation. At pH 7.4, the nanoparticles (platelets and cylinders) spontaneously adsorb proteins, such as insulin, directly from solution. Partial desorption of the protein in its native configuration can be induced by simple dilution. The reversibility of the insulin-nanoparticle complex is the basis for a potential new delivery system. Copyright 1999 Academic Press.

Biomimetic synthesis of raspberry-like hybrid polymer-silica core-shell nanoparticles by templating colloidal particles with hairy polyamine shell.

PubMed

Pi, Mengwei; Yang, Tingting; Yuan, Jianjun; Fujii, Syuji; Kakigi, Yuichi; Nakamura, Yoshinobu; Cheng, Shiyuan

2010-07-01

The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 degrees C for 2.5h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 2010 Elsevier B.V. All rights reserved.

Dynamics of Fractal Cluster Gels with Embedded Active Colloids

NASA Astrophysics Data System (ADS)

Szakasits, Megan E.; Zhang, Wenxuan; Solomon, Michael J.

2017-08-01

We find that embedded active colloids increase the ensemble-averaged mean squared displacement of particles in otherwise passively fluctuating fractal cluster gels. The enhancement in dynamics occurs by a mechanism in which the active colloids contribute to the average dynamics both directly through their own active motion and indirectly through their excitation of neighboring passive colloids in the fractal network. Fractal cluster gels are synthesized by addition of magnesium chloride to an initially stable suspension of 1.0 μ m polystyrene colloids in which a dilute concentration of platinum coated Janus colloids has been dispersed. The Janus colloids are thereby incorporated into the fractal network. We measure the ensemble-averaged mean squared displacement of all colloids in the gel before and after the addition of hydrogen peroxide, a fuel that drives diffusiophoretic motion of the Janus particles. The gel mean squared displacement increases by up to a factor of 3 for an active to passive particle ratio of 1 ∶20 and inputted active energy—defined based on the hydrogen peroxide's effect on colloid swim speed and run length—that is up to 9.5 times thermal energy, on a per particle basis. We model the enhancement in gel particle dynamics as the sum of a direct contribution from the displacement of the Janus particles themselves and an indirect contribution from the strain field that the active colloids induce in the surrounding passive particles.

Influence of a depletion interaction on dynamical heterogeneity in a dense quasi-two-dimensional colloid liquid.

PubMed

Ho, Hau My; Cui, Bianxiao; Repel, Stephen; Lin, Binhua; Rice, Stuart A

2004-11-01

We report the results of digital video microscopy studies of the large particle displacements in a quasi-two-dimensional binary mixture of large (L) and small (S) colloid particles with diameter ratio sigma(L)/sigma(S)=4.65, as a function of the large and small colloid particle densities. As in the case of the one-component quasi-two-dimensional colloid system, the binary mixtures exhibit structural and dynamical heterogeneity. The distribution of large particle displacements over the time scale examined provides evidence for (at least) two different mechanisms of motion, one associated with particles in locally ordered regions and the other associated with particles in locally disordered regions. When rhoL*=Npisigma(L) (2)/4A< or =0.35, the addition of small colloid particles leads to a monotonic decrease in the large particle diffusion coefficient with increasing small particle volume fraction. When rhoL* > or =0.35 the addition of small colloid particles to a dense system of large colloid particles at first leads to an increase in the large particle diffusion coefficient, which is then followed by the expected decrease of the large particle diffusion coefficient with increasing small colloid particle volume fraction. The mode coupling theory of the ideal glass transition in three-dimensional systems makes a qualitative prediction that agrees with the initial increase in the large particle diffusion coefficient with increasing small particle density. Nevertheless, because the structural and dynamical heterogeneities of the quasi-two-dimensional colloid liquid occur within the field of equilibrium states, and the fluctuations generate locally ordered domains rather than just disordered regions of higher and lower density, it is suggested that mode coupling theory does not account for all classes of relevant fluctuations in a quasi-two-dimensional liquid. (c) 2004 American Institute of Physics.

Electrochemistry in Colloids and Dispersions. Volume 1. Electroanalytical Methods and Applications, Electrosynthesis and Electrocatalysis, Polymers and Latexes

DTIC Science & Technology

1992-02-04

derived from dissociation of surface acid groups of the microparticles. The surface charges of these particles are provided by sulfate groups... sulfate micellar solution as a function of electrolyte concentration3 Jon R. Kirchhoff, John D. Skelton, Jr., and Kregg T. Brooks Department of...films on the voltamnmetric curve obtained for the oxidation of benzilic acid on a platinum anode in 2M sodium hydroxide. The acid is soluble in this

Low density, resorcinol-formaldehyde aerogels

DOEpatents

Pekala, Richard W.

1991-01-01

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer "Clusters". The covalent crosslinking of these "clusters" produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density.ltoreq.100 mg/cc; cell size .ltoreq.0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100.circle.. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

Low density, resorcinol-formaldehyde aerogels

DOEpatents

Pekala, Richard W.

1989-01-01

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer "clusters". The covalent crosslinking of these "clusters" produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density .ltoreq.100 mg/cc; cell size .ltoreq.0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 .ANG.. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

Low density, resorcinol-formaldehyde aerogels

DOEpatents

Pekala, R.W.

1989-10-10

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer clusters. The covalent crosslinking of these clusters produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density [<=]100 mg/cc; cell size [<=]0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 [angstrom]. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

Wetting Behavior in Colloid-Polymer Mixtures at Different Substrates.

PubMed

Wijting, Willem K; Besseling, Nicolaas A M; Cohen Stuart, Martien A

2003-09-25

We present experimental observations on wetting phenomena in depletion interaction driven, phase separated colloidal dispersions. The contact angle of the colloidal liquid-gas interface at a solid substrate was determined for a series of compositions. Upon approach to the critical point, a transition occurs from partial to complete wetting. The interaction with the substrate was manipulated by modifying the substrate with a polymer. In that case, a transition from partial to complete drying is observed upon approach to the critical point.

Attachment of micro- and nano-particles on tipless cantilevers for colloidal probe microscopy.

PubMed

D'Sa, Dexter J; Chan, Hak-Kim; Chrzanowski, Wojciech

2014-07-15

Current colloidal probe preparation techniques face several challenges in the production of functional probes using particles ⩽5 μm. Challenges include: glue encapsulated particles, glue altered particle properties, improper particle or agglomerate attachment, and lengthy procedures. We present a method to rapidly and reproducibly produce functional micro and nano-colloidal probes. Using a six-step procedure, cantilevers mounted on a custom designed 45° holder were used to approach and obtain a minimal amount of epoxy resin (viscosity of ∼14,000 cP) followed by a single micron/nano particle on the apex of a tipless cantilever. The epoxy and particles were prepared on individual glass slides and subsequently affixed to a 10× or 40× optical microscope lens using another custom designed holder. Scanning electron microscopy and comparative glue-colloidal probe measurements were used to confirm colloidal probe functionality. The method presented allowed rapid and reproducible production of functional colloidal probes (80% success). Single nano-particles were prominently affixed to the apex of the cantilever, unaffected by the epoxy. Nano-colloidal probes were used to conduct topographical, instantaneous force, and adhesive force mapping measurements in dry and liquid media conveying their versatility and functionality in studying nano-colloidal systems. Copyright © 2014 Elsevier Inc. All rights reserved.

Thermal diffusion behavior of hard-sphere suspensions.

PubMed

Ning, Hui; Buitenhuis, Johan; Dhont, Jan K G; Wiegand, Simone

2006-11-28

We studied the thermal diffusion behavior of octadecyl coated silica particles (R(h)=27 nm) in toluene between 15.0 and 50.0 degrees C in a volume fraction range of 1%-30% by means of thermal diffusion forced Rayleigh scattering. The colloidal particles behave like hard spheres at high temperatures and as sticky spheres at low temperatures. With increasing temperature, the obtained Soret coefficient S(T) of the silica particles changed sign from negative to positive, which implies that the colloidal particles move to the warm side at low temperatures, whereas they move to the cold side at high temperatures. Additionally, we observed also a sign change of the Soret coefficient from positive to negative with increasing volume fraction. This is the first colloidal system for which a sign change with temperature and volume fraction has been observed. The concentration dependence of the thermal diffusion coefficient of the colloidal spheres is related to the colloid-colloid interactions, and will be compared with an existing theoretical description for interacting spherical particles. To characterize the particle-particle interaction parameters, we performed static and dynamic light scattering experiments. The temperature dependence of the thermal diffusion coefficient is predominantly determined by single colloidal particle properties, which are related to colloid-solvent molecule interactions.

Bioreduction of U(VI)-Phthalate to a Polymeric U(IV)-Phthalate Colloid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vazquez, G.; Dodge, C; Francis, A

2009-01-01

Phthalic acid, a ubiquitous organic ligand, formed soluble mono- and biligand complexes with a uranyl ion that was then reduced to a U(IV)-phthalate by a Clostridium species under anaerobic conditions. We confirmed the reduction of the hexavalent uranium to the tetravalent oxidation state by UV-vis absorption and X-ray absorption near edge structure spectroscopy. Sequential micro- and ultrafiltration of the solution revealed that the bioreduced uranium was present as a colloid with particles between 0.03 and 0.45 {mu}m. Analysis with extended X-ray absorption fine structure revealed the association of the reduced uranium with the phthalic acid as a repeating biligand 1:2more » U(IV):phthalic acid polymer. This is the first report of the formation of a U(IV) complexed to two phthalic acid molecules in the form of a polymeric colloid. Although it was proposed that the bioreduction and the precipitation of uranium might be an invaluable strategy to immobilize uranium in contaminated environments, our results suggest that the organic ligands present there might hinder the precipitation of the bioreduced uranium under anaerobic conditions and, thereby, enhance its environmental mobility as uranium organic complexes or colloids.« less

An evaporation model of colloidal suspension droplets

NASA Astrophysics Data System (ADS)

Sartori, Silvana; Li\\ Nán, Amable; Lasheras, Juan C.

2009-11-01

Colloidal suspensions of polymers in water or other solvents are widely used in the pharmaceutical industry to coat tablets with different agents. These allow controlling the rate at which the drug is delivered, taste or physical appearance. The coating is performed by simultaneously spraying and drying the tablets with the colloidal suspension at moderately high temperatures. The spreading of the coating on the pills surface depends on the droplet Webber and Reynolds numbers, angle of impact, but more importantly on the rheological properties of the drop. We present a model for the evaporation of a colloidal suspension droplet in a hot air environment with temperatures substantially lower than the boiling temperature of the carrier fluid. As the liquid vaporizes from the surface, a compacting front advances into the droplet faster than the liquid surface regresses, forming a shell of a porous medium where the particles reach their maximum packing density. While the surface regresses, the evaporation rate is determined by both the rate at which heat is transported to the droplet surface and the rate at which liquid vapor is diffused away from it. This regime continues until the compacting front reaches the center of the droplet, at which point the evaporation rate is drastically reduced.

Active structuring of colloidal armour on liquid drops

NASA Astrophysics Data System (ADS)

Dommersnes, Paul; Rozynek, Zbigniew; Mikkelsen, Alexander; Castberg, Rene; Kjerstad, Knut; Hersvik, Kjetil; Otto Fossum, Jon

2013-06-01

Adsorption and assembly of colloidal particles at the surface of liquid droplets are at the base of particle-stabilized emulsions and templating. Here we report that electrohydrodynamic and electro-rheological effects in leaky-dielectric liquid drops can be used to structure and dynamically control colloidal particle assemblies at drop surfaces, including electric-field-assisted convective assembly of jammed colloidal ‘ribbons’, electro-rheological colloidal chains confined to a two-dimensional surface and spinning colloidal domains on that surface. In addition, we demonstrate the size control of ‘pupil’-like openings in colloidal shells. We anticipate that electric field manipulation of colloids in leaky dielectrics can lead to new routes of colloidosome assembly and design for ‘smart armoured’ droplets.

Active structuring of colloidal armour on liquid drops.

PubMed

Dommersnes, Paul; Rozynek, Zbigniew; Mikkelsen, Alexander; Castberg, Rene; Kjerstad, Knut; Hersvik, Kjetil; Otto Fossum, Jon

2013-01-01

Adsorption and assembly of colloidal particles at the surface of liquid droplets are at the base of particle-stabilized emulsions and templating. Here we report that electrohydrodynamic and electro-rheological effects in leaky-dielectric liquid drops can be used to structure and dynamically control colloidal particle assemblies at drop surfaces, including electric-field-assisted convective assembly of jammed colloidal 'ribbons', electro-rheological colloidal chains confined to a two-dimensional surface and spinning colloidal domains on that surface. In addition, we demonstrate the size control of 'pupil'-like openings in colloidal shells. We anticipate that electric field manipulation of colloids in leaky dielectrics can lead to new routes of colloidosome assembly and design for 'smart armoured' droplets.

Stable colloids in molten inorganic salts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hao; Dasbiswas, Kinjal; Ludwig, Nicholas B.

2017-02-15

A colloidal solution is a homogeneous dispersion of particles or droplets of one phase (solute) in a second, typically liquid, phase (solvent). Colloids are ubiquitous in biological, chemical and technological processes1, 2, homogenizing highly dissimilar constituents. To stabilize a colloidal system against coalescence and aggregation, the surface of each solute particle is engineered to impose repulsive forces strong enough to overpower van der Waals attraction and keep the particles separated from each other2. Electrostatic stabilization3, 4 of charged solutes works well in solvents with high dielectric constants, such as water (dielectric constant of 80). In contrast, colloidal stabilization in solventsmore » with low polarity, such as hexane (dielectric constant of about 2), can be achieved by decorating the surface of each particle of the solute with molecules (surfactants) containing flexible, brush-like chains2, 5. Here we report a class of colloidal systems in which solute particles (including metals, semiconductors and magnetic materials) form stable colloids in various molten inorganic salts. The stability of such colloids cannot be explained by traditional electrostatic and steric mechanisms. Screening of many solute–solvent combinations shows that colloidal stability can be traced to the strength of chemical bonding at the solute–solvent interface. Theoretical analysis and molecular dynamics modelling suggest that a layer of surface-bound solvent ions produces long-ranged charge-density oscillations in the molten salt around solute particles, preventing their aggregation. Colloids composed of inorganic particles in inorganic melts offer opportunities for introducing colloidal techniques to solid-state science and engineering applications.« less

The role of ligands in coinage-metal nanoparticles for electronics

PubMed Central

Kanelidis, Ioannis

2017-01-01

Coinage-metal nanoparticles are key components of many printable electronic inks. They can be combined with polymers to form conductive composites and have been used as the basis of molecular electronic devices. This review summarizes the multidimensional role of surface ligands that cover their metal cores. Ligands not only passivate crystal facets and determine growth rates and shapes; they also affect size and colloidal stability. Particle shapes can be tuned via the ligand choice while ligand length, size, ω-functionalities, and chemical nature influence shelf-life and stability of nanoparticles in dispersions. When particles are deposited, ligands affect the electrical properties of the resulting film, the morphology of particle films, and the nature of the interfaces. The effects of the ligands on sintering, cross-linking, and self-assembly of particles in electronic materials are discussed. PMID:29259877

Chiral liquid crystal colloids

NASA Astrophysics Data System (ADS)

Yuan, Ye; Martinez, Angel; Senyuk, Bohdan; Tasinkevych, Mykola; Smalyukh, Ivan I.

2018-01-01

Colloidal particles disturb the alignment of rod-like molecules of liquid crystals, giving rise to long-range interactions that minimize the free energy of distorted regions. Particle shape and topology are known to guide this self-assembly process. However, how chirality of colloidal inclusions affects these long-range interactions is unclear. Here we study the effects of distortions caused by chiral springs and helices on the colloidal self-organization in a nematic liquid crystal using laser tweezers, particle tracking and optical imaging. We show that chirality of colloidal particles interacts with the nematic elasticity to predefine chiral or racemic colloidal superstructures in nematic colloids. These findings are consistent with numerical modelling based on the minimization of Landau-de Gennes free energy. Our study uncovers the role of chirality in defining the mesoscopic order of liquid crystal colloids, suggesting that this feature may be a potential tool to modulate the global orientated self-organization of these systems.

Centrifugation-assisted Assembly of Colloidal Silica into Crack-Free and Transferrable Films with Tunable Crystalline Structures

PubMed Central

Fan, Wen; Chen, Min; Yang, Shu; Wu, Limin

2015-01-01

Self-assembly of colloidal particles into colloidal films has many actual and potential applications. While various strategies have been developed to direct the assembly of colloidal particles, fabrication of crack-free and transferrable colloidal film with controllable crystal structures still remains a major challenge. Here we show a centrifugation-assisted assembly of colloidal silica spheres into free-standing colloidal film by using the liquid/liquid interfaces of three immiscible phases. Through independent control of centrifugal force and interparticle electrostatic repulsion, polycrystalline, single-crystalline and quasi-amorphous structures can be readily obtained. More importantly, by dehydration of silica particles during centrifugation, the spontaneous formation of capillary water bridges between particles enables the binding and pre-shrinkage of the assembled array at the fluid interface. Thus the assembled colloidal films are not only crack-free, but also robust and flexible enough to be easily transferred on various planar and curved substrates. PMID:26159121

Plasmonic Nanodiamonds – Targeted Core-shell Type Nanoparticles for Cancer Cell Thermoablation

PubMed Central

Rehor, Ivan; Lee, Karin L.; Chen, Kevin; Hajek, Miroslav; Havlik, Jan; Lokajova, Jana; Masat, Milan; Slegerova, Jitka; Shukla, Sourabh; Heidari, Hamed; Bals, Sara

2015-01-01

Targeted biocompatible nanostructures with controlled plasmonic and morphological parameters are promising materials for cancer treatment based on selective thermal ablation of cells. Here, core-shell plasmonic nanodiamonds consisting of a silica-encapsulated diamond nanocrystal coated in a gold shell is designed and synthesized. The architecture of particles is analyzed and confirmed in detail using 3-dimensional transmission electron microscope tomography. The particles are biocompatibilized using a PEG polymer terminated with bioorthogonally reactive alkyne groups. Azide-modified transferrin is attached to these particles, and their high colloidal stability and successful targeting to cancer cells overexpressing the transferrin receptor is demonstrated. The particles are nontoxic to the cells and they are readily internalized upon binding to the transferrin receptor. The high plasmonic cross section of the particles in the near-infrared region is utilized to quantitatively ablate the cancer cells with a short, one-minute irradiation by a pulse 750-nm laser. PMID:25336437

Characterization of magnetic colloids by means of magnetooptics.

PubMed

Baraban, L; Erbe, A; Leiderer, P

2007-05-01

A new, efficient method for the characterization of magnetic colloids based on the Faraday effect is proposed. According to the main principles of this technique, it is possible to detect the stray magnetic field of the colloidal particles induced inside the magnetooptical layer. The magnetic properties of individual particles can be determined providing measurements in a wide range of magnetic fields. The magnetization curves of capped colloids and paramagnetic colloids were measured by means of the proposed approach. The registration of the magnetooptical signals from each colloidal particle in an ensemble permits the use of this technique for testing the magnetic monodispersity of colloidal suspensions.

SERS active colloidal nanoparticles for the detection of small blood biomarkers using aptamers

NASA Astrophysics Data System (ADS)

Marks, Haley; Mabbott, Samuel; Jackson, George W.; Graham, Duncan; Cote, Gerard L.

2015-03-01

Functionalized colloidal nanoparticles for SERS serve as a promising multifunctional assay component for blood biomarker detection. Proper design of these nanoprobes through conjugation to spectral tags, protective polymers, and sensing ligands can provide experimental control over the sensitivity, range, reproducibility, particle stability, and integration with biorecognition assays. Additionally, the optical properties and degree of electromagnetic SERS signal enhancement can be altered and monitored through tuning the nanoparticle shape, size, material and the colloid's local surface plasmon resonance (LSPR). Aptamers, synthetic affinity ligands derived from nucleic acids, provide a number of advantages for biorecognition of small molecules and toxins with low immunogenicity. DNA aptamers are simpler and more economical to produce at large scale, are capable of greater specificity and affinity than antibodies, are easily tailored to specific functional groups, can be used to tune inter-particle distance and shift the LSPR, and their intrinsic negative charge can be utilized for additional particle stability.1,2 Herein, a "turn-off" competitive binding assay platform involving two different plasmonic nanoparticles for the detection of the toxin bisphenol A (BPA) using SERS is presented. A derivative of the toxin is immobilized onto a silver coated magnetic nanoparticle (Ag@MNP), and a second solid silver nanoparticle (AgNP) is functionalized with the BPA aptamer and a Raman reporter molecule (RRM). The capture (Ag@MNP) and probe (AgNP) particles are mixed and the aptamer binding interaction draws the nanoparticles closer together, forming an assembly that results in an increased SERS signal intensity. This aptamer mediated assembly of the two nanoparticles results in a 100x enhancement of the SERS signal intensity from the RRM. These pre-bound aptamer/nanoparticle conjugates were then exposed to BPA in free solution and the competitive binding event was monitored by the decrease in SERS intensity.

Observation of motion of colloidal particles undergoing flowing Brownian motion using self-mixing laser velocimetry with a thin-slice solid-state laser.

PubMed

Sudo, S; Ohtomo, T; Otsuka, K

2015-08-01

We achieved a highly sensitive method for observing the motion of colloidal particles in a flowing suspension using a self-mixing laser Doppler velocimeter (LDV) comprising a laser-diode-pumped thin-slice solid-state laser and a simple photodiode. We describe the measurement method and the optical system of the self-mixing LDV for real-time measurements of the motion of colloidal particles. For a condensed solution, when the light scattered from the particles is reinjected into the solid-state laser, the laser output is modulated in intensity by the reinjected laser light. Thus, we can capture the motion of colloidal particles from the spectrum of the modulated laser output. For a diluted solution, when the relaxation oscillation frequency coincides with the Doppler shift frequency, f_d, which is related to the average velocity of the particles, the spectrum reflecting the motion of the colloidal particles is enhanced by the resonant excitation of relaxation oscillations. Then, the spectral peak reflecting the motion of colloidal particles appears at 2×f_d. The spectrum reflecting the motion of colloidal particles in a flowing diluted solution can be measured with high sensitivity, owing to the enhancement of the spectrum by the thin-slice solid-state laser.

Estuarine mixing behavior of colloidal organic carbon and colloidal mercury in Galveston Bay, Texas.

PubMed

Lee, Seyong; Han, Seunghee; Gill, Gary A

2011-06-01

Mercury (Hg) in estuarine water is distributed among different physical phases (i.e. particulate, colloidal, and truly dissolved). This phase speciation influences the fate and cycling of Hg in estuarine systems. However, limited information exists on the estuarine distribution of colloidal phase Hg, mainly due to the technical difficulties involved in measuring it. In the present study, we determined Hg and organic carbon levels from unfiltered, filtered (<0.45 μm), colloidal (10 kDa-0.45 μm), and truly dissolved (<10 kDa) fractions of Galveston Bay surface water in order to understand the estuarine mixing behavior of Hg species as well as interactions of Hg with colloidal organic matter. For the riverine end-member, the colloidal fraction comprised 43 ± 11% of the total dissolved Hg pool and decreased to 17 ± 8% in brackish water. In the estuarine mixing zone, dissolved Hg and colloidal organic carbon showed non-conservative removal behavior, particularly in the low salinity (<15 ppt) region. This removal may be caused by salt-induced coagulation of colloidal matter and consequent removal of dissolved Hg. The particle-water interaction, K(d) ([particulate Hg (mol kg(-1))]/[dissolved Hg (mol L(-1))]) of Hg decreased as particle concentration increased, while the particle-water partition coefficient based on colloidal Hg and the truly dissolved Hg fraction, K(c) ([colloidal Hg (mol kg(-1))]/[truly dissolved Hg (mol L(-1))]) of Hg remained constant as particle concentration increased. This suggests that the particle concentration effect is associated with the amount of colloidal Hg, increasing in proportion to the amount of suspended particulate matter. This work demonstrates that, colloidal organic matter plays an important role in the transport, particle-water partitioning, and removal of dissolved Hg in estuarine waters.

Active structuring of colloidal armour on liquid drops

PubMed Central

Dommersnes, Paul; Rozynek, Zbigniew; Mikkelsen, Alexander; Castberg, Rene; Kjerstad, Knut; Hersvik, Kjetil; Otto Fossum, Jon

2013-01-01

Adsorption and assembly of colloidal particles at the surface of liquid droplets are at the base of particle-stabilized emulsions and templating. Here we report that electrohydrodynamic and electro-rheological effects in leaky-dielectric liquid drops can be used to structure and dynamically control colloidal particle assemblies at drop surfaces, including electric-field-assisted convective assembly of jammed colloidal ‘ribbons’, electro-rheological colloidal chains confined to a two-dimensional surface and spinning colloidal domains on that surface. In addition, we demonstrate the size control of ‘pupil’-like openings in colloidal shells. We anticipate that electric field manipulation of colloids in leaky dielectrics can lead to new routes of colloidosome assembly and design for ‘smart armoured’ droplets. PMID:23811716

Polyelectrolyte multilayer capsules as vehicles with tunable permeability.

PubMed

Antipov, Alexei A; Sukhorukov, Gleb B

2004-11-29

This review is devoted to a novel type of polymer micro- and nanocapsules. The shell of the capsule is fabricated by alternate adsorption of oppositely charged polyelectrolytes (PEs) onto the surface of colloidal particles. Cores of different nature (organic or inorganic) with size varied from 0.1 to 10 mum can be used for templating such PE capsules. The shell thickness can be tuned in nanometer range by assembling of defined number of PE layers. The permeability of capsules depends on the pH, ionic strength, solvent, polymer composition, and shell thickness; it can be controlled and varied over wide range of substances regarding their molecular weight and charge. Including functional polymers into capsule wall, such as weak PEs or thermosensitive polymers, makes the capsule permeability sensitive to correspondent external stimuli. Permeability of the capsules is of essential interest in diverse areas related to exploitation of systems with controlled and sustained release properties. The envisaged applications of such capsules/vesicles cover biotechnology, medicine, catalysis, food industry, etc.

Long-Ranged Oppositely Charged Interactions for Designing New Types of Colloidal Clusters

NASA Astrophysics Data System (ADS)

Demirörs, Ahmet Faik; Stiefelhagen, Johan C. P.; Vissers, Teun; Smallenburg, Frank; Dijkstra, Marjolein; Imhof, Arnout; van Blaaderen, Alfons

2015-04-01

Getting control over the valency of colloids is not trivial and has been a long-desired goal for the colloidal domain. Typically, tuning the preferred number of neighbors for colloidal particles requires directional bonding, as in the case of patchy particles, which is difficult to realize experimentally. Here, we demonstrate a general method for creating the colloidal analogs of molecules and other new regular colloidal clusters without using patchiness or complex bonding schemes (e.g., DNA coating) by using a combination of long-ranged attractive and repulsive interactions between oppositely charged particles that also enable regular clusters of particles not all in close contact. We show that, due to the interplay between their attractions and repulsions, oppositely charged particles dispersed in an intermediate dielectric constant (4 <ɛ <10 ) provide a viable approach for the formation of binary colloidal clusters. Tuning the size ratio and interactions of the particles enables control of the type and shape of the resulting regular colloidal clusters. Finally, we present an example of clusters made up of negatively charged large and positively charged small satellite particles, for which the electrostatic properties and interactions can be changed with an electric field. It appears that for sufficiently strong fields the satellite particles can move over the surface of the host particles and polarize the clusters. For even stronger fields, the satellite particles can be completely pulled off, reversing the net charge on the cluster. With computer simulations, we investigate how charged particles distribute on an oppositely charged sphere to minimize their energy and compare the results with the solutions to the well-known Thomson problem. We also use the simulations to explore the dependence of such clusters on Debye screening length κ-1 and the ratio of charges on the particles, showing good agreement with experimental observations.

Modulation of mesenchymal stem cell behavior by nano- and micro-sized β-tricalcium phosphate particles in suspension and composite structures

NASA Astrophysics Data System (ADS)

Smoak, Mollie; Hogan, Katie; Kriegh, Lisa; Chen, Cong; Terrell, LeKeith B.; Qureshi, Ammar T.; Todd Monroe, W.; Gimble, Jeffrey M.; Hayes, Daniel J.

2015-04-01

Interest has grown in the use of microparticles and nanoparticles for modifying the mechanical and biological properties of synthetic bone composite structures. Micro- and nano-sized calcium phosphates are of interest for their osteoinductive behavior. Engineered composites incorporating polymers and ceramics, such as poly-l-lactic acid (PLLA) and beta-tricalcium phosphate (β-TCP), for bone tissue regeneration have been well investigated for their proliferative and osteoinductive abilities. Only limited research has been done to investigate the effects of different sizes of β-TCP particles on human mesenchymal stromal cell behavior. As such, the aim of this study was to investigate the modulations of human adipose-derived stem cell (hASCs) behavior within cell/particle and cell/composite systems as functions of particle size, concentration, and exposure time. The incorporation of nanoscale calcium phosphate resulted in improved mechanical properties and osteogenic behavior within the scaffold compared to the microscale calcium phosphate additives. Particle exposure results indicate that cytotoxicity on hASCs correlates inversely with particle size and increases with the increasing exposure time and particle concentration. Composites with increasing β-TCP content, whether microparticles or nanoparticles, were less toxic than colloidal micro- and nano-sized β-TCP particles directly supplied to hASCs. The difference in viability observed as a result of varying exposure route is likely related to the increased cell-particle interactions in the direct exposure compared to the particles becoming trapped within the scaffold/polymer matrix.

Fabrication of quantum dot/silica core-shell particles immobilizing Au nanoparticles and their dual imaging functions

NASA Astrophysics Data System (ADS)

Kobayashi, Yoshio; Matsudo, Hiromu; Li, Ting-ting; Shibuya, Kyosuke; Kubota, Yohsuke; Oikawa, Takahiro; Nakagawa, Tomohiko; Gonda, Kohsuke

2016-03-01

The present work proposes preparation methods for quantum dot/silica (QD/SiO2) core-shell particles that immobilize Au nanoparticles (QD/SiO2/Au). A colloid solution of QD/SiO2 core-shell particles with an average size of 47.0 ± 6.1 nm was prepared by a sol-gel reaction of tetraethyl orthosilicate in the presence of the QDs with an average size of 10.3 ± 2.1 nm. A colloid solution of Au nanoparticles with an average size of 17.9 ± 1.3 nm was prepared by reducing Au3+ ions with sodium citrate in water at 80 °C. Introduction of amino groups to QD/SiO2 particle surfaces was performed using (3-aminopropyl)-triethoxysilane (QD/SiO2-NH2). The QD/SiO2/Au particles were fabricated by mixing the Au particle colloid solution and the QD/SiO2-NH2 particle colloid solution. Values of radiant efficiency and computed tomography for the QD/SiO2/Au particle colloid solution were 2.23 × 107 (p/s/cm2/sr)/(μW/cm2) at a QD concentration of 8 × 10-7 M and 1180 ± 314 Hounsfield units and an Au concentration of 5.4 × 10-2 M. The QD/SiO2/Au particle colloid solution was injected into a mouse chest wall. Fluorescence emitted from the colloid solution could be detected on the skin covering the chest wall. The colloid solution could also be X-ray-imaged in the chest wall. Consequently, the QD/SiO2/Au particle colloid solution was found to have dual functions, i.e., fluorescence emission and X-ray absorption in vivo, which makes the colloid solution suitable to function as a contrast agent for dual imaging processes.

Tailoring superelasticity of soft magnetic materials

NASA Astrophysics Data System (ADS)

Cremer, Peet; Löwen, Hartmut; Menzel, Andreas M.

2015-10-01

Embedding magnetic colloidal particles in an elastic polymer matrix leads to smart soft materials that can reversibly be addressed from outside by external magnetic fields. We discover a pronounced nonlinear superelastic stress-strain behavior of such materials using numerical simulations. This behavior results from a combination of two stress-induced mechanisms: a detachment mechanism of embedded particle aggregates and a reorientation mechanism of magnetic moments. The superelastic regime can be reversibly tuned or even be switched on and off by external magnetic fields and thus be tailored during operation. Similarities to the superelastic behavior of shape-memory alloys suggest analogous applications, with the additional benefit of reversible switchability and a higher biocompatibility of soft materials.

Controlling placement of nonspherical (boomerang) colloids in nematic cells with photopatterned director

NASA Astrophysics Data System (ADS)

Peng, Chenhui; Turiv, Taras; Zhang, Rui; Guo, Yubing; Shiyanovskii, Sergij V.; Wei, Qi-Huo; de Pablo, Juan; Lavrentovich, Oleg D.

2017-01-01

Placing colloidal particles in predesigned sites represents a major challenge of the current state-of-the-art colloidal science. Nematic liquid crystals with spatially varying director patterns represent a promising approach to achieve a well-controlled placement of colloidal particles thanks to the elastic forces between the particles and the surrounding landscape of molecular orientation. Here we demonstrate how the spatially varying director field can be used to control placement of non-spherical particles of boomerang shape. The boomerang colloids create director distortions of a dipolar symmetry. When a boomerang particle is placed in a periodic splay-bend director pattern, it migrates towards the region of a maximum bend. The behavior is contrasted to that one of spherical particles with normal surface anchoring, which also produce dipolar director distortions, but prefer to compartmentalize into the regions with a maximum splay. The splay-bend periodic landscape thus allows one to spatially separate these two types of particles. By exploring overdamped dynamics of the colloids, we determine elastic driving forces responsible for the preferential placement. Control of colloidal locations through patterned molecular orientation can be explored for future applications in microfluidic, lab on a chip, sensing and sorting devices.

Controlling placement of nonspherical (boomerang) colloids in nematic cells with photopatterned director.

PubMed

Peng, Chenhui; Turiv, Taras; Zhang, Rui; Guo, Yubing; Shiyanovskii, Sergij V; Wei, Qi-Huo; de Pablo, Juan; Lavrentovich, Oleg D

2017-01-11

Placing colloidal particles in predesigned sites represents a major challenge of the current state-of-the-art colloidal science. Nematic liquid crystals with spatially varying director patterns represent a promising approach to achieve a well-controlled placement of colloidal particles thanks to the elastic forces between the particles and the surrounding landscape of molecular orientation. Here we demonstrate how the spatially varying director field can be used to control placement of non-spherical particles of boomerang shape. The boomerang colloids create director distortions of a dipolar symmetry. When a boomerang particle is placed in a periodic splay-bend director pattern, it migrates towards the region of a maximum bend. The behavior is contrasted to that one of spherical particles with normal surface anchoring, which also produce dipolar director distortions, but prefer to compartmentalize into the regions with a maximum splay. The splay-bend periodic landscape thus allows one to spatially separate these two types of particles. By exploring overdamped dynamics of the colloids, we determine elastic driving forces responsible for the preferential placement. Control of colloidal locations through patterned molecular orientation can be explored for future applications in microfluidic, lab on a chip, sensing and sorting devices.

BOOK REVIEW: Soft Condensed Matter

NASA Astrophysics Data System (ADS)

Jones, Richard A. L.

2002-11-01

The author states in the preface of the book that the aim is '...to give a unified overview of the various aspects of the physics of soft condensed matter'. The book succeeds in fulfilling this aim in many respects. i) The style is fluent and concise and gives the necessary explanations to make its content understandable to people with some knowledge of the basic principles of physics. ii) The content of the book is complete enough to give a panoramic view of the landscape of soft condensed matter. The first two chapters give, respectively, a short introduction and a presentation of forces, energies and timescales, giving a general overview and pointing out the particular importance of different aspects such as timescales, which are much more important in soft condensed matter than in traditional or 'hard' condensed matter. The next chapter, devoted to phase transition, recalls that the equilibrium between two phases is controlled by free energy considerations. Spinodal decomposition is presented as a counterpart of nucleation and growth. Again, characteristic length scales are considered and applied to a phase separation mixture of polymers in a common solvent. The following three chapters are devoted respectively to specific topics: colloidal dispersion, polymers and gelation. The stability and phase behaviour of colloids are related to the interaction between colloidal particles. Properties of colloidal crystals as well as colloidal dispersion are depicted in terms of stabilization of crystalline colloids. The flow properties of colloidal dispersion are presented in terms of free energy minimization and the structure of the dispersion. After a brief introduction to polymer chemistry and architecture, the coil-globule transition is discussed. Viscoelasticity of polymers is described and discussed by introducing the notion of entanglement. This leads to the introduction of the tube model and the theory of reptation. The sol-gel transition is presented phenomenologically and formulated through the current percolation model and the Flory-Stockmayer model. The next two chapters consider the molecular order in soft condensed matter. The rich complexity of liquid crystals is emphasized and the Frederiks transition is described in relation to liquid crystal displays. The crystallinity in polymers is discussed and its usual semi-crystallinity presented as a consequence of entanglement and timescales. The next chapter describes the self-assembly of phases and the great importance of the self-assembly phenomenon in solutions of amphiphilic molecules is largely discussed in several specific phenomena. The book ends with a chapter devoted to the description of soft matter realizations in nature. Special attention is paid to the components and structure of life: nucleic acids, proteins, polysaccharides and membranes. There are two appendixes recalling the basic concepts of thermodynamics and statistical mechanics. In each chapter, several problems are included, and solutions to a selection of them are given. The bibliography proposed is pertinent and each chapter gives details of further reading, mostly addressed to known books on the topic. iii) The presentation of the book is good. Throughout the book, the relevant, basic or new concepts of each topic are typed in bold characters and succinctly defined. The figures are abundant and adequately illustrate the text either by plots of experimental data or by computed predictions from models. Many schematic representations of structures, molecular distributions or arrangements are also included. In summary, the author has succeeded in producing a scientifically rigorous book of affordable size (around 200 pages) that is well illustrated (about 120 figures) and written in a fluent style that describes the many different physical phenomena involved in soft condensed matter. N Clavaguera

The rheology and phase separation kinetics of mixed-matrix membrane dopes

NASA Astrophysics Data System (ADS)

Olanrewaju, Kayode Olaseni

Mixed-matrix hollow fiber membranes are being developed to offer more efficient gas separations applications than what the current technologies allow. Mixed-matrix membranes (MMMs) are membranes in which molecular sieves incorporated in a polymer matrix enhance separation of gas mixtures based on the molecular size difference and/or adsorption properties of the component gases in the molecular sieve. The major challenges encountered in the efficient development of MMMs are associated with some of the paradigm shifts involved in their processing, as compared to pure polymer membranes. For instance, mixed-matrix hollow fiber membranes are prepared by a dry-wet jet spinning method. Efficient large scale processing of hollow fibers by this method requires knowledge of two key process variables: the rheology and kinetics of phase separation of the MMM dopes. Predicting the rheological properties of MMM dopes is not trivial; the presence of particles significantly affects neat polymer membrane dopes. Therefore, the need exists to characterize and develop predictive capabilities for the rheology of MMM dopes. Furthermore, the kinetics of phase separation of polymer solutions is not well understood. In the case of MMM dopes, the kinetics of phase separation are further complicated by the presence of porous particles in a polymer solution. Thus, studies on the phase separation kinetics of polymer solutions and suspensions of zeolite particles in polymer solutions are essential. Therefore, this research thesis aims to study the rheology and phase separation kinetics of mixed-matrix membrane dopes. In our research efforts to develop predictive models for the shear rheology of suspensions of zeolite particles in polymer solutions, it was found that MFI zeolite suspensions have relative viscosities that dramatically exceed the Krieger-Dougherty predictions for hard sphere suspensions. Our investigations showed that the major origin of this discrepancy is the selective absorption of solvent molecules from the suspending polymer solution into the zeolite pores. Consequently, both the viscosity of the polymer solution and the particle contribution to the suspension viscosity are greatly increased. A predictive model for the viscosity of porous zeolite suspensions incorporating a solvent absorption parameter, alpha, into the Krieger-Dougherty model was developed. We experimentally determined the solvent absorption parameter and our results are in good agreement with the theoretical pore volume of MFI particles. In addition, fundamental studies were conducted with spherical nonporous silica suspensions to elucidate the role of colloidal and hydrodynamic forces on the rheology of mixed-matrix membrane dopes. Also in this thesis, details of a novel microfluidic device for measuring the phase separation kinetics of membrane dopes are presented. We have used this device to quantify the phase separation kinetics (PSK) of polymer solutions and MMM dopes upon contact with an array of relevant nonsolvent. For the polymer solution, we found that PSK is governed by the micro-rheological and thermodynamic properties of the polymer solution and nonsolvent. For the MMM dopes, we found that the PSK may increase with increase in particles surface area due to surface diffusion enhancement. In addition, it was found that the dispersed particles alter the thermodynamic properties of the dope based on the hydrophilicity and porosity of the particle.

Anomalous Drag Reduction and Hydrodynamic Interactions of Nanoparticles in Polymer Nanocomposite Thin Films

NASA Astrophysics Data System (ADS)

Basu, Jaydeep; Begam, Nafisa; Chandran, Sivasurender; Sprung, Michael

2015-03-01

One of the central dogma of fluid physics is the no-slip boundary condition whose validity has come under intense scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective drag experienced by polymer grafted nanoparticles moving through a highly viscous film of polymer, well above its glass transition temperature. The extent of drag reduction increases with decreasing temperature and polymer film thickness. We also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these nanoparticles with an anomalous power law exponent of ~ 2 at the lowest temperatures and film thickness. Such strong hydrodynamic interactions are not expected in polymer melts where these interactions are known to be screened to molecular dimensions. We provide evidence for the presence of large hydrodynamic slip at the nanoparticle-polymer interface and demonstrate its tunability with temperature and confinement. Our study suggests novel physics emerging in dynamics nanoparticles due to confinement and interface wettability in thin films of polymer nanocomposites.

Brush in the bath of active particles: Anomalous stretching of chains and distribution of particles

NASA Astrophysics Data System (ADS)

Li, Hui-shu; Zhang, Bo-kai; Li, Jian; Tian, Wen-de; Chen, Kang

2015-12-01

The interaction between polymer brush and colloidal particles has been intensively studied in the last two decades. Here, we consider a flat chain-grafted substrate immersed in a bath of active particles. Simulations show that an increase in the self-propelling force causes an increase in the number of particles that penetrate into the brush. Anomalously, the particle density inside the main body of the brush eventually becomes higher than that outside the brush at very large self-propelling force. The grafted chains are further stretched due to the steric repulsion from the intruded particles. Upon the increase of the self-propelling force, distinct stretching behaviors of the chains were observed for low and high grafting densities. Surprisingly, we find a weak descent of the average end-to-end distance of chains at high grafting density and very large force which is reminiscent of the compression effect of a chain in the active bath.

Aggregation of montmorillonite and organic matter in aqueous media containing artificial seawater

PubMed Central

2009-01-01

Background The dispersion-aggregation behaviors of suspended colloids in rivers and estuaries are affected by the compositions of suspended materials (i.e., clay minerals vs. organic macromolecules) and salinity. Laboratory experiments were conducted to investigate the dispersion and aggregation mechanisms of suspended particles under simulated river and estuarine conditions. The average hydrodynamic diameters of suspended particles (representing degree of aggregation) and zeta potential (representing the electrokinetic properties of suspended colloids and aggregates) were determined for systems containing suspended montmorillonite, humic acid, and/or chitin at the circumneutral pH over a range of salinity (0 – 7.2 psu). Results The montmorillonite-only system increased the degree of aggregation with salinity increase, as would be expected for suspended colloids whose dispersion-aggregation behavior is largely controlled by the surface electrostatic properties and van der Waals forces. When montmorillonite is combined with humic acid or chitin, the aggregation of montmorillonite was effectively inhibited. The surface interaction energy model calculations reveal that the steric repulsion, rather than the increase in electronegativity, is the primary cause for the inhibition of aggregation by the addition of humic acid or chitin. Conclusion These results help explain the range of dispersion-aggregation behaviors observed in natural river and estuarine systems. It is postulated that the composition of suspended particles, specifically the availability of steric polymers such as those contained in humic acid, determine whether the river suspension is rapidly aggregated and settled or remains dispersed in suspension when it encounters increasingly saline environments of estuaries and oceans. PMID:19166595

Sodium caseinate stabilized zein colloidal particles.

PubMed

Patel, Ashok R; Bouwens, Elisabeth C M; Velikov, Krassimir P

2010-12-08

The present work deals with the preparation and stabilization of zein colloidal particles using sodium caseinate as electrosteric stabilizer. Colloidal particles with well-defined size range (120-150 nm) and negative surface potential (-29 to -47 mV) were obtained using a simple antisolvent precipitation method. Due to the presence of caseinate, the stabilized colloidal particles showed a shift of isoelectric point (IEP) from 6.0 to around pH 5.0 and thus prevent the aggregation of zein near its native IEP (pH 6.2). The particles also showed good stability to varying ionic strength (15 mM-1.5 M NaCl). Furthermore, stabilized particles retained the property of redispersibility after drying. In vitro protein hydrolysis study confirmed that the presence of caseinate did not alter the digestibility of zein. Such colloidal particles could potentially serve as all-natural delivery systems for bioactive molecules in food, pharmaceutical, and agricultural formulations.

Dynamic Colloidal Molecules Maneuvered by Light-Controlled Janus Micromotors.

PubMed

Gao, Yirong; Mou, Fangzhi; Feng, Yizheng; Che, Shengping; Li, Wei; Xu, Leilei; Guan, Jianguo

2017-07-12

In this work, we propose and demonstrate a dynamic colloidal molecule that is capable of moving autonomously and performing swift, reversible, and in-place assembly dissociation in a high accuracy by manipulating a TiO 2 /Pt Janus micromotor with light irradiation. Due to the efficient motion of the TiO 2 /Pt Janus motor and the light-switchable electrostatic interactions between the micromotor and colloidal particles, the colloidal particles can be captured and assembled one by one on the fly, subsequently forming into swimming colloidal molecules by mimicking space-filling models of simple molecules with central atoms. The as-demonstrated dynamic colloidal molecules have a configuration accurately controlled and stabilized by regulating the time-dependent intensity of UV light, which controls the stop-and-go motion of the colloidal molecules. The dynamic colloidal molecules are dissociated when the light irradiation is turned off due to the disappearance of light-switchable electrostatic interaction between the motor and the colloidal particles. The strategy for the assembly of dynamic colloidal molecules is applicable to various charged colloidal particles. The simulated optical properties of a dynamic colloidal molecule imply that the results here may provide a novel approach for in-place building functional microdevices, such as microlens arrays, in a swift and reversible manner.

Motion of Colloidal Particles near Plateau Border in Freely Suspended Soap Film

NASA Astrophysics Data System (ADS)

Pak, Hyuk Kyu; Sur, Jeanman

2000-03-01

We study the motion of colloidal particle near Plateau border in free-standing soap film which is placed perpendicularly to the gravitational direction. When the thickness of soap film is a micron order, two air/water interfacial surfaces of the film can be deformed by the presence of the colloidal particle. When the colloidal particles are in the central area of soap film, they move in random directions. But, as the particles approach near Plateau border, they are accelerated to the border of the film. The travelling distance, before the accelerated particle stops, depends on particle size. We propose a simple model to explain the motion of particle near Plateau border using a surface energy argument and compare the results with experimental measurements.

Mechanical and Thermal Characterization of Silica Nanocomposites

NASA Astrophysics Data System (ADS)

Cunningham, Anthony Lamar

Polymer nanocomposites are a class of materials containing nanoparticles with a large interfacial surface area. Only a small quantity of nanoparticles are needed to provide superior multifunctional properties; such as mechanical, thermal, electrical, and moisture absorption properties in polymers. Nanoparticles tend to agglomerate, so special techniques are required for homogeneous distribution. Nanosilica is now readily available as colloidal sols, for example; Nanopox RTM F400 (supplied by Evonik Nanoresins AG, Germany). The nanoparticles are first synthesized from aqueous sodium silicate solution, and then undergo a surface modification process with organosilane and matrix exchange. F400 contains 40%wt silica nanoparticles colloidally dispersed in a DGEBA epoxy resin. The mean particle diameter is about 20 nm with a narrow distribution range of about 5 to 35 nm. The objectives of this study are to develop a reproducible processing method for nanosilica enhanced resin systems used in the manufacturing of fiber reinforced composites that will be characterized for mechanical and thermal properties. Research has concluded that shows improvements in the properties of the matrix material when processed in loading variations of 0 to 25%wt silica nanoparticles. The loadings were also used to manufacture fiberglass reinforced nanocomposite laminates and also tested for mechanical and thermal properties.

Synthesis of polymer coated Co0.5Zn0.5Fe2O4 nanoparticles and their enhanced anticancer activity against HepG2 cell line

NASA Astrophysics Data System (ADS)

Ali, Z.; Abbasi, R.; Khan, A. J.; Arshad, J.; Atif, M.; Ahmad, N.; Khalid, W.

2018-05-01

Cobalt zinc ferrite nanoparticles with stoichiometry Co0.5Zn0.5Fe2O4 (CZFN) were synthesized by sol-gel method with high colloidal stability having room temperature ferromagnetism. For biological applications, CZFN were transferred to aqueous phase by polymer coating with amphiphilic polymer, whereas fluorescent dye (ATTO-590) was used as model system for anti-cancer drug loaded polymer shell. The amount of functional molecule varied up to 25% of the anhydride rings, which provides greater affinity of drug loading in polymer shell. CZFN were characterized by x-ray diffraction, Fourier transformed infrared spectroscopy, UV–vis absorption spectroscopy, gel electrophoresis and vibrating sample magnetometer. The in vitro cytotoxicity of CZFN was examined against HepG2 which revealed that CZFN (IC50:3.01 nM) strongly inhabits growth of the cells. Further the particles did not induce any significant hemolysis. Stimulatingly, this seems to be a noteworthy improvement towards the ability of surface functionalized multifunctional CZFN as carriers for drugs for anti-cancer therapy and their use as nanomedicine.

Formation of Polyelectrolyte Complex Colloid Particles between Chitosan and Pectin with Different Degree of Esterification

NASA Astrophysics Data System (ADS)

Wang, Hui; Sun, Hongyuan; He, Jieyu

2017-12-01

The effects of degree of esterification, pectin/chitosan ratio and pH on the formation of polyelectrolyte complex colloid particles between chitosan (CS) and pectin (PE) were investigated. Low methoxyl pectin (LPE) was achieved by de-esterifying high methoxyl pectin (HPE) with pectin methyl esterase. Turbidity titration and colorimetric method was used to determine the stability of complex colloid particles. The structure and morphology of complex particles were characterized by FTIR and TEM. When pectin solution was dropped into chitosan solution, complex colloidal dispersion was stable as PE/CS mass ratio was no more than 3:2. Colloidal particles of HPE-CS complex coagulated at larger ratio of PE/CS than LPE-CS. The maximum complex occurred at pH 6.1 for HPE-CS and pH 5.7 for LPE-CS, and decreasing pH leaded to the dissociation of complex particles. Electrostatic interactions between carboxyl groups on pectin and amino groups on chitosan were confirmed by FTIR. Colloidal particle sizes ranged from about 100 nm to 400 nm with spherical shape.

Redox Active Colloids as Discrete Energy Storage Carriers.

PubMed

Montoto, Elena C; Nagarjuna, Gavvalapalli; Hui, Jingshu; Burgess, Mark; Sekerak, Nina M; Hernández-Burgos, Kenneth; Wei, Teng-Sing; Kneer, Marissa; Grolman, Joshua; Cheng, Kevin J; Lewis, Jennifer A; Moore, Jeffrey S; Rodríguez-López, Joaquín

2016-10-12

Versatile and readily available battery materials compatible with a range of electrode configurations and cell designs are desirable for renewable energy storage. Here we report a promising class of materials based on redox active colloids (RACs) that are inherently modular in their design and overcome challenges faced by small-molecule organic materials for battery applications, such as crossover and chemical/morphological stability. RACs are cross-linked polymer spheres, synthesized with uniform diameters between 80 and 800 nm, and exhibit reversible redox activity as single particles, as monolayer films, and in the form of flowable dispersions. Viologen-based RACs display reversible cycling, accessing up to 99% of their capacity and 99 ± 1% Coulombic efficiency over 50 cycles by bulk electrolysis owing to efficient, long-distance intraparticle charge transfer. Ferrocene-based RACs paired with viologen-based RACs cycled efficiently in a nonaqueous redox flow battery employing a simple size-selective separator, thus demonstrating a possible application that benefits from their colloidal dimensions. The unprecedented versatility in RAC synthetic and electrochemical design opens new avenues for energy storage.

Superelastic stress-strain behavior in ferrogels with different types of magneto-elastic coupling

NASA Astrophysics Data System (ADS)

Cremer, Peet; Löwen, Hartmut; Menzel, Andreas M.

Colloidal magnetic particles embedded in an elastic polymer matrix constitute a smart material called ferrogel. It responds to an applied external magnetic field by changes in elastic properties, which can be exploited for various applications like dampers, vibration absorbers, or actuators. Under appropriate conditions, the stress-strain behavior of a ferrogel can display a fascinating feature: superelasticity, the capability to reversibly deform by a huge amount while barely altering the applied load. In a previous work, using numerical simulations, we investigated this behavior assuming that the magnetic moments carried by the embedded particles can freely reorient to minimize their magnetic interaction energy. Here, we extend the analysis to ferrogels where restoring torques by the surrounding matrix hinder rotations towards a magnetically favored configuration. For example, the particles can be chemically cross-linked into the polymer matrix and the magnetic moments can be fixed to the particle axes. We demonstrate that these systems still feature a superelastic regime. As before, the nonlinear stress-strain behavior can be reversibly tailored during operation by external magnetic fields. Yet, the different coupling of the magnetic moments causes different types of response to external stimuli. For instance, an external magnetic field applied parallel to the stretching axis hardly affects the superelastic regime but stiffens the system beyond it. Other smart materials featuring superelasticity, e.g. metallic shape-memory alloys, have already found widespread applications. Our soft polymer systems offer many additional advantages like a typically higher deformability and enhanced biocompatibility combined with high tunability.

Versatile theranostics agents designed by coating ferrite nanoparticles with biocompatible polymers

NASA Astrophysics Data System (ADS)

Zahraei, M.; Marciello, M.; Lazaro-Carrillo, A.; Villanueva, A.; Herranz, F.; Talelli, M.; Costo, R.; Monshi, A.; Shahbazi-Gahrouei, D.; Amirnasr, M.; Behdadfar, B.; Morales, M. P.

2016-06-01

Three biocompatible polymers, polyethylene glycol (PEG), dextran and chitosan, have been used in this work to control the colloidal stability of magnetic nanoparticles (14 ± 5 nm in diameter) and to vary the aggregation state in order to study their effect on relaxometric and heating properties. Two different coating strategies have been deeply developed; one based on the formation of an amide bond between citric acid coated nanoparticles (NPs) and amine groups present on the polymer surface and the other based on the NP encapsulation. Relaxometric properties revealed that proton relaxation rates strongly depend on the coating layer hydrophilicity and the aggregation state of the particles due to the presence of magnetic interactions. Thus, while PEG coating reduces particle aggregation by increasing inter-particle spacing leading to reduction of both T1 and T2 relaxation, dextran and chitosan lead to an increase mainly in T2 values due to the aggregation of particles in bigger clusters where they are in close contact. Dextran and chitosan coated NPs have also shown a remarkable heating effect during the application of an alternating magnetic field. They have proved to be potential candidates as theranostic agents for cancer diagnosis and treatment. Finally, cytotoxicity of PEG conjugated NPs, which seem to be ideal for intravenous administration because of their small hydrodynamic size, was investigated resulting in high cell viability even at 0.2 mg Fe ml-1 after 24 h of incubation. This suspension can be used as drug/biomolecule carrier for in vivo applications.

Unusually large acrylamide induced effect on the droplet size in AOT/Brij30 water-in-oil microemulsions.

PubMed

Poulsen, Allan K; Arleth, Lise; Almdal, Kristoffer; Scharff-Poulsen, Anne Marie

2007-02-01

Droplet microemulsions are widely used as templates for controlled synthesis of nanometer sized polymer gel beads for use as, e.g., nanobiosensors. Here we examine water-in-oil microemulsions typically used for preparation of sensors. The cores of the microemulsion droplets are constituted by an aqueous component consisting of water, reagent monomer mixture, buffer salts, and the relevant dyes and/or enzymes. The cores are encapsulated by a mixture of the surfactants Brij30 and AOT and the resulting microemulsion droplets are suspended in a continuous hexane phase. The size of the final polymer particles may be of great importance for the applications of the sensors. Our initial working hypothesis was that the size of the droplet cores and therefore the size of the synthesized polymer gel beads could be controlled by the surfactant-to-water ratio of the template microemulsion. In the present work we have tested this hypothesis and investigated how the monomers and the ratio between the two surfactants affect the size of the microemulsion droplets and the microemulsion domain. We find that the monomers in water have a profound effect on the microemulsion domain as well as on the size of the microemulsion droplets. The relation between microemulsion composition and droplet size is in this case more complicated than assumed in standard descriptions of microemulsions [R. Strey, Colloid Polym. Sci. 272 (1994) 1005-1019; I. Danielsson, B. Lindman, Colloids Surf. 3 (1981) 391-392; Y. Chevalier, T. Zemb, Rep. Progr. Phys. 53 (1990) 279-371].

USAXS analysis of concentration-dependent self-assembling of polymer-brush-modified nanoparticles in ionic liquid: [I] concentrated-brush regime

NASA Astrophysics Data System (ADS)

Nakanishi, Yohei; Ishige, Ryohei; Ogawa, Hiroki; Sakakibara, Keita; Ohno, Kohji; Morinaga, Takashi; Sato, Takaya; Kanaya, Toshiji; Tsujii, Yoshinobu

2018-03-01

Using ultra-small angle X-ray scattering (USAXS), we analyzed the higher-order structures of nanoparticles with a concentrated brush of an ionic liquid (IL)-type polymer (concentrated-polymer-brush-modified silica particle; PSiP) in an IL and the structure of the swollen shell layer of PSiP. Homogeneous mixtures of PSiP and IL were successfully prepared by the solvent-casting method involving the slow evaporation of a volatile solvent, which enabled a systematic study over an exceptionally wide range of compositions. Different diffraction patterns as a function of PSiP concentration were observed in the USAXS images of the mixtures. At suitably low PSiP concentrations, the USAXS intensity profile was analyzed using the Percus-Yevick model by matching the contrast between the shell layer and IL, and the swollen structure of the shell and "effective diameter" of the PSiP were evaluated. This result confirms that under sufficiently low pressures below and near the liquid/crystal-threshold concentration, the studied PSiP can be well described using the "hard sphere" model in colloidal science. Above the threshold concentration, the PSiP forms higher-order structures. The analysis of diffraction patterns revealed structural changes from disorder to random hexagonal-closed-packing and then face-centered-cubic as the PSiP concentration increased. These results are discussed in terms of thermodynamically stable "hard" and/or "semi-soft" colloidal crystals, wherein the swollen layer of the concentrated polymer brush and its structure play an important role.

Nematic Liquid-Crystal Colloids

PubMed Central

Muševič, Igor

2017-01-01

This article provides a concise review of a new state of colloidal matter called nematic liquid-crystal colloids. These colloids are obtained by dispersing microparticles of different shapes in a nematic liquid crystal that acts as a solvent for the dispersed particles. The microparticles induce a local deformation of the liquid crystal, which then generates topological defects and long-range forces between the neighboring particles. The colloidal forces in nematic colloids are much stronger than the forces in ordinary colloids in isotropic solvents, exceeding thousands of kBT per micrometer-sized particle. Of special interest are the topological defects in nematic colloids, which appear in many fascinating forms, such as singular points, closed loops, multitudes of interlinked and knotted loops or soliton-like structures. The richness of the topological phenomena and the possibility to design and control topological defects with laser tweezers make colloids in nematic liquid crystals an excellent playground for testing the basic theorems of topology. PMID:29295574

Shear-banding and superdiffusivity in entangled polymer solutions

NASA Astrophysics Data System (ADS)

Shin, Seunghwan; Dorfman, Kevin D.; Cheng, Xiang

2017-12-01

Using high-resolution confocal rheometry, we study the shear profiles of well-entangled DNA solutions under large-amplitude oscillatory shear in a rectilinear planar shear cell. With increasing Weissenberg number (Wi), we observe successive transitions from normal Newtonian linear shear profiles to wall-slip dominant shear profiles and, finally, to shear-banding profiles at high Wi. To investigate the microscopic origin of the observed shear banding, we study the dynamics of micron-sized tracers embedded in DNA solutions. Surprisingly, tracer particles in the shear frame exhibit transient superdiffusivity and strong dynamic heterogeneity. The probability distribution functions of particle displacements follow a power-law scaling at large displacements, indicating a Lévy-walk-type motion, reminiscent of tracer dynamics in entangled wormlike micelle solutions and sheared colloidal glasses. We further characterize the length and time scales associated with the abnormal dynamics of tracer particles. We hypothesize that the unusual particle dynamics arise from localized shear-induced chain disentanglement.

The electrostatic interaction between interfacial colloidal particles

NASA Astrophysics Data System (ADS)

Hurd, A. J.

1985-11-01

The electrostatic interaction between charged, colloidal particles trapped at an air-water interface is considered using linearised Poisson-Boltzmann results for point particles. In addition to the expected screened-Coulomb contribution, which decays exponentially, an algebraic dipole-dipole interaction occurs that may account for long-range interactions in interfacial colloidal systems.

Inventions Utilizing Microfluidics and Colloidal Particles

NASA Technical Reports Server (NTRS)

Marr, David W.; Gong, Tieying; Oakey, John; Terray, Alexander V.; Wu, David T.

2009-01-01

Several related inventions pertain to families of devices that utilize microfluidics and/or colloidal particles to obtain useful physical effects. The families of devices can be summarized as follows: (1) Microfluidic pumps and/or valves wherein colloidal-size particles driven by electrical, magnetic, or optical fields serve as the principal moving parts that propel and/or direct the affected flows. (2) Devices that are similar to the aforementioned pumps and/or valves except that they are used to manipulate light instead of fluids. The colloidal particles in these devices are substantially constrained to move in a plane and are driven to spatially order them into arrays that function, variously, as waveguides, filters, or switches for optical signals. (3) Devices wherein the ultra-laminar nature of microfluidic flows is exploited to effect separation, sorting, or filtering of colloidal particles or biological cells in suspension. (4) Devices wherein a combination of confinement and applied electrical and/or optical fields forces the colloidal particles to become arranged into three-dimensional crystal lattices. Control of the colloidal crystalline structures could be exploited to control diffraction of light. (5) Microfluidic devices, incorporating fluid waveguides, wherein switching of flows among different paths would be accompanied by switching of optical signals.

Study of adhesion and friction properties on a nanoparticle gradient surface: transition from JKR to DMT contact mechanics.

PubMed

Ramakrishna, Shivaprakash N; Nalam, Prathima C; Clasohm, Lucy Y; Spencer, Nicholas D

2013-01-08

We have previously investigated the dependence of adhesion on nanometer-scale surface roughness by employing a roughness gradient. In this study, we correlate the obtained adhesion forces on nanometer-scale rough surfaces to their frictional properties. A roughness gradient with varying silica particle (diameter ≈ 12 nm) density was prepared, and adhesion and frictional forces were measured across the gradient surface in perfluorodecalin by means of atomic force microscopy with a polyethylene colloidal probe. Similarly to the pull-off measurements, the frictional forces initially showed a reduction with decreasing particle density and later an abrupt increase as the colloidal sphere began to touch the flat substrate beneath, at very low particle densities. The friction-load relation is found to depend on the real contact area (A(real)) between the colloid probe and the underlying particles. At high particle density, the colloidal sphere undergoes large deformations over several nanoparticles, and the contact adhesion (JKR type) dominates the frictional response. However, at low particle density (before the colloidal probe is in contact with the underlying surface), the colloidal sphere is suspended by a few particles only, resulting in local deformations of the colloid sphere, with the frictional response to the applied load being dominated by long-range, noncontact (DMT-type) interactions with the substrate beneath.

Brownian motion studies of viscoelastic colloidal gels by rotational single particle tracking

DOE PAGES

Liang, Mengning; Harder, Ross; Robinson, Ian K.

2014-04-14

Colloidal gels have unique properties due to a complex microstructure which forms into an extended network. Although the bulk properties of colloidal gels have been studied, there has been difficulty correlating those properties with individual colloidal dynamics on the microscale due to the very high viscosity and elasticity of the material. We utilize rotational X-ray tracking (RXT) to investigate the rotational motion of component crystalline colloidal particles in a colloidal gel of alumina and decanoic acid. Our investigation has determined that the high elasticity of the bulk is echoed by a high elasticity experienced by individual colloidal particles themselves butmore » also finds an unexpected high degree of rotational diffusion, indicating a large degree of freedom in the rotational motion of individual colloids even within a tightly bound system.« less

Clustering of Cyclodextrin-Functionalized Microbeads by an Amphiphilic Biopolymer: Real-Time Observation of Structures Resembling Blood Clots.

PubMed

Arya, Chandamany; Saez Cabesas, Camila A; Huang, Hubert; Raghavan, Srinivasa R

2017-10-25

Colloidal particles can be induced to cluster by adding polymers in a process called bridging flocculation. For bridging to occur, the polymer must bind strongly to the surfaces of adjacent particles, such as via electrostatic interactions. Here, we introduce a new system where bridging occurs due to specific interactions between the side chains of an amphiphilic polymer and supramolecules on the particle surface. The polymer is a hydrophobically modified chitosan (hmC) while the particles are uniform polymeric microbeads (∼160 μm in diameter) made by a microfluidic technique and functionalized on their surface by α-cyclodextrins (CDs). The CDs have hydrophobic binding pockets that can capture the n-alkyl hydrophobes present along the hmC chains. Clustering of CD-coated microbeads in water by hmC is visualized in real time using optical microscopy. Interestingly, the clustering follows two distinct stages: first, the microbeads are bridged into clusters by hmC chains, which occurs by the interaction of individual chains with the CDs on adjacent particles. Thereafter, additional hmC from the solution adsorbs onto the surfaces of the microbeads and an hmC "mesh" grows around the clusters. This growing nanostructured mesh can trap surrounding microsized objects and sequester them within the overall cluster. Such clustering is reminiscent of blood clotting where blood platelets initially cluster at a wound site, whereupon they induce growth of a protein (fibrin) mesh around the clusters, which entraps other passive cells. Clustering does not occur with the native chitosan (lacking hydrophobes) or with the bare particles (lacking CDs); these results confirm that the clustering is indeed due to hydrophobic interactions between the hmC and the CDs. Microbead clustering via amphiphilic biopolymers could be applicable in embolization, which is a surgical technique used to block blood flow to a particular area of the body, or in agglutination assays.

Aggregation and breakup of colloidal particle aggregates in shear flow, studied with video microscopy.

PubMed

Tolpekin, V A; Duits, M H G; van den Ende, D; Mellema, J

2004-03-30

We used video microscopy to study the behavior of aggregating suspensions in shear flow. Suspensions consisted of 920 nm diameter silica spheres, dispersed in a methanol/bromoform solvent, to which poly(ethylene glycol) (M = 35.000 g) was added to effect weak particle aggregation. With our solvent mixture, the refractive index of the particles could be closely matched, to allow microscopic observations up to 80 microm deep into the suspension. Also the mass density is nearly equal to that of the particles, thus allowing long observation times without problems due to aggregate sedimentation. Particles were visualized via fluorescent molecules incorporated into their cores. Using a fast confocal scanning laser microscope made it possible to characterize the (flowing) aggregates via their contour-area distributions as observed in the focal plane. The aggregation process was monitored from the initial state (just after adding the polymer), until a steady state was reached. The particle volume fraction was chosen at 0.001, to obtain a characteristic aggregation time of a few hundred seconds. On variation of polymer concentration, cP (2.2-12.0 g/L), and shear rate, gamma (3-6/s), it was observed that the volume-averaged size, Dv, in the steady state became larger with polymer concentration and smaller with shear rate. This demonstrates that the aggregate size is set by a competition between cohesive forces caused by the polymer and rupture forces caused by the flow. Also aggregate size distributions were be measured (semiquantitatively). Together with a description for the internal aggregate structure they allowed a modeling of the complete aggregation curve, from t = 0 up to the steady state. A satisfactory description could be obtained by describing the aggregates as fractal objects, with Df = 2.0, as measured from CSLM images after stopping the flow. In this modeling, the fitted characteristic breakup time was found to increase with cP.

Understanding Subsurface Colloid Behavior: A New Visualization Technique and the Application of Geo-Centrifuge Modeling

NASA Astrophysics Data System (ADS)

Yoon, J. S.; Culligan, P. J.; Germaine, J. T.

2003-12-01

Subsurface colloid behavior has recently drawn attention because colloids are suspected of enhancing contaminant transport in groundwater systems. To better understand the processes by which colloids move through the subsurface, and in particular the vadose zone, a new technique that enables real-time visualization of colloid particles as they move through a porous medium has been developed. This visualization technique involves the use of laser induced fluorescent particles and digital image processing to directly observe particles moving through a porous medium consisting of soda-lime glass beads and water in a transparent experimental box of 10.0cm\\x9D27.9cm\\x9D2.38cm. Colloid particles are simulated using commercially available micron sized particles that fluoresce under argon-ion laser light. The fluorescent light given off from the particles is captured through a camera filter, which lets through only the emitted wavelength of the colloid particles. The intensity of the emitted light is proportional to the colloid particle concentration. The images of colloid movement are captured by a MagnaFire digital camera; a cooled CCD digital camera produced by Optronics. This camera enables real-time capture of images to a computer, thereby allowing the images to be processed immediately. The images taken by the camera are analyzed by the ImagePro software from Media Cybernetics, which contains a range of counting, sizing, measuring, and image enhancement tools for image processing. Laboratory experiments using the new technique have demonstrated the existence of both irreversible and reversible sites for colloid entrapment during uniform saturated flow in a homogeneous porous medium. These tests have also shown a dependence of colloid entrapment on velocity. Models for colloid transport currently available in the literature have proven to be inadequate predictors for the experimental observations, despite the simplicity of the system studied. To further extend the work, the visualization technique has been developed for use on the geo-centrifuge. The advantage that the geo-centrifuge has for investigating subsurface colloid behavior, is the ability to simulate unsaturated transport mechanisms under well simulated field moisture profiles and in shortened periods of time. A series of tests to investigate colloid transport during uniform saturated flow is being used to examine basic scaling laws for colloid transport under enhanced gravity. The paper will describe the new visualization technique, its use in geo-centrifuge testing and observations on scaling relationships for colloid transport during geo-centrifuge experiments. Although the visualization technique has been developed for investigating subsurface colloid behavior, it does have application in other areas of investigation, including the investigation of microbial behavior in the subsurface.

Patterning of colloidal particles in the galvanic microreactor

NASA Astrophysics Data System (ADS)

Jan, Linda

A Cu-Au galvanic microreactor is used to demonstrate the autonomous patterning of two-dimensional colloidal crystals with spatial and orientational order which are adherent to the electrode substrate. The microreactor is comprised of a patterned array of copper and gold microelectrodes in a coplanar arrangement that is immersed in a dilute hydrochloric acid solution in which colloidal polystyrene microspheres are suspended. During the electrochemical dissolution of copper, polystyrene colloids are transported to the copper electrodes. The spatial arrangement of the electrodes determines whether the colloids initiate aggregation at the edges or centers of the copper electrodes. Depending on the microreactor parameters, two-dimensional colloidal crystals can form and adhere to the electrode. This thesis investigates the mechanisms governing the autonomous particle motion, the directed particle trajectory (inner- versus edge-aggregation) as affected by the spatial patterning of the electrodes, and the adherence of the colloidal particles onto the substrate. Using in situ current density measurements, particle velocimetry, and order-of-magnitude arguments, it is shown that particle motion is governed by bulk fluid motion and electrophoresis induced by the electrochemical reactions. Bulk electrolyte flow is most likely driven by electrochemical potential gradients of reaction products formed during the inhomogeneous copper dissolution, particularly due to localized high current density at the electrode junction. Preferential aggregation of the colloidal particles resulting in inner- and edge-aggregation is influenced by changes to the flow pattern in response to difference in current density profiles as affected by the spatial patterning of the electrode. Finally, by determining the onset of particle cementation through particle tracking analysis, and by monitoring the deposition of reaction products through the observation of color changes of the galvanic electrodes in situ, it is shown that particle cementation coincides with the precipitation and deposition of reaction products. The precipitation process is caused by shifts in the chemical equilibria of the microreactor due to changes in the composition of the electrolyte during the reactions, which can be used to control particle cementation. The corrosion driven transport, deposition and adherence of colloidal particles at corrosion sites have implications for the development of autonomous self-healing materials.

Magnetically actuated and controlled colloidal sphere-pair swimmer

NASA Astrophysics Data System (ADS)

Ran, Sijie; Guez, Allon; Friedman, Gary

2016-12-01

Magnetically actuated swimming of microscopic objects has been attracting attention partly due to its promising applications in the bio-medical field and partly due to interesting physics of swimming in general. While colloidal particles that are free to move in fluid can be an attractive swimming system due it its simplicity and ability to assemble in situ, stability of their dynamics and the possibility of stable swimming behavior in periodically varying magnetic fields has not been considered. Dynamic behavior of two magnetically interacting colloidal particles subjected to rotating magnetic field of switching frequency is analyzed here and is shown to result in stable swimming without any stabilizing feedback. A new mechanism of swimming that relies only on rotations of the particles themselves and of the particle pair axis is found to dominate the swimming dynamics of the colloidal particle pair. Simulation results and analytical arguments demonstrate that this swimming strategy compares favorably to dragging the particles with an external magnetic force when colloidal particle sizes are reduced.

Apparatus for electrohydrodynamically assembling patterned colloidal structures

NASA Technical Reports Server (NTRS)

Trau, Mathias (Inventor); Aksay, Ilhan A. (Inventor); Saville, Dudley A. (Inventor)

2000-01-01

A method apparatus is provided for electrophoretically depositing particles onto an electrode, and electrohydrodynamically assembling the particles into crystalline structures. Specifically, the present method and apparatus creates a current flowing through a solution to cause identically charged electrophoretically deposited colloidal particles to attract each other over very large distances (<5 particle diameters) on the surface of electrodes to form two-dimensional colloidal crystals. The attractive force can be created with both DC and AC fields and can modulated by adjusting either the field strength or frequency of the current. Modulating this lateral attraction between the particles causes the reversible formation of two-dimensional fluid and crystalline colloidal states on the electrode surface. Further manipulation allows for the formation of two or three-dimensional colloidal crystals, as well as more complex designed structures. Once the required structures are formed, these three-dimension colloidal crystals can be permanently frozen or glued by controlled coagulation induced by to the applied field to form a stable crystalline structure.

Multiple electrokinetic actuators for feedback control of colloidal crystal size.

PubMed

Juárez, Jaime J; Mathai, Pramod P; Liddle, J Alexander; Bevan, Michael A

2012-10-21

We report a feedback control method to precisely target the number of colloidal particles in quasi-2D ensembles and their subsequent assembly into crystals in a quadrupole electrode. Our approach relies on tracking the number of particles within a quadrupole electrode, which is used in a real-time feedback control algorithm to dynamically actuate competing electrokinetic transport mechanisms. Particles are removed from the quadrupole using DC-field mediated electrophoretic-electroosmotic transport, while high-frequency AC-field mediated dielectrophoretic transport is used to concentrate and assemble colloidal crystals. Our results show successful control of the size of crystals containing 20 to 250 colloidal particles with less than 10% error. Assembled crystals are characterized by their radius of gyration, crystallinity, and number of edge particles, and demonstrate the expected size-dependent properties. Our findings demonstrate successful ensemble feedback control of the assembly of different sized colloidal crystals using multiple actuators, which has broad implications for control over nano- and micro- scale assembly processes involving colloidal components.

Method for electrohydrodynamically assembling patterned colloidal structures

NASA Technical Reports Server (NTRS)

Trau, Mathias (Inventor); Aksay, Ilhan A. (Inventor); Saville, Dudley A. (Inventor)

1999-01-01

A method apparatus is provided for electrophoretically depositing particles onto an electrode, and electrohydrodynamically assembling the particles into crystalline structures. Specifically, the present method and apparatus creates a current flowing through a solution to cause identically charged electrophoretically deposited colloidal particles to attract each other over very large distances (<5 particle diameters) on the surface of electrodes to form two-dimensional colloidal crystals. The attractive force can be created with both DC and AC fields and can modulated by adjusting either the field strength or frequency of the current. Modulating this lateral attraction between the particles causes the reversible formation of two-dimensional fluid and crystalline colloidal states on the electrode surface. Further manipulation allows for the formation of two or three-dimensional colloidal crystals, as well as more complex designed structures. Once the required structures are formed, these three-dimension colloidal crystals can be permanently frozen or glued by controlled coagulation induced by to the applied field to form a stable crystalline structure.

Live Imaging of Cellular Internalization of Single Colloidal Particle by Combined Label-Free and Fluorescence Total Internal Reflection Microscopy.

PubMed

Byrne, Gerard D; Vllasaliu, Driton; Falcone, Franco H; Somekh, Michael G; Stolnik, Snjezana

2015-11-02

In this work we utilize the combination of label-free total internal reflection microscopy and total internal reflectance fluorescence (TIRM/TIRF) microscopy to achieve a simultaneous, live imaging of single, label-free colloidal particle endocytosis by individual cells. The TIRM arm of the microscope enables label free imaging of the colloid and cell membrane features, while the TIRF arm images the dynamics of fluorescent-labeled clathrin (protein involved in endocytosis via clathrin pathway), expressed in transfected 3T3 fibroblasts cells. Using a model polymeric colloid and cells with a fluorescently tagged clathrin endocytosis pathway, we demonstrate that wide field TIRM/TIRF coimaging enables live visualization of the process of colloidal particle interaction with the labeled cell structure, which is valuable for discerning the membrane events and route of colloid internalization by the cell. We further show that 500 nm in diameter model polystyrene colloid associates with clathrin, prior to and during its cellular internalization. This association is not apparent with larger, 1 μm in diameter colloids, indicating an upper particle size limit for clathrin-mediated endocytosis.

Controlling the scattering properties of thin, particle-doped coatings

NASA Astrophysics Data System (ADS)

Rogers, William; Corbett, Madeleine; Manoharan, Vinothan

2013-03-01

Coatings and thin films of small particles suspended in a matrix possess optical properties that are important in several industries from cosmetics and paints to polymer composites. Many of the most interesting applications require coatings that produce several bulk effects simultaneously, but it is often difficult to rationally formulate materials with these desired optical properties. Here, we focus on the specific challenge of designing a thin colloidal film that maximizes both diffuse and total hemispherical transmission. We demonstrate that these bulk optical properties follow a simple scaling with two microscopic length scales: the scattering and transport mean free paths. Using these length scales and Mie scattering calculations, we generate basic design rules that relate scattering at the single particle level to the film's bulk optical properties. These ideas will be useful in the rational design of future optically active coatings.

Measurement of correlations between low-frequency vibrational modes and particle rearrangements in quasi-two-dimensional colloidal glasses.

PubMed

Chen, Ke; Manning, M L; Yunker, Peter J; Ellenbroek, Wouter G; Zhang, Zexin; Liu, Andrea J; Yodh, A G

2011-09-02

We investigate correlations between low-frequency vibrational modes and rearrangements in two-dimensional colloidal glasses composed of thermosensitive microgel particles, which readily permit variation of the sample packing fraction. At each packing fraction, the particle displacement covariance matrix is measured and used to extract the vibrational spectrum of the "shadow" colloidal glass (i.e., the particle network with the same geometry and interactions as the sample colloid but absent damping). Rearrangements are induced by successive, small reductions in the packing fraction. The experimental results suggest that low-frequency quasilocalized phonon modes in colloidal glasses, i.e., modes that present low energy barriers for system rearrangements, are spatially correlated with rearrangements in this thermal system.

Collection and analysis of colloidal particles transported in the Mississippi River, U.S.A.

USGS Publications Warehouse

Rees, T.F.; Ranville, J.F.

1990-01-01

Sediment transport has long been recognized as an important mechanism for the transport of contaminants in surface waters. Suspended sediment has traditionally been divided into three size classes: sand-sized (>63 ??m), silt-sized ( 63 ??m), silt-sized (< 63 ??m but settleable) and clay-sized (non-settleable). The first two classes are easily collected and characterized using screens (sand) and settling (silt). The clay-sized particles, more properly called colloids, are more difficult to collect and characterize, and until recently received little attention. From the hydrologic perspective, a colloid is a particle, droplet, or gas bubble with at least one dimension between 0.001 and 1 ??m. Because of their small size, colloids have large specific surface areas and high surface free energies which may facilitate sorption of hydrophobic materials. Understanding what types of colloids are present in a system, how contaminants of interest interact with these colloids, and what parameters control the transport of colloids in natural systems is critical if the relative importance of colloid-mediated transport is to be understood. This paper describes the collection, concentration and characterization of colloidal materials in the Mississippi River. Colloid concentrations, particle-size distributions, mineral composition and electrophoretic mobilities were determined. Techniques used are illustrated with samples collected at St. Louis, Missouri, U.S.A.

The development and characterization of stimuli-responsive systems for performance materials

NASA Astrophysics Data System (ADS)

Gordon, Melissa B.

In nature, living organisms adjust to their surroundings by responding to environmental cues, such as light, temperature or force. Stimuli-triggered processes, such as the contraction of eyes in response to bright light or wound healing in skin after a cut, motivate the design of "smart" materials which are designed to respond to environmental stimuli. Responsive materials are used as self-healing materials, shape memory polymers and responsive coatings; moreover, responsive materials may also be employed as model systems, which enhance understanding of complex behavior. The overall goal of this work is to design a material that offers self-healing functionality, which will allow for self-repair following material fatigue or failure, and increased strength in response to ballistic or puncture threats through the incorporation of colloidal particles. The target application for this material is as a protective barrier in extreme environments, such as outer space. Towards this end, the dissertation is focused on the development and characterization of each component of the protective material by (1) designing and testing novel light- and force-sensitive polymers for self-healing applications and (2) examining and characterizing long-time behavior (i.e., aging) in model thermoreversible colloidal gels and glasses. Towards the development of novel stimuli-responsive materials, a photo-responsive polymer network is developed in which a dynamic bond is incorporated into the network architecture to enable a light-triggered, secondary polymerization, which increases the modulus by two orders of magnitude while strengthening the network by over 100%. Unlike traditional two-stage polymerization systems, in which the secondary polymerization is triggered by a leachable photoinitiator, the dynamic nature is imparted by the material itself via the dissociation of its own crosslinks to become stronger in response to light. Several attributes of the photo-responsive network are shown including: (1) photo-induced healing and strengthening of a specimen after it has been severed, (2) photopatterning for effecting spatially confined property changes on demand, and (3) locking in the film's 3D geometry using light after reshaping. The utility of the photo-responsive dynamic bond is enhanced by demonstrating that it is also responsive to mechanical force. Force-responsive materials are activated by the energy from the damage event itself, thereby enabling healing without human intervention. Specifically, selective cleavage of a polymer containing a dynamic trithiocarbonate group initiates a force-driven radical polymerization, thus enabling the material to constructively respond to force via gelation on an experimentally relevant timescale. To enhance the stress response of the self-healing materials described above, a protective material composed of colloidal particles is proposed. Toward this goal, the second half of this dissertation investigates the microstructural basis of rheological aging in colloidal gels and glasses using a model thermoreversible colloidal dispersion. In this work, rheological aging is quantitatively related to microstructural aging in glasses and gels by simultaneously measuring the bulk properties and sample microstructure using rheometry and small angle neutron scattering (Rheo-SANS), respectively. A one-to-one correspondence between the evolution in storage modulus and microstructure as the sample ages is observed, which is investigated as a function of thermal and shear history. The microstructural measurements are consistent with the hypothesis of aging as a trajectory in a free energy landscape, which combined with analysis with mode coupling theory, support local particle rearrangements as the mechanism of aging. Moreover, by using a system that is fully rejuvenated by thermal cycling, the effectiveness of shear as a rejuvenation method is investigated by directly comparing microstructure and bulk properties following thermal and mechanical rejuvenation. The conclusions of this study may be industrially relevant to products that age on commercial timescales, such as pharmaceuticals, applicable to other dynamically arrested systems, such as metallic glasses, and provide pathways to advanced composite materials such as those envisioned in this work.

Shear-induced clustering of Brownian colloids in associative polymer networks at moderate Péclet number

NASA Astrophysics Data System (ADS)

Kim, Juntae; Helgeson, Matthew E.

2016-08-01

We investigate shear-induced clustering and its impact on fluid rheology in polymer-colloid mixtures at moderate colloid volume fraction. By employing a thermoresponsive system that forms associative polymer-colloid networks, we present experiments of rheology and flow-induced microstructure on colloid-polymer mixtures in which the relative magnitudes of the time scales associated with relaxation of viscoelasticity and suspension microstructure are widely and controllably varied. In doing so, we explore several limits of relative magnitude of the relevant dimensionless shear rates, the Weissenberg number Wi and the Péclet number Pe. In all of these limits, we find that the fluid exhibits two distinct regimes of shear thinning at relatively low and high shear rates, in which the rheology collapses by scaling with Wi and Pe, respectively. Using three-dimensionally-resolved flow small-angle neutron scattering measurements, we observe clustering of the suspension above a critical shear rate corresponding to Pe ˜0.1 over a wide range of fluid conditions, having anisotropy with projected orientation along both the vorticity and compressional axes of shear. The degree of anisotropy is shown to scale with Pe. From this we formulate an empirical model for the shear stress and viscosity, in which the viscoelastic network stress is augmented by an asymptotic shear thickening contribution due to hydrodynamic clustering. Overall, our results elucidate the significant role of hydrodynamic interactions in contributing to shear-induced clustering of Brownian suspensions in viscoelastic liquids.

Charactrisation of particle assemblies by 3D cross correlation light scattering and diffusing wave spectroscopy

NASA Astrophysics Data System (ADS)

Scheffold, Frank

2014-08-01

To characterize the structural and dynamic properties of soft materials and small particles, information on the relevant mesoscopic length scales is required. Such information is often obtained from traditional static and dynamic light scattering (SLS/DLS) experiments in the single scattering regime. In many dense systems, however, these powerful techniques frequently fail due to strong multiple scattering of light. Here I will discuss some experimental innovations that have emerged over the last decade. New methods such as 3D static and dynamic light scattering (3D LS) as well as diffusing wave spectroscopy (DWS) can cover a much extended range of experimental parameters ranging from dilute polymer solutions, colloidal suspensions to extremely opaque viscoelastic emulsions.

Direct numerical simulations of agglomeration of circular colloidal particles in two-dimensional shear flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Young Joon, E-mail: yjchoi@uvic.ca; Djilali, Ned, E-mail: ndjilali@uvic.ca

2016-01-15

Colloidal agglomeration of nanoparticles in shear flow is investigated by solving the fluid-particle and particle-particle interactions in a 2D system. We use an extended finite element method in which the dynamics of the particles is solved in a fully coupled manner with the flow, allowing an accurate description of the fluid-particle interfaces without the need of boundary-fitted meshes or of empirical correlations to account for the hydrodynamic interactions between the particles. Adaptive local mesh refinement using a grid deformation method is incorporated with the fluid-structure interaction algorithm, and the particle-particle interaction at the microscopic level is modeled using the Lennard-Jonesmore » potential. Motivated by the process used in fabricating fuel cell catalysts from a colloidal ink, the model is applied to investigate agglomeration of colloidal particles under external shear flow in a sliding bi-periodic Lees-Edwards frame with varying shear rates and particle fraction ratios. Both external shear and particle fraction are found to have a crucial impact on the structure formation of colloidal particles in a suspension. Segregation intensity and graph theory are used to analyze the underlying agglomeration patterns and structures, and three agglomeration regimes are identified.« less

Nonlinear machine learning and design of reconfigurable digital colloids.

PubMed

Long, Andrew W; Phillips, Carolyn L; Jankowksi, Eric; Ferguson, Andrew L

2016-09-14

Digital colloids, a cluster of freely rotating "halo" particles tethered to the surface of a central particle, were recently proposed as ultra-high density memory elements for information storage. Rational design of these digital colloids for memory storage applications requires a quantitative understanding of the thermodynamic and kinetic stability of the configurational states within which information is stored. We apply nonlinear machine learning to Brownian dynamics simulations of these digital colloids to extract the low-dimensional intrinsic manifold governing digital colloid morphology, thermodynamics, and kinetics. By modulating the relative size ratio between halo particles and central particles, we investigate the size-dependent configurational stability and transition kinetics for the 2-state tetrahedral (N = 4) and 30-state octahedral (N = 6) digital colloids. We demonstrate the use of this framework to guide the rational design of a memory storage element to hold a block of text that trades off the competing design criteria of memory addressability and volatility.

EFFECT OF NONCLASSICAL POLARIZATION OF Na+ AND K+ ON THE STABILITY OF SOIL COLLOIDAL PARTICLES IN SUSPENSION

NASA Astrophysics Data System (ADS)

Wu-Quan, Ding; Jia-Hong, He; Lei, Wang; Xin-Min, Liu; Hang, Li

The study of soil colloids is essential because the stability of soil colloidal particles are important processes of interest to researchers in environmental fields. The strong nonclassical polarization of the adsorbed cations (Na+ and K+) decreased the electric field and the electrostatic repulsion between adjacent colloidal particles. The decrease of the absolute values of surface potential was greater for K+ than for Na+. The lower the concentration of Na+ and K+ in soil colloids, the greater the electrostatic repulsion between adjacent colloidal particles. The net pressure and the electrostatic repulsion was greater for Na+ than for K+ at the same ion concentration. For K+ and Na+ concentrations higher than 50mmol L-1 or 100 mmol L-1, there was a net negative (or attractive) pressure between two adjacent soil particles. The increasing total average aggregation (TAA) rate of soil colloids with increasing Na+ and K+ concentrations exhibited two stages: the growth rates of TAA increased rapidly at first and then increased slowly and eventually almost negligibly. The critical coagulation concentrations of soil colloids in Na+ and K+ were 91.6mmol L-1 and 47.8mmol L-1, respectively, and these were similar to the concentrations at the net negative pressure.

Coffee-rings and glasses: Colloids out of equilibrium

NASA Astrophysics Data System (ADS)

Yunker, Peter Joseph

This thesis describes experiments that utilize colloids to explore nonequilibrium phenomena. Specifically, the deposition of particles during evaporation and the glass transition are explored. In the first set of experiments, we found that particle shape has a profound effect on particle deposition. We evaporated drops of colloidal suspensions containing micron-sized particles that range in shape from isotropic spheres to very anisotropic ellipsoids. For sessile drops, i.e., drops sitting on a solid surface, spheres are deposited in a ring-like stain, while ellipsoids are deposited uniformly. We also confined drops between glass plates and allowed them to evaporate. During evaporation, colloidal particles coat the air-water interface, forming colloidal monolayer membranes (CMMs). As particle anisotropy increases, CMM bending rigidity was found to increase. This increase in bending rigidity provides a new mechanism that produces a uniform deposition of ellipsoids and a heterogeneous deposition of spheres. In the second set of experiments, we employed colloidal suspensions to investigate the character of glassy materials. "Anisotropic glasses'' were investigated with ellipsoidal particles confined to two-dimensional chambers at high packing fractions; this system enabled the study of the effects of particle shape on the vibrational properties of colloidal glasses. Low frequency modes in glasses composed of slightly anisotropic particles are found to have predominantly rotational character. Conversely, low frequency modes in glasses of highly anisotropic particles exhibit a mix of rotational and translational character. Aging effects in glasses were explored using suspensions of temperature-sensitive microgel spheres. We devised a method to rapidly quench from liquid to glass states, and then observed the resultant colloidal glasses as they aged. Particle rearrangements in glasses occur collectively, i.e., many particles move in a correlated manner. During aging, we observed that the size of these collective rearrangements increases. Thus, the slowing dynamics of aging appear governed by growing correlated domains of particles required for relaxation. Using the same microgel particles, the transformation of a crystal into a glass due to added disorder was investigated by adding smaller particles into a quasi-two-dimensional colloidal crystal. The crystal-glass transition bears structural signatures similar to those of the crystal-fluid transition, but also exhibits a sharp change in dynamic heterogeneity which ``turns-on'' abruptly as a function of increasing disorder. Finally, we investigated the influence of morphology and size on the vibrational properties of disordered clusters of colloidal particles. Spectral features of cluster vibrational modes are found to depend strongly on the average number of nearest neighbors but only weakly on the number of particles in each glassy cluster. The scaling of the median phonon frequency with nearest neighbor number is reminiscent of athermal simulations of the jamming transition.

Gold nanostar-polymer hybrids for siRNA delivery: Polymer design towards colloidal stability and in vitro studies on breast cancer cells.

PubMed

Sardo, Carla; Bassi, Barbara; Craparo, Emanuela F; Scialabba, Cinzia; Cabrini, Elisa; Dacarro, Giacomo; D'Agostino, Agnese; Taglietti, Angelo; Giammona, Gaetano; Pallavicini, Piersandro; Cavallaro, Gennara

2017-03-15

To overcome the low bioavailability of siRNA (small interfering RNA) and to improve their transfection efficiency, the use of non-viral delivery carriers is today a feasible approach to transform the discovery of these incredibly potent and versatile drugs into clinical practice. Polymer-modified gold nanoconstructs (AuNCs) are currently viewed as efficient and safe intracellular delivery carriers for siRNA, as they have the possibility to conjugate the ability to stably entrap and deliver siRNAs inside cells with the advantages of gold nanoparticles, which can act as theranostic agents and radiotherapy enhancers through laser-induced hyperthermia. In this study, AuNCs were prepared by coating Gold Nano Stars (GNS) with suitable functionalised polymers, to give new insight on the choice of the coating in order to obtain colloidal stability, satisfying in vitro transfection behaviour and reliability in terms of homogeneous results upon GNS type changing. For this goal, GNS synthesized with three different sizes and shapes were coated with two different polymers: i) α-mercapto-ω-amino polyethylene glycol 3000Da (SH-PEG 3000 -NH 2 ), a hydrophilic linear polymer; ii) PHEA-PEG 2000 -EDA-LA (PPE-LA), an amphiphilic hydroxyethylaspartamide copolymer containing a PEG moiety. Both polymers contain SH or SS groups for anchoring on gold surface and NH 2 groups, which can be protonated in order to obtain a positive surface for successive siRNA layering. The effect of the features of the coating polymers on siRNA layering, and the extent of intracellular uptake and luciferase gene silencing effect were evaluated for each of the obtained coated GNS. The results highlight that amphiphilic biocompatible polymers with multi-grafting function are more suitable for ensuring the colloidal stability and the effectiveness of these colloidal systems, compared to the coating with linear PEG. Copyright © 2017 Elsevier B.V. All rights reserved.

Rigorous theoretical framework for particle sizing in turbid colloids using light refraction.

PubMed

García-Valenzuela, Augusto; Barrera, Rubén G; Gutierrez-Reyes, Edahí

2008-11-24

Using a non-local effective-medium approach, we analyze the refraction of light in a colloidal medium. We discuss the theoretical grounds and all the necessary precautions to design and perform experiments to measure the effective refractive index in dilute colloids. As an application, we show that it is possible to retrieve the size of small dielectric particles in a colloid by measuring the complex effective refractive index and the volume fraction occupied by the particles.

Characterization, origin and aggregation behavior of colloids in eutrophic shallow lake.

PubMed

Xu, Huacheng; Xu, Mengwen; Li, Yani; Liu, Xin; Guo, Laodong; Jiang, Helong

2018-05-31

Stability of colloidal particles contributes to the turbidity in the water column, which significantly influences water quality and ecological functions in aquatic environments especially shallow lakes. Here we report characterization, origin and aggregation behavior of aquatic colloids, including natural colloidal particles (NCPs) and total inorganic colloidal particles (TICPs), in a highly turbid shallow lake, via field observations, simulation experiments, ultrafiltration, spectral and microscopic, and light scattering techniques. The colloidal particles were characterized with various shapes (spherical, polygonal and elliptical) and aluminum-, silicon-, and ferric-containing mineralogical structures, with a size range of 20-200 nm. The process of sediment re-suspension under environmentally relevant conditions contributed 78-80% of TICPs and 54-55% of NCPs in Lake Taihu, representing an important source of colloids in the water column. Both mono- and divalent electrolytes enhanced colloidal aggregation, while a reverse trend was observed in the presence of natural organic matter (NOM). The influence of NOM on colloidal stability was highly related to molecular weight (MW) properties with the high MW fraction exhibiting higher stability efficiency than the low MW counterparts. However, the MW-dependent aggregation behavior for NCPs was less significant than that for TICPs, implying that previous results on colloidal behavior using model inorganic colloids alone should be reevaluated. Further studies are needed to better understand the mobility/stability and transformation of aquatic colloids and their role in governing the fate and transport of pollutants in natural waters. Copyright © 2018. Published by Elsevier Ltd.

A paradigm for peptide vaccine delivery using viral epitopes encapsulated in degradable polymer hydrogel capsules.

PubMed

Chong, Siow-Feng; Sexton, Amy; De Rose, Robert; Kent, Stephen J; Zelikin, Alexander N; Caruso, Frank

2009-10-01

We report on the use of degradable polymer capsules as carriers for the delivery of oligopeptide antigens to professional antigen presenting cells (APCs). To achieve encapsulation, oligopeptide sequences were covalently linked to a negatively charged carrier polymer via biodegradable linkages and the resulting conjugate was then adsorbed onto amine-functionalized silica particles. These peptide-coated particles were then used as templates for the layer-by-layer (LbL) deposition of thiolated poly(methacrylic acid) (PMA(SH)) and poly(vinylpyrrolidone) (PVPON) multilayers. Removal of the silica core and disruption of the hydrogen bonding between PMA(SH) and PVPON by altering the solution pH yielded disulfide-stabilized PMA capsules that retain the encapsulated cargo in an oxidative environment. In the presence of a natural reducing agent, glutathione, cleavage of the disulfide bonds causes release of the peptide from the capsules. The developed strategy provides control over peptide loading into polymer capsules and yields colloidally stable micron- and submicron-sized carriers with uniform size and peptide loading. The conjugation and encapsulation procedures were proven to be non-degrading to the peptide vaccines. The peptide-loaded capsules were successfully used to deliver their cargo to APCs and activate CD8 T lymphocytes in a non-human primate model of SIV infection ex vivo. The reported approach represents a novel paradigm in the delivery of peptide vaccines and other therapeutic agents.

Supracolloidal Architectures Self-Assembled in Microdroplets.

PubMed

Xu, Xuejiao; Tian, Feng; Liu, Xin; Parker, Richard M; Lan, Yang; Wu, Yuchao; Yu, Ziyi; Scherman, Oren A; Abell, Chris

2015-10-26

We demonstrate a novel method for the formation of a library of structured colloidal assemblies by exploiting the supramolecular heteroternary host-guest interaction between cucurbit[8]uril (CB[8]) and methyl viologen- and naphthalene-functionalised particles. The approach is dependent upon compartmentalisation in microdroplets generated by a microfluidic platform. Though the distribution of colloidal particles encapsulated within each microdroplet followed a Poisson distribution, tuning the concentration of the initial colloidal particle suspensions provided some level of control over the structure of the formed colloidal assemblies. This ability to direct the assembly of complementarily-functionalised colloids through a supramolecular interaction, without the need for complex modification of the colloidal surface or external stimuli, presents an exciting new approach towards the design of structured colloidal materials with the potential to produce many challenging structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioflocculation of mesophilic and thermophilic activated sludge.

PubMed

Vogelaar, J C T; De Keizer, A; Spijker, S; Lettinga, G

2005-01-01

Thermophilic activated sludge treatment is often hampered by a turbid effluent. Reasons for this phenomenon are so far unknown. Here, the hypothesis of the temperature dependency of the hydrophobic interaction as a possible cause for diminished thermophilic activated sludge bioflocculation was tested. Adsorption of wastewater colloidal particles was monitored on different flat surfaces as a function of temperature. Adsorption on a hydrophobic surface varied with temperature between 20 and 60 degrees C and no upward or downward trend could be observed. This makes the hydrophobic interaction hypothesis unlikely in explaining the differences in mesophilic and thermophilic activated sludge bioflocculation. Both mesophilic and thermophilic biomass did not flocculate with wastewater colloidal particles under anaerobic conditions. Only in the presence of oxygen, with biologically active bacteria, the differences in bioflocculation behavior became evident. Bioflocculation was shown only to occur with the combination of wastewater and viable mesophilic biomass at 30 degrees C, in the presence of oxygen. Bioflocculation did not occur in case the biomass was inactivated or when oxygen was absent. Thermophilic activated sludge hardly showed any bioflocculation, also under mesophilic conditions. Despite the differences in bioflocculation behavior, sludge hydrophobicity and sludge zetapotentials were almost similar. Theoretical calculations using the DLVO (Derjaguin, Landau, Verweij and Overbeek) theory showed that flocculation is unlikely in all cases due to long-range electrostatic forces. These calculations, combined with the fact that bioflocculation actually did occur at 30 degrees C and the unlikelyness of the hydrophobic interaction, point in the direction of bacterial exo-polymers governing bridging flocculation. Polymer interactions are not included in the DLVO theory and may vary as a function of temperature.

The effect of nanoparticle degradation on amphiphilic polymer-coated quantum dot toxicity: the importance of particle functionality assessment in toxicology [corrected].

PubMed

Soenen, Stefaan J; Montenegro, José-Maria; Abdelmonem, Abuelmagd M; Manshian, Bella B; Doak, Shareen H; Parak, Wolfgang J; De Smedt, Stefaan C; Braeckmans, Kevin

2014-02-01

Colloidal semiconductor nanoparticles (quantum dots) have attracted a lot of interest in technological and biomedical research, given their potent fluorescent properties. However, the use of heavy-metal-containing nanoparticles remains an issue of debate. The possible toxic effects of quantum dots remain a hot research topic and several questions such as possible intracellular degradation of quantum dots and the effect thereof on both cell viability and particle functionality remain unresolved. In the present work, amphiphilic polymer [corrected] coated CdSe/ZnS quantum dots were synthesized and characterized, after which their effects on cultured cells were evaluated using a multiparametric setup. The data reveal that the quantum dots are taken up through endocytosis and when exposed to the low pH of the endosomal structures, they partially degrade and release cadmium ions, which lowers their fluorescence intensity and augments particle toxicity. Using the multiparametric method, the quantum dots were evaluated at non-toxic doses in terms of their ability to visualize labeled cells for longer time periods. The data revealed that comparing different particles in terms of their applied dose is challenging, likely due to difficulties in obtaining accurate nanoparticle concentrations, but evaluating particle toxicity in terms of their biological functionality enables an easy and straightforward comparison. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Cementation of colloidal particles on electrodes in a galvanic microreactor.

PubMed

Jan, Linda; Punckt, Christian; Aksay, Ilhan A

2013-07-10

We have studied the processes leading to the cementation of colloidal particles during their autonomous assembly on corroding copper electrodes within a Cu-Au galvanic microreactor. We determined the onset of particle immobilization through particle tracking, monitored the dissolution of copper as well as the deposition of insoluble products of the corrosion reactions in situ, and showed that particle immobilization initiated after reaction products (RPs) began to deposit on the electrode substrate. We further demonstrated that the time and the extent of RP precipitation and thus the strength of the particle-substrate bond could be tuned by varying the amount of copper in the system and the microreactor pH. The ability to cement colloidal particles at locations undergoing corrosion illustrates that the studied colloidal assembly approach holds potential for applications in dynamic material property adaptation.

Plasmonic nanodiamonds: targeted core-shell type nanoparticles for cancer cell thermoablation.

PubMed

Rehor, Ivan; Lee, Karin L; Chen, Kevin; Hajek, Miroslav; Havlik, Jan; Lokajova, Jana; Masat, Milan; Slegerova, Jitka; Shukla, Sourabh; Heidari, Hamed; Bals, Sara; Steinmetz, Nicole F; Cigler, Petr

2015-02-18

Targeted biocompatible nanostructures with controlled plasmonic and morphological parameters are promising materials for cancer treatment based on selective thermal ablation of cells. Here, core-shell plasmonic nanodiamonds consisting of a silica-encapsulated diamond nanocrystal coated in a gold shell are designed and synthesized. The architecture of particles is analyzed and confirmed in detail using electron tomography. The particles are biocompatibilized using a PEG polymer terminated with bioorthogonally reactive alkyne groups. Azide-modified transferrin is attached to these particles, and their high colloidal stability and successful targeting to cancer cells overexpressing the transferrin receptor are demonstrated. The particles are nontoxic to the cells and they are readily internalized upon binding to the transferrin receptor. The high plasmonic cross section of the particles in the near-infrared region is utilized to quantitatively ablate the cancer cells with a short, one-minute irradiation by a pulse 750-nm laser. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental Studies of the Brownian Diffusion of Boomerang Colloidal Particle in a Confined Geometry

NASA Astrophysics Data System (ADS)

Chakrabarty, Ayan; Wang, Feng; Joshi, Bhuwan; Wei, Qi-Huo

2011-03-01

Recent studies shows that the boomerang shaped molecules can form various kinds of liquid crystalline phases. One debated topic related to boomerang molecules is the existence of biaxial nematic liquid crystalline phase. Developing and optical microscopic studies of colloidal systems of boomerang particles would allow us to gain better understanding of orientation ordering and dynamics at ``single molecule'' level. Here we report the fabrication and experimental studies of the Brownian motion of individual boomerang colloidal particles confined between two glass plates. We used dark-field optical microscopy to directly visualize the Brownian motion of the single colloidal particles in a quasi two dimensional geometry. An EMCCD was used to capture the motion in real time. An indigenously developed imaging processing algorithm based on MatLab program was used to precisely track the position and orientation of the particles with sub-pixel accuracy. The experimental finding of the Brownian diffusion of a single boomerang colloidal particle will be discussed.

Poly(vinyl alcohol) stabilization of acrylic emulsion polymers using the miniemulsion approach

NASA Astrophysics Data System (ADS)

Kim, Noma

Miniemulsion approach was employed to obtain stable acrylic latexes of n-butyl acrylate and methyl methacrylate (50/50 wt%) stabilized with poly(vinyl alcohol) (PVA) and to enhance the grafting reaction between PVA and acrylic monomers at the water/droplet interface. The stability of miniemulsions were studied in terms of the type and concentration of' the stabilizer, and the PVA partitioning were determined as a function of the PVA concentration. Using the comparison of PVA partitioning at droplet surface and grafted PVA as a function of concentration, it was suggested that the water/monomer interface is the main grafting site in the miniemulsion polymerization. Seeded emulsion and miniemulsion copolymerizations initiated with water-soluble (hydrogen peroxide, HPO), partially water-soluble (t-butyl peroxide, TBHP), and oil-soluble (t-butyl peroxyoctoate, TBPO) initiators were carried out to further investigate the oil/water interface as the grafting site for PVA. The interaction between the capillary wall in the CHDF (capillary hydrodynamic fractionation) chromatographic particle sizer and the water-soluble polymers adsorbed on the particle surface was studied using different types of water-soluble polymers and eluants. Different grafting architectures depending on the initiation site were suggested based on the CHDF results. The amounts of grafted PVA produced in miniemulsion polymers initiated with TBHP and TBPO were substantially less than those in the corresponding seeded emulsion polymerizations. The effect on the internal viscosity at the interface was proposed to explain the difference in grafting in terms of polymerization methods. Aqueous phase and interface grafting were studied using the measurement of the degree of hydrolysis (DH) of the serum PVA and adsorbed PVA after miniemulsion polymerizations. Based on the results, it was found that aqueous phase and interface grafting occurred in the HPO system; however, interface grafting dominated the TBHP system. Colloidal instability in conventional emulsion polymerizations was investigated and compared with the corresponding miniemulsion polymerization. It was found that the grafted PVA in conventional emulsion polymerizations was more hydrophobic presumably due to a greater amount of grafted chains than that in similar miniemulsion polymerizations and this could be correlated with the colloidal instability during conventional emulsion polymerizations.

Achiral symmetry breaking and positive Gaussian modulus lead to scalloped colloidal membranes

PubMed Central

Gibaud, Thomas; Kaplan, C. Nadir; Sharma, Prerna; Zakhary, Mark J.; Ward, Andrew; Oldenbourg, Rudolf; Meyer, Robert B.; Kamien, Randall D.; Powers, Thomas R.; Dogic, Zvonimir

2017-01-01

In the presence of a nonadsorbing polymer, monodisperse rod-like particles assemble into colloidal membranes, which are one-rod-length–thick liquid-like monolayers of aligned rods. Unlike 3D edgeless bilayer vesicles, colloidal monolayer membranes form open structures with an exposed edge, thus presenting an opportunity to study elasticity of fluid sheets. Membranes assembled from single-component chiral rods form flat disks with uniform edge twist. In comparison, membranes composed of a mixture of rods with opposite chiralities can have the edge twist of either handedness. In this limit, disk-shaped membranes become unstable, instead forming structures with scalloped edges, where two adjacent lobes with opposite handedness are separated by a cusp-shaped point defect. Such membranes adopt a 3D configuration, with cusp defects alternatively located above and below the membrane plane. In the achiral regime, the cusp defects have repulsive interactions, but away from this limit we measure effective long-ranged attractive binding. A phenomenological model shows that the increase in the edge energy of scalloped membranes is compensated by concomitant decrease in the deformation energy due to Gaussian curvature associated with scalloped edges, demonstrating that colloidal membranes have positive Gaussian modulus. A simple excluded volume argument predicts the sign and magnitude of the Gaussian curvature modulus that is in agreement with experimental measurements. Our results provide insight into how the interplay between membrane elasticity, geometrical frustration, and achiral symmetry breaking can be used to fold colloidal membranes into 3D shapes. PMID:28411214

Silver distribution and release from an antimicrobial denture base resin containing silver colloidal nanoparticles.

PubMed

Monteiro, Douglas Roberto; Gorup, Luiz Fernando; Takamiya, Aline Satie; de Camargo, Emerson Rodrigues; Filho, Adhemar Colla Ruvolo; Barbosa, Debora Barros

2012-01-01

The aim of this study was to evaluate a denture base resin containing silver colloidal nanoparticles through morphological analysis to check the distribution and dispersion of these particles in the polymer and by testing the silver release in deionized water at different time periods. A Lucitone 550 denture resin was used, and silver nanoparticles were synthesized by reduction of silver nitrate with sodium citrate. The acrylic resin was prepared in accordance with the manufacturers' instructions, and silver nanoparticle suspension was added to the acrylic resin monomer in different concentrations (0.05, 0.5, and 5 vol% silver colloidal). Controls devoid of silver nanoparticles were included. The specimens were stored in deionized water at 37°C for 7, 15, 30, 60, and 120 days, and each solution was analyzed using atomic absorption spectroscopy. Silver was not detected in deionized water regardless of the silver nanoparticles added to the resin and of the storage period. Micrographs showed that with lower concentrations, the distribution of silver nanoparticles was reduced, whereas their dispersion was improved in the polymer. Moreover, after 120 days of storage, nanoparticles were mainly located on the surface of the nanocomposite specimens. Incorporation of silver nanoparticles in the acrylic resin was evidenced. Moreover, silver was not detected by the detection limit of the atomic absorption spectrophotometer used in this study, even after 120 days of storage in deionized water. Silver nanoparticles are incorporated in the PMMA denture resin to attain an effective antimicrobial material to help control common infections involving oral mucosal tissues in complete denture wearers. © 2011 by the American College of Prosthodontists.

Key-lock colloids in a nematic liquid crystal.

PubMed

Silvestre, Nuno M; Tasinkevych, M

2017-01-01

The Landau-de Gennes free energy is used to study theoretically the effective interaction of spherical "key" and anisotropic "lock" colloidal particles. We assume identical anchoring properties of the surfaces of the key and of the lock particles, and we consider planar degenerate and perpendicular anchoring conditions separately. The lock particle is modeled as a spherical particle with a spherical dimple. When such a particle is introduced into a nematic liquid crystal, it orients its dimple at an oblique angle θ_{eq} with respect to the far field director n_{∞}. This angle depends on the depth of the dimple. Minimization results show that the free energy of a pair of key and lock particles exhibits a global minimum for the configuration when the key particle is facing the dimple of the lock colloidal particle. The preferred orientation ϕ_{eq} of the key-lock composite doublet relative to n_{∞} is robust against thermal fluctuations. The preferred orientation θ_{eq}^{(2)} of the dimple particle in the doublet is different from the isolated situation. This is related to the "direct" interaction of defects accompanying the key particle with the edge of the dimple. We propose that this nematic-amplified key-lock interaction can play an important role in self-organization and clustering of mixtures of colloidal particles with dimple colloids present.

Sedimentation of iron deposits in Nagahama Bay, Satsuma Iwo-jima Island:Precipitation behavior of colloidal particle

NASA Astrophysics Data System (ADS)

Harada, T.; Kiyokawa, S.; Ikehara, M.

2016-12-01

Satsuma Iwo-Jima Island, with volcanic activities, is located about 40km south of Kyushu Island, Japan. This island is one of the best places to observe a shallow water hydrothermal system. Nagahama Bay, in the south of Satsuma Iwo-Jima Island, is partly separated from open sea. The seawater appears dark reddish brown color due to colloidal iron hydroxide by the mixing of volcanic fluids (pH=5.5, 50-60 degree Celsius) and oceanic water (Ninomiya & kiyokawa, 2009; Kiyokawa et al., 2012; Ueshiba & kiyokawa, 2012). Very high deposition rate (33 cm per year) of iron-rich sediments was observed in the bay (Kiyokawa et al., 2012). However, precipitation behavior of colloidal iron hydroxide has not been clarified. In this study, I report the results of analysis of deposition experiments of the colloidal particles at the Nagahama bay. Since the size of the colloidal particles is 1nm 1μm, single particle cannot be precipitated. This arise from precipitation of the particles in the viscous fluid is according to the Stokes' law. Colloidal iron hydroxide has the property of having the electric charges on the surface. The charge on the colloids is affected by pH of its surrounding seawater and can become more positively or negatively charged due to the gain or loss, respectively, of protons (H+) in the seawater. This property affects the stability of the colloidal dispersion. FE-SEM observation shows that the suspended particles consist of colloidal iron hydroxide (about 0.2μm), on the other hand, the iron-rich sediments are composed of bigger one (>1 μm). This indicates the colloidal iron hydroxide is precipitated by flocculation. We examined the precipitation amount of colloidal iron hydroxide under the various pH environments. The precipitation amount of pH=7.8 seawater 10% higher than that of pH=7.2. This result is roughly follows the theoretical value.

Utilizing stretch-tunable thermochromic elastomeric opal films as novel reversible switchable photonic materials.

PubMed

Schäfer, Christian G; Lederle, Christina; Zentel, Kristina; Stühn, Bernd; Gallei, Markus

2014-11-01

In this work, the preparation of highly thermoresponsive and fully reversible stretch-tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate-co-ethyl acrylate) (PDEGMEMA-co-PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt-shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano- and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV-induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross-linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA-containing colloidal architectures, application of the melt-shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli-responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rheological Properties of Aqueous Colloidal Silica Suspensions Related to Amendment Delivery for Subsurface Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Shuo; Zhong, Lirong; Li, Guanghe

Colloidal silica (fumed silica) suspensions are being tested as carriers for remedial amendment delivery in subsurface remediation and as media for underground contamination containment. The knowledge of the rheological behavior of the silica suspensions is lack in the literature while it is essential for the preparation and field injection of the suspensions. This contribution is focused on the rheological characteristics of colloidal silica suspensions under various environmental conditions relevant to amendment delivery for subsurface remediation. We investigated the influence of silica particle concentration, water source, ionic strength, pH, aging, amendment type and concentration, and subsurface sediment on the rheological behaviormore » of the suspensions. All tested suspension formulations exhibited shear thinning before gelation. Higher silica particle concentration and salinity (Na+ and K+) increased suspensions’ viscosity and the degree of shear thinning. The viscosity of suspensions increased with aging. The suspensions at natural pH exhibited the highest viscosity compared to the acidic and alkaline suspensions with the same silica concentration. Addition of KMnO4 amendment to aqueous silica suspensions increased viscosity, while addition of alcohol amendment decreased suspensions’ viscosity. The presence of amendment did not reduce shear thinning. The gelation rate of silica suspensions was increased with silica concentration and with the addition of sediments. The rheological characteristics of shear thinning aqueous fumed silica suspensions were compared to that of shear thinning solutions formed with organic polymer xanthan gum, which was applied for amendment delivery in subsurface remediation.« less

Dynamic properties of polydisperse colloidal particles in the presence of thermal gradient studied by a modified Brownian dynamic model

NASA Astrophysics Data System (ADS)

Song, Dongxing; Jin, Hui; Jing, Dengwei; Wang, Xin

2018-03-01

Aggregation and migration of colloidal particles under the thermal gradient widely exists in nature and many industrial processes. In this study, dynamic properties of polydisperse colloidal particles in the presence of thermal gradient were studied by a modified Brownian dynamic model. Other than the traditional forces on colloidal particles, including Brownian force, hydrodynamic force, and electrostatic force from other particles, the electrostatic force from the asymmetric ionic diffusion layer under a thermal gradient has been considered and introduced into the Brownian dynamic model. The aggregation ratio of particles (R A), the balance time (t B) indicating the time threshold when {{R}A} becomes constant, the porosity ({{P}BA} ), fractal dimension (D f) and distributions of concentration (DISC) and aggregation (DISA) for the aggregated particles were discussed based on this model. The aggregated structures formed by polydisperse particles are less dense and the particles therein are loosely bonded. Also it showed a quite large compressibility as the increases of concentration and interparticle potential can significantly increase the fractal dimension. The thermal gradient can induce two competitive factors leading to a two-stage migration of particles. When t<{{t}B} , the unsynchronized aggregation is dominant and the particles slightly migrate along the thermal gradient. When t>{{t}B} , the thermophoresis becomes dominant thus the migrations of particles are against the thermal gradient. The effect of thermophoresis on the aggregate structures was found to be similar to the effect of increasing particle concentration. This study demonstrates how the thermal gradient affects the aggregation of monodisperse and polydisperse particles and can be a guide for the biomimetics and precise control of colloid system under the thermal gradient. Moreover, our model can be easily extended to other more complex colloidal systems considering shear, temperature fluctuation, surfactant, etc.

Laboratory investigation of the factors impact on bubble size, pore blocking and enhanced oil recovery with aqueous Colloidal Gas Aphron.

PubMed

Shi, Shenglong; Wang, Yefei; Li, Zhongpeng; Chen, Qingguo; Zhao, Zenghao

Colloidal Gas Aphron as a mobility control in enhanced oil recovery is becoming attractive; it is also designed to block porous media with micro-bubbles. In this paper, the effects of surfactant concentration, polymer concentration, temperature and salinity on the bubble size of the Colloidal Gas Aphron were studied. Effects of injection rates, Colloidal Gas Aphron fluid composition, heterogeneity of reservoir on the resistance to the flow of Colloidal Gas Aphron fluid through porous media were investigated. Effects of Colloidal Gas Aphron fluid composition and temperature on residual oil recovery were also studied. The results showed that bubble growth rate decreased with increasing surfactant concentration, polymer concentration, and decreasing temperature, while it decreased and then increased slightly with increasing salinity. The obvious increase of injection pressure was observed as more Colloidal Gas Aphron fluid was injected, indicating that Colloidal Gas Aphron could block the pore media effectively. The effectiveness of the best blend obtained through homogeneous sandpack flood tests was modestly improved in the heterogeneous sandpack. The tertiary oil recovery increased 26.8 % by Colloidal Gas Aphron fluid as compared to 20.3 % by XG solution when chemical solution of 1 PV was injected into the sandpack. The maximum injected pressure of Colloidal Gas Aphron fluid was about three times that of the XG solution. As the temperature increased, the Colloidal Gas Aphron fluid became less stable; the maximum injection pressure and tertiary oil recovery of Colloidal Gas Aphron fluid decreased.

Autonomous colloidal crystallization in a galvanic microreactor

NASA Astrophysics Data System (ADS)

Punckt, Christian; Jan, Linda; Jiang, Peng; Frewen, Thomas A.; Saville, Dudley A.; Kevrekidis, Ioannis G.; Aksay, Ilhan A.

2012-10-01

We report on a technique that utilizes an array of galvanic microreactors to guide the assembly of two-dimensional colloidal crystals with spatial and orientational order. Our system is comprised of an array of copper and gold electrodes in a coplanar arrangement, immersed in a dilute hydrochloric acid solution in which colloidal micro-spheres of polystyrene and silica are suspended. Under optimized conditions, two-dimensional colloidal crystals form at the anodic copper with patterns and crystal orientation governed by the electrode geometry. After the aggregation process, the colloidal particles are cemented to the substrate by co-deposition of reaction products. As we vary the electrode geometry, the dissolution rate of the copper electrodes is altered. This way, we control the colloidal motion as well as the degree of reaction product formation. We show that particle motion is governed by a combination of electrokinetic effects acting directly on the colloidal particles and bulk electrolyte flow generated at the copper-gold interface.

Preparation of silica-coated poly(styrene-co-4-vinylpyridine) particles and hollow particles.

PubMed

Zou, Hua; Wu, Shishan; Shen, Jian

2008-09-16

This paper presents a novel method for preparation of polymer-silica colloidal nanocomposites based on emulsion polymerization and subsequent sol-gel nanocoating process. The polystyrene latex particles bearing basic groups on their surfaces were successfully synthesized through emulsion polymerization using 4-vinylpyridine (4VP) as a functional comonomer and polyvinylpyrrolidone (PVP) as a surfactant. A series of poly(styrene-co-4-vinylpyridine)/SiO2 nanocomposite particles with smooth or rough core-shell morphology were obtained through the coating process. The poly(styrene-co-4-vinylpyridine) particles could be dissolved subsequently or simultaneously during the sol-gel coating process to form hollow particles. The effects of the amount of 4VP, PVP, NH(4)OH, and tetraethoxysilane (TEOS) on both the nanocomposite particles and hollow particles were investigated. Transmission electron microscopy showed that the morphology of the nanocomposite particles and hollow particles was strongly influenced by the initial feed of the comonomer 4VP and the coupling agent PVP. The conditions to obtain all hollow particles were also studied. Thermogravimetric analysis and energy dispersive X-ray spectroscopy analyses indicated that the interiors of hollow particles were not really "hollow".

Structural Coloration of a Colloidal Amorphous Array is Intensified by Carbon Nanolayers.

PubMed

Takeoka, Yukikazu; Iwata, Masanori; Seki, Takahiro; Nueangnoraj, Khanin; Nishihara, Hirotomo; Yoshioka, Shinya

2018-04-10

In this study, we introduce the possibility of applying a colloidal amorphous array composed of fine silica particles as a structural-color material to invisible information technology. The appearance of a thick filmlike colloidal amorphous array formed from fine silica particles is considerably influenced by incoherent light scattering across the entire visible region. Therefore, regardless of the diameter of the fine silica particles, the thick colloidal amorphous array exhibits a white color to the naked eye. When carbon is uniformly deposited in the colloidal amorphous array by a pressure-pulsed chemical vapor deposition method, incoherent light scattering in the colloidal amorphous array is suppressed. As a result, coherent light scattering due to the short-range order in the colloidal amorphous array becomes conspicuous and the array exhibits a vivid structural color. As structures, such as letters and pictures, can be drawn using this technology, the colloidal amorphous array as a structural-colored material may also be applicable for invisible information technology.

Equivalence of Brownian dynamics and dynamic Monte Carlo simulations in multicomponent colloidal suspensions.

PubMed

Cuetos, Alejandro; Patti, Alessandro

2015-08-01

We propose a simple but powerful theoretical framework to quantitatively compare Brownian dynamics (BD) and dynamic Monte Carlo (DMC) simulations of multicomponent colloidal suspensions. By extending our previous study focusing on monodisperse systems of rodlike colloids, here we generalize the formalism described there to multicomponent colloidal mixtures and validate it by investigating the dynamics in isotropic and liquid crystalline phases containing spherical and rodlike particles. In order to investigate the dynamics of multicomponent colloidal systems by DMC simulations, it is key to determine the elementary time step of each species and establish a unique timescale. This is crucial to consistently study the dynamics of colloidal particles with different geometry. By analyzing the mean-square displacement, the orientation autocorrelation functions, and the self part of the van Hove correlation functions, we show that DMC simulation is a very convenient and reliable technique to describe the stochastic dynamics of any multicomponent colloidal system. Our theoretical formalism can be easily extended to any colloidal system containing size and/or shape polydisperse particles.

Programming Hierarchical Self-Assembly of Patchy Particles into Colloidal Crystals via Colloidal Molecules.

PubMed

Morphew, Daniel; Shaw, James; Avins, Christopher; Chakrabarti, Dwaipayan

2018-03-27

Colloidal self-assembly is a promising bottom-up route to a wide variety of three-dimensional structures, from clusters to crystals. Programming hierarchical self-assembly of colloidal building blocks, which can give rise to structures ordered at multiple levels to rival biological complexity, poses a multiscale design problem. Here we explore a generic design principle that exploits a hierarchy of interaction strengths and employ this design principle in computer simulations to demonstrate the hierarchical self-assembly of triblock patchy colloidal particles into two distinct colloidal crystals. We obtain cubic diamond and body-centered cubic crystals via distinct clusters of uniform size and shape, namely, tetrahedra and octahedra, respectively. Such a conceptual design framework has the potential to reliably encode hierarchical self-assembly of colloidal particles into a high level of sophistication. Moreover, the design framework underpins a bottom-up route to cubic diamond colloidal crystals, which have remained elusive despite being much sought after for their attractive photonic applications.

Solution-processed photodetectors from colloidal silicon nano/micro particle composite.

PubMed

Tu, Chang-Ching; Tang, Liang; Huang, Jiangdong; Voutsas, Apostolos; Lin, Lih Y

2010-10-11

We demonstrate solution-processed photodetectors composed of heavy-metal-free Si nano/micro particle composite. The colloidal Si particles are synthesized by electrochemical etching of Si wafers, followed by ultra-sonication to pulverize the porous surface. With alkyl ligand surface passivation through hydrosilylation reaction, the particles can form a stable colloidal suspension which exhibits bright photoluminescence under ultraviolet excitation and a broadband extinction spectrum due to enhanced scattering from the micro-size particles. The efficiency of the thin film photodetectors has been substantially improved by preventing oxidation of the particles during the etching process.

Colloidal suspensions in external rotating electric field: experimental studies and prospective applications in physics, material science, and biomedicine

NASA Astrophysics Data System (ADS)

Yakovlev, Egor V.; Troshina, Anna V.; Korsakova, Sofia A.; Andronik, Mikhail; Rodionov, Ilya A.; Aliev, Ismail N.; Zaytsev, Kirill I.; Cherkasova, Olga P.; Tuchin, Valery V.; Yurchenko, Stanislav O.

2018-04-01

Colloidal suspensions and tunable self-assembly of colloidal particles attract a great interest in recent years. In this paper, we propose a new setup and technology for studies of self-assembly of colloidal particles, interection of which between themselves is tuned by external rotating electric fields. We reveal wide prospectives of electric field employment for tunable self-assembly, from suspensions of inorganic particles to ensembles of biological cells. These results make enable particle-resolved studies of various collective phenomena and fundamental processes in many-particle systems in equilibrium state and far from it, while the dynamics can be resolved at the level of individual particles using video microscopy. For the first time, we demonstrate that, apart from ability to prepare photonic crystalline films of inorganic silica particles, the tunable self-assembly provides a novel technological way for manipulation with ensembles of biological cells by control of interactions between them.

MOLSIM: A modular molecular simulation software

PubMed Central

Jurij, Reščič

2015-01-01

The modular software MOLSIM for all‐atom molecular and coarse‐grained simulations is presented with focus on the underlying concepts used. The software possesses four unique features: (1) it is an integrated software for molecular dynamic, Monte Carlo, and Brownian dynamics simulations; (2) simulated objects are constructed in a hierarchical fashion representing atoms, rigid molecules and colloids, flexible chains, hierarchical polymers, and cross‐linked networks; (3) long‐range interactions involving charges, dipoles and/or anisotropic dipole polarizabilities are handled either with the standard Ewald sum, the smooth particle mesh Ewald sum, or the reaction‐field technique; (4) statistical uncertainties are provided for all calculated observables. In addition, MOLSIM supports various statistical ensembles, and several types of simulation cells and boundary conditions are available. Intermolecular interactions comprise tabulated pairwise potentials for speed and uniformity and many‐body interactions involve anisotropic polarizabilities. Intramolecular interactions include bond, angle, and crosslink potentials. A very large set of analyses of static and dynamic properties is provided. The capability of MOLSIM can be extended by user‐providing routines controlling, for example, start conditions, intermolecular potentials, and analyses. An extensive set of case studies in the field of soft matter is presented covering colloids, polymers, and crosslinked networks. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:25994597

Size-Dependent Melting Behavior of Colloidal In, Sn, and Bi Nanocrystals

PubMed Central

Liu, Minglu; Wang, Robert Y.

2015-01-01

Colloidal nanocrystals are a technologically important class of nanostructures whose phase change properties have been largely unexplored. Here we report on the melting behavior of In, Sn, and Bi nanocrystals dispersed in a polymer matrix. This polymer matrix prevents the nanocrystals from coalescing with one another and enables previously unaccessed observations on the melting behavior of colloidal nanocrystals. We measure the melting temperature, melting enthalpy, and melting entropy of colloidal nanocrystals with diameters of approximately 10 to 20 nm. All of these properties decrease as nanocrystal size decreases, although the depression rate for melting temperature is comparatively slower than that of melting enthalpy and melting entropy. We also observe an elevated melting temperature during the initial melt-freeze cycle that we attribute to surface stabilization from the organic ligands on the nanocrystal surface. Broad endothermic melting valleys and very large supercoolings in our calorimetry data suggest that colloidal nanocrystals exhibit a significant amount of surface pre-melting and low heterogeneous nucleation probabilities during freezing. PMID:26573146

Colloid particle sizes in the Mississippi River and some of its tributaries, from Minneapolis to below New Orleans

USGS Publications Warehouse

Rostad, C.E.; Rees, T.F.; Daniel, S.R.

1998-01-01

An on-board technique was developed that combined discharge-weighted pumping to a high-speed continuous-flow centrifuge for isolation of the particulate-sized material with ultrafiltration for isolation of colloid-sized material. In order to address whether these processes changed the particle sizes during isolation, samples of particles in suspension were collected at various steps in the isolation process to evaluate changes in particle size. Particle sizes were determined using laser light-scattering photon correlation spectroscopy and indicated no change in size during the colloid isolation process. Mississippi River colloid particle sizes from twelve sites from Minneapolis to below New Orleans were compared with sizes from four tributaries and three seasons, and from predominantly autochthonous sources upstream to more allochthonous sources downstream. ?? 1998 John Wiley Sons, Ltd.

Transient bleaching of small PbS colloids. Influence of surface properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nenadovic, M.T.; Comor, M.I.; Vasic, V.

1990-08-09

Small PbS colloids with a particle diameter of 40 {angstrom} were prepared in aqueous solution, and their absorption spectra exhibit several maxima. Injection of electrons into these particles was achieved by using the pulse radiolysis technique. Excess electrons trapped on the surface lead to a blue shift in the absorption edge of colloids. The appearance of this shift depends critically on the method of colloid preparation. PbS and CdS colloids prepared at pH < 6 have long-lived bleaching, which disappears after several seconds. On the other hand, absorption bleaching does not appear after the addition of hydroxide ions to colloidalmore » solutions (pH > 8). The existence of a hydroxide ion on the particle surface most likely removes surface defects on which electrons are trapped. PbS colloids prepared in the presence of 3-mercapto-1,2-propanediol have an unstructured absorption spectrum, which is due to a wide particle size distribution (10-50 {angstrom}).« less

Synthesis and chromatographic characterization of dextran-coated zirconia high-performance liquid chromatographic stationary phases.

PubMed

Dunlap, C J; Carr, P W

1996-10-11

Porous zirconia particles made by the oil emulsion (OE) method and the polymerization-induced colloid aggregation (PICA) method have been coated with a small, carboxymethylated (approximately 5%) dextran polymer and crosslinked in place. The parameters of the coating process (dextran concentration, adsorption time and crosslinker concentration) have all been examined and an optimum value for each determined. The coated and uncoated materials were characterized by nitrogen sorptometry and size-exclusion chromatography (SEC) using solutes (polystyrenes and dextrans) of well-defined molecular masses. Nitrogen sorptometry results show that the PICA material has a much lower pore volume and smaller pore diameter than do the OE materials. Despite this, the elution volumes of the SEC probes change very little upon polymer coating the PICA material while the OE material shows a very large change upon coating.

Dielectric function of two-phase colloid-polymer nanocomposite.

PubMed

Mitzscherling, S; Cui, Q; Koopman, W; Bargheer, M

2015-11-28

The plasmon resonance of metal nanoparticles determines their optical response in the visible spectral range. Many details such as the electronic properties of gold near the particle surface and the local environment of the particles influence the spectra. We show how the cheap but highly precise fabrication of composite nanolayers by spin-assisted layer-by-layer deposition of polyelectrolytes can be used to investigate the spectral response of gold nanospheres (GNS) and gold nanorods (GNR) in a self-consistent way, using the established Maxwell-Garnett effective medium (MGEM) theory beyond the limit of homogeneous media. We show that the dielectric function of gold nanoparticles differs from the bulk value and experimentally characterize the shape and the surrounding of the particles thoroughly by SEM, AFM and ellipsometry. Averaging the dielectric functions of the layered surrounding by an appropriate weighting with the electric field intensity yields excellent agreement for the spectra of several nanoparticles and nanorods with various cover-layer thicknesses.

Colloid-probe AFM studies of the interaction forces of proteins adsorbed on colloidal crystals.

PubMed

Singh, Gurvinder; Bremmell, Kristen E; Griesser, Hans J; Kingshott, Peter

2015-04-28

In recent years, colloid-probe AFM has been used to measure the direct interaction forces between colloidal particles of different size or surface functionality in aqueous media, as one can study different forces in symmerical systems (i.e., sphere-sphere geometry). The present study investigates the interaction between protein coatings on colloid probes and hydrophilic surfaces decorated with hexagonally close packed single particle layers that are either uncoated or coated with proteins. Controlled solvent evaporation from aqueous suspensions of colloidal particles (coated with or without lysozyme and albumin) produces single layers of close-packed colloidal crystals over large areas on a solid support. The measurements have been carried out in an aqueous medium at different salt concentrations and pH values. The results show changes in the interaction forces as the surface charge of the unmodified or modified particles, and ionic strength or pH of the solution is altered. At high ionic strength or pH, electrostatic interactions are screened, and a strong repulsive force at short separation below 5 nm dominates, suggesting structural changes in the absorbed protein layer on the particles. We also study the force of adhesion, which decreases with an increment in the salt concentration, and the interaction between two different proteins indicating a repulsive interaction on approach and adhesion on retraction.

Low density, resorcinol-formaldehyde aerogels

DOEpatents

Pekala, R.W.

1988-05-26

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer ''clusters''. The covalent crosslinking of these ''clusters'' produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density less than or equal to100 mg/cc; cell size less than or equal to0.1 microns). The aerogels are transparent,dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 A/degree/. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron. 1 fig., 1 tab.

Mechanism of nanoparticle actuation by responsive polymer brushes: from reconfigurable composite surfaces to plasmonic effects.

PubMed

Roiter, Yuri; Minko, Iryna; Nykypanchuk, Dmytro; Tokarev, Ihor; Minko, Sergiy

2012-01-07

The mechanism of nanoparticle actuation by stimuli-responsive polymer brushes triggered by changes in the solution pH was discovered and investigated in detail in this study. The finding explains the high spectral sensitivity of the composite ultrathin film composed of a poly(2-vinylpyridine) (P2VP) brush that tunes the spacing between two kinds of nanoparticles-gold nanoislands immobilized on a transparent support and gold colloidal particles adsorbed on the brush. The optical response of the film relies on the phenomenon of localized surface plasmon resonances in the noble metal nanoparticles, giving rise to an extinction band in visible spectra, and a plasmon coupling between the particles and the islands that has a strong effect on the band position and intensity. Since the coupling is controlled by the interparticle spacing, the pH-triggered swelling-shrinking transition in the P2VP brush leads to pronounced changes in the transmission spectra of the hybrid film. It was not established in the previous publications how the actuation of gold nanoparticles within a 10-15 nm interparticle distance could result in the 50-60 nm shift in the absorbance maximum in contrast to the model experiments and theoretical estimations of several nanometer shifts. In this work, the extinction band was deconvoluted into four spectrally separated and overlapping contributions that were attributed to different modes of interactions between the particles and the islands. These modes came into existence due to variations in the thickness of the grafted polymeric layer on the profiled surface of the islands. In situ atomic force microscopy measurements allowed us to explore the behavior of the Au particles as the P2VP brush switched between the swollen and collapsed states. In particular, we identified an interesting, previously unanticipated regime when a particle position in a polymer brush was switched between two distinct states: the particle exposed to the surface of the collapsed layer and the particle engulfed by the swollen brush. On average, the characteristic distance between the particles and the islands increased upon the brush swelling. The observed behavior was a result of the anchoring of the particles to polymeric chains that limited the particles' vertical motion range. The experimental findings will be used to design highly sensitive optical nanosensors based on a polymer-brush-modulated interparticle plasmon coupling.

Method to separate lignin-rich solid phase from acidic biomass suspension at an acidic pH

DOEpatents

Yasarla, Kumar Lakshmi Rakesh; Ramarao, Bandaru V; Amidon, Thomas

2017-09-05

A method of separating a lignin-rich solid phase from a solution suspension, by pretreating a lignocellulosic biomass with a pretreatment fluid having remove soluble components, colloidal material and primarily lignin containing particles; separating the pretreated lignocellulosic biomass from the pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles; flocculating the separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles using polyethylene oxide (i.e., PEO) or cationic Poly acrylamide (i.e., CPAM) as a flocculating agent; and filtering the flocculated separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles to remove agglomerates.

Preparation of SMART wound dressings based on colloidal microgels and textile fibres

NASA Astrophysics Data System (ADS)

Cornelius, Victoria J.; Majcen, Natasa; Snowden, Martin J.; Mitchell, John C.; Voncina, Bojana

2007-01-01

Wound dressings and other types of wound healing technologies are experiencing fast-paced development and rapid growth. As the population ages, demand will continue to rise for advanced dressings used to treat chronic wounds, such as pressure ulcers, venous stasis ulcers, and diabetic ulcers. Moist wound dressings, which facilitate natural wound healing in a cost-effective manner, will be increasingly important. In commercially available hydrogel / gauze wound dressings the gel swells to adsorb wound excreta and provide an efficient non adhesive particle barrier. An alternative to hydrogels are microgels. Essentially discrete colloidal gel particles, as a result of their very high surface area to volume ratio compared to bulk gels, they have a much faster response to external stimuli such as temperature or pH. In response to either an increase or decrease in solvent quality these porous networks shrink and swell reversibly. When swollen the interstitial regions within the polymer matrix are available for further chemistry; such as the incorporation of small molecules. The reversible shrinking and swelling as a function of external stimuli provides a novel drug release system. As the environmental conditions of a wound change over its lifetime, tending to increase in pH if there is an infection combining these discrete polymeric particles with a substrate such as cotton, results in a smart wound dressing.

Dendrimer-assisted patch-clamp sizing of nuclear pores

PubMed Central

Bustamante, J.O.; Michelette, E.R.F.; Geibel, J.P.; Hanover, J.A.; McDonnell, T.J.; Dean, D.A.

2015-01-01

Macromolecular translocation (MMT) across the nuclear envelope (NE) occurs exclusively through the nuclear pore complex (NPC). Therefore, the diameter of the NPC aqueous/electrolytic channel (NPCC) is important for cellular structure and function. The NPCC diameter was previously determined to be ≅10 nm with electron microscopy (EM) using the translocation of colloidal gold particles. Here we present patch-clamp and fluorescence microscopy data from adult cardiomyocyte nuclei that demonstrate the use of patch-clamp for assessing NPCC diameter. Fluorescence microscopy with B-phycoerythrin (BPE, 240 kDa) conjugated to a nuclear localization signal (NLS) demonstrated that these nuclei were competent for NPC-mediated MMT (NPC-MMT). Furthermore, when exposed to an appropriate cell lysate, the nuclei expressed enhanced green fluorescence protein (EGFP) after 5–10 h of incubation with the plasmid for this protein (pEGFP, 3.1 MDa). Nucleus-attached patch-clamp showed that colloidal gold particles were not useful probes; they modified NPCC gating. As a result of this finding, we searched for an inert class of particles that could be used without irreversibly affecting NPCC gating and found that fluorescently labeled Star-burst dendrimers, a distinct class of polymers, were useful. Our patch-clamp and fluorescence microscopy data with calibrated dendrimers indicate that the cardiomyocyte NPCC diameter varies between 8 and 9 nm. These studies open a new direction in the investigation of live, continuous NPC dynamics under physiological conditions. PMID:10784359

Coulomb-like elastic interaction induced by symmetry breaking in nematic liquid crystal colloids.

PubMed

Lee, Beom-Kyu; Kim, Sung-Jo; Kim, Jong-Hyun; Lev, Bohdan

2017-11-21

It is generally thought that colloidal particles in a nematic liquid crystal do not generate the first multipole term called deformation elastic charge as it violates the mechanical equilibrium. Here, we demonstrate theoretically and experimentally that this is not the case, and deformation elastic charges, as well as dipoles and quadrupoles, can be induced through anisotropic boundary conditions. We report the first direct observation of Coulomb-like elastic interactions between colloidal particles in a nematic liquid crystal. The behaviour of two spherical colloidal particles with asymmetric anchoring conditions induced by asymmetric alignment is investigated experimentally; the interaction of two particles located at the boundary of twist and parallel aligned regions is observed. We demonstrate that such particles produce deformation elastic charges and interact by Coulomb-like interactions.

Surface chemical effects on colloid stability and transport through natural porous media

USGS Publications Warehouse

Puls, Robert W.; Paul, Cynthia J.; Clark, Donald A.

1993-01-01

Surface chemical effects on colloidal stability and transport through porous media were investigated using laboratory column techniques. Approximately 100 nm diameter, spherical, iron oxide particles were synthesized as the mobile colloidal phase. The column packing material was retrieved from a sand and gravel aquifer on Cape Cod, MA. Previous studies have indicated enhanced stability and transport of iron oxide particles due to specific adsorption of some inorganic anions on the iron oxide surface. This phenomenon was further evaluated with an anionic surfactant, sodium dodecyl sulfate. Surfactants constitute a significant mass of the contaminant loading at the Cape Cod site and their presence may contribute to colloidal transport as a significant transport mechanism at the site. Other studies at the site have previously demonstrated the occurrence of this transport mechanism for iron phosphate particles. Photon correlation spectroscopy, micro-electrophoretic mobility, and scanning electron microscopy were used to evaluate particle stability, mobility and size. Adsorption of negatively charged organic and inorganic species onto the surface of the iron oxide particles was shown to significantly enhance particle stability and transport through alterations of the electrokinetic properties of the particle surface. Particle breakthrough generally occurred simultaneously with tritiated water, a conservative tracer. The extent of particle breakthrough was primarily dependent upon colloidal stability and surface charge.

Early Dynamics and Stabilization Mechanisms of Oil-in-Water Emulsions Containing Colloidal Particles Modified with Short Amphiphiles: A Numerical Study.

PubMed

Cerbelaud, Manuella; Videcoq, Arnaud; Alison, Lauriane; Tervoort, Elena; Studart, André R

2017-12-19

Emulsions stabilized by mixtures of particles and amphiphilic molecules are relevant for a wide range of applications, but their dynamics and stabilization mechanisms on the colloidal level are poorly understood. Given the challenges to experimentally probe the early dynamics and mechanisms of droplet stabilization, Brownian dynamics simulations are developed here to study the behavior of oil-in-water emulsions stabilized by colloidal particles modified with short amphiphiles. Simulation parameters are based on an experimental system that consists of emulsions obtained with octane as the oil phase and a suspension of alumina colloidal particles modified with short carboxylic acids as the continuous aqueous medium. The numerical results show that attractive forces between the colloidal particles favor the formation of closely packed clusters on the droplet surface or of a percolating network of particles throughout the continuous phase, depending on the amphiphile concentration. Simulations also reveal the importance of a strong adsorption of particles at the liquid interface to prevent their depletion from the droplet surface when another droplet approaches. Strongly adsorbed particles remain immobile on the droplet surface, generating an effective steric barrier against droplet coalescence. These findings provide new insights into the early dynamics and mechanisms of stabilization of emulsions using particles and amphiphilic molecules.

Nonequilibrium self-organization of colloidal particles on substrates: adsorption, relaxation, and annealing.

PubMed

Araújo, Nuno A M; Dias, Cristóvão S; Telo da Gama, Margarida M

2017-01-11

Colloidal particles are considered ideal building blocks to produce materials with enhanced physical properties. The state-of-the-art techniques for synthesizing these particles provide control over shape, size, and directionality of the interactions. In spite of these advances, there is still a huge gap between the synthesis of individual components and the management of their spontaneous organization towards the desired structures. The main challenge is the control over the dynamics of self-organization. In their kinetic route towards thermodynamically stable structures, colloidal particles self-organize into intermediate (mesoscopic) structures that are much larger than the individual particles and become the relevant units for the dynamics. To follow the dynamics and identify kinetically trapped structures, one needs to develop new theoretical and numerical tools. Here we discuss the self-organization of functionalized colloids (also known as patchy colloids) on attractive substrates. We review our recent results on the adsorption and relaxation and explore the use of annealing cycles to overcome kinetic barriers and drive the relaxation towards the targeted structures.

Continuous separation of colloidal particles using dielectrophoresis.

PubMed

Yunus, Nurul Amziah Md; Nili, Hossein; Green, Nicolas G

2013-04-01

Dielectrophoresis is the movement of particles in nonuniform electric fields and has been of interest for application to manipulation and separation at and below the microscale. This technique has the advantages of being noninvasive, nondestructive, and noncontact, with the movement of particle achieved by means of electric fields generated by miniaturized electrodes and microfluidic systems. Although the majority of applications have been above the microscale, there is increasing interest in application to colloidal particles around a micron and smaller. This paper begins with a review of colloidal and nanoscale dielectrophoresis with specific attention paid to separation applications. An innovative design of integrated microelectrode array and its application to flow-through, continuous separation of colloidal particles is then presented. The details of the angled chevron microelectrode array and the test microfluidic system are then discussed. The variation in device operation with applied signal voltage is presented and discussed in terms of separation efficiency, demonstrating 99.9% separation of a mixture of colloidal latex spheres. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of non-hexagonal close packed colloidal array on a substrate by transfer

NASA Astrophysics Data System (ADS)

Banik, Meneka; Mukherjee, Rabibrata

Self-organized colloidal arrays find application in fabrication of solar cells with advanced light management strategies. We report a simple spincoating based approach for fabricating two dimensional colloidal crystals with hexagonal and non-hexagonal close packed assembly on flat and nanopatterned substrates. The non-HCP arrays were fabricated by spin coating the particles onto soft lithographically fabricated substrates. The substrate patterns impose directionality to the particles by confining them within the grooves. We have developed a technique by which the HCP and non-HCP arrays can be transferred to any surface. For this purpose the colloidal arrays were fabricated on a UV degradable PMMA layer, resulting in transfer of the particles on UV exposure. This allows the colloidal structures to be transported across substrates irrespective of their surface energy, wettability or morphology. Since the particles are transferred without exposing it to any kind of chemical or thermal environment, it can be utilized for placing particles on top of thin film solar cells for improving their absorption efficiency.

Synthesis of blue-shifted luminescent colloidal GaN nanocrystals through femtosecond pulsed laser ablation in organic solution

NASA Astrophysics Data System (ADS)

Demirel, Abdülmelik; Öztaş, Tuğba; Kurşungöz, Canan; Yılmaz, İbrahim; Ortaç, Bülend

2016-05-01

We demonstrate the synthesis of GaN nanocrystals (NCs) with the sizes of less than the doubled exciton Bohr radius leading quantum confinement effects via a single-step technique. The generation of colloidal GaN nanoparticles (NPs) in organic solution through nanosecond (ns) and femtosecond (fs) pulsed laser ablation (PLA) of GaN powder was carried out. Ns PLA in ethanol and polymer matrix resulted in amorphous GaN-NPs with the size distribution of 12.4 ± 7.0 and 6.4 ± 2.3 nm, respectively, whereas fs PLA in ethanol produced colloidal GaN-NCs with spherical shape within 4.2 ± 1.9 nm particle size distribution. XRD and selected area electron diffraction analysis of the product via fs PLA revealed that GaN-NCs are in wurtzite structure. Moreover, X-ray photoelectron spectroscopy measurements also confirm the presence of GaN nanomaterials. The colloidal GaN-NCs solution exhibits strong blue shift in the absorption spectrum compared to that of the GaN-NPs via ns PLA in ethanol. Furthermore, the photoluminescence emission behavior of fs PLA-generated GaN-NCs in the 295-400 nm wavelength range is observed with a peak position located at 305 nm showing a strong blue shift with respect to the bulk GaN.

Dynamic self-assembly of charged colloidal strings and walls in simple fluid flows.

PubMed

Abe, Yu; Zhang, Bo; Gordillo, Leonardo; Karim, Alireza Mohammad; Francis, Lorraine F; Cheng, Xiang

2017-02-22

Colloidal particles can self-assemble into various ordered structures in fluid flows that have potential applications in biomedicine, materials synthesis and encryption. These dynamic processes are also of fundamental interest for probing the general principles of self-assembly under non-equilibrium conditions. Here, we report a simple microfluidic experiment, where charged colloidal particles self-assemble into flow-aligned 1D strings with regular particle spacing near a solid boundary. Using high-speed confocal microscopy, we systematically investigate the influence of flow rates, electrostatics and particle polydispersity on the observed string structures. By studying the detailed dynamics of stable flow-driven particle pairs, we quantitatively characterize interparticle interactions. Based on the results, we construct a simple model that explains the intriguing non-equilibrium self-assembly process. Our study shows that the colloidal strings arise from a delicate balance between attractive hydrodynamic coupling and repulsive electrostatic interaction between particles. Finally, we demonstrate that, with the assistance of transverse electric fields, a similar mechanism also leads to the formation of 2D colloidal walls.

Brownian motion on random dynamical landscapes

NASA Astrophysics Data System (ADS)

Suñé Simon, Marc; Sancho, José María; Lindenberg, Katja

2016-03-01

We present a study of overdamped Brownian particles moving on a random landscape of dynamic and deformable obstacles (spatio-temporal disorder). The obstacles move randomly, assemble, and dissociate following their own dynamics. This landscape may account for a soft matter or liquid environment in which large obstacles, such as macromolecules and organelles in the cytoplasm of a living cell, or colloids or polymers in a liquid, move slowly leading to crowding effects. This representation also constitutes a novel approach to the macroscopic dynamics exhibited by active matter media. We present numerical results on the transport and diffusion properties of Brownian particles under this disorder biased by a constant external force. The landscape dynamics are characterized by a Gaussian spatio-temporal correlation, with fixed time and spatial scales, and controlled obstacle concentrations.

Pseudotannins Self-assembled into Antioxidant Complexes

PubMed Central

Cheng, H. A.; Drinnan, C. T.; Pleshko, N.; Fisher, O. Z.

2015-01-01

Natural tannins are attractive as building blocks for biomaterials due to their antioxidant properties and ability to form interpolymer complexes (IPCs) with other macromolecules. One of the major challenges to tannin usage in biomedical applications is their instability at physiological conditions and a lack of control over the purity and reactivity. Herein, we report the synthesis and characterization of tannin-like polymers with controlled architecture, reactivity, and size. These pseudotannins were synthesized by substituting linear dextran chains with gallic, resorcylic, and protocatechuic pendant groups to mimic the structure of natural hydrolysable tannins. We demonstrate that these novel materials can self-assemble to form reductive and colloidally stable nanoscale and microscale particles. Specifically, the synthesis, turbidity, particle size, antioxidant power, and cell uptake of IPCs derived from pseudotannins and poly(ethylene glycol) was evaluated. PMID:26313262

Pseudotannins self-assembled into antioxidant complexes.

PubMed

Cheng, H A; Drinnan, C T; Pleshko, N; Fisher, O Z

2015-10-21

Natural tannins are attractive as building blocks for biomaterials due to their antioxidant properties and ability to form interpolymer complexes (IPCs) with other macromolecules. One of the major challenges to tannin usage in biomedical applications is their instability at physiological conditions and a lack of control over the purity and reactivity. Herein, we report the synthesis and characterization of tannin-like polymers with controlled architecture, reactivity, and size. These pseudotannins were synthesized by substituting linear dextran chains with gallic, resorcylic, and protocatechuic pendant groups to mimic the structure of natural hydrolysable tannins. We demonstrate that these novel materials can self-assemble to form reductive and colloidally stable nanoscale and microscale particles. Specifically, the synthesis, turbidity, particle size, antioxidant power, and cell uptake of IPCs derived from pseudotannins and poly(ethylene glycol) was evaluated.

Silver Nanoparticles Formed in a Colloidal System and a Polymer Matrix

NASA Astrophysics Data System (ADS)

Potapov, A. L.; Agabekov, V. E.; Belyi, V. N.

2018-05-01

The growth kinetics and particle-size distribution of Ag particles in a polyvinyl alcohol (PVA) composite, PVA film, and aqueous sol were studied using UV and visible spectroscopy, atomic force microscopy, and dynamic light scattering. A hypsochromic shift (55 nm) of the Ag nanoparticle (NP) surface plasmon absorption maximum was measured on going from the PVA composite to the film. The kinetics of Ag NP formation and their sizes were shown to depend considerably on UV irradiation, ultrasound action, and PVA concentration. It was established that UV irradiation accelerated Ag NP formation in the presence of reductants and destroyed the resulting NPs with a deficit of reductant. Partial destruction of the Ag NPs occurred under the influence of ultrasound whereas ultrasound action after UV irradiation reduced Ag+ on the clusters.

Feedback Controlled Colloidal Assembly at Fluid Interfaces

NASA Astrophysics Data System (ADS)

Bevan, Michael

The autonomous and reversible assembly of colloidal nano- and micro- scale components into ordered configurations is often suggested as a scalable process capable of manufacturing meta-materials with exotic electromagnetic properties. As a result, there is strong interest in understanding how thermal motion, particle interactions, patterned surfaces, and external fields can be optimally coupled to robustly control the assembly of colloidal components into hierarchically structured functional meta-materials. We approach this problem by directly relating equilibrium and dynamic colloidal microstructures to kT-scale energy landscapes mediated by colloidal forces, physically and chemically patterned surfaces, multiphase fluid interfaces, and electromagnetic fields. 3D colloidal trajectories are measured in real-space and real-time with nanometer resolution using an integrated suite of evanescent wave, video, and confocal microscopy methods. Equilibrium structures are connected to energy landscapes via statistical mechanical models. The dynamic evolution of initially disordered colloidal fluid configurations into colloidal crystals in the presence of tunable interactions (electromagnetic field mediated interactions, particle-interface interactions) is modeled using a novel approach based on fitting the Fokker-Planck equation to experimental microscopy and computer simulated assembly trajectories. This approach is based on the use of reaction coordinates that capture important microstructural features of crystallization processes and quantify both statistical mechanical (free energy) and fluid mechanical (hydrodynamic) contributions. Ultimately, we demonstrate real-time control of assembly, disassembly, and repair of colloidal crystals using both open loop and closed loop control to produce perfectly ordered colloidal microstructures. This approach is demonstrated for close packed colloidal crystals of spherical particles at fluid-solid interfaces and is being extended to anisotropic particles and multiphase fluid interfaces.

A general and robust strategy for the synthesis of nearly monodisperse colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Pang, Xinchang; Zhao, Lei; Han, Wei; Xin, Xukai; Lin, Zhiqun

2013-06-01

Colloidal nanocrystals exhibit a wide range of size- and shape-dependent properties and have found application in myriad fields, incuding optics, electronics, mechanics, drug delivery and catalysis, to name but a few. Synthetic protocols that enable the simple and convenient production of colloidal nanocrystals with controlled size, shape and composition are therefore of key general importance. Current strategies include organic solution-phase synthesis, thermolysis of organometallic precursors, sol-gel processes, hydrothermal reactions and biomimetic and dendrimer templating. Often, however, these procedures require stringent experimental conditions, are difficult to generalize, or necessitate tedious multistep reactions and purification. Recently, linear amphiphilic block co-polymer micelles have been used as templates to synthesize functional nanocrystals, but the thermodynamic instability of these micelles limits the scope of this approach. Here, we report a general strategy for crafting a large variety of functional nanocrystals with precisely controlled dimensions, compositions and architectures by using star-like block co-polymers as nanoreactors. This new class of co-polymers forms unimolecular micelles that are structurally stable, therefore overcoming the intrinsic instability of linear block co-polymer micelles. Our approach enables the facile synthesis of organic solvent- and water-soluble nearly monodisperse nanocrystals with desired composition and architecture, including core-shell and hollow nanostructures. We demonstrate the generality of our approach by describing, as examples, the synthesis of various sizes and architectures of metallic, ferroelectric, magnetic, semiconductor and luminescent colloidal nanocrystals.

Quantification of hydrophobic interaction affinity of colloids

NASA Astrophysics Data System (ADS)

Saini, G.; Nasholm, N.; Wood, B. D.

2009-12-01

Colloids play an important role in a wide variety of disciplines, including water and wastewater treatment, subsurface transport of metals and organic contaminants, migration of fines in oil reservoirs, biocolloid (virus and bacteria) transport in subsurface, and are integral to laboratory transport studies. Although the role of hydrophobicity in adhesion and transport of colloids, particularly bacteria, is well known; there is scarcity of literature regarding hydrophobicity measurement of non-bacterial colloids and other micron-sized particles. Here we detail an experimental approach based on differential partitioning of colloids between two liquid phases (hydrocarbon and buffer) as a measure of the hydrophobic interaction affinity of colloids. This assay, known as Microbial adhesion to hydrocarbons or MATH, is frequently used in microbiology and bacteriology for quantifying the hydrophobicity of microbes. Monodispersed colloids and particles, with sizes ranging from 1 micron to 33 micron, were used for the experiments. A range of hydrophobicity values were observed for different particles. The hydrophobicity results are also verified against water contact angle measurements of these particles. This liquid-liquid partitioning assay is quick, easy-to-perform and requires minimal instrumentation. Estimation of the hydrophobic interaction affinity of colloids would lead to a better understanding of their adhesion to different surfaces and subsequent transport in porous media.

Patchy particles made by colloidal fusion

NASA Astrophysics Data System (ADS)

Gong, Zhe; Hueckel, Theodore; Yi, Gi-Ra; Sacanna, Stefano

2017-10-01

Patches on the surfaces of colloidal particles provide directional information that enables the self-assembly of the particles into higher-order structures. Although computational tools can make quantitative predictions and can generate design rules that link the patch motif of a particle to its internal microstructure and to the emergent properties of the self-assembled materials, the experimental realization of model systems of particles with surface patches (or `patchy' particles) remains a challenge. Synthetic patchy colloidal particles are often poor geometric approximations of the digital building blocks used in simulations and can only rarely be manufactured in sufficiently high yields to be routinely used as experimental model systems. Here we introduce a method, which we refer to as colloidal fusion, for fabricating functional patchy particles in a tunable and scalable manner. Using coordination dynamics and wetting forces, we engineer hybrid liquid-solid clusters that evolve into particles with a range of patchy surface morphologies on addition of a plasticizer. We are able to predict and control the evolutionary pathway by considering surface-energy minimization, leading to two main branches of product: first, spherical particles with liquid surface patches, capable of forming curable bonds with neighbouring particles to assemble robust supracolloidal structures; and second, particles with a faceted liquid compartment, which can be cured and purified to yield colloidal polyhedra. These findings outline a scalable strategy for the synthesis of patchy particles, first by designing their surface patterns by computer simulation, and then by recreating them in the laboratory with high fidelity.

Directed assembly of colloidal particles for micro/nano photonics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Zheng, Yuebing

2017-02-01

Bottom-up fabrication of complex structures with chemically synthesized colloidal particles as building blocks pave an efficient and cost-effective way towards micro/nano photonics with unprecedented functionality and tunability. Novel properties can arise from quantum effects of colloidal particles, as well as inter-particle interactions and spatial arrangement in particle assemblies. Herein, I discuss our recent developments and applications of three types of techniques for directed assembly of colloidal particles: moiré nanosphere lithography (MNSL), bubble-pen lithography (BPL), and optothermal tweezers (OTTs). Specifically, MNSL provides an efficient approach towards creating moiré metasurface with tunable and multiband optical responses from visible to mid-infrared regime. Au moiré metasurfaces have been applied for surface-enhanced infrared spectroscopy, optical capture and patterning of bacteria, and photothermal denaturation of proteins. BPL is developed to pattern a variety of colloidal particles on plasmonic substrates and two-dimensional atomic-layer materials in an arbitrary manner. The laser-directed microbubble captures and immobilizes nanoparticles through coordinated actions of Marangoni convection, surface tension, gas pressure, and substrate adhesion. OTTs are developed to create dynamic nanoparticle assemblies at low optical power. Such nanoparticle assemblies have been used for surface-enhanced Raman spectroscopy for molecular analysis in their native environments.

Size effects of solvent molecules on the phase behavior and effective interaction of colloidal systems with the bridging attraction.

PubMed

Chen, Jie; Wang, Xuewu; Kline, Steven R; Liu, Yun

2016-11-16

There has been much recent research interest towards understanding the phase behavior of colloidal systems interacting with a bridging attraction, where the small solvent particles and large solute colloidal particles can be reversibly associated with each other. These systems show interesting phase behavior compared to the more widely studied depletion attraction systems. Here, we use Baxter's two-component sticky hard sphere model with a Percus-Yevick closure to solve the Ornstein-Zernike equation and study the size effect on colloidal systems with bridging attractions. The spinodal decomposition regions, percolation transition boundaries and binodal regions are systematically investigated as a function of the relative size of the small solvent and large solute particles as well as the attraction strength between the small and large particles. In the phase space determined by the concentrations of small and large particles, the spinodal and binodal regions form isolated islands. The locations and shapes of the spinodal and binodal regions sensitively depend on the relative size of the small and large particles and the attraction strength between them. The percolation region shrinks by decreasing the size ratio, while the binodal region slightly expands with the decrease of the size ratio. Our results are very important in understanding the phase behavior for a bridging attraction colloidal system, a model system that provides insight into oppositely charged colloidal systems, protein phase behavior, and colloidal gelation mechanisms.

Plasmonic particles of colloidal silver in high-resolution recording media

NASA Astrophysics Data System (ADS)

Andreeva, O. V.; Andreeva, N. V.; Kuzmina, T. B.

2017-01-01

The optical properties of colloidal silver particles formed photographically in high-resolution silver halide photographic materials have been considered. The conditions that allow one to obtain exposed and developed light-sensitive silver halide particles in the form of colloidal particles of metallic silver having the properties of localized plasmons have been described. The results of the studies of the developed silver particles in traditional photographic materials for image holography and in nanoporous silver halide photographic materials for volume holography have been presented. The perspectives of using plasmonic silver nanoparticles produced photographically have been discussed.

Asymmetrical Polyhedral Configuration of Giant Vesicles Induced by Orderly Array of Encapsulated Colloidal Particles

PubMed Central

Natsume, Yuno; Toyota, Taro

2016-01-01

Giant vesicles (GVs) encapsulating colloidal particles by a specific volume fraction show a characteristic configuration under a hypertonic condition. Several flat faces were formed in GV membrane with orderly array of inner particles. GV shape changed from the spherical to the asymmetrical polyhedral configuration. This shape deformation was derived by entropic interaction between inner particles and GV membrane. Because a part of inner particles became to form an ordered phase in the region neighboring the GV membrane, free volume for the other part of particles increased. Giant vesicles encapsulating colloidal particles were useful for the model of “crowding effect” which is the entropic interaction in the cell. PMID:26752650

Asymmetrical Polyhedral Configuration of Giant Vesicles Induced by Orderly Array of Encapsulated Colloidal Particles.

PubMed

Natsume, Yuno; Toyota, Taro

2016-01-01

Giant vesicles (GVs) encapsulating colloidal particles by a specific volume fraction show a characteristic configuration under a hypertonic condition. Several flat faces were formed in GV membrane with orderly array of inner particles. GV shape changed from the spherical to the asymmetrical polyhedral configuration. This shape deformation was derived by entropic interaction between inner particles and GV membrane. Because a part of inner particles became to form an ordered phase in the region neighboring the GV membrane, free volume for the other part of particles increased. Giant vesicles encapsulating colloidal particles were useful for the model of "crowding effect" which is the entropic interaction in the cell.

Swelling, Structure, and Phase Stability of Soft, Compressible Microgels

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Urich, Matthew

Microgels are soft colloidal particles that swell when dispersed in a solvent. The equilibrium particle size is governed by a delicate balance of osmotic pressures, which can be tuned by varying single-particle properties and externally controlled conditions, such as temperature, pH, ionic strength, and concentration. Because of their tunable size and ability to encapsulate dye or drug molecules, microgels have practical relevance for biosensing, drug delivery, carbon capture, and filtration. Using Monte Carlo simulation, we model suspensions of microgels that interact via Hertzian elastic interparticle forces and can expand or contract via trial size changes governed by the Flory-Rehner free energy of cross-linked polymer gels. We analyze the influence of particle compressibility and size fluctuations on bulk structural and thermal properties by computing swelling ratios, radial distribution functions, static structure factors, osmotic pressures, and freezing densities. With increasing density, microgels progressively deswell and their intrinsic polydispersity broadens, while compressibility acts to forestall crystallization. This work was supported by the National Science Foundation under Grant No. DMR- 1106331.

Colloidal assembly directed by virtual magnetic moulds

NASA Astrophysics Data System (ADS)

Demirörs, Ahmet F.; Pillai, Pramod P.; Kowalczyk, Bartlomiej; Grzybowski, Bartosz A.

2013-11-01

Interest in assemblies of colloidal particles has long been motivated by their applications in photonics, electronics, sensors and microlenses. Existing assembly schemes can position colloids of one type relatively flexibly into a range of desired structures, but it remains challenging to produce multicomponent lattices, clusters with precisely controlled symmetries and three-dimensional assemblies. A few schemes can efficiently produce complex colloidal structures, but they require system-specific procedures. Here we show that magnetic field microgradients established in a paramagnetic fluid can serve as `virtual moulds' to act as templates for the assembly of large numbers (~108) of both non-magnetic and magnetic colloidal particles with micrometre precision and typical yields of 80 to 90 per cent. We illustrate the versatility of this approach by producing single-component and multicomponent colloidal arrays, complex three-dimensional structures and a variety of colloidal molecules from polymeric particles, silica particles and live bacteria and by showing that all of these structures can be made permanent. In addition, although our magnetic moulds currently resemble optical traps in that they are limited to the manipulation of micrometre-sized objects, they are massively parallel and can manipulate non-magnetic and magnetic objects simultaneously in two and three dimensions.

In-situ chemical barrier and method of making

DOEpatents

Cantrell, K.J.; Kaplan, D.I.

1999-01-12

A chemical barrier is formed by injecting a suspension of solid particles or colloids into the subsurface. First, a stable colloid suspension is made including a surfactant and a non-Newtonian fluid. This stable colloid suspension is characterized by colloid concentration, colloid size, colloid material, solution ionic strength, and chemical composition. A second step involves injecting the optimized stable colloid suspension at a sufficiently high flow rate to move the colloids through the subsurface sediment, but not at such a high rate so as to induce resuspending indigenous soil particles in the aquifer. While injecting the stable colloid suspension, a withdrawal well may be used to draw the injected colloids in a direction perpendicular to the flow path of a contaminant plume. The withdrawal well, may then be used as an injection well, and a third well, in line with the first two wells, may then be used as a withdrawal well, thereby increasing the length of the colloid barrier. This process would continue until emplacement of the colloid barrier is complete. 7 figs.

In-situ chemical barrier and method of making

DOEpatents

Cantrell, Kirk J.; Kaplan, Daniel I.

1999-01-01

A chemical barrier is formed by injecting a suspension of solid particles or colloids into the subsurface. First, a stable colloid suspension is made including a surfactant and a non-Newtonian fluid. This stable colloid suspension is characterized by colloid concentration, colloid size, colloid material, solution ionic strength, and chemical composition. A second step involves injecting the optimized stable colloid suspension at a sufficiently high flow rate to move the colloids through the subsurface sediment, but not at such a high rate so as to induce resuspending indigenous soil particles in the aquifer. While injecting the stable colloid suspension, a withdrawal well may be used to draw the injected colloids in a direction perpendicular to the flow path of a contaminant plume. The withdrawal well, may then be used as an injection well, and a third well, in line with the first two wells, may then be used as a withdrawal well, thereby increasing the length of the colloid barrier. This process would continue until emplacement of the colloid barrier is complete.

Surface preparation of substances for continuous convective assembly of fine particles

DOEpatents

Rossi, Robert

2003-01-01

A method for producing periodic nanometer-scale arrays of metal or semiconductor junctions on a clean semiconductor substrate surface is provided comprising the steps of: etching the substrate surface to make it hydrophilic, forming, under an inert atmosphere, a crystalline colloid layer on the substrate surface, depositing a metal or semiconductor material through the colloid layer onto the surface of the substrate, and removing the colloid from the substrate surface. The colloid layer is grown on the clean semiconductor surface by withdrawing the semiconductor substrate from a sol of colloid particles.

Get Beyond Limits: From Colloidal Tectonics Concept to the Engineering of Eco-friendly Catalytic Systems

NASA Astrophysics Data System (ADS)

Leclercq, Loïc

2018-05-01

The interactions between two or more molecules or colloidal particles can be used to obtain a variety of self-assembled systems called supramolecules or supracolloids. There is a clear, but neglected, convergence between these two fields. Indeed, the packing of molecules into colloidal or supracolloidal particles emerges as a smart solution to build an infinite variety of reversible systems with predictable properties. In this respect, the molecular building blocks are called “tectons” whereas “colloidal tectonics” describes the spontaneous formation of (supra)colloidal structures using tectonic subunits. As a consequence, a bottom-up edification is allowed from tectons into (supra)colloidal particles with higher degrees of organization. These (supra)colloidal systems can be very useful to obtain catalysts with tunable amphiphilic properties. In this perspective, an overview of colloidal tectonics concept is presented as well as its use for the design of new, smart and flexible catalytic systems. Finally, the advantages of these catalytic devices are discussed and the perspective of future developments is addressed especially in the context of “green chemistry”.

Get Beyond Limits: From Colloidal Tectonics Concept to the Engineering of Eco-Friendly Catalytic Systems

PubMed Central

Leclercq, Loïc

2018-01-01

The interactions between two or more molecules or colloidal particles can be used to obtain a variety of self-assembled systems called supramolecules or supracolloids. There is a clear, but neglected, convergence between these two fields. Indeed, the packing of molecules into colloidal or supracolloidal particles emerges as a smart solution to build an infinite variety of reversible systems with predictable properties. In this respect, the molecular building blocks are called “tectons” whereas “colloidal tectonics” describes the spontaneous formation of (supra)colloidal structures using tectonic subunits. As a consequence, a bottom-up edification is allowed from tectons into (supra)colloidal particles with higher degrees of organization (Graphical Abstract). These (supra)colloidal systems can be very useful to obtain catalysts with tunable amphiphilic properties. In this perspective, an overview of colloidal tectonics concept is presented as well as its use for the design of new, smart, and flexible catalytic systems. Finally, the advantages of these catalytic devices are discussed and the perspective of future developments is addressed especially in the context of “green chemistry.”

Dynamics and structure of an aging binary colloidal glass

NASA Astrophysics Data System (ADS)

Lynch, Jennifer M.; Cianci, Gianguido C.; Weeks, Eric R.

2008-09-01

We study aging in a colloidal suspension consisting of micron-sized particles in a liquid. This system is made glassy by increasing the particle concentration. We observe samples composed of particles of two sizes, with a size ratio of 1:2.1 and a volume fraction ratio 1:6, using fast laser scanning confocal microscopy. This technique yields real-time, three-dimensional movies deep inside the colloidal glass. Specifically, we look at how the size, motion, and structural organization of the particles relate to the overall aging of the glass. Particles move in spatially heterogeneous cooperative groups. These mobile regions tend to be richer in small particles, and these small particles facilitate the motion of nearby particles of both sizes.

Determining Number Concentrations and Diameters of Polystyrene Particles by Measuring the Effective Refractive Index of Colloids Using Surface Plasmon Resonance.

PubMed

Tuoriniemi, Jani; Moreira, Beatriz; Safina, Gulnara

2016-10-04

The capabilities of surface plasmon resonance (SPR) for characterization of colloidal particles were evaluated for 100, 300, and 460 nm nominal diameter polystyrene (PS) latexes. First the accuracy of measuring the effective refractive index (n eff ) of turbid colloids using SPR was quantified. It was concluded that for submicrometer sized PS particles the accuracy is limited by the reproducibility between replicate injections of samples. An SPR method was developed for obtaining the particle mean diameter (d part ) and the particle number concentration (c p ) by fitting the measured n eff of polystyrene (PS) colloids diluted in series with theoretical values calculated using the coherent scattering theory (CST). The d part and c p determined using SPR agreed with reference values obtained from size distributions measured by scanning electron microscopy (SEM), and the mass concentrations stated by the manufacturer. The 100 nm particles adsorbed on the sensing surface, which hampered the analysis. Once the adsorption problem has been overcome, the developed SPR method has potential to become a versatile tool for characterization of colloidal particles. In particular, SPR could form the basis of rapid and accurate methods for measuring the c p of submicrometer particles in dispersion.

Fabrication of Polyhedral Particles from Spherical Colloids and Their Self-Assembly into Rotator Phases**

PubMed Central

Vutukuri, Hanumantha Rao; Imhof, Arnout; van Blaaderen, Alfons

2014-01-01

Particle shape is a critical parameter that plays an important role in self-assembly, for example, in designing targeted complex structures with desired properties. Over the last decades, an unprecedented range of monodisperse nanoparticle systems with control over the shape of the particles have become available. In contrast, the choice of micrometer-sized colloidal building blocks of particles with flat facets, that is, particles with polygonal shapes, is significantly more limited. This can be attributed to the fact that in contrast to nanoparticles, the larger colloids are significantly harder to synthesize as single crystals. It is now shown that a very simple building block, such as a micrometer-sized polymeric spherical colloidal particle, is already enough to fabricate particles with regularly placed flat facets, including completely polygonal shapes with sharp edges. As an illustration that the yields are high enough for further self-assembly studies, the formation of three-dimensional rotator phases of fluorescently labelled, micrometer-sized, and charged rhombic dodecahedron particles was demonstrated. This method for fabricating polyhedral particles opens a new avenue for designing new materials. PMID:25366869

Charging and discharging of single colloidal particles at oil/water interfaces

PubMed Central

Gao, Peng; Xing, XiaoChen; Li, Ye; Ngai, To; Jin, Fan

2014-01-01

The physical behavior of solid colloids trapped at a fluid-fluid interface remains in itself an open fundamental issue. Here, we show that the gradients of surface tension can induce particles to jet towards the oil/water interface with velocities as high as ≈ 60 mm/s when particle suspensions come in contact with the interface. We hypothesize that rubbing between the particles and oil lead to the spontaneous accumulation of negative charges on the hemisphere of those interfacial particles that contact the oil phase by means of triboelectrification. The charging process is highly dependent on the sliding distances, and gives rise to long-ranged repulsions that protect interfacial particles from coagulating at the interface by the presence of electrolyte. These triboelectric charges, however, are compensated within several hours, which affect the stability of interfacial particles. Importantly, by charging different kinds of colloidal particles using various spreading solvents and dispersion methods, we have demonstrated that charging and discharging of single colloidal particles at oil/water interfaces impacts a broad range of dynamical behavior. PMID:24786477

Physical foundation of the fluid particle dynamics method for colloid dynamics simulation.

PubMed

Furukawa, Akira; Tateno, Michio; Tanaka, Hajime

2018-05-16

Colloid dynamics is significantly influenced by many-body hydrodynamic interactions mediated by a suspending fluid. However, theoretical and numerical treatments of such interactions are extremely difficult. To overcome this situation, we developed a fluid particle dynamics (FPD) method [H. Tanaka and T. Araki, Phys. Rev. Lett., 2000, 35, 3523], which is based on two key approximations: (i) a colloidal particle is treated as a highly viscous particle and (ii) the viscosity profile is described by a smooth interfacial profile function. Approximation (i) makes our method free from the solid-fluid boundary condition, significantly simplifying the treatment of many-body hydrodynamic interactions while satisfying the incompressible condition without the Stokes approximation. Approximation (ii) allows us to incorporate an extra degree of freedom in a fluid, e.g., orientational order and concentration, as an additional field variable. Here, we consider two fundamental problems associated with these approximations. One is the introduction of thermal noise and the other is the incorporation of coupling of the colloid surface with an order parameter introduced into a fluid component, which is crucial when considering colloidal particles suspended in a complex fluid. Here, we show that our FPD method makes it possible to simulate colloid dynamics properly while including full hydrodynamic interactions, inertia effects, incompressibility, thermal noise, and additional degrees of freedom of a fluid, which may be relevant for wide applications in colloidal and soft matter science.

Photochemistry in Organized Media.

ERIC Educational Resources Information Center

Fendler, Janos H.

1983-01-01

Describes common artificially produced organized media such as colloids, surfactants, and polymers and their usefulness in studying complex biochemical processes. Discusses selected recent photophysical and photochemical exploitations of these systems, including artificial photosynthesis, in situ generation of colloidal gold and platinum,…

The effects of aggregation and protein corona on the cellular internalization of iron oxide nanoparticles.

PubMed

Safi, M; Courtois, J; Seigneuret, M; Conjeaud, H; Berret, J-F

2011-12-01

Engineered inorganic nanoparticles are essential components in the development of nanotechnologies. For applications in nanomedicine, particles need to be functionalized to ensure a good dispersibility in biological fluids. In many cases however, functionalization is not sufficient: the particles become either coated by a corona of serum proteins or precipitate out of the solvent. In the present paper, we show that by changing the coating of iron oxide nanoparticles from a low-molecular weight ligand (citrate ions) to small carboxylated polymers (poly(acrylic acid)), the colloidal stability of the dispersion is improved and the adsorption/internalization of iron toward living mammalian cells is profoundly affected. Citrate-coated particles are shown to destabilize in all fetal-calf-serum based physiological conditions tested, whereas the polymer coated particles exhibit an outstanding dispersibility as well as a structure devoid of protein corona. The interactions between nanoparticles and human lymphoblastoid cells are investigated by transmission electron microscopy and flow cytometry. Two types of nanoparticle/cell interactions are underlined. Iron oxides are found either adsorbed on the cellular membranes, or internalized into membrane-bound endocytosis compartments. For the precipitating citrate-coated particles, the kinetics of interactions reveal a massive and rapid adsorption of iron oxide on the cell surfaces. The quantification of the partition between adsorbed and internalized iron was performed from the cytometry data. The results highlight the importance of resilient adsorbed nanomaterials at the cytoplasmic membrane. Copyright © 2011 Elsevier Ltd. All rights reserved.

Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

NASA Astrophysics Data System (ADS)

Safi, M.; Sarrouj, H.; Sandre, O.; Mignet, N.; Berret, J.-F.

2010-04-01

Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), MW = 2000 g mol - 1). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l - 1). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

Reconfigurable interactions and three-dimensional patterning of colloidal particles and defects in lamellar soft media

PubMed Central

Trivedi, Rahul P.; Klevets, Ivan I.; Senyuk, Bohdan; Lee, Taewoo; Smalyukh, Ivan I.

2012-01-01

Colloidal systems find important applications ranging from fabrication of photonic crystals to direct probing of phenomena typically encountered in atomic crystals and glasses. New applications—such as nanoantennas, plasmonic sensors, and nanocircuits—pose a challenge of achieving sparse colloidal assemblies with tunable interparticle separations that can be controlled at will. We demonstrate reconfigurable multiscale interactions and assembly of colloids mediated by defects in cholesteric liquid crystals that are probed by means of laser manipulation and three-dimensional imaging. We find that colloids attract via distance-independent elastic interactions when pinned to the ends of cholesteric oily streaks, line defects at which one or more layers are interrupted. However, dislocations and oily streaks can also be optically manipulated to induce kinks, allowing one to lock them into the desired configurations that are stabilized by elastic energy barriers for structural transformation of the particle-connecting defects. Under the influence of elastic energy landscape due to these defects, sublamellar-sized colloids self-assemble into structures mimicking the cores of dislocations and oily streaks. Interactions between these defect-embedded colloids can be varied from attractive to repulsive by optically introducing dislocation kinks. The reconfigurable nature of defect–particle interactions allows for patterning of defects by manipulation of colloids and, in turn, patterning of particles by these defects, thus achieving desired colloidal configurations on scales ranging from the size of defect core to the sample size. This defect-colloidal sculpturing may be extended to other lamellar media, providing the means for optically guided self-assembly of mesoscopic composites with predesigned properties. PMID:22411822

MOBILIZATION AND CHARACTERIZATION OF COLLOIDS GENERATED FROM CEMENT LEACHATES MOVING THROUGH A SRS SANDY SEDIMENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, D.; Roberts, K.; Kaplan, D.

Naturally occurring mobile colloids are ubiquitous and are involved in many important processes in the subsurface zone. For example, colloid generation and subsequent mobilization represent a possible mechanism for the transport of contaminants including radionuclides in the subsurface environments. For colloid-facilitated transport to be significant, three criteria must be met: (1) colloids must be generated; (2) contaminants must associate with the colloids preferentially to the immobile solid phase (aquifer); and (3) colloids must be transported through the groundwater or in subsurface environments - once these colloids start moving they become 'mobile colloids'. Although some experimental investigations of particle release inmore » natural porous media have been conducted, the detailed mechanisms of release and re-deposition of colloidal particles within natural porous media are poorly understood. Even though this vector of transport is known, the extent of its importance is not known yet. Colloid-facilitated transport of trace radionuclides has been observed in the field, thus demonstrating a possible radiological risk associated with the colloids. The objective of this study was to determine if cementitious leachate would promote the in situ mobilization of natural colloidal particles from a SRS sandy sediment. The intent was to determine whether cementitious surface or subsurface structure would create plumes that could produce conditions conducive to sediment dispersion and mobile colloid generation. Column studies were conducted and the cation chemistries of influents and effluents were analyzed by ICP-OES, while the mobilized colloids were characterized using XRD, SEM, EDX, PSD and Zeta potential. The mobilization mechanisms of colloids in a SRS sandy sediment by cement leachates were studied.« less

Note: Production of stable colloidal probes for high-temperature atomic force microscopy applications

NASA Astrophysics Data System (ADS)

Ditscherlein, L.; Peuker, U. A.

2017-04-01

For the application of colloidal probe atomic force microscopy at high temperatures (>500 K), stable colloidal probe cantilevers are essential. In this study, two new methods for gluing alumina particles onto temperature stable cantilevers are presented and compared with an existing method for borosilicate particles at elevated temperatures as well as with cp-cantilevers prepared with epoxy resin at room temperature. The durability of the fixing of the particle is quantified with a test method applying high shear forces. The force is calculated with a mechanical model considering both the bending as well as the torsion on the colloidal probe.

Colloidal titration of aqueous zirconium solutions with poly(vinyl sulfate) by potentiometric endpoint detection using a toluidine blue selective electrode.

PubMed

Sakurada, Osamu; Kato, Yasutake; Kito, Noriyoshi; Kameyama, Keiichi; Hattori, Toshiaki; Hashiba, Minoru

2004-02-01

Zirconium oxy-salts were hydrolyzed to form positively charged polymer or cluster species in acidic solutions. The zirconium hydrolyzed polymer was found to react with a negatively charged polyelectrolyte, such as poly(vinyl sulfate), and to form a stoichiometric polyion complex. Thus, colloidal titration with poly(vinyl sulfate) was applied to measure the zirconium concentration in an acidic solution by using a Toluidine Blue selective plasticized poly(vinyl chloride) membrane electrode as a potentiometric end-point detecting device. The determination could be performed with 1% of the relative standard deviation. The colloidal titration stoichiometry at pH < or = 2 was one mol of zirconium per equivalent mol of poly(vinyl sulfate).

Impact of nZVI stability on mobility in porous media.

PubMed

Kocur, Chris M; O'Carroll, Denis M; Sleep, Brent E

2013-02-01

Nano-scale zero valent iron (nZVI) has received significant attention because of its potential to rapidly reduce a number of priority source zone contaminants. In order to effectively deliver nZVI to the source zone the nZVI particles must be stable. Previous laboratory studies have demonstrated the mobility of polymer modified suspensions of low concentration nZVI. More recently studies have shown potential for higher concentration nZVI suspensions to be transmitted through porous media. However, with increasing nZVI concentration aggregation is accelerated, reducing the available time for injection before nZVI settles. In this study the colloidal stability and mobility of nZVI concurrently synthesized and stabilized in the presence of carboxy-methyl-cellulose (CMC) are evaluated in one-dimensional column experiments. Low pore water velocity nZVI injections (4, 2, and 0.25 m/day) conducted over periods as long as 80 h with no mixing of the influent reservoir were used to investigate the effects of prolonged aggregation and settling of colloids on transport. A numerical simulator, based on colloid filtration theory, but accounting for particle aggregation and settling was used to evaluate the contributions of aggregation and settling on nZVI mobility. Results suggest that the prediction of nZVI sticking efficiency in column experiments becomes increasingly influenced by aggregation and settling in the influent reservoir as the period of injection increases. Consideration of nZVI stability is required for the prediction of nZVI mobility at the field scale and for the design of successful nZVI remediation plans. Copyright © 2012 Elsevier B.V. All rights reserved.

Size-dependent control of colloid transport via solute gradients in dead-end channels

PubMed Central

Shin, Sangwoo; Um, Eujin; Sabass, Benedikt; Ault, Jesse T.; Rahimi, Mohammad; Warren, Patrick B.; Stone, Howard A.

2016-01-01

Transport of colloids in dead-end channels is involved in widespread applications including drug delivery and underground oil and gas recovery. In such geometries, Brownian motion may be considered as the sole mechanism that enables transport of colloidal particles into or out of the channels, but it is, unfortunately, an extremely inefficient transport mechanism for microscale particles. Here, we explore the possibility of diffusiophoresis as a means to control the colloid transport in dead-end channels by introducing a solute gradient. We demonstrate that the transport of colloidal particles into the dead-end channels can be either enhanced or completely prevented via diffusiophoresis. In addition, we show that size-dependent diffusiophoretic transport of particles can be achieved by considering a finite Debye layer thickness effect, which is commonly ignored. A combination of diffusiophoresis and Brownian motion leads to a strong size-dependent focusing effect such that the larger particles tend to concentrate more and reside deeper in the channel. Our findings have implications for all manners of controlled release processes, especially for site-specific delivery systems where localized targeting of particles with minimal dispersion to the nontarget area is essential. PMID:26715753

Characterization of Mixed Polypeptide Colloidal Particles by Light Scattering

NASA Astrophysics Data System (ADS)

Shuman, Hannah E.; Gaeckle, Grace K.; Gavin, John; Holland, Nolan B.; Streletzky, Kiril A.

2014-03-01

Temperature-dependent polymer surfactants have been developed by connecting three elastin-like polypeptide (ELP) chains to a charged protein domain (foldon), forming a three-armed star polymer. At low temperatures the polymer is soluble, while at higher temperatures it forms micelles. The behavior of mixtures of the three-armed star ELP (E20-Foldon) and H40-Linear ELP chains was analyzed under different salt and protein concentrations and various foldon to linear ELP ratio using Depolarized Dynamic Light Scattering. It was expected that under certain conditions the pure E20-Foldon would form spherical micelles, which upon adding the linear ELP would change in size and possibly shape. The pure E20-Foldon indeed formed largely spherical micelles with Rh of 10-20nm in solutions with 15-100mM salt and protein concentration between 10 μM and 100 μM. For the mixtures of 50 μM E20-Foldon and varying concentrations of H40-Linear in 25mM of salt, it was discovered that low and high H40-Linear concentration (4 μM and 50 μM) had only one transition. For the mixtures with of 10 and 25 μM of H40-Linear the two distinct transition temperatures were observed by spectrophotometry. The first transition corresponded to significantly elongated diffusive particles of apparent Rh of 30-50nm, while the second transition corresponded to slightly anisotropic diffusive particles with apparent Rh of about 20nm. At all H40-Linear concentrations studied, diffusive particles were seen above the second transition. Their radius and ability to depolarize light increased with the increase of H40-Linear concentration.

Refractive index of colloidal dispersions of spheroidal particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meeten, G.H.

1980-09-01

The effect of particle shape on the refractive index of a colloidal dispersion of spheroidal particles is investigated theoretically, using the Rayleigh, Rayleigh- Gans-Debye, and the anomalous diffraction light-scattering approximations. It is shown that departure from particle sphericity modify the dispersion refractive index, both size and shape being of importance.

Exploring the dynamics of phase separation in colloid-polymer mixtures with long range attraction.

PubMed

Sabin, Juan; Bailey, Arthur E; Frisken, Barbara J

2016-06-28

We have studied the kinetics of phase separation and gel formation in a low-dispersity colloid - non-adsorbing polymer system with long range attraction using small-angle light scattering. This system exhibits two-phase and three-phase coexistence of gas, liquid and crystal phases when the strength of attraction is between 2 and 4kBT and gel phases when the strength of attraction is increased. For those samples that undergo macroscopic phase separation, whether to gas-crystal, gas-liquid or gas-liquid-crystal coexistence, we observe dynamic scaling of the structure factor and growth of a characteristic length scale that behaves as expected for phase separation in fluids. In samples that gel, the power law associated with the growth of the dominant length scale is not equal to 1/3, but appears to depend mainly on the strength of attraction, decreasing from 1/3 for samples near the coexistence region to 1/27 at 8kBT, over a wide range of colloid and polymer concentrations.

Formation of Helically Structured Chitin/CaCO3 Hybrids through an Approach Inspired by the Biomineralization Processes of Crustacean Cuticles.

PubMed

Matsumura, Shunichi; Kajiyama, Satoshi; Nishimura, Tatsuya; Kato, Takashi

2015-10-01

Chitin/CaCO3 hybrids with helical structures are formed through a biomineralization-inspired crystallization process under ambient conditions. Liquid-crystalline chitin whiskers are used as helically ordered templates. The liquid-crystalline structures are stabilized by acidic polymer networks which interact with the chitin templates. The crystallization of CaCO3 is conducted by soaking the templates in the colloidal suspension of amorphous CaCO3 (ACC) at room temperature. At the initial stage of crystallization, ACC particles are introduced inside the templates, and they crystallize to CaCO3 nanocrystals. The acidic polymer networks induce CaCO3 crystallization. The characterization of the resultant hybrids reveals that they possess helical order and homogeneous hybrid structures of chitin and CaCO3 , which resemble the structure and composition of the exoskeleton of crustaceans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Screening of formulation variables for the preparation of poly(epsilon-caprolactone) nanocapsules containing the local anesthetic benzocaine.

PubMed

Moraes, Carolina Morales; de Matos, Angélica Prado; Grillo, Renato; de Melo, Nathalie F S; de Paula, Eneida; Dias Filho, Newton Luiz; Rosa, André Henrique; Fraceto, Leonardo Fernandes

2011-03-01

In this work we describe the screening of four parameters in the preparation, by nanoprecipitation, of poly(epsilon-caprolactone) nanocapsules, used as a drug carrier system for the local anesthetic, benzocaine. A 2(4-1) factorial experimental design was used to study the influence of four different independent variables (polymer, oily phase, Span 60 and Tween 80) on nanocapsule characteristics (size, polydispersion index, zeta potential) and drug loading capability. Best results were obtained using an aqueous formulation comprising 100 mg of polymer, 200 mg of oily phase, 40 mg of Span 60 and 60 mg of Tween 80 in a final volume of 10 mL which produced a colloidal system with particle size of 188 nm, zeta potential -32 mV, polydispersion index 0.07, and benzocaine association efficiency > 87%. These findings open the way for future clinical studies using such formulations.

Acquisition of a High Voltage/High resolution Transmission Electron Microscope.

DTIC Science & Technology

1988-08-21

microstructural design starts at the nanometer level. One such method is colloidal processing of materials with ultrafine particles in which particle...applications in the colloidal processing of ceramics with ultrafine particles . Aftervards, nanometer-sized particles will be synthesized and...STRUCTURAL CONTROL WITH ULTRAFINE PARTICLES Jun Liu. Mehmet Sarikaya, and I. A. Aksay Department of Materials Science and Engineering. Advanced

Solid colloidal optical wavelength filter

DOEpatents

Alvarez, Joseph L.

1992-01-01

A solid colloidal optical wavelength filter includes a suspension of spheal particles dispersed in a coagulable medium such as a setting plastic. The filter is formed by suspending spherical particles in a coagulable medium; agitating the particles and coagulable medium to produce an emulsion of particles suspended in the coagulable medium; and allowing the coagulable medium and suspended emulsion of particles to cool.

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2016-12-01

Aggregation kinetics and stability of colloidal particles have been extensively studied using bulk techniques such as dynamic light scattering; these techniques involve large ensembles of particles and interpretation of results is difficult when particles are non-spherical and poorly characterized, as is always the case with non-ideal natural hazardous materials such as asbestos fibers. These difficulties hinder greatly progress on fundamental understanding of whether the classic colloidal aggregation theories can be applied to natural materials and how the heterogeneity of particles (e.g., shape) affects the colloidal aggregation kinetics and structure. By using in-situ microscopy and particle tracking techniques, we were able to observe the particle-by-particle growth of aggregated formed by elongated particles (synthetic glass rods and natural asbestos fibers) and demonstrated the rod-shaped geometry induced novel structures and growth dynamics that challenge existing theory. In this study, we continue to use asbestos as model system of elongated colloidal contaminant, and investigate the effects of changing solution chemistry (e.g., ionic strength, pH, and natural organic matter (NOM)), on growth dynamics and aggregates structure. The results show that aggregate growth curves are self-similar with a characteristic timescale that increases with increasing pH. By varying ionic strength for fixed pH values, we determine that the ccc is sensitive to pH. Fractal dimension decreases slightly with increasing pH and decreasing ionic strength, indicating that stronger inter-particle repulsion create sparser aggregates; however, the magnitude of the solution chemistry effects is much smaller than that of colloid shape. In monovalent solutions, regardless of their concentration, HA drastically reduces the aggregation kinetics of asbestos fiber. This work may lead to enhanced prediction of the colloidal contaminants' mobility in the environment, bioavailability, and toxicity to organisms.

Self-Sorting of Bidispersed Colloidal Particles Near Contact Line of an Evaporating Sessile Droplet.

PubMed

Patil, Nagesh D; Bhardwaj, Rajneesh; Sharma, Atul

2018-06-13

Here, we investigate deposit patterns and associated morphology formed after the evaporation of an aqueous droplet containing mono- and bidispersed colloidal particles. In particular, the combined effect of substrate heating and particle diameter is investigated. We employ high-speed visualization, optical microscopy, and scanning electron microscopy to characterize the evaporating droplets, particle motion, and deposit morphology, respectively. In the context of monodispersed colloidal particles, an inner deposit and a typical ring form for smaller and larger particles, respectively, on a nonheated surface. The formation of the inner deposit is attributed to early depinning of the contact line, explained by a mechanistic model based on the balance of several forces acting on a particle near the contact line. At larger substrate temperature, a thin ring with inner deposit forms, explained by the self-pinning of the contact line and advection of the particles from the contact line to the center of the droplet due to the Marangoni flow. In the context of bidispersed colloidal particles, self-sorting of the colloidal particles within the ring occurs at larger substrate temperature. The smaller particles deposit at the outermost edge compared to the larger particles, and this preferential deposition in a stagnation region near the contact line is due to the spatially varying height of the liquid-gas interface above the substrate. The sorting occurs at a smaller ratio of the diameters of the smaller and larger particles. At larger substrate temperature and larger ratio, the particles do not get sorted and mix into each other. Our measurements show that there exists a critical substrate temperature as well as a diameter ratio to achieve the sorting. We propose regime maps on substrate temperature-particle diameter and substrate temperature-diameter ratio plane for mono- and bidispersed solutions, respectively.

Colloidal interactions and fouling of NF and RO membranes: a review.

PubMed

Tang, Chuyang Y; Chong, T H; Fane, Anthony G

2011-05-11

Colloids are fine particles whose characteristic size falls within the rough size range of 1-1000 nm. In pressure-driven membrane systems, these fine particles have a strong tendency to foul the membranes, causing a significant loss in water permeability and often a deteriorated product water quality. There have been a large number of systematic studies on colloidal fouling of reverse osmosis (RO) and nanofiltration (NF) membranes in the last three decades, and the understanding of colloidal fouling has been significantly advanced. The current paper reviews the mechanisms and factors controlling colloidal fouling of both RO and NF membranes. Major colloidal foulants (including both rigid inorganic colloids and organic macromolecules) and their properties are summarized. The deposition of such colloidal particles on an RO or NF membrane forms a cake layer, which can adversely affect the membrane flux due to 1) the cake layer hydraulic resistance and/or 2) the cake-enhanced osmotic pressure. The effects of feedwater compositions, membrane properties, and hydrodynamic conditions are discussed in detail for inorganic colloids, natural organic matter, polysaccharides, and proteins. In general, these effects can be readily explained by considering the mass transfer near the membrane surface and the colloid-membrane (or colloid-colloid) interaction. The critical flux and limiting flux concepts, originally developed for colloidal fouling of porous membranes, are also applicable to RO and NF membranes. For small colloids (diameter≪100 nm), the limiting flux can result from two different mechanisms: 1) the diffusion-solubility (gel formation) controlled mechanism and 2) the surface interaction controlled mechanism. The former mechanism probably dominates for concentrated solutions, while the latter mechanism may be more important for dilute solutions. Future research needs on RO and NF colloidal fouling are also identified in the current paper. Copyright © 2010 Elsevier B.V. All rights reserved.

Regiospecific Nucleation and Growth of Silane Coupling Agent Droplets onto Colloidal Particles

PubMed Central

2017-01-01

Nucleation-and-growth processes are used extensively in the synthesis of spherical colloids, and more recently regiospecific nucleation-and-growth processes have been exploited to prepare more complex colloids such as patchy particles. We demonstrate that surface geometry alone can be made to play the dominant role in determining the final particle geometry in such syntheses, meaning that intricate chemical surface patternings are not required. We present a synthesis method for “lollipop”-shaped colloidal heterodimers (patchy particles), combining a recently published nucleation-and-growth technique with our recent findings that particle geometry influences the locus of droplet adsorption onto anisotropic template particles. Specifically, 3-methacryloxypropyl trimethoxysilane (MPTMS) is nucleated and grown onto bullet-shaped and nail-shaped colloids. The shape of the template particle can be chosen such that the MPTMS adsorbs regiospecifically onto the flat ends. In particular, we find that particles with a wider base increase the range of droplet volumes for which the minimum in the free energy of adsorption is located at the flat end of the particle compared with bullet-shaped particles of the same aspect ratio. We put forward an extensive analysis of the synthesis mechanism and experimentally determine the physical properties of the heterodimers, supported by theoretical simulations. Here we numerically optimize, for the first time, the shape of finite-sized droplets as a function of their position on the rod-like silica particle surface. We expect that our findings will give an impulse to complex particle creation by regiospecific nucleation and growth. PMID:29057028

Modeling particle-facilitated solute transport using the C-Ride module of HYDRUS

NASA Astrophysics Data System (ADS)

Simunek, Jiri; Bradford, Scott A.

2017-04-01

Strongly sorbing chemicals (e.g., heavy metals, radionuclides, pharmaceuticals, and/or explosives) in soils are associated predominantly with the solid phase, which is commonly assumed to be stationary. However, recent field- and laboratory-scale observations have shown that, in the presence of mobile colloidal particles (e.g., microbes, humic substances, clays and metal oxides), the colloids could act as pollutant carriers and thus provide a rapid transport pathway for strongly sorbing contaminants. Such transport can be further accelerated since these colloidal particles may travel through interconnected larger pores where the water velocity is relatively high. Additionally, colloidal particles have a considerable adsorption capacity for other species present in water because of their large specific surface areas and their high concentrations in soil-water and groundwater. As a result, the transport of contaminants can be significantly, sometimes dramatically, enhanced when they are adsorbed to mobile colloids. To address this problem, we have developed the C-Ride module for HYDRUS-1D. This one-dimensional numerical module is based on the HYDRUS-1D software package and incorporates mechanisms associated with colloid and colloid-facilitated solute transport in variably saturated porous media. This numerical model accounts for both colloid and solute movement due to convection, diffusion, and dispersion in variably-saturated soils, as well as for solute movement facilitated by colloid transport. The colloids transport module additionally considers processes of attachment/detachment to/from the solid phase, straining, and/or size exclusion. Various blocking and depth dependent functions can be used to modify the attachment and straining coefficients. The module additionally considers the effects of changes in the water content on colloid/bacteria transport and attachment/detachment to/from solid-water and air-water interfaces. For example, when the air-water interface disappears during imbibition, particles residing on this interface are released into the liquid phase. Similarly, during drainage, particles residing at the solid-water interface may be detached from this interface by capillary forces and released into the liquid phase or become attached to the air-water interface. The solute transport module uses the concept of two-site sorption to describe nonequilibrium adsorption-desorption reactions to the solid phase. The module further assumes that the contaminant can be sorbed onto surfaces of both deposited and mobile colloids, fully accounting for the dynamics of colloids movement between different phases. We will demonstrate the use of the module using selected datasets and numerical examples.

Folding dynamics of linear emulsion polymers into 3D architectures

NASA Astrophysics Data System (ADS)

McMullen, Angus; Bargteil, Dylan; Brujic, Jasna

Colloidal polymers have been limited to inflexible, solid colloids. Here we show that the fluidity of emulsion droplets allows for the self-assembly of flexible droplet chains, which can subsequently be folded into 3D structures via secondary interactions. We achieve this using DNA-guided interactions, to initially form the chain, and then program its folding pathways. When two emulsion droplets labeled with complementary DNA meet, the balance of hybridization energy and droplet deformation yields an equilibrium patch size. Therefore, the concentration of DNA on the surface determines the number of droplet-droplet bonds in the assembly. We find that 96 % of bound droplets successfully self-assemble into chains. Droplet binding is a stochastic process, following a Poisson distribution of lengths. Since the fluid droplets can rearrange, we compare the dynamics of emulsion chains to that of polymers. We also trigger secondary interactions along the chain, causing the formation of specific loops or compact clusters. This approach will allow us to fold our emulsion polymers into a wide array of soft structures, giving us a powerful biomimetic colloidal system to investigate protein folding on the mesoscopic scale. This work was supported by the NSF MRSEC Program (DMR-0820341).

Robust surface coating for a fast, facile fluorine-18 labeling of iron oxide nanoparticles for PET/MR dual-modality imaging

DOE PAGES

Sun, Ziyan; Cheng, Kai; Wu, Fengyu; ...

2016-10-31

Grafting a robust organic shell around inorganic nanoparticles can optimize their colloidal features to dramatically improve their physicochemical properties. Here, we have developed a polymer coating procedure for providing colloidal stability to the nanoparticles and, more importantly, for applying a fast, facile fluorine-18 labeling of iron oxide nanoparticles (IONPs) for positron emission tomography (PET)/magnetic resonance (MR) dual-modality imaging. The structure of the amphiphilic polymer is based on a backbone of polyacrylic acid, conjugated with multiple oleylamines to form a comb-like branched structure. The dense polymer shell provides high colloidal stability to the IONPs against harsh conditions such as high temperature,more » low pH value, and high ion strength. By incorporating a 1,4,7-triazacyclononane (NOTA) chelator to the comb-like amphiphilic polymer for the chelation of aluminum fluoride ions, we applied a one-step radiolabeling approach for a fast, facile radiofluorination of magnetic nanoparticles. The new strategy can significantly reduce the procedure time and radiation exposure. In conclusion, the PET/MR dual modality imaging was successfully achieved in living subjects by using 18F labeled magnetic nanoparticles.« less

Robust surface coating for a fast, facile fluorine-18 labeling of iron oxide nanoparticles for PET/MR dual-modality imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Ziyan; Cheng, Kai; Wu, Fengyu

Grafting a robust organic shell around inorganic nanoparticles can optimize their colloidal features to dramatically improve their physicochemical properties. Here, we have developed a polymer coating procedure for providing colloidal stability to the nanoparticles and, more importantly, for applying a fast, facile fluorine-18 labeling of iron oxide nanoparticles (IONPs) for positron emission tomography (PET)/magnetic resonance (MR) dual-modality imaging. The structure of the amphiphilic polymer is based on a backbone of polyacrylic acid, conjugated with multiple oleylamines to form a comb-like branched structure. The dense polymer shell provides high colloidal stability to the IONPs against harsh conditions such as high temperature,more » low pH value, and high ion strength. By incorporating a 1,4,7-triazacyclononane (NOTA) chelator to the comb-like amphiphilic polymer for the chelation of aluminum fluoride ions, we applied a one-step radiolabeling approach for a fast, facile radiofluorination of magnetic nanoparticles. The new strategy can significantly reduce the procedure time and radiation exposure. In conclusion, the PET/MR dual modality imaging was successfully achieved in living subjects by using 18F labeled magnetic nanoparticles.« less

Self-assembly of colloid-cholesteric composites provides a possible route to switchable optical materials

NASA Astrophysics Data System (ADS)

Stratford, K.; Henrich, O.; Lintuvuori, J. S.; Cates, M. E.; Marenduzzo, D.

2014-06-01

Colloidal particles dispersed in liquid crystals can form new materials with tunable elastic and electro-optic properties. In a periodic ‘blue phase’ host, particles should template into colloidal crystals with potential uses in photonics, metamaterials and transformational optics. Here we show by computer simulation that colloid/cholesteric mixtures can give rise to regular crystals, glasses, percolating gels, isolated clusters, twisted rings and undulating colloidal ropes. This structure can be tuned via particle concentration, and by varying the surface interactions of the cholesteric host with both the particles and confining walls. Many of these new materials are metastable: two or more structures can arise under identical thermodynamic conditions. The observed structure depends not only on the formulation protocol but also on the history of an applied electric field. This new class of soft materials should thus be relevant to design of switchable, multistable devices for optical technologies such as smart glass and e-paper.

Mesoporous Colloidal Superparticles of Platinum-Group Nanocrystals with Surfactant-Free Surfaces and Enhanced Heterogeneous Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Yongxing; Liu, Yuzi; Sun, Yugang

2015-01-23

Synthesis of colloidal superparticles (CSPs) of nanocrystals, a class of assembled nanocrystals in the form of colloidal particles, has been emerging as a new frontier in the field of nanotechnology because of their potential novel properties originated from coupling of individual nanocrystals in CSPs. Here, a facile approach is reported for the controlled synthesis of mesoporous CSPs made of various platinum-group nanocrystals that exhibit high colloidal stability and ligand-free surfaces to significantly benefit their applications in solution-phase heterogeneous catalysis. The synthesis relies on self-limiting growth of composite particles through coprecipitation of both Pt-group nanocrystals (or their precursor compounds) and silvermore » halides on sacrificial substrates of colloidal silver particles. The intermediate silver halides in the composite particles play the critical role in limiting the continuous growth (and/or coalescence) of individual Pt-group nanocrystals and they can be selectively dissolved to create nanoscale pores in the resulting CSPs.« less

Flocking ferromagnetic colloids

PubMed Central

Kaiser, Andreas; Snezhko, Alexey; Aranson, Igor S.

2017-01-01

Assemblages of microscopic colloidal particles exhibit fascinating collective motion when energized by electric or magnetic fields. The behaviors range from coherent vortical motion to phase separation and dynamic self-assembly. Although colloidal systems are relatively simple, understanding their collective response, especially under out-of-equilibrium conditions, remains elusive. We report on the emergence of flocking and global rotation in the system of rolling ferromagnetic microparticles energized by a vertical alternating magnetic field. By combing experiments and discrete particle simulations, we have identified primary physical mechanisms, leading to the emergence of large-scale collective motion: spontaneous symmetry breaking of the clockwise/counterclockwise particle rotation, collisional alignment of particle velocities, and random particle reorientations due to shape imperfections. We have also shown that hydrodynamic interactions between the particles do not have a qualitative effect on the collective dynamics. Our findings shed light on the onset of spatial and temporal coherence in a large class of active systems, both synthetic (colloids, swarms of robots, and biopolymers) and living (suspensions of bacteria, cell colonies, and bird flocks). PMID:28246633

Flocking ferromagnetic colloids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaiser, Andreas; Snezhko, Alexey; Aranson, Igor S.

Assemblages of microscopic colloidal particles exhibit fascinating collective motion when energized by electric or magnetic fields. The behaviors range from coherent vortical motion to phase separation and dynamic self-assembly. While colloidal systems are relatively simple, understanding their collective response, especially in out of equilibrium conditions, remains elusive. Here, we report on the emergence of flocking and global rotation in the system of rolling ferromagnetic microparticles energized by a vertical alternating magnetic field. By combing experiments and discrete particle simulations, we have identified primary physical mechanisms leading to the emergence of largescale collective motion: spontaneous symmetry breaking of the clock /more » counterclockwise particle rotation, collisional alignment of particle velocities, and random particle re-orientations due to shape imperfections. We have also shown that hydrodynamic interactions between the particles do not have a qualitative effect on the collective dynamics. Lastly, our findings shed light on the onset of spatial and temporal coherence in a large class of active systems, both synthetic (colloids, swarms of robots, biopolymers) and living (suspensions of bacteria, cell colonies, bird flocks).« less

Flocking ferromagnetic colloids

DOE PAGES

Kaiser, Andreas; Snezhko, Alexey; Aranson, Igor S.

2017-02-15

Assemblages of microscopic colloidal particles exhibit fascinating collective motion when energized by electric or magnetic fields. The behaviors range from coherent vortical motion to phase separation and dynamic self-assembly. While colloidal systems are relatively simple, understanding their collective response, especially in out of equilibrium conditions, remains elusive. Here, we report on the emergence of flocking and global rotation in the system of rolling ferromagnetic microparticles energized by a vertical alternating magnetic field. By combing experiments and discrete particle simulations, we have identified primary physical mechanisms leading to the emergence of largescale collective motion: spontaneous symmetry breaking of the clock /more » counterclockwise particle rotation, collisional alignment of particle velocities, and random particle re-orientations due to shape imperfections. We have also shown that hydrodynamic interactions between the particles do not have a qualitative effect on the collective dynamics. Lastly, our findings shed light on the onset of spatial and temporal coherence in a large class of active systems, both synthetic (colloids, swarms of robots, biopolymers) and living (suspensions of bacteria, cell colonies, bird flocks).« less

The Fluctuation-Dissipation Theorem of Colloidal Particle's energy on 2D Periodic Substrates: A Monte Carlo Study of thermal noise-like fluctuation and diffusion like Brownian motion

NASA Astrophysics Data System (ADS)

Najafi, Amin

2014-05-01

Using the Monte Carlo simulations, we have calculated mean-square fluctuations in statistical mechanics, such as those for colloids energy configuration are set on square 2D periodic substrates interacting via a long range screened Coulomb potential on any specific and fixed substrate. Random fluctuations with small deviations from the state of thermodynamic equilibrium arise from the granular structure of them and appear as thermal diffusion with Gaussian distribution structure as well. The variations are showing linear form of the Fluctuation-Dissipation Theorem on the energy of particles constitutive a canonical ensemble with continuous diffusion process of colloidal particle systems. The noise-like variation of the energy per particle and the order parameter versus the Brownian displacement of sum of large number of random steps of particles at low temperatures phase are presenting a markovian process on colloidal particles configuration, too.

Soil colloidal behavior

USDA-ARS?s Scientific Manuscript database

Recent understanding that organic and inorganic contaminants are often transported via colloidal particles has increased interest in colloid science. The primary importance of colloids in soil science stems from their surface reactivity and charge characteristics. Characterizations of size, shape,...

Avalanches and plasticity for colloids in a time dependent optical trap

DOE PAGES

Olson Reichhardt, Cynthia Jane; McDermott, Danielle Marie; Reichhardt, Charles

2015-08-25

Here, with the use of optical traps it is possible to confine assemblies of colloidal particles in two-dimensional and quasi-one-dimensional arrays. Here we examine how colloidal particles rearrange in a quasi-one-dimensional trap with a time dependent confining potential. The particle motion occurs both through slow elastic uniaxial distortions as well as through abrupt large-scale two-dimensional avalanches associated with plastic rearrangements. During the avalanches the particle velocity distributions extend over a broad range and can be fit to a power law consistent with other studies of plastic events mediated by dislocations.

Elasticity and critical bending moment of model colloidal aggregates.

PubMed

Pantina, John P; Furst, Eric M

2005-04-08

The bending mechanics of singly bonded colloidal aggregates are measured using laser tweezers. We find that the colloidal bonds are capable of supporting significant torques, providing a direct measurement of the tangential interactions between particles. A critical bending moment marks the limit of linear bending elasticity, past which small-scale rearrangements occur. These mechanical properties underlie the rheology and dynamics of colloidal gels formed by diffusion-limited cluster aggregation, and give critical insight into the contact interactions between Brownian particles.

Accelerated stability assay (ASA) for colloidal systems.

PubMed

Chong, Josephine Y T; Mulet, Xavier; Boyd, Ben J; Drummond, Calum J

2014-05-12

Assessment of the stability of colloidal systems, in particular lyotropic liquid crystalline dispersions, such as cubosomes and hexosomes, is typically performed qualitatively or with limited throughput on specialized instruments. Here, an accelerated stability assay for colloidal particles has been developed in 384-well plates with standard laboratory equipment. These protocols enable quantitative assessments of colloidal stability. To demonstrate the applicability of the assay, several steric stabilizers for cubic phase nanostructured particles (cubosomes) have been compared to the current "gold standard" Pluronic F127.

Selectively Patterning Polymer Opal Films via Microimprint Lithography.

PubMed

Ding, Tao; Zhao, Qibin; Smoukov, Stoyan K; Baumberg, Jeremy J

2014-11-01

Large-scale structural color flexible coatings have been hard to create, and patterning color on them is key to many applications, including large-area strain sensors, wall-size displays, security devices, and smart fabrics. To achieve controlled tuning, a micro-imprinting technique is applied here to pattern both the surface morphology and the structural color of the polymer opal films (POFs). These POFs are made of 3D ordered arrays of hard spherical particles embedded inside soft shells. The soft outer shells cause the POFs to deform upon imprinting with a pre-patterned stamp, driving a flow of the soft polymer and a rearrangement of the hard spheres within the films. As a result, a patterned surface morphology is generated within the POFs and the structural colors are selectively modified within different regions. These changes are dependent on the pressure, temperature, and duration of imprinting, as well as the feature sizes in the stamps. Moreover, the pattern geometry and structural colors can then be further tuned by stretching. Micropattern color generation upon imprinting depends on control of colloidal transport in a polymer matrix under shear flow and brings many potential properties including stretchability and tunability, as well as being of fundamental interest.

pH Reversible Encapsulation of Oppositely Charged Colloids Mediated by Polyelectrolytes

PubMed Central

2017-01-01

We report the first example of reversible encapsulation of micron-sized particles by oppositely charged submicron smaller colloids. The reversibility of this encapsulation process is regulated by pH-responsive poly(acrylic acid) (PAA) present in solution. The competitive adsorption between the small colloids and the poly(acrylic acid) on the surface of the large colloids plays a key role in the encapsulation behavior of the system. pH offers an experimental knob to tune the electrostatic interactions between the two oppositely charged particle species via regulation of the charge density of the poly(acrylic acid). This results in an increased surface coverage of the large colloids by the smaller colloids when decreasing pH. Furthermore, the poly(acrylic acid) also acts as a steric barrier limiting the strength of the attractive forces between the oppositely charged particle species, thereby enabling detachment of the smaller colloids. Finally, based on the pH tunability of the encapsulation behavior and the ability of the small colloids to detach, reversible encapsulation is achieved by cycling pH in the presence of the PAA polyelectrolytes. The role of polyelectrolytes revealed in this work provides a new and facile strategy to control heteroaggregation behavior between oppositely charged colloids, paving the way to prepare sophisticated hierarchical assemblies. PMID:28419800

Macroscale lateral alignment of semiconductor nanorods into freestanding thin films.

PubMed

Wang, Tie; Wang, Xirui; LaMontagne, Derek; Wang, Zhongwu; Cao, Y Charles

2013-04-24

This Communication reports that needle-like supercrystalline colloidal particles can be synthesized through anisotropy-driven self-assembly of 1,12-dodecanediamine-functionalized CdSe/CdS core/shell nanorods. The resulting superparticles exhibit both 1D lamellar and 2D hexagonal supercrystalline orders along directions parallel and perpendicular to the long axis of constituent nanorods, respectively. Our results show that the needle-like superparticles can be unidirectionally aligned through capillary forces on a patterned solid surface and further transferred into macroscopic, uniform, freestanding polymer films, which exhibit strong linear polarized PL with an enhanced polarization ratio, and are useful as energy down-conversion phosphors in polarized LEDs.

Solvent extraction system for plutonium colloids and other oxide nano-particles

DOEpatents

Soderholm, Lynda; Wilson, Richard E; Chiarizia, Renato; Skanthakumar, Suntharalingam

2014-06-03

The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.

Equilibrium Gold Nanoclusters Quenched with Biodegradable Polymers

PubMed Central

Murthy, Avinash K.; Stover, Robert J.; Borwankar, Ameya U.; Nie, Golay D.; Gourisankar, Sai; Truskett, Thomas M.; Sokolov, Konstantin V.; Johnston, Keith P.

2013-01-01

Although sub-100 nm nanoclusters of metal nanoparticles are of interest in many fields including biomedical imaging, sensors and catalysis, it has been challenging to control their morphologies and chemical properties. Herein, a new concept is presented to assemble equilibrium Au nanoclusters of controlled size by tuning the colloidal interactions with a polymeric stabilizer, PLA(1k)-b-PEG(10k)-b-PLA(1k). The nanoclusters form upon mixing a dispersion of ~5 nm Au nanospheres with a polymer solution followed by partial solvent evaporation. A weakly adsorbed polymer quenches the equilibrium nanocluster size and provides steric stabilization. Nanocluster size is tuned from ~20 nm to ~40 nm by experimentally varying the final Au nanoparticle concentration and the polymer/Au ratio, along with the charge on the initial Au nanoparticle surface. Upon biodegradation of the quencher, the nanoclusters reversibly and fully dissociate to individual ~5 nm primary particles. Equilibrium cluster size is predicted semi-quantitatively with a free energy model that balances short-ranged depletion and van der Waals attractions with longer-ranged electrostatic repulsion, as a function of the Au and polymer concentrations. The close spacings of the Au nanoparticles in the clusters produce strong NIR extinction over a broad range of wavelengths from 650 to 900 nm, which is of practical interest in biomedical imaging. PMID:23230905

Transparent bulk-size nanocomposites with high inorganic loading

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Shi; Gaume, Romain, E-mail: gaume@ucf.edu; Department of Materials Science and Engineering, University of Central Florida, Orlando, Florida 32816

2015-12-14

With relatively high nanoparticle loading in polymer matrices, hybrid nanocomposites made by colloidal dispersion routes suffer from severe inhomogeneous agglomeration, a phenomenon that deteriorates light transmission even when the refractive indices of the inorganic and organic phases are closely matched. The dispersion of particles in a matrix is of paramount importance to obtain composites of high optical quality. Here, we describe an innovative, yet straightforward method to fabricate monolithic transparent hybrid nanocomposites with very high particle loading and high refractive index mismatch tolerance between the inorganic and organic constituents. We demonstrate 77% transmission at 800 nm in a 2 mm-thick acrylate polymermore » nanocomposite containing 61 vol. % CaF{sub 2} nanoparticles. Modeling shows that similar performance could easily be obtained with various inorganic phases relevant to a number of photonic applications.« less

Size-fractionation of groundwater arsenic in alluvial aquifers of West Bengal, India: the role of organic and inorganic colloids.

PubMed

Majumder, Santanu; Nath, Bibhash; Sarkar, Simita; Chatterjee, Debashis; Roman-Ross, Gabriela; Hidalgo, Manuela

2014-01-15

Dissolved organic carbon (DOC) and Fe mineral phases are known to influence the mobility of arsenic (As) in groundwater. Arsenic can be associated with colloidal particles containing organic matter and Fe. Currently, no data is available on the dissolved phase/colloidal association of As in groundwater of alluvial aquifers in West Bengal, India. This study investigated the fractional distribution of As (and other metals/metalloids) among the particulate, colloidal and dissolved phases in groundwater to decipher controlling behavior of organic and inorganic colloids on As mobility. The result shows that 83-94% of As remained in the 'truly dissolved' phases (i.e., <0.05 μm size). Strong positive correlation between Fe and As (r(2) between 0.65 and 0.94) is mainly observed in the larger (i.e., >0.05 μm size) colloidal particles, which indicates the close association of As with larger Fe-rich inorganic colloids. In smaller (i.e., <0.05 μm size) colloidal particles strong positive correlation is observed between As and DOC (r(2)=0.85), which highlights the close association of As with smaller organic colloids. As(III) is mainly associated with larger inorganic colloids, whereas, As(V) is associated with smaller organic/organometallic colloids. Scanning Electron Microscopy and Energy Dispersive X-ray spectroscopy confirm the association of As with DOC and Fe mineral phases suggesting the formation of dissolved organo-Fe complexes and colloidal organo-Fe oxide phases. Attenuated total reflectance-Fourier transform infrared spectroscopy further confirms the formation of As-Fe-NOM organometallic colloids, however, a detailed study of these types of colloids in natural waters is necessary to underpin their controlling behavior. © 2013 Elsevier B.V. All rights reserved.

Shape recognition of microbial cells by colloidal cell imprints

NASA Astrophysics Data System (ADS)

Borovička, Josef; Stoyanov, Simeon D.; Paunov, Vesselin N.

2013-08-01

We have engineered a class of colloids which can recognize the shape and size of targeted microbial cells and selectively bind to their surfaces. These imprinted colloid particles, which we called ``colloid antibodies'', were fabricated by partial fragmentation of silica shells obtained by templating the targeted microbial cells. We successfully demonstrated the shape and size recognition between such colloidal imprints and matching microbial cells. High percentage of binding events of colloidal imprints with the size matching target particles was achieved. We demonstrated selective binding of colloidal imprints to target microbial cells in a binary mixture of cells of different shapes and sizes, which also resulted in high binding selectivity. We explored the role of the electrostatic interactions between the target cells and their colloid imprints by pre-coating both of them with polyelectrolytes. Selective binding occurred predominantly in the case of opposite surface charges of the colloid cell imprint and the targeted cells. The mechanism of the recognition is based on the amplification of the surface adhesion in the case of shape and size match due to the increased contact area between the target cell and the colloidal imprint. We also tested the selective binding for colloid imprints of particles of fixed shape and varying sizes. The concept of cell recognition by colloid imprints could be used for development of colloid antibodies for shape-selective binding of microbes. Such colloid antibodies could be additionally functionalized with surface groups to enhance their binding efficiency to cells of specific shape and deliver a drug payload directly to their surface or allow them to be manipulated using external fields. They could benefit the pharmaceutical industry in developing selective antimicrobial therapies and formulations.

[Spectroscopic Study of Salbutamol Molecularly Imprinted Polymers].

PubMed

Ren, Hui-peng; Guan, Yu-yu; Dai, Rong-hua; Liu, Guo-yan; Chai, Chun-yan

2016-02-01

In order to solve the problem of on-site rapid detection of salbutamol residues in feed and animal products, and develop a new method of fast detection of salbutamol on the basis of the molecular imprinting technology, this article uses the salbutamol (SAL) working as template molecule, methacrylic acid (MAA) working as functional monomer. On this basis, a new type of core-shell type salbutamol molecularly imprinted polymers were prepared with colloidal gold particles as triggering core. Superficial characteristics of the MIPs and the related compounds were investigated by ultraviolet (UV) spectra and infrared (IR) spectra, Raman spectra, Scanning electron microscopy (SEM) respectively. The results indicated that a stable hydrogen bonding complex has been formed between the carboxyl groups of SAL and MA with a matching ratio of 1:1. The complex can be easily eluted by the reagent containing hydrogen bonding. The chemical binding constant K reaches -0.245 x 10⁶ L² · mol⁻². The possible binding sites of the hydrogen bonding was formed between the hydrogen atoms of -COOH in MA and the oxygen atoms of C==O in SAL. IR and Raman spectrum showed that, compared with MA, a significant red shift of -OH absorption peak was manifested in MIPs, which proved that SAL as template molecule occurred a specific bond between MA. Red shift of stretching vibration absorption peak of C==O was also detected in the un-eluted MIPs and obvious energy loss happened, which demonstrated a possible binding sites is SAL intramolecular of C==O atom of oxygen. If the hydrogen atoms of -COOH in MA wanted to generate hydrogen bond. However, the shapes of absorption peak of other functional groups including C==C, C==O, and -OH were very similar both in MIPs and NIPs. Specific cavities were formed after the template molecules in MIPs were removed. It was proved by the adsorption experiment that the specific sites in these cavities highly match with the chemical and space structure of SAL. Besides, colloidal gold type core-shell molecularly imprinted polymers have looser surface, more cavities in the surface compared with ordinary molecularly imprinted polymers, which increased the effective area of adsorption to target molecules. So it have better performance in adsorption. Based on the principle that these cavities can specificly recognize and combine with target molecule in the test sample, and the excellent ability of colloidal gold core-shell molecularly imprinted polymers, the development of novel methods for fast determination of SAL based on the molecular imprinting technology can be expected in the near future.

Short-time dynamics of monomers and dimers in quasi-two-dimensional colloidal mixtures.

PubMed

Sarmiento-Gómez, Erick; Villanueva-Valencia, José Ramón; Herrera-Velarde, Salvador; Ruiz-Santoyo, José Arturo; Santana-Solano, Jesús; Arauz-Lara, José Luis; Castañeda-Priego, Ramón

2016-07-01

We report on the short-time dynamics in colloidal mixtures made up of monomers and dimers highly confined between two glass plates. At low concentrations, the experimental measurements of colloidal motion agree well with the solution of the Navier-Stokes equation at low Reynolds numbers; the latter takes into account the increase in the drag force on a colloidal particle due to wall-particle hydrodynamic forces. More importantly, we find that the ratio of the short-time diffusion coefficient of the monomer and that of the center of mass of the dimmer is almost independent of both the dimer molar fraction, x_{d}, and the total packing fraction, ϕ, up to ϕ≈0.5. At higher concentrations, this ratio displays a small but systematic increase. A similar physical scenario is observed for the ratio between the parallel and the perpendicular components of the short-time diffusion coefficients of the dimer. This dynamical behavior is corroborated by means of molecular dynamics computer simulations that include explicitly the particle-particle hydrodynamic forces induced by the solvent. Our results suggest that the effects of colloid-colloid hydrodynamic interactions on the short-time diffusion coefficients are almost identical and factorable in both species.

Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

DOEpatents

McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

2006-11-21

A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

DOEpatents

McCormick, III, Charles L.; Lowe, Andrew B [Hattiesburg, MS; Sumerlin, Brent S [Pittsburgh, PA

2011-12-27

A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Inverse opal photonic crystal of chalcogenide glass by solution processing.

PubMed

Kohoutek, Tomas; Orava, Jiri; Sawada, Tsutomu; Fudouzi, Hiroshi

2011-01-15

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors. Copyright © 2010 Elsevier Inc. All rights reserved.

Equilibrium state of a cylindrical particle with flat ends in nematic liquid crystals.

PubMed

Hashemi, S Masoomeh; Ejtehadi, Mohammad Reza

2015-01-01

A continuum theory is employed to numerically study the equilibrium orientation and defect structures of a circular cylindrical particle with flat ends under a homeotropic anchoring condition in a uniform nematic medium. Different aspect ratios of this colloidal geometry from thin discotic to long rodlike shapes and several colloidal length scales ranging from mesoscale to nanoscale are investigated. We show that the equilibrium state of this colloidal geometry is sensitive to the two geometrical parameters: aspect ratio and length scale of the particle. For a large enough mesoscopic particle, there is a specific asymptotic equilibrium angle associated to each aspect ratio. Upon reducing the particle size to nanoscale, the equilibrium angle follows a descending or ascending trend in such a way that the equilibrium angle of a particle with the aspect ratio bigger than 1:1 (a discotic particle) goes to a parallel alignment with respect to the far-field nematic, whereas the equilibrium angle for a particle with the aspect ratio 1:1 and smaller (a rodlike particle) tends toward a perpendicular alignment to the uniform nematic direction. The discrepancy between the equilibrium angles of the mesoscopic and nanoscopic particles originates from the significant differences between their defect structures. The possible defect structures related to mesoscopic and nanoscopic colloidal particles of this geometry are also introduced.

EDITORIAL: Colloidal dispersions in external fields Colloidal dispersions in external fields

NASA Astrophysics Data System (ADS)

Löwen, Hartmut

2012-11-01

Colloidal dispersions have long been proven as pivotal model systems for equilibrium phase transition such as crystallization, melting and liquid-gas phase transition. The last decades have revealed that this is also true for nonequilibrium phenomena. In fact, the fascinating possibility to track the individual trajectories of colloidal particles has greatly advanced our understanding of collective behaviour in classical many-body systems and has helped to reveal the underlying physical principles of glass transition, crystal nucleation, and interfacial dynamics (to name just a few typical nonequilibrium effects). External fields can be used to bring colloids out of equilibrium in a controlled way. Different kinds of external fields can be applied to colloidal dispersions, namely shear flow, electric, magnetic and laser-optical fields, and confinement. Typical research areas can be sketched with the by now traditional complexity diagram (figure 1). The complexity of the colloidal system itself as embodied in statistical degrees of freedom is shown on the x-axis while the complexity of the problem posed, namely bulk, an inhomogeneity in equilibrium, steady state nonequilibrium and full time-dependent nonequilibrium are shown on the y-axis. The different external fields which can be imposed are indicated by the different hatched areas. figure1 Figure 1. Diagram of complexity for colloidal dispersions in external fields: while the x-axis shows the complexity of the system, the y-axis shows the complexity of the problem. Regions which can be accessed by different kinds of external fields are indicated. The arrows indicate recent research directions. Active particles are also indicated with a special complexity of internal degrees of freedom [1]. This collection of papers reflects the scientific programme of the International Conference on Colloidal Dispersions in External Fields III (CODEF III) which took place in Bonn-Bad Godesberg from 20-23 March 2012. This was the third conference in a series that began in 2004 [2] and was continued in 2008 [3]. The CODEF meeting series is held in conjunction with the German Dutch Transregional Collaborative Research Centre SFB TR6 with the title Physics of Colloidal Dispersions in External Fields. Papers from scientists working within this network as well as those from further invited contributors are summarized in this issue. They are organized according to the type of field applied, namely: shear flow electric field laser-optical and magnetic field confinement other fields and active particles To summarize the highlights of this special issue as regards shear fields, the response of depletion-induced colloidal clusters to shear is explored in [4]. Soft particles deform under shear and their structural and dynamical behaviour is studied both by experiment [5] and theory [6]. Transient dynamics after switching on shear is described by a joint venture of theory, simulation and experiment in [7]. Colloids provide the fascinating possibility to drag single particles through the suspension, which gives access to microrheology (as opposed to macrorheology, where macroscopic boundaries are moved). Several theoretical aspects of microrheology are discussed in this issue [8-10]. Moreover, a microscopic theory for shear viscosity is presented [11]. Various aspects of colloids in electric fields are also included in this issue. Electrokinetic phenomena for charged suspensions couple flow and electric phenomena in an intricate way and are intensely discussed both by experiment and simulation in contributions [12-14]. Dielectric phenomena are also influenced by electric fields [15]. Electric fields can induce effective dipolar forces between colloids leading to string formation [16]. Finally, binary mixtures in an electric driving field exhibit laning [17]. Simulation [18] and theoretical [19] studies of this nonequilibrium phenomenon are also discussed in this issue. Laser-optical fields can be used to tailor a random substrate potential for colloids [20] or to bind colloids optically [21]. External magnetic fields are typically used to create dipolar repulsions of colloids pending at an air-water interface. This provides an avenue to two-dimensional systems, where the freezing transition [22] and various transport phenomena through channels are the focus of recent research [23, 24]. Confinement typically leads to interfaces. The classical problem of the Tolman length for a fluid-fluid interface is reviewed in detail in [25]. In fact, colloid-polymer mixtures constitute ideal model systems for liquid-gas interfaces in various geometries [26] and are also suitable for measuring the Tolman length experimentally. Crystalline phases in confinement [27] and crystal-fluid interfaces [28] are even more complex due to the inhomogeneity of the solid phase. Also in the confined fluid phase, there are still open issues in slit-pore geometry. These include how to scale the interparticle distance [29] and how to measure hydrodynamic interactions between colloidal particles [30]. Other external fields which can be applied to colloids are gravity [31] and temperature [32]. An important field of recently emerging research is active colloidal particles (so-called microswimmers) which possess fascinating nonequilibrium properties; for recent reviews see [33-35]. Two examples are also included in this issue: an active deformable particle [36] moving in gravity and the collective turbulent swarming behaviour of dense self-propelled colloidal rod suspensions [37]. References [1]Löwen H 2001 J. Phys. Condens. Matter 13 R415 [2]Löwen H and Likos C N (ed) 2004 J. Phys. Condens. Matter 16 (special issue) [3]Löwen H 1976 J. Phys. Condens. Matter 20 404201 [4]Guu D, Dhont J K G, Vliegenthart G A and Lettinga M P 2012 J. Phys. Condens. Matter 24 464101 [5]Gupta S, Kundu S, Stellbrink J, Willner L, Allgaier J and Richter D 2012 J. Phys. Condens. Matter 24 464102 [6]Singh S P, Fedosov D A, Chatterji A, Winkler R G, Gompper G 2012 J. Phys. Condens. Matter 24 464103 [7]Laurati M et al 2012 J. Phys. Condens. Matter 24 464104 [8]Harrer C J, Winter D, Horbach J, Fuchs M and Voigtmann T 2012 J. Phys. Condens. Matter 24 464105 [9]De Puit R J and Squires T M 2012 J. Phys. Condens. Matter 24 464106 [10]De Puit R J and Squires T M 2012 J. Phys. Condens. Matter 24 464107 [11]Contreras-Aburto C and Nägele G 2012 J. Phys. Condens. Matter 24 464108 [12]Palberg T, Köller T, Sieber B, Schweinfurth H, Reiber H and Nägele G 2012 J. Phys. Condens. Matter 24 464109 [13]Papadopoulos P, Deng X and Vollmer D 2012 J. Phys. Condens. Matter 24 464110 [14]Schmitz R and Dünweg B 2012 J. Phys. Condens. Matter 24 464111 [15]Zhou J and Schmid F 2012 J. Phys. Condens. Matter 24 464112 [16]Smallenburg F, Vutukuri H R, Imhof A, van Blaaderen A and Dijkstra M 2012 J. Phys. Condens. Matter 24 464113 [17]Vissers T, Wysocki A, Rex M, Löwen H, Royall C P, Imhof A and van Blaaderen A 2011 Soft Matter 7 2352 [18]Glanz T and Löwen H 2012 J. Phys. Condens. Matter 24 464114 [19]Kohl M, Ivlev A, Brand P, Morfill G E and Löwen H 2012 J. Phys. Condens. Matter 24 464115 [20]Hanes R D L and Egelhaaf S U 2012 J. Phys. Condens. Matter 24 464116 [21]Mazilu M, Rudhall A, Wright E M and Dholakia K 2012 J. Phys. Condens. Matter 24 464117 [22]Dillmann P, Maret G and Keim P 2012 J. Phys. Condens. Matter 24 464118 [23]Wilms D et al 2012 J. Phys. Condens. Matter 24 464119 [24]Kreuter C, Siems U, Henseler P, Nielaba P, Leiderer P and Erbe A 2012 J. Phys. Condens. Matter 24 464120 [25]Malijevsky A and Jackson G 2012 J. Phys. Condens. Matter 24 464121 [26]Statt A, Winkler A, Virnau P and Binder K 2012 J. Phys. Condens. Matter 24 464122 [27]Oğuz E C, Löwen H, Reinmüller A, Schöpe H J, Palberg T and Messina R 2012 J. Phys. Condens. Matter 24 464123 [28]Oettel M 2012 J. Phys. Condens. Matter 24 464124 [29]Zeng Y and van Klitzing R 2012 J. Phys. Condens. Matter 24 464125 [30]Bonilla-Capilla B, Ramirez-Saito A, Ojeda-Lopez M A and Arauz-Lara J L 2012 J. Phys. Condens. Matter 24 464126 [31]Leferink op Reinink A B G M, van den Pol E, Byelov D V, Petukhov A V and Vroege G J 2012 J. Phys. Condens. Matter 24 464127 [32]Taylor S L, Evans R and Royall C P 2012 J. Phys. Condens. Matter 24 464128 [33]Toner J, Tu Y H and Ramaswamy S 2012 J. Phys. Condens. Matter 24 464110 [34]Schmitz R and Dünweg B 2005 J. Phys. Condens. Matter 318 170 [35]Cates M E 2012 Rep. Prog. Phys. 75 042601 [36]Tarama M and Ohta T 2012 J. Phys. Condens. Matter 24 464129 [37]Wensink H H and Löwen H 2012 J. Phys. Condens. Matter 24 464130 Colloidal dispersions in external fields contents Colloidal dispersions in external fieldsHartmut Löwen Depletion induced clustering in mixtures of colloidal spheres and fd-virusD Guu, J K G Dhont, G A Vliegenthart and M P Lettinga Advanced rheological characterization of soft colloidal model systemsS Gupta, S K Kundu, J Stellbrink, L Willner, J Allgaier and D Richter Conformational and dynamical properties of ultra-soft colloids in semi-dilute solutions under shear flowSunil P Singh, Dmitry A Fedosov, Apratim Chatterji, Roland G Winkler and Gerhard Gompper Transient dynamics in dense colloidal suspensions under shear: shear rate dependenceM Laurati, K J Mutch, N Koumakis, J Zausch, C P Amann, A B Schofield, G Petekidis, J F Brady, J Horbach, M Fuchs and S U Egelhaaf Force-induced diffusion in microrheologyCh J Harrer, D Winter, J Horbach, M Fuchs and Th Voigtmann Micro-macro-discrepancies in nonlinear microrheology: I. Quantifying mechanisms in a suspension of Brownian ellipsoidsRyan J DePuit and Todd M Squires Micro-macro discrepancies in nonlinear microrheology: II. Effect of probe shapeRyan J DePuit and Todd M Squires Viscosity of electrolyte solutions: a mode-coupling theoryClaudio Contreras-Aburto and Gerhard Nägele Electro-kinetics of charged-sphere suspensions explored by integral low-angle super-heterodyne laser Doppler velocimetryThomas Palberg, Tetyana Köller, Bastian Sieber, Holger Schweinfurth, Holger Reiber and Gerhard Nägele Electrokinetics on superhydrophobic surfacesPeriklis Papadopoulos, Xu Deng, Doris Vollmer and Hans-Jürgen Butt Numerical electrokineticsR Schmitz and B Dünweg Dielectric response of nanoscopic spherical colloids in alternating electric fields: a dissipative particle dynamics simulationJiajia Zhou and Friederike Schmid Self-assembly of colloidal particles into strings in a homogeneous external electric or magnetic fieldFrank Smallenburg, Hanumantha Rao Vutukuri, Arnout Imhof, Alfons van Blaaderen and Marjolein Dijkstra The nature of the laning transition in two dimensionsT Glanz and H Löwen Microscopic theory for anisotropic pair correlations in driven binary mixturesMatthias Kohl, Alexei V Ivlev, Philip Brandt, Gregor E Morfill and Hartmut Löwen Dynamics of individual colloidal particles in one-dimensional random potentials: a simulation studyRichard D L Hanes and Stefan U Egelhaaf An interacting dipole model to explore broadband transverse optical bindingMichael Mazilu, Andrew Rudhall, Ewan M Wright and Kishan Dholakia Comparison of 2D melting criteria in a colloidal systemPatrick Dillmann, Georg Maret and Peter Keim Effects of confinement and external fields on structure and transport in colloidal dispersions in reduced dimensionalityD Wilms, S Deutschländer, U Siems, K Franzrahe, P Henseler, P Keim, N Schwierz, P Virnau, K Binder, G Maret and P Nielaba Stochastic transport of particles across single barriersChristian Kreuter, Ullrich Siems, Peter Henseler, Peter Nielaba, Paul Leiderer and Artur Erbe A perspective on the interfacial properties of nanoscopic liquid dropsAlexandr Malijevský and George Jackson Controlling the wetting properties of the Asakura-Oosawa model and applications to spherical confinementA Statt, A Winkler, P Virnau and K Binder Crystalline multilayers of charged colloids in soft confinement: experiment versus theoryE C Oğuz, A Reinmüller, H J Schöpe, T Palberg, R Messina and H Löwen Mode expansion for the density profiles of crystal-fluid interfaces: hard spheres as a test caseM Oettel Scaling of layer spacing of charged particles under slit-pore confinement: an effect of concentration or of effective particle diameter?Yan Zeng and Regine von Klitzing Hydrodynamic interactions between colloidal particles in a planar poreB Bonilla-Capilla, A Ramírez-Saito, M A Ojeda-López and J L Arauz-Lara Ageing in a system of polydisperse goethite boardlike particles showing rich phase behaviourA B G M Leferink op Reinink, E van den Pol, D V Byelov, A V Petukhov and G J Vroege Temperature as an external field for colloid-polymer mixtures: 'quenching' by heating and 'melting' by coolingShelley L Taylor, Robert Evans and C Patrick Royall Spinning motion of a deformable self-propelled particle in two dimensionsMitsusuke Tarama and Takao Ohta Emergent states in dense systems of active rods: from swarming to turbulenceH H Wensink and H Löwen

Effect of fluid-colloid interactions on the mobility of a thermophoretic microswimmer in non-ideal fluids.

PubMed

Fedosov, Dmitry A; Sengupta, Ankush; Gompper, Gerhard

2015-09-07

Janus colloids propelled by light, e.g., thermophoretic particles, offer promising prospects as artificial microswimmers. However, their swimming behavior and its dependence on fluid properties and fluid-colloid interactions remain poorly understood. Here, we investigate the behavior of a thermophoretic Janus colloid in its own temperature gradient using numerical simulations. The dissipative particle dynamics method with energy conservation is used to investigate the behavior in non-ideal and ideal-gas like fluids for different fluid-colloid interactions, boundary conditions, and temperature-controlling strategies. The fluid-colloid interactions appear to have a strong effect on the colloid behavior, since they directly affect heat exchange between the colloid surface and the fluid. The simulation results show that a reduction of the heat exchange at the fluid-colloid interface leads to an enhancement of colloid's thermophoretic mobility. The colloid behavior is found to be different in non-ideal and ideal fluids, suggesting that fluid compressibility plays a significant role. The flow field around the colloid surface is found to be dominated by a source-dipole, in agreement with the recent theoretical and simulation predictions. Finally, different temperature-control strategies do not appear to have a strong effect on the colloid's swimming velocity.

Pattern formation in binary colloidal assemblies: hidden symmetries in a kaleidoscope of structures.

PubMed

Lotito, Valeria; Zambelli, Tomaso

2018-06-10

In this study we present a detailed investigation of the morphology of binary colloidal structures formed by self-assembly at air/water interface of particles of two different sizes, with a size ratio such that the larger particles do not retain a hexagonal arrangement in the binary assembly. While the structure and symmetry of binary mixtures in which such hexagonal order is preserved has been thoroughly scrutinized, binary colloids in the regime of non-preservation of the hexagonal order have not been examined with the same level of detail due also to the difficulty in finding analysis tools suitable to recognize hidden symmetries in seemingly amorphous and disordered arrangements. For this purpose, we resorted to a combination of different analysis tools based on computational geometry and computational topology in order to get a comprehensive picture of the morphology of the assemblies. By carrying out an extensive investigation of binary assemblies in this regime with variable concentration of smaller particles with respect to larger particles, we identify the main patterns that coexist in the apparently disordered assemblies and detect transitions in the symmetries upon increase in the number of small particles. As the concentration of small particles increases, large particle arrangements become more dilute and a transition from hexagonal to rhombic and square symmetries occurs, accompanied also by an increase in clusters of small particles; the relative weight of each specific symmetry can be controlled by varying the composition of the assemblies. The demonstration of the possibility to control the morphology of apparently disordered binary colloidal assemblies by varying experimental conditions and the definition of a route for the investigation of disordered assemblies are precious for future studies of complex colloidal patterns to understand self-assembly mechanisms and to tailor physical properties of colloidal assemblies.

Exploring the Dynamics and Structure of Soft Colloids at Oil-water Interfaces

NASA Astrophysics Data System (ADS)

Kwok, Man Hin

The ability of solid colloidal particles to physically stabilize emulsions, also referred to as Pickering emulsions, has been studied for a long time since their activity at the interface was discovered one hundred years ago. Pickering emulsions display various interesting phenomena because of it high desorption energy at the interface compared with conventional surfactant stabilizers. In addition, Pickering emulsions are considered to be 'surfactant free' emulsion and the adverse effects of using surfactants could be eliminated. In the past few years, the use of submicrometer, poly(N-isopropylacrylamide) (PNIPAM)-based mcirogel particles for stabilizing emulsions has captured the interest of many scientists. Being soft, the microgels, which are spherical in solution, become deformed at the oil-water interface. This deformability leads to the special dynamic properties of interfacial layers and packing structures, which in turn alters the interfacial tension and the rheological properties of the interface. In addition, being responsiveness, PNIPAM microgels enable emulsions to be prepared and broken on demand. Despite all of the practical advantages and unique properties that have already been demonstrated, the mechanisms that govern emulsion stabilization and destabilization using microgels are far from completely understood. The study of soft colloids at the interface thus is of great academic interest and the fundamental understanding of them is the key to achieve the application potential of such novel materials. This thesis focuses on the dynamics and structure of soft colloidal particles at the oil-water interfaces. First, in order to prepare tailored colloids for the study, the syntheses of multi-responsive PNIPAM microgels with different size, co-monomers, deformability and morphologies were thoroughly investigated. The combination of semi-batch synthesis and temperature-programmed technique resulted in a novel preparation of micron-sized PNIPAM microgels. Various experimental parameters were tested and modified in order to give microgels with optimized quality. The thermo- and pH- responsiveness of these microgels were characterized by laser diffraction and dynamic light scattering (DLS). Next, a novel labeling technique of the soft PNIPAM microgel particles was developed. This technique was based on the physical adsorption of small fluorescent molecules. Instead of chemically bonded dye molecules, these adsorbed fluorescent dyes could move freely inside the polymer network of the microgel particle. It was also found that the fluorescent dye interacted with different parts of the microgel differently. Therefore, the internal structure and morphology of microgels could be directly visualized by confocal laser scanning microscopy (CLSM) in aqueous environment. The improvement of imaging techniques of microgel particles is essential for studying their behavior at the oil-water interface. It is because conventional scanning electron microscopy (SEM) requires dried sample, which might not reflects the actual states of microgels in aqueous environment. With the improved labeling method under CLSM mentioned above, the conformation of micron-sized PNIPAM microgel particles was captured at the oil-water interface. Particularly, anisotropic deformation of soft pH-responsive microgels was observed at the oil-water interface. Nevertheless, it was found that microgels were not likely to deform significantly unless they were extremely swollen. We also use Langmuir trough to study the dynamics of microgel at an interface with changing area. Forced desorption-spontaneous adsorption cycles of microgel particles at the oil-water interface were successfully demonstrated. More interestingly, it was discovered that the microgel particles would be desorbed before having a significant deformation in Langmuir trough compression. Finally, the emulsion stability of the microgel stabilized Pickering emulsion was characterized by centrifugation. By comparing the stability of different microgels in different conditions, the correlation between the microgel properties and the corresponding Pickering emulsion stability was found. The emulsion stability and the interfacial behaviors of PNIPAM based microgels can now be better controlled and predicted, which gives great advantages for future applications using soft colloids as stabilizers.

Foam capacity and stability of Sodium Dodecyl Sulfate (SDS) on the presence of contaminant coffee and Cd ions in solution

NASA Astrophysics Data System (ADS)

Haryanto, B.; Chang, C. H.; Kuo, A. T.; Siswarni, M. Z.; Sinaga, T. M. A.

2018-02-01

In this study, the effect of the coffee colloidal particle and Cd ion contaminant on the foam capacity and stability of sodium dodecyl sulfate (SDS) solution was investigated. The foam was generated by using a foam generator. The foam capacity of SDS was first evaluated at different concentrations. After the foam capacity reaching a constant value, the foam stability was then measured by flowing to a column. The results showed that the presence the coffee colloidal particles or Cd ions in the solution would decrease the foam capacity and stability of SDS. In addition, the decreased foam capacity and stability was more pronounced in the presence of coffee colloidal particles than Cd ions. The colloidal particles may have stronger interaction with SDS and thus reduce the formation of the foam.

Cyclodextrin based nanosponges for pharmaceutical use: a review.

PubMed

Tejashri, Gursalkar; Amrita, Bajaj; Darshana, Jain

2013-09-01

Nanosponges are a novel class of hyper-crosslinked polymer based colloidal structures consisting of solid nanoparticles with colloidal sizes and nanosized cavities. These nano-sized colloidal carriers have been recently developed and proposed for drug delivery, since their use can solubilize poorly water-soluble drugs and provide prolonged release as well as improve a drug's bioavailability by modifying the pharmacokinetic parameters of actives. Development of nanosponges as drug delivery systems, with special reference to cyclodextrin based nanosponges, is presented in this article. In the current review, attempts have been made to illustrate the features of cyclodextrin based nanosponges and their applications in pharmaceutical formulations. Special emphasis has been placed on discussing the methods of preparation, characterization techniques and applications of these novel drug delivery carriers for therapeutic purposes. Nanosponges can be referred to as solid porous particles having a capacity to load drugs and other actives into their nanocavity; they can be formulated as oral, parenteral, topical or inhalation dosage forms. Nanosponges offer high drug loading compared to other nanocarriers and are thus suitable for solving issues related to stability, solubility and delayed release of actives. Controlled release of the loaded actives and solubility enhancement of poorly water-soluble drugs are major advantages of nanosponge drug delivery systems.

Colloidal Confinement of Polyphosphate on Gold Nanoparticles Robustly Activates the Contact Pathway of Blood Coagulation.

PubMed

Szymusiak, Magdalena; Donovan, Alexander J; Smith, Stephanie A; Ransom, Ross; Shen, Hao; Kalkowski, Joseph; Morrissey, James H; Liu, Ying

2016-01-20

Platelet-sized polyphosphate (polyP) was functionalized on the surface of gold nanoparticles (GNPs) via a facile conjugation scheme entailing EDAC (N-(3-(dimethylamino)propyl)-N'-ethylcarbodiimide hydrochloride)-catalyzed phosphoramidation of the terminal phosphate of polyP to cystamine. Subsequent reduction of the disulfide moiety allowed for anchoring to the colloidal surface. The ability of the synthesized polyP-GNPs to initiate the contact pathway of clotting in human pooled normal plasma (PNP) was then assayed by quantifying changes in viscous, mechanical, and optical properties upon coagulation. It is revealed that the polyP-GNPs are markedly superior contact activators compared to molecularly dissolved, platelet-sized polyP (of equivalent polymer chain length). Moreover, the particles' capacity to mobilize Factor XII (FXII) and its coactivating proteins appear to be identical to very-long-chain polyP typically found in bacteria. These data imply that nanolocalization of anionic procoagulants on colloidal surfaces, achieved through covalent anchoring, may yield a robust contact surface with the ability to sufficiently cluster active clotting factors together above their threshold concentrations to cease bleeding. The polyP-GNPs therefore serve as a promising foundation in the development of a nanoparticle hemostat to treat a range of hemorrhagic scenarios.

Comparison across Three Hybrid Lipid-Based Drug Delivery Systems for Improving the Oral Absorption of the Poorly Water-Soluble Weak Base Cinnarizine.

PubMed

Joyce, Paul; Yasmin, Rokhsana; Bhatt, Achal; Boyd, Ben J; Pham, Anna; Prestidge, Clive A

2017-11-06

Three state-of-the-art drug delivery vehicles engineered by nanostructuring lipid colloids within solid particle matrices were fabricated for the oral delivery of the poorly water-soluble, weak base, cinnarizine (CIN). The lipid and solid phase of each formulation was varied to systematically analyze the impact of key material characteristics, such as nanostructure and surface chemistry, on the in vitro and in vivo fate of CIN. The three systems formulated were: silica-stabilized lipid cubosomes (SSLC), silica-solid lipid hybrid (SSLH), and polymer-lipid hybrid (PLH) particles. Significant biopharmaceutical advantages were presented for CIN when solubilized in the polymer (poly(lactic-co-glycolic) acid; PLGA) and lipid phase of PLH particles compared to the lipid phases of SSLC and SSLH particles. In vitro dissolution in simulated intestinal conditions highlighted reduced precipitation of CIN when administered within PLH particles, given by a 4-5-fold improvement in the extent of CIN dissolution compared to the other delivery vehicles. Furthermore, CIN solubilization was enhanced 1.5-fold and 6-fold under simulated fasted state lipid digestion conditions when formulated with PLH particles compared to SSLH and SSLC particles, respectively. In vivo pharmacokinetics correlated well with in vitro solubilization data, whereby oral CIN bioavailability in rats, when encapsulated in the corresponding formulations, increased from SSLC < SSLH < PLH. The pharmacokinetic data obtained throughout this study indicated a synergistic effect between PLGA nanoparticles and lipid droplets in preventing CIN precipitation and thus, enhancing oral absorption. This synergy can be harnessed to efficiently deliver challenging poorly water-soluble, weak bases through oral administration.

Synthesis and self-assembly of Janus and patchy colloidal particles

NASA Astrophysics Data System (ADS)

Jiang, Shan

Colloidal particles are considered classically as spherical particles with homogeneous surface chemistry. When this is so, the interactions between particles are isotropic and governed only by their separations. One can take advantage of this to simulate atoms, visualizing them one-by-one in a microscope, albeit at a larger length scale and longer time scale than for true atoms. However if the particles are not homogeneous, but Janus or patchy instead, with different surface chemistry on different hemispheres or otherwise different surface sites that are addressably controlled, the interactions between these particles depend not only on their separation, but also on their orientation. Research on Janus and patchy colloidal particles has opened a new chapter in the colloid research field, allowing us to mimic the behavior of these colloidal analogues of molecules, and in this way to ask new and exciting questions of condensed matter physics. In this dissertation, I investigated the synthesis and self-assembly of Janus and patchy colloidal particles with emphasis on Janus amphiphilic particles, which are the colloidal counterpart of surfactant molecules. Improving the scale-up capability, and also the capacity to control the geometry of Janus particles, I developed a simple and versatile method to synthesize Janus particles using an approach based on Pickering emulsions with particles adsorbed at the liquid-liquid interface. I showed that this method can be scaled up to synthesize Janus particles in large quantity. Also, the Janus balance can be predictably controlled by adding surfactant molecules during emulsification. In addition, going beyond the Janus geometry, I developed another synthetic method to fabricate trivalent patchy colloidal particles using micro-contact printing. With these synthetic methods in hand, I explored the self-assembly of Janus amphiphilic particles in aqueous solutions, while controlling systematically the salt concentration, the particle concentration, and the Janus balance. Various cluster and chain structures were observed. Using in situ optical microscopy, I found these structures to be dynamic in structure, in this respect analogous to the micelles formed by small surfactant molecules. A qualitative explanation about the possible underlying mechanism was proposed, based on considering the tradeoff between enthalpy gain from hydrophobic contacts, and entropy involving rotational orientation between neighboring particles. Monolayer crystals of Janus amphiphilic particles were investigated in a system of silica-based particles. Regarding positional order, these particles adopted a conventional hexagonal packing, but their orientations formed strikingly ordered linear clusters that extended the length of tens of particles. Study of their rotational dynamics using single particle tracking showed rotation to be strongly coupled between adjacent particles, with a correlation length extending to sevearl particle diameters. This is a beautiful example of a unique physical phenomenon that simply does not exist when dealing with classical particles whose surface chemical makeup is homogeneous. At the oil-water interface, Janus amphiphilic particles adsorb strongly. With simple calculations, I showed that the adsorption energy depends not only on surface tension but also on the Janus balance. I developed a rigorous mathematical definition of "Janus balance" that may find application in emulsions stabilized by Janus particles. On the experimental side, I performed experiments to quantify the efficacy of Janus particles to stabilize emulsions for extended times.

Thermal Motion and Forced Migration of Colloidal Particles Generate Hydrostatic Pressure in Solvent

PubMed Central

Hammel, H. T.; Scholander, P. F.

1973-01-01

A colloidal solution of ferrite particles in an osmometer has been used to demonstrate that the property that propels water across the semipermeable membrane is the decrease in hydrostatic pressure in the water of the solution. A magnetic field gradient directed so as to force the ferrite particles away from the semipermeable membrane of the osmometer and toward the free surface of the solution enhanced the colloidal osmotic pressure. The enhancement of this pressure was always exactly equal to the augmentation of the pressure as measured by the outward force of the particles, against the area of the free surface. Contrariwise, directing the magnetic field gradient so as to force the ferrite particles away from the free surface and toward the semipermeable membrane diminished the colloidal osmotic pressure of the solution. For a sufficiently forceful field gradient, the initial colloidal osmotic pressure could be negative, followed by an equilibrium pressure approaching zero regardless of the force of the particles against the membrane. Thus, the osmotic pressure of a solution is to be attributed to the pressure in the solvent generated in opposition to the pressure of the solute particles caused by their interaction with the free surface (Brownian motion and/or an external field force), or by their viscous shear when they migrate through the solvent, or both. PMID:16592046

An Experimental Examination of Combustion of Isolated Liquid Fuel Droplets with Polymeric and Nanoparticle Additives

NASA Astrophysics Data System (ADS)

Ghamari, Mohsen

In spite of recent attention to renewable sources of energy, liquid hydrocarbon fuels are still the main source of energy for industrial and transportation systems. Manufactures and consumers are consistently looking for ways to optimize the efficiency of fuel combustion in terms of cost, emissions and consumer safety. In this regard, increasing burning rate of liquid fuels has been of special interest in both industrial and transportation systems. Recent studies have shown that adding combustible nano-particles could have promising effects on improving combustion performance of liquid fuels. Combustible nano-particles could enhance radiative and conductive heat transfer and also mixing within the droplet. Polymeric additive have also shown promising effect on improving fire safety by suppressing spreading behavior and splatter formation in case of crash scenario. Polymers are also known to have higher burning rate than regular hydrocarbon fuels. Therefore adding polymeric additive could have the potential to increase the burning rate. In this work, combustion dynamics of liquid fuel droplets with both polymeric and nanoparticle additives is studied in normal gravity. High speed photography is employed and the effect of additive concentration on droplet burning rate, burning time, extinction and soot morphology is investigated. Polymer added fuel was found to have a volatility controlled combustion with four distinct regimes. The first three zones are associated with combustion of base fuel while the polymer burns last and after a heating zone because of its higher boiling point. Polymer addition reduces the burning rate of the base fuel in the first zone by means of increasing viscosity and results in nucleate boiling and increased burning rates in the second and third stages. Overall, polymer addition resulted in a higher burning rate and shorter burning time in most of the scenarios. Colloidal suspensions of carbon-based nanomaterials in liquid fuels were also tested at different particle loadings. It was found that dispersing nanoparticles results in higher burning rate by means of enhanced radiative heat absorption and thermal conductivity. An optimum particle loading was found for each particle type at which the maximum burning rate was achieved. It was observed that the burning rate again starts to reduce after this optimum point most likely due to the formation of large aggregates that reduce thermal conductivity and suppress the diffusion of species.

Bio-Inspired Bright Structurally Colored Colloidal Amorphous Array Enhanced by Controlling Thickness and Black Background.

PubMed

Iwata, Masanori; Teshima, Midori; Seki, Takahiro; Yoshioka, Shinya; Takeoka, Yukikazu

2017-07-01

Inspired by Steller's jay, which displays angle-independent structural colors, angle-independent structurally colored materials are created, which are composed of amorphous arrays of submicrometer-sized fine spherical silica colloidal particles. When the colloidal amorphous arrays are thick, they do not appear colorful but almost white. However, the saturation of the structural color can be increased by (i) appropriately controlling the thickness of the array and (ii) placing the black background substrate. This is similar in the case of the blue feather of Steller's jay. Based on the knowledge gained through the biomimicry of structural colored materials, colloidal amorphous arrays on the surface of a black particle as the core particle are also prepared as colorful photonic pigments. Moreover, a structural color on-off system is successfully built by controlling the background brightness of the colloidal amorphous arrays. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Active Approach to Colloidal Self-Assembly

NASA Astrophysics Data System (ADS)

Mallory, Stewart A.; Valeriani, Chantal; Cacciuto, Angelo

2018-04-01

In this review, we discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field, with a specific focus on dry active matter. We explore this phenomenology through the lens of the complexity of the colloidal building blocks. We begin by considering the behavior of isotropic spherical particles. We then discuss the case of amphiphilic and dipolar Janus particles. Finally, we show how the geometry of the colloids and/or the directionality of their interactions can be used to control the physical properties of the assembled active aggregates, and we suggest possible strategies for how to exploit activity as a tunable driving force for self-assembly. The unique properties of active colloids lend promise to the design of the next generation of functional, environment-sensing microstructures able to perform specific tasks in an autonomous and targeted manner.

Monitoring solute interactions with poly(ethylene oxide)-modified colloidal silica nanoparticles via fluorescence anisotropy decay.

PubMed

Tleugabulova, Dina; Duft, Andy M; Brook, Michael A; Brennan, John D

2004-01-06

The fluorescence-based nanosize metrology approach, proposed recently by Geddes and Birch (Geddes, C. D.; Birch, D. J. S. J. Non-Cryst. Solids 2000, 270, 191), was used to characterize the extent of binding of a fluorescent cationic solute, rhodamine 6G (R6G), to the surface of silica particles after modification of the surface with the hydrophilic polymer poly(ethylene oxide) (PEO) of various molecular weights. The measurement of the rotational dynamics of R6G in PEO solutions showed the absence of strong interactions between R6G and PEO chains in water and the ability of the dye to sense the presence of polymer clusters in 30 wt % solutions. Time-resolved anisotropy decays of polymer-modified Ludox provided direct evidence for distribution of the dye between bound and free states, with the bound dye showing two decay components: a nanosecond decay component that is consistent with local motions of bound probes and a residual anisotropy component due to slow rotation of large silica particles. The data showed that the dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Addition of PEO blocked the adsorption of the dye to a significant degree, with up to 50% of the probe being present in the aqueous solution for Ludox samples containing 30 wt % of low molecular weight PEO. The addition of such agents also decreased the value and increased the fractional contribution of the nanosecond rotational correlation time, suggesting that polymer adsorption altered the degree of local motion of the bound probe. Atomic force microscopy imaging studies provided no evidence for a change in the particle size upon surface modification but did suggest interparticle aggregation after polymer adsorption. Thus, this redistribution of the probe is interpreted as being due to coverage of particles with the polymer, resulting in lower adsorption of R6G to the silica. The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the modification of silica surfaces and suggest that this method should prove useful in characterization of new chromatographic stationary phases and nanocomposite materials.

Microgel mechanics in biomaterial design.

PubMed

Saxena, Shalini; Hansen, Caroline E; Lyon, L Andrew

2014-08-19

The field of polymeric biomaterials has received much attention in recent years due to its potential for enhancing the biocompatibility of systems and devices applied to drug delivery and tissue engineering. Such applications continually push the definition of biocompatibility from relatively straightforward issues such as cytotoxicity to significantly more complex processes such as reducing foreign body responses or even promoting/recapitulating natural body functions. Hydrogels and their colloidal analogues, microgels, have been and continue to be heavily investigated as viable materials for biological applications because they offer numerous, facile avenues in tailoring chemical and physical properties to approach biologically harmonious integration. Mechanical properties in particular are recently coming into focus as an important manner in which biological responses can be altered. In this Account, we trace how mechanical properties of microgels have moved into the spotlight of research efforts with the realization of their potential impact in biologically integrative systems. We discuss early experiments in our lab and in others focused on synthetic modulation of particle structure at a rudimentary level for fundamental drug delivery studies. These experiments elucidated that microgel mechanics are a consequence of polymer network distribution, which can be controlled by chemical composition or particle architecture. The degree of deformability designed into the microgel allows for a defined response to an imposed external force. We have studied deformation in packed colloidal phases and in translocation events through confined pores; in all circumstances, microgels exhibit impressive deformability in response to their environmental constraints. Microgels further translate their mechanical properties when assembled in films to the properties of the bulk material. In particular, microgel films have been a large focus in our lab as building blocks for self-healing materials. We have shown that their ability to heal after damage arises from polymer mobility during hydration. Furthermore, we have shown film mobility dictates cell adhesion and spreading in a manner that is fundamentally different from previous work on mechanotransduction. In total, we hope that this Account presents a broad introduction to microgel research that intersects polymer chemistry, physics, and regenerative medicine. We expect that research intersection will continue to expand as we fill the knowledge gaps associated with soft materials in biological milieu.

Correlated diffusion of colloidal particles near a liquid-liquid interface.

PubMed

Zhang, Wei; Chen, Song; Li, Na; Zhang, Jia Zheng; Chen, Wei

2014-01-01

Optical microscopy and multi-particle tracking are used to investigate the cross-correlated diffusion of quasi two-dimensional colloidal particles near an oil-water interface. The behaviors of the correlated diffusion along longitudinal and transverse direction are asymmetric. It is shown that the characteristic length for longitudinal and transverse correlated diffusion are particle diameter d and the distance z from particle center to the interface, respectively, for large particle separation z. The longitudinal and transverse correlated diffusion coefficient D||(r) and D[perpendicular](r) are independent of the colloidal area fraction n when n < 0.3, which indicates that the hydrodynamic interactions(HIs) among the particles are dominated by HIs through the surrounding fluid for small n. For high area fraction n > 0.4 the power law exponent for the spatial decay of [Formula: see text] begins to decrease, which suggests the HIs are more contributed from the 2D particle monolayer self for large n.

Bead-Based Microfluidic Sediment Analogues: Fabrication and Colloid Transport.

PubMed

Guo, Yang; Huang, Jingwei; Xiao, Feng; Yin, Xiaolong; Chun, Jaehun; Um, Wooyong; Neeves, Keith B; Wu, Ning

2016-09-13

Mobile colloids can act as carriers for low-solubility contaminants in the environment. However, the dominant mechanism for this colloid-facilitated transport of chemicals is unclear. Therefore, we developed a bead-based microfluidic platform of sediment analogues and measured both single and population transport of model colloids. The porous medium is assembled through a bead-by-bead injection method. This approach has the versatility to build both electrostatically homogeneous and heterogeneous media at the pore scale. A T-junction at the exit also allowed for encapsulation and enumeration of colloids effluent at single particle resolution to give population dynamics. Tortuosity calculated from pore-scale trajectory analysis and its comparison with lattice Boltzmann simulations revealed that transport of colloids was influenced by the size exclusion effect. The porous media packed by positively and negatively charged beads into two layers showed distinctive colloidal particle retention and significant remobilization and re-adsorption of particles during water flushing. We demonstrated the potential of our method to fabricate porous media with surface heterogeneities at the pore scale. With both single and population dynamics measurement, our platform has the potential to connect pore-scale and macroscale colloid transport on a lab scale and to quantify the impact of grain surface heterogeneities that are natural in the subsurface environment.

Drainage and Stratification Kinetics of Foam Films

NASA Astrophysics Data System (ADS)

Zhang, Yiran; Sharma, Vivek

2014-03-01

Baking bread, brewing cappuccino, pouring beer, washing dishes, shaving, shampooing, whipping eggs and blowing bubbles all involve creation of aqueous foam films. Foam lifetime, drainage kinetics and stability are strongly influenced by surfactant type (ionic vs non-ionic), and added proteins, particles or polymers modify typical responses. The rate at which fluid drains out from a foam film, i.e. drainage kinetics, is determined in the last stages primarily by molecular interactions and capillarity. Interestingly, for certain low molecular weight surfactants, colloids and polyelectrolyte-surfactant mixtures, a layered ordering of molecules, micelles or particles inside the foam films leads to a stepwise thinning phenomena called stratification. Though stratification is observed in many confined systems including foam films containing particles or polyelectrolytes, films containing globular proteins seem not to show this behavior. Using a Scheludko-type cell, we experimentally study the drainage and stratification kinetics of horizontal foam films formed by protein-surfactant mixtures, and carefully determine how the presence of proteins influences the hydrodynamics and thermodynamics of foam films.

[Automobile tyre colloidal particle induced allergic damage of respiratory system in traffic policemen and its allergenicity].

PubMed

Zhang, Yong-xing; Wei, Qing-yu; Wang, Juan; Qiao, Ting-hui; Bai, Hong-bing; Cai, Li-na

2007-06-01

To explore the damage of respiratory system in the traffic policemen induced by automobile tyre colloidal particle and its allergenicity. The respiratory system symptoms in 445 traffic policemen working outside their offices and 243 controls were investigated and their pulmonary ventilation function index such as FVC, FEV(1.0), MMF and V(50) were determined. The specific IgE antibody of automobile tyre colloidal particle of their serum was determined and the skin-prick test of automobile tyre colloidal particle antigen was performed. Sixty-six traffic policemen working outside their offices and 5 controls with the positive of IgE antibody among them were detected by nasal mucosa provocation test. Sixty-six traffic policemen working outside their offices with the positive of IgE antibody were determined by Terbutaline inhalation test. The positive rate of respiratory system symptoms of traffic policemen such as cough, stethocatharsis, short breath, nasal obstruction, sneeze and nose running was 38.02%, 27.03%, 20.00%, 23.08%, 27.47%, 32.09% and 34.95% respectively and significantly higher than those of the control with significant difference (P < 0.01) or (P < 0.05). The positive rate of specific IgE antibody of automobile tyre colloidal particle, skin- prick test and nasal mucosa provocation test was 14.51%, 23.73% and 54.55% respectively with significant difference (P < 0.01) and (P < 0.05). The percentage, the actual figure compared with the prediction figure, of the index of pulmonary ventilation function (FVC, FEV(1.0) MMF and V(50)) of traffic policemen were significantly lower than those of the control. Terbutaline inhalation test in 66 positive subjects of specific IgE antibody of automobile tyre colloidal particle was positive in 44 subjects, accounting for 9.67% in all policemen investigated. The automobile tyre colloidal particle is one of etiological factors that induce pulmonary ventilation function damage and could result in allergic asthma of traffic police.

Estimating Colloidal Contact Model Parameters Using Quasi-Static Compression Simulations.

PubMed

Bürger, Vincent; Briesen, Heiko

2016-10-05

For colloidal particles interacting in suspensions, clusters, or gels, contact models should attempt to include all physical phenomena experimentally observed. One critical point when formulating a contact model is to ensure that the interaction parameters can be easily obtained from experiments. Experimental determinations of contact parameters for particles either are based on bulk measurements for simulations on the macroscopic scale or require elaborate setups for obtaining tangential parameters such as using atomic force microscopy. However, on the colloidal scale, a simple method is required to obtain all interaction parameters simultaneously. This work demonstrates that quasi-static compression of a fractal-like particle network provides all the necessary information to obtain particle interaction parameters using a simple spring-based contact model. These springs provide resistances against all degrees of freedom associated with two-particle interactions, and include critical forces or moments where such springs break, indicating a bond-breakage event. A position-based cost function is introduced to show the identifiability of the two-particle contact parameters, and a discrete, nonlinear, and non-gradient-based global optimization method (simplex with simulated annealing, SIMPSA) is used to minimize the cost function calculated from deviations of particle positions. Results show that, in principle, all necessary contact parameters for an arbitrary particle network can be identified, although numerical efficiency as well as experimental noise must be addressed when applying this method. Such an approach lays the groundwork for identifying particle-contact parameters from a position-based particle analysis for a colloidal system using just one experiment. Spring constants also directly influence the time step of the discrete-element method, and a detailed knowledge of all necessary interaction parameters will help to improve the efficiency of colloidal particle simulations.

Inverse Photonic Glasses by Packing Bidisperse Hollow Microspheres with Uniform Cores.

PubMed

Kim, Seung-Hyun; Magkiriadou, Sofia; Rhee, Do Kyung; Lee, Doo Sung; Yoo, Pil J; Manoharan, Vinothan N; Yi, Gi-Ra

2017-07-19

A major fabrication challenge is producing disordered photonic materials with an angle-independent structural red color. Theoretical work has shown that such a color can be produced by fabricating inverse photonic glasses with monodisperse, nontouching voids in a silica matrix. Here, we demonstrate a route toward such materials and show that they have an angle-independent red color. We first synthesize monodisperse hollow silica particles with precisely controlled shell thickness and then make glassy colloidal structures by mixing two types of hollow particles with the same core size and different shell thicknesses. We then infiltrate the interstices with index-matched polymers, producing disordered porous materials with uniform, nontouching air voids. This procedure allows us to control the light-scattering form factor and structure factor of these porous materials independently, which is not possible to do in photonic glasses consisting of packed solid particles. The structure factor can be controlled by the shell thickness, which sets the distance between pores, whereas the pore size determines the peak wave vector of the form factor, which can be set below the visible range to keep the main structural color pure. By using a binary mixture of 246 and 268 nm hollow silica particles with 180 nm cores in an index-matched polymer matrix, we achieve angle-independent red color that can be tuned by controlling the shell thickness. Importantly, the width of the reflection peak can be kept constant, even for larger interparticle distances.

Modulation of Spatiotemporal Particle Patterning in Evaporating Droplets: Applications to Diagnostics and Materials Science.

PubMed

Guha, Rajarshi; Mohajerani, Farzad; Mukhopadhyay, Ahana; Collins, Matthew D; Sen, Ayusman; Velegol, Darrell

2017-12-13

Spatiotemporal particle patterning in evaporating droplets lacks a common design framework. Here, we demonstrate autonomous control of particle distribution in evaporating droplets through the imposition of a salt-induced self-generated electric field as a generalized patterning strategy. Through modeling, a new dimensionless number, termed "capillary-phoresis" (CP) number, arises, which determines the relative contributions of electrokinetic and convective transport to pattern formation, enabling one to accurately predict the mode of particle assembly by controlling the spontaneous electric field and surface potentials. Modulation of the CP number allows the particles to be focused in a specific region in space or distributed evenly. Moreover, starting with a mixture of two different particle types, their relative placement in the ensuing pattern can be controlled, allowing coassemblies of multiple, distinct particle populations. By this approach, hypermethylated DNA, prevalent in cancerous cells, can be qualitatively distinguished from normal DNA of comparable molecular weights. In other examples, we show uniform dispersion of several particle types (polymeric colloids, multiwalled carbon nanotubes, and molecular dyes) on different substrates (metallic Cu, metal oxide, and flexible polymer), as dictated by the CP number. Depending on the particle, the highly uniform distribution leads to surfaces with a lower sheet resistance, as well as superior dye-printed displays.

Size-controlled synthesis of transition metal nanoparticles through chemical and photo-chemical routes

NASA Astrophysics Data System (ADS)

Tangeysh, Behzad

The central objective of this work is developing convenient general procedures for controlling the formation and stabilization of nanoscale transition metal particles. Contemporary interest in developing alternative synthetic approaches for producing nanoparticles arises in large part from expanding applications of the nanomaterials in areas such as catalysis, electronics and medicine. This research focuses on advancing the existing nanoparticle synthetic routes by using a new class of polymer colloid materials as a chemical approach, and the laser irradiation of metal salt solution as a photo-chemical method to attain size and shape selectivity. Controlled synthesis of small metal nanoparticles with sizes ranging from 1 to 5nm is still a continuing challenge in nanomaterial synthesis. This research utilizes a new class of polymer colloid materials as nano-reactors and protective agents for controlling the formation of small transition metal nanoparticles. The polymer colloid particles were formed from cross-linking of dinegatively charged metal precursors with partially protonated poly dimethylaminoethylmethacrylate (PDMAEMA). Incorporation of [PtCl6]2- species into the colloidal particles prior to the chemical reduction was effectively employed as a new strategy for synthesis of unusually small platinum nanoparticles with narrow size distributions (1.12 +/-0.25nm). To explore the generality of this approach, in a series of proof-of-concept studies, this method was successfully employed for the synthesis of small palladium (1.4 +/-0.2nm) and copper nanoparticles (1.5 +/-0.6nm). The polymer colloid materials developed in this research are pH responsive, and are designed to self-assemble and/or disassemble by varying the levels of protonation of the polymer chains. This unique feature was used to tune the size of palladium nanoparticles in a small range from 1nm to 5nm. The procedure presented in this work is a new convenient room temperature route for synthesis of small nanoparticles, and its application can be extended to the formation of other transition metals and alloy nanoparticles. This research also focuses on developing new photo-chemical routes for controlling the size and shape of the nanoparticles through high-intensity ultra-fast laser irradiation of metal salt solution. One of the core objectives of this work is to explore the special capabilities of shaped laser pulses in formation of metal nanoparticles through irradiation of the solutions by using simultaneous spatial and temporal focusing (SSTF). Femtosecond laser irradiation has not yet been widely applied for nanoparticle synthesis, and offers new regimes of energy deposition for synthesis of nanomaterials. Photo-reduction of aqueous [AuCl4]- solution to the gold nanoparticles (AuNPs) has been applied as a model process for optimizing the experimental procedures, and evaluating the potential of shaped laser pulses in the synthesis of AuNPs. Systematic manipulation of the laser parameters and experimental conditions provided effective strategies to control the size of Au nanoparticles in strong laser fields. Varying the concentration of polyethylene glycol (PEG45) as a surfactant effectively tuned the size of AuNPs from 3.9 +/-0.7nm to 11.0 +/-2.4nm, and significantly increased the rate of Au(III) reduction during irradiation. Comparative studies revealed the capability of shaped laser pulses in the generation of smaller and more uniform AuNPs (5.8 +/-1.1nm) relative to the other conventional laser irradiation methods (7.2 +/-2.9nm). Furthermore, a new laser-assisted approach has been developed for selective formation of triangular Au nanoplates in the absence of any surfactant molecule. This method relies on rapid energy deposition by using shaped, ultra-intense laser pulses to generate Au seeds in aqueous [AuCl4]- solution, and the slow post-irradiation reduction of un-reacted [AuCl4]- species by using H2O2 as a mild reducing agent. Variation of the laser irradiation-time was found as an effective strategy to tune the morphology of Au nanomaterials from nanospheres to triangular nanoplates. The surfactant-free Au nanoplates produced in this research can be readily functionalized with a variety of target molecules or surfactants for desirable applications such as biomedicine. The concept of rapid laser processing followed by in situ chemical reduction can be expanded as a general methodology for high-yield production of nanomaterials, and provides a series of new laser dependent parameters for controlling the nanoparticle formation.

Functionalized patchy particles using colloidal lenses

NASA Astrophysics Data System (ADS)

Middleton, Christine

2014-03-01

Colloidal assembly had been limited by the isotropic, nonspecific nature of interactions between spherical colloidal particles. By giving particles patches functionalized with single stranded DNA, these interactions can be made both directional and specific. We create patchy particles by adding patches to spherical emulsion droplets using the depletion interaction. First we make polystyrene particles in the shape of contact lenses to be the patches. The lenses are functionalized with single stranded DNA on their convex side. Then we put the lenses on the surface of oil emulsion droplets using the depletion interaction, creating a patch (or multiple patches) on the surface of each emulsion droplet. The emulsion droplets can now interact with each other in a specific, directional way through DNA functionalized patches.

Effect of barrier properties of zein colloidal particles and oil-in-water emulsions on oxidative stability of encapsulated bioactive compounds

USDA-ARS?s Scientific Manuscript database

Oxidation of encapsulated bioactive compounds is a key challenge that limits shelf-life of bioactive containing products. The objectives of this study were to compare differences between the oxidative barrier properties of biopolymer particle based encapsulation system (zein colloidal particles) and...

Universal Features of the Fluid to Solid Transition for Attractive Colloidal Particles

NASA Technical Reports Server (NTRS)

Cipelletti, L.; Prasad, V.; Dinsmore, A.; Segre, P. N.; Weitz, D. A.; Trappe, V.

2002-01-01

Attractive colloidal particles can exhibit a fluid to solid phase transition if the magnitude of the attractive interaction is sufficiently large, if the volume fraction is sufficiently high, and if the applied stress is sufficiently small. The nature of this fluid to solid transition is similar for many different colloid systems, and for many different forms of interaction. The jamming phase transition captures the common features of these fluid to solid translations, by unifying the behavior as a function of the particle volume fraction, the energy of interparticle attractions, and the applied stress. This paper describes the applicability of the jamming state diagram, and highlights those regions where the fluid to solid transition is still poorly understood. It also presents new data for gelation of colloidal particles with an attractive depletion interaction, providing more insight into the origin of the fluid to solid transition.

Quercetin loaded biopolymeric colloidal particles prepared by simultaneous precipitation of quercetin with hydrophobic protein in aqueous medium.

PubMed

Patel, Ashok R; Heussen, Patricia C M; Hazekamp, Johan; Drost, Ellen; Velikov, Krassimir P

2012-07-15

Quercetin loaded biopolymeric colloidal particles were prepared by precipitating quercetin (water insoluble polyphenol) and zein (hydrophobic protein), simultaneously, by adding their hydro-alcoholic solution to aqueous solution in presence of sodium caseinate as an electrosteric stabiliser. The presence of protein resulted in altering the shape of quercetin precipitates from needle-like to spherical shape at higher zein proportions, as confirmed by transmission electron microscopy. The average particle size of zein:quercetin composite particles was below 200 nm (130-161 nm) with negative surface charge (-30 to -41 mV), as confirmed by dynamic light scattering and electrophoretic mobility data. Solid state characterisation (X-ray diffraction) and spectroscopic measurements (UV-Vis and IR spectroscopy) confirmed characteristic changes in quercetin due to the entrapment in the biopolymeric matrix of colloidal particles. Results from anti-oxidant study demonstrated the advantage of entrapping quercetin in the colloidal particles in terms of the chemical stability in the alkaline pH and against photodegradation under UV-light irradiation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interactions in charged colloidal suspensions: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Padidela, Uday Kumar; Behera, Raghu Nath

2017-07-01

Colloidal suspensions are extensively used in everyday life and find several applications in the pharmaceutical, chemical, food industries, etc. We present the classical molecular dynamics simulation results of the structural and transport properties of charged colloidal suspensions as a function of its size, charge and concentration. The system is viewed as a two-component (colloids and counterions) primitive model consisting of spherical colloid particle (macroion) and the counterions (micro-particles), which are treated explicitly. The solvent is treated as dielectric continuum. A systematic trend in the radial distribution functions g(r), potential of mean force W(r), different thermodynamic properties and diffusion coefficients is obtained as a function of colloid charge, size and concentration. An attractive minimum in W(r) is obtained at short interparticle distance.

Synthesis of a colloid solution of silica-coated gold nanoparticles for X-ray imaging applications

NASA Astrophysics Data System (ADS)

Kobayashi, Yoshio; Nagasu, Ryoko; Shibuya, Kyosuke; Nakagawa, Tomohiko; Kubota, Yohsuke; Gonda, Kohsuke; Ohuchi, Noriaki

2014-08-01

This work proposes a method for fabricating silica-coated gold (Au) nanoparticles, surface modified with poly(ethylene glycol) (PEG) (Au/SiO2/PEG), with a particle size of 54.8 nm. X-ray imaging of a mouse is performed with the colloid solution. A colloid solution of 17.9 nm Au nanoparticles was prepared by reducing Au ions (III) with sodium citrate in water at 80 °C. The method used for silica-coating the Au nanoparticles was composed of surface-modification of the Au nanoparticles with (3-aminopropyl)-trimethoxysilane (APMS) and a sol-gel process. The sol-gel process was performed in the presence of the surface-modified Au nanoparticles using tetraethylorthosilicate, APMS, water, and sodium hydroxide, in which the formation of silica shells and the introduction of amino groups to the silica-coated particles took place simultaneously (Au/SiO2-NH2). Surface modification of the Au/SiO2-NH2 particles with PEG, or PEGylation of the particle surface, was performed by adding PEG with a functional group that reacted with an amino group in the Au/SiO2-NH2 particle colloid solution. A computed tomography (CT) value of the aqueous colloid solution of Au/SiO2/PEG particles with an actual Au concentration of 0.112 M was as high as 922 ± 12 Hounsfield units, which was higher than that of a commercial X-ray contrast agent with the same iodine concentration. Injecting the aqueous colloid solution of Au/SiO2/PEG particles into a mouse increased the light contrast of tissues. A CT value of the heart rose immediately after the injection, and this rise was confirmed for up to 6 h.

Colloidal stability of CeO2 nanoparticles coated with either natural organic matter or organic polymers under various hydrochemical conditions

NASA Astrophysics Data System (ADS)

Dippon, Urs; Pabst, Silke; Klitzke, Sondra

2016-04-01

The worldwide marked for engineered nanoparticles (ENPs) is growing and concerns on the environmental fate- and toxicity of ENPs are rising. Understanding the transport of ENPs within and between environmental compartments such as surface water and groundwater is crucial for exposition modeling, risk assessment and ultimately the protection of drinking water resources. The transport of ENPs is strongly influenced by the surface properties and aggregation behavior of the particles, which is strongly controlled by synthetic and natural organic coatings. Both, surface properties and aggregation characteristics are also key properties for the industrial application of ENPs, which leads to the development and commercialization of an increasing number of surface-functionalized ENPs. These include metals and oxides such as Cerium dioxide (CeO2) with various organic coatings. Therefore, we investigate CeO2 ENPs with different surface coatings such as weakly anionic polyvinyl alcohol (PVA) or strongly anionic poly acrylic acid (PAA) with respect to their colloidal stability in aqueous matrix under various hydrochemical conditions (pH, ionic strength) and their transport behavior in sand filter columns. Furthermore, we investigate the interaction of naturally occurring organic matter (NOM) with CeO2 ENPs and its effect on surface charge (zeta potential), colloidal stability and transport. While uncoated CeO2 ENPs aggregate at pH > 4 in aqueous matrix, our results show that PAA and PVA surface coatings as well as NOM sorbed to CeO2-NP surfaces can stabilize CeO2 ENPs under neutral and alkaline pH conditions in 1 mM KCl solution. Under slightly acidic conditions, differences between the three particle types were observed. PVA can stabilize particle suspensions in presence of 1 mM KCl at pH > 4.3, PAA at pH >4.0 and NOM at >3.2. While the presence of KCl did not influence particle size of NOM-CeO2 ENPs, CaCl2 at >2 mM lead to aggregation. Further results on the influence of KCl and CaCl2 on aggregation of coated CeO2 ENPs and transport in sand filter columns will be presented.

Manipulating colloids with charges and electric fields

NASA Astrophysics Data System (ADS)

Leunissen, M. E.

2007-02-01

This thesis presents the results of experimental investigations on a variety of colloidal suspensions. Colloidal particles are at least a hundred times larger than atoms or molecules, but suspended in a liquid they display the same phase behavior, including fluid and crystalline phases. Due to their relatively large size, colloids are much easier to investigate and manipulate, though. This makes them excellent condensed matter model systems. With this in mind, we studied micrometer-sized perspex (‘PMMA’) spheres, labeled with a fluorescent dye for high-resolution confocal microscopy imaging, and suspended in a low-polar mixture of the organic solvents cyclohexyl bromide and cis-decalin. This system offered us the flexibility to change the interactions between the particles from ‘hard-sphere-like’ to long-ranged repulsive (between like-charged particles), long-ranged attractive (between oppositely charged particles) and dipolar (in an electric field). We investigated the phase behavior of our suspensions as a function of the particle concentration, the ionic strength of the solvent and the particles’ charges. In this way, we obtained new insight in the freezing and melting behavior of like-charged and oppositely charged colloids. Interestingly, we found that the latter can readily form large crystals, thus defying the common belief that plus-minus interactions inevitably lead to aggregation. Moreover, we demonstrated that these systems can serve as a reliable model system for classical ionic matter (‘salts’), and that opposite-charge interactions can greatly facilitate the self-assembly of new structures with special properties for applications. On a slightly different note, we also studied electrostatic effects in mixtures of the cyclohexyl bromide solvent and water, both with and without colloidal particles present. This provided new insight in the stabilization mechanisms of oil-water emulsions and gave us control over the self-assembly of various useful colloidal structures. Besides modifying the particle charge, we employed the sensitivity of colloids to ‘external fields’ to manipulate the structure and dynamics of our suspensions. In particular, we used an electric field, in which the particles acquired a dipole moment. The induced dipole-dipole interactions gave rise to uniquely different crystalline and non-crystalline structures, due to their anisotropic nature. We explored the phase behavior as a function of the particle concentration, the electric field strength and the field geometry, and showed how one can rapidly switch from one structure to another. The latter is particularly interesting for applications. Finally, we also studied much weaker, inhomogeneous electric fields. In this case, the dipole moment of the particles was too small to change the phase behavior, but large enough to induce dielectrophoretic motion, driving the particles to the areas with the lowest field strength. We demonstrated how this can be used to manipulate the local particle concentration inside a sealed sample, on a time scale of minutes-weeks. The combination with real-time confocal microscopy allowed us to follow all particle rearrangements during the densification. Such controlled compression is of interest to colloidal model studies and the fabrication of high-quality crystals for applications. After all, for all suspensions the particle concentration is one of the most important factors determining the behavior.

Sorption of vanadium (V) onto natural soil colloids under various solution pH and ionic strength conditions.

PubMed

Luo, Xiuhua; Yu, Lin; Wang, Changzhao; Yin, Xianqiang; Mosa, Ahmed; Lv, Jialong; Sun, Huimin

2017-02-01

Batch sorption kinetics and isothermal characteristics of V(V) were investigated on three natural soil colloids (manual loessial soil colloid (MSC), aeolian sandy soil colloid (ASC), and cultivated loessial soil colloid (CSC)) under various solution pH and ionic strength (IS) conditions. Colloids were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). AFM micrographs showed CSC with an aggregated shape with larger particle diameter as compared with ASC and MSC. XRD spectra revealed the presence of different minerals in natural soil colloids including biotite, kaolinite, calcite and quartz, which might contribute to sorption process. The sorption ability decreased with increase of colloidal particle size. The sorption was mainly attributed to complexation by active carboxylate and alcohol groups of colloidal components. Sorption kinetics and isotherms of V(V) onto natural soil colloids were best fitted with Pseudo-second-order and Freundlich models. Langmuir model indicated that sorption capacity of MSC and ASC was comparable (285.7 and 238.1 mg g -1 ); however, CSC exhibited the lowest sorption capacity (41.5 mg g -1 ) due to its larger particle diameter and aggregated shape. The maximum V(V) sorption capacity reached plateau values at a solution pH ranged between 5.0 and 9.0 for MSC and ASC, and 6.0-8.0 for CSC. Sorption capacity of V(V) onto natural soil colloids decreased with increasing IS. Based on result of this study we can conclude that sorption of V(V) onto natural soil colloids is pH- and IS-dependent. These findings provide insights on the remediation of vanadium-contaminated soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystallization of DNA-coated colloids

PubMed Central

Wang, Yu; Wang, Yufeng; Zheng, Xiaolong; Ducrot, Étienne; Yodh, Jeremy S.; Weck, Marcus; Pine, David J.

2015-01-01

DNA-coated colloids hold great promise for self-assembly of programmed heterogeneous microstructures, provided they not only bind when cooled below their melting temperature, but also rearrange so that aggregated particles can anneal into the structure that minimizes the free energy. Unfortunately, DNA-coated colloids generally collide and stick forming kinetically arrested random aggregates when the thickness of the DNA coating is much smaller than the particles. Here we report DNA-coated colloids that can rearrange and anneal, thus enabling the growth of large colloidal crystals from a wide range of micrometre-sized DNA-coated colloids for the first time. The kinetics of aggregation, crystallization and defect formation are followed in real time. The crystallization rate exhibits the familiar maximum for intermediate temperature quenches observed in metallic alloys, but over a temperature range smaller by two orders of magnitude, owing to the highly temperature-sensitive diffusion between aggregated DNA-coated colloids. PMID:26078020

Magnetic field gradient driven self-assembly of superparamagnetic nanoparticles using programmable magnetically-recorded templates

NASA Astrophysics Data System (ADS)

Ye, L.; Qi, B.; Lawton, T. G.; Mefford, O. T.; Rinaldi, C.; Garzon, S.; Crawford, T. M.

2013-03-01

Using the enormous magnetic field gradients (100 MT/m @ z =20 nm) present near the surface of magnetic recording media, we demonstrate the fabrication of diffraction gratings with lines consisting entirely of magnetic nanoparticles assembled from a colloidal fluid onto a disk drive medium, followed by transfer to a flexible and transparent polymer thin film. These nanomanufactured gratings have line spacings programmed with commercial magnetic recording and are inherently concave with radii of curvature controlled by varying the polymer film thickness. The diffracted intensity increases non-monotonically with the length of time the colloidal fluid remains on the disk surface. In addition to comparing longitudinal and perpendicular magnetic recording, a combination of spectral diffraction efficiency measurements, magnetometry, scanning electron microscopy and inductively coupled plasma atomic emmission spectroscopy of these gratings are employed to understand colloidal nanoparticle dynamics in this extreme gradient limit. Such experiments are necessary to optimize nanoparticle assembly and obtain uniform patterned features. This low-cost and sustainable approach to nanomanufacturing could enable low-cost, high-quality diffraction gratings as well as more complex polymer nanocomposite materials assembled with single-nanometer precision.

Polymer coated gold nanoparticles for tracing the mobility of engineered nanoparticles in the subsurface

NASA Astrophysics Data System (ADS)

Uthuppu, Basil; Sidelmann Fjordbøge, Annika; Caspersen, Eva; Broholm, Mette Martina; Havsteen Jakobsen, Mogens

2014-05-01

Nanoparticles (NPs) are manufactured for their specific properties providing possibilities for new and improved products and applications. The use of engineered nanoparticles (ENPs) has therefore brought significant innovation and advances to society, including benefits for human health and the environment. At the same time, little is known about the potential risk associated with the inevitable release of these new materials to the environment, and their new properties are poorly understood . Suspensions of ENPs are not very stable, as they tend to aggregate thereby losing their properties as single particles. Coatings, including a large variety of natural and synthetic polymers, are used to enhance the colloid stability in high concentrations . However, increasing the stability of these materials may lead to unintended effects, such as enhancing their mobility in surface water and groundwater leading to inadvertent impacts on aquatic ecosystems and human health. Detection of ENPs in natural water systems, however, has proved very challenging. Hence, there is a need for tracing of ENP behaviour in the environment. We suggest a possibility of introducing inert gold NPs with the same mobility as the reactive NPs, as tracer particles. Colloidal gold has been of great interest for centuries due to its vibrant colors produced by the interaction with visible light. The unusual optical-electronic properties, high chemical stability and relatively low toxicity have made them the model system of choice in this context. Also, the natural occurrence of these particles in the proposed environment is very rare. Laboratory based experiments conducted in sand columns show that stable aqueous suspensions of gold NPs coated with amphiphilic block co polymers (PVP-VA and PVA-COOH) are extremely mobile (retardation factors of 1.0-1.2) with high recovery values (50-95 %). The specific retardation and recovery depends on the coating type, concentration and grafting method. The NPs also show significant partitioning to organic phases such as tetrachloroethylene (PCE) and trichloroethylene (TCE), which are considered as potential ground water pollutants accumulated in the subsurface as DNAPLs (dense non-aqueous phase liquids). Being a noble metal, nanogold is to be detected by nondestructive optical methods at a concentration of at least 1000 fold lower than ENPs. Using conventional spectrophotometric technique equipped with liquid waveguide capillary cell (LWCC), nanogold is detected at very low concentration range (1 ppm - 62.5 ppb). Compared to uncoated particles, surface modified nanogold with polymers retains the plasmonic peaks at 520 nm when diluted with artificial ground water. Acknowledgement: The low level detection of nanogold using LWCC was done at the department of nuclear and quantum engineering, KAIST (Korea Advance Institute of Science and Technology), 291 Daehak-ro, (373-1, Guseong-dong), Yuseong-gu, Daejeon 305-701, Republic of KOREA. We acknowledge Prof. Woojin Lee, Prof. Jong-Il Yun, Kim A Young and Tae Hyeong Kim for the same.

Enzyme activity and expression pattern of intra- and extracellular chitinase and β-1,3-glucanase of Wickerhamomyces anomalus EG2 using glycol chitin and glucan-containing high polymer complex.

PubMed

Hong, Sin-Hyoung; Song, Yong-Su; Seo, Dong-Jun; Kim, Kil-Yong; Jung, Woo-Jin

2017-12-01

We investigated cell growth and activity of intra- and extracellular chitinase, β-1,3-glucanase, and chitin deacetylase with SDS-PAGE by incubating W. anomalus EG2 in PDB and YPD media for 24h in presence of different concentrations (0%, 0.1%, 0.3%, and 0.5%) of colloidal chitin. Maximum cell growth was observed in both PDB and YPD media without colloidal chitin. In the absence of colloidal chitin, maximum extracellular β-1,3-glucanase activity of 32.96 and 47.28 units/mL was reported at 18h in PDB medium and 6h in YPD medium, respectively. In addition, extracellular chitinase was unaffected by various concentrations of carboxymethyl chitin in both PDB and YPD media. In the absence of colloidal chitin, maximum intracellular chitinase activity was indicated to be 9.82 and 9.86 units/mg protein in PDB and YPD media, respectively. Maximum intracellular β-1,3-glucanase activity reported was 17.34 units/mg protein in PDB medium containing 0.5% colloidal chitin and 15.0 units/mg protein in YPD medium containing 0.3% colloidal chitin. Five major isozymes, GN1, GN2, GN3, GN4, and GN5, of intracellular β-1,3-glucanase were detected with glucan-containing high polymer complex as a substrate with or without colloidal chitin. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnetic assembly of nonmagnetic particles into photonic crystal structures.

PubMed

He, Le; Hu, Yongxing; Kim, Hyoki; Ge, Jianping; Kwon, Sunghoon; Yin, Yadong

2010-11-10

We report the rapid formation of photonic crystal structures by assembly of uniform nonmagnetic colloidal particles in ferrofluids using external magnetic fields. Magnetic manipulation of nonmagnetic particles with size down to a few hundred nanometers, suitable building blocks for producing photonic crystals with band gaps located in the visible regime, has been difficult due to their weak magnetic dipole moment. Increasing the dipole moment of magnetic holes has been limited by the instability of ferrofluids toward aggregation at high concentration or under strong magnetic field. By taking advantage of the superior stability of highly surface-charged magnetite nanocrystal-based ferrofluids, in this paper we have been able to successfully assemble 185 nm nonmagnetic polymer beads into photonic crystal structures, from 1D chains to 3D assemblies as determined by the interplay of magnetic dipole force and packing force. In a strong magnetic field with large field gradient, 3D photonic crystals with high reflectance (83%) in the visible range can be rapidly produced within several minutes, making this general strategy promising for fast creation of large-area photonic crystals using nonmagnetic particles as building blocks.

One-pot fabrication of graphene oxide-patched hollow-structured microgel particles in a microcapillary device

NASA Astrophysics Data System (ADS)

Byun, Aram; Jeong, Eun Seon; Kim, Jin Woong

2014-03-01

Microgels are colloidal gel particles that consist of chemically cross-linked three-dimensional polymer networks. They play an essential role in delivery and release of active ingredients in medicine, cosmetics, food, and even autonomic self-healing applications. Despite their wide applicability, permeability control through the hydrogel phase is limited due to its intrinsic loose network nature. Herein, we introduce generation of hollow-structured microgel particles whose interfaces were patched with graphene oxide (GO) sheets. The whole fabrication procedure was carried out in a microcapillary device in a single step. GO sheets have an ability to adhere to both O/W and W/O interfaces. Taking advantages of this behavior, we generated monodisperse O/W/O double emulsion whose interfaces were patched with GO sheets. Solidification of the aqueous middle phase to the hydrogel phase gave rise to uniform GO-patched microgel shell particles. Furthermore, we demonstrated that the permeation of molecules through the shell could be controlled even to small molecular length scales due to the adsorption of GO.

Structure and Symmetry of Ground States of Colloidal Clusters

NASA Astrophysics Data System (ADS)

Klein, Ellen D.; Rogers, W. Benjamin; Manoharan, Vinothan N.

We experimentally study colloidal clusters consisting of 6 to 100 spherical particles bound together with short range, DNA-mediated attractions. These clusters are a model system for understanding colloidal self-assembly and dynamics, since the positions and motion of all particles can be observed in real space. For 10 particles and fewer, the ground states are degenerate, and, as shown in previous work, the probabilities of observing specific clusters depend primarily on their rotational entropy, which is determined by symmetry. Thus less symmetric structures are more frequently observed. However, for larger numbers of particles the ground states appear to be subsets of close-packed lattices, which tend to have higher symmetry. To understand how this transition occurs as a function of the number of particles, we coat colloidal particles with complementary DNA strands that induce a short-range, temperature-dependent interparticle attraction. We then assemble and anneal an ensemble of clusters with 10 or more particles. We characterize the number of apparent ground states, their symmetries, and their probabilities as a function of the size of the cluster using confocal microscopy. This work is supported by NSF DMR-1306410. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program.

Colloidal Particle Adsorption at Water-Water Interfaces with Ultralow Interfacial Tension

NASA Astrophysics Data System (ADS)

Keal, Louis; Colosqui, Carlos E.; Tromp, R. Hans; Monteux, Cécile

2018-05-01

Using fluorescence confocal microscopy we study the adsorption of single latex microparticles at a water-water interface between demixing aqueous solutions of polymers, generally known as a water-in-water emulsion. Similar microparticles at the interface between molecular liquids have exhibited an extremely slow relaxation preventing the observation of expected equilibrium states. This phenomenon has been attributed to "long-lived" metastable states caused by significant energy barriers Δ F ˜γ Ad≫kBT induced by high interfacial tension (γ ˜10-2 N /m ) and nanoscale surface defects with characteristic areas Ad≃10 - 30 nm2 . For the studied water-water interface with ultralow surface tension (γ ˜10-4 N /m ) we are able to characterize the entire adsorption process and observe equilibrium states prescribed by a single equilibrium contact angle independent of the particle size. Notably, we observe crossovers from fast initial dynamics to slower kinetic regimes analytically predicted for large surface defects (Ad≃500 nm2). Moreover, particle trajectories reveal a position-independent damping coefficient that is unexpected given the large viscosity contrast between phases. These observations are attributed to the remarkably diffuse nature of the water-water interface and the adsorption and entanglement of polymer chains in the semidilute solutions. This work offers some first insights on the adsorption dynamics or kinetics of microparticles at water-water interfaces in biocolloidal systems.

Structure and stability of charged colloid-nanoparticle mixtures

NASA Astrophysics Data System (ADS)

Weight, Braden M.; Denton, Alan R.

2018-03-01

Physical properties of colloidal materials can be modified by addition of nanoparticles. Within a model of like-charged mixtures of particles governed by effective electrostatic interactions, we explore the influence of charged nanoparticles on the structure and thermodynamic phase stability of charge-stabilized colloidal suspensions. Focusing on salt-free mixtures of particles of high size and charge asymmetry, interacting via repulsive Yukawa effective pair potentials, we perform molecular dynamics simulations and compute radial distribution functions and static structure factors. Analysis of these structural properties indicates that increasing the charge and concentration of nanoparticles progressively weakens correlations between charged colloids. We show that addition of charged nanoparticles to a suspension of like-charged colloids can induce a colloidal crystal to melt and can facilitate aggregation of a fluid suspension due to attractive van der Waals interactions. We attribute the destabilizing influence of charged nanoparticles to enhanced screening of electrostatic interactions, which weakens repulsion between charged colloids. This interpretation is consistent with recent predictions of an effective interaction theory of charged colloid-nanoparticle mixtures.

Entropically Driven Self-Assembly of Colloidal Crystals on Templates in Space

NASA Technical Reports Server (NTRS)

Yodh, Arjun G.; Zimmerli, Gregory A.

2002-01-01

These experiments aim to create new colloidal crystalline materials, to study the assembly and thermodynamics of these materials, to measure the optical properties of these materials. and to fix the resulting structures so that they can be brought back and studied on earth. In microgravity, the elimination of particle sedimentation effects creates a purely "thermodynamic" environment for colloidal suspensions wherein particle size, volume fraction, and interparticle interactions are the primary determinants of the assembled structures. We will control the colloidal assembly process using attractive, entropic particle interactions brought about by the depletion effect. By using attractive interactions for colloidal assembly we create conditions for growth that resemble those associated with "conventional" microscopic systems such as atoms and molecules. This approach differs qualitatively from the more common "space-filling" mode of colloidal crystal growth that is driven purely by packing constraints. It is anticipated that at least some of the solidified structures will survive reentry to earth's gravitational field, and that their optical, magnetic, and electrical properties can then be studied in detail upon return.

Exploring Thermoresponsive Affinity Agents to Enhance Microdialysis Sampling Efficiency of Proteins

NASA Astrophysics Data System (ADS)

Vasicek, Thaddeus

Affinity agents increase microdialysis protein relative recovery, yet they have not seen widespread use within the microdialysis community due to their additional instrumentation requirements and prohibitive cost. This dissertation describes new affinity agents for microdialysis that require no additional instrumentation to use, have nearly 100% particle recovery, are 7 times more cost efficient than alternatives, and have low specificity enabling their use for a wide variety of proteins. Initially gold nanoparticles were chosen as an affinity ligand support due to their high surface area/volume ratio and colloidal stability. Poly (N-isopropylacrylamide) was immobilized to the gold nanoparticles, which served to sterically stabilize the particles and to act as a generic, reversible protein capture agent. A method was developed to reproducibly vary and quantify poly (N-isopropylacrylamide) graft density from 0.09 to 0.40 ligands/nm2 on gold nanoparticles. During characterization of the polymer coated gold nanoparticles, irreversible particle agglomeration was observed at low polymer graft density in ionic solutions, which prevented further development as a protein capture agent. Poly (N-isopropylacrylamide) nanogels, which have low nonspecific adsorption, low interparticle attractive forces owing to the low curvature of the particle, and a low Hamaker constant, were synthesized to overcome the agglomeration problem. A generic protein affinity ligand cibacron blue, was immobilized to the nanogels, which enabled rapid determination of particle recovery. The perfusion of the nanogels through a microdialysis probe was optimized yielding 100% particle recovery using a combination of a syringe and peristaltic pump. The microdialysis collection efficiency of CCL2, a physiologically relevant cytokine, was increased 3-fold with addition of the nanogel to the microdialysis perfusion fluid. The reduction in instrumentation requirements, low cost, and low specificity obtained with the new affinity agents will lead to increased affinity agent use for microdiaylsis protein sampling.

TOPICAL REVIEW: Surface modification and characterization for dispersion stability of inorganic nanometer-scaled particles in liquid media

NASA Astrophysics Data System (ADS)

Kamiya, Hidehiro; Iijima, Motoyuki

2010-08-01

Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM). Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface modification on the nanoparticle dispersion in liquids.

Taming contact line instability for pattern formation

PubMed Central

Deblais, A.; Harich, R.; Colin, A.; Kellay, H.

2016-01-01

Coating surfaces with different fluids is prone to instability producing inhomogeneous films and patterns. The contact line between the coating fluid and the surface to be coated is host to different instabilities, limiting the use of a variety of coating techniques. Here we take advantage of the instability of a receding contact line towards cusp and droplet formation to produce linear patterns of variable spacings. We stabilize the instability of the cusps towards droplet formation by using polymer solutions that inhibit this secondary instability and give rise to long slender cylindrical filaments. We vary the speed of deposition to change the spacing between these filaments. The combination of the two gives rise to linear patterns into which different colloidal particles can be embedded, long DNA molecules can be stretched and particles filtered by size. The technique is therefore suitable to prepare anisotropic structures with variable properties. PMID:27506626

Taming contact line instability for pattern formation.

PubMed

Deblais, A; Harich, R; Colin, A; Kellay, H

2016-08-10

Coating surfaces with different fluids is prone to instability producing inhomogeneous films and patterns. The contact line between the coating fluid and the surface to be coated is host to different instabilities, limiting the use of a variety of coating techniques. Here we take advantage of the instability of a receding contact line towards cusp and droplet formation to produce linear patterns of variable spacings. We stabilize the instability of the cusps towards droplet formation by using polymer solutions that inhibit this secondary instability and give rise to long slender cylindrical filaments. We vary the speed of deposition to change the spacing between these filaments. The combination of the two gives rise to linear patterns into which different colloidal particles can be embedded, long DNA molecules can be stretched and particles filtered by size. The technique is therefore suitable to prepare anisotropic structures with variable properties.

Lindemann histograms as a new method to analyse nano-patterns and phases

NASA Astrophysics Data System (ADS)

Makey, Ghaith; Ilday, Serim; Tokel, Onur; Ibrahim, Muhamet; Yavuz, Ozgun; Pavlov, Ihor; Gulseren, Oguz; Ilday, Omer

The detection, observation, and analysis of material phases and atomistic patterns are of great importance for understanding systems exhibiting both equilibrium and far-from-equilibrium dynamics. As such, there is intense research on phase transitions and pattern dynamics in soft matter, statistical and nonlinear physics, and polymer physics. In order to identify phases and nano-patterns, the pair correlation function is commonly used. However, this approach is limited in terms of recognizing competing patterns in dynamic systems, and lacks visualisation capabilities. In order to solve these limitations, we introduce Lindemann histogram quantification as an alternative method to analyse solid, liquid, and gas phases, along with hexagonal, square, and amorphous nano-pattern symmetries. We show that the proposed approach based on Lindemann parameter calculated per particle maps local number densities to material phase or particles pattern. We apply the Lindemann histogram method on dynamical colloidal self-assembly experimental data and identify competing patterns.

Charging and Screening in Nonpolar Solutions of Nonionizable Surfactants

NASA Astrophysics Data System (ADS)

Behrens, Sven

2010-03-01

Nonpolar liquids do not easily accommodate electric charges, but surfactant additives are often found to dramatically increase the solution conductivity and promote surface charging of suspended colloid particles. Such surfactant-mediated electrostatic effects have been associated with equilibrium charge fluctuations among reverse surfactant micelles and in some cases with the statistically rare ionization of individual surfactant molecules. Here we present experimental evidence that even surfactants without any ionizable group can mediate charging and charge screening in nonpolar oils, and that they can do so at surfactant concentrations well below the critical micelle concentration (cmc). Precision conductometry, light scattering, and Karl-Fischer titration of sorbitan oleate solutions in hexane, paired with electrophoretic mobility measurements on suspended polymer particles, reveal a distinctly electrostatic action of the surfactant. We interpret our observations in terms of a charge fluctuation model and argue that the observed charging processes are likely facilitated, but not limited, by the presence of ionizable impurities.

Westinghouse modular grinding process - improvement for follow on processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fehrmann, Henning

2013-07-01

In nuclear power plants (NPP) ion exchange (IX) resins are used in several systems for water treatment. The resins can be in bead or powdered form. For waste treatment of spent IX resins, two methods are basically used: Direct immobilization (e.g. with cement, bitumen, polymer or High Integrity Container (HIC)); Thermal treatment (e.g. drying, oxidation or pyrolysis). Bead resins have some properties (e.g. particle size and density) that can have negative impacts on following waste treatment processes. Negative impacts could be: Floatation of bead resins in cementation process; Sedimentation in pipeline during transportation; Poor compaction properties for Hot Resin Supercompactionmore » (HRSC). Reducing the particle size of the bead resins can have beneficial effects enhancing further treatment processes and overcoming prior mentioned effects. Westinghouse Electric Company has developed a modular grinding process to crush/grind the bead resins. This modular process is designed for flexible use and enables a selective adjustment of particle size to tailor the grinding system to the customer needs. The system can be equipped with a crusher integrated in the process tank and if necessary a colloid mill. The crusher reduces the bead resins particle size and converts the bead resins to a pump able suspension with lower sedimentation properties. With the colloid mill the resins can be ground to a powder. Compared to existing grinding systems this equipment is designed to minimize radiation exposure of the worker during operation and maintenance. Using the crushed and/or ground bead resins has several beneficial effects like facilitating cementation process and recipe development, enhancing oxidation of resins, improving the Hot Resin Supercompaction volume reduction performance. (authors)« less

Rediscovering the Schulze-Hardy rule in competitive adsorption to an air-water interface.

PubMed

Stenger, Patrick C; Isbell, Stephen G; St Hillaire, Debra; Zasadzinski, Joseph A

2009-09-01

The ratio of divalent to monovalent ion concentration necessary to displace the surface-active protein, albumin, by lung surfactant monolayers and multilayers at an air-water interface scales as 2(-6), the same concentration dependence as the critical flocculation concentration (CFC) for colloids with a high surface potential. Confirming this analogy between competitive adsorption and colloid stability, polymer-induced depletion attraction and electrostatic potentials are additive in their effects; the range of the depletion attraction, twice the polymer radius of gyration, must be greater than the Debye length to have an effect on adsorption.

Design of intelligent mesoscale periodic array structures utilizing smart hydrogel

NASA Technical Reports Server (NTRS)

Sunkara, H. B.; Penn, B. G.; Frazier, D. O.; Weissman, J. M.; Asher, S. A.

1996-01-01

Mesoscale Periodic Array Structures (MPAS, also known as crystalline colloidal arrays), composed of aqueous or nonaqueous dispersions of self-assembled submicron colloidal spheres are emerging toward the development of advanced optical devices for technological applications. This is because of their unique optical diffraction properties and the ease with which these intriguing properties can be modulated experimentally. Moreover our recent advancements in this area which include 'locking' the liquid MPAS into solid or semisolid polymer matrices for greater stability with longer life span, and incorporation of CdS quantum dots and laser dyes into colloidal spheres to obtain nonlinear optical (NLO) responses further corroborate the use of MPAS in optical technology. Our long term goal is fabrication of all-optical and electro-optical devices such as spatial light modulators for optical signal processing and flat panel display devices by utilizing intelligent nonlinear periodic array structural materials. Here we show further progress in the design of novel linear MPAS which have the ability to sense and respond to an external source such as temperature. This is achieved by combining the self-assembly properties of polymer colloidal spheres and thermoshrinking properties of smart polymer gels. At selected temperatures the periodic array efficiently Bragg diffracts light and transmits most of the light at other temperatures. Hence these intelligent systems are of potential use as fixed notch filters optical switches or limiters to protect delicate optical sensors from high intensity laser radiation.

Metastable and unstable cellular solidification of colloidal suspensions

NASA Astrophysics Data System (ADS)

Deville, Sylvain; Maire, Eric; Bernard-Granger, Guillaume; Lasalle, Audrey; Bogner, Agnès; Gauthier, Catherine; Leloup, Jérôme; Guizard, Christian

2009-12-01

Colloidal particles are often seen as big atoms that can be directly observed in real space. They are therefore becoming increasingly important as model systems to study processes of interest in condensed-matter physics such as melting, freezing and glass transitions. The solidification of colloidal suspensions has long been a puzzling phenomenon with many unexplained features. Here, we demonstrate and rationalize the existence of instability and metastability domains in cellular solidification of colloidal suspensions, by direct in situ high-resolution X-ray radiography and tomography observations. We explain such interface instabilities by a partial Brownian diffusion of the particles leading to constitutional supercooling situations. Processing under unstable conditions leads to localized and global kinetic instabilities of the solid/liquid interface, affecting the crystal morphology and particle redistribution behaviour.

Building micro-soccer-balls with evaporating colloidal fakir drops

NASA Astrophysics Data System (ADS)

Gelderblom, Hanneke; Marín, Álvaro G.; Susarrey-Arce, Arturo; van Housselt, Arie; Lefferts, Leon; Gardeniers, Han; Lohse, Detlef; Snoeijer, Jacco H.

2013-11-01

Drop evaporation can be used to self-assemble particles into three-dimensional microstructures on a scale where direct manipulation is impossible. We present a unique method to create highly-ordered colloidal microstructures in which we can control the amount of particles and their packing fraction. To this end, we evaporate colloidal dispersion drops from a special type of superhydrophobic microstructured surface, on which the drop remains in Cassie-Baxter state during the entire evaporative process. The remainders of the drop consist of a massive spherical cluster of the microspheres, with diameters ranging from a few tens up to several hundreds of microns. We present scaling arguments to show how the final particle packing fraction of these balls depends on the drop evaporation dynamics, particle size, and number of particles in the system.

The Role of Citric Acid in the Stabilization of Nanoparticles and Colloidal Particles in the Environment: Measurement of Surface Forces between Hafnium Oxide Surfaces in the Presence of Citric Acid.

PubMed

Shinohara, Shuhei; Eom, Namsoon; Teh, E-Jen; Tamada, Kaoru; Parsons, Drew; Craig, Vincent S J

2018-02-27

The interactions between colloidal particles and nanoparticles determine solution stability and the structures formed when the particles are unstable to flocculation. Therefore, knowledge of the interparticle interactions is important for understanding the transport, dissolution, and fate of particles in the environment. The interactions between particles are governed by the surface properties of the particles, which are altered when species adsorb to the surface. The important interactions in the environment are almost never those between the bare particles but rather those between particles that have been modified by the adsorption of natural organic materials. Citric acid is important in this regard not only because it is present in soil but also as a model of humic and fulvic acids. Here we have studied the surface forces between the model metal oxide surface hafnia in the presence of citric acid in order to understand the stability of colloidal particles and nanoparticles. We find that citric acid stabilizes the particles over a wide range of pH at low to moderate ionic strength. At high ionic strength, colloidal particles will flocculate due to a secondary minimum, resulting in aggregates that are dense and easily redispersed. In contrast, nanoparticles stabilized by citric acid remain stable at high ionic strengths and therefore exist in solution as individual particles; this will contribute to their dispersion in the environment and the uptake of nanoparticles by mammalian cells.

Magnetic Assisted Colloidal Pattern Formation

NASA Astrophysics Data System (ADS)

Yang, Ye

Pattern formation is a mysterious phenomenon occurring at all scales in nature. The beauty of the resulting structures and myriad of resulting properties occurring in naturally forming patterns have attracted great interest from scientists and engineers. One of the most convenient experimental models for studying pattern formation are colloidal particle suspensions, which can be used both to explore condensed matter phenomena and as a powerful fabrication technique for forming advanced materials. In my thesis, I have focused on the study of colloidal patterns, which can be conveniently tracked in an optical microscope yet can also be thermally equilibrated on experimentally relevant time scales, allowing for ground states and transitions between them to be studied with optical tracking algorithms. In particular, I have focused on systems that spontaneously organize due to particle-surface and particle-particle interactions, paying close attention to systems that can be dynamically adjusted with an externally applied magnetic or acoustic field. In the early stages of my doctoral studies, I developed a magnetic field manipulation technique to quantify the adhesion force between particles and surfaces. This manipulation technique is based on the magnetic dipolar interactions between colloidal particles and their "image dipoles" that appear within planar substrate. Since the particles interact with their own images, this system enables massively parallel surface force measurements (>100 measurements) in a single experiment, and allows statistical properties of particle-surface adhesion energies to be extracted as a function of loading rate. With this approach, I was able to probe sub-picoNewton surface interactions between colloidal particles and several substrates at the lowest force loading rates ever achieved. In the later stages of my doctoral studies, I focused on studying patterns formed from particle-particle interaction, which serve as an experimental model of phase transitions in condensed matter systems that can be tracked with single particle resolution. Compared with other research on colloidal crystal formation, my research has focused on multi-component colloidal systems of magnetic and non-magnetic colloids immersed in a ferrofluid. Initially, I studied the types of patterns that form as a function of the concentrations of the different particles and ferrofluid, and I discovered a wide variety of chains, rings and crystals forming in bi-component and tri-component systems. Based on these results, I narrowed my focus to one specific crystal structure (checkerboard lattice) as a model of phase transformations in alloy. Liquid/solid phase transitions were studied by slowly adjusting the magnetic field strength, which serves to control particle-particle interactions in a manner similar to controlling the physical temperature of the fluid. These studies were used to determine the optimal conditions for forming large single crystal structures, and paved the way for my later work on solid/solid phase transitions when the angle of the external field was shifted away from the normal direction. The magnetostriction coefficient of these crystals was measured in low tilt angle of the applied field. At high tilt angles, I observed a variety of martensitic transformations, which followed different pathways depending on the crystal direction relative to the in-plane field. In the last part of my doctoral studies, I investigated colloidal patterns formed in a superimposed acoustic and magnetic field. In this approach, the magnetic field mimics "temperature", while the acoustic field mimics "pressure". The ability to simultaneously tune both temperature and pressure allows for more efficient exploration of phase space. With this technique I demonstrated a large class of particle structures ranging from discrete molecule-like clusters to well ordered crystal phases. Additionally, I demonstrated a crosslinking strategy based on photoacids, which stabilized the structures after the external field was removed. This approach has potential applications in the fabrication of advanced materials. My thesis is arranged as follows. In Chapter 1, I present a brief background of general pattern formation and why I chose to investigate patterns formed in colloidal systems. I also provide a brief review of field-assisted manipulation techniques in order to motivate why I selected magnetic and acoustic field to study colloidal patterns. In chapter 2, I present the theoretical background of magnetic manipulation, which is the main technique used in my research. In this chapter, I will introduce the basic knowledge on magnetic materials and theories behind magnetic manipulation. The underlining thermodynamic mechanisms and theoretical/computational approaches in colloidal pattern formation are also briefly reviewed. In Chapter 3, I focus on using these concepts to study adhesion forces between particle and surfaces. In Chapter 4, I focus on exploring the ground states of colloidal patterns formed from the anti-ferromagnetic interactions of mixtures of particles, as a function of the particle volume fractions. In Chapter 5, I discuss my research on phase transformations of the well-ordered checkerboard phase formed from the equimolar mixture of magnetic and non-magnetic beads in ferrofluid, and I focus mainly on phase transformations in a slowly varying magnetic field. In Chapter 6, I discuss my work on the superimposed magnetic and acoustic field to study patterns formed from monocomponent colloidal suspensions under vertical confinement. Finally, I conclude my thesis in Chapter 7 and discuss future directions and open questions that can be explored in magnetic field directed self-organization in colloidal systems.

In house development of (99m)Tc-Rhenium sulfide colloidal nanoparticles for sentinel lymph node detection.

PubMed

Dar, Ume-Kalsoom; Khan, Irfanullah; Javed, Muhammad; Ali, Muhammad; Hyder, Syed Waqar; Murad, Sohail; Anwar, Jamil

2013-03-01

In this study, rhenium sulfide colloidal nanoparticles were developed as radiopharmaceutical for sentinel lymph node detection. We directly used rhenium sulfide as a starting material for the preparation of colloidal nanoparticles. UV-visible spectrophotometry was used for characterization of in house developed colloidal particles. The size distribution of radioactive particles was studied by using membrane filtration method. The percentage of radiolabeled colloidal nanoparticles was determined by paper chromatography (PC). The study also includes in vitro stability, protein binding in human blood and bioevaluation in a rabbit model. The results indicate that 77.27 ± 3.26 % particles of size less than 20nm (suitable for lymphoscintigraphy) were radiolabeled. (99m)Tc labeled rhenium sulfide labeling efficacy with the radiometal is 98.5 ± 0.5%, which remains considerably stable beyond 5h at room temperature. Furthermore, it was observed that 70.2 ± 1.3% radiolabeled colloid complex showed binding with the blood protein. Bioevaluation results show the remarkable achievement of our radiopharmaceutical. The in house prepared (99m)Tc labeled rhenium sulfide colloidal nanoparticles reached the sentinel node within 15 min of post injection. These results indicate that (99m)Tc labeled rhenium sulfide colloid nanoparticles kit produced by a novel procedure seems of significant potential as a feasible candidate for further development to be used in clinical practice.

Nanostructured raspberry-like gelatin microspheres for local delivery of multiple biomolecules.

PubMed

Diba, Mani; Pape, Bram; Klymov, Alexey; Zhang, Yang; Song, Jiankang; Löwik, Dennis W P M; Seyednejad, Hajar; Leeuwenburgh, Sander C G

2017-08-01

Multicompartment particles, which are particles composed of smaller building units, have gained considerable interest during the past decade to facilitate simultaneous and differential delivery of several biomolecules in various applications. Supercritical carbon dioxide (CO 2 ) processing is an industrial technology widely used for large-scale synthesis and processing of materials. However, the application of this technology for production of multicompartment particles from colloidal particles has not yet been explored. Here, we report the formation of raspberry-like gelatin (RLG) microparticles composed of gelatin nanoparticles as colloidal building blocks through supercritical CO 2 processing. We show that these RLG microparticles exhibit a high stability upon dispersion in aqueous media without requiring chemical cross-linking. We further demonstrate that these microparticles are cytocompatible and facilitate differential release of two different model compounds. The strategy presented here can be utilized as a cost-effective route for production of various types of multicompartment particles using colloidal particles with suitable interparticle interactions. Multicompartment particles have gained considerable interest during the past decade to facilitate simultaneous and differential delivery of multiple biomolecules in various biomedical applications. Nevertheless, common methods employed for the production of such particles are often complex and only offer small-scale production. Here, we report the formation of raspberry-like gelatin (RLG) microparticles composed of gelatin nanoparticles as colloidal building blocks through supercritical CO 2 processing. We show that these microparticles are cytocompatible and facilitate differential release of two model compounds with different molecular sizes, promising successful applications in various biomedical areas. Summarizing, this paper presents a novel strategy that can be utilized as a cost-effective route for production of various types of multicompartment particles using a wide range of colloidal building blocks. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis of u-channelled spherical Fex(CoyNi1-y)100-x Janus colloidal particles with excellent electromagnetic wave absorption performance.

PubMed

Li, Hao; Cao, Zhenming; Lin, Jiayao; Zhao, Hui; Jiang, Qiaorong; Jiang, Zhiyuan; Liao, Honggang; Kuang, Qin; Xie, Zhaoxiong

2018-01-25

Due to their distinctive structure, inherently anisotropic properties and broad applications, Janus colloidal particles have attracted tremendous attention and it is significant to synthesize high yield Janus colloidal particles in a cost-effective and reliable way. On the other hand, due to the expanded electromagnetic interference problems, it is highly desired to develop excellent electromagnetic wave absorbing materials with an ultra-wide absorption bandwidth for practical application. Herein, a confined liquid-solid redox reaction strategy has been developed to fabricate a series of Fe x (Co y Ni 1-y ) 100-x ternary alloy particles. The as-prepared particles are in the form of u-channelled noncentrosymmetric spheres, one kind of Janus colloidal particles which have been rarely observed. Due to the combination and synergy effects of multi-magnetic metals, the polycrystalline structure and their specific morphology, the as-prepared particles possess multiple magnetic resonance and multiple dielectric relaxation processes, and therefore show excellent electromagnetic wave absorption performances. In particular, the strongest reflection loss (RL) of the Fe 15 (Co 0.2 Ni 0.8 ) 85 Janus colloidal particles is up to -36.9 dB with a thickness of 2.5 mm, and the effective absorption (RL < -10 dB) bandwidth can reach 9.2 GHz (8-17.2 GHz) with a thickness of 2 mm. Such a wide bandwidth has barely been reported for magnetic metal alloys under a single thickness. These results suggest that the Fe x (Co y Ni 1-y ) 100-x Janus particles could be a promising candidate for highly efficient electromagnetic wave absorbing materials for practical application.

Microbial effects on colloidal agglomeration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hersman, L.

1995-11-01

Colloidal particles are known to enhance the transport of radioactive metals through soil and rock systems. This study was performed to determine if a soil microorganism, isolated from the surface samples collected at Yucca Mountain, NV, could affect the colloidal properties of day particles. The agglomeration of a Wyoming bentonite clay in a sterile uninoculated microbial growth medium was compared to the agglomeration in the medium inoculated with a Pseudomonas sp. In a second experiment, microorganisms were cultured in the succinate medium for 50 h and removed by centrifugation. The agglomeration of the clay in this spent was compared tomore » sterile uninoculated medium. In both experiments, the agglomeration of the clay was greater than that of the sterile, uninoculated control. Based on these results, which indicate that this microorganism enhanced the agglomeration of the bentonite clay, it is possible to say that in the presence of microorganisms colloidal movement through a rock matrix could be reduced because of an overall increase in the size of colloidal particle agglomerates. 32 refs.« less

Binary Colloidal Alloy Test Conducted on Mir

NASA Technical Reports Server (NTRS)

Hoffmann, Monica I.; Ansari, Rafat R.

1999-01-01

Colloids are tiny (submicron) particles suspended in fluid. Paint, ink, and milk are examples of colloids found in everyday life. The Binary Colloidal Alloy Test (BCAT) is part of an extensive series of experiments planned to investigate the fundamental properties of colloids so that scientists can make colloids more useful for technological applications. Some of the colloids studied in BCAT are made of two different sized particles (binary colloidal alloys) that are very tiny, uniform plastic spheres. Under the proper conditions, these colloids can arrange themselves in a pattern to form crystals. These crystals may form the basis of new classes of light switches, displays, and optical devices. Windows made of liquid crystals are already in the marketplace. These windows change their appearance from transparent to opaque when a weak electric current is applied. In the future, if the colloidal crystals can be made to control the passage of light through them, such products could be made much more cheaply. These experiments require the microgravity environment of space because good quality crystals are difficult to produce on Earth because of sedimentation and convection in the fluid. The BCAT experiment hardware included two separate modules for two different experiments. The "Slow Growth" hardware consisted of a 35-mm camera with a 250- exposure photo film cartridge. The camera was aimed toward the sample module, which contained 10 separate colloid samples. A rack of small lights provided backlighting for the photographs. The BCAT hardware was launched on the shuttle and was operated aboard the Russian space station Mir by American astronauts John Blaha and David Wolf (launched September 1996 and returned January 1997; reflown September 1997 and returned January 1998). To begin the experiment, one of these astronauts would mix the samples to disperse the colloidal particles and break up any crystals that might have already formed. Once the samples were mixed and the experiment was powered on, the hardware operated autonomously, taking photos of the colloidal samples over a 90-day period.

Deposition of gold nano-particles and nano-layers on polyethylene modified by plasma discharge and chemical treatment

NASA Astrophysics Data System (ADS)

Švorčík, V.; Chaloupka, A.; Záruba, K.; Král, V.; Bláhová, O.; Macková, A.; Hnatowicz, V.

2009-08-01

Polyethylene (PE) was treated in Ar plasma discharge and then grafted from methanol solution of 1,2-ethanedithiol to enhance adhesion of gold nano-particles or sputtered gold layers. The modified PE samples were either immersed into freshly prepared colloid solution of Au nano-particles or covered by sputtered, 50 nm thick gold nano-layer. Properties of the plasma modified, dithiol grafted and gold coated PE were studied using XPS, UV-VIS, AFM, EPR, RBS methods and nanoindentation. It was shown that the plasma treatment results in degradation of polymer chain, creation of excessive free radicals and conjugated double bonds. After grafting with 1,2-ethanedithiol the concentration of free radicals declined but the concentration of double bonds remained unchanged. Plasma treatment changes PE surface morphology and increases surface roughness too. Another significant change in the surface morphology and roughness was observed after deposition of Au nano-particles. The presence of Au on the sample surface after the coating with Au nano-particles was proved by XPS and RBS methods. Nanoindentation measurements shown that the grafting of plasma activated PE surface with dithiol increases significantly adhesion of sputtered Au nano-layer.

Topological Interaction by Entanglement of DNA

NASA Astrophysics Data System (ADS)

Feng, Lang; Sha, Ruojie; Seeman, Nadrian; Chaikin, Paul

2012-02-01

We find and study a new type of interaction between colloids, Topological Interaction by Entanglement of DNA (TIED), due to concatenation of loops formed by palindromic DNA. Consider a particle coated with palindromic DNA of sequence ``P1.'' Below the DNA hybridization temperature (Tm), loops of the self-complementary DNA form on the particle surface. Direct hybridization with similar particle covered with a different sequence P2 do not occur. However when particles are held together at T > Tm, then cooled to T < Tm, some of the loops entangle and link, similar to a Olympic Gel. We quantitatively observe and measure this topological interaction between colloids in a ˜5^o C temperature window, ˜6^o C lower than direct binding of complementary DNA with similar strength and introduce the concept of entanglement binding free energy. To prove our interaction to be topological, we unknot the purely entangled binding sites between colloids by adding Topoisomerase I which unconcatenates our loops. This research suggests novel history dependent ways of binding particles and serves as a new design tool in colloidal self-assembly.

Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis

NASA Astrophysics Data System (ADS)

Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.; Stone, Howard A.

2017-10-01

The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formed at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. We also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.

Simulation of the self-assembly of colloidal droplets in a micro-channel

NASA Astrophysics Data System (ADS)

Ge, Zhouyang; Brandt, Luca

2016-11-01

In colloidal sciences, much progress has been made on the synthesis of complex building blocks mimicking molecular structures to elaborate innovative materials. The basic elements of such colloidal molecules are particles or droplets less than one millimeter in size. Their self-assembly relies on either lengthy brownian motion or careful microfludic designs, on top of typical colloidal interactions, e.g. depletion attraction. Regardless of the approach, however, questions remain why the colloids undergo certain path to organize themselves and how such process can be optimized. Here, we perform direct numerical simulations using a Navier-Stokes solver at low Reynolds number, combined with either the immersed boundary method (IBM) or a newly-proposed level set (LS) method for interface description. In the IBM simulations, the colloids are treated as rigid, spherical particles under a Lennard-Jones-like potential, reproducing attractive depletion force. Results show that, for four particles, a planar diamond is formed under a weak potential while a 3D tetrahedron is formed under a strong potential, which agree qualitatively with experiments. In the next step, LS simulation of colloidal droplets will be performed to investigate the roles of surface tension in the self-assembly. This project has received funding from the European Union's Horizon 2020 research and innovation programme under Grant agreement No 664823.

Comparison of photon correlation spectroscopy with photosedimentation analysis for the determination of aqueous colloid size distributions

USGS Publications Warehouse

Rees, Terry F.

1990-01-01

Colloidal materials, dispersed phases with dimensions between 0.001 and 1 μm, are potential transport media for a variety of contaminants in surface and ground water. Characterization of these colloids, and identification of the parameters that control their movement, are necessary before transport simulations can be attempted. Two techniques that can be used to determine the particle-size distribution of colloidal materials suspended in natural waters are compared. Photon correlation Spectroscopy (PCS) utilizes the Doppler frequency shift of photons scattered off particles undergoing Brownian motion to determine the size of colloids suspended in water. Photosedimentation analysis (PSA) measures the time-dependent change in optical density of a suspension of colloidal particles undergoing centrifugation. A description of both techniques, important underlying assumptions, and limitations are given. Results for a series of river water samples show that the colloid-size distribution means are statistically identical as determined by both techniques. This also is true of the mass median diameter (MMD), even though MMD values determined by PSA are consistently smaller than those determined by PCS. Because of this small negative bias, the skew parameters for the distributions are generally smaller for the PCS-determined distributions than for the PSA-determined distributions. Smaller polydispersity indices for the distributions are also determined by PCS.

Fractionation of Exosomes and DNA using Size-Based Separation at the Nanoscale

NASA Astrophysics Data System (ADS)

Wunsch, Benjamin; Smith, Joshua; Wang, Chao; Gifford, Stacey; Brink, Markus; Bruce, Robert; Solovitzky, Gustavo; Austin, Robert; Astier, Yann

Exosomes, a key target of ``liquid biopsies'', are nano-vesicles found in nearly all biological fluids. Exosomes are secreted by eukaryotic and prokaryotic cells alike, and contain information about their originating cells, including surface proteins, cytoplasmic proteins, and nucleic acids. One challenge in studying exosome morphology is the difficulty of sorting exosomes by size and surface markers. Common separation techniques for exosomes include ultracentrifugation and ultrafiltration, for preparation of large volume samples, but these techniques often show contamination and significant heterogeneity between preparations. To date, deterministic lateral displacement (DLD) pillar arrays in silicon have proven an efficient technology to sort, separate, and enrich micron-scale particles including human parasites, eukaryotic cells, blood cells, and circulating tumor cells in blood; however, the DLD technology has never been translated to the true nanoscale, where it could function on bio-colloids such as exosomes. We have fabricated nanoscale DLD (nanoDLD) arrays capable of rapidly sorting colloids down to 20 nm in continuous flow, and demonstrated size sorting of individual exosome vesicles and dsDNA polymers, opening the potential for on-chip biomolecule separation and diagnosti

[The study of antimicrobial properties of silver nanoparticles in the form of a colloidal solution in the matrix of finely dispersed silica].

PubMed

Korchak, G I; Surmasheva, E V; Mikhienkova, A I; Nikonova, N A; Romanenko, L I; Oliĭnyk, Z A; Gorval', A K; Rosada, M A

2012-01-01

In the experimental study obtained with chemical method colloid solution of nanoparticles (NPs) of silver (Ag) and a composite on his base in the matrix of finely dispersed silica with particle size of 8-12 nm and NPs concentration in basic solution of 0,0016% (0,016 mg/cm3) were established to exhibit high antimicrobial activity against the test organisms: E. coli, P. aeruginosa, S. Aureus and C. Albicans, which depended on a set of factors. Antibacterial properties of tissue impregnated with Ag-NPs were studied. As stabilizing substances a mixture of surface-active substance sodium dodecyl sulfate and polymer polyvinylpyrrolidone was used Before the beginning of the study effective neutralizer was tailored. Times of preservation of antimicrobial activity of test samples have been established, and also their stability throughout long term of supervision (24 months) has been shown. Effect of organic pollution on antimicrobal activity of the samples has been studied. Based on obtained results the algorithm of the study of antimicrobial properties of nanopreparations has been elaborated.

Formulation and characterization of lutetium-177-labeled stannous (tin) colloid for radiosynovectomy.

PubMed

Arora, Geetanjali; Singh, Manoranjan; Jha, Pragati; Tripathy, Sarthak; Bal, Chandrasekhar; Mukherjee, Anirban; Shamim, Shamim A

2017-07-01

Easy large-scale production, easy availability, cost-effectiveness, long half-life, and favorable radiation characteristics have made lutetium-177 (Lu) a preferred radionuclide for use in therapy. Lutetium-177-labeled stannous (Lu-Sn) colloid particles were formulated for application in radiosynovectomy, followed by in-vitro and in-vivo characterization. Stannous chloride (SnCl2) solution and Lu were heated together, the pH was adjusted, and the particles were recovered by centrifugation. The heating time and amount of SnCl2 were varied to optimize the labeling protocol. The labeling efficiency (LE) and radiochemical purity (RCP) of the product were determined. The size and shape of the particles were determined by means of electron microscopy. In-vitro stability was tested in PBS and synovial fluid, and in-vivo stability was tested in humans. LE and RCP were greater than 95% and ∼99% (Rf=0-0.1), respectively. Aggregated colloidal particles were spherical (mean size: 241±47 nm). The product was stable in vitro for up to 7 days in PBS as well as in synovial fluid. Injection of the product into the infected knee joint of a patient resulted in its homogenous distribution in the intra-articular space, as seen on the scan. No leakage of activity was seen outside the knee joint even 7 days after injection, indicating good tracer binding and in-vivo stability. Lu-Sn colloid was successfully prepared with a high LE (>95%) and high RCP (99%) under optimized reaction conditions. Because of the numerous benefits of Lu and the ease of preparation of tin colloid particles, Lu-Sn colloid particles are significantly superior to its currently available counterparts for use in radiosynovectomy.

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

PubMed Central

2018-01-01

High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184

Light-activated self-propelled colloids

PubMed Central

Palacci, J.; Sacanna, S.; Kim, S.-H.; Yi, G.-R.; Pine, D. J.; Chaikin, P. M.

2014-01-01

Light-activated self-propelled colloids are synthesized and their active motion is studied using optical microscopy. We propose a versatile route using different photoactive materials, and demonstrate a multiwavelength activation and propulsion. Thanks to the photoelectrochemical properties of two semiconductor materials (α-Fe2O3 and TiO2), a light with an energy higher than the bandgap triggers the reaction of decomposition of hydrogen peroxide and produces a chemical cloud around the particle. It induces a phoretic attraction with neighbouring colloids as well as an osmotic self-propulsion of the particle on the substrate. We use these mechanisms to form colloidal cargos as well as self-propelled particles where the light-activated component is embedded into a dielectric sphere. The particles are self-propelled along a direction otherwise randomized by thermal fluctuations, and exhibit a persistent random walk. For sufficient surface density, the particles spontaneously form ‘living crystals’ which are mobile, break apart and reform. Steering the particle with an external magnetic field, we show that the formation of the dense phase results from the collisions heads-on of the particles. This effect is intrinsically non-equilibrium and a novel principle of organization for systems without detailed balance. Engineering families of particles self-propelled by different wavelength demonstrate a good understanding of both the physics and the chemistry behind the system and points to a general route for designing new families of self-propelled particles. PMID:25332383

Physics in ordered and disordered colloidal matter composed of poly(N-isopropylacrylamide) microgel particles.

PubMed

Yunker, Peter J; Chen, Ke; Gratale, Matthew D; Lohr, Matthew A; Still, Tim; Yodh, A G

2014-05-01

This review collects and describes experiments that employ colloidal suspensions to probe physics in ordered and disordered solids and related complex fluids. The unifying feature of this body of work is its clever usage of poly(N-isopropylacrylamide) (PNIPAM) microgel particles. These temperature-sensitive colloidal particles provide experimenters with a 'knob' for in situ control of particle size, particle interaction and particle packing fraction that, in turn, influence the structural and dynamical behavior of the complex fluids and solids. A brief summary of PNIPAM particle synthesis and properties is given, followed by a synopsis of current activity in the field. The latter discussion describes a variety of soft matter investigations including those that explore formation and melting of crystals and clusters, and those that probe structure, rearrangement and rheology of disordered (jammed/glassy) and partially ordered matter. The review, therefore, provides a snapshot of a broad range of physics phenomenology which benefits from the unique properties of responsive microgel particles.

Nontoxic colloidal particles impede antibiotic resistance of swarming bacteria by disrupting collective motion and speed

NASA Astrophysics Data System (ADS)

Lu, Shengtao; Liu, Fang; Xing, Bengang; Yeow, Edwin K. L.

2015-12-01

A monolayer of swarming B. subtilis on semisolid agar is shown to display enhanced resistance against antibacterial drugs due to their collective behavior and motility. The dynamics of swarming motion, visualized in real time using time-lapse microscopy, prevents the bacteria from prolonged exposure to lethal drug concentrations. The elevated drug resistance is significantly reduced when the collective motion of bacteria is judiciously disrupted using nontoxic polystyrene colloidal particles immobilized on the agar surface. The colloidal particles block and hinder the motion of the cells, and force large swarming rafts to break up into smaller packs in order to maneuver across narrow spaces between densely packed particles. In this manner, cohesive rafts rapidly lose their collectivity, speed, and group dynamics, and the cells become vulnerable to the drugs. The antibiotic resistance capability of swarming B. subtilis is experimentally observed to be negatively correlated with the number density of colloidal particles on the engineered surface. This relationship is further tested using an improved self-propelled particle model that takes into account interparticle alignment and hard-core repulsion. This work has pertinent implications on the design of optimal methods to treat drug resistant bacteria commonly found in swarming colonies.

Fast Evaporation of Spreading Droplets of Colloidal Suspensions

NASA Astrophysics Data System (ADS)

Maki, Kara; Kumar, Satish

2011-11-01

When a coffee droplet dries on a countertop, a dark ring of coffee solute is left behind, a phenomenon often referred to as ``the coffee-ring effect.'' A closely related yet less-well-explored phenomenon is the formation of a layer of particles, or skin, at the surface of the droplet. In this work, we explore the behavior of a mathematical model that can qualitatively describe both phenomena. We consider a thin axisymmetric droplet of a colloidal suspension on a horizontal substrate undergoing spreading and rapid evaporation. The lubrication approximation is applied to simplify the mass and momentum conservation equations, and the colloidal particles are allowed to influence droplet rheology through their effect on the viscosity. By describing the transport of the colloidal particles with the full convection-diffusion equation, we are able to capture depthwise gradients in particle concentration and thus describe skin formation, a feature neglected in prior models of droplet evaporation. Whereas capillarity creates a flow that drives particles to the contact line to produce a coffee-ring, Marangoni flows can compete with this and promote skin formation. Increases in viscosity due to particle concentration slow down droplet dynamics, and can lead to a significant reduction in the spreading rate.

Large-Scale Noniridescent Structural Color Printing Enabled by Infiltration-Driven Nonequilibrium Colloidal Assembly.

PubMed

Bai, Ling; Mai, Van Cuong; Lim, Yun; Hou, Shuai; Möhwald, Helmuth; Duan, Hongwei

2018-03-01

Structural colors originating from interaction of light with intricately arranged micro-/nanostructures have stimulated considerable interest because of their inherent photostability and energy efficiency. In particular, noniridescent structural color with wide viewing angle has been receiving increasing attention recently. However, no method is yet available for rapid and large-scale fabrication of full-spectrum structural color patterns with wide viewing angles. Here, infiltration-driven nonequilibrium assembly of colloidal particles on liquid-permeable and particle-excluding substrates is demonstrated to direct the particles to form amorphous colloidal arrays (ACAs) within milliseconds. The infiltration-assisted (IFAST) colloidal assembly opens new possibilities for rapid manufacture of noniridescent structural colors of ACAs and straightforward structural color mixing. Full-spectrum noniridescent structural colors are successfully produced by mixing primary structural colors of red, blue, and yellow using a commercial office inkjet printer. Rapid fabrication of large-scale structural color patterns with sophisticated color combination/layout by IFAST printing is realized. The IFAST technology is versatile for developing structural color patterns with wide viewing angles, as colloidal particles, inks, and substrates are flexibly designable for diverse applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloid Surface Chemistry Critically Affects Multiple Particle Tracking Measurements of Biomaterials

PubMed Central

Valentine, M. T.; Perlman, Z. E.; Gardel, M. L.; Shin, J. H.; Matsudaira, P.; Mitchison, T. J.; Weitz, D. A.

2004-01-01

Characterization of the properties of complex biomaterials using microrheological techniques has the promise of providing fundamental insights into their biomechanical functions; however, precise interpretations of such measurements are hindered by inadequate characterization of the interactions between tracers and the networks they probe. We here show that colloid surface chemistry can profoundly affect multiple particle tracking measurements of networks of fibrin, entangled F-actin solutions, and networks of cross-linked F-actin. We present a simple protocol to render the surface of colloidal probe particles protein-resistant by grafting short amine-terminated methoxy-poly(ethylene glycol) to the surface of carboxylated microspheres. We demonstrate that these poly(ethylene glycol)-coated tracers adsorb significantly less protein than particles coated with bovine serum albumin or unmodified probe particles. We establish that varying particle surface chemistry selectively tunes the sensitivity of the particles to different physical properties of their microenvironments. Specifically, particles that are weakly bound to a heterogeneous network are sensitive to changes in network stiffness, whereas protein-resistant tracers measure changes in the viscosity of the fluid and in the network microstructure. We demonstrate experimentally that two-particle microrheology analysis significantly reduces differences arising from tracer surface chemistry, indicating that modifications of network properties near the particle do not introduce large-scale heterogeneities. Our results establish that controlling colloid-protein interactions is crucial to the successful application of multiple particle tracking techniques to reconstituted protein networks, cytoplasm, and cells. PMID:15189896

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

PubMed

Bourgeat-Lami, Elodie; Insulaire, Mickaelle; Reculusa, Stéphane; Perro, Adeline; Ravaine, Serge; Duguet, Etienne

2006-02-01

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

Effects of nanoparticle shape on the morphology and properties of porous CdSe assemblies (aerogels).

PubMed

Yu, Hongtao; Brock, Stephanie L

2008-08-01

We demonstrate the effect of differently shaped CdSe nanoscale building blocks (dots, rods, branched nanoparticles, and hyperbranched nanoparticles) on the morphologies, surface characteristics, and optical properties of resultant porous CdSe nanostructured aerogels. Monolithic CdSe aerogels were produced by controlled oxidative removal of surface thiolate ligands from differently shaped CdSe nanoparticles to yield a wet gel, followed by CO(2) supercritical drying. The X-ray diffraction data show that the resultant CdSe aerogels maintain the crystalline phase of the building blocks without significant grain growth. However, the transmission electron microscopy images indicate that the morphology of CdSe aerogels changes from a colloid-type morphology to a polymer-type morphology when the building block changes from dot to rod or the branched nanoparticle. The morphology of the CdSe aerogel assembled from hyperbranched nanoparticles appears to be intermediate between the colloid-type and the polymer-type. Nitrogen physisorption measurements suggest that the surface areas and porosity are a direct function of the shape of the primary building blocks, with aerogels formed from rods or branched particles exhibiting the greatest surface areas (>200 m(2)/g) and those prepared from hyperbranched nanoparticles exhibiting the least (<100 m(2)/g). Band gap measurements and photoluminescence studies show that the as-prepared CdSe aerogels retain to a large extent the intrinsic quantum confinement of the differently shaped building blocks, despite being connected into a 3D network.

SERS-barcoded colloidal gold NP assemblies as imaging agents for use in biodiagnostics

NASA Astrophysics Data System (ADS)

Dey, Priyanka; Olds, William; Blakey, Idriss; Thurecht, Kristofer J.; Izake, Emad L.; Fredericks, Peter M.

2014-03-01

There is a growing need for new biodiagnostics that combine high throughput with enhanced spatial resolution and sensitivity. Gold nanoparticle (NP) assemblies with sub-10 nm particle spacing have the benefits of improving detection sensitivity via Surface enhanced Raman scattering (SERS) and being of potential use in biomedicine due to their colloidal stability. A promising and versatile approach to form solution-stable NP assemblies involves the use of multi-branched molecular linkers which allows tailoring of the assembly size, hot-spot density and interparticle distance. We have shown that linkers with multiple anchoring end-groups can be successfully employed as a linker to assemble gold NPs into dimers, linear NP chains and clustered NP assemblies. These NP assemblies with diameters of 30-120 nm are stable in solution and perform better as SERS substrates compared with single gold NPs, due to an increased hot-spot density. Thus, tailored gold NP assemblies are potential candidates for use as biomedical imaging agents. We observed that the hot-spot density and in-turn the SERS enhancement is a function of the linker polymer concentration and polymer architecture. New deep Raman techniques like Spatially Offset Raman Spectroscopy (SORS) have emerged that allow detection from beneath diffusely scattering opaque materials, including biological media such as animal tissue. We have been able to demonstrate that the gold NP assemblies could be detected from within both proteinaceous and high lipid containing animal tissue by employing a SORS technique with a backscattered geometry.

A universal approach to fabricate ordered colloidal crystals arrays based on electrostatic self-assembly.

PubMed

Zhang, Xun; Zhang, Junhu; Zhu, Difu; Li, Xiao; Zhang, Xuemin; Wang, Tieqiang; Yang, Bai

2010-12-07

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.

Macroporous ceramics by colloidal templating

NASA Astrophysics Data System (ADS)

Subramaniam, G.; Pine, David J.

2000-04-01

We describe a novel method of fabricating macroporous ceramics employing colloidal dispersion of ultrafine ceramic particles with latex particles as the templates. The colloidal particles form a particulate gel on drying and fill the voids of the ordered latex templates. Subsequent removal of the template by calcination results in the formation of an ordered macroporous ceramic. The process has significant advantages over the traditional sol-gel process employing alkoxide precursors. Most importantly, the much lower shrinkage compared to the sol-gel process enabled us to produce larger pieces of the sample. The larger shrinkage involved in the sol-gel process often results in small and fragile pieces of the macroporous material which has to be subsequently heat treated to induce crystallization. The ability to choose crystalline colloidal particles in our method obviates the need for heat treatment to achieve crystallinity. We have synthesized a variety of materials such as macroporous silica, titania, alumina and recently have also extended the approach to macroporous silicon which is not amenable to the sol-gel process.

Manipulating semiconductor colloidal stability through doping.

PubMed

Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

2014-10-10

The interface between a doped semiconductor material and electrolyte solution is of considerable fundamental interest, and is relevant to systems of practical importance. Both adjacent domains contain mobile charges, which respond to potential variations. This is exploited to design electronic and optoelectronic sensors, and other enabling semiconductor colloidal materials. We show that the charge mobility in both phases leads to a new type of interaction between semiconductor colloids suspended in aqueous electrolyte solutions. This interaction is due to the electrostatic response of the semiconductor interior to disturbances in the external field upon the approach of two particles. The electrostatic repulsion between two charged colloids is reduced from the one governed by the charged groups present at the particles surfaces. This type of interaction is unique to semiconductor particles and may have a substantial effect on the suspension dynamics and stability.

Oppositely charged colloids out of equilibrium

NASA Astrophysics Data System (ADS)

Vissers, T.

2010-11-01

Colloids are particles with a size in the range of a few nanometers up to several micrometers. Similar to atomic and molecular systems, they can form gases, liquids, solids, gels and glasses. Colloids can be used as model systems because, unlike molecules, they are sufficiently large to be studied directly with light microscopy and move sufficiently slow to study their dynamics. In this thesis, we study binary systems of polymethylmethacrylate (PMMA) colloidal particles suspended in low-polar solvent mixtures. Since the ions can still partially dissociate, a surface charge builds up which causes electrostatic interactions between the colloids. By carefully tuning the conditions inside the suspension, we make two kinds of particles oppositely charged. To study our samples, we use Confocal Laser Scanning Microscopy (CLSM). The positively and negatively charged particles can be distinguished by a different fluorescent dye. Colloids constantly experience a random motion resulting from random kicks of surrounding solvent molecules. When the attractions between the oppositely charged particles are weak, the particles can attach and detach many times and explore a lot of possible configurations and the system can reach thermodynamic equilibrium. For example, colloidal ‘ionic’ crystals consisting of thousands to millions of particles can form under the right conditions. When the attractions are strong, the system can become kinetically trapped inside a gel-like state. We observe that when the interactions change again, crystals can even emerge again from this gel-like phase. By using local order parameters, we quantitatively study the crystallization of colloidal particles and identify growth defects inside the crystals. We also study the effect of gravity on the growth of ionic crystals by using a rotating stage. We find that sedimentation can completely inhibit crystal growth and plays an important role in crystallization from the gel-like state. The surface potential and charge are studied by electrophoresis. Here, the velocity of the particles is measured while they are moving in an electric field. Using our real-space CLSM setup, we find that for a single-component system, the charge on the particles decreases with increasing volume fraction. Apart from structures that oppositely charged particles form close to thermodynamic equilibrium, we also study pattern formation when the system is driven out of equilibrium by an electric field. When oppositely charged particles are driven in opposite directions, the collisions between them cause particle of the same kind to form lanes. By combining our CLSM experiments with Brownian dynamics computer simulations, we study the structure and the dynamics of the suspension on the single-particle level. We find that the number of particles in a lane increases continuously with the field strength. By studying the dynamics and fluctuations parallel and perpendicular to the electric field direction, we identify the key mechanism of lane-formation. We show that pattern formation can easily become more complicated when we introduce alternating current (AC) fields. In addition to the formation of lanes parallel to the field-axis, bands of like-charged particles can form perpendicular to it. When the particles are sufficiently mobile, the system can be remixed again by changing the frequency. When AC-fields with higher field strengths are used, we show that complex patterns, including rotating instabilities, can emerge. The results in this thesis yield fundamental insight in electrophoresis, crystallization and pattern formation when systems are driven out of equilibrium. The results on lane- and band-formation can be relevant for the design of electronic ink (e-ink), where electrically driven oppositely charged particles are used to change the image on a piece of electronic paper.

Patterned assembly of colloidal particles by confined dewetting lithography.

PubMed

Celio, Hugo; Barton, Emily; Stevenson, Keith J

2006-12-19

We report the assembly of colloidal particles into confined arrangements and patterns on various cleaned and chemically modified solid substrates using a method which we term "confined dewetting lithography" or CDL for short. The experimental setup for CDL is a simple deposition cell where an aqueous suspension of colloidal particles (e.g., polystyrene spheres) is placed between a floating deposition template (i.e., metal microgrid) and the solid substrate. The voids of the deposition template serve as an array of micrometer-sized reservoirs where several hydrodynamic processes are confined. These processes include water evaporation, meniscus formation, convective flow, rupturing, dewetting, and capillary-bridge formation. We discuss the optimal conditions where the CDL has a high efficiency to deposit intricate patterns of colloidal particles using polystyrene spheres (PS; 4.5, 2.0, 1.7, 0.11, 0.064 microm diameter) and square and hexagonal deposition templates as model systems. We find that the optimization conditions of the CDL method, when using submicrometer, sulfate-functionalized PS particles, are primarily dependent on minimizing attractive particle-substrate interactions. The CDL methodology described herein presents a relatively simple and rapid method to assemble virtually any geometric pattern, including more complex patterns assembled using PS particles with different diameters, from aqueous suspensions by choosing suitable conditions and materials.

Colloidal heat engines: a review.

PubMed

Martínez, Ignacio A; Roldán, Édgar; Dinis, Luis; Rica, Raúl A

2016-12-21

Stochastic heat engines can be built using colloidal particles trapped using optical tweezers. Here we review recent experimental realizations of microscopic heat engines. We first revisit the theoretical framework of stochastic thermodynamics that allows to describe the fluctuating behavior of the energy fluxes that occur at mesoscopic scales, and then discuss recent implementations of the colloidal equivalents to the macroscopic Stirling, Carnot and steam engines. These small-scale motors exhibit unique features in terms of power and efficiency fluctuations that have no equivalent in the macroscopic world. We also consider a second pathway for work extraction from colloidal engines operating between active bacterial reservoirs at different temperatures, which could significantly boost the performance of passive heat engines at the mesoscale. Finally, we provide some guidance on how the work extracted from colloidal heat engines can be used to generate net particle or energy currents, proposing a new generation of experiments with colloidal systems.

Colloidal layers in magnetic fields and under shear flow

NASA Astrophysics Data System (ADS)

Löwen, H.; Messina, R.; Hoffmann, N.; Likos, C. N.; Eisenmann, C.; Keim, P.; Gasser, U.; Maret, G.; Goldberg, R.; Palberg, T.

2005-11-01

The behaviour of colloidal mono- and bilayers in external magnetic fields and under shear is discussed and recent progress is summarized. Superparamagnetic colloidal particles form monolayers when they are confined to a air-water interface in a hanging water droplet. An external magnetic field allows us to tune the strength of the mutual dipole-dipole interaction between the colloids and the anisotropy of the interaction can be controlled by the tilt angle of the magnetic field relative to the surface normal of the air-water interface. For sufficiently large magnetic field strength crystalline monolayers are found. The role of fluctuations in these two-dimensional crystals is discussed. Furthermore, clustering phenomena in binary mixtures of superparamagnetic particles forming fluid monolayers are predicted. Finally, we address sheared colloidal bilayers and find that the orientation of confined colloidal crystals can be tailored by a previously applied shear direction.

PCS: The First Fluid Physics Payload on ISS

NASA Technical Reports Server (NTRS)

Doherty, M.; Sankaran, S.

2002-01-01

The Physics of Colloids in Space (PCS) experiment was accommodated within International Space Station (ISS) EXpedite the PRocessing of Experiments to Space Station (EXPRESS) Rack 2 and was remotely operated from early June 2001 until February 2002 from NASA Glenn Research Center's Telescience Support Center in Cleveland, Ohio and from a remote site at Harvard University in Cambridge, Massachusetts. PCS is an experiment conceived by Professor David A. Weitz of Harvard University (the Principal Investigator), focusing on the behavior of three different classes of colloid mixtures. The sophisticated light scattering instrumentation comprising PCS is capable of color imaging, and dynamic and static light scattering from 11 to 169 degrees, Bragg scattering over the range from 10 to 60 degrees, and laser light scattering at low angles from 0.3 to 6.0 degrees. The PCS instrumentation performed remarkably well, demonstrating a flexibility that enabled experiments to be performed that had not been envisioned prior to launch. While on-orbit, PCS accomplished 2400 hours of science operations, and was declared a resounding success. Each of the eight sample cells worked well and produced interesting and important results. Crystal nucleation and growth and the resulting structures of two binary colloidal crystal alloys were studied, with the long duration microgravity environment of the ISS facilitating extended studies on the growth and coarsening characteristics of the crystals. In another experiment run, the de-mixing of the colloid-polymer critical-point sample was studied as it phase-separates into two phases, one that resembles a gas and one that resembles a liquid. This process was studied over four decades of length scale, from 1 micron to 1 centimeter, behavior that cannot be observed in this sample on Earth because sedimentation would cause the colloids to fall to the bottom of the cell faster than the de-mixing process could occur. Similarly, the study of gelation and aging of another colloid-polymer sample, the colloid-polymer gel, also provided valuable information on gelation mechanisms, as did investigations on the extremely the low concentration silica and polystyrene fractal gel samples.