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.
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.
Design of latex-layered double hydroxide composites by tuning the aggregation in suspensions.
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.
Nanoparticle engineering of colloidal suspension behavior
NASA Astrophysics Data System (ADS)
Chan, Angel Thanda
We investigate the effects of highly charged nanoparticles on the phase behavior, structure, and assembly of colloidal microsphere suspensions. Specifically, by selectively tuning the electrostatic interactions between silica microspheres and polystyrene nanoparticles, we study the behavior of four key systems: (i) strongly repulsive, (ii) haloing, (iii) weakly attractive, and (iv) strongly attractive systems. In each system, a combination of nanoparticle adsorption, zeta potential, and confocal microscopy measurements are carried out to systematically study the effects of nanoparticle volume fraction, microsphere/nanoparticle size ratios, and interparticle interactions on their behavior. Our observations indicate that minimal adsorption of highly charged nanoparticles occurs on like-charged and negligibly-charged microspheres, whereas their extent of association increases dramatically with increasing microsphere-nanoparticle attraction. A rich phase behavior emerges in these systems based on whether the nanoparticle species serve as depletants, haloing, or bridging species. The phase transitions in the haloing system occur at constant nanoparticle volume fractions, φnano, over a broad range of microsphere volume fractions, φmicro . By contrast, the observed transitions in the weakly and strongly attractive mixtures occur at a constant number ratio of nanoparticles per microsphere, Nnano/Nmicro. Important structural differences emerge, which can be exploited in the assembly of colloidal gels for direct ink writing and colloidal crystals on epitaxially patterned substrates. Finally, for the first time, we explore nanoparticle haloing as a new route for stabilizing hydrophobic colloidal drugs in aqueous suspensions media for preparation of injectable pharmaceuticals. These microsphere suspensions exhibit improved stability relative to their surfactant-stabilized counterparts after autoclaving, a critical processing step for this target applications. This research opens up a new avenue for stabilization of hydrophobic particles, when surfactant additions alone do not provide sufficient stabilization.
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.
Evaluating the DLVO Model for Non-Aqueous Colloidal Suspensions
NASA Astrophysics Data System (ADS)
DeCarlo, Keith Joseph
Application of DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory for suspensions utilizing non-aqueous suspension mediums has been tested. Prediction of suspension stability using DLVO theory requires the calculation of the attractive and repulsive forces between the suspended colloids and that the only significant stabilization mechanism present is electrostatic stabilization which was tested. The van der Waals attractive potential was calculated for 12 different colloids in 11 suspending mediums in accord with Lifshitz's treatment and a new approximation proposing that the material bandgap energy can be used to approximate the Hamaker constant was developed. This treatment requires the complete knowledge of the permittivity as a function of frequency for all the components in the respective suspension. The permittivity data was simplified using a damped oscillator model described by Ninham and Parsegian. All permittivity data was compiled from the literature. Microwave data was tabulated by NIST, infrared parameters were determined from FTIR data, and the ultraviolet/visual parameters were determined via Cauchy plots or estimated by the bandgap. Using the bandgap to approximate the ultraviolet/visual parameters proved to be more accurate than other approximations when compared to the accepted values. It was found that the non-oxide and non-stoichiometric colloids tested had the largest associated van der Waals attractive force. The van der Waals potential calculated for oxide particles was found to follow a direct relationship with the ionic character of the bonding. Repulsive forces were calculated for 12 different colloids in 11 suspending mediums. The calculated repulsive potential generated is a function of both the magnitude of charge generated on each colloid (zeta-potential) and the size of the interacting double-layers. zeta-potential was measured for each suspension using a microelectrophoretic technique and the double-layer thickness was calculated. It was demonstrated that as the polarity of the suspending medium increased, the thickness of the double-layer also increased. A large double-layer thickness was found to directly correlate to the suspension stability. A large double-layer thickness results in a decreased slope of the charge degradation from the colloidal surface to the bulk suspension. This coupled with a large magnitude of surface charge increases the probability of dispersion. Through viscosity measurements, the stability mechanism of each suspension was determined by comparison of the viscosity at a shear rate of 1.0s -1 with the shear thinning exponent. It was determined that, of the suspension mediums tested, heptane, octanoic acid, and poly(ethylene glycol) introduce non-electrostatic stabilization mechanisms significant enough to invalidate the DLVO predictions for suspensions made using those mediums. Consistent with DLVO theory, the total interaction potential was calculated by summation of the repulsive and attractive potentials of each suspension (84 suspensions total) as a function of separation distance. Based upon the results of the summation, the suspension stability can be predicted. 64 of the 84 suspensions were determined to be unstable as the colloids agglomerated in the primary minimum, 11 suspensions were determined to be weakly flocculated, and nine suspensions were found to be stable. Viscosity was used to determine the critical value for the thermal energy barrier and to test the DLVO predictions. The critical value of the thermal energy barrier was found to be 2.0 x 10 -6J/m2. Therefore, for suspensions calculated to have a thermal energy barrier less than the critical value, the Brownian motion of the colloids in suspension at 298K were enough to overcome it, resulting in agglomeration at the primary minimum. For suspensions with a thermal barrier larger than 2.0 x 10-6J/m2, the interacting colloids moved into the secondary energy minimum. All suspensions tested in which the thermal energy barrier was less than 2.0 x 10-6J/m 2 had a specific viscosity at a shear rate of 1.0s-1 greater than the cut-off viscosity for stability. If the colloids moved into the secondary minimum, the resulting suspension was characterized as either being weakly flocculated or stable. Weakly flocculated suspensions had an equilibrium separation distance of colloids less than 40nm resulting in a viscosity at a shear rate of 1.0s-1 larger than the determined specific viscosity cut-off (1.1x 104), but a shear thinning exponent greater than 1.0. Stable suspensions were defined by the colloids as having an equilibrium separation distance greater than 40nm, resulting in viscosity values at a shear rate of 1.0s-1 smaller than that of the determined cut-off viscosity value.
Effective charges and virial pressure of concentrated macroion solutions
Boon, Niels; Guerrero-García, Guillermo Ivan; van Roij, René; ...
2015-07-13
The stability of colloidal suspensions is crucial in a wide variety of processes, including the fabrication of photonic materials and scaffolds for biological assemblies. The ionic strength of the electrolyte that suspends charged colloids is widely used to control the physical properties of colloidal suspensions. The extensively used two-body Derjaguin-Landau-Verwey-Overbeek (DLVO) approach allows for a quantitative analysis of the effective electrostatic forces between colloidal particles. DLVO relates the ionic double layers, which enclose the particles, to their effective electrostatic repulsion. Nevertheless, the double layer is distorted at high macroion volume fractions. Therefore, DLVO cannot describe the many-body effects that arisemore » in concentrated suspensions. In this paper, we show that this problem can be largely resolved by identifying effective point charges for the macroions using cell theory. This extrapolated point charge (EPC) method assigns effective point charges in a consistent way, taking into account the excluded volume of highly charged macroions at any concentration, and thereby naturally accounting for high volume fractions in both salt-free and added-salt conditions. We provide an analytical expression for the effective pair potential and validate the EPC method by comparing molecular dynamics simulations of macroions and monovalent microions that interact via Coulombic potentials to simulations of macroions interacting via the derived EPC effective potential. The simulations reproduce the macroion-macroion spatial correlation and the virial pressure obtained with the EPC model. Finally, our findings provide a route to relate the physical properties such as pressure in systems of screened Coulomb particles to experimental measurements.« less
Mesoscopic electrohydrodynamic simulations of binary colloidal suspensions.
Rivas, Nicolas; Frijters, Stefan; Pagonabarraga, Ignacio; Harting, Jens
2018-04-14
A model is presented for the solution of electrokinetic phenomena of colloidal suspensions in fluid mixtures. We solve the discrete Boltzmann equation with a Bhatnagar-Gross-Krook collision operator using the lattice Boltzmann method to simulate binary fluid flows. Solvent-solvent and solvent-solute interactions are implemented using a pseudopotential model. The Nernst-Planck equation, describing the kinetics of dissolved ion species, is solved using a finite difference discretization based on the link-flux method. The colloids are resolved on the lattice and coupled to the hydrodynamics and electrokinetics through appropriate boundary conditions. We present the first full integration of these three elements. The model is validated by comparing with known analytic solutions of ionic distributions at fluid interfaces, dielectric droplet deformations, and the electrophoretic mobility of colloidal suspensions. Its possibilities are explored by considering various physical systems, such as breakup of charged and neutral droplets and colloidal dynamics at either planar or spherical fluid interfaces.
Mesoscopic electrohydrodynamic simulations of binary colloidal suspensions
NASA Astrophysics Data System (ADS)
Rivas, Nicolas; Frijters, Stefan; Pagonabarraga, Ignacio; Harting, Jens
2018-04-01
A model is presented for the solution of electrokinetic phenomena of colloidal suspensions in fluid mixtures. We solve the discrete Boltzmann equation with a Bhatnagar-Gross-Krook collision operator using the lattice Boltzmann method to simulate binary fluid flows. Solvent-solvent and solvent-solute interactions are implemented using a pseudopotential model. The Nernst-Planck equation, describing the kinetics of dissolved ion species, is solved using a finite difference discretization based on the link-flux method. The colloids are resolved on the lattice and coupled to the hydrodynamics and electrokinetics through appropriate boundary conditions. We present the first full integration of these three elements. The model is validated by comparing with known analytic solutions of ionic distributions at fluid interfaces, dielectric droplet deformations, and the electrophoretic mobility of colloidal suspensions. Its possibilities are explored by considering various physical systems, such as breakup of charged and neutral droplets and colloidal dynamics at either planar or spherical fluid interfaces.
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.
Manipulating semiconductor colloidal stability through doping.
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.
Camargo, Manuel; Téllez, Gabriel
2008-04-07
The renormalized charge of a simple two-dimensional model of colloidal suspension was determined by solving the hypernetted chain approximation and Ornstein-Zernike equations. At the infinite dilution limit, the asymptotic behavior of the correlation functions is used to define the effective interactions between the components of the system and these effective interactions were compared to those derived from the Poisson-Boltzmann theory. The results we obtained show that, in contrast to the mean-field theory, the renormalized charge does not saturate, but exhibits a maximum value and then decays monotonically as the bare charge increases. The results also suggest that beyond the counterion layer near to the macroion surface, the ionic cloud is not a diffuse layer which can be handled by means of the linearized theory, as the two-state model claims, but a more complex structure is settled by the correlations between microions.
Colloidal behavior of aluminum oxide nanoparticles as affected by pH and natural organic matter.
Ghosh, Saikat; Mashayekhi, Hamid; Pan, Bo; Bhowmik, Prasanta; Xing, Baoshan
2008-11-04
The colloidal behavior of aluminum oxide nanoparticles (NPs) was investigated as a function of pH and in the presence of two structurally different humic acids (HAs), Aldrich HA (AHA) and the seventh HA fraction extracted from Amherst peat soil (HA7). Dynamic light scattering (DLS) and atomic force microscopy (AFM) were employed to determine the colloidal behavior of the NPs. Influence of pH and HAs on the surface charges of the NPs was determined. zeta-Potential data clearly showed that the surface charge of the NPs decreased with increasing pH and reached the point of zero charge (ZPC) at pH 7.9. Surface charge of the NPs also decreased with the addition of HAs. The NPs tend to aggregate as the pH of the suspension approaches ZPC, where van der Waals attraction forces dominate over electrostatic repulsion. However, the NP colloidal suspension was stable in the pHs far from ZPC. Colloidal stability was strongly enhanced in the presence of HAs at the pH of ZPC or above it, but in acidic conditions NPs showed strong aggregation in the presence of HAs. AFM imaging revealed the presence of long-chain fractions in HA7, which entangled with the NPs to form large aggregates. The association of HA with the NP surface can be assumed to follow a two-step process, possibly the polar fractions of the HA7 sorbed on the NP surface followed by entanglement with the long-chain fractions. Thus, our study demonstrated that the hydrophobic nature of the HA molecules strongly influenced the aggregation of colloidal NPs, possibly through their conformational behavior in a particular solution condition. Therefore, various organic matter samples will result in different colloidal behavior of NPs, subsequently their environmental fate and transport.
Domínguez-García, P; Pastor, J M; Rubio, M A
2011-04-01
This article presents results on the aggregation and disaggregation kinetics on a 1 μm diameter charged superparamagnetic particles dispersed in water under a constant uniaxial magnetic field in experiments with salt (KCl) added to the suspension in order to observe the behaviour of the system when the electrical properties of the particles have been screened. These particles have an electric charge and are confined between two separated 100 μm thick quartz windows, and sediment near the charged bottom wall. The electrostatic interactions that take place in this experimental setup may affect the micro-structure and colloidal stability of the suspension and thus, the dynamics of aggregation and disaggregation.
Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen
2013-04-23
Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.
From crystal chemistry to colloid stability
NASA Astrophysics Data System (ADS)
Gilbert, B.; Burrows, N.; Penn, R. L.
2008-12-01
Aqueous suspensions of ferrihydrite nanoparticles form a colloid with properties that can be understood using classical theories but which additionally exhibit the distinctive phenomenon of nanocluster formation. While use of in situ light and x-ray scattering methods permit the quantitative determination of colloid stability, interparticle interactions, and cluster or aggregate geometry, there are currently few approaches to predict the colloidal behavior of mineral nanoparticles. A longstanding goal of aqueous geochemistry is the rationalization and prediction of the chemical properties of hydrated mineral interfaces from knowledge of interface structure at the molecular scale. Because interfacial acid-base reactions typically lead to the formation of a net electrostatic charge at the surfaces of oxide, hydroxide, and oxyhydroxide mineral surfaces, quantitative descriptions of this behavior have the potential to permit the prediction of long-range interactions between mineral particles. We will evaluate the feasibility of this effort by constructing a model for surface charge formation for ferrihydrite that combines recent insights into the crystal structure of this phase and proposed methods for estimating the pKa of acidic surface groups. We will test the ability of this model to predict the colloidal stability of ferrihydrite suspensions as a function of solution chemistry.
Potential application of SERS for arsenic speciation in biological matrices.
Yang, Mingwei; Matulis, Shannon; Boise, Lawrence H; McGoron, Anthony J; Cai, Yong
2017-08-01
Speciation of arsenic is usually carried out using chromatography-based methods coupled with spectroscopic determination; however, the inevitable procedures involving sample preparation and separation could potentially alter the integrity of the arsenic metabolites present in biological samples. Surface-enhanced Raman spectroscopy (SERS) could be a promising alternative for providing a reliable arsenic analysis under the influence of a cellular matrix. A method for arsenic speciation using SERS in cellular matrix was developed in this study and four arsenicals were selected, including arsenite (As III ), arsenate (As V ), monomethylarsonic acid (MMA V ) and dimethylarsinic acid (DMA V ). Silver nanoparticles in the form of colliodal suspension with different surface charges, i.e., coated with citrate (AgNPs-Citrate) and spermine (AgNPs-Spermine) were employed as SERS substrates. Adsorption of arsenicals on nanoparticles in colloidal suspensions and the cellular matrix and the pH, size, and zeta potential of the colloidal suspensions were investigated for a better understanding of the SERS signal response of arsenicals in the colloidal suspensions or under the influence of cellular matrix. Arsenicals showed substantially different SERS responses in the two colloidal suspensions, mainly because of the distinct difference in the interaction between the arsenicals and the nanoparticles. Arsenic speciation in cell lysate could be successfully carried out in AgNPs-Spermine suspension, while AgNPs-Citrate could not yield significant SERS signals under the experimental conditions. This study proved that AgNPs-Spermine colloidal suspension could be a promising SERS substrate for studying arsenic metabolism in a biological matrix, reducing the bias caused by traditional techniques that involve sample extraction and pretreatment.
Dispersions of Goethite Nanorods in Aprotic Polar Solvents
Coursault, Delphine; Dozov, Ivan; Nobili, Maurizio; Dupont, Laurent; Chanéac, Corinne
2017-01-01
Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation). For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH) nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles. PMID:29039797
Charging and discharging of single colloidal particles at oil/water interfaces
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
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.
NASA Astrophysics Data System (ADS)
Xie, Jinchuan; Lin, Jianfeng; Wang, Yu; Li, Mei; Zhang, Jihong; Zhou, Xiaohua; He, Yifeng
2015-01-01
The fate and transport of colloidal contaminants in natural media are complicated by physicochemical properties of the contaminants and heterogeneous characteristics of the media. Size and charge exclusion are two key microscopic mechanisms dominating macroscopic transport velocities. Faster velocities of colloid-associated actinides than that of 3H2O were consistently indicated in many studies. However, dissociation/dissolution of these sorbed actinides (e.g., Pu and Np), caused by their redox reactions on mineral surfaces, possibly occurred under certain chemical conditions. How this dissolution is related to transport velocities remains unanswered. In this study, aging of the colloid-associated Pu (pseudo-colloid) at room temperature and transport through the saturated coarse-grained granites were performed to study whether Pu could exhibit slower velocity than that of 3H2O (UPu/UT < 1). The results show that oxidative dissolution of Pu(IV) associated with the surfaces of colloidal granite particles took place during the aging period. The relative velocity of UPu/UT declined from 1.06 (unaged) to 0.745 (135 d) over time. Size exclusion limited to the uncharged nano-sized particles could not explain such observed UPu/UT < 1. Therefore, the decline in UPu/UT was ascribed to the presence of electrostatic attraction between the negatively charged wall of granite pore channels and the Pu(V)O2+, as evidenced by increasing Pu(V)O2+ concentrations in the suspensions aged in sealed vessels. As a result of this attraction, Pu(V)O2+ was excluded from the domain closer to the centerline of pore channels. This reveals that charge exclusion played a more important role in dominating UPu than the size exclusion under the specific conditions, where oxidative dissolution of colloid-associated Pu(IV) was observed in the aged suspensions.
Origins of microstructural transformations in charged vesicle suspensions: the crowding hypothesis.
Seth, Mansi; Ramachandran, Arun; Murch, Bruce P; Leal, L Gary
2014-09-02
It is observed that charged unilamellar vesicles in a suspension can spontaneously deflate and subsequently transition to form bilamellar vesicles, even in the absence of externally applied triggers such as salt or temperature gradients. We provide strong evidence that the driving force for this deflation-induced transition is the repulsive electrostatic pressure between charged vesicles in concentrated suspensions, above a critical effective volume fraction. We use volume fraction measurements and cryogenic transmission electron microscopy imaging to quantitatively follow both the macroscopic and microstructural time-evolution of cationic diC18:1 DEEDMAC vesicle suspensions at different surfactant and salt concentrations. A simple model is developed to estimate the extent of deflation of unilamellar vesicles caused by electrostatic interactions with neighboring vesicles. It is determined that when the effective volume fraction of the suspension exceeds a critical value, charged vesicles in a suspension can experience "crowding" due to overlap of their electrical double layers, which can result in deflation and subsequent microstructural transformations to reduce the effective volume fraction of the suspension. Ordinarily in polydisperse colloidal suspensions, particles interacting via a repulsive potential transform into a glassy state above a critical volume fraction. The behavior of charged vesicle suspensions reported in this paper thus represents a new mechanism for the relaxation of repulsive interactions in crowded situations.
The Use of Clay-Polymer Nanocomposites in Wastewater Pretreatment
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
The Limitations of an Exclusively Colloidal View of Protein Solution Hydrodynamics and Rheology
Sarangapani, Prasad S.; Hudson, Steven D.; Migler, Kalman B.; Pathak, Jai A.
2013-01-01
Proteins are complex macromolecules with dynamic conformations. They are charged like colloids, but unlike colloids, charge is heterogeneously distributed on their surfaces. Here we overturn entrenched doctrine that uncritically treats bovine serum albumin (BSA) as a colloidal hard sphere by elucidating the complex pH and surface hydration-dependence of solution viscosity. We measure the infinite shear viscosity of buffered BSA solutions in a parameter space chosen to tune competing long-range repulsions and short-range attractions (2 mg/mL ≤ [BSA] ≤ 500 mg/mL and 3.0 ≤ pH ≤ 7.4). We account for surface hydration through partial specific volume to define volume fraction and determine that the pH-dependent BSA intrinsic viscosity never equals the classical hard sphere result (2.5). We attempt to fit our data to the colloidal rheology models of Russel, Saville, and Schowalter (RSS) and Krieger-Dougherty (KD), which are each routinely and successfully applied to uniformly charged suspensions and to hard-sphere suspensions, respectively. We discover that the RSS model accurately describes our data at pH 3.0, 4.0, and 5.0, but fails at pH 6.0 and 7.4, due to steeply rising solution viscosity at high concentration. When we implement the KD model with the maximum packing volume fraction as the sole floating parameter while holding the intrinsic viscosity constant, we conclude that the model only succeeds at pH 6.0 and 7.4. These findings lead us to define a minimal framework for models of crowded protein solution viscosity wherein critical protein-specific attributes (namely, conformation, surface hydration, and surface charge distribution) are addressed. PMID:24268154
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.
Stability of aggregates in the environment: role of solid bridging
NASA Astrophysics Data System (ADS)
Seiphoori, A.; Jerolmack, D. J.; Arratia, P. E.
2017-12-01
Colloids in suspension may form larger flocs under favorable conditions, via diffusion- or reaction-limited aggregation. In addition, the process of drying colloidal suspensions drives colloids together via hydrodynamic forces to form aggregates, that may be stable or unstable when subject to re-wetting and transport. Channel banks, shorelines and hillslopes are examples where the periodic wetting and drying results in the aggregation of muds. If aggregates disperse, the mud structure is unstable to subsequent wetting or fluid shear and can easily be detached and transported to rivers and coasts. The effective friction that governs hillslope and channel-bank soil creep rates also depends on the stability of the soil aggregates. Yet, few studies probe the particle-scale assembly or stability of aggregates subject to environmental loads, and the effects of shape or size heterogeneity have not been examined in detail. Here we investigate the formation and stability of aggregates subject to passive re-wetting (by misting) and shearing using a simple Poiseuille flow in a microfluidic device. We study the kinetics of a wide range of silicate colloids of different size and surface charge properties using in situ microscopy and particle tracking. We find that negatively charged silica microspheres are dragged by the retreating edge of an evaporating drop and are resuspended easily on re-wetting, showing that aggregates are unstable. In contrast, a bi-disperse suspension created by the addition of silica nanoparticles forms stable deposits, where nanoparticles bind larger particles by bridging the interparticle space, a mechanism similar to capillary bridging that we refer to as "solid bridging." Although aggregate structure and dynamics of the bi-disperse system changes quantitatively with surface-charge of the nanoparticles, smaller particles always conferred stability on the aggregates. Investigation of other colloids, including asbestos fibers and various clays, reveals that this solid bridging effect is robust across variations in particle shape and material composition. These experiments suggest that natural mud and soil may form more stable aggregates than would naively be expected by considering the charge effects alone, because their inherent size heterogeneity is conducive to solid bridging.
Ruiz-Reina, Emilio; Carrique, Félix; Lechuga, Luis
2014-03-01
Most of the suspensions usually found in industrial applications are concentrated, aqueous and in contact with the atmospheric CO2. The case of suspensions with a high concentration of added salt is relatively well understood and has been considered in many studies. In this work we are concerned with the case of concentrated suspensions that have no ions different than: (1) those stemming from the charged colloidal particles (the added counterions, that counterbalance their surface charge); (2) the H(+) and OH(-) ions from water dissociation, and (3) the ions generated by the atmospheric CO2 contamination. We call this kind of systems "realistic salt-free suspensions". We show some theoretical results about the electrophoretic mobility of a colloidal particle and the electroviscous effect of realistic salt-free concentrated suspensions. The theoretical framework is based on a cell model that accounts for particle-particle interactions in concentrated suspensions, which has been successfully applied to many different phenomena in concentrated suspensions. On the other hand, the water dissociation and CO2 contamination can be described following two different levels of approximation: (a) by local equilibrium mass-action equations, because it is supposed that the reactions are so fast that chemical equilibrium is attained everywhere in the suspension, or (b) by non-equilibrium dissociation-association kinetic equations, because it is considered that some reactions are not rapid enough to ensure local chemical equilibrium. Both approaches give rise to different results in the range from dilute to semidilute suspensions, causing possible discrepancies when comparing standard theories and experiments concerning transport properties of realistic salt-free suspensions. Copyright © 2013 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Shim, Suin; Shardt, Orest; Stone, Howard A.
2017-11-01
We introduce a phenomenon that is observed when deionized (DI) water with suspended charged particles flows through a single microfluidic channel. When an aqueous suspension of amine-modified, positively charged polystyrene particles (volume fraction = 0.01) flows steadily through a serpentine polydimethylsiloxane (PDMS) channel, a pulse of particles is generated, which then flows through the channel at a slower speed than the mean flow velocity. We quantify the results and rationalize the observations by considering the diffusiophoresis of charged particles driven by gas leakage through the permeable PDMS walls. A mathematical model will be compared with the experimental observations.
Computational and Experimental Studies of Electrospray Deposition of Nanoparticle Suspensions
NASA Astrophysics Data System (ADS)
Yong, Xin; Li, Ao; Brown, Nicholas; Zhao, Mingfei; Zhu, Yaqun; German, Guy; Chiarot, Paul
2017-11-01
Electrospray offers unique capabilities for deploying colloidal suspensions to create nanoparticle films and coatings. It can deliver precise quantities of particles in a dry state and overcomes many limitations of other technologies. We integrate simulations and experiments to elucidate the relationship between the key operating parameters and the structure of an electrospray deposit. We investigate the role of the electrospray time, the target substrate properties, and the polydispersity of the colloidal suspensions. The deposition patterns are similar for all spray times and substrates. In particular, the deposited particles segregate to the center and edge of a deposit, leaving a depletion region in between. Using a Lagrangian particle tracking method with convective droplet evaporation, we highlight the critical role of the space charge interactions inside the plume in governing the trajectory of the emitted particles and the ensuing deposit morphology. The microstructure of a deposit is also influenced by the electrical conductivity of the target substrate. The residual charges on the particles deposited on to a dielectric substrate influence the deposition of subsequent in-flight particles.
Analysis of dependent scattering mechanism in hard-sphere Yukawa random media
NASA Astrophysics Data System (ADS)
Wang, B. X.; Zhao, C. Y.
2018-06-01
The structural correlations in the microscopic structures of random media can induce the dependent scattering mechanism and thus influence the optical scattering properties. Based on our recent theory on the dependent scattering mechanism in random media composed of discrete dipolar scatterers [B. X. Wang and C. Y. Zhao, Phys. Rev. A 97, 023836 (2018)], in this paper, we study the hard-sphere Yukawa random media, in order to further elucidate the role of structural correlations in the dependent scattering mechanism and hence optical scattering properties. Here, we consider charged colloidal suspensions, whose effective pair interaction between colloids is described by a screened Coulomb (Yukawa) potential. By means of adding salt ions, the pair interaction between the charged particles can be flexibly tailored and therefore the structural correlations are modified. It is shown that this strategy can affect the optical properties significantly. For colloidal TiO2 suspensions, the modification of electric and magnetic dipole excitations induced by the structural correlations can substantially influence the optical scattering properties, in addition to the far-field interference effect described by the structure factor. However, this modification is only slightly altered by different salt concentrations and is mainly because of the packing-density-dependent screening effect. On the other hand, for low refractive index colloidal polystyrene suspensions, the dependent scattering mechanism mainly involves the far-field interference effect, and the effective exciting field amplitude for the electric dipole almost remains unchanged under different structural correlations. The present study has profound implications for understanding the role of structural correlations in the dependent scattering mechanism.
Materials for suspension (semi-solid) electrodes for energy and water technologies
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hatzell, Kelsey B.; Boota, Muhammad; Gogotsi, Yury
2015-01-01
Suspension or semi-solid electrodes have recently gained increased attention for large-scale applications such as grid energy storage, capacitive water deionization, and wastewater treatment. A suspension electrode is a multiphase material system comprised of an active (charge storing) material suspended in ionic solution (electrolyte). Gravimetrically, the electrolyte is the majority component and aids in physical transport of the active material. For the first time, this principle enables, scalability of electrochemical energy storage devices (supercapacitors and batteries) previously limited to small and medium scale applications. This critical review describes the ongoing material challenges encompassing suspension-based systems. The research described here combines classicalmore » aspects of electrochemistry, colloidal science, material science, fluid mechanics, and rheology to describe ion and charge percolation, adsorption of ions, and redox charge storage processes in suspension electrodes. Our review summarizes the growing inventory of material systems, methods and practices used to characterize suspension electrodes, and describes universal material system properties (rheological, electrical, and electrochemical) that are pivotal in the design of high performing systems. We include a discussion of the primary challenges and future research directions.« less
Crystal nucleation and metastable bcc phase in charged colloids: A molecular dynamics study
NASA Astrophysics Data System (ADS)
Ji, Xinqiang; Sun, Zhiwei; Ouyang, Wenze; Xu, Shenghua
2018-05-01
The dynamic process of homogenous nucleation in charged colloids is investigated by brute-force molecular dynamics simulation. To check if the liquid-solid transition will pass through metastable bcc, simulations are performed at the state points that definitely lie in the phase region of thermodynamically stable fcc. The simulation results confirm that, in all of these cases, the preordered precursors, acting as the seeds of nucleation, always have predominant bcc symmetry consistent with Ostwald's step rule and the Alexander-McTague mechanism. However, the polymorph selection is not straightforward because the crystal structures formed are not often determined by the symmetry of intermediate precursors but have different characters under different state points. The region of the state point where bcc crystal structures of large enough size are formed during crystallization is narrow, which gives a reasonable explanation as to why the metastable bcc phase in charged colloidal suspensions is rarely detected in macroscopic experiments.
Ion size effects on the electrokinetics of spherical particles in salt-free concentrated suspensions
NASA Astrophysics Data System (ADS)
Roa, Rafael; Carrique, Felix; Ruiz-Reina, Emilio
2012-02-01
In this work we study the influence of the counterion size on the electrophoretic mobility and on the dynamic mobility of a suspended spherical particle in a salt-free concentrated colloidal suspension. Salt-free suspensions contain charged particles and the added counterions that counterbalance their surface charge. A spherical cell model approach is used to take into account particle-particle electro-hydrodynamic interactions in concentrated suspensions. The finite size of the counterions is considered including an entropic contribution, related with the excluded volume of the ions, in the free energy of the suspension, giving rise to a modified counterion concentration profile. We are interested in studying the linear response of the system to an electric field, thus we solve the different electrokinetic equations by using a linear perturbation scheme. We find that the ionic size effect is quite important for moderate to high particles charges at a given particle volume fraction. In addition for such particle surface charges, both the electrophoretic mobility and the dynamic mobility suffer more important changes the larger the particle volume fraction for each ion size. The latter effects are more relevant the larger the ionic size.
Fracture in Kaolinite clay suspensions
NASA Astrophysics Data System (ADS)
Kosgodagan Acharige, Sebastien; Jerolmack, Douglas J.; Arratia, Paulo E.
2017-11-01
Clay minerals are involved in many natural (landslides, river channels) and industrial processes (ceramics, cosmetics, oil recovery). They are plate shaped charged colloids and exhibit different flow properties than simpler colloids when suspended in a liquid such as thixotropy and shear-banding. kaolinite platelets are non-swelling, meaning that the stacks formed by the platelets do not have water layers, and thus the suspension does not have a sol-gel transition. However, it has been shown that kaolinite suspensions possesses a non-zero yield stress even at low concentrations, indicating that the particles arrange themselves in a structure through attractive interactions. Here, we experimentally investigate the sedimentation of kaolinite suspensions in a Hele-Shaw cell. The sedimentation of these dilute suspensions can display solid behavior like fracture, revealed in cross-polarized light, which is linked to the failure of the weakly-bonded structure (typical yield stress 10-2 Pa). By changing the interaction potential of the particles (by sonication or introducing salts), we show through these sedimentation experiments, how the fracture pattern can be avoided. Research was sponsored by the Army Research Laboratory and was accomplished under Grant Number 569074.
In-situ chemical barrier and method of making
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
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.
Origins of the anomalous stress behavior in charged colloidal suspensions under shear.
Kumar, Amit; Higdon, Jonathan J L
2010-11-01
Numerical simulations are conducted to determine microstructure and rheology of sheared suspensions of charged colloidal particles at a volume fraction of ϕ=0.33. Over broad ranges of repulsive force strength F0 and Péclet number Pe, dynamic simulations show coexistence of ordered and disordered stable states with the state dependent on the initial condition. In contrast to the common view, at low shear rates, the disordered phase exhibits a lower viscosity (μ(r)) than the ordered phase, while this behavior is reversed at higher shear rates. Analysis shows the stress reversal is associated with different shear induced microstructural distortions in the ordered and disordered systems. Viscosity vs shear rate data over a wide range of F0 and Pe collapses well upon rescaling with the long-time self-diffusivity. Shear thinning viscosity in the ordered phase scaled as μ(r)∼Pe(-0.81) at low shear rates. The microstructural dynamics revealed in these studies explains the anomalous behavior and hysteresis loops in stress data reported in the literature.
Truzzolillo, D; Bordi, F; Sciortino, F; Sennato, S
2010-07-14
We study the effective interaction between differently charged polyelectrolyte-colloid complexes in electrolyte solutions via Monte Carlo simulations. These complexes are formed when short and flexible polyelectrolyte chains adsorb onto oppositely charged colloidal spheres, dispersed in an electrolyte solution. In our simulations the bending energy between adjacent monomers is small compared to the electrostatic energy, and the chains, once adsorbed, do not exchange with the solution, although they rearrange on the particles surface to accommodate further adsorbing chains or due to the electrostatic interaction with neighbor complexes. Rather unexpectedly, when two interacting particles approach each other, the rearrangement of the surface charge distribution invariably produces antiparallel dipolar doublets that invert their orientation at the isoelectric point. These findings clearly rule out a contribution of dipole-dipole interactions to the observed attractive interaction between the complexes, pointing out that such suspensions cannot be considered dipolar fluids. On varying the ionic strength of the electrolyte, we find that a screening length kappa(-1), short compared with the size of the colloidal particles, is required in order to observe the attraction between like-charged complexes due to the nonuniform distribution of the electric charge on their surface ("patch attraction"). On the other hand, by changing the polyelectrolyte/particle charge ratio xi(s), the interaction between like-charged polyelectrolyte-decorated particles, at short separations, evolves from purely repulsive to strongly attractive. Hence, the effective interaction between the complexes is characterized by a potential barrier, whose height depends on the net charge and on the nonuniformity of their surface charge distribution.
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.
Agra, R; Trizac, E; Bocquet, L
2004-12-01
The electrostatic potential of a highly charged disc (clay platelet) in an electrolyte is investigated in detail. The corresponding non-linear Poisson-Boltzmann (PB) equation is solved numerically, and we show that the far-field behaviour (relevant for colloidal interactions in dilute suspensions) is exactly that obtained within linearized PB theory, with the surface boundary condition of a uniform potential. The latter linear problem is solved by a new semi-analytical procedure and both the potential amplitude (quantified by an effective charge) and potential anisotropy coincide closely within PB and linearized PB, provided the disc bare charge is high enough. This anisotropy remains at all scales; it is encoded in a function that may vary over several orders of magnitude depending on the azimuthal angle under which the disc is seen. The results allow to construct a pair potential for discs interaction, that is strongly orientation dependent.
Colloidal motion under the action of a thermophoretic force.
Burelbach, Jerome; Zupkauskas, Mykolas; Lamboll, Robin; Lan, Yang; Eiser, Erika
2017-09-07
We present thermophoretic measurements in aqueous suspensions of three different polystyrene (PS) particles of varying negative charge, size, and surface coating. Our measurement technique is based on the observation of the colloidal steady-state distribution using conventional bright-field microscopy, which avoids undesirable effects such as laser-induced convection or local heating. We find that the colloids with the weakest zeta potential exhibit the strongest thermophoretic effect, suggesting that the Soret coefficient has a more intricate dependence on surface functionality than predicted by existing theoretical approaches. We also study the relaxation of the colloids to steady-state and propose a model to quantify the relaxation speed, based on the time evolution of the colloidal center of mass. Our observations are well described by this model and show that the relaxation speed tends to increase with the magnitude of the thermophoretic force.
Colloidal motion under the action of a thermophoretic force
NASA Astrophysics Data System (ADS)
Burelbach, Jerome; Zupkauskas, Mykolas; Lamboll, Robin; Lan, Yang; Eiser, Erika
2017-09-01
We present thermophoretic measurements in aqueous suspensions of three different polystyrene (PS) particles of varying negative charge, size, and surface coating. Our measurement technique is based on the observation of the colloidal steady-state distribution using conventional bright-field microscopy, which avoids undesirable effects such as laser-induced convection or local heating. We find that the colloids with the weakest zeta potential exhibit the strongest thermophoretic effect, suggesting that the Soret coefficient has a more intricate dependence on surface functionality than predicted by existing theoretical approaches. We also study the relaxation of the colloids to steady-state and propose a model to quantify the relaxation speed, based on the time evolution of the colloidal center of mass. Our observations are well described by this model and show that the relaxation speed tends to increase with the magnitude of the thermophoretic force.
Labille, J; Thomas, F; Milas, M; Vanhaverbeke, C
2005-04-01
The molecular mechanism of montmorillonite flocculation by bacterial polysaccharides was investigated, with special emphasis on the effect of carboxylic charges in the macromolecules on the mechanisms of interaction with the clay surface. An indirect way to quantify the energy of interaction was used, by comparing the flocculation ability of variously acidic polysaccharides. Data on tensile strength of aggregates in diluted suspension were collected by timed size measurements in the domain 0.1-600 microm, using laser diffraction. The flow behavior of settled aggregates was studied by rheology measurements. Flocculation of colloidal clay suspension by polysaccharides requires cancelling of the electrostatic repulsions by salts, which allows approach of clay surfaces close enough to be bridged by adsorbing macromolecules. The amount of acidic charges of the polysaccharides, and especially their location in the molecular structure, governs the bridging mechanism and the resulting tensile strength of the aggregates. The exposure of carboxylate groups located on side chains strongly promotes flocculation. In turn, charges located on the backbone of the polysaccharide are less accessible to interaction, and the flocculation ability of such polysaccharides is lowered. Measurements at different pH indicate that adsorption of acidic polysaccharides occurs via electrostatic interactions on the amphoteric edge surface of clay platelets, whereas neutral polysaccharides rather adsorb via weak interactions. Increased tensile strength in diluted aggregates due to strong surface interactions results in proportionally increased viscosity of the concentrated aggregates.
NASA Astrophysics Data System (ADS)
Rowe, Jeffrey D.; Baird, James K.
2007-06-01
A colloidal crystal suspended in an electrolyte solution will ordinarily exchange ions with the surrounding solution and develop a net surface charge density and a corresponding double layer. The interfacial tension of the charged surface has contributions arising from: (a) background interfacial tension of the uncharged surface, (b) the entropy associated with the adsorption of ions on the surface, and (c) the polarizing effect of the electrostatic field within the double layer. The adsorption and polarization effects make negative contributions to the surface free energy and serve to reduce the interfacial tension below the value to be expected for the uncharged surface. The diminished interfacial tension leads to a reduced capillary length scale. According to the Ostwald ripening theory of particle coarsening, the reduced capillary length will cause the solute supersaturation to decay more rapidly and the colloidal particles to be smaller in size and greater in number than in the absence of the double layer. Although the length scale for coarsening should be little affected in the case of inorganic colloids, such as AgI, it should be greatly reduced in the case of suspensions of protein crystals, such as apoferritin, catalase, and thaumatin.
Sedimentation dynamics and equilibrium profiles in multicomponent mixtures of colloidal particles.
Spruijt, E; Biesheuvel, P M
2014-02-19
In this paper we give a general theoretical framework that describes the sedimentation of multicomponent mixtures of particles with sizes ranging from molecules to macroscopic bodies. Both equilibrium sedimentation profiles and the dynamic process of settling, or its converse, creaming, are modeled. Equilibrium profiles are found to be in perfect agreement with experiments. Our model reconciles two apparently contradicting points of view about buoyancy, thereby resolving a long-lived paradox about the correct choice of the buoyant density. On the one hand, the buoyancy force follows necessarily from the suspension density, as it relates to the hydrostatic pressure gradient. On the other hand, sedimentation profiles of colloidal suspensions can be calculated directly using the fluid density as apparent buoyant density in colloidal systems in sedimentation-diffusion equilibrium (SDE) as a result of balancing gravitational and thermodynamic forces. Surprisingly, this balance also holds in multicomponent mixtures. This analysis resolves the ongoing debate of the correct choice of buoyant density (fluid or suspension): both approaches can be used in their own domain. We present calculations of equilibrium sedimentation profiles and dynamic sedimentation that show the consequences of these insights. In bidisperse mixtures of colloids, particles with a lower mass density than the homogeneous suspension will first cream and then settle, whereas particles with a suspension-matched mass density form transient, bimodal particle distributions during sedimentation, which disappear when equilibrium is reached. In all these cases, the centers of the distributions of the particles with the lowest mass density of the two, regardless of their actual mass, will be located in equilibrium above the so-called isopycnic point, a natural consequence of their hard-sphere interactions. We include these interactions using the Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equation of state. Finally, we demonstrate that our model is not limited to hard spheres, by extending it to charged spherical particles, and to dumbbells, trimers and short chains of connected beads.
Rouster, Paul; Pavlovic, Marko; Szilagyi, Istvan
2017-07-13
Ion specific effects on colloidal stability of titania nanosheets (TNS) were investigated in aqueous suspensions. The charge of the particles was varied by the pH of the solutions, therefore, the influence of mono- and multivalent anions on the charging and aggregation behavior could be studied when they were present either as counter or co-ions in the systems. The aggregation processes in the presence of inorganic salts were mainly driven by interparticle forces of electrostatic origin, however, chemical interactions between more complex ions and the surface led to additional attractive forces. The adsorption of anions significantly changed the surface charge properties and hence, the resistance of the TNS against salt-induced aggregation. On the basis of their ability in destabilization of the dispersions, the monovalent ions could be ordered according to the Hofmeister series in acidic solutions, where they act as counterions. However, the behavior of the biphosphate anion was atypical and its adsorption induced charge reversal of the particles. The multivalent anions destabilized the oppositely charged TNS more effectively and the aggregation processes followed the Schulze-Hardy rule. Only weak or negligible interactions were observed between the anions and the particles in alkaline suspensions, where the TNS possessed negative charge.
Pierre Turq, an inspirational scientist in charge and at interfaces
NASA Astrophysics Data System (ADS)
Ancian, Bernard; Bernard, Olivier; Chevalet, Jean; Dahirel, Vincent; Devilliers, Didier; Dubois, Emmanuelle; Dufrêche, Jean-François; Durand-Vidal, Serge; Groult, Henri; Jardat, Marie; Lantelme, Frédéric; Malikova, Natalie; Marry, Virginie; Mériguet, Guillaume; Perzynski, Régine; Rollet, Anne-Laure; Rotenberg, Benjamin; Salanne, Mathieu; Simon, Christian
2014-05-01
Pierre Turq has made decisive contributions to the theory and to the multiscale simulation of charged systems, such as molten salts, electrolyte solutions and colloidal suspensions, in the bulk, at interfaces and under confinement. His research line focussed on dynamical properties and was characterised by constant efforts to connect his theoretical work to both experiments and practical applications. In this article, his colleagues and former students pay a tribute to his past and current research interests by illustrating some recent developments accomplished in his laboratory.
Kang, K; Dhont, J K G
2009-11-01
Experiments on suspensions of charged colloidal rods (fd-virus particles) in external electric fields are performed, which show that a non-equilibrium critical point can be identified. Several transition lines of field-induced phases and states meet at this point and it is shown that there is a length- and time-scale which diverge at the non-equilibrium critical point. The off-critical and critical behavior is characterized, with both power law and logarithmic divergencies. These experiments show that analogous features of the classical, critical divergence of correlation lengths and relaxation times in equilibrium systems are also exhibited by driven systems that are far out of equilibrium, related to phases/states that do not exist in the absence of the external field.
NASA Astrophysics Data System (ADS)
Ghosh, Saikat
The colloidal behavior of engineered nanomaterials exposed in an aquatic environment may significantly influence their bioavailability as well as toxicity to different species. Natural organic matter (NOM) is one of the major colloidal materials ubiquitous in the environment with significant structural heterogeneity. Therefore, role of NOM molecules on environmental fate of these engineered NPs needs to be addressed. Colloidal behavior of aluminum (Al2O 3) and magnetic iron oxide (gammaFe2O3) NPs was studied in the presence of structurally different HAs and synthetic polyacrylic acids (PAAs). The conformation behavior of the adsorobed NOM/polyelectrolyte under specific solution conditions were determined with dynamic light scattering, atomic force microscopy measurements. Al2O3 NPs followed the classical DLVO model of colloidal behavior in their pristine state. However, a significant deviation from the classical DLVO model was observed when these NPs were coated with structurally different HAs. Low polar, high molecular weight HA fractions showed much stronger stabilization against Ca2+ induced aggregation. Previously, we observed that these low polar, high molecular weight fractions strongly destabilized the NP suspension when added in a small quantity. A significant transformation in suspension stability was observed possibly due to steric effect of these adsorbed HAs. The colloidal behavior of PAA/NOM coated ferrimagnetic gammaFe 2O3 NPs were investigated. Pure gammaFe2O 3 NPs were extremely unstable in aqueous solution but a significant enhancement in colloidal stability was observed after coating with polyelectrolytes/NOM. The steric as well as electrostatic stabilization introduced by the polyelectrolyte coating strongly dictated the colloidal stability. The alteration of electrosteric stabilization mechanisms by pH-induced conformation change profoundly influences the colloidal stability. Atomic force microscopy (AFM) study revealed a highly stretched conformation of the HA molecular chains adsorbed on gammaFe 2O3 NP surface with increasing pH from 5 to 9 which enhanced the colloidal stability trough long range electrosteric stabilization. The depletion of the polyelectrolytes during dilution of the suspension in the acidic solution conditions and in the presence of Na+ or Ca 2+ decreased the colloidal stability. The conformation of the polyelectrolytes adsorbed on the NP surface altered significantly as a function of substrate surface charge as viewed from the AFM imaging.
Primera-Pedrozo, Oliva M; Rodríguez, Gabriela Del Mar; Castellanos, Jorge; Felix-Rivera, Hilsamar; Resto, Oscar; Hernández-Rivera, Samuel P
2012-02-15
This work focused on establishing the parameters for enhancing the Raman signals of DNA and RNA constituents: nitrogenous bases, nucleosides and nucleotides, using metallic nanoparticles as surface enhanced Raman scattering substrates. Silver nanospheres were synthesized using sodium borohydride as a reducing agent and sodium citrate as a capping agent. The prepared nanoparticles had a surface plasmon band at ∼384nm and an average size of 12±3nm. The nanoparticles' surface charge was manipulated by changing the pH of the Ag colloidal suspensions in the range of 1-13. Low concentrations as 0.7μM were detected under the experimental conditions. The optimum pH values were: 7 for adenine, 9 for AMP, 5 for adenosine, 7 for dAMP and 11 for deoxyadenosine. Copyright © 2011 Elsevier B.V. All rights reserved.
Membraneless water filtration using CO2
NASA Astrophysics Data System (ADS)
Shin, Sangwoo; Shardt, Orest; Warren, Patrick B.; Stone, Howard A.
2017-05-01
Water purification technologies such as microfiltration/ultrafiltration and reverse osmosis utilize porous membranes to remove suspended particles and solutes. These membranes, however, cause many drawbacks such as a high pumping cost and a need for periodic replacement due to fouling. Here we show an alternative membraneless method for separating suspended particles by exposing the colloidal suspension to CO2. Dissolution of CO2 into the suspension creates solute gradients that drive phoretic motion of particles. Due to the large diffusion potential generated by the dissociation of carbonic acid, colloidal particles move either away from or towards the gas-liquid interface depending on their surface charge. Using the directed motion of particles induced by exposure to CO2, we demonstrate a scalable, continuous flow, membraneless particle filtration process that exhibits low energy consumption, three orders of magnitude lower than conventional microfiltration/ultrafiltration processes, and is essentially free from fouling.
Membraneless water filtration using CO2
Shin, Sangwoo; Shardt, Orest; Warren, Patrick B.; Stone, Howard A.
2017-01-01
Water purification technologies such as microfiltration/ultrafiltration and reverse osmosis utilize porous membranes to remove suspended particles and solutes. These membranes, however, cause many drawbacks such as a high pumping cost and a need for periodic replacement due to fouling. Here we show an alternative membraneless method for separating suspended particles by exposing the colloidal suspension to CO2. Dissolution of CO2 into the suspension creates solute gradients that drive phoretic motion of particles. Due to the large diffusion potential generated by the dissociation of carbonic acid, colloidal particles move either away from or towards the gas–liquid interface depending on their surface charge. Using the directed motion of particles induced by exposure to CO2, we demonstrate a scalable, continuous flow, membraneless particle filtration process that exhibits low energy consumption, three orders of magnitude lower than conventional microfiltration/ultrafiltration processes, and is essentially free from fouling. PMID:28462929
Martoïa, F; Dumont, P J J; Orgéas, L; Belgacem, M N; Putaux, J-L
2016-02-14
In this study, we characterized and modeled the rheology of TEMPO-oxidized cellulose nanofibril (NFC) aqueous suspensions with electrostatically stabilized and unflocculated nanofibrous structures. These colloidal suspensions of slender and wavy nanofibers exhibited a yield stress and a shear thinning behavior at low and high shear rates, respectively. Both the shear yield stress and the consistency of these suspensions were power-law functions of the NFC volume fraction. We developed an original multiscale model for the prediction of the rheology of these suspensions. At the nanoscale, the suspensions were described as concentrated systems where NFCs interacted with the Newtonian suspending fluid through Brownian motion and long range fluid-NFC hydrodynamic interactions, as well as with each other through short range hydrodynamic and repulsive colloidal interaction forces. These forces were estimated using both the experimental results and 3D networks of NFCs that were numerically generated to mimic the nanostructures of NFC suspensions under shear flow. They were in good agreement with theoretical and measured forces for model colloidal systems. The model showed the primary role played by short range hydrodynamic and colloidal interactions on the rheology of NFC suspensions. At low shear rates, the origin of the yield stress of NFC suspensions was attributed to the combined contribution of repulsive colloidal interactions and the topology of the entangled NFC networks in the suspensions. At high shear rates, both concurrent colloidal and short (in some cases long) range hydrodynamic interactions could be at the origin of the shear thinning behavior of NFC suspensions.
Electrohydrodynamic Flows in Electrochemical Systems
NASA Technical Reports Server (NTRS)
Saville, D. A.
2005-01-01
Recent studies have established a new class of assembly processes with colloidal suspensions. Particles are driven together to form large crystalline structures in both dc and ac fields. The current work centers on this new class of flows in ac fields. In the research carried out under the current award, it was established that: (i) Small colloidal particles crystallize near an electrode due to electrohydrodynamic flows induced by an sinusoidally varying applied potential. (ii) These flows originate due to disturbances in the electrode polarization layer arising from the presence of the particles. Inasmuch as the charge and the field strength both scale on the applied field, the flows are proportional to the square of the applied voltage. (iii) Suspensions of two different sorts of particles can be crystallized and will form well-ordered binary crystals. (iv) At high frequencies the EHD flows die out. Thus, with a homogeneous system the particles become widely spaced due to dipolar repulsion. With a binary suspension, however, the particles may become attractive due to dipolar attraction arising from differences in electrokinetic dipoles. Consequently binary crystals form at both high and low frequencies.
NASA Astrophysics Data System (ADS)
Emoto, Akira; Kamei, Tadayoshi; Shioda, Tatsutoshi; Kawatsuki, Nobuhiro; Ono, Hiroshi
2009-06-01
We report the experimental results of two-dimensional patterning of colloidal crystals using edge-patterned cells. Solvent evaporation of a colloidal suspension from the edge of the cell induces self-organized crystallization of spherical colloidal particles. From a reservoir of colloidal suspension in the cell, different colloidal suspensions are injected repetitively. An edge-patterned substrate is introduced into the cell as an upper substrate. As a result, different colloidal crystals are alternately stacked in the lateral direction according to the edge pattern. The characteristics of cloning formation are specifically showed including deformations from the original pattern. This two-dimensional patterning of three-dimensional colloidal crystals by means of lateral autocloning is promising for the development of photonic crystal arrays for use in optic and photonic devices.
Computation of shear viscosity of colloidal suspensions by SRD-MD
DOE Office of Scientific and Technical Information (OSTI.GOV)
Laganapan, A. M. K.; Videcoq, A., E-mail: arnaud.videcoq@unilim.fr; Bienia, M.
2015-04-14
The behaviour of sheared colloidal suspensions with full hydrodynamic interactions (HIs) is numerically studied. To this end, we use the hybrid stochastic rotation dynamics-molecular dynamics (SRD-MD) method. The shear viscosity of colloidal suspensions is computed for different volume fractions, both for dilute and concentrated cases. We verify that HIs help in the collisions and the streaming of colloidal particles, thereby increasing the overall shear viscosity of the suspension. Our results show a good agreement with known experimental, theoretical, and numerical studies. This work demonstrates the ability of SRD-MD to successfully simulate transport coefficients that require correct modelling of HIs.
Drude-type conductivity of charged sphere colloidal crystals: Density and temperature dependence
NASA Astrophysics Data System (ADS)
Medebach, Martin; Jordán, Raquel Chuliá; Reiber, Holger; Schöpe, Hans-Joachim; Biehl, Ralf; Evers, Martin; Hessinger, Dirk; Olah, Julianna; Palberg, Thomas; Schönberger, Ernest; Wette, Patrick
2005-09-01
We report on extensive measurements in the low-frequency limit of the ac conductivity of colloidal fluids and crystals formed from charged colloidal spheres suspended in de-ionized water. Temperature was varied in a range of 5°C<Θ<35°C and the particle number density n between 0.2 and 25μm-3 for the larger, respectively, 2.75 and 210μm-3 for the smaller of two investigated species. At fixed Θ the conductivity increased linearly with increasing n without any significant change at the fluid-solid phase boundary. At fixed n it increased with increasing Θ and the increase was more pronounced for larger n. Lacking a rigorous electrohydrodynamic treatment for counterion-dominated systems we describe our data with a simple model relating to Drude's theory of metal conductivity. The key parameter is an effectively transported particle charge or valence Z*. All temperature dependencies other than that of Z* were taken from literature. Within experimental resolution Z* was found to be independent of n irrespective of the suspension structure. Interestingly, Z* decreases with temperature in near quantitative agreement with numerical calculations.
Characterizing Fullerene Nanoparticles in Aqueous Suspensions
Studies have indicated that fullerenes can form stable colloidal suspensions in water when introduced to the aqueous phase through solvent exchange, sonication, or extended mixing. The colloidal suspensions created using these techniques have effective aqueous phase concentratio...
Hydration Repulsion between Carbohydrate Surfaces Mediated by Temperature and Specific Ions
Chen, Hsieh; Cox, Jason R.; Ow, Hooisweng; Shi, Rena; Panagiotopoulos, Athanassios Z.
2016-01-01
Stabilizing colloids or nanoparticles in solution involves a fine balance between surface charges, steric repulsion of coating molecules, and hydration forces against van der Waals attractions. At high temperature and electrolyte concentrations, the colloidal stability of suspensions usually decreases rapidly. Here, we report a new experimental and simulation discovery that the polysaccharide (dextran) coated nanoparticles show ion-specific colloidal stability at high temperature, where we observed enhanced colloidal stability of nanoparticles in CaCl2 solution but rapid nanoparticle-nanoparticle aggregation in MgCl2 solution. The microscopic mechanism was unveiled in atomistic simulations. The presence of surface bound Ca2+ ions increases the carbohydrate hydration and induces strongly polarized repulsive water structures beyond at least three hydration shells which is farther-reaching than previously assumed. We believe leveraging the binding of strongly hydrated ions to macromolecular surfaces represents a new paradigm in achieving absolute hydration and colloidal stability for a variety of materials, particularly under extreme conditions. PMID:27334145
Hydration Repulsion between Carbohydrate Surfaces Mediated by Temperature and Specific Ions
NASA Astrophysics Data System (ADS)
Chen, Hsieh; Cox, Jason R.; Ow, Hooisweng; Shi, Rena; Panagiotopoulos, Athanassios Z.
2016-06-01
Stabilizing colloids or nanoparticles in solution involves a fine balance between surface charges, steric repulsion of coating molecules, and hydration forces against van der Waals attractions. At high temperature and electrolyte concentrations, the colloidal stability of suspensions usually decreases rapidly. Here, we report a new experimental and simulation discovery that the polysaccharide (dextran) coated nanoparticles show ion-specific colloidal stability at high temperature, where we observed enhanced colloidal stability of nanoparticles in CaCl2 solution but rapid nanoparticle-nanoparticle aggregation in MgCl2 solution. The microscopic mechanism was unveiled in atomistic simulations. The presence of surface bound Ca2+ ions increases the carbohydrate hydration and induces strongly polarized repulsive water structures beyond at least three hydration shells which is farther-reaching than previously assumed. We believe leveraging the binding of strongly hydrated ions to macromolecular surfaces represents a new paradigm in achieving absolute hydration and colloidal stability for a variety of materials, particularly under extreme conditions.
Engineering of Novel Biocolloid Suspensions
NASA Technical Reports Server (NTRS)
Hammer, D. A.; Rodges, S.; Hiddessen, A.; Weitz, D. A.
1999-01-01
Colloidal suspensions are materials with a variety of uses from cleaners and lubricants to food, cosmetics, and coatings. In addition, they can be used as a tool for testing the fundamental tenets of statistical physics. Colloidal suspensions can be synthesized from a wide variety of materials, and in the form of monodisperse particles, which can self-assemble into highly ordered colloidal crystal structures. As such they can also be used as templates for the construction of highly ordered materials. Materials design of colloids has, to date, relied on entropic self-assembly, where crystals form as result of lower free energy due to a transition to order. Here, our goal is to develop a completely new method for materials fabrication using colloidal precursors, in which the self-assembly of the ordered colloidal structures is driven by a highly controllable, attractive interaction. This will greatly increase the range of potential structures that can be fabricated with colloidal particles. In this work, we demonstrate that colloidal suspensions can be crosslinked through highly specific biological crosslinking reactions. In particular, the molecules we use are protein-carbohydrate interactions derived from the immune system. This different driving force for self-assembly will yield different and novel suspensions structures. Because the biological interactions are heterotypic (A binding to B), this chemical system can be used to make binary alloys in which the two colloid subpopulations vary in some property - size, density, volume fraction, magnetic susceptibility, etc. An additional feature of these molecules which is unique - even within the realm of biological recognition - is that the molecules bind reversibly on reasonable time-scales, which will enable the suspension to sample different configurations, and allow us to manipulate and measure the size of the suspension dynamically. Because of the wide variety of structures that can be made from these novel colloids, and because the suspension structure can be altered dynamically, we believe this biocolloid system will yield a novel set of materials with many technological applications, including sensors (both biological and non-biological), optical filters and separation media.
Physics of a rapid CD4 lymphocyte count with colloidal gold.
Hansen, P; Barry, D; Restell, A; Sylvia, D; Magnin, O; Dombkowski, D; Preffer, F
2012-03-01
The inherent surface charges and small diameters that confer colloidal stability to gold particle conjugates (immunogold) are detrimental to rapid cell surface labeling and distinct cluster definition in flow cytometric light scatter assays. Although the inherent immunogold surface charge prevents self aggregation when stored in liquid suspension, it also slows binding to cells to timeframes of hours and inhibits cell surface coverage. Although the small diameter of immunogold particles prevents settling when in liquid suspension, small particles have small light scattering cross sections and weak light scatter signals. We report a new, small particle lyophilized immunogold reagent that maintains activity after 42°C storage for a year and can be rapidly dissolved into stable liquid suspension for use in labelling cells with larger particle aggregates that have enhanced scattering cross section. Labeling requires less than 1 min at 20°C, which is ∼30 times faster than customary fluorescent antibody labeling. The labeling step involves neutralizing the surface charge of immunogold and creating specifically bound aggregates of gold on the cell surface. This process provides distinct side-scatter cluster separation with blue laser light at 488 nm, which is further improved by using red laser light at 640 nm. Similar comparisons using LED light sources showed less improvement with red light, thereby indicating that coherent light scatter is of significance in enhancing side-scatter cluster separation. The physical principles elucidated here for this technique are compatible with most flow cytometers; however, future studies of its clinical efficacy should be of primary interest in point-of-care applications where robust reagents and rapid results are important. Copyright © 2011 International Society for Advancement of Cytometry.
Ho, Hau My; Lin, Binhua; Rice, Stuart A
2006-11-14
We report the results of experimental determinations of the triplet correlation functions of quasi-two-dimensional one-component and binary colloid suspensions in which the colloid-colloid interaction is short ranged. The suspensions studied range in density from modestly dilute to solid. The triplet correlation function of the one-component colloid system reveals extensive ordering deep in the liquid phase. At the same density the ordering of the larger diameter component in a binary colloid system is greatly diminished by a very small amount of the smaller diameter component. The possible utilization of information contained in the triplet correlation function in the theory of melting of a quasi-two-dimensional system is briefly discussed.
Colloidal approach to dispersion and enhanced deaggregation of aqueous ferrite suspensions
NASA Astrophysics Data System (ADS)
Mandanas, Michael Patrick M.
The role of solution and surface chemistry on deaggregation of calcined ferrites during attrition (stirred-media) milling of aqueous suspensions were investigated. Suspensions of commercially calcined Fe2O 3 powder (d50 ˜ 5.0 mum) were milled at different solid loadings and suspension pH. The drift of suspension pH, from pH 2.5 to pH 7.0, during solid loading experiments accounted for the observed reagglomeration with milling time. The observed deaggregation rates during pH stat milling, in the acidic region, can be related to (i) elevated solubility and (ii) enhanced dispersion via surface charge. Proton adsorption density during pH stat milling at different pH values is also comparable to existing potentiometric titration plots and can be related to deaggregation rates. A passivation-dispersion approach for dispersing manganese zinc ferrite (MnxZn(1 - x)Fe2O4) powder is presented. Addition of oxalic acid can help control dissolution reactions from particle surfaces and is subsequently dispersed with polyethyleneimine (PEI). Fully dissociated oxalic acid (pK1 = 1.2, pK2 = 4.3) solutions reacted with MnxZn(1 - x)Fe 2O4 leads to the formation of a uniform negative charge on the particle surface, resulting from the sparingly soluble salt formed on the surface. The resulting rheological data for passivation/dispersion of relatively high solid MnxZn(1 - x)Fe2O 4 suspensions (˜80 w/o, (˜40 v/o)) demonstrate improved colloid stability with improved rheological properties. Using the passivation dispersion scheme developed, deaggregation of commercially calcined MnxZn(1 - x)Fe2O4 powders during attrition milling was investigated. Reagglomeration is apparent when using a typical treatment, 2 w/w of a sulfonated based naphthalene condensate, during deaggregation of the calcined MnxZn(1 - x)Fe 2O4. However, is not observed for select oxalate/PEI treatments. The determined ideal treatment is 2 w/w oxalate and 3 w/w PEI based on the particle size and rheological characteristics of the suspensions during milling. (Abstract shortened by UMI.)
Solution synthesis of mixed-metal chalcogenide nanoparticles and spray deposition of precursor films
Schulz, Douglas L.; Curtis, Calvin J.; Ginley, David S.
2000-01-01
A colloidal suspension comprising metal chalcogenide nanoparticles and a volatile capping agent. The colloidal suspension is made by reacting a metal salt with a chalcogenide salt in an organic solvent to precipitate a metal chalcogenide, recovering the metal chalcogenide, and admixing the metal chalcogenide with a volatile capping agent. The colloidal suspension is spray deposited onto a substrate to produce a semiconductor precursor film which is substantially free of impurities.
NASA Astrophysics Data System (ADS)
Gen, Masao; Kakuta, Hideo; Kamimoto, Yoshihito; Wuled Lenggoro, I.
2011-06-01
A detection method based on the surface-enhanced Raman spectroscopy (SERS)-active substrate derived from aerosol nanoparticles and a colloidal suspension for detecting organic molecules of a model analyte (a pesticide) is proposed. This approach can detect the molecules of the derived from its solution with the concentration levels of ppb. For substrate fabrication, a gas-phase method is used to directly deposit Ag nanoparticles on to a silicon substrate having pyramidal structures. By mixing the target analyte with a suspension of Ag colloids purchased in advance, clotianidin analyte on Ag colloid can exist in junctions of co-aggregated Ag colloids. Using (i) a nanostructured substrate made from aerosol nanoparticles and (ii) colloidal suspension can increase the number of activity spots.
Coricovac, Dorina-Elena; Moacă, Elena-Alina; Pinzaru, Iulia; Cîtu, Cosmin; Soica, Codruta; Mihali, Ciprian-Valentin; Păcurariu, Cornelia; Tutelyan, Victor A.; Tsatsakis, Aristidis; Dehelean, Cristina-Adriana
2017-01-01
The use of magnetic iron oxide nanoparticles in biomedicine has evolved intensely in the recent years due to the multiple applications of these nanomaterials, mainly in domains like cancer. The aim of the present study was: (i) to develop biocompatible colloidal suspensions based on magnetic iron oxide nanoparticles as future theranostic tools for skin pathology and (ii) to test their effects in vitro on human keratinocytes (HaCat cells) and in vivo by employing an animal model of acute dermal toxicity. Biocompatible colloidal suspensions were obtained by coating the magnetic iron oxide nanoparticles resulted during the solution combustion synthesis with a double layer of oleic acid, as innovative procedure in increasing bioavailability. The colloidal suspensions were characterized in terms of dynamic light scattering (DLS) and transmission electron microscopy (TEM). The in vitro effects of these suspensions were tested by means of Alamar blue assay and the noxious effects at skin level were measured using non-invasive methods. The in vitro results indicated a lack of toxicity on normal human cells induced by the iron oxide nanoparticles colloidal suspensions after an exposure of 24 h to different concentrations (5, 10, and 25 μg·mL−1). The dermal acute toxicity test showed that the topical applications of the colloidal suspensions on female and male SKH-1 hairless mice were not associated with significant changes in the quality of barrier skin function. PMID:28400730
Formation Kinetics of Aqueous Suspensions of Fullerenes:Meeting in New Orleans.
Stable colloidal suspension of C60 is commonly achieved through various solvent exchange techniques. Nevertheless, the additives such as tetrahydrofuran may be retained in the C60 aggregates, which may influence the surface properties of the suspension. In this study, colloidal...
Effect of sonication on the colloidal stability of iron oxide nanoparticles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sodipo, Bashiru Kayode; Aziz, Azlan Abdul
2015-04-24
Colloidal stability of superparamagnetic iron oxide nanoparticles’ (SPION) suspensions, ultrasonically irradiated at various pH was studied. Electrophoresis measurement of the sonicated SPION showed that the shock waves and other unique conditions generated from the acoustic cavitation process (formation, growth and collapse of bubbles) affect the zeta potential value of the suspension. In this work, stabled colloidal suspensions of SPION were prepared and their pH is varied between 3 and 5. Prior to ultrasonic irradiation of the suspensions, their initial zeta potential values were determined. After ultrasonic irradiation of the suspensions, we observed that the sonication process interacts with colloidal stabilitymore » of the nanoparticles. The results demonstrated that only suspensions with pH less 4 were found stable and able to retain more than 90% of its initial zeta potential value. However, at pH greater than 4, the suspensions were found unstable. The result implies that good zeta potential value of SPION can be sustained in sonochemical process as long as the pH of the mixture is kept below 4.« less
Modified Mason number for charged paramagnetic colloidal suspensions
NASA Astrophysics Data System (ADS)
Du, Di; Hilou, Elaa; Biswal, Sibani Lisa
2016-06-01
The dynamics of magnetorheological fluids have typically been described by the Mason number, a governing parameter defined as the ratio between viscous and magnetic forces in the fluid. For most experimental suspensions of magnetic particles, surface forces, such as steric and electrostatic interactions, can significantly influence the dynamics. Here we propose a theory of a modified Mason number that accounts for surface forces and show that this modified Mason number is a function of interparticle distance. We demonstrate that this modified Mason number is accurate in describing the dynamics of a rotating pair of paramagnetic colloids of identical or mismatched sizes in either high or low salt solutions. The modified Mason number is confirmed to be pseudoconstant for particle pairs and particle chains undergoing a stable-metastable transition during rotation. The interparticle distance term can be calculated using theory or can be measured experimentally. This modified Mason number is more applicable to magnetorheological systems where surface forces are not negligible.
Automated video-microscopic imaging and data acquisition system for colloid deposition measurements
Abdel-Fattah, Amr I.; Reimus, Paul W.
2004-12-28
A video microscopic visualization system and image processing and data extraction and processing method for in situ detailed quantification of the deposition of sub-micrometer particles onto an arbitrary surface and determination of their concentration across the bulk suspension. The extracted data includes (a) surface concentration and flux of deposited, attached and detached colloids, (b) surface concentration and flux of arriving and departing colloids, (c) distribution of colloids in the bulk suspension in the direction perpendicular to the deposition surface, and (d) spatial and temporal distributions of deposited colloids.
Weak correlations between local density and dynamics near the glass transition.
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.
Transport of Intrinsic Plutonium Colloids in Saturated Porous Media
NASA Astrophysics Data System (ADS)
Zhou, D.; Abdel-Fattah, A.; Boukhalfa, H.; Ware, S. D.; Tarimala, S.; Keller, A. A.
2011-12-01
Actinide contaminants were introduced to the subsurface environment as a result of nuclear weapons development and testing, as well as for nuclear power generation and related research activities for defense and civilian applications. Even though most actinide species were believed to be fairly immobile once in the subsurface, recent studies have shown the transport of actinides kilometers away from their disposal sites. For example, the treated liquid wastes released into Mortandad Canyon at the Los Alamos National Laboratory were predicted to travel less than a few meters; however, plutonium and americium have been detected 3.4 km away from the waste outfall. A colloid-facilitated mechanism has been suggested to account for this unexpected transport of these radioactive wastes. Clays, oxides, organic matters, and actinide hydroxides have all been proposed as the possible mobile phase. Pu ions associated with natural colloids are often referred to as pseudo-Pu colloids, in contrast with the intrinsic Pu colloids that consist of Pu oxides. Significant efforts have been made to investigate the role of pseudo-Pu colloids, while few studies have evaluated the environmental behavior of the intrinsic Pu colloids. Given the fact that Pu (IV) has extremely low solubility product constant, it can be inferred that the transport of Pu in the intrinsic form is highly likely at suitable environmental conditions. This study investigates the transport of intrinsic Pu colloids in a saturated alluvium material packed in a cylindrical column (2.5-cm Dia. x 30-cm high) and compares the results to previous data on the transport of pseudo Pu colloids in the same material. A procedure to prepare a stable intrinsic Pu colloid suspension that produced consistent and reproducible electrokinetic and stability data was developed. Electrokinetic properties and aggregation stability were characterized. The Pu colloids, together with trillium as a conservative tracer, were injected into the column at a flow rate of ~ 6 mL/hr. Despite that the Pu intrinsic colloids are positively charged while the alluvium grain surfaces are negatively charged under the current experimental conditions, about 30% of the Pu colloids population transported through the column and broke through earlier than trillium. Our previous experiments in the same column have shown a highly unretarded transport of the negatively charged pseudo Pu colloids (Pu sorbed onto smectite colloids) and complete retardation of the dissolved Pu. The enhanced transport of Pu colloids was explained by the effective pore volume concept. Combining the results of these two experiments, it is concluded that the intrinsic Pu colloids transported in the column by adsorbing onto the background clay colloids due to electrostatic repulsion.
Role of air-water interfaces in colloid transport in porous media: A review
NASA Astrophysics Data System (ADS)
Flury, Markus; Aramrak, Surachet
2017-07-01
Air-water interfaces play an important role in unsaturated porous media, giving rise to phenomena like capillarity. Less recognized and understood are interactions of colloids with the air-water interface in porous media and the implications of these interactions for fate and transport of colloids. In this review, we discuss how colloids, both suspended in the aqueous phase and attached at pore walls, interact with air-water interfaces in porous media. We discuss the theory of colloid/air-water interface interactions, based on the different forces acting between colloids and the air-water interface (DLVO, hydrophobic, capillary forces) and based on thermodynamic considerations (Gibbs free energy). Subsurface colloids are usually electrostatically repelled from the air-water interface because most subsurface colloids and the air-water are negatively charged. However, hydrophobic interactions can lead to attraction to the air-water interface. When colloids are at the air-water interface, capillary forces are usually dominant over other forces. Moving air-water interfaces are effective in mobilizing and transporting colloids from surfaces. Thermodynamic considerations show that, for a colloid, the air-water interface is the favored state as compared with the suspension phase, except for hydrophilic colloids in the nanometer size range. Experimental evidence indicates that colloid mobilization in soils often occurs through macropores, although matrix transport is also prevalent in absence of macropores. Moving air-water interfaces, e.g., occurring during infiltration, imbibition, or drainage, have been shown to scour colloids from surfaces and translocate colloids. Colloids can also be pinned to surfaces by thin water films and capillary menisci at the air-water-solid interface line, causing colloid retention and immobilization. Air-water interfaces thus can both mobilize or immobilize colloids in porous media, depending on hydrodynamics and colloid and surface chemistry.
Moving charged particles in lattice Boltzmann-based electrokinetics
NASA Astrophysics Data System (ADS)
Kuron, Michael; Rempfer, Georg; Schornbaum, Florian; Bauer, Martin; Godenschwager, Christian; Holm, Christian; de Graaf, Joost
2016-12-01
The motion of ionic solutes and charged particles under the influence of an electric field and the ensuing hydrodynamic flow of the underlying solvent is ubiquitous in aqueous colloidal suspensions. The physics of such systems is described by a coupled set of differential equations, along with boundary conditions, collectively referred to as the electrokinetic equations. Capuani et al. [J. Chem. Phys. 121, 973 (2004)] introduced a lattice-based method for solving this system of equations, which builds upon the lattice Boltzmann algorithm for the simulation of hydrodynamic flow and exploits computational locality. However, thus far, a description of how to incorporate moving boundary conditions into the Capuani scheme has been lacking. Moving boundary conditions are needed to simulate multiple arbitrarily moving colloids. In this paper, we detail how to introduce such a particle coupling scheme, based on an analogue to the moving boundary method for the pure lattice Boltzmann solver. The key ingredients in our method are mass and charge conservation for the solute species and a partial-volume smoothing of the solute fluxes to minimize discretization artifacts. We demonstrate our algorithm's effectiveness by simulating the electrophoresis of charged spheres in an external field; for a single sphere we compare to the equivalent electro-osmotic (co-moving) problem. Our method's efficiency and ease of implementation should prove beneficial to future simulations of the dynamics in a wide range of complex nanoscopic and colloidal systems that were previously inaccessible to lattice-based continuum algorithms.
Colloid-probe AFM studies of the interaction forces of proteins adsorbed on colloidal crystals.
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.
Yoshikawa, Taro; Zuerbig, Verena; Gao, Fang; Hoffmann, René; Nebel, Christoph E; Ambacher, Oliver; Lebedev, Vadim
2015-05-19
Monosized (∼4 nm) diamond nanoparticles arranged on substrate surfaces are exciting candidates for single-photon sources and nucleation sites for ultrathin nanocrystalline diamond film growth. The most commonly used technique to obtain substrate-supported diamond nanoparticles is electrostatic self-assembly seeding using nanodiamond colloidal suspensions. Currently, monodisperse nanodiamond colloids, which have a narrow distribution of particle sizes centering on the core particle size (∼4 nm), are available for the seeding technique on different substrate materials such as Si, SiO2, Cu, and AlN. However, the self-assembled nanoparticles tend to form small (typically a few tens of nanometers or even larger) aggregates on all of those substrate materials. In this study, this major weakness of self-assembled diamond nanoparticles was solved by modifying the salt concentration of nanodiamond colloidal suspensions. Several salt concentrations of colloidal suspensions were prepared using potassium chloride as an inserted electrolyte and were examined with respect to seeding on SiO2 surfaces. The colloidal suspensions and the seeded surfaces were characterized by dynamic light scattering and atomic force microscopy, respectively. Also, the interaction energies between diamond nanoparticles in each of the examined colloidal suspensions were compared on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From these investigations, it became clear that the appropriate salt concentration suppresses the formation of small aggregates during the seeding process owing to the modified electrostatic repulsive interaction between nanoparticles. Finally, monosized (<10 nm) individual diamond nanoparticles arranged on SiO2 surfaces have been successfully obtained.
Adsorption of silica colloids onto like-charged silica surfaces of different roughness
Dylla-Spears, R.; Wong, L.; Shen, N.; ...
2017-01-17
Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption tomore » measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles—far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface.« less
First experimental feasibility study of VIPIC: a custom-made detector for X-ray speckle measurements
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rumaiz, Abdul K.; Siddons, D. Peter; Deptuch, Grzegorz
2016-02-10
The Vertically Integrated Photon Imaging Chip (VIPIC) was custom-designed for X-ray photon correlation spectroscopy, an application in which occupancy per pixel is low but high time resolution is needed. VIPIC operates in a sparsified streaming mode in which each detected photon is immediately read out as a time- and position-stamped event. This event stream can be fed directly to an autocorrelation engine or accumulated to form a conventional image. The detector only delivers non-zero data (sparsified readout), greatly reducing the communications overhead typical of conventional frame-oriented detectors such as charge-coupled devices or conventional hybrid pixel detectors. This feature allowscontinuousacquisition ofmore » data with timescales from microseconds to hours. In this work VIPIC has been used to measure X-ray photon correlation spectroscopy data on polystyrene latex nano-colliodal suspensions in glycerol and on colloidal suspensions of silica spheres in water. Relaxation times of the nano-colloids have been measured for different temperatures. These results demonstrate that VIPIC can operatecontinuouslyin the microsecond time frame, while at the same time probing longer timescales.« less
VIPIC: a custom-made detector for X-ray speckle measurements
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rumaiz, Abdul K.; Siddons, D. Peter; Deptuch, Grzegorz
2016-03-01
The Vertically Integrated Photon Imaging Chip (VIPIC) was custom-designed for X-ray photon correlation spectroscopy, an application in which occupancy per pixel is low but high time resolution is needed. VIPIC operates in a sparsified streaming mode in which each detected photon is immediately read out as a time- and position-stamped event. This event stream can be fed directly to an autocorrelation engine or accumulated to form a conventional image. The detector only delivers non-zero data (sparsified readout), greatly reducing the communications overhead typical of conventional frame-oriented detectors such as charge-coupled devices or conventional hybrid pixel detectors. This feature allows continuousmore » acquisition of data with timescales from microseconds to hours. In this work VIPIC has been used to measure X-ray photon correlation spectroscopy data on polystyrene latex ano-colliodal suspensions in glycerol and on colloidal suspensions of silica spheres in water. Relaxation times of the nano-colloids have been measured for different temperatures. These results demonstrate that VIPIC can operate continuously in the microsecond time frame, while at the same time probing longer timescales.« less
First experimental feasibility study of VIPIC: a custom-made detector for X-ray speckle measurements
Rumaiz, Abdul K.; Siddons, D. Peter; Deptuch, Grzegorz; Maj, Piotr; Kuczewski, Anthony J.; Carini, Gabriella A.; Narayanan, Suresh; Dufresne, Eric M.; Sandy, Alec; Bradford, Robert; Fluerasu, Andrei; Sutton, Mark
2016-01-01
The Vertically Integrated Photon Imaging Chip (VIPIC) was custom-designed for X-ray photon correlation spectroscopy, an application in which occupancy per pixel is low but high time resolution is needed. VIPIC operates in a sparsified streaming mode in which each detected photon is immediately read out as a time- and position-stamped event. This event stream can be fed directly to an autocorrelation engine or accumulated to form a conventional image. The detector only delivers non-zero data (sparsified readout), greatly reducing the communications overhead typical of conventional frame-oriented detectors such as charge-coupled devices or conventional hybrid pixel detectors. This feature allows continuous acquisition of data with timescales from microseconds to hours. In this work VIPIC has been used to measure X-ray photon correlation spectroscopy data on polystyrene latex nano-colliodal suspensions in glycerol and on colloidal suspensions of silica spheres in water. Relaxation times of the nano-colloids have been measured for different temperatures. These results demonstrate that VIPIC can operate continuously in the microsecond time frame, while at the same time probing longer timescales. PMID:26917126
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.
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.
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.
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.
Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William
2015-10-01
Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater-bentonite-fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L(-1)) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10(-10) M (241)Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k(f)) of 0.01-0.02 h(-1). Am recoveries in each column were 55-60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h(-1) in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. Our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because of the ability of the fracture materials to rapidly strip Am from the bentonite colloids and the apparent lack of a strong binding site that would keep a fraction of the Am strongly-associated with the colloids. Published by Elsevier Ltd.
Formation of Aqueous Suspensions of Fullerenes
Colloidal suspensions of C60, C70 and a derivative of C60, PCBM ([6,6]-Phenyl C61-butyric acid methyl ester) were produced by extended mixing in water. We examined the contribution of background solution chemistry (pH, ionic strength) on the formation kinetics of colloidal suspe...
Coulomb Crystallization of Charged Microspheres Levitated in a Gas Discharge Plasma
NASA Technical Reports Server (NTRS)
Goree, John
1998-01-01
The technical topic of the project was the experimental observation of Coulomb crystallization of charged microspheres levitated in a gas discharge plasma. This suspension, sometimes termed a dusty plasma, is closely analogous to a colloidal suspension, except that it has a much faster time response, is more optically thin, and has no buoyancy forces to suspend the particles. The particles are levitated by electric fields. Through their collective Coulomb repulsions, the particles arrange themselves in a lattice with a crystalline symmetry, which undergoes an order-disorder phase transition analogous to melting when the effective temperature of the system is increased. Due to gravitational sedimentation, the particles form a thin layer in the laboratory, so that the experimental system is nearly 2D, whereas in future microgravity experiments they are expected to fill a larger volume and behave like a 3D solid or liquid. The particles are imaged using a video camera by illuminating them with a sheet of laser light. Because the suspension is optically thin, this imaging method will work as well in a 3D microgravity experiment as it does in a 2D laboratory system.
Enhanced gel formation in binary mixtures of nanocolloids with short-range attraction
NASA Astrophysics Data System (ADS)
Harden, James L.; Guo, Hongyu; Bertrand, Martine; Shendruk, Tyler N.; Ramakrishnan, Subramanian; Leheny, Robert L.
2018-01-01
Colloidal suspensions transform between fluid and disordered solid states as parameters such as the colloid volume fraction and the strength and nature of the colloidal interactions are varied. Seemingly subtle changes in the characteristics of the colloids can markedly alter the mechanical rigidity and flow behavior of these soft composite materials. This sensitivity creates both a scientific challenge and an opportunity for designing suspensions for specific applications. In this paper, we report a novel mechanism of gel formation in mixtures of weakly attractive nanocolloids with modest size ratio. Employing a combination of x-ray photon correlation spectroscopy, rheometry, and molecular dynamics simulations, we find that gels are stable at remarkably weaker attraction in mixtures with size ratio near two than in the corresponding monodisperse suspensions. In contrast with depletion-driven gelation at larger size ratio, gel formation in the mixtures is triggered by microphase demixing of the species into dense regions of immobile smaller colloids surrounded by clusters of mobile larger colloids that is not predicted by mean-field thermodynamic considerations. These results point to a new route for tailoring nanostructured colloidal solids through judicious combination of interparticle interaction and size distribution.
Freezing lines of colloidal Yukawa spheres. II. Local structure and characteristic lengths
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gapinski, Jacek, E-mail: gapinski@amu.edu.pl; Patkowski, Adam; NanoBioMedical Center, A. Mickiewicz University, Umultowska 85, 61-614 Poznań
Using the Rogers-Young (RY) integral equation scheme for the static pair correlation functions combined with the liquid-phase Hansen-Verlet freezing rule, we study the generic behavior of the radial distribution function and static structure factor of monodisperse charge-stabilized suspensions with Yukawa-type repulsive particle interactions at freezing. In a related article, labeled Paper I [J. Gapinski, G. Nägele, and A. Patkowski, J. Chem. Phys. 136, 024507 (2012)], this hybrid method was used to determine two-parameter freezing lines for experimentally controllable parameters, characteristic of suspensions of charged silica spheres in dimethylformamide. A universal scaling of the RY radial distribution function maximum is shownmore » to apply to the liquid-bcc and liquid-fcc segments of the universal freezing line. A thorough analysis is made of the behavior of characteristic distances and wavenumbers, next-neighbor particle coordination numbers, osmotic compressibility factor, and the Ravaché-Mountain-Streett minimum-maximum radial distribution function ratio.« less
An Automatic Phase-Change Detection Technique for Colloidal Hard Sphere Suspensions
NASA Technical Reports Server (NTRS)
McDowell, Mark; Gray, Elizabeth; Rogers, Richard B.
2005-01-01
Colloidal suspensions of monodisperse spheres are used as physical models of thermodynamic phase transitions and as precursors to photonic band gap materials. However, current image analysis techniques are not able to distinguish between densely packed phases within conventional microscope images, which are mainly characterized by degrees of randomness or order with similar grayscale value properties. Current techniques for identifying the phase boundaries involve manually identifying the phase transitions, which is very tedious and time consuming. We have developed an intelligent machine vision technique that automatically identifies colloidal phase boundaries. The algorithm utilizes intelligent image processing techniques that accurately identify and track phase changes vertically or horizontally for a sequence of colloidal hard sphere suspension images. This technique is readily adaptable to any imaging application where regions of interest are distinguished from the background by differing patterns of motion over time.
Hallez, Yannick; Meireles, Martine
2016-10-11
Electrostatic interactions play a key role in hollow shell suspensions as they determine their structure, stability, thermodynamics, and rheology and also the loading capacity of small charged species for nanoreservoir applications. In this work, fast, reliable modeling strategies aimed at predicting the electrostatics of hollow shells for one, two, and many colloids are proposed and validated. The electrostatic potential inside and outside a hollow shell with a finite thickness and a specific permittivity is determined analytically in the Debye-Hückel (DH) limit. An expression for the interaction potential between two such hollow shells is then derived and validated numerically. It follows a classical Yukawa form with an effective charge depending on the shell geometry, permittivity, and inner and outer surface charge densities. The predictions of the Ornstein-Zernike (OZ) equation with this pair potential to determine equations of state are then evaluated by comparison to results obtained with a Brownian dynamics algorithm coupled to the resolution of the linearized Poisson-Boltzmann and Laplace equations (PB-BD simulations). The OZ equation based on the DLVO-like potential performs very well in the dilute regime as expected, but also quite well, and more surprisingly, in the concentrated regime in which full spheres exhibit significant many-body effects. These effects are shown to vanish for shells with small thickness and high permittivity. For highly charged hollow shells, we propose and validate a charge renormalization procedure. Finally, using PB-BD simulations, we show that the cell model predicts the ion distribution inside and outside hollow shells accurately in both electrostatically dilute and concentrated suspensions. We then determine the shell loading capacity as a function of salt concentration, volume fraction, and surface charge density for nanoreservoir applications such as drug delivery, sensing, or smart coatings.
A Navier-Stokes phase-field crystal model for colloidal suspensions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Praetorius, Simon, E-mail: simon.praetorius@tu-dresden.de; Voigt, Axel, E-mail: axel.voigt@tu-dresden.de
2015-04-21
We develop a fully continuous model for colloidal suspensions with hydrodynamic interactions. The Navier-Stokes Phase-Field Crystal model combines ideas of dynamic density functional theory with particulate flow approaches and is derived in detail and related to other dynamic density functional theory approaches with hydrodynamic interactions. The derived system is numerically solved using adaptive finite elements and is used to analyze colloidal crystallization in flowing environments demonstrating a strong coupling in both directions between the crystal shape and the flow field. We further validate the model against other computational approaches for particulate flow systems for various colloidal sedimentation problems.
A Navier-Stokes phase-field crystal model for colloidal suspensions.
Praetorius, Simon; Voigt, Axel
2015-04-21
We develop a fully continuous model for colloidal suspensions with hydrodynamic interactions. The Navier-Stokes Phase-Field Crystal model combines ideas of dynamic density functional theory with particulate flow approaches and is derived in detail and related to other dynamic density functional theory approaches with hydrodynamic interactions. The derived system is numerically solved using adaptive finite elements and is used to analyze colloidal crystallization in flowing environments demonstrating a strong coupling in both directions between the crystal shape and the flow field. We further validate the model against other computational approaches for particulate flow systems for various colloidal sedimentation problems.
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
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.
Confocal Imaging of Confined Quiescent and Flowing Colloid-polymer Mixtures
Conrad, Jacinta C.
2014-01-01
The behavior of confined colloidal suspensions with attractive interparticle interactions is critical to the rational design of materials for directed assembly1-3, drug delivery4, improved hydrocarbon recovery5-7, and flowable electrodes for energy storage8. Suspensions containing fluorescent colloids and non-adsorbing polymers are appealing model systems, as the ratio of the polymer radius of gyration to the particle radius and concentration of polymer control the range and strength of the interparticle attraction, respectively. By tuning the polymer properties and the volume fraction of the colloids, colloid fluids, fluids of clusters, gels, crystals, and glasses can be obtained9. Confocal microscopy, a variant of fluorescence microscopy, allows an optically transparent and fluorescent sample to be imaged with high spatial and temporal resolution in three dimensions. In this technique, a small pinhole or slit blocks the emitted fluorescent light from regions of the sample that are outside the focal volume of the microscope optical system. As a result, only a thin section of the sample in the focal plane is imaged. This technique is particularly well suited to probe the structure and dynamics in dense colloidal suspensions at the single-particle scale: the particles are large enough to be resolved using visible light and diffuse slowly enough to be captured at typical scan speeds of commercial confocal systems10. Improvements in scan speeds and analysis algorithms have also enabled quantitative confocal imaging of flowing suspensions11-16,37. In this paper, we demonstrate confocal microscopy experiments to probe the confined phase behavior and flow properties of colloid-polymer mixtures. We first prepare colloid-polymer mixtures that are density- and refractive-index matched. Next, we report a standard protocol for imaging quiescent dense colloid-polymer mixtures under varying confinement in thin wedge-shaped cells. Finally, we demonstrate a protocol for imaging colloid-polymer mixtures during microchannel flow. PMID:24894062
Viscosity of colloidal suspensions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cohen, E.G.D.; Schepper, I.M. de
Simple expressions are given for the effective Newtonian viscosity as a function of concentration as well as for the effective visco-elastic response as a function of concentration and imposed frequency, of monodisperse neutral colloidal suspensions over the entire fluid range. The basic physical mechanisms underlying these formulae are discussed. The agreement with existing experiments is very good.
Powdered Chitin Agar as a Selective Medium for Enumeration of Actinomycetes in Water and Soil1
Hsu, S. C.; Lockwood, J. L.
1975-01-01
Agar media made with 0.4% colloidal chitin plus mineral salts and adjusted to pH 8.0 was superior to four other commonly used media for the isolation and enumeration of actinomycetes from water samples. More actinomycetes developed on chitin agar, and the development of bacteria and fungi was suppressed. Frozen and vacuum-dried chitin from aqueous colloidal suspensions was finely divided and gave results comparable to those obtained with media prepared from colloidal suspensions. Images PMID:234719
Schierz, A; Zänker, H
2009-04-01
The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid.
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.
Short- and long-time diffusion and dynamic scaling in suspensions of charged colloidal particles
NASA Astrophysics Data System (ADS)
Banchio, Adolfo J.; Heinen, Marco; Holmqvist, Peter; Nägele, Gerhard
2018-04-01
We report on a comprehensive theory-simulation-experimental study of collective and self-diffusion in concentrated suspensions of charge-stabilized colloidal spheres. In theory and simulation, the spheres are assumed to interact directly by a hard-core plus screened Coulomb effective pair potential. The intermediate scattering function, fc(q, t), is calculated by elaborate accelerated Stokesian dynamics (ASD) simulations for Brownian systems where many-particle hydrodynamic interactions (HIs) are fully accounted for, using a novel extrapolation scheme to a macroscopically large system size valid for all correlation times. The study spans the correlation time range from the colloidal short-time to the long-time regime. Additionally, Brownian Dynamics (BD) simulation and mode-coupling theory (MCT) results of fc(q, t) are generated where HIs are neglected. Using these results, the influence of HIs on collective and self-diffusion and the accuracy of the MCT method are quantified. It is shown that HIs enhance collective and self-diffusion at intermediate and long times. At short times self-diffusion, and for wavenumbers outside the structure factor peak region also collective diffusion, are slowed down by HIs. MCT significantly overestimates the slowing influence of dynamic particle caging. The dynamic scattering functions obtained in the ASD simulations are in overall good agreement with our dynamic light scattering (DLS) results for a concentration series of charged silica spheres in an organic solvent mixture, in the experimental time window and wavenumber range. From the simulation data for the time derivative of the width function associated with fc(q, t), there is indication of long-time exponential decay of fc(q, t), for wavenumbers around the location of the static structure factor principal peak. The experimental scattering functions in the probed time range are consistent with a time-wavenumber factorization scaling behavior of fc(q, t) that was first reported by Segrè and Pusey [Phys. Rev. Lett. 77, 771 (1996)] for suspensions of hard spheres. Our BD simulation and MCT results predict a significant violation of exact factorization scaling which, however, is approximately restored according to the ASD results when HIs are accounted for, consistent with the experimental findings for fc(q, t). Our study of collective diffusion is amended by simulation and theoretical results for the self-intermediate scattering function, fs(q, t), and its non-Gaussian parameter α2(t) and for the particle mean squared displacement W(t) and its time derivative. Since self-diffusion properties are not assessed in standard DLS measurements, a method to deduce W(t) approximately from fc(q, t) is theoretically validated.
Emergent structures and dynamics in suspensions of self-phoretic colloids
NASA Astrophysics Data System (ADS)
Scagliarini, Andrea; Pagonabarraga, Ignacio
2013-11-01
Active fluids, such as suspensions of self-propelled particles , are a fascinating example of Soft Matter displaying complex collective behaviours which provide challenges in non-equilibrium Statistical Physics. The recent development of techniques to assemble miniaturized devices has led to a growing interest for micro and nanoscale engines that can perform autonomous motion (``microrobots''), as, for instance, self-phoretic colloids, for which the propulsion is induced by the generation of a chemical species in a reaction catalyzed at the particle surface. We perform a mesoscopic numerical study of suspensions of self-phoretic colloids. We show that, at changing the sign of the phoretic mobility (which accounts for the colloid-solute interactions), the system switches from a cluster phase to a state with slowed dynamics. We find that the cluster size distribution follows an exponential behaviour, with a characteristic size growing linearly with the colloid activity, while the density fluctuations grow as a power-law with an exponent depending on the cluster fractal dimension.We single out hydrodynamic interactions, showing that their effect is to work against cluster formation. For positive μ, we observe that colloids tend to reach an ordered state on a triangular lattice.
Large Scale Brownian Dynamics of Confined Suspensions of Rigid Particles
NASA Astrophysics Data System (ADS)
Donev, Aleksandar; Sprinkle, Brennan; Balboa, Florencio; Patankar, Neelesh
2017-11-01
We introduce new numerical methods for simulating the dynamics of passive and active Brownian colloidal suspensions of particles of arbitrary shape sedimented near a bottom wall. The methods also apply for periodic (bulk) suspensions. Our methods scale linearly in the number of particles, and enable previously unprecedented simulations of tens to hundreds of thousands of particles. We demonstrate the accuracy and efficiency of our methods on a suspension of boomerang-shaped colloids. We also model recent experiments on active dynamics of uniform suspensions of spherical microrollers. This work was supported in part by the National Science Foundation under award DMS-1418706, and by the U.S. Department of Energy under award DE-SC0008271.
Rheology of concentrated suspensions of non-colloidal rigid fibers
NASA Astrophysics Data System (ADS)
Guazzelli, Elisabeth; Tapia, Franco; Shaikh, Saif; Butler, Jason E.; Pouliquen, Olivier
2017-11-01
Pressure and volume-imposed rheology is used to study suspensions of non-colloidal, rigid fibers in the concentrated regime for aspect ratios ranging from 3 to 15. The suspensions exhibit yield-stresses. Subtracting these apparent yield-stresses reveals a viscous scaling for both the shear and normal stresses. The variation in aspect ratio does not affect the friction coefficient (ratio of shear and normal stresses), but increasing the aspect ratio lowers the maximum volume fraction at which the suspension flows. Constitutive laws are proposed for the viscosities and the friction coefficient close to this maximum flowable fraction. The scaling of the stresses near this jamming transition are found to differ substantially from that of a suspension of spheres.
Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; ...
2015-07-13
Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. Themore » colloidal suspension (100 mg L –1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10 –10 M 241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k f) of 0.01–0.02 h –1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h –1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. As a result, our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because of the ability of the fracture materials to rapidly strip Am from the bentonite colloids and the apparent lack of a strong binding site that would keep a fraction of the Am strongly-associated with the colloids.« less
Physics of Colloids in Space: Flight Hardware Operations on ISS
NASA Technical Reports Server (NTRS)
Doherty, Michael P.; Bailey, Arthur E.; Jankovsky, Amy L.; Lorik, Tibor
2002-01-01
The Physics of Colloids in Space (PCS) experiment was launched on Space Shuttle STS-100 in April 2001 and integrated into EXpedite the PRocess of Experiments to Space Station Rack 2 on the International Space Station (ISS). This microgravity fluid physics investigation is being conducted in the ISS U.S. Lab 'Destiny' Module over a period of approximately thirteen months during the ISS assembly period from flight 6A through flight 9A. PCS is gathering data on the basic physical properties of simple colloidal suspensions by studying the structures that form. A colloid is a micron or submicron particle, be it solid, liquid, or gas. A colloidal suspension consists of these fine particles suspended in another medium. Common colloidal suspensions include paints, milk, salad dressings, cosmetics, and aerosols. Though these products are routinely produced and used, we still have much to learn about their behavior as well as the underlying properties of colloids in general. The long-term goal of the PCS investigation is to learn how to steer the growth of colloidal structures to create new materials. This experiment is the first part of a two-stage investigation conceived by Professor David Weitz of Harvard University (the Principal Investigator) along with Professor Peter Pusey of the University of Edinburgh (the Co-Investigator). This paper describes the flight hardware, experiment operations, and initial science findings of the first fluid physics payload to be conducted on ISS: The Physics of Colloids in Space.
Detection of molecular interactions
Groves, John T [Berkeley, CA; Baksh, Michael M [Fremont, CA; Jaros, Michal [Brno, CH
2012-02-14
A method and assay are described for measuring the interaction between a ligand and an analyte. The assay can include a suspension of colloidal particles that are associated with a ligand of interest. The colloidal particles are maintained in the suspension at or near a phase transition state from a condensed phase to a dispersed phase. An analyte to be tested is then added to the suspension. If the analyte binds to the ligand, a phase change occurs to indicate that the binding was successful.
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.
NASA Astrophysics Data System (ADS)
Sangeetha, Neralagatta M.; Moutet, Pierre; Lagarde, Delphine; Sallen, Gregory; Urbaszek, Bernhard; Marie, Xavier; Viau, Guillaume; Ressier, Laurence
2013-09-01
Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags.Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags. Electronic supplementary information (ESI) available: Detailed experimental procedures for the synthesis of upconverting NaYF4 nanocrystals and their transmission electron microscopy images. KFM and AFM images corresponding to the assembly of positively charged β-NaYF4:Er3+,Yb3+ nanocrystals from water suspensions by AFM nanoxerography. Photoluminescence spectra of β-NaYF4:Er3+,Yb3+ nanocrystals in a hexane suspension and assembled on charge patterns. See DOI: 10.1039/c3nr02734a
A mass-balance model to separate and quantify colloidal and solute redistributions in soil
Bern, C.R.; Chadwick, O.A.; Hartshorn, A.S.; Khomo, L.M.; Chorover, J.
2011-01-01
Studies of weathering and pedogenesis have long used calculations based upon low solubility index elements to determine mass gains and losses in open systems. One of the questions currently unanswered in these settings is the degree to which mass is transferred in solution (solutes) versus suspension (colloids). Here we show that differential mobility of the low solubility, high field strength (HFS) elements Ti and Zr can trace colloidal redistribution, and we present a model for distinguishing between mass transfer in suspension and solution. The model is tested on a well-differentiated granitic catena located in Kruger National Park, South Africa. Ti and Zr ratios from parent material, soil and colloidal material are substituted into a mixing equation to quantify colloidal movement. The results show zones of both colloid removal and augmentation along the catena. Colloidal losses of 110kgm-2 (-5% relative to parent material) are calculated for one eluviated soil profile. A downslope illuviated profile has gained 169kgm-2 (10%) colloidal material. Elemental losses by mobilization in true solution are ubiquitous across the catena, even in zones of colloidal accumulation, and range from 1418kgm-2 (-46%) for an eluviated profile to 195kgm-2 (-23%) at the bottom of the catena. Quantification of simultaneous mass transfers in solution and suspension provide greater specificity on processes within soils and across hillslopes. Additionally, because colloids include both HFS and other elements, the ability to quantify their redistribution has implications for standard calculations of soil mass balances using such index elements. ?? 2011.
Sol processing of conjugated carbon nitride powders for thin-film fabrication.
Zhang, Jinshui; Zhang, Mingwen; Lin, Lihua; Wang, Xinchen
2015-05-18
The chemical protonation of graphitic carbon nitride (CN) solids with strong oxidizing acids, for example HNO3, is demonstrated as an efficient pathway for the sol processing of a stable CN colloidal suspension, which can be translated into thin films by dip/disperse-coating techniques. The unique features of CN colloids, such as the polymeric matrix and the reversible hydrogen bonding, result in the thin-film electrodes derived from the sol solution exhibiting a high mechanical stability with improved conductivity for charge transport, and thus show a remarkably enhanced photo-electrochemical performance. The polymer system can in principle be broadly tuned by hybridization with desired functionalities, thus paving the way for the application of CN for specific tasks, as exemplified here by coupling with carbon nanotubes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Method to separate lignin-rich solid phase from acidic biomass suspension at an acidic pH
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.
Strain heterogeneity in sheared colloids revealed by neutron scattering
Chen, Kevin; Wu, Bin; He, Lilin; ...
2018-02-07
Recent computational and theoretical studies have shown that the deformation of colloidal suspensions under a steady shear is highly heterogeneous at the particle level and demonstrate a critical influence on the macroscopic deformation behavior. Despite its relevance to a wide variety of industrial applications of colloidal suspensions, scattering studies focusing on addressing the heterogeneity of the non-equilibrium colloidal structure are scarce thus far. Here in this paper, we report the first experimental result using small-angle neutron scattering. From the evolution of strain heterogeneity, we conclude that the shear-induced deformation transforms from nearly affine behavior at low shear rates, to plasticmore » rearrangements when the shear rate is high.« less
Elasticity and yielding of a calcite paste: scaling laws in a dense colloidal suspension.
Liberto, Teresa; Le Merrer, Marie; Barentin, Catherine; Bellotto, Maurizio; Colombani, Jean
2017-03-08
We address the mechanical characterization of a calcite paste as a model system to investigate the relation between the microstructure and macroscopic behavior of colloidal suspensions. The ultimate goal is to achieve control of the elastic and yielding properties of calcite which will prove valuable in several domains, from paper coating to paint manufacture and eventually in the comprehension and control of the mechanical properties of carbonate rocks. Rheological measurements have been performed on calcite suspensions over a wide range of particle concentrations. The calcite paste exhibits a typical colloidal gel behavior, with an elastic regime and a clear yield strain above which it enters a plastic regime. The yield strain shows a minimum when increasing the solid concentration, connected to a change in the power law scaling of the storage modulus. In the framework of the classical fractal elasticity model for colloidal suspensions proposed by Shih et al. [Phys. Rev. A, 1990, 42, 4772], we interpret this behavior as a switch with the concentration from the strong-link regime to the weak-link regime, which had never been observed so far in one well-defined system without external or chemical forcing.
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.
NASA Astrophysics Data System (ADS)
Clement, Sandhya; Gardner, Brint; Razali, Wan Aizuddin W.; Coleman, Victoria A.; Jämting, Åsa K.; Catchpoole, Heather J.; Goldys, Ewa M.; Herrmann, Jan; Zvyagin, Andrei
2017-11-01
The estimation of nanoparticle number concentration in colloidal suspensions is a prerequisite in many procedures, and in particular in multi-stage, low-yield reactions. Here, we describe a rapid, non-destructive method based on optical extinction and dynamic light scattering (DLS), which combines measurements using common bench-top instrumentation with a numerical algorithm to calculate the particle size distribution (PSD) and concentration. These quantities were derived from Mie theory applied to measurements of the optical extinction spectrum of homogeneous, non-absorbing nanoparticles, and the relative PSD of a colloidal suspension. The work presents an approach to account for PSDs achieved by DLS which, due to the underlying model, may not be representative of the true sample PSD. The presented approach estimates the absolute particle number concentration of samples with mono-, bi-modal and broad size distributions with <50% precision. This provides a convenient and practical solution for number concentration estimation required during many applications of colloidal nanomaterials.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lai, Yenjung; Borden, Robert C.; Alperin, Ed
There are numerous acidic plumes throughout the DOE complex and the nation as a whole. Low aquifer pH is a major concern since many important radionuclides (Pu, Ra, Sr, Tc) and metals (Cd, Co, Cs, Mn, Ni, Pb, Zn) strongly sorb to iron hydroxides and aluminosilicates under neutral to alkaline conditions, but are mobile in acidic plumes. To effectively use natural and enhanced attenuation (NEA) for management of these contaminants, we must be able to raise aquifer pH and maintain it at background levels until the external acid loading to the aquifer has dissipated. Geochemical modeling showed that a permeablemore » reactive barrier (PRB) formed by injection of colloidal Mg(OH){sub 2} would last much longer than colloidal Ca(OH){sub 2} due to the much lower solubility of Mg(OH){sub 2}. Assuming a 1,000 meq/L suspension of colloidal Mg(OH)2 could be effectively distributed, the PRB could last over twenty years before rejuvenation was required. Preliminary bench-scale treatability studies were conducted to demonstrate the efficacy of increasing the aquifer pH using a colloidal pH buffer. Laboratory studies demonstrated that three different colloidal Mg(OH){sub 2} suspensions (concentration varied from 1,000 to 1,250 meq/L) could be transported through the columns packed with aquifer sand without significant permeability loss. The time before suspension breakthrough into the column effluent varied with surface treatment, indicating the Mg(OH)2 retention and PRB longevity could be controlled by varying the suspension surface treatment. (authors)« less
Aqueous suspensions of natural swelling clay minerals. 2. Rheological characterization.
Paineau, Erwan; Michot, Laurent J; Bihannic, Isabelle; Baravian, Christophe
2011-06-21
We report in this article a comprehensive investigation of the viscoelastic behavior of different natural colloidal clay minerals in aqueous solution. Rheological experiments were carried out under both dynamic and steady-state conditions, allowing us to derive the elasticity and yield stress. Both parameters can be renormalized for all sizes, ionic strength, and type of clay using in a first approach only the volume of the particles. However, applying such a treatment to various clays of similar shapes and sizes yields differences that can be linked to the repulsion strength and charge location in the swelling clays. The stronger the repulsive interactions, the better the orientation of clay particles in flows. In addition, a master linear relationship between the elasticity and yield stress whose value corresponds to a critical deformation of 0.1 was evidenced. Such a relationship may be general for any colloidal suspension of anisometric particles as revealed by the analysis of various experimental data obtained on either disk-shaped or lath- and rod-shaped particles. The particle size dependence of the sol-gel transition was also investigated in detail. To understand why suspensions of larger particles gel at a higher volume fraction, we propose a very simplified view based on the statistical hydrodynamic trapping of a particle by an another one in its neighborhood upon translation and during a short period of time. We show that the key parameter describing this hydrodynamic trapping varies as the cube of the average diameter and captures most features of the sol-gel transition. Finally, we pointed out that in the high shear limit the suspension viscosity is still closely related to electrostatic interactions and follows the same trends as the viscoelastic properties. © 2011 American Chemical Society
Immobilization of Superoxide Dismutase on Polyelectrolyte-Functionalized Titania Nanosheets.
Rouster, Paul; Pavlovic, Marko; Szilagyi, Istvan
2018-02-16
The superoxide dismutase (SOD) enzyme was successfully immobilized on titania nanosheets (TNS) functionalized with the poly(diallyldimethylammonium chloride) (PDADMAC) polyelectrolyte. The TNS-PDADMAC solid support was prepared by hydrothermal synthesis followed by self-assembled polyelectrolyte layer formation. It was found that SOD strongly adsorbed onto oppositely charged TNS-PDADMAC through electrostatic and hydrophobic interactions. The TNS-PDADMAC-SOD material was characterized by light scattering and microscopy techniques. Colloidal stability studies revealed that the obtained nanocomposites possessed good resistance against salt-induced aggregation in aqueous suspensions. The enzyme kept its functional integrity upon immobilization; therefore, TNS-PDADMAC-SOD showed excellent superoxide radical anion scavenging activity. The developed system is a promising candidate for applications in which suspensions of antioxidant activity are required in the manufacturing processes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Effect of starting powders on the sintering of nanostructured ZrO2 ceramics by colloidal processing
NASA Astrophysics Data System (ADS)
Suárez, Gustavo; Sakka, Yoshio; Suzuki, Tohru S.; Uchikoshi, Tetsuo; Zhu, Xinwen; Aglietti, Esteban F.
2009-04-01
The effect of starting powders on the sintering of nanostructured tetragonal zirconia was evaluated. Suspensions were prepared with a concentration of 10 vol.% by mixing a bicomponent mixture of commercial powders (97 mol.% monoclinic zirconia with 3 mol.% yttria) and by dispersing commercially available tetragonal zirconia (3YTZ, Tosoh). The preparation of the slurry by bead-milling was optimized. Colloidal processing using 50 μm zirconia beads at 4000 rpm generated a fully deagglomerated suspension leading to the formation of high-density consolidated compacts (62% of the theoretical density (TD) for the bicomponent suspension). Optimum colloidal processing of the bicomponent suspension followed by the sintering of yttria and zirconia allowed us to obtain nanostructured tetragonal zirconia. Three different sintering techniques were investigated: normal sintering, two-step sintering and spark plasma sintering. The inhibition of grain growth in the bicomponent mixed powders in comparison with 3YTZ was demonstrated. The inhibition of the grain growth may have been caused by inter-diffusion of cations during the sintering.
Uskoković, Vuk; Odsinada, Roselyn; Djordjevic, Sonia; Habelitz, Stefan
2011-01-01
The concept of zeta-potential has been used for more than a century as a basic parameter in controlling the stability of colloidal suspensions, irrespective of the nature of their particulate ingredients – organic or inorganic. There are prospects that self-assembly of peptide species and the protein-mineral interactions related to biomineralization may be controlled using this fundamental physicochemical parameter. In this study, we have analyzed the particle size and zeta-potential of the full-length recombinant human amelogenin (rH174), the main protein of the developing enamel matrix, in the presence of calcium and phosphate ions and hydroxyapatite (HAP) particles. As calcium and phosphate salts are introduced to rH174 sols in increments, zeta-potential of the rH174 nanospheres is more affected by negatively charged ions, suggesting their tendency to locate within the double charge layer. Phosphate ions have a more pronounced effect on both the zeta-potential and aggregation propensity of rH174 nanospheres compared to calcium ions. The isoelectric point of amelogenin was independent on the ionic strength of the solution and the concentration of calcium and/or phosphate ions. Whereas rH174 shows a higher affinity for phosphate than for calcium, HAP attracts both of these ions to the shear plane of the double layer. The parallel size and zeta-potential analysis of HAP and rH174 colloidal mixtures indicated that at pH 7.4, despite both HAP and rH174 particles being negatively charged, rH174 adsorbs well onto HAP particles. The process is slower at pH 7.4 than at pH 4.5 when the HAP surface is negatively charged and the rH174 nanosphere carries an overall positive charge. The results presented hereby demonstrate that electrostatic interactions can affect the kinetics of the adsorption of rH174 onto HAP. PMID:21146151
Rheological State Diagrams for Rough Colloids in Shear Flow.
Hsiao, Lilian C; Jamali, Safa; Glynos, Emmanouil; Green, Peter F; Larson, Ronald G; Solomon, Michael J
2017-10-13
To assess the role of particle roughness in the rheological phenomena of concentrated colloidal suspensions, we develop model colloids with varying surface roughness length scales up to 10% of the particle radius. Increasing surface roughness shifts the onset of both shear thickening and dilatancy towards lower volume fractions and critical stresses. Experimental data are supported by computer simulations of spherical colloids with adjustable friction coefficients, demonstrating that a reduction in the onset stress of thickening and a sign change in the first normal stresses occur when friction competes with lubrication. In the quasi-Newtonian flow regime, roughness increases the effective packing fraction of colloids. As the shear stress increases and suspensions of rough colloids approach jamming, the first normal stresses switch signs and the critical force required to generate contacts is drastically reduced. This is likely a signature of the lubrication films giving way to roughness-induced tangential interactions that bring about load-bearing contacts in the compression axis of flow.
Rheological State Diagrams for Rough Colloids in Shear Flow
NASA Astrophysics Data System (ADS)
Hsiao, Lilian C.; Jamali, Safa; Glynos, Emmanouil; Green, Peter F.; Larson, Ronald G.; Solomon, Michael J.
2017-10-01
To assess the role of particle roughness in the rheological phenomena of concentrated colloidal suspensions, we develop model colloids with varying surface roughness length scales up to 10% of the particle radius. Increasing surface roughness shifts the onset of both shear thickening and dilatancy towards lower volume fractions and critical stresses. Experimental data are supported by computer simulations of spherical colloids with adjustable friction coefficients, demonstrating that a reduction in the onset stress of thickening and a sign change in the first normal stresses occur when friction competes with lubrication. In the quasi-Newtonian flow regime, roughness increases the effective packing fraction of colloids. As the shear stress increases and suspensions of rough colloids approach jamming, the first normal stresses switch signs and the critical force required to generate contacts is drastically reduced. This is likely a signature of the lubrication films giving way to roughness-induced tangential interactions that bring about load-bearing contacts in the compression axis of flow.
Source of cytotoxicity in a colloidal silver nanoparticle suspension.
Hatipoglu, Manolya Kukut; Keleştemur, Seda; Altunbek, Mine; Culha, Mustafa
2015-05-15
Silver nanoparticles (AgNPs) are increasingly used in a variety of applications because of their potential antimicrobial activity and their plasmonic and conductivity properties. In this study, we investigated the source of cytotoxicity, genotoxicity, and reactive oxygen species (ROS) production on human dermal fibroblast and human lung cancer (A549) cell lines upon exposure to AgNP colloidal suspensions prepared with the simplest and most commonly used Lee–Meisel method with a variety of reaction times and the concentrations of the reducing agent. The AgNPs synthesized with shorter reaction times were more cytotoxic and genotoxic due to the presence of a few nanometer-sized AgNP seeds. The suspensions prepared with an increased citrate concentration were not cytotoxic, but they induced more ROS generation on A549 cells due to the high citrate concentration. The genotoxicity of the suspension decreased significantly at the higher citrate concentrations. The analysis of both transmission electron microscopy images from the dried droplet areas of the colloidal suspensions and toxicity data indicated that the AgNP seeds were the major source of toxicity. The completion of the nucleation step and the formation of larger AgNPs effectively decreased the toxicity.
Short- and long-time diffusion and dynamic scaling in suspensions of charged colloidal particles.
Banchio, Adolfo J; Heinen, Marco; Holmqvist, Peter; Nägele, Gerhard
2018-04-07
We report on a comprehensive theory-simulation-experimental study of collective and self-diffusion in concentrated suspensions of charge-stabilized colloidal spheres. In theory and simulation, the spheres are assumed to interact directly by a hard-core plus screened Coulomb effective pair potential. The intermediate scattering function, f c (q, t), is calculated by elaborate accelerated Stokesian dynamics (ASD) simulations for Brownian systems where many-particle hydrodynamic interactions (HIs) are fully accounted for, using a novel extrapolation scheme to a macroscopically large system size valid for all correlation times. The study spans the correlation time range from the colloidal short-time to the long-time regime. Additionally, Brownian Dynamics (BD) simulation and mode-coupling theory (MCT) results of f c (q, t) are generated where HIs are neglected. Using these results, the influence of HIs on collective and self-diffusion and the accuracy of the MCT method are quantified. It is shown that HIs enhance collective and self-diffusion at intermediate and long times. At short times self-diffusion, and for wavenumbers outside the structure factor peak region also collective diffusion, are slowed down by HIs. MCT significantly overestimates the slowing influence of dynamic particle caging. The dynamic scattering functions obtained in the ASD simulations are in overall good agreement with our dynamic light scattering (DLS) results for a concentration series of charged silica spheres in an organic solvent mixture, in the experimental time window and wavenumber range. From the simulation data for the time derivative of the width function associated with f c (q, t), there is indication of long-time exponential decay of f c (q, t), for wavenumbers around the location of the static structure factor principal peak. The experimental scattering functions in the probed time range are consistent with a time-wavenumber factorization scaling behavior of f c (q, t) that was first reported by Segrè and Pusey [Phys. Rev. Lett. 77, 771 (1996)] for suspensions of hard spheres. Our BD simulation and MCT results predict a significant violation of exact factorization scaling which, however, is approximately restored according to the ASD results when HIs are accounted for, consistent with the experimental findings for f c (q, t). Our study of collective diffusion is amended by simulation and theoretical results for the self-intermediate scattering function, f s (q, t), and its non-Gaussian parameter α 2 (t) and for the particle mean squared displacement W(t) and its time derivative. Since self-diffusion properties are not assessed in standard DLS measurements, a method to deduce W(t) approximately from f c (q, t) is theoretically validated.
Shahbazi, Mohammad-Ali; Almeida, Patrick V; Mäkilä, Ermei; Correia, Alexandra; Ferreira, Mónica P A; Kaasalainen, Martti; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A
2014-03-01
Currently, developing a stable nanocarrier with high cellular internalization and low toxicity is a key bottleneck in nanomedicine. Here, we have developed a successful method to covalently conjugate poly(methyl vinyl ether-co-maleic acid) (PMVE-MA) copolymer on the surface of (3-aminopropyl)triethoxysilane-functionalized thermally carbonized porous silicon nanoparticles (APSTCPSi NPs), forming a surface negatively charged nanovehicle with unique properties. This polymer conjugated NPs could modify surface smoothness, charge, and hydrophilicity of the developed NPs, leading to considerable improvement in the colloidal and plasma stabilities via enhanced suspensibility and charge repulsion. Furthermore, despite the surface negative charge of the polymer-conjugated NPs, the cellular internalization was increased in both MDA-MB-231 and MCF-7 breast cancer cells. These results provide a proof-of-concept evidence that such polymer-based PSi nanocomposite can be extensively used as a promising candidate for intracellular drug delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Brownian dynamics of sterically-stabilized colloidal suspensions
DOE Office of Scientific and Technical Information (OSTI.GOV)
TeGrotenhuis, W.E.; Radke, C.J.; Denn, M.M.
1994-02-01
One application where microstructure plays a critical role is in the production of specialty ceramics, where colloidal suspensions act as precursors; here the microstructure influences the structural, thermal, optical and electrical properties of the ceramic products. Using Brownian dynamics, equilibrium and dynamic properties are calculated for colloidal suspensions that are stabilized through the Milner, Witten and Cates (1988) steric potential. Results are reported for osmotic pressures, radial distributions functions, static structure factors, and self-diffusion coefficients. The sterically-stabilized systems are also approximated by equivalent hard spheres, with good agreement for osmotic pressure and long-range structure. The suitability of the potential tomore » model the behavior of a real system is explored by comparing static structure factors calculated from Brownian dynamics simulations to those measured using SANS. Finally, the effects of Hamaker and hydrodynamic forces on calculated properties are investigated.« less
Structural rearrangement and dispersion of functionalized graphene sheets in aqueous solutions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lee, Yun Jung; Huang, Liwei; Wang, Howard
2015-09-01
Surfactants are widely used for dispersing graphene and functionalized graphene sheets (FGS) in colloidal suspensions, but there have been few studies of the structure of the dispersed graphene-surfactant complexes in suspension and of their time evolution. Here, we combine experimental study of efficiencies of ionic surfactants/polymers in suspending FGS in water with characterization using atomic force microscopy, small angle neutron scattering, and molecular simulations to probe the detailed structures of FGSs. A systematic study of FGS dispersions using ionic surfactants with varying chain lengths revealed that the effective charge density of surfactant layer defines the concentration of dispersed FGS whilemore » the strength of interfacial binding defines the stability of graphene dispersion over long time aging. Ionic surfactants with strong interfacial binding and large molecular weight increase the dispersing power by over an order of magnitude.« less
Lewis-Russ, A.; Ranville, J.; Kashuba, A.T.
1991-01-01
A method is described that differentiates between solutions containing silica-dominated colloids and solutions that are essentially free of colloids. Suspensions of tuff particles were treated to remove colloids by centrifugation, filtration or both. Agreement of silica concentrations determined by inductively coupled plasma atomic emission spectrometry and by a spectrophotometric method was taken as an indication of colloid-free solutions. For two tuffs, centrifugation was effective for removing colloids. For the third, highly altered tuff, filtration was more effective for removing colloids.
NASA Astrophysics Data System (ADS)
Abbas, Samir; Dupont, Laurent; Dozov, Ivan; Davidson, Patrick; Chanéac, Corinne
2018-02-01
We have investigated the feasibility of optical tunable filters based on a Fabry-Perot etalon that uses a suspension of goethite (α-FeOOH) nanorods as electro-optic material for application in optical telecommunications in the near IR range. These synthetic nanoparticles have a high optical anisotropy that give rise to a very strong Kerr effect in their colloidal suspensions. Currently, these particles are dispersed in aqueous solvent, with pH2 to ensure the colloidal electrostatic stability. However, the high conductivity of these suspensions requires using high-frequency electric fields (f > 1 MHz), which brings about a high power consumption of the driver. To decrease the field frequency, we have changed the solvent to ethylene glycol which has a lower electrical conductivity than the aqueous solvent. We have built a Fabry-Perot cell, filled with this colloidal suspension in the isotropic phase, and showed that a phase shift of 14 nm can be obtained in a field of 3V/μm. Therefore, the device can operate as a tunable filter. A key advantage of this filter is that it is, by principle, completely insensitive to the polarization of the input light. However, several technological issues still need to be solved, such as ionic contamination of the suspension from the blocking layers, and dielectrophoretic and thermal effects.
NASA Astrophysics Data System (ADS)
Sanz, Eduardo
2009-03-01
We study the kinetics of the liquid-to-crystal transformation and of gel formation in colloidal suspensions of oppositely charged particles. We analyse, by means of both computer simulations and experiments, the evolution of a fluid quenched to a state point of the phase diagram where the most stable state is either a homogeneous crystalline solid or a solid phase in contact with a dilute gas. On the one hand, at high temperatures and high packing fractions, close to an ordered-solid/disordered-solid coexistence line, we find that the fluid-to-crystal pathway does not follow the minimum free energy route. On the other hand, a quench to a state point far from the ordered-crystal/disordered-crystal coexistence border is followed by a fluid-to-solid transition through the minimum free energy pathway. At low temperatures and packing fractions we observe that the system undergoes a gas-liquid spinodal decomposition that, at some point, arrests giving rise to a gel-like structure. Both our simulations and experiments suggest that increasing the interaction range favors crystallization over vitrification in gel-like structures. [4pt] In collaboration with Chantal Valeriani, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands and SUPA, School of Physics, University of Edinburgh, JCMB King's Buildings, Mayfield Road, Edinburgh EH9 3JZ, UK; Teun Vissers, Andrea Fortini, Mirjam E. Leunissen, and Alfons van Blaaderen, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University; Daan Frenke, FOM Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands and Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK; and Marjolein Dijkstra, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University.
Contribution of Surface Chemistry to the Shear Thickening of Silica Nanoparticle Suspensions.
Yang, Wufang; Wu, Yang; Pei, Xiaowei; Zhou, Feng; Xue, Qunji
2017-01-31
Shear thickening is a general process crucial for many processed products ranging from food and personal care to pharmaceuticals. Theoretical calculations and mathematical simulations of hydrodynamic interactions and granular-like contacts have proved that contact forces between suspended particles dominate the rheological characteristic of colloidal suspensions. However, relevant experimental studies are very rare. This study was conducted to reveal the influence of nanoparticle (NP) interactions on the rheological behavior of shear-thickening fluids (STFs) by changing the colloidal surface chemistries. Silica NPs with various surface chemical compositions are fabricated and used to prepare dense suspensions. Rheological experiments are conducted to determine the influence of NP interactions on corresponding dense suspension systems. The results suggest that the surface chemistries of silica NPs determine the rheological behavior of dense suspensions, including shear-thickening behavior, onset stress, critical volume fraction, and jamming volume fraction. This study provides useful reference for designing effective STFs and regulating their characteristics.
pH Reversible Encapsulation of Oppositely Charged Colloids Mediated by Polyelectrolytes
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
Mesoscale Particle-Based Model of Electrophoresis
Giera, Brian; Zepeda-Ruiz, Luis A.; Pascall, Andrew J.; ...
2015-07-31
Here, we develop and evaluate a semi-empirical particle-based model of electrophoresis using extensive mesoscale simulations. We parameterize the model using only measurable quantities from a broad set of colloidal suspensions with properties that span the experimentally relevant regime. With sufficient sampling, simulated diffusivities and electrophoretic velocities match predictions of the ubiquitous Stokes-Einstein and Henry equations, respectively. This agreement holds for non-polar and aqueous solvents or ionic liquid colloidal suspensions under a wide range of applied electric fields.
Mesoscale Particle-Based Model of Electrophoresis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Giera, Brian; Zepeda-Ruiz, Luis A.; Pascall, Andrew J.
Here, we develop and evaluate a semi-empirical particle-based model of electrophoresis using extensive mesoscale simulations. We parameterize the model using only measurable quantities from a broad set of colloidal suspensions with properties that span the experimentally relevant regime. With sufficient sampling, simulated diffusivities and electrophoretic velocities match predictions of the ubiquitous Stokes-Einstein and Henry equations, respectively. This agreement holds for non-polar and aqueous solvents or ionic liquid colloidal suspensions under a wide range of applied electric fields.
Li, Dien; Kaplan, Daniel I; Roberts, Kimberly A; Seaman, John C
2012-03-06
Cementitious materials are increasingly used as engineered barriers and waste forms for radiological waste disposal. Yet their potential effect on mobile colloid generation is not well-known, especially as it may influence colloid-facilitated contaminant transport. Whereas previous papers have studied the introduction of cement colloids into sediments, this study examined the influence of cement leachate chemistry on the mobilization of colloids from a subsurface sediment collected from the Savannah River Site, USA. A sharp mobile colloid plume formed with the introduction of a cement leachate simulant. Colloid concentrations decreased to background concentrations even though the aqueous chemical conditions (pH and ionic strength) remained unchanged. Mobile colloids were mainly goethite and to a lesser extent kaolinite. The released colloids had negative surface charges and the mean particle sizes ranged primarily from 200 to 470 nm. Inherent mineralogical electrostatic forces appeared to be the controlling colloid removal mechanism in this system. In the background pH of ~6.0, goethite had a positive surface charge, whereas quartz (the dominant mineral in the immobile sediment) and kaolinite had negative surface charges. Goethite acted as a cementing agent, holding kaolinite and itself onto the quartz surfaces due to the electrostatic attraction. Once the pH of the system was elevated, as in the cementitious high pH plume front, the goethite reversed to a negative charge, along with quartz and kaolinite, then goethite and kaolinite colloids were mobilized and a sharp spike in turbidity was observed. Simulating conditions away from the cementitious source, essentially no colloids were mobilized at 1:1000 dilution of the cement leachate or when the leachate pH was ≤ 8. Extreme alkaline pH environments of cementitious leachate may change mineral surface charges, temporarily promoting the formation of mobile colloids.
Optical limiting in gelatin stabilized Cu-PVP nanocomposite colloidal suspension
NASA Astrophysics Data System (ADS)
Tamgadge, Y. S.; Gedam, P. P.; Thakare, N. B.; Talwatkar, S. S.; Sunatkari, A. L.; Muley, G. G.
2018-05-01
This article illustrates investigations on optical limiting properties of Cu-PVP nanocomposite colloidal suspension. Gelatin stabilized Cu nanoparticles have been synthesized using chemical reduction method and thin films in PVP matrix have been obtained using spin coating technique. Thin films have been characterized by X-ray diffraction (XRD), Ultraviolet-visible (UV-vis) spectroscopy, etc. for structural and linear optical studies. Optical limiting properties of Colloidal Cu-PVP nanocomposites have been investigated at 808 nm diode CW laser. Minimum optical limiting threshold was found for GCu3-PVP nanocomposites sample. The strong optical limiting is thermal in origin as CW laser is used and effects are attributed to thermal lensing effect.
Convection in colloidal suspensions with particle-concentration-dependent viscosity.
Glässl, M; Hilt, M; Zimmermann, W
2010-07-01
The onset of thermal convection in a horizontal layer of a colloidal suspension is investigated in terms of a continuum model for binary-fluid mixtures where the viscosity depends on the local concentration of colloidal particles. With an increasing difference between the viscosity at the warmer and the colder boundary the threshold of convection is reduced in the range of positive values of the separation ratio psi with the onset of stationary convection as well as in the range of negative values of psi with an oscillatory Hopf bifurcation. Additionally the convection rolls are shifted downwards with respect to the center of the horizontal layer for stationary convection psi>0 and upwards for the Hopf bifurcation (psi<0.
Local phase transitions in driven colloidal suspensions
NASA Astrophysics Data System (ADS)
Scacchi, A.; Brader, J. M.
2018-02-01
Using dynamical density functional theory and Brownian dynamics simulations, we investigate the influence of a driven tracer particle on the density distribution of a colloidal suspension at a thermodynamic state point close to the liquid side of the binodal. In bulk systems, we find that a localised region of the colloid-poor phase, a 'cavitation bubble', forms behind the moving tracer. The extent of the cavitation bubble is investigated as a function of both the size and velocity of the tracer. The addition of a confining boundary enables us to investigate the interaction between the local phase instability at the substrate and that at the particle surface. When both the substrate and tracer interact repulsively with the colloids we observe the formation of a colloid-poor bridge between the substrate and the tracer. When a shear flow is applied parallel to the substrate the bridge becomes distorted and, at sufficiently high shear-rates, disconnects from the substrate to form a cavitation bubble.
Rafferty, A; Alsebaie, A M; Olabi, A G; Prescott, T
2009-01-15
Alumina-zirconia composites were prepared by two routes: powder processing, and colloidal processing. Unstabilised zirconia powder was added to alumina in 5 wt%, 10 wt% and 20 wt% quantities. For the colloidal method, zirconium(IV) propoxide solution was added to alumina powder, also in 5 wt%, 10 wt% and 20 wt% quantities. Additions of glacial acetic acid were needed to form stable suspensions. Suspension stability was verified by pH measurements and sedimentation testing. For the powder processed samples Vickers hardness decreased indefinitely with increasing ZrO(2) additions, but for colloidal samples the hardness at first decreased but then increased again above >10 wt% ZrO(2). Elastic modulus (E) values decreased with ZrO(2) additions. However, samples containing 20 wt% zirconia prepared via a colloidal method exhibited a much higher modulus than the powder processed equivalent. This was due to the homogeneous dispersion of zirconia yielding a sample which was less prone to microcracking.
Anti-iridescent colloidal photonic nanostructure from thermal gradients and polymeric brush effects
NASA Astrophysics Data System (ADS)
Lee, Seung Yeol; Kim, Hyoungsoo; Kim, Shin-Hyun; Stone, Howard
2017-11-01
Colloidal nanostructures induced by self-assembly are important in reflective displays, plasmonic or photonic sensors, and color pigments. During the evaporation of droplets of colloidal suspension, due to the non-uniform evaporation rate along the droplet interface, a radially outward flow is created and it carries colloidal particles to the pinned contact line of the droplet. We document that the packing at the contact line is a face-center-cubic (fcc) colloidal nanostructure in a ring shape. The fcc structure of the colloidal nanoparticles exhibits angle-dependent color. In particular, we introduce a novel method to suppress the familiar coffee-ring effect and modify colloidal nanostructures to exhibit angle-independent optical properties. A suspension of polyethylene oxide (PEO)-coated silica nanoparticles dispersed in ethanol-water mixture is prepared. The droplet containing the nanoparticles dries on a heated substrate, which creates a thermal gradient along the interface of the droplet. This thermal gradient induces thermal-Marangoni stresses that suppress the coffee-ring effects. PEO adsorbed on the surface of silica nanoparticles produces an additional interaction between colloidal nanoparticles, which makes the final structure disordered. The disordered photonic nanostructures in our experiments exhibit angle-independent structural color. This technique can be applied to printing or optical filtering systems.
Zhao, Z; Corredig, M
2016-08-01
The research investigated the influence of NaCl on the colloidal and rennet coagulation properties of concentrated milk. Milk was concentrated to 1×, 3×, and 5× using ultrafiltration. Rennet gelation was followed by rheology and diffusing wave spectroscopy. Soluble protein, total and diffusible calcium and phosphate, size, and zeta potential were also measured as a function of concentration history. In the presence of 300mM NaCl, colloidal calcium phosphate solubilized and pH and the negative charge on the surface of casein micelles decreased. Increasing the volume fraction caused the formation of stiffer gels for both samples with or without NaCl. The addition of NaCl caused a significant increase in the bulk viscosity of the milk concentrated 5× and a decrease in turbidity. The concentration had no effect on the gelation time of control samples, nor on the kinetics of caseinomacropeptide release. On the other hand, rennet gelation was retarded by the addition of NaCl, and the gels showed lower elastic moduli compared with those obtained with control milk. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.
Stability and rheology of dispersions of silicon nitride and silicon carbide
NASA Technical Reports Server (NTRS)
Feke, Donald L.
1987-01-01
The relationship between the surface and colloid chemistry of commercial ultra-fine silicon carbide and silicon nitride powders was examined by a variety of standard characterization techniques and by methodologies especially developed for ceramic dispersions. These include electrokinetic measurement, surface titration, and surface spectroscopies. The effects of powder pretreatment and modification strategies, which can be utilized to augment control of processing characteristics, were monitored with these technologies. Both silicon carbide and nitride were found to exhibit silica-like surface chemistries, but silicon nitride powders possess an additional amine surface functionality. Colloidal characteristics of the various nitride powders in aqueous suspension is believed to be highly dependent on the relative amounts of the two types of surface groups, which in turn is determined by the powder synthesis route. The differences in the apparent colloidal characteristics for silicon nitride powders cannot be attributed to the specific absorption of ammonium ions. Development of a model for the prediction of double-layer characteristics of materials with a hybrid site interface facilitated understanding and prediction of the behavior of both surface charge and surface potential for these materials. The utility of the model in application to silicon nitride powders was demonstrated.
Sensing aggregation in highly turbid plasmonic and non-plasmonic colloidal suspensions
NASA Astrophysics Data System (ADS)
Ducay, Rey Nann Mark; Philip, Nathan; Boivin, Jordan; Judge, Patrick; Berberich, Jason; Scaffidi, Jonathan; Bali, Lalit; Bali, Samir
2015-05-01
We demonstrate a method for sensing the presence of aggregation in highly turbid aqueous suspensions of polystyrene and gold nanospheres. Aggregation is induced either by changing the pH or the ionic strength, by adding small, controlled amounts of an acid or base solution. The particle concentrations used are at least two orders of magnitude higher than previously reported. To the best of our knowledge, this is a first observation of aggregation in highly dense colloidal suspensions without any sample dilution or special sample preparation. We gratefully acknowledge support from the American Chemical Society Petroleum Research Fund and Miami University's Interdisciplinary Roundtable Fund. We also gratefully acknowledge experimental help from the Miami University Instrumentation Laboratory.
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.
Angular rheology study of colloidal nanocrystals using Coherent X-ray Diffraction
NASA Astrophysics Data System (ADS)
Liang, Mengning; Harder, Ross; Robinson, Ian
2007-03-01
A new method using coherent x-ray diffraction provides a way to investigate the rotational motion of a colloidal suspension of crystals in real time. Coherent x-ray diffraction uses the long coherence lengths of synchrotron sources to illuminate a nanoscale particle coherently over its spatial dimensions. The penetration of high energy x-rays into various media allows for in-situ measurements making it ideal for suspensions. This technique has been used to image the structure of nanocrystals for some time but also has the capability of providing information about the orientation and dynamics of crystals. The particles are imaged in a specific diffraction condition allowing us to determine their orientation and observe how they rotate in real time with exceptional resolution. Such sensitivity allows for the study of rotational Brownian motion of nanocrystals in various suspensions and conditions. We present a study of the angular rheology of alumina and TiO2 colloidal nanocrystals in media using coherent x-ray diffraction.
NASA Astrophysics Data System (ADS)
Del Rosso, T.; Rey, N. A.; Rosado, T.; Landi, S.; Larrude, D. G.; Romani, E. C.; Freire Junior, F. L.; Quinteiro, S. M.; Cremona, M.; Aucelio, R. Q.; Margheri, G.; Pandoli, O.
2016-06-01
Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.
Del Rosso, T; Rey, N A; Rosado, T; Landi, S; Larrude, D G; Romani, E C; Junior, F L Freire; Quinteiro, S M; Cremona, M; Aucelio, R Q; Margheri, G; Pandoli, O
2016-06-24
Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.
Cordelair, Jens; Greil, Peter
2003-09-15
A new solution for the Poisson equation for the diffuse part of the double layer around spherical particles will be presented. The numerical results are compared with the solution of the well-known DLVO theory. The range of the diffuse layer differs considerably in the two theories. Also, the inconsistent representation of the surface and diffuse layer charge in the DLVO theory do not occur in the new theory. Experimental zeta potential measurements were used to determine the charge of colloidal Al2O3 and ZrO2 particles. It is shown that the calculated charge can be interpreted as a superposition of independent H+ and OH- adsorption isotherms. The corresponding Langmuir adsorption isotherms are taken to model the zeta potential dependence on pH. In the vicinity of the isoelectric point the model fits well with the experimental data, but at higher ion concentrations considerable deviations occur. The deviations are discussed. Furthermore, the numerical results for the run of the potential in the diffuse part of the double layer were used to determine the electrostatic interaction potential between the particles in correlation with the zeta potential measurements. The corresponding total interaction potentials, including the van der Waals attraction, were taken to calculate the coagulation half-life for a suspension with a particle loading of 2 vol%. It is shown that stability against coagulation is maintained for Al2O3 particles in the pH region between 3.3 and 7 and for ZrO2 only around pH 5. Stability against flocculation can be achieved in the pH regime between 4.5 and 7 for Al2O3, while the examined ZrO2 particles are not stable against flocculation in aqueous suspensions.
Adhesion of Mycobacterium smegmatis to Charged Surfaces and Diagnostics Implications
NASA Astrophysics Data System (ADS)
Gorse, Diane; Dhinojwala, Ali; Moore, Francisco
Pulmonary tuberculosis (PTB) causes more than 1 million deaths annually. Smear microscopy is a primary rapid detection tool in areas where 95 % of PTB cases occur. This technique, in which the sputum of a symptomatic patient is stained and examined using a light microscope for Mycobacterium tuberculosis (MTB) shows sensitivity between 20 and 60 %. Insufficient bacterial isolation during sample preparation may be a reason for low sensitivity. We are optimizing a system to capture bacteria on the basis of electrostatic interactions to more thoroughly isolate bacteria from suspension and facilitate more accurate detection. Silica supports coated with positively-charged polyelectrolyte, poly(diallyldimethylammonium chloride), captured approximately 4.1 times more Mycobacterium smegmatis, a model organism for MTB, than was captured on negatively-charged silica substrates. Future experimentation will employ branched polymer systems and seek to justify the use of colloidal stability theories to describe initial capture. Supported by University of Akron, Department of Polymer Science, Department of Biology; LORD Corporation.
Detecting Phase Boundaries in Hard-Sphere Suspensions
NASA Technical Reports Server (NTRS)
McDowell, Mark; Rogers, Richard B.; Gray, Elizabeth
2009-01-01
A special image-data-processing technique has been developed for use in experiments that involve observation, via optical microscopes equipped with electronic cameras, of moving boundaries between the colloidal-solid and colloidal-liquid phases of colloidal suspensions of monodisperse hard spheres. During an experiment, it is necessary to adjust the position of a microscope to keep the phase boundary within view. A boundary typically moves at a speed of the order of microns per hour. Because an experiment can last days or even weeks, it is impractical to require human intervention to keep the phase boundary in view. The present image-data-processing technique yields results within a computation time short enough to enable generation of automated-microscope-positioning commands to track the moving phase boundary
Shear-induced criticality near a liquid-solid transition of colloidal suspensions
NASA Astrophysics Data System (ADS)
Miyama, Masamichi J.; Sasa, Shin-Ichi
2011-02-01
We investigate colloidal suspensions under shear flow through numerical experiments. By measuring the time-correlation function of a bond-orientational order parameter, we find a divergent time scale near a transition point from a disordered fluid phase to an ordered fluid phase, where the order is characterized by a nonzero value of the bond-orientational order parameter. We also present a phase diagram in the (ρ,γ˙ex) plane, where ρ is the density of the colloidal particles and γ˙ex is the shear rate of the solvent. The transition line in the phase diagram terminates at the equilibrium transition point, while a critical region near the transition line vanishes continuously as γ˙ex→0.
Accelerated lattice Boltzmann model for colloidal suspensions rheology and interface morphology
NASA Astrophysics Data System (ADS)
Farhat, Hassan
Colloids are ubiquitous in the food, medical, cosmetic, polymer, water purification and pharmaceutical industries. Colloids thermal, mechanical and storage properties are highly dependent on their interface morphology and their rheological behavior. Numerical methods provide a cheap and reliable virtual laboratory for the study of colloids. However efficiency is a major concern to address when using numerical methods for practical applications. This work introduces the main building-blocks for an improved lattice Boltzmann-based numerical tool designed for the study of colloidal rheology and interface morphology. The efficiency of the proposed model is enhanced by using the recently developed and validated migrating multi-block algorithms for the lattice Boltzmann method (LBM). The migrating multi-block was used to simulate single component, multi-component, multiphase and single component multiphase flows. Results were validated by experimental, numerical and analytical solutions. The contamination of the fluid-fluid interface influences the colloids morphology. This issue was addressed by the introduction of the hybrid LBM for surfactant-covered droplets. The module was used for the simulation of surfactant-covered droplet deformation under shear and uniaxial extensional flows respectively and under buoyancy. Validation with experimental and theoretical results was provided. Colloids are non-Newtonian fluids which exhibit rich rheological behavior. The suppression of coalescence module is the part of the proposed model which facilitates the study of colloids rheology. The model results for the relative viscosity were in agreement with some theoretical results. Biological suspensions such as blood are macro-colloids by nature. The study of the blood flow in the microvasculature was heuristically approached by assuming the red blood cells as surfactant covered droplets. The effects of interfacial tension on the flow velocity and the droplet exclusion from the walls in parabolic flows were in qualitative agreement with some experimental and numerical results. The Fahraeus and the Fahraeus-Lindqvist effects were reproduced. The proposed LBM model provides a flexible numerical platform consisting of various modules which could be used separately or in combination for the study of a variety of colloids and biological suspensions flow deformation problems.
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.
Characterization of magnetic colloids by means of magnetooptics.
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.
PREFACE: Ionic fluids Ionic fluids
NASA Astrophysics Data System (ADS)
Levin, Yan; Kornyshev, Alexei; Barbosa, Marcia C.
2009-10-01
In spite of its apparent simplicity Coulomb law, when applied to many body systems, leads to an amazingly rich mathematical structure. The simple idea that two similarly charged objects always repel, is not necessarily true in a colloidal suspension or a dusty plasma. Neither can one simply predict the direction of the electrophoretic motion of a polyion from only knowing its chemical charge. Strong Coulomb correlations in ionic fluids result in instabilities very similar to the gas--liquid phase separation observed in atomic fluids. It is fair to say that bulk behavior of simple aqueous monovalent electrolytes is now very well understood. Unfortunately this is not the case for multivalent electrolytes or molten salts. In these systems cation-anion association leads to strong non-linear effects which manifest themselves in formations of tightly bound ionic clusters. In spite of the tremendous effort invested over the years, our understanding of these systems remains qualitative. In this special issue we have collected articles from some of the biggest experts working on ionic fluids. The papers are both experimental and theoretical. They range from simple electrolytes in the bulk and near interfaces, to polyelectrolytes, colloids, and molten salts. The special issue, covers a wide spectrum of the ongoing research on ionic fluids. All readers should find something of interest here.
Bench-scale evaluation of drinking water treatment parameters on iron particles and water quality.
Rahman, M Safiur; Gagnon, Graham A
2014-01-01
Discoloration of water resulting from suspended iron particles is one of the main customer complaints received by water suppliers. However, understanding of the mechanisms of discoloration as well as role of materials involved in the process is limited. In this study, an array of bench scale experiments were conducted to evaluate the impact of the most common variables (pH, PO4, Cl2 and DOM) on the properties of iron particles and suspensions derived from the oxygenation of Fe(II) ions in NaHCO3 buffered synthetic water systems. The most important factors as well as their rank influencing iron suspension color and turbidity formation were identified for a range of water quality parameters. This was accomplished using a 2(4) full factorial design approach at a 95% confidence level. The statistical analysis revealed that phosphate was found to be the most significant factor to alter color (contribution: 37.9%) and turbidity (contribution: 45.5%) in an iron-water system. A comprehensive study revealed that phosphate and chlorine produced iron suspension with reduced color and turbidity, made ζ-potential more negative, reduced the average particle size, and increased iron suspension stability. In the presence of DOM, color was observed to increase but a reverse trend was observed to decrease the turbidity and to alter particle size distribution. HPSEC results suggest that higher molecular weight fractions of DOM tend to adsorb onto the surfaces of iron particles at early stages, resulting in alteration of the surface charge of iron particles. This in turn limits particles aggregation and makes iron colloids highly stable. In the presence of a phosphate based corrosion inhibitor, this study demonstrated that color and turbidity resulting from suspended iron were lower at a pH value of 6.5 (compared to pH of 8.5). The same trend was observed in presence of DOM. This study also suggested that iron colloid suspension color and turbidity in chlorinated drinking water systems could be lower than non-chlorinated systems. Copyright © 2013 Elsevier Ltd. All rights reserved.
Friction factors of colloidal suspension containing silicon dioxide nanoparticles in water
NASA Astrophysics Data System (ADS)
Tang, Clement; Pant, Sarbottam; Sharif, Md. Tanveer
2015-11-01
The purpose of this study is to experimentally characterize the friction factor of a colloidal suspension flow in circular and square tubes. The suspension contained silicon dioxide nanoparticles dispersed in distilled water at 9.58% volume concentration. Rheological measurements indicated that the suspension exhibits non-Newtonian behavior, and could be modelled as a power-law generalized Newtonian fluid. The experimental study showed that, with proper characterization of the consistency and flow behavior indices, the suspension flow friction factors in circular and square tubes exhibit similarities with those of Newtonian fluid flow. In the laminar fully-developed flow region, the Poiseuille numbers are similar to those established for Newtonian fluid flow. In the turbulent region, the Dodge and Metzner relation between the friction factor and a generalized Reynolds number can adequately describe the flow. The onsets of transition to turbulent flow for the suspension vary with the shape of the tube and differ from those of Newtonian fluid flow. The deviations suggest that the flow passage shape and the presence of nanoparticles affect the onset of transition to turbulent flow. Supported by North Dakota NASA EPSCoR.
NASA Astrophysics Data System (ADS)
Liu, Y.; Meng, X.; Guo, Z.; Zhang, C.; Nguyen, T. H.; Hu, D.; Ji, J.; Yang, X.
2017-12-01
Colloidal attachment on charge heterogeneous grains has significant environmental implications for transport of hazardous colloids, such as pathogens, in the aquifer, where iron, manganese, and aluminium oxide minerals are the major source of surface charge heterogeneity of the aquifer grains. A patchwise surface charge model is often used to describe the surface charge heterogeneity of the grains. In the patchwise model, the colloidal attachment efficiency is linearly correlated with the fraction of the favorable patches (θ=λ(θf - θu)+θu). However, our previous microfluidic study showed that the attachment efficiency of oocysts of Cryptosporidium parvum, a waterborne protozoan parasite, was not linear correlated with the fraction of the favorable patches (λ). In this study, we developed a pore scale model to simulate colloidal transport and attachment on charge heterogeneous grains. The flow field was simulated using the LBM method and colloidal transport and attachment were simulated using the Lagrange particle tracking method. The pore scale model was calibrated with experimental results of colloidal and oocyst transport in microfluidic devices and was then used to simulate oocyst transport in charge heterogeneous porous media under a variety of environmental relative conditions, i.e. the fraction of favorable patchwise, ionic strength, and pH. The results of the pore scale simulations were used to evaluate the effect of surface charge heterogeneity on upscaling of oocyst transport from pore to continuum scale and to develop an applicable correlation between colloidal attachment efficiency and the fraction of the favorable patches.
Improvements in SiC{sub w}/Al{sub 2}O{sub 3} composites through colloidally stabilized suspensions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Crimp, M.J.; Oppermann, D.A.; Zhang, M.
1994-12-31
Through manipulation of colloidal parameters, suspensions of SiC(whisker)/Al{sub 2}O{sub 3} were prepared, at 5, 10 and 20 vol% SiC whisker, using processing conditions established in Stable Suspension{copyright}. Utilizing Hogg, Healy and Furstenau`s modifications to DLVO theory, this program predicts stability conditions for composite suspensions. Variations in the suspension pH induce changes in the attractive/repulsive interactions between components. This type of interaction in turn influences the packing and green density. Composite suspensions were prepared, freeze dried, then cold consolidated. The distribution of the SiC whiskers within the Al{sub 2}O{sub 3} matrix was determined from SEM micrographs and the composite green densitymore » correlated to the extent of homo- versus heterostability within the composite suspension. The green density of the pure Al{sub 2}O{sub 3} and the 5 vol% SiC whisker additions was the highest at the pH of maximum stability for each interaction. In contrast, at whisker additions of 10 and 20 vol%, the green density is the highest at a pH of low heterostability.« less
Reverse Electrorheological Effect:. a Suspension of Colloidal Motors
NASA Astrophysics Data System (ADS)
Lemaire, E.; Lobry, L.
We present an experimental evidence of a "colloidal motor" behavior of a suspension. Previous attempts to observe such a phenomenon with ferrofluids under alternating magnetic fields have failed. Here, negative viscosity is obtained by making use of Quincke rotation: the spontaneous rotation of insulating particles suspended in a weakly conducting liquid when the system is submitted to a DC electric field. In such a case, particles rotate around any axis perpendicular to the applied field, nevertheless, when a velocity gradient (simple shear rate) is applied along the E field direction, the particles rotation axes will be favored in the vorticity direction (the direction perpendicular to the suspension velocity and the velocity gradient). The collective movement of particles drives the surrounding liquid and then leads to a reduction of the apparent viscosity of the suspension. The decrease in viscosity is sufficiently important for the liquid to flow while no submitted to any mechanical stress.
Anomalous electrical conductivity of nanoscale colloidal suspensions.
Chakraborty, Suman; Padhy, Sourav
2008-10-28
The electrical conductivity of colloidal suspensions containing nanoscale conducting particles is nontrivially related to the particle volume fraction and the electrical double layer thickness. Classical electrochemical models, however, tend to grossly overpredict the pertinent effective electrical conductivity values, as compared to those obtained under experimental conditions. We attempt to address this discrepancy by appealing to the complex interconnection between the aggregation kinetics of the nanoscale particles and the electrodynamics within the double layer. In particular, we model the consequent alterations in the effective electrophoretic mobility values of the suspension by addressing the fundamentals of agglomeration-deagglomeration mechanisms through the pertinent variations in the effective particulate dimensions, solid fractions, as well as the equivalent suspension viscosity. The consequent alterations in the electrical conductivity values provide a substantially improved prediction of the corresponding experimental findings and explain the apparent anomalous behavior predicted by the classical theoretical postulates.
Physics of Colloids in Space (PCS) Flight Hardware Developed
NASA Technical Reports Server (NTRS)
Koudelka, John M.
2001-01-01
investigation that will be located in an Expedite the Process of Experiments to Space Station (EXPRESS) Rack. The investigation will be conducted in the International Space Station U.S. laboratory, Destiny, over a period of approximately 10 months during the station assembly period from flight 6A through flight UF-2. This experiment will gather data on the basic physical properties of colloids by studying three different colloid systems with the objective of understanding how they grow and what structures they form. A colloidal suspension consists of fine particles (micrometer to submicrometer) suspended in a fluid for example, paints, milk, salad dressings, and aerosols. The long-term goal of this investigation is to learn how to steer the growth of colloidal suspensions to create new materials and new structures. This experiment is part of a two-stage investigation conceived by Professor David Weitz of Harvard University along with Professor Peter Pusey of the University of Edinburgh. The experiment hardware was developed by the NASA Glenn Research Center through contracts with Dynacs, Inc., and ZIN Technologies.
An Active Approach to Engineering the Microscopic
NASA Astrophysics Data System (ADS)
Mallory, Stewart A.
Active colloids, which can be thought of as the synthetic analog of swimming bacteria, exhibit remarkable collective behavior. Using a combination of computer simulations and analytical theory, I have looked to provide quantitative answers to fundamental questions concerning the phase behavior and material properties of active suspensions. A primary focus of my Ph.D work has been devoted to developing novel techniques to exploit the active nature of these particles to manipulate and self-assemble matter at the colloidal scale. In the introductory chapter, I discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field. The remaining chapters are each self-contained and focus on a particular topic within active colloidal self-assembly. These chapters are ordered in terms of system complexity, and begins with characterizing the thermomechanical properties of an ideal active fluid. The next three chapters are centered around characterizing the effective interactions induced by an active suspension. The last two chapters focus on using self-propulsion as a tool to improve colloidal self-assembly, and understanding the interplay between self-propulsion and anisotropic pair interaction.
Pore water colloid properties in argillaceous sedimentary rocks.
Degueldre, Claude; Cloet, Veerle
2016-11-01
The focus of this work is to evaluate the colloid nature, concentration and size distribution in the pore water of Opalinus Clay and other sedimentary host rocks identified for a potential radioactive waste repository in Switzerland. Because colloids could not be measured in representative undisturbed porewater of these host rocks, predictive modelling based on data from field and laboratory studies is applied. This approach allowed estimating the nature, concentration and size distributions of the colloids in the pore water of these host rocks. As a result of field campaigns, groundwater colloid concentrations are investigated on the basis of their size distribution quantified experimentally using single particle counting techniques. The colloid properties are estimated considering data gained from analogue hydrogeochemical systems ranging from mylonite features in crystalline fissures to sedimentary formations. The colloid concentrations were analysed as a function of the alkaline and alkaline earth element concentrations. Laboratory batch results on clay colloid generation from compacted pellets in quasi-stagnant water are also reported. Experiments with colloids in batch containers indicate that the size distribution of a colloidal suspension evolves toward a common particle size distribution independently of initial conditions. The final suspension size distribution was found to be a function of the attachment factor of the colloids. Finally, calculations were performed using a novel colloid distribution model based on colloid generation, aggregation and sedimentation rates to predict under in-situ conditions what makes colloid concentrations and size distributions batch- or fracture-size dependent. The data presented so far are compared with the field and laboratory data. The colloid occurrence, stability and mobility have been evaluated for the water of the considered potential host rocks. In the pore water of the considered sedimentary host rocks, the clay colloid concentration is expected to be very low (<1ppb, for 10-100nm) which restricts their relevance for radionuclide transport. Copyright © 2016. Published by Elsevier B.V.
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.
Bubenhofer, S B; Athanassiou, E K; Grass, R N; Koehler, F M; Rossier, M; Stark, W J
2009-12-02
Two-particle colloids containing nanomagnets and microscale mirrors can be prepared from iron oxide nanoparticles, microscale metal flakes and high-density liquids stabilizing the mirror suspension against sedimentation by matching the constituent's density. The free Brownian rotation of the micromirrors can be magnetically controlled through an anisotropic change in impulse transport arising from impacts of the magnetic nanoparticles onto the anisotropic flakes. The resulting rapid mirror orientation allows large changes in light transmission and switchable optical reflectivity. The preparation of a passive display was conceptually demonstrated through colloid confinement in a planar cavity over an array of individually addressable solenoids and resulted in 4 x 4 digit displays with a reaction time of less than 100 ms.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hanna, Lauren; Kucheryavy, Pavel; Liu, Cunming
2017-06-14
The presence of long-lived charge-separated excited states in metal-organic frameworks (MOFs) can enhance their photocatalytic activity by decreasing the probability that photogenerated electrons and holes recombine before accessing adsorbed reactants. Detecting these charge separated states via optical transient absorption, however, can be challenging when they lack definitive optical signatures. Here, we investigate the long-lived excited state of a MOF with such vague optical properties, MIL-100(Fe), comprised of Fe3-μ3-oxo clusters and trimesic acid linkers using Fe K-edge X-ray transient absorption (XTA) spectroscopy, to unambiguously determine its ligand-to-metal charge transfer character. Spectra measured at time delays up to 3.6 μs confirm themore » long lived nature of the charge separated excited state. Several trinuclear iron μ3- oxo carboxylate complexes, which model the trinuclear cores of the MOF structure, are measured for comparison using both steady state XAS and XTA to further support this assignment and corresponding decay time. The MOF is prepared as a colloidal nanoparticle suspension for these measurements so both its fabrication and particle size analysis are presented, as well.« less
Visible Light Photocatalysis via CdS/ TiO 2 Nanocomposite Materials
Srinivasan, Sesha S.; Wade, Jeremy; Stefanakos, Elias K.
2006-01-01
Nmore » anostructured colloidal semiconductors with heterogeneous photocatalytic behavior have drawn considerable attention over the past few years. This is due to their large surface area, high redox potential of the photogenerated charge carriers, and selective reduction/oxidation of different classes of organic compounds. In the present paper, we have carried out a systematic synthesis of nanostructured CdS- TiO 2 via reverse micelle process. The structural and microstructural characterizations of the as-prepared CdS- TiO 2 nanocomposites are determined using XRD and SEM-EDS techniques. The visible light assisted photocatalytic performance is monitored by means of degradation of phenol in water suspension.« less
THE EFFECT OF WATER CHEMISTRY ON THE PROPERTIES OF IRON PARTICLES AND IRON SUSPENSIONS
The structure and properties of iron colloids in aquatic systems is important in understanding their behavior in environmental and engineering systems. For example the adsorption of contaminants onto iron colloids and subsequent transport through ground water aquifers and surface...
Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.
Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias
2013-03-14
A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.
NASA Astrophysics Data System (ADS)
Osterday, Kathryn; Aliseda, Alberto; Lasheras, Juan
2009-11-01
The atomization of colloidal suspensions is of particular interest to the manufacturing of tablets and pills used as drug delivery systems by the pharmaceutical industry. At various stages in the manufacturing process, the tablets are coated with a spray of droplets produced by co-axial atomizers. The mechanisms of droplet size and spray formation in these types of atomizers are dominated by Kelvin-Helmholtz and Raleigh-Taylor instabilities for both low[1] and high[2] Ohnesorge numbers. We present detailed phase Doppler measurements of the Sauter Mean Diameter of the droplets produced by co-axial spray atomizers using water-based colloidal suspensions with solid concentrations ranging from fifteen to twenty percent and acetone-based colloidal suspensions with solid concentrations ranging from five to ten percent. Our results compare favorably with predictions by Aliseda's model. This suggests that the final size distribution is mainly determined by the instabilities caused by the sudden acceleration of the liquid interface. [1]Varga, C. M., et al. (2003) J. Fluid Mech. 497:405-434 [2]Aliseda, A. et al. (2008). J. Int. J. Multiphase Flow, 34(2), 161-175.
Spontaneous liquid crystal and ferromagnetic ordering of colloidal magnetic nanoplates
Shuai, M.; Klittnick, A.; Shen, Y.; Smith, G. P.; Tuchband, M. R.; Zhu, C.; Petschek, R. G.; Mertelj, A.; Lisjak, D.; Čopič, M.; Maclennan, J. E.; Glaser, M. A.; Clark, N. A.
2016-01-01
Ferrofluids are familiar as colloidal suspensions of ferromagnetic nanoparticles in aqueous or organic solvents. The dispersed particles are randomly oriented but their moments become aligned if a magnetic field is applied, producing a variety of exotic and useful magnetomechanical effects. A longstanding interest and challenge has been to make such suspensions macroscopically ferromagnetic, that is having uniform magnetic alignment in the absence of a field. Here we report a fluid suspension of magnetic nanoplates that spontaneously aligns into an equilibrium nematic liquid crystal phase that is also macroscopically ferromagnetic. Its zero-field magnetization produces distinctive magnetic self-interaction effects, including liquid crystal textures of fluid block domains arranged in closed flux loops, and makes this phase highly sensitive, with it dramatically changing shape even in the Earth's magnetic field. PMID:26817823
Imaging the microscopic structure of shear thinning and thickening colloidal suspensions.
Cheng, Xiang; McCoy, Jonathan H; Israelachvili, Jacob N; Cohen, Itai
2011-09-02
The viscosity of colloidal suspensions varies with shear rate, an important effect encountered in many natural and industrial processes. Although this non-Newtonian behavior is believed to arise from the arrangement of suspended particles and their mutual interactions, microscopic particle dynamics are difficult to measure. By combining fast confocal microscopy with simultaneous force measurements, we systematically investigate a suspension's structure as it transitions through regimes of different flow signatures. Our measurements of the microscopic single-particle dynamics show that shear thinning results from the decreased relative contribution of entropic forces and that shear thickening arises from particle clustering induced by hydrodynamic lubrication forces. This combination of techniques illustrates an approach that complements current methods for determining the microscopic origins of non-Newtonian flow behavior in complex fluids.
Physics of Hard Spheres Experiment (PhaSE) or "Making Jello in Space"
NASA Technical Reports Server (NTRS)
Ling, Jerri S.; Doherty, Michael P.
1998-01-01
The Physics of Hard Spheres Experiment (PHaSE) is a highly successful experiment that flew aboard two shuttle missions to study the transitions involved in the formation of jellolike colloidal crystals in a microgravity environment. A colloidal suspension, or colloid, consists of fine particles, often having complex interactions, suspended in a liquid. Paint, ink, and milk are examples of colloids found in everyday life. In low Earth orbit, the effective force of gravity is thousands of times less than at the Earth's surface. This provides researchers a way to conduct experiments that cannot be adequately performed in an Earth-gravity environment. In microgravity, colloidal particles freely interact without the complications of settling that occur in normal gravity on Earth. If the particle interactions within these colloidal suspensions could be predicted and accurately modeled, they could provide the key to understanding fundamental problems in condensed matter physics and could help make possible the development of wonderful new "designer" materials. Industries that make semiconductors, electro-optics, ceramics, and composites are just a few that may benefit from this knowledge. Atomic interactions determine the physical properties (e.g., weight, color, and hardness) of ordinary matter. PHaSE uses colloidal suspensions of microscopic solid plastic spheres to model the behavior of atomic interactions. When uniformly sized hard spheres suspended in a fluid reach a certain concentration (volume fraction), the particle-fluid mixture changes from a disordered fluid state, in which the spheres are randomly organized, to an ordered "crystalline" state, in which they are structured periodically. The thermal energy of the spheres causes them to form ordered arrays, analogous to crystals. Seven of the eight PHaSE samples ranged in volume fraction from 0.483 to 0.624 to cover the range of interest, while one sample, having a concentration of 0.019, was included for instrument calibration.
Charged systems in bulk and at interfaces
NASA Astrophysics Data System (ADS)
Moreira, André Guérin
2001-05-01
One of the rules-of-thumb of colloid and surface physics is that most surfaces are charged when in contact with a solvent, usually water. This is the case, for instance, in charge-stabilized colloidal suspensions, where the surface of the colloidal particles are charged (usually with a charge of hundreds to thousands of e, the elementary charge), monolayers of ionic surfactants sitting at an air-water interface (where the water-loving head groups become charged by releasing counterions), or bilayers containing charged phospholipids (as cell membranes). In this work, we look at some model-systems that, although being a simplified version of reality, are expected to capture some of the physical properties of real charged systems (colloids and electrolytes). We initially study the simple double layer, composed by a charged wall in the presence of its counterions. The charges at the wall are smeared out and the dielectric constant is the same everywhere. The Poisson-Boltzmann (PB) approach gives asymptotically exact counterion density profiles around charged objects in the weak-coupling limit of systems with low-valent counterions, surfaces with low charge density and high temperature (or small Bjerrum length). Using Monte Carlo simulations, we obtain the profiles around the charged wall and compare it with both Poisson-Boltzmann (in the low coupling limit) and the novel strong coupling (SC) theory in the opposite limit of high couplings. In the latter limit, the simulations show that the SC leads in fact to asymptotically correct density profiles. We also compare the Monte Carlo data with previously calculated corrections to the Poisson-Boltzmann theory. We also discuss in detail the methods used to perform the computer simulations. After studying the simple double layer in detail, we introduce a dielectric jump at the charged wall and investigate its effect on the counterion density distribution. As we will show, the Poisson-Boltzmann description of the double layer remains a good approximation at low coupling values, while the strong coupling theory is shown to lead to the correct density profiles close to the wall (and at all couplings). For very large couplings, only systems where the difference between the dielectric constants of the wall and of the solvent is small are shown to be well described by SC. Another experimentally relevant modification to the simple double layer is to make the charges at the plane discrete. The counterions are still assumed to be point-like, but we constraint the distance of approach between ions in the plane and counterions to a minimum distance D. The ratio between D and the distance between neighboring ions in the plane is, as we will see, one of the important quantities in determining the influence of the discrete nature of the charges at the wall over the density profiles. Another parameter that plays an important role, as in the previous case, is the coupling as we will demonstrate, systems with higher coupling are more subject to discretization effects than systems with low coupling parameter. After studying the isolated double layer, we look at the interaction between two double layers. The system is composed by two equally charged walls at distance d, with the counterions confined between them. The charge at the walls is smeared out and the dielectric constant is the same everywhere. Using Monte-Carlo simulations we obtain the inter-plate pressure in the global parameter space, and the pressure is shown to be negative (attraction) at certain conditions. The simulations also show that the equilibrium plate separation (where the pressure changes from attractive to repulsive) exhibits a novel unbinding transition. We compare the Monte Carlo results with the strong-coupling theory, which is shown to describe well the bound states of systems with moderate and high couplings. The regime where the two walls are very close to each other is also shown to be well described by the SC theory. Finally, Using a field-theoretic approach, we derive the exact low-density ("virial") expansion of a binary mixture of positively and negatively charged hard spheres (two-component hard-core plasma, TCPHC). The free energy obtained is valid for systems where the diameters d_+ and d_- and the charge valences q_+ and q_- of positive and negative ions are unconstrained, i.e., the same expression can be used to treat dilute salt solutions (where typically d_+ ~ d_- and q_+ ~ q_-) as well as colloidal suspensions (where the difference in size and valence between macroions and counterions can be very large). We also discuss some applications of our results. Eine der Faustregeln der Kolloid- und Oberflächenphysik ist, dass die meisten Oberflächen geladen sind, wenn sie mit einem Lösungsmittel, normalerweise Wasser, in Kontakt treten. Dies ist zum Beispiel bei ladungsstabilisierten Kolloidalen Suspensionen der Fall, bei denen die Oberfläche der Kolloidteilchen geladen ist (gewöhnlich mit einer Ladung von mehreren Hunderttausend Elementarladungen), oder bei Monoschichten ionischer Tenside, die auf einer Luft-Wasser Grenzfläche sitzen (wobei die wasserliebenden Kopfgruppen durch die Freisetzung von Gegenionen geladen werden), sowie bei Doppelschichten, die geladene phospholipide enthalten (wie Zellmembranen). In dieser Arbeit betrachten wir einige Modellsysteme, die zwar eine vereinfachte Fassung der Realität darstellen, von denen wir aber dennoch erwarten koennen, dass wir mit ihrer Hilfe einige physikalische Eigenschaften realer geladener Systeme (Kolloide und Elektrolyte) einfangen können.
Electrostatics of colloids in mixtures
NASA Astrophysics Data System (ADS)
Samin, Sela; Tsori, Yoav
2013-03-01
We examine the force between two charged colloids immersed in salty aqueous mixtures close to the coexistence curve. In an initially water-poor phase, the short-range solvation-related forces promote the condensation of a water-rich phase at a distance in the range 1-100nm. This leads to a strong long-range attraction between the colloids and hence to a deep metastable or globally stable energetic state. Our calculations are in good agreement with recent experiments on the reversible aggregation of colloids in critical mixtures. The specific nature of the solvation energy of ions can lead to some surprising effects, whereby positively charged surfaces attract while negatively charged surfaces repel. For hydrophilic anions and hydrophobic cations, a repulsive interaction is predicted between oppositely charged and hydrophilic colloids even though both the electrostatic and adsorption forces alone are attractive.
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.
METHOD OF SEPARATING URANIUM SUSPENSIONS
Wigner, E.P.; McAdams, W.A.
1958-08-26
A process is presented for separating colloidally dissed uranium oxides from the heavy water medium in upwhich they are contained. The method consists in treating such dispersions with hydrogen peroxide, thereby converting the uranium to non-colloidal UO/sub 4/, and separating the UO/sub 4/ sfter its rapid settling.
Electrode effects in dielectric spectroscopy of colloidal suspensions
NASA Astrophysics Data System (ADS)
Cirkel, P. A.; van der Ploeg, J. P. M.; Koper, G. J. M.
1997-02-01
We present a simple model to account for electrode polarization in colloidal suspensions. Apart from correctly predicting the ω {-3}/{2} dependence for the dielectric permittivity at low frequencies ω, the model provides an explicit dependence of the effect on electrode spacing. The predictions are tested for the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) water-in-oil microemulsion with iso-octane as continuous phase. In particular, the dependence of electrode polarization effects on electrode spacing has been measured and is found to be in accordance with the model prediction. Methods to reduce or account for electrode polarization are briefly discussed.
ELECTROKINETIC DENSIFICATION OF COAL FINES IN WASTE PONDS
DOE Office of Scientific and Technical Information (OSTI.GOV)
E. James Davis
1999-12-18
The objective of this research was to demonstrate that electrokinetics can be used to remove colloidal coal and mineral particles from coal-washing ponds and lakes without the addition of chemical additives such as salts and polymeric flocculants. The specific objectives were: Design and develop a scaleable electrophoresis apparatus to clarify suspensions of colloidal coal and clay particles; Demonstrate the separation process using polluted waste water from the coal-washing facilities at the coal-fired power plants in Centralia, WA; Develop a mathematical model of the process to predict the rate of clarification and the suspension electrical properties needed for scale up.
Akuzum, Bilen; Maleski, Kathleen; Anasori, Babak; Lelyukh, Pavel; Alvarez, Nicolas Javier; Kumbur, E Caglan; Gogotsi, Yury
2018-03-27
Understanding the rheological properties of two-dimensional (2D) materials in suspension is critical for the development of various solution processing and manufacturing techniques. 2D carbides and nitrides (MXenes) constitute one of the largest families of 2D materials with >20 synthesized compositions and applications already ranging from energy storage to medicine to optoelectronics. However, in spite of a report on clay-like behavior, not much is known about their rheological response. In this study, rheological behavior of single- and multilayer Ti 3 C 2 T x in aqueous dispersions was investigated. Viscous and viscoelastic properties of MXene dispersions were studied over a variety of concentrations from colloidal dispersions to high loading slurries, showing that a multilayer MXene suspension with up to 70 wt % can exhibit flowability. Processing guidelines for the fabrication of MXene films, coatings, and fibers have been established based on the rheological properties. Surprisingly, high viscosity was observed at very low concentrations for solutions of single-layer MXene flakes. Single-layer colloidal solutions were found to exhibit partial elasticity even at the lowest tested concentrations (<0.20 mg/mL) due to the presence of strong surface charge and excellent hydrophilicity of MXene, making them amenable to fabrication at dilute concentrations. Overall, the findings of this study provide fundamental insights into the rheological response of this quickly growing 2D family of materials in aqueous environments as well as offer guidelines for processing of MXenes.
Homma, Rika; Johnson, David R; McClements, D Julian; Decker, Eric A
2016-05-15
The impact of iron compounds with different solubilities on lipid oxidation was studied in the presence and absence of association colloids. Iron (III) sulfate only accelerated lipid oxidation in the presence of association colloids while iron (III) oleate accelerated oxidation in the presence and absence of association colloids. Further, iron (III) oxide retarded lipid oxidation both with and without association colloids. The impact of charged association colloids on lipid oxidation in ethyl oleate was also investigated. Association colloids consisting of the anionic surface-active compound dodecyl sulphosuccinate sodium salt (AOT), cationic surface-active compound hexadecyltrimethylammonium bromide (CTAB), and nonionic surface-active compound 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100) retarded, promoted, and had no effect on lipid oxidation rates, respectively. These results indicate that the polarity of metal compounds and the charge of association colloids play a big role in lipid oxidation. Copyright © 2015 Elsevier Ltd. All rights reserved.
Stress modeling in colloidal dispersions undergoing non-viscometric flows
NASA Astrophysics Data System (ADS)
Dolata, Benjamin; Zia, Roseanna
2017-11-01
We present a theoretical study of the stress tensor for a colloidal dispersion undergoing non-viscometric flow. In such flows, the non-homogeneous suspension stress depends on not only the local average total stresslet-the sum of symmetric first moments of both the hydrodynamic traction and the interparticle force-but also on the average quadrupole, octupole, and higher-order moments. To compute the average moments, we formulate a six dimensional Smoluchowski equation governing the microstructural evolution of a suspension in an arbitrary fluid velocity field. Under the conditions of rheologically slow flow, where the Brownian relaxation of the particles is much faster than the spatiotemporal evolution of the flow, the Smoluchowski equation permits asymptotic solution, revealing a suspension stress that follows a second-order fluid constitutive model. We obtain a reciprocal theorem and utilize it to show that all constitutive parameters of the second-order fluid model may be obtained from two simpler linear-response problems: a suspension undergoing simple shear and a suspension undergoing isotropic expansion. The consequences of relaxing the assumption of rheologically slow flow, including the appearance of memory and microcontinuum behaviors, are discussed.
Majewski, P; Krysiński, P
2008-01-01
We report on the spontaneous covalent growth of monomolecular adlayers on mixed nickel-zinc nanoferrite colloidal suspensions (ferrofluids). Synthesized nanoparticles were subjected to surface modification by means of acid chloride chemistry, leading to the formation of covalent bonds between the hydroxy groups at the nanoparticle surface and the acid chloride molecules. This procedure can be easily tailored to allow for the formation of adlayers containing both hydrophobic and hydrophilic regions stacked at predetermined distances from the magnetic core, and also providing the nanoferrites with functional carboxy groups capable of further modifications with, for example, drug molecules. Here, fluorophore aminopyrene molecules were bound to such modified nanoferrites through amide bonds. We also used the same chemistry to modify the surface with covalently bound long-chain palmitoyl moieties, and for comparison we also modified the nanoferrite surface by simple adsorption of oleic acid. Both procedures made the surface highly hydrophobic. These hydrophobic colloids were subsequently spread on an aqueous surface to form Langmuir monolayers with different characteristics. Moreover, since uniformity of size is crucial in a number of applications, we propose an efficient way of sorting the magnetic nanoparticles by size in their colloidal suspension. The suspension is centrifuged at increasing rotational speed and the fractions are collected after each run. The mean size of nanoferrite in each fraction was measured by the powder X-ray diffraction (PXRD) technique.
Liquid crystalline phases in suspensions of pigments in non-polar solvents
NASA Astrophysics Data System (ADS)
Klein, Susanne; Richardson, Robert M.; Eremin, Alexey
We will discuss colloid suspensions of pigments and compare their electro-optic properties with those of traditional dyed low molecular weight liquid crystal systems. There are several potential advantages of colloidal suspensions over low molecular weight liquid crystal systems: a very high contrast because of the high orientational order parameter of suspensions of rod shaped nano-particles, the excellent light fastness of pigments as compared to dyes and high colour saturations resulting from the high loading of the colour stuff. Although a weak `single-particle' electro-optic response can be observed in dilute suspensions, the response is very much enhanced when the concentration of the particles is sufficient to lead to a nematic phase. Excellent stability of suspensions is beneficial for experimental observation and reproducibility, but it is a fundamental necessity for display applications. We therefore discuss a method to achieve long term stability of dispersed pigments and the reasons for its success. Small angle X-ray scattering was used to determine the orientational order parameter of the suspensions as a function of concentration and the dynamic response to an applied electric field. Optical properties were investigated for a wide range of pigment concentrations. Electro-optical phenomena, such as field-induced birefringence and switching, were characterised. In addition, mixtures of pigment suspensions with small amounts of ferrofluids show promise as future magneto-optical materials.
Huang, Fei; Ge, Ling; Zhang, Bo; Wang, Yun; Tian, Hao; Zhao, Liping; He, Yiliang; Zhang, Xiaojun
2014-08-01
Fullerene (C60) is a nanoparticle that has been widely studied and applied in numerous commodities. However, there are concerns regarding its potential negative impact on the environment. A fullerene colloidal suspension (nC60) is known for its property of selectively inhibiting the growth of microorganisms. In this study, using denaturing gradient gel electrophoresis fingerprinting technology, we found that fullerene altered the structure of a sludge-derived microbial community. Specifically, the bacteria from Bacillus, Acidovorax and Cloacibacterium genera were enriched in abundance when supplemented with nC60 at pH 6.5 under aerobic conditions. The effects of the fullerene colloidal suspension on a strain of Bacillus isolated from the same microbial community were evaluated to further characterize the growth-stimulating effect of nC60. The biomass of cultures of this strain incubated with nC60 concentrations ranging from 3 mg L(-1) to 7 mg L(-1) was approximately twice that of the control during the stationary phase. The fullerene also induced higher superoxide dismutase activity in Bacillus cereus. Furthermore, the nitrate removal rate of B. cereus increased to nearly 55% in the presence of 5 mg L(-1) nC60, compared to 35% for the control. Meanwhile, the cumulative loading amount of nitrite was reduced from 33 μg mL(-1) to 25 μg mL(-1) by the addition of 5 mg L(-1) nC60. Our results demonstrate that the fullerene colloidal suspension is conditionally capable of promoting the growth and denitrification metabolism of certain bacteria, such as B. cereus. Fullerene might have both inhibitory and stimulatory effects on microorganisms in various environments. Copyright © 2014 Elsevier Ltd. All rights reserved.
Chassagne, Claire; Dubois, Emmanuelle; Jiménez, María L.; van der Ploeg, J. P. M; van Turnhout, Jan
2016-01-01
Dielectric spectroscopy can be used to determine the dipole moment of colloidal particles from which important interfacial electrokinetic properties, for instance their zeta potential, can be deduced. Unfortunately, dielectric spectroscopy measurements are hampered by electrode polarization (EP). In this article, we review several procedures to compensate for this effect. First EP in electrolyte solutions is described: the complex conductivity is derived as function of frequency, for two cell geometries (planar and cylindrical) with blocking electrodes. The corresponding equivalent circuit for the electrolyte solution is given for each geometry. This equivalent circuit model is extended to suspensions. The complex conductivity of a suspension, in the presence of EP, is then calculated from the impedance. Different methods for compensating for EP are critically assessed, with the help of the theoretical findings. Their limit of validity is given in terms of characteristic frequencies. We can identify with one of these frequencies the frequency range within which data uncorrected for EP may be used to assess the dipole moment of colloidal particles. In order to extract this dipole moment from the measured data, two methods are reviewed: one is based on the use of existing models for the complex conductivity of suspensions, the other is the logarithmic derivative method. An extension to multiple relaxations of the logarithmic derivative method is proposed. PMID:27486575
Observations of the initial stages of colloidal band formation
NASA Astrophysics Data System (ADS)
Li, Yanrong; Tagawa, Yoshiyuki; Yee, Andrew; Yoda, Minami
2017-11-01
A number of studies have shown that particles suspended in a conducting fluid near a wall are subject to wall-normal repulsive ``lift'' forces, even in the absence of interparticle interactions, in a flowing suspension. Evanescent-wave visualizations have shown that colloidal particles in a dilute (volume fractions <0.4%) suspension are instead attracted to the wall when the suspension is driven through 30 μm deep channels by a pressure gradient and an electric field when the resulting combined Poiseuille and electroosmotic (EO) flow are in opposite direction, i.e., ``counterflow,'' although the particles and channel walls both have negative zeta-potentials. Above a minimum ``threshold'' electric field magnitude |Emin | , the particles assemble into dense ``bands'' with cross-sectional dimensions of a few μm and length comparable to that of the channel (i.e., a few cm). The results suggest that the threshold field |Emin | is large enough so that there is a region of ``reverse'' flow, along the direction of the EO flow, near the wall. Visualization of a large segment of the channel (>300 hydraulic diameters) at frame rates as great as 1 kHz is used to determine banding maps for a variety of dilute colloidal suspensions and to investigate the initial stages of band formation over a wide range of flow conditions. Supported by US Army Research Office.
Brader, J M; Siebenbürger, M; Ballauff, M; Reinheimer, K; Wilhelm, M; Frey, S J; Weysser, F; Fuchs, M
2010-12-01
Using a combination of theory, experiment, and simulation we investigate the nonlinear response of dense colloidal suspensions to large amplitude oscillatory shear flow. The time-dependent stress response is calculated using a recently developed schematic mode-coupling-type theory describing colloidal suspensions under externally applied flow. For finite strain amplitudes the theory generates a nonlinear response, characterized by significant higher harmonic contributions. An important feature of the theory is the prediction of an ideal glass transition at sufficiently strong coupling, which is accompanied by the discontinuous appearance of a dynamic yield stress. For the oscillatory shear flow under consideration we find that the yield stress plays an important role in determining the nonlinearity of the time-dependent stress response. Our theoretical findings are strongly supported by both large amplitude oscillatory experiments (with Fourier transform rheology analysis) on suspensions of thermosensitive core-shell particles dispersed in water and Brownian dynamics simulations performed on a two-dimensional binary hard-disk mixture. In particular, theory predicts nontrivial values of the exponents governing the final decay of the storage and loss moduli as a function of strain amplitude which are in good agreement with both simulation and experiment. A consistent set of parameters in the presented schematic model achieves to jointly describe linear moduli, nonlinear flow curves, and large amplitude oscillatory spectroscopy.
Spontaneous liquid crystal and ferromagnetic ordering of colloidal magnetic nanoplates
Shuai, M.; Klittnick, A.; Shen, Y.; ...
2016-01-28
Ferrofluids are familiar as colloidal suspensions of ferromagnetic nanoparticles in aqueous or organic solvents. The dispersed particles are randomly oriented but their moments become aligned if a magnetic field is applied, producing a variety of exotic and useful magnetomechanical effects. A longstanding interest and challenge has been to make such suspensions macroscopically ferromagnetic, that is having uniform magnetic alignment in the absence of a field. Here we report a fluid suspension of magnetic nanoplates that spontaneously aligns into an equilibrium nematic liquid crystal phase that is also macroscopically ferromagnetic. We find Its zero-field magnetization produces distinctive magnetic self-interaction effects, includingmore » liquid crystal textures of fluid block domains arranged in closed flux loops, and makes this phase highly sensitive, with it dramatically changing shape even in the Earth’s magnetic field.« less
Photosystem I assembly on chemically tailored SAM/ Au substrates for bio-hybrid device fabrication
NASA Astrophysics Data System (ADS)
Mukherjee, Dibyendu; Khomami, Bamin
2011-03-01
Photosystem I (PS I), a supra-molecular protein complex and a biological photodiode responsible for driving natural photosynthesis mechanism, charge separates upon exposure to light. Effective use of the photo-electrochemical activities of PS I for future bio-hybrid electronic devices requires controlled attachment of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface topography of PS I deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate SAM /Au substrates, thereby resulting in complex columnar structures that affect the electron capture pathway of PS I. Specifically, solution phase characterizations indicate that specific detergents used for PS I stabilization in buffer solutions drive the unique colloidal chemistry to tune protein-protein interactions and prevent aggregation, thereby allowing us to tailor the morphology of surface immobilized PS I. We present surface topographical, adsorption, and electrochemical characterizations of PSI /SAM/Au substrates to elucidate protein-surface attachment dynamics and its effect on the photo-activated electronic activities of surface immobilized PS I. Sustainable Energy Education and Research Center (SEERC).
Convection in a colloidal suspension in a closed horizontal cell
DOE Office of Scientific and Technical Information (OSTI.GOV)
Smorodin, B. L., E-mail: bsmorodin@yandex.ru; Cherepanov, I. N.
2015-02-15
The experimentally detected [1] oscillatory regimes of convection in a colloidal suspension of nanoparticles with a large anomalous thermal diffusivity in a closed horizontal cell heated from below have been simulated numerically. The concentration inhomogeneity near the vertical cavity boundaries arising from the interaction of thermal-diffusion separation and convective mixing has been proven to serve as a source of oscillatory regimes (traveling waves). The dependence of the Rayleigh number at the boundary of existence of the traveling-wave regime on the aspect ratio of the closed cavity has been established. The spatial characteristics of the emerging traveling waves have been determined.
Effect of bovine manure on fecal coliform attachment to soil and soil particles of different sizes.
Guber, Andrey K; Pachepsky, Yakov A; Shelton, Daniel R; Yu, Olivia
2007-05-01
Manure-borne bacteria can be transported in runoff as free cells, cells attached to soil particles, and cells attached to manure particles. The objectives of this work were to compare the attachment of fecal coliforms (FC) to different soils and soil fractions and to assess the effect of bovine manure on FC attachment to soil and soil fractions. Three sand fractions of different sizes, the silt fraction, and the clay fraction of loam and sandy clay loam soils were separated and used along with soil samples in batch attachment experiments with water-FC suspensions and water-manure-FC suspensions. In the absence of manure colloids, bacterial attachment to soil, silt, and clay particles was much higher than the attachment to sand particles having no organic coating. The attachment to the coated sand particles was similar to the attachment to silt and clay. Manure colloids in suspensions decreased bacterial attachment to soils, clay and silt fractions, and coated sand fractions, but did not decrease the attachment to sand fractions without the coating. The low attachment of bacteria to silt and clay particles in the presence of manure colloids may cause predominantly free-cell transport of manure-borne FC in runoff.
Mesoscale fabrication and design
NASA Astrophysics Data System (ADS)
Hayes, Gregory R.
A strong link between mechanical engineering design and materials science and engineering fabrication can facilitate an effective and adaptable prototyping process. In this dissertation, new developments in the lost mold-rapid infiltration forming (LM-RIF) process is presented which demonstrates the relationship between these two fields of engineering in the context of two device applications. Within the LM-RIF process, changes in materials processing and mechanical design are updated iteratively, often aided by statistical design of experiments (DOE). The LM-RIF process was originally developed by Antolino and Hayes et al to fabricate mesoscale components. In this dissertation the focus is on advancements in the process and underlying science. The presented advancements to the LM-RIF process include an augmented lithography procedure, the incorporation of engineered aqueous and non-aqueous colloidal suspensions, an assessment of constrained drying forces during LM-RIF processing, mechanical property evaluation, and finally prototype testing and validation. Specifically, the molding procedure within the LM-RIF process is capable of producing molds with thickness upwards of 1mm, as well as multi-layering to create three dimensional structures. Increasing the mold thickness leads to an increase in the smallest feature resolvable; however, the increase in mold thickness and three dimensional capability has expanded the mechanical design space. Tetragonally stabilized zirconia (3Y-TZP) is an ideal material for mesoscale instruments, as it is biocompatible, exhibits high strength, and is chemically stable. In this work, aqueous colloidal suspensions were formulated with two new gel-binder systems, increasing final natural orifice translumenal endoscopic surgery (NOTES) instrument yield from 0% to upwards of 40% in the best case scenario. The effects of the gel-binder system on the rheological behavior of the suspension along with the thermal characteristics of the gel-binder system were characterized. Finally, mechanical properties of ceramic specimens were obtained via 3-point bend testing. Another candidate material for NOTES devices as well as cellular contact aided compliant mechanisms (C3M) devices is 300 series stainless steel (300 series stainless steel). 300 series stainless steel is a common biocompatible material; it is used in surgical applications, exhibits a high corrosion resistance, and has high strength to failure. New, high solids loading, non-aqueous colloidal suspensions of 300 series stainless steel were formulated and incorporated into the LM-RIF process. The rheological behavior and thermal characteristics of the non-aqueous colloidal suspensions were analyzed and engineered to operate within the LM-RIF process. Final part yield with the non-aqueous colloidal suspensions was higher than that of the aqueous ceramic suspensions. Mechanical properties of 300 series stainless steel specimens were determined via 3-point bend testing. Furthermore, new composite non-aqueous colloidal suspensions of 3Y-TZP and 300 series stainless steel were formulated and incorporated into the LM-RIF process. The composite materials showed an increase in final part yield, and an increase in yield strength compared to pure 300 series stainless steel was determined by Vickers hardness testing. The successful incorporation of composite suspensions in the LM-RIF process was facilitated through an analysis of the rheological behavior as a function of solids loading and ceramic to metal ratio. Optimized designs of NOTES instruments, as well as C3M devices were manufactured using the LM-RIF process with the non-aqueous 300 series stainless steel suspension. The performance of the prototype NOTES instruments was evaluated and compared against the theoretically predicted performance results, showing good agreement. Similarly, good agreement was seen between the stress-displacement behavior of prototype C3M devices when compared to the theoretically calculated stress-displacement results. Finally, in a comparison by endoscopic surgeons at Hershey Medical Center between an existing industry standard endoscopic device and the mesoscale instrument prototypes fabricated via the LM-RIF process, the prototype design performed favorably in almost all categories. (Abstract shortened by UMI.)
Self-assembled tunable networks of sticky colloidal particles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Demortiere, Arnaud; Snezhko, Oleksiy Alexey; Sapozhnikov, Maksim
Self-assembled tunable networks of microscopic polymer fibers ranging from wavy colloidal "fur" to highly interconnected networks are created from polymer systems and an applied electric field. The networks emerge via dynamic self-assembly in an alternating (ac) electric field from a non-aqueous suspension of "sticky" polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles.
"Red water" describes the appearance of drinking water that contains suspended particulate iron although the actual suspension color may be light yellow to brown depending on water chemistry and particle properties. Iron can originate from the source water and from distribution ...
Sandu, Ion; Fleaca, Claudiu Teodor
2011-06-15
The focus of the present article is the study of the influence of gravity on the particle deposition profiles on a solid substrate during the evaporation of sessile, hanging and sandwiched hanging drops of colloidal particle suspensions. For concentrations of nanoparticles in the colloidal solutions in the range 0.0001-1 wt.%, highly diluted suspensions will preferentially form rings while concentrated suspensions will preferentially form spots in both sessile and hanging drop evaporation. For intermediary concentrations, the particle deposition profiles will depend on the nanoparticle aggregation dynamics in the suspension during the evaporation process, gravity and on the detailed evaporation geometry. The evaporation of a drop of toluene/carbon nanoparticle suspension hanging from a pendant water drop will leave on the substrate a circular spot with no visible external ring. By contrast, a clear external ring is formed on the substrate by the sessile evaporation of a similar drop of suspension sandwiched between a water drop and the substrate. From the application viewpoint, these processes can be used to create preferential electrical conductive carbon networks and contacts for arrays of self-assembled nanostructures fabricated on solid substrates as well as on flexible polymeric substrates. Copyright © 2011 Elsevier Inc. All rights reserved.
Bratskaya, S; Golikov, A; Lutsenko, T; Nesterova, O; Dudarchik, V
2008-09-01
Charge characteristics of humic and fulvic acids of a different origin (inshore soils, peat, marine sediments, and soil (lysimetric) waters) were evaluated by means of two alternative methods - colloid titration and potentiometric titration. In order to elucidate possible limitations of the colloid titration as an express method of analysis of low content of humic substances we monitored changes in acid-base properties and charge densities of humic substances with soil depth, fractionation, and origin. We have shown that both factors - strength of acidic groups and molecular weight distribution in humic and fulvic acids - can affect the reliability of colloid titration. Due to deviations from 1:1 stoichiometry in interactions of humic substances with polymeric cationic titrant, the colloid titration can underestimate total acidity (charge density) of humic substances with domination of weak acidic functional groups (pK>6) and high content of the fractions with molecular weight below 1kDa.
A comment on the position dependent diffusion coefficient representation of structural heterogeneity
NASA Astrophysics Data System (ADS)
Wolfson, Molly; Liepold, Christopher; Lin, Binhua; Rice, Stuart A.
2018-05-01
Experimental studies of the variation of the mean square displacement (MSD) of a particle in a confined colloid suspension that exhibits density variations on the scale length of the particle diameter are not in agreement with the prediction that the spatial variation in MSD should mimic the spatial variation in density. The predicted behavior is derived from the expectation that the MSD of a particle depends on the system density and the assumption that the force acting on a particle is a point function of position. The experimental data are obtained from studies of the MSDs of particles in narrow ribbon channels and between narrowly spaced parallel plates and from new data, reported herein, of the radial and azimuthal MSDs of a colloid particle in a dense colloid suspension confined to a small circular cavity. In each of these geometries, a dense colloid suspension exhibits pronounced density oscillations with spacing of a particle diameter. We remove the discrepancy between prediction and experiment using the Fisher-Methfessel interpretation of how local equilibrium in an inhomogeneous system is maintained to argue that the force acting on a particle is delocalized over a volume with radius equal to a particle diameter. Our interpretation has relevance to the relationship between the scale of inhomogeneity and the utility of translation of the particle MSD into a position dependent diffusion coefficient and to the use of a spatially dependent diffusion coefficient to describe mass transport in a heterogeneous system.
Generation of cavitation luminescence by laser-induced exothermic chemical reaction
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jung Park, Han; Diebold, Gerald J.
2013-08-14
Absorption of high power laser radiation by aqueous carbon suspensions is known to result in the formation of highly compressed bubbles of hydrogen and carbon monoxide through the endothermic carbon-steam reaction. The bubbles expand rapidly, overreaching their equilibrium diameter, and then collapse tens to hundreds of microseconds after formation to give a flash of radiation. Here we report on the effects of laser-initiated exothermic chemical reaction on cavitation luminescence. Experiments with hydrogen peroxide added to colloidal carbon suspensions show that both the time of the light flash following the laser pulse and the intensity of luminescence increase with hydrogen peroxidemore » concentration, indicating that large, highly energetic gas bubbles are produced. Additional experiments with colloidal carbon suspensions show the effects of high pressure on the luminescent intensity and its time of appearance following firing of the laser.« less
Structure and dynamics of optically directed self-assembly of nanoparticles
Roy, Debjit; Mondal, Dipankar; Goswami, Debabrata
2016-01-01
Self-assembly of nanoparticles leading to the formation of colloidal clusters often serves as the representative analogue for understanding molecular assembly. Unravelling the in situ structure and dynamics of such clusters in liquid suspensions is highly challenging. Presently colloidal clusters are first isolated from their generating environment and then their structures are probed by light scattering methods. In order to measure the in situ structure and dynamics of colloidal clusters, we have generated them using the high-repetition-rate femtosecond laser pulse optical tweezer. Since the constituent of our dimer, trimer or tetramer clusters are 250 nm radius two-photon resonant fluorophore coated nanospheres under the optical trap, they inherently produce Two-Photon Fluorescence, which undergo intra-nanosphere Fluorescence Energy Transfer. This unique energy transfer signature, in turn, enables us to visualize structures and orientations of these colloidal clusters during the process of their formation and subsequent dynamics in a liquid suspension. We also show that due to shape-birefringence, orientation and structural control of these colloidal clusters are possible as the polarization of the trapping laser is changed from linear to circular. We thus report important progress in sampling the smallest possible aggregates of nanoparticles, dimers, trimers or tetramers, formed early in the self-assembly process. PMID:27006305
A new model for the spectral induced polarization signature of bacterial growth in porous media
NASA Astrophysics Data System (ADS)
Revil, A.; Atekwana, E.; Zhang, C.; Jardani, A.; Smith, S.
2012-09-01
The complex conductivity of porous materials and colloidal suspensions comprises two components: an in-phase conductivity associated with electromigration of the charge carriers and a quadrature conductivity associated with the reversible storage of the charges at some polarization length scales. We developed a quantitative model to investigate the frequency domain induced polarization response of suspensions of bacteria and bacteria growth in porous media. Induced polarization of bacteria (α polarization) is related to the properties of the electrical double layer of the bacteria. Surface conductivity and α polarization are due to the Stern layer of counterions occurring in a brush of polymers coating the surface of the bacteria. These phenomena can be related to their cation exchange capacity. The mobility of the counterions in this Stern layer is found to be very small (4.7 × 10-10 m2 s-1 V-1 at 25°C). This implies a very low relaxation frequency for the αpolarization of the bacteria cells (typically around 0.1-5 Hz), in agreement with experimental observations. This new model can be coupled to reactive transport modeling codes in which the evolution of bacterial populations are usually described by Monod kinetics. We show that the growth rate and endogenous decay coefficients of bacteria in a porous sand can be inferred nonintrusively from time-lapse frequency domain induced polarization data.
Entropic effects in the electric double layer of model colloids with size-asymmetric monovalent ions
NASA Astrophysics Data System (ADS)
Guerrero-García, Guillermo Iván; González-Tovar, Enrique; Olvera de la Cruz, Mónica
2011-08-01
The structure of the electric double layer of charged nanoparticles and colloids in monovalent salts is crucial to determine their thermodynamics, solubility, and polyion adsorption. In this work, we explore the double layer structure and the possibility of charge reversal in relation to the size of both counterions and coions. We examine systems with various size-ratios between counterions and coions (ion size asymmetries) as well as different total ion volume fractions. Using Monte Carlo simulations and integral equations of a primitive-model electric double layer, we determine the highest charge neutralization and electrostatic screening near the electrified surface. Specifically, for two binary monovalent electrolytes with the same counterion properties but differing only in the coion's size surrounding a charged nanoparticle, the one with largest coion size is found to have the largest charge neutralization and screening. That is, in size-asymmetric double layers with a given counterion's size the excluded volume of the coions dictates the adsorption of the ionic charge close to the colloidal surface for monovalent salts. Furthermore, we demonstrate that charge reversal can occur at low surface charge densities, given a large enough total ion concentration, for systems of monovalent salts in a wide range of ion size asymmetries. In addition, we find a non-monotonic behavior for the corresponding maximum charge reversal, as a function of the colloidal bare charge. We also find that the reversal effect disappears for binary salts with large-size counterions and small-size coions at high surface charge densities. Lastly, we observe a good agreement between results from both Monte Carlo simulations and the integral equation theory across different colloidal charge densities and 1:1-elec-trolytes with different ion sizes.
Supracolloidal Architectures Self-Assembled in Microdroplets.
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.
NASA Astrophysics Data System (ADS)
Zhong, L.; Lee, M. H.; Lee, B.; Yang, S.
2016-12-01
Delivery of nutrient to and establish a slow release carbon source in the vadose zone and capillary fringe zone is essential for setting up of a long-lasting bioremediation of contaminations in those zones. Conventional solution-based injection and infiltration approaches are facing challenges to achieve the delivery and remedial goals. Aqueous silica suspensions undergo a delayed gelation process under favorite geochemical conditions. The delay in gelation provides a time window for the injection of the suspension into the subsurface; and the gelation of the amendment-silica suspension enables the amendment-laden gel to stay in the target zone and slowly release the constituents for contaminant remediation. This approach can potentially be applied to deliver bio-nutrients to the vadose zone and capillary fringe zone for enhanced bioremediation and achieve remedial goals. This research was conducted to demonstrate delayed gelation of colloidal silica suspensions when carbon sources were added and to prove the gelation occurs in sediments under vadose conditions. Sodium lactate, vegetable oil, ethanol, and molasses were tested as the examples of carbon source (or nutrient) amendments. The rheological properties of the silica suspensions during the gelation were characterized. The influence of silica, salinity, nutrient concentrations, and the type of nutrients was studied. The kinetics of nutrient release from silica-nutrient gel was quantified using molasses as the example, and the influence of suspension gelation time was evaluated. The injection behavior of the suspensions was investigated by monitoring their viscosity changes and the injection pressures when the suspensions were delivered into sediment columns.
NASA Astrophysics Data System (ADS)
Aponte-Rivera, Christian; Zia, Roseanna N.
2017-11-01
We study hydrodynamic entrainment in spherically confined colloidal suspensions of hydrodynamically interacting particles as a model system for intracellular and other micro-confined biophysical transport. Modeling of transport and rheology in such materials requires an accurate description of the microscopic forces driving particle motion and of particle interactions with nearby boundaries. We carry out dynamic simulations of concentrated, spherically confined colloids as a model system to study the effect of 3D confinement on entrainment and rheology. We show that entrainment between two tracer particles exhibits qualitatively different functional dependence on inter-particle separation as compared to an unbound suspension, and develop a scaling theory that collapses the concentrated mobility of spherically confined suspensions for all volume fractions and particle to cavity size ratios onto a master curve. For widely separated particles, the master curve can be predicted via a Green's function, which suggests a framework with which to conduct two-point microrheology measurements near confining boundaries. The implications of these results for experiments in micro-confined biophysical systems, such as the interior of eukaryotic cells, are discussed.
Dynamics of highly polydisperse colloidal suspensions as a model system for bacterial cytoplasm.
Hwang, Jiye; Kim, Jeongmin; Sung, Bong June
2016-08-01
There are various kinds of macromolecules in bacterial cell cytoplasm. The size polydispersity of the macromolecules is so significant that the crystallization and the phase separation could be suppressed, thus stabilizing the liquid state of bacterial cytoplasm. On the other hand, recent experiments suggested that the macromolecules in bacterial cytoplasm should exhibit glassy dynamics, which should be also affected significantly by the size polydispersity of the macromolecules. In this work, we investigate the anomalous and slow dynamics of highly polydisperse colloidal suspensions, of which size distribution is chosen to mimic Escherichia coli cytoplasm. We find from our Langevin dynamics simulations that the diffusion coefficient (D_{tot}) and the displacement distribution functions (P(r,t)) averaged over all colloids of different sizes do not show anomalous and glassy dynamic behaviors until the system volume fraction ϕ is increased up to 0.82. This indicates that the intrinsic polydispersity of bacterial cytoplasm should suppress the glass transition and help maintain the liquid state of the cytoplasm. On the other hand, colloids of each kind show totally different dynamic behaviors depending on their size. The dynamics of colloids of different size becomes non-Gaussian at a different range of ϕ, which suggests that a multistep glass transition should occur. The largest colloids undergo the glass transition at ϕ=0.65, while the glass transition does not occur for smaller colloids in our simulations even at the highest value of ϕ. We also investigate the distribution (P(θ,t)) of the relative angles of displacement for macromolecules and find that macromolecules undergo directionally correlated motions in a sufficiently dense system.
Dynamics of highly polydisperse colloidal suspensions as a model system for bacterial cytoplasm
NASA Astrophysics Data System (ADS)
Hwang, Jiye; Kim, Jeongmin; Sung, Bong June
2016-08-01
There are various kinds of macromolecules in bacterial cell cytoplasm. The size polydispersity of the macromolecules is so significant that the crystallization and the phase separation could be suppressed, thus stabilizing the liquid state of bacterial cytoplasm. On the other hand, recent experiments suggested that the macromolecules in bacterial cytoplasm should exhibit glassy dynamics, which should be also affected significantly by the size polydispersity of the macromolecules. In this work, we investigate the anomalous and slow dynamics of highly polydisperse colloidal suspensions, of which size distribution is chosen to mimic Escherichia coli cytoplasm. We find from our Langevin dynamics simulations that the diffusion coefficient (Dtot) and the displacement distribution functions (P (r ,t ) ) averaged over all colloids of different sizes do not show anomalous and glassy dynamic behaviors until the system volume fraction ϕ is increased up to 0.82. This indicates that the intrinsic polydispersity of bacterial cytoplasm should suppress the glass transition and help maintain the liquid state of the cytoplasm. On the other hand, colloids of each kind show totally different dynamic behaviors depending on their size. The dynamics of colloids of different size becomes non-Gaussian at a different range of ϕ , which suggests that a multistep glass transition should occur. The largest colloids undergo the glass transition at ϕ =0.65 , while the glass transition does not occur for smaller colloids in our simulations even at the highest value of ϕ . We also investigate the distribution (P (θ ,t ) ) of the relative angles of displacement for macromolecules and find that macromolecules undergo directionally correlated motions in a sufficiently dense system.
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,...
Nanoparticle halos: A new colloid stabilization mechanism
Tohver, Valeria; Smay, James E.; Braem, Alan; Braun, Paul V.; Lewis, Jennifer A.
2001-01-01
A new mechanism for regulating the stability of colloidal particles has been discovered. Negligibly charged colloidal microspheres, which flocculate when suspended alone in aqueous solution, undergo a remarkable stabilizing transition upon the addition of a critical volume fraction of highly charged nanoparticle species. Zeta potential analysis revealed that these microspheres exhibited an effective charge buildup in the presence of such species. Scanning angle reflectometry measurements indicated, however, that these nanoparticle species did not adsorb on the microspheres under the experimental conditions of interest. It is therefore proposed that highly charged nanoparticles segregate to regions near negligibly charged microspheres because of their repulsive Coulombic interactions in solution. This type of nanoparticle haloing provides a previously unreported method for tailoring the behavior of complex fluids. PMID:11447264
Clements, Andrew F; Haley, Joy E; Urbas, Augustine M; Kost, Alan; Rauh, R David; Bertone, Jane F; Wang, Fei; Wiers, Brian M; Gao, De; Stefanik, Todd S; Mott, Andrew G; Mackie, David M
2009-06-11
We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.
Plasmonic nanostructures for bioanalytical applications of SERS
NASA Astrophysics Data System (ADS)
Kahraman, Mehmet; Wachsmann-Hogiu, Sebastian
2016-03-01
Surface-enhanced Raman scattering (SERS) is a potential analytical technique for the detection and identification of chemicals and biological molecules and structures in the close vicinity of metallic nanostructures. We present a novel method to fabricate tunable plasmonic nanostructures and perform a comprehensive structural and optical characterization of the structures. Spherical latex particles are uniformly deposited on glass slides and used as templates to obtain nanovoid structures on polydimethylsiloxane surfaces. The diameter and depth of the nanovoids are controlled by the size of the latex particles. The nanovoids are coated with a thin Ag layer for fabrication of uniform plasmonic nanostructures. Structural characterization of the surfaces is performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Optical properties of these plasmonic nanostructures are evaluated via UV/Vis spectroscopy, and SERS. The sample preparation step is the key point to obtain strong and reproducible SERS spectra from the biological structures. When the colloidal suspension is used as a SERS substrate for the protein detection, the electrostatic interaction of the proteins with the nanoparticles is described by the nature of their charge status, which influences the aggregation properties such as the size and shape of the aggregates, which is critical for the SERS experiment. However, when the solid SERS substrates are fabricated, SERS signal of the proteins that are background free and independent of the protein charge. Pros and cons of using plasmonic nano colloids and nanostructures as SERS substrate will be discussed for label-free detection of proteins using SERS.
Quincke rotors in colloidal suspensions
NASA Astrophysics Data System (ADS)
Xiao, Junjun; Huang, Jiping; Yu, Kin Wah; Gu, Guoqing
2004-03-01
When a polarized colloidal particle rotates in an applied electric field, the rotational motion of the particle leads to a displacement of the polarized charge on the surface of the particle. In this connection, the relaxation of the surface charge tends to restore the polarization, leading to a steady-state which is distinct from the equilibrium state in the absence of the rotational motion. There are three relevant cases, namely, rotating particles in a DC field[1, 2], particle rotation due to a rotating field[3, 4] as well as spontaneous rotation of particles in a DC field[5]. In this work, we have focused on the spontaneous rotation of colloidal particles in a DC field, which is known as Quincke rotation. In the collective behaviors of Quincke rotors, the mutual interactions between the individual rotors lead to the assembly of chain-like structures which make an angle with the applied field. We can solve the transient polarization relaxation of two approaching colloidal rotors numerically. More interestingly, we have been able to work out analytically the steady state of two nose-to-tail rotors, in an attempt to take into account the effect of the multipolar interaction between the rotors. As a result, we found that the multipolar interaction does not change the value of the induced dipole moment inside the rotor, but with one of the components of this dipole moment being reduced and the other being enhanced concomitantly. More results of interest have been reported as well. Based on the different dynamic behavior and interaction of Quincke rotors, a totally new class of material is expected to be designed. [1] J.T.K. Wan, K.W. Yu and G.Q. Gu, Phys. Rev. E 64, 061501 (2001). [2] J.T.K. Wan, K.W. Yu and G.Q. Gu, Phys. Rev. E 62, 6848 (2000). [3] J.P. Huang, K.W. Yu and G.Q. Gu, Phys. Rev. E 65, 021401 (2002). [4] J.P. Huang, K.W. Yu, G.Q. Gu and Mikko Karttunen, Phys. Rev. E 67, 051405 (2003). [5] G. Quinke, Ann. Phy. Chem 59, 417 (1896).
Solid colloidal optical wavelength filter
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.
Aqueous colloidal suspensions of C-60 (aqu/C-60) and the C-60 derivatives PCBM ([6,6]-phenyl C-61-butyric acid methyl ester) and the corresponding butyl and octyl esters, PCBB and PCBO (aqu/PCB-R, where R is an alkyl group), were produced by stirring in double deionized water for...
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.
Thermoreversible Gels Composed of Colloidal Silica Rods with Short-Range Attractions
Murphy, Ryan P.; Hong, Kunlun; Wagner, Norman J.
2016-07-28
Dynamic arrest transitions of colloidal suspensions containing non-spherical particles are of interest for the design and processing of various particle technologies. To better understand the effects of particle shape anisotropy and attraction strength on gel and glass formation, we present a colloidal model system of octadecyl-coated silica rods, termed as adhesive hard rods (AHR), which enables control of rod aspect ratio and temperature-dependent interactions. The aspect ratios of silica rods were controlled by varying the initial TEOS concentration following the work of Kuijk et al. (J. Am. Chem. Soc., 2011, 133, 2346–2349) and temperature-dependent attractions were introduced by coating themore » calcined silica rods with an octadecyl-brush and suspending in tetradecane. The rod length and aspect ratio were found to increase with TEOS concentration as expected, while other properties such as the rod diameter, coating coverage, density, and surface roughness were nearly independent of the aspect ratio. Ultra-small angle X-ray scattering measurements revealed temperature-dependent attractions between octadecyl-coated silica rods in tetradecane, as characterized by a low-q upturn in the scattered intensity upon thermal quenching. Lastly, the rheology of a concentrated AHR suspension in tetradecane demonstrated thermoreversible gelation behavior, displaying a nearly 5 orders of magnitude change in the dynamic moduli as the temperature was cycled between 15 and 40 °C. We find the adhesive hard rod model system serves as a tunable platform to explore the combined influence of particle shape anisotropy and attraction strength on the dynamic arrest transitions in colloidal suspensions with thermoreversible, short-range attractions.« less
PRELIMINARY STUDIES OF THE GASTROINTESTINAL TRACT WITH COLLOIDAL BARIUM
Windholz, Frank; Kaplan, Henry S.; Jones, Henry H.
1951-01-01
A stable colloidal suspension of barium sulfate has been developed and tested in roentgen examination of the gastrointestinal tract. The new material is rather distinctive in radiographic appearance and can usually be differentiated from simple barium-water mixtures by inspection of roentgenograms of the opacified stomach and small intestine. It usually affords a satisfactory demonstration of the mucosal folds of the stomach and duodenal bulb and is considerably more resistant to flocculation and precipitation by retained gastric secretions. In the small intestine, it has little tendency to undergo flocculation and fragmentation, and permits visualization of fine mucosal configurations with unusual clarity. Its motility is about the same as that of conventional suspensions. Air contrast colon examinations with the colloidal preparation exhibit a very uniform, opaque, and stable coating of the bowel wall and are more consistently satisfactory than when simple barium-water mixtures are used. ImagesFigure 1.Figure 1.Figure 1.Figure 1.Figure 2.Figure 2.Figure 3.Figure 4.Figure 4.Figure 5.Figure 5.Figure 6. PMID:14812347
Aging of a Binary Colloidal Glass
NASA Astrophysics Data System (ADS)
Lynch, Jennifer M.; Cianci, Gianguido C.; Weeks, Eric R.
2008-03-01
After having undergone a glass transition, a glass is in a non-equilibrium state, and its properties depend on the time elapsed since vitrification. We study this phenomenon, known as aging. In particular, we study a colloidal suspension consisting of micron-sized particles in a liquid --- a good model system for studying the glass transition. In this system, the glass transition is approached by increasing the particle concentration, instead of decreasing the temperature. We observe samples composed of particles of two sizes (d1= 1.0μm and d2= 2.0μm) using fast laser scanning confocal microscopy, which yields real-time, three-dimensional movies deep inside the colloidal glass. We then analyze the trajectories of several thousand particles as the glassy suspension ages. Specifically, we look at how the size, motion and structural organization of the particles relate to the overall aging of the glass. We find that areas richer in small particles are more mobile and therefore contribute more to the structural changes found in aging glasses.
Probing surface charge potentials of clay basal planes and edges by direct force measurements.
Zhao, Hongying; Bhattacharjee, Subir; Chow, Ross; Wallace, Dean; Masliyah, Jacob H; Xu, Zhenghe
2008-11-18
The dispersion and gelation of clay suspensions have major impact on a number of industries, such as ceramic and composite materials processing, paper making, cement production, and consumer product formulation. To fundamentally understand controlling mechanisms of clay dispersion and gelation, it is necessary to study anisotropic surface charge properties and colloidal interactions of clay particles. In this study, a colloidal probe technique was employed to study the interaction forces between a silica probe and clay basal plane/edge surfaces. A muscovite mica was used as a representative of 2:1 phyllosilicate clay minerals. The muscovite basal plane was prepared by cleavage, while the edge surface was obtained by a microtome cutting technique. Direct force measurements demonstrated the anisotropic surface charge properties of the basal plane and edge surface. For the basal plane, the long-range forces were monotonically repulsive within pH 6-10 and the measured forces were pH-independent, thereby confirming that clay basal planes have permanent surface charge from isomorphic substitution of lattice elements. The measured interaction forces were fitted well with the classical DLVO theory. The surface potentials of muscovite basal plane derived from the measured force profiles were in good agreement with those reported in the literature. In the case of edge surfaces, the measured forces were monotonically repulsive at pH 10, decreasing with pH, and changed to be attractive at pH 5.6, strongly suggesting that the charge on the clay edge surfaces is pH-dependent. The measured force profiles could not be reasonably fitted with the classical DLVO theory, even with very small surface potential values, unless the surface roughness was considered. The surface element integration (SEI) method was used to calculate the DLVO forces to account for the surface roughness. The surface potentials of the muscovite edges were derived by fitting the measured force profiles with the surface element integrated DLVO model. The point of zero charge of the muscovite edge surface was estimated to be pH 7-8.
On the Applicability of DLVO Theory to the Prediction of Clay Colloids Stability.
Missana; Adell
2000-10-01
The stability behavior of Na-montmorillonite colloids has been studied by combining the analysis of their surface charge properties and time-resolved dynamic light scattering experiments. The chemical surface model for several types of clays, including montmorillonite, has to take into account the double surface charge contribution due to their permanent structural charge and to their pH-dependent charge, which is developed at the edge sites, therefore, these stability studies were carried out as a function of both ionic strength and pH. DLVO theory is largely applied for the prediction of the stability of many colloidal systems, including the natural ones. This work shows that the stability behavior of Na-montmorillonite colloids cannot be satisfactorily reproduced by DLVO theory, using the surface parameters experimentally obtained. Particularly, this theory is unable to explain their pH-dependent stability behavior caused by the small charge at the edge sites. Based on these results, a literature review of DLVO stability prediction of clay colloids was performed. It confirmed that this theory is not capable of taking into account the double contribution to the total surface charge and, at the same time, pointed out the main uncertainties related to the appropriate use of the input parameters for the calculation as, for example, the Hamaker constant or the surface potential. Copyright 2000 Academic Press.
Generation of colloidal granules and capsules from double emulsion drops
NASA Astrophysics Data System (ADS)
Hess, Kathryn S.
Assemblies of colloidal particles are extensively used in ceramic processing, pharmaceuticals, inks and coatings. In this project, the aim was to develop a new technique to fabricate monodispersed colloidal assemblies. The use of microfluidic devices and emulsion processing allows for the fabrication of complex materials that can be used in a variety of applications. A microfluidic device is used to create monodispersed water/oil/water (w/o/w) double emulsions with interior droplets of colloidal silica suspension ranging in size from tens to hundreds of microns. By tailoring the osmotic pressure using glycerol as a solute in the continuous and inner phases of the emulsion, we can control the final volume size of the monodispersed silica colloidal crystals that form in the inner droplets of the double emulsion. Modifying the ionic strength in the colloidal dispersion can be used to affect the particle-particle interactions and crystal formation of the final colloidal particle. This w/o/w technique has been used with other systems of metal oxide colloids and cellulose nanocrystals. Encapsulation of the colloidal suspension in a polymer shell for the generation of ceramic-polymer core-shell particles has also been developed. These core-shell particles have spawned new research in the field of locally resonant acoustic metamaterials. Systems and chemistries for creating cellulose hydrogels within the double emulsions have also been researched. Water in oil single emulsions and double emulsions have been used to create cellulose hydrogel spheres in the sub-100 micron diameter range. Oil/water/oil double emulsions allow us to create stable cellulose capsules. The addition of a second hydrogel polymer, such as acrylate or alginate, further strengthens the cellulose gel network and can also be processed into capsules and particles using the microfluidic device. This work could have promising applications in acoustic metamaterials, personal care products, pharmaceuticals, and agricultural applications, among others.
Ferraro, D; Lin, Y; Teste, B; Talbot, D; Malaquin, L; Descroix, S; Abou-Hassan, A
2015-12-11
We present a microfluidic platform that allows undergoing different chemical operations in a nanoliter droplet starting from the colloidal suspension of magnetic iron oxide (γ-Fe2O3) nanoparticles "NPs" (ferrofluid). These operations include: mixing, flocculation, magnetic decantation, colloidal redispersion, washing, surface functionalization, heating and colloidal assembly. To prove the platform capabilities, we produced fluorescent and magnetic nanoassemblies composed of fluorescent silica and magnetic NPs.
Tseng, Kuo-Hsiung; Chung, Meng-Yun; Chang, Chaur-Yang
2017-06-02
In this study, the Electric Spark Discharge Method (ESDM) was employed with micro-electrical discharge machining (m-EDM) to create an electric arc that melted two electrodes in deionized water (DW) and fabricated nano-Au colloids through pulse discharges with a controlled on-off duration (T ON -T OFF ) and a total fabrication time of 1 min. A total of six on-off settings were tested under normal experimental conditions and without the addition of any chemical substances. Ultraviolet-visible spectroscopy (UV-Vis), Zetasizer Nano measurements, and scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analyses suggested that the nano-Au colloid fabricated at 10-10 µs (10 µs on, 10 µs off) had higher concentration and suspension stability than products made at other T ON -T OFF settings. The surface plasmon resonance (SPR) of the colloid was 549 nm on the first day of fabrication and stabilized at 532 nm on the third day. As the T ON -T OFF period increased, the absorbance (i.e., concentration) of all nano-Au colloids decreased. Absorbance was highest at 10-10 µs. The SPR peaks stabilized at 532 nm across all T ON -T OFF periods. The Zeta potential at 10-10 µs was -36.6 mV, indicating that no nano-Au agglomeration occurred and that the particles had high suspension stability.
Tseng, Kuo-Hsiung; Chung, Meng-Yun; Chang, Chaur-Yang
2017-01-01
In this study, the Electric Spark Discharge Method (ESDM) was employed with micro-electrical discharge machining (m-EDM) to create an electric arc that melted two electrodes in deionized water (DW) and fabricated nano-Au colloids through pulse discharges with a controlled on–off duration (TON–TOFF) and a total fabrication time of 1 min. A total of six on–off settings were tested under normal experimental conditions and without the addition of any chemical substances. Ultraviolet–visible spectroscopy (UV–Vis), Zetasizer Nano measurements, and scanning electron microscopy–energy dispersive X-ray (SEM–EDX) analyses suggested that the nano-Au colloid fabricated at 10–10 µs (10 µs on, 10 µs off) had higher concentration and suspension stability than products made at other TON–TOFF settings. The surface plasmon resonance (SPR) of the colloid was 549 nm on the first day of fabrication and stabilized at 532 nm on the third day. As the TON–TOFF period increased, the absorbance (i.e., concentration) of all nano-Au colloids decreased. Absorbance was highest at 10–10 µs. The SPR peaks stabilized at 532 nm across all TON–TOFF periods. The Zeta potential at 10–10 µs was −36.6 mV, indicating that no nano-Au agglomeration occurred and that the particles had high suspension stability. PMID:28574476
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.
Burkert, Klaus; Neumann, Thomas; Wang, Jianjun; Jonas, Ulrich; Knoll, Wolfgang; Ottleben, Holger
2007-03-13
Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.
NASA Astrophysics Data System (ADS)
Perera, M. Tharanga D.
Microstructure is key to understanding rheological behaviors of flowing particulate suspensions. During the past decade, Stokesian Dynamics simulations have been the dominant method of determining suspension microstructure. Structure results obtained numerically reveal that an anisotropic structure is formed under high Peclet (Pe) number conditions. Researchers have used various experimental techniques such as small angle neutron scattering (SANS) and light scattering methods to validate microstructure. This work outlines an experimental technique based on confocal microscopy to study microstructure of a colloidal suspension in an index-matched fluid flowing in a microchannel. High resolution scans determining individual particle locations in suspensions 30-50 vol % yield quantitative results of the local microstructure in the form of the pair distribution function, g(r). From these experimentally determined g(r), the effect of shear rate, quantified by the Peclet number as a ratio of shear and Brownian stress, on the suspension viscosity and normal stress follow that seen in macroscopic rheological measurements and simulations. It is generally believed that shear thickening behavior of colloidal suspensions is driven by the formation of hydroclusters. From measurements of particle locations, hydroclusters are identified. The number of hydroclusters grows exponentially with increasing Pe, and the onset of shear thickening is driven by the increase in formation of clusters having 5-8 particles. At higher Pe, we notice the emergence of 12 or more particle clusters. The internal structure of these hydroclusters has been investigated, and there is some evidence that particles internal to hydroclusters preferentially align along the 45° and 135° axis. Beyond observations of bulk suspension behavior, the influence of boundaries on suspension microstructure is also investigated. Experiments were performed for suspensions flowing over smooth walls, made of glass coverslips, and over rough walls having a high density coating of particles. These results show that there is more order in structure near smooth boundaries while near rough boundaries the structure is similar to that found in the bulk. The relative viscosity and normal stress differences also indicate that boundaries have an effect up as far as 6 particle diameters away from the boundary. Finally, we investigate the microstructure evolvement in a model porous medium and notice that such boundary effects come into play in such real process flows. The confocal microscopy technique also provides us with the advantage of measuring structure in real process flows. We have investigated how the microstructure evolves upstream and downstream in a porous medium. We notice more structure in a high volume fraction suspension and notice anisotropic behavior at regions where shear from the wall of the posts dominate. In other cases, a mixed flow behavior is observed due to collisions between pore surfaces and other particles resulting in a deviation from flow streamlines.
Coulomb-like elastic interaction induced by symmetry breaking in nematic liquid crystal colloids.
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.
Nanoparticle assembly on patterned "plus/minus" surfaces from electrospray of colloidal dispersion.
Lenggoro, I Wuled; Lee, Hye Moon; Okuyama, Kikuo
2006-11-01
Selective deposition of metal (Au) and oxide (SiO2) nanoparticles with a size range of 10-30 nm on patterned silicon-silicon oxide substrate was performed using the electrospray method. Electrical charging characteristics of particles produced by the electrospray and patterned area created by contact charging of the electrical conductor with non- or semi-conductors were investigated. Colloidal droplets were electrosprayed and subsequently dried as individual nanoparticles which then were deposited on substrates, and observed using field emission-scanning electron microscopy. The number of elementary charge units on particles generated by the electrospray was 0.4-148, and patterned area created by contact charging contained sufficient negative charges to attract multiple charged particles. Locations where nanoparticles were (reversibly) deposited depended on voltage polarity applied to the spraying colloidal droplet and the substrate, and the existence of additional ions such as those from a stabilizer.
Anisotropic magnetic particles in a magnetic field
Martchenko, Ilya; Mihut, Adriana M.; Bialik, Erik; Hirt, Ann M.; Rufier, Chantal; Menzel, Andreas; Dietsch, Hervé; Linse, Per
2016-01-01
We characterize the structural properties of magnetic ellipsoidal hematite colloids with an aspect ratio ρ ≈ 2.3 using a combination of small-angle X-ray scattering and computer simulations. The evolution of the phase diagram with packing fraction φ and the strength of an applied magnetic field B is described, and the coupling between orientational order of magnetic ellipsoids and the bulk magnetic behavior of their suspension addressed. We establish quantitative structural criteria for the different phase and arrest transitions and map distinct isotropic, polarized non-nematic, and nematic phases over an extended range in the φ–B coordinates. We show that upon a rotational arrest of the ellipsoids around φ = 0.59, the bulk magnetic behavior of their suspension switches from superparamagnetic to ordered weakly ferromagnetic. If densely packed and arrested, these magnetic particles thus provide persisting remanent magnetization of the suspension. By exploring structural and magnetic properties together, we extend the often used colloid-atom analogy to the case of magnetic spins. PMID:27722439
Second-harmonic generation of ZnO nanoparticles synthesized by laser ablation of solids in liquids
NASA Astrophysics Data System (ADS)
Rocha-Mendoza, Israel; Camacho-López, Santiago; Luna-Palacios, Yryx Y.; Esqueda-Barrón, Yasmín; Camacho-López, Miguel A.; Camacho-López, Marco; Aguilar, Guillermo
2018-02-01
We report the synthesis of small zinc oxide nanoparticles (ZnO NPs) based colloidal suspensions and the study of second-harmonic generation from aggregated ZnO NPs deposited on glass substrates. The colloidal suspensions were obtained using the laser ablation of solids in liquids technique, ablating a Zn solid target immersed in acetone as the liquid medium, with ns-laser pulses (1064 nm) of a Nd-YAG laser. The per pulse laser fluence, the laser repetition rate frequency and the ablation time were kept constant. The absorption evolution of the obtained suspensions was optically characterized through absorption spectroscopy until stabilization. Raman spectroscopy, SEM and HRTEM were used to provide evidence of the ZnO NPs structure. HRTEM results showed that 5-8 nm spheroids ZnO NPs were obtained. Strong second-harmonic signal is obtained from random ZnO monocrystalline NPs and from aggregated ZnO NPs, suggesting that the high efficiency of the nonlinear process may not depend on the NPs size or aggregation state.
Modeling the viscosity of polydisperse suspensions: Improvements in prediction of limiting behavior
NASA Astrophysics Data System (ADS)
Mwasame, Paul M.; Wagner, Norman J.; Beris, Antony N.
2016-06-01
The present study develops a fully consistent extension of the approach pioneered by Farris ["Prediction of the viscosity of multimodal suspensions from unimodal viscosity data," Trans. Soc. Rheol. 12, 281-301 (1968)] to describe the viscosity of polydisperse suspensions significantly improving upon our previous model [P. M. Mwasame, N. J. Wagner, and A. N. Beris, "Modeling the effects of polydispersity on the viscosity of noncolloidal hard sphere suspensions," J. Rheol. 60, 225-240 (2016)]. The new model captures the Farris limit of large size differences between consecutive particle size classes in a suspension. Moreover, the new model includes a further generalization that enables its application to real, complex suspensions that deviate from ideal non-colloidal suspension behavior. The capability of the new model to predict the viscosity of complex suspensions is illustrated by comparison against experimental data.
Khair, Aditya S
2018-01-23
The deformation of the electric double layer around a charged colloidal particle during sedimentation or electrophoresis in a binary, symmetric electrolyte is studied. The surface potential of the particle is assumed to be small compared to the thermal voltage scale. Additionally, the Debye length is assumed to be large compared to the particle size. These assumptions enable a linearization of the electrokinetic equations. The particle appears as a point charge in this thick-double-layer limit; the distribution of charge in the diffuse cloud surrounding it is determined by a balance of advection due to the particle motion, Brownian diffusion of ions, and electrostatic screening of the particle by the cloud. The ability of advection to deform the charge cloud from its equilibrium state is parametrized by a Péclet number, Pe. For weak advection (Pe ≪ 1), the cloud is only slightly deformed. In contrast, the cloud can be completely stripped from the particle at Pe ≫ 1; consequently, electrokinetic effects on the particle motion vanish in this regime. Therefore, in sedimentation the drag limits to Stokes' law for an uncharged particle as Pe → ∞. Likewise, the particle velocity for electrophoresis approaches Huckel's result. The strongly deformed cloud at large Pe is predicted to generate a concomitant increase in the sedimentation field in a dilute settling suspension.
Nag, Angshuman; Chung, Dae Sung; Dolzhnikov, Dmitriy S; Dimitrijevic, Nada M; Chattopadhyay, Soma; Shibata, Tomohiro; Talapin, Dmitri V
2012-08-22
Colloidal semiconductor nanocrystals (NCs) provide convenient "building blocks" for solution-processed solar cells, light-emitting devices, photocatalytic systems, etc. The use of inorganic ligands for colloidal NCs dramatically improved inter-NC charge transport, enabling fast progress in NC-based devices. Typical inorganic ligands (e.g., Sn(2)S(6)(4-), S(2-)) are represented by negatively charged ions that bind covalently to electrophilic metal surface sites. The binding of inorganic charged species to the NC surface provides electrostatic stabilization of NC colloids in polar solvents without introducing insulating barriers between NCs. In this work we show that cationic species needed for electrostatic balance of NC surface charges can also be employed for engineering almost every property of all-inorganic NCs and NC solids, including photoluminescence efficiency, electron mobility, doping, magnetic susceptibility, and electrocatalytic performance. We used a suite of experimental techniques to elucidate the impact of various metal ions on the characteristics of all-inorganic NCs and developed strategies for engineering and optimizing NC-based materials.
Single charging events on colloidal particles in a nonpolar liquid with surfactant
NASA Astrophysics Data System (ADS)
Schreuer, Caspar; Vandewiele, Stijn; Brans, Toon; Strubbe, Filip; Neyts, Kristiaan; Beunis, Filip
2018-01-01
Electrical charging of colloidal particles in nonpolar liquids due to surfactant additives is investigated intensively, motivated by its importance in a variety of applications. Most methods rely on average electrophoretic mobility measurements of many particles, which provide only indirect information on the charging mechanism. In the present work, we present a method that allows us to obtain direct information on the charging mechanism, by measuring the charge fluctuations on individual particles with a precision higher than the elementary charge using optical trapping electrophoresis. We demonstrate the capabilities of the method by studying the influence of added surfactant OLOA 11000 on the charging of single colloidal PMMA particles in dodecane. The particle charge and the frequency of charging events are investigated both below and above the critical micelle concentration (CMC) and with or without applying a DC offset voltage. It is found that at least two separate charging mechanisms are present below the critical micelle concentration. One mechanism is a process where the particle is stripped from negatively charged ionic molecules. An increase in the charging frequency with increased surfactant concentration suggests a second mechanism that involves single surfactant molecules. Above the CMC, neutral inverse micelles can also be involved in the charging process.
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
In-situ groundwater remediation by selective colloid mobilization
Seaman, J.C.; Bertch, P.M.
1998-12-08
An in-situ groundwater remediation pump and treat technique is described which is effective for reclamation of aquifers that have been contaminated with a mixed, metal-containing waste, and which promotes selective mobilization of metal oxide colloids with a cationic surfactant, preferably a quaternary alkylammonium surfactant, without significantly reducing formation permeability that often accompanies large-scale colloid dispersion, thus increasing the efficiency of the remediation effort by enhancing the capture of strongly sorbing contaminants associated with the oxide phases. The resulting suspension can be separated from the bulk solution with controlled pH adjustments to destabilize the oxide colloids, and a clear supernatant which results that can be recycled through the injection well without further waste treatment. 3 figs.
In-situ groundwater remediation by selective colloid mobilization
Seaman, John C.; Bertch, Paul M.
1998-01-01
An in-situ groundwater remediation pump and treat technique effective for reclamation of aquifers that have been contaminated with a mixed, metal-containing waste, which promotes selective mobilization of metal oxide colloids with a cationic surfactant, preferably a quaternary alkylammonium surfactant, without significantly reducing formation permeability that often accompanies large-scale colloid dispersion, thus increasing the efficiency of the remediation effort by enhancing the capture of strongly sorbing contaminants associated with the oxide phases. The resulting suspension can be separated from the bulk solution with controlled pH adjustments to destabilize the oxide colloids, and a clear supernatant which results that can be recycled through the injection well without further waste treatment.
Zhang, Ming; Guiraud, Pascal
2017-12-01
The treatment of nanoparticle (NP) polluted aqueous suspensions by flotation can be problematic due to the low probability of collision between particles and bubbles. To overcome this limitation, the present work focuses on developing an enhanced flotation technique using the surface-functionalized microbubbles - colloidal gas aphrons (CGAs). The CGA generator was adapted to be air flow rate controlled based on the classical Sebba system; thus it could be well adopted in a continuous flotation process. Cetyl trimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) were employed for CGA creation. Positively surface-charged CTAB-CGAs (∼44.1 μm in size) and negatively surface-charged SDS-CGAs (∼42.1 μm in size) were produced at the optimum stirring speed of 8000 rpm. The half-life of CGAs varied from 100 s to 340 s under the tested conditions, which was largely sufficient for transferring CGAs from bubble generator to flotation cell. The air flow led to less stable CTAB-CGAs but apparently enhanced the stability of SDS-CGAs at higher air flow rates. In the presence of air flow, the drainage behavior was not much related to the type of surfactants. The continuous CGA-flotation trials highlighted the effective separation of silica nanoparticles - the removal efficiencies of different types of SiO 2 NPs could reach approximately 90%-99%; however, at equivalent surfactant concentrations, no greater than 58% of NPs were removed when surfactants and bubbles were separately added into the flotation cell. The SiO 2 NPs with small size were removed more efficiently by the CGA-flotation process. For the flotation with CTAB-CGAs, the neutral and basic initial SNP suspension was recommended, whereas the SDS-CGAs remained high flotation efficiency over all investigated pH. The good performance of CGA-flotation might be interpreted: most of the surfactant molecules well covered/coated on the surfaces of stable CGAs and thus fully contacted with NPs, resulting in the efficient utilization of surfactants. Copyright © 2017 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Seo, Youngsang; Ha, Jeonghong; Kim, Dongsik, E-mail: dskim87@postech.ac.kr
2015-09-21
In this work, we report substantially enhanced colloidal stability of aqueous nanoparticle suspensions by ultrashort laser pulse irradiation. A Ti:Sapphire femtosecond laser (wavelength: 800 nm; pulse duration: 50 fs at full width at half maximum) was used to modify the electrochemical properties of nanoparticle suspensions at laser fluences below the particle ablation threshold. The colloidal stability of the suspension was evaluated by zeta potential and dynamic light scattering (DLS). The DLS results along with the images from transmission electron microscopy revealed that the laser irradiation caused no distinct morphological change to the individual alumina particles, but a substantial portion of themore » clustered particles was fragmented by the laser pulses, decreasing the apparent size of the suspended particles. Also, X-ray photoelectron spectroscopy analysis indicates that the laser irradiation modified the surface chemistry of the alumina particles. The stabilizing capability of the proposed technique was turned out to be better than that of conventional ultrasonic treatments. The stability of the laser-treated sample with no added surfactant was maintained for up to 30 days, without requiring an additional homogenizing process such as magnetic stirring.« less
Arbab, Alvira Ayoub; Sun, Kyung Chul; Sahito, Iftikhar Ali; Qadir, Muhammad Bilal; Jeong, Sung Hoon
2015-05-21
Textile wearable electronics offers the combined advantages of both electronics and textile characteristics. The essential properties of these flexible electronics such as lightweight, stretchable, and wearable power sources are in strong demand. Here, we have developed a facile route to fabricate multi walled carbon nanotube (MWCNT) coated polyester fabric as a flexible counter electrode (CE) for dye sensitized solar cells (DSSCs). A variety of MWCNT and enzymes with different structures were used to generate individual enzyme-dispersed MWCNT (E-MWCNT) suspensions by non-covalent functionalization. A highly concentrated colloidal suspension of E-MWCNT was deposited on polyester fabric via a simple tape casting method using an air drying technique. In view of the E-MWCNT coating, the surface structure is represented by topologically randomly assembled tubular graphene units. This surface morphology has a high density of colloidal edge states and oxygen-containing surface groups which execute multiple catalytic sites for iodide reduction. A highly conductive E-MWCNT coated fabric electrode with a surface resistance of 15 Ω sq(-1) demonstrated 5.69% power conversion efficiency (PCE) when used as a flexible CE for DSSCs. High photo voltaic performance of our suggested system of E-MWCNT fabric-based DSSCs is associated with high sheet conductivity, low charge transfer resistance (RCT), and excellent electro catalytic activity (ECA). Such a conductive fabric demonstrated stable conductivity against bending cycles and strong mechanical adhesion of E-MWCNT on polyester fabric. Moreover, the polyester fabric is hydrophobic and, therefore, has good sealing capacity and retains the polymer gel electrolyte without seepage. This facile E-MWCNT fabric CE configuration provides a concrete fundamental background towards the development of textile-integrated solar cells.
Nakato, Teruyuki; Yamada, Yoshimi; Miyamoto, Nobuyoshi
2009-02-05
We investigated photoinduced charge separation occurring in a multicomponent colloidal system composed of oxide nanosheets of photocatalytically active niobate and photochemically inert clay and electron accepting methylviologen dications (MV2+). The inorganic nanosheets were obtained by exfoliation of layered hexaniobate and hectorite clay. The niobate and clay nanosheets were spatially separated in the colloidally dispersed state, and the MV2+ molecules were selectively adsorbed on the clay platelets. UV irradiation of the colloids led to electron transfer from the niobate nanosheets to the MV2+ molecules adsorbed on clay. The photoinduced electron transfer produced methylviologen radical cations (MV*+), which was characterized by high yield and long lifetime. The yield and stability of the MV*+ species were found to depend strongly on the clay content of the colloid: from a few mol % to approximately 70 mol % of the yield and several tens of minutes to more than 40 h of the lifetime. The contents of the niobate nanosheets and MV2+ molecules and the aging of the colloid also affected the photoinduced charge separation. In the absence of MV2+ molecules in the colloid, UV irradiation induced electron accumulation in the niobate nanosheets. The stability of the electron-accumulated state also depended on the clay content. The variation in the photochemical behavior is discussed in relation to the viscosity of the colloid.
NASA Astrophysics Data System (ADS)
Martínez-Ratón, Yuri; Velasco, Enrique
2012-10-01
We use a fundamental-measure density functional for hard board-like polydisperse particles, in the restricted-orientation approximation, to explain the phase behaviour of platelet colloidal suspensions studied in recent experiments. In particular, we focus our attention on the behavior of the total packing fraction of the mixture, η, in the region of two-phase isotropic-nematic coexistence as a function of mean aspect ratio, polydispersity, and fraction of total volume γ occupied by the nematic phase. In our model, platelets are polydisperse in the square section, of side length σ, but have constant thickness L (and aspect ratio κ ≡ L/⟨σ⟩ < 1, with ⟨σ⟩ the mean side length). Good agreement between our theory and recent experiments is obtained by mapping the real system onto an effective one, with excluded volume interactions but with thicker particles (due to the presence of long-ranged repulsive interactions between platelets). The effect of polydispersity in both shape and particle size has been taken into account by using a size distribution function with an effective mean-square deviation that depends on both polydispersities. We also show that the bimodality of the size distribution function is required to correctly describe the huge two-phase coexistence gap and the nonlinearity of the function γ(η), two important features that these colloidal suspensions exhibit.
Hao, Tian
2015-09-14
The underlying relationships among viscosity equations of glass liquids and colloidal suspensions are explored with the aid of free volume concept. Viscosity equations of glass liquids available in literature are focused and found to have a same physical basis but different mathematical expressions for the free volume. The glass transitions induced by temperatures in glass liquids and the percolation transition induced by particle volume fractions in colloidal suspensions essentially are a second order phase transition: both those two transitions could induce the free volume changes, which in turn determines how the viscosities are going to change with temperatures and/or particle volume fractions. Unified correlations of the free volume to both temperatures and particle volume fractions are thus proposed. The resulted viscosity equations are reducible to many popular viscosity equations currently widely used in literature; those equations should be able to cover many different types of materials over a wide temperature range. For demonstration purpose, one of the simplified versions of those newly developed equations is compared with popular viscosity equations and the experimental data: it can well fit the experimental data over a wide temperature range. The current work reveals common physical grounds among various viscosity equations, deepening our understanding on viscosity and unifying the free volume theory across many different systems.
Physics of Colloids in Space-2 (PCS-2)
NASA Technical Reports Server (NTRS)
Sankaran, Subramanian; Gasser, Urs; Manley, Suliana; Valentine, Megan; Prasad, Vikram; Rudhardt, Daniel; Bailey, Arthur; Dinsmore, Anthony; Segre, Phil; Doherty, Michael P.
2001-01-01
The Physics of Colloids-2 (PCS-2) experiment is aimed at investigating the basic physical properties of several types of colloidal suspensions. The three broad classes of colloidal systems of interest are binary colloids, colloid-polymer mixtures, and fractal gels. The objective is to understand their phase behavior as well as the kinetics of the phase transitions in the absence of gravity. The nucleation, growth, and morphology characteristics of the crystals and gels that form would be studied using confocal microscopy. These will be observed directly with excellent time resolution, and therefore extensive information about the different phases and their growth mechanisms will be gained. With the laser tweezers, it will be possible to measure the strength of these structures and to modify them in a controlled way, and the spectrophotometer will provide the possibility to probe their optical properties. We believe that this experiment will provide the basis for future 'colloid engineering' in which complicated structures with novel properties (e.g., photonic crystals) will be grown by controlled self-assembly.
NASA Astrophysics Data System (ADS)
Morales, V. L.; Gao, B.; Steenhuis, T. S.
2008-12-01
Soil colloids and biocolloids can facilitate contaminant transport within the soil profile through the complexation of pollutants previously thought to have limited mobility. Dissolved organic substances are qualitatively known to alter the behavior of colloids and surface chemistry of soil particles in aquatic environments when adsorbed to their surfaces. Specifically, it has been observed that even small amounts of adsorbed humic acids result in a pronounced increase in colloid mobility in saturated porous systems, presumably by a combination of electrostatic and steric stabilization. However, the degree to which adsorbed humic acids stabilize colloidal suspension is highly sensitive to the system's solution chemistry; mainly in terms of pH, ionic strength, and metal ions present. The objective of this study is to expound quantitatively on the role that combined stabilizing and destabilizing solution chemistry components have on humic acid-colloid transport in unsaturated media by isolating experimentally some underlying mechanisms that regulate colloid transport in realistic aquatic systems. We hypothesize that in chemically heterogeneous porous media, with ionic strength values above 0 and pH ranges from 4 to 9, the effect of humic acid on colloid suspensions cannot be simply characterized by increased stability and mobility. That a critical salt concentration must exists for a given humic acid concentration and pH, above which the network of humic acid collapses by forming coordination complexes with other suspended or adsorbed humic acids, thus increasing greatly the retention of colloids in the porous medium by sweep flocculation. In addition, capillary forces in unsaturated media may contribute further to overcome repulsive forces that prevent flocculation of humic acid-colloid complexes. The experimental work in this study will include: jar tests to determine critical solution concentration combinations for desired coagulation/flocculation rates, column experiments to obtain effluent breakthrough data, in-situ visualization of internal processes with bright field microscopy, batch adsorption measurements, and changes in hydrophobic interaction energy of colloid and media surfaces for realistic aqueous ionic strength and pH ranges. Such experimental results are expected to provide sufficient evidence to corroborate our speculations that under natural soil water conditions, humic acids may greatly contribute to the immobilization of colloidal particles.
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
Patterned assembly of colloidal particles by confined dewetting lithography.
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.
Continuous Isotropic-Nematic Transition in Amyloid Fibril Suspensions Driven by Thermophoresis.
Vigolo, Daniele; Zhao, Jianguo; Handschin, Stephan; Cao, Xiaobao; deMello, Andrew J; Mezzenga, Raffaele
2017-04-27
The isotropic and nematic (I + N) coexistence for rod-like colloids is a signature of the first-order thermodynamics nature of this phase transition. However, in the case of amyloid fibrils, the biphasic region is too small to be experimentally detected, due to their extremely high aspect ratio. Herein, we study the thermophoretic behaviour of fluorescently labelled β-lactoglobulin amyloid fibrils by inducing a temperature gradient across a microfluidic channel. We discover that fibrils accumulate towards the hot side of the channel at the temperature range studied, thus presenting a negative Soret coefficient. By exploiting this thermophoretic behaviour, we show that it becomes possible to induce a continuous I-N transition with the I and N phases at the extremities of the channel, starting from an initially single N phase, by generating an appropriate concentration gradient along the width of the microchannel. Accordingly, we introduce a new methodology to control liquid crystal phase transitions in anisotropic colloidal suspensions. Because the induced order-order transitions are achieved under stationary conditions, this may have important implications in both applied colloidal science, such as in separation and fractionation of colloids, as well as in fundamental soft condensed matter, by widening the accessibility of target regions in the phase diagrams.
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.
Near Wall Dynamics in Colloidal Suspensions Studied by Evansescent Wave Dynamic Light Scattering
NASA Astrophysics Data System (ADS)
Lang, Peter R.
2011-03-01
The dynamics of dispersed colloidal particles is slowed down, and becomes anisotropic in the ultimate vicinity of a flat wall due to the wall drag effect. Although theoretically predicted in the early 20th century, experimental verification of this effect for Brownian particles became possible only in the late 80s. Since then a variety of experimental investigations on near wall Brownian dynamics by evanescent wave dynamic light scattering (EWDLS) has been published. In this contribution the method of EWDLS will be briefly introduced, experiments at low and high colloid concentration for hard-sphere suspensions, and the theoretical prediction for measured initial slopes of correlation functions will be discussed. On increasing the particle concentration the influence of the wall drag effect is found to diminishes gradually, until it becomes negligible at volume fractions above ϕ 0.35. The effect that a wall exerts on the orientational dynamics was investigated for different kinds of colloids. Experiments, simulations and a virial expansion theory show that rotational dynamics is slowed down as well. However, the effect is prominent in EWDLS only if the particles' short axis is of the order of the evanescent wave penetration depth. The author acknowledges financial support from the EU through FP7, project Nanodirect (Grant 395 No. NMP4-SL-2008-213948).
Solution-processed photodetectors from colloidal silicon nano/micro particle composite.
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.
Nonuniform flow in soft glasses of colloidal rods
NASA Astrophysics Data System (ADS)
Dhont, J. K. G.; Kang, K.; Kriegs, H.; Danko, O.; Marakis, J.; Vlassopoulos, D.
2017-04-01
Despite our reasonably advanced understanding of the dynamics and flow of glasses made of spherical colloids, the role of shape, i.e., the respective behavior of glasses formed by rodlike, particles is virtually unexplored. Recently, long, thin and highly charged rods (fd-virus particles) were found to vitrify in aqueous suspensions at low ionic strength [Phys. Rev. Lett. 110, 015901 (2013), 10.1103/PhysRevLett.110.015901]. The glass transition of these long-ranged repulsive rods occurs at a concentration far above the isotropic-nematic coexistence region and is characterized by the unique arrest of both the dynamics of domains that constitute the chiral-nematic orientational texture, as well as individual rods inside the domains. Hence, two relevant length scales exist: the domain size of a few hundreds of microns, and the rod-cage size of a few microns, inside the domains. We show that the unique dual dynamic arrest and the existing of two widely separated length scales imparts an unprecedented, highly heterogeneous flow behavior with three distinct signatures. Beyond a weak stress plateau at very small shear rates that characterizes the glass, the kinetic arrest of the domain dynamics gives rise to internal fracture, as a result of domain-domain interactions, as well as wall partial slip. It is shown that, on increasing the shear rate, the fractured plug flow changes to a shear-banded flow profile due to the stress response of the kinetically arrested aligned rods within the domains. Shear-gradient banding occurs due to the strong thinning of the uniform chiral-nematic phase within the domains, i.e., complying with the classic shear-banding scenario, giving rise to a stress plateau in the flow curve. Finally, a linear (uniform) velocity profile is found at the highest shear rates. Vorticity banding is also observed at intermediate and high shear rates. These results point to the crucial role of particle shape in tailoring the flow properties of dense colloidal suspensions. Moreover, they strongly support the argument that the origin of shear banding in soft-particle glasses with long-ranged repulsive interactions is fundamentally different from that of hard-particle glasses with short-ranged repulsive interactions.
NASA Astrophysics Data System (ADS)
Zhang, Wenyan; Chen, Jiahua; Wang, Wei; Lu, GongXuan; Hao, Lingyun; Ni, Yaru; Lu, Chunhua; Xu, Zhongzi
2017-03-01
Super-paramagnetic core-shell microspheres were synthesized by ultrasonic assisted routine under low ultrasonic irradiation powers. Compared with conventional routine, ultrasonic effect could not only improve the uniformity of the core-shell structure of Fe3O4@SiO2, but shorten the synthesis time in large scale. Owing to their hydrophilicity and high surface charge, the Fe3O4@SiO2 microspheres could be dispersed well in distilled water to form homogeneous colloidal suspension. The suspensions have favorable magneto-chromatic ability that they sensitively exhibit brilliant colorful ribbons by magnetic attraction. The colorful ribbons, which distributed along the magnetic lines, make morphology of the magnetic fields become "visible" to naked eyed. Those colorful ribbons originate from strong magnetic interaction between the microspheres and magnetic fields. Furthermore, the magneto-chromatic performance is reversible as the colorful ribbons vanished rapidly with the removing of magnetic fields. The silica layer effectively enhanced the acid resistance and surface-oxidation resistance of theFe3O4@SiO2 microspheres, so they could exhibit stable magnetic nature and robust magneto-chromatic property in acid environment.
Column study for the evaluation of the transport properties of polyphenol-coated nanoiron.
Mystrioti, C; Papassiopi, N; Xenidis, A; Dermatas, D; Chrysochoou, M
2015-01-08
Injection of a nano zero valent iron (nZVI) suspension in the subsurface is a remedial option for obtaining the in situ reduction and immobilization of hexavalent chromium in contaminated aquifers. Prerequisite for the successful implementation of this technology is that the nanoparticles form a stable colloidal suspension with good transport properties when delivered in the subsurface. In this study we produced stable suspensions of polyphenol-coated nZVI (GT-nZVI) and we evaluated their transport behavior through representative porous media. Two types of porous materials were tested: (a) silica sand as a typical inert medium and (b) a mixture of calcareous soil and sand. The transport of GT-nZVI through the sand column was effectively described using a classic 1-D convection-dispersion flow equation (CDE) in combination with the colloid filtration theory (CFT). The calculations indicate that nZVI travel distance will be limited in the range 2.5-25cm for low Darcy velocities (0.1-1m/d) and in the order of 2.5m at higher velocities (10m/d). The mobility of GT-nZVI suspension in the soil-sand column is lower and is directly related to the progress of the neutralization reactions between the acidic GT-nZVI suspension and soil calcite. Copyright © 2014 Elsevier B.V. All rights reserved.
Su, Yu; Yang, Guoqing; Lu, Kun; Petersen, Elijah J.; Mao, Liang
2017-01-01
Understanding the colloidal stability of graphene is essential for predicting its transport and ecological risks in aquatic environments. We investigated the agglomeration of 14C-labeled few-layer graphene (FLG) at concentrations spanning nearly four orders of magnitude (2 μg/L to 10 mg/L) using dynamic light scattering and sedimentation measurements. FLG agglomerates formed rapidly in deionized water at concentrations > 3 mg/L. From 1 mg/L to 3 mg/L, salt-induced agglomeration was decreased with dilution of FLG suspensions; the critical coagulation concentration of the more concentrated suspension (3 mg/L) was significantly lower than the dilute suspension (1 mg/L) in the presence of NaCl (1.6 mmol/L and 10 mmol/L, respectively). In contrast, FLG underwent slow agglomeration and settling at concentrations ≤ 0.1 mg/L in NaCl solutions and ambient waters with low ionic strength (< 10 mmol/L). Although salt-induced agglomeration led to 67 % reduction in number of small FLG (25 nm to 50 nm) according to atomic force microscopy characterization, transition from concentrated to dilute suspension retarded the removal of the small FLG. Additionally, the small FLG exhibited greater bioaccumulation in zebrafish embryo and stronger chorion penetration ability than larger ones. These findings suggest that FLG at more environmentally relevant concentration is relatively stable and may have implications for exposure of small FLG to ecological receptors. PMID:27720543
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.
Filter-feeding bivalves store and biodeposit colloidally stable gold nanoparticles.
Hull, Matthew S; Chaurand, Perrine; Rose, Jerome; Auffan, Melanie; Bottero, Jean-Yves; Jones, Jason C; Schultz, Irvin R; Vikesland, Peter J
2011-08-01
Nanoparticles resistant to salt-induced aggregation are continually being developed for biomedical and industrial applications. Because of their colloidal stability these functionalized nanoparticles are anticipated to be persistent aquatic contaminants. Here, we show that Corbicula fluminea, a globally distributed clam that is a known sentinel of aquatic ecosystem contamination, can uptake and biodeposit bovine serum albumin (BSA) stabilized gold nanoparticles. Nanoparticle clearance rates from suspension were dictated by diameter and concentration, with the largest particles cleared most quickly on a mass basis. Particle capture facilitates size-selective 'biopurification' of particle suspensions with nanoscale resolution. Nanoparticles were retained either within the clam digestive tract or excreted in feces. Our results suggest that biotransformation and biodeposition will play a significant role in the fate and transport of persistent nanoparticles in aquatic systems.
NASA Astrophysics Data System (ADS)
Lin, Neil Y. C.; Bierbaum, Matthew; Cohen, Itai
2017-09-01
By combining confocal microscopy and stress assessment from local structural anisotropy, we directly measure stresses in 3D quiescent colloidal liquids. Our noninvasive and nonperturbative method allows us to measure forces ≲50 fN with a small and tunable probing volume, enabling us to resolve the stress fluctuations arising from particle thermal motions. We use the Green-Kubo relation to relate these measured stress fluctuations to the bulk Brownian viscosity at different volume fractions, comparing against simulations and conventional rheometry measurements. We find that the Green-Kubo analysis gives excellent agreement with these prior results, suggesting that similar methods could be applied to investigations of local flow properties in many poorly understood far-from-equilibrium systems, including suspensions that are glassy, strongly sheared, or highly confined.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Leonard, T.; Lander, B.; Seifert, U.
2013-11-28
We discuss the stochastic thermodynamics of systems that are described by a time-dependent density field, for example, simple liquids and colloidal suspensions. For a time-dependent change of external parameters, we show that the Jarzynski relation connecting work with the change of free energy holds if the time evolution of the density follows the Kawasaki-Dean equation. Specifically, we study the work distributions for the compression and expansion of a two-dimensional colloidal model suspension implementing a practical coarse-graining scheme of the microscopic particle positions. We demonstrate that even if coarse-grained dynamics and density functional do not match, the fluctuation relations for themore » work still hold albeit for a different, apparent, change of free energy.« less
Tran, Emily; Klein Ben-David, Ofra; Teutch, Nadya; Weisbrod, Noam
2016-09-01
Colloid facilitated transport of radionuclides has been implicated as a major transport vector for leaked nuclear waste in the subsurface. Sorption of radionuclides onto mobile carrier colloids such as bentonite and humic acid often accelerates their transport through saturated rock fractures. Here, we employ column studies to investigate the impact of intrinsic, bentonite and humic acid colloids on the transport and recovery of Ce(III) through a fractured chalk core. Ce(III) recovery where either bentonite or humic colloids were added was 7.7-26.9% Ce for all experiments. Greater Ce(III) recovery was observed when both types of carrier colloids were present (25.4-37.4%). When only bentonite colloids were present, Ce(III) appeared to be fractionated between chemical sorption to the bentonite colloid surfaces and heteroaggregation of bentonite colloids with intrinsic carbonate colloids, precipitated naturally in solution. However, scanning electron microscope (SEM) images and colloid stability experiments reveal that in suspensions of humic acid colloids, colloid-facilitated Ce(III) migration results only from the latter attachment mechanism rather than from chemical sorption. This observed heteroaggregation of different colloid types may be an important factor to consider when predicting potential mobility of leaked radionuclides from geological repositories for spent fuel located in carbonate rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.
Attachment dynamics of Photosystem I on nano-tailored surfaces for photovoltaic applications
NASA Astrophysics Data System (ADS)
Mukherjee, Dibyendu; Bruce, Barry D.; Khomami, Bamin
2010-03-01
Photosystem I (PSI), a biological photodiode, is a supra-molecular protein complex that charge separates upon exposure to light. Effective use of photo-electrochemical activities of PSI for hybrid photovoltaic (PV) device fabrications requires optimal encapsulation of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface attachment dynamics of PSI deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate/Au SAM substrates, thereby resulting in complex structural arrangements which affect the electron transfer and capture pathway of PSI. We present surface topographical, specific adsorption and polarization fluorescence characterizations of PSI/Au SAM substrates to elucidate the protein-surface interaction kinetics as well as the directional attachment dynamics of PSI. Our final goal is to enable site-specific homogeneous attachment of directionally aligned PSI onto chemically tailored nano-patterned substrates.
Hybrid Hydroxyapatite Nanoparticle Colloidal Gels are Injectable Fillers for Bone Tissue Engineering
Gu, Zhen; Jamal, Syed; Detamore, Michael S.
2013-01-01
Injectable bone fillers have emerged as an alternative to the invasive surgery often required to treat bone defects. Current bone fillers may benefit from improvements in dynamic properties such as shear thinning during injection and recovery of material stiffness after placement. Negatively charged inorganic hydroxyapatite (HAp) nanoparticles (NPs) were assembled with positively charged organic poly(d,l-lactic-co-glycolic acid) (PLGA) NPs to create a cohesive colloidal gel. This material is held together by electrostatic forces that may be disrupted by shear to facilitate extrusion, molding, or injection. Scanning electron micrographs of the dried colloidal gels showed a well-organized, three-dimensional porous structure. Rheology tests revealed that certain colloidal gels could recover after being sheared. Human umbilical cord mesenchymal stem cells were also highly viable when seeded on the colloidal gels. HAp/PLGA NP colloidal gels offer an attractive scheme for injectable filling and regeneration of bone tissue. PMID:23815275
NASA Astrophysics Data System (ADS)
Wiśniewska, Małgorzata; Ostolska, Iwona; Szewczuk-Karpisz, Katarzyna; Chibowski, Stanisław; Terpiłowski, Konrad; Gun'ko, Vladimir Moiseevich; Zarko, Vladimir Iljich
2015-01-01
A new adsorbent consisting of fumed, mixed alumina, silica, and titania in various proportions (AST 50) was investigated. The studied material was prepared by chemical vapor deposition method. The diameter of AST 50 primary particles was equal to about 51 nm which denotes that it can be classified as a nanomaterial. In the presented paper, the adsorption properties of polyvinyl alcohol on the ternary oxide were investigated. The polymer macromolecules were characterized by two different molecular weights and degree of hydrolysis. The polymer adsorption reaches the maximum at pH 3 and decreases with the solution pH rise. The reduction of the adsorbed PVA macromolecules is related to the electrostatic repulsion forces occurring in the studied system. The AST 50 point of zero charge (pHpzc) obtained from the potentiometric titration is equal to 4.7. Due to the nonionic character of the analyzed macromolecular compound, the polymer attendance has an insignificant effect on the AST 50 surface charge density. In the case of the adsorbent particles zeta potential, the obtained dependencies are different in the absence and presence of PVA. The shift of the slipping plane and displacement of the counter-ions from Stern layer by the adsorbed polymer chains have the greatest effect on the ζ potential value. The stability measurements indicate that the AST 50 suspensions in the presence of the background electrolyte at pH 3 and 6 are unstable. In turn, in an alkaline medium the mixed oxide suspensions exhibit the highest durability, which is a result of a large number of the negative charges on the AST 50 surface. The addition of PVA 100 significantly improves the suspension stability at pH 3 and 6; at higher pH value, the polymer presence does not influence the system durability. It is related to the steric and electrosteric stabilization of the colloidal particles by the adsorbed polyvinyl alcohol macromolecules.
Microrheology close to an equilibrium phase transition
DOE Office of Scientific and Technical Information (OSTI.GOV)
Reinhardt, J.; Scacchi, A.; Brader, J. M., E-mail: joseph.brader@unifr.ch
2014-04-14
We investigate the microstructural and microrheological response to a tracer particle of a two-dimensional colloidal suspension under thermodynamic conditions close to a liquid-gas phase boundary. On the liquid side of the binodal, increasing the velocity of the (repulsive) tracer leads to the development of a pronounced cavitation bubble, within which the concentration of colloidal particles is strongly depleted. The tendency of the liquid to cavitate is characterized by a dimensionless “colloidal cavitation” number. On the gas side of the binodal, a pulled (attractive) tracer leaves behind it an extended trail of colloidal liquid, arising from downstream advection of a wettingmore » layer on its surface. For both situations the velocity dependent friction is calculated.« less
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.
NASA Astrophysics Data System (ADS)
Gleber, S.-C.; Vogt, S.; Niemeyer, J.; Finney, L.; McNulty, I.; Thieme, J.
2011-09-01
A prominent feature of soil colloids is their huge specific surface. It determines colloidal properties such as adsorption capacity or diffusion. The colloidal interactions differ significantly from the behavior of the same materials in a bulk system. Interactions in the colloidal regime are crucial, for example, for the transport and release of nutrients and toxicants in soils, which then influences directly the growth of plants. However, there is still a need for more analytical resources to study those interactions. To reveal the correlation of the particular trace elements and their distribution in correlation to colloidal interactions as well as changing pH values, experiments at the hard x-ray fluorescence microprobe at beamline 2-ID-E of the Advanced Photon Source (APS), were performed with colloidal clay and soil samples in an aqueous environment as naturally relevant. To obtain further spatial information, stereo imaging has been used. To study the dynamical behavior of these colloidal suspensions at changing pH, a wet sample chamber allowing in situ manipulation was developed and utilized.
Structural evolution of Colloidal Gels under Flow
NASA Astrophysics Data System (ADS)
Boromand, Arman; Maia, Joao; Jamali, Safa
Colloidal suspensions are ubiquitous in different industrial applications ranging from cosmetic and food industries to soft robotics and aerospace. Owing to the fact that mechanical properties of colloidal gels are controlled by its microstructure and network topology, we trace the particles in the networks formed under different attraction potentials and try to find a universal behavior in yielding of colloidal gels. Many authors have implemented different simulation techniques such as molecular dynamics (MD) and Brownian dynamics (BD) to capture better picture during phase separation and yielding mechanism in colloidal system with short-ranged attractive force. However, BD neglects multi-body hydrodynamic interactions (HI) which are believed to be responsible for the second yielding of colloidal gels. We envision using dissipative particle dynamics (DPD) with modified depletion potential and hydrodynamic interactions, as a coarse-grain model, can provide a robust simulation package to address the gel formation process and yielding in short ranged-attractive colloidal systems. The behavior of colloidal gels with different attraction potentials under flow is examined and structural fingerprints of yielding in these systems will be discussed.
NASA Astrophysics Data System (ADS)
Li, WeiBin; Lan, Ding; Sun, ZhiBin; Geng, BaoMing; Wang, XiaoQing; Tian, WeiQian; Zhai, GuangJie; Wang, YuRen
2016-05-01
To study the self-assembly behavior of colloidal spheres in the solid/liquid interface and elucidate the mechanism of liquid crystal phase transition under microgravity, a Colloidal Material Box (CMB) was designed which consists of three modules: (i) colloidal evaporation experimental module, made up of a sample management unit, an injection management unit and an optical observation unit; (ii) liquid crystal phase transition experimental module, including a sample management unit and an optical observation unit; (iii) electronic control module. The following two experimental plans will be performed inside the CMB aboard the SJ-10 satellite in space. (i) Self-assembly of colloidal spheres (with and without Au shell) induced by droplet evaporation, allowing observation of the dynamic process of the colloidal spheres within the droplet and the change of the droplet outer profile during evaporation; (ii) Phase behavior of Mg2Al LDHs suspensions in microgravity. The experimental results will be the first experimental observations of depositing ordered colloidal crystals and their self-assembly behavior under microgravity, and will illustrate the influence of gravity on liquid crystal phase transition.
Direct observation of impact propagation and absorption in dense colloidal monolayers
NASA Astrophysics Data System (ADS)
Buttinoni, Ivo; Cha, Jinwoong; Lin, Wei-Hsun; Job, Stéphane; Daraio, Chiara; Isa, Lucio
2017-11-01
Dense colloidal suspensions can propagate and absorb large mechanical stresses, including impacts and shocks. The wave transport stems from the delicate interplay between the spatial arrangement of the structural units and solvent-mediated effects. For dynamic microscopic systems, elastic deformations of the colloids are usually disregarded due to the damping imposed by the surrounding fluid. Here, we study the propagation of localized mechanical pulses in aqueous monolayers of micron-sized particles of controlled microstructure. We generate extreme localized deformation rates by exciting a target particle via pulsed-laser ablation. In crystalline monolayers, stress propagation fronts take place, where fast-moving particles (V approximately a few meters per second) are aligned along the symmetry axes of the lattice. Conversely, more viscous solvents and disordered structures lead to faster and isotropic energy absorption. Our results demonstrate the accessibility of a regime where elastic collisions also become relevant for suspensions of microscopic particles, behaving as “billiard balls” in a liquid, in analogy with regular packings of macroscopic spheres. We furthermore quantify the scattering of an impact as a function of the local structural disorder.
Direct observation of impact propagation and absorption in dense colloidal monolayers
Cha, Jinwoong; Lin, Wei-Hsun; Job, Stéphane; Daraio, Chiara
2017-01-01
Dense colloidal suspensions can propagate and absorb large mechanical stresses, including impacts and shocks. The wave transport stems from the delicate interplay between the spatial arrangement of the structural units and solvent-mediated effects. For dynamic microscopic systems, elastic deformations of the colloids are usually disregarded due to the damping imposed by the surrounding fluid. Here, we study the propagation of localized mechanical pulses in aqueous monolayers of micron-sized particles of controlled microstructure. We generate extreme localized deformation rates by exciting a target particle via pulsed-laser ablation. In crystalline monolayers, stress propagation fronts take place, where fast-moving particles (V approximately a few meters per second) are aligned along the symmetry axes of the lattice. Conversely, more viscous solvents and disordered structures lead to faster and isotropic energy absorption. Our results demonstrate the accessibility of a regime where elastic collisions also become relevant for suspensions of microscopic particles, behaving as “billiard balls” in a liquid, in analogy with regular packings of macroscopic spheres. We furthermore quantify the scattering of an impact as a function of the local structural disorder. PMID:29087329
NASA Astrophysics Data System (ADS)
Johnson, William; Farnsworth, Anna; Vanness, Kurt; Hilpert, Markus
2017-04-01
The key element of a mechanistic theory to predict colloid attachment in porous media under environmental conditions where colloid-collector repulsion exists (unfavorable conditions for attachment) is representation of the nano-scale surface heterogeneity (herein called discrete heterogeneity) that drives colloid attachment under unfavorable conditions. The observed modes of colloid attachment under unfavorable conditions emerge from simulations that incorporate discrete heterogeneity. Quantitative prediction of attachment (and detachment) requires capturing the sizes, spatial frequencies, and other properties of roughness asperities and charge heterodomains in discrete heterogeneity representations of different surfaces. The fact that a given discrete heterogeneity representation will interact differently with different-sized colloids as well as different ionic strengths for a given sized colloid allows backing out representative discrete heterogeneity via comparison of simulations to experiments performed across a range of colloid size, solution IS, and fluid velocity. This has been achieved on unfavorable smooth surfaces yielding quantitative prediction of attachment, and qualitative prediction of detachment in response to ionic strength or flow perturbations. Extending this treatment to rough surfaces, and representing the contributions of nanoscale roughness as well as charge heterogeneity is a focus of this talk. Another focus of this talk is the upscaling the pore scale simulations to produce contrasting breakthrough-elution behaviors at the continuum (column) scale that are observed, for example, for different-sized colloids, or same-sized colloids under different ionic strength conditions. The outcome of mechanistic pore scale simulations incorporating discrete heterogeneity and subsequent upscaling is that temporal processes such as blocking and ripening will emerge organically from these simulations, since these processes fundamentally stem from the limited sites available for attachment as represented in discrete heterogeneity.
Cadmium removal from water using thiolactic acid-modified titanium dioxide nanoparticles.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Skubal, L. R.; Meshkov, N. K.; Rajh, T.
2002-05-31
This study investigated the use of titanium dioxide (TiO{sub 2}) nanoparticles to remove aqueous cadmium from simulated wastewaters. Nanosized (45 A) colloids of anatase TiO{sub 2} were synthesized through the controlled hydrolysis of TiCl4 and their surfaces modified with the bidental chelating agent thiolactic acid (TLA). Colloids were introduced into 65 ppm cadmium-laden waters, and the suspensions were purged aerobically, anoxically with an inert gas, or by a sequential aerobic/anoxic purge. Suspensions were illuminated with 253.7 nm light. In each experiment, samples were taken from the reactor, filtered, and the filtrates analyzed by atomic absorption spectroscopy for residual cadmium. Resultsmore » from the aerobic experiments exhibited minimal (approximately 10%) removal of the cadmium from solution and no reduction of the metal on either the modified or the unmodified colloid. Anoxic results were more promising, showing no cadmium reduction on the unmodified colloid but a 40% adsorption and reduction (from a +2 valence state to elemental cadmium as determined by methyl viologen tests) of cadmium on TLA-modified colloid in the presence of light. Results from the mixed atmospheric conditions fared the best and demonstrated that in the absence of light, approximately 20% of aqueous cadmium was sorbed to the modified colloid via a Freundlich adsorption isotherm. Upon illumination, greater than 90% of cadmium was removed by both adsorption and reduction processes onto the TLA-modified TiO{sub 2}. These removal and reduction processes were catalytic in nature. Results from this study are significant because to date, no other research in the literature has been able to accomplish cadmium removal and reduction using TiO{sub 2}.« less
Potentiometric Titrations for Measuring the Capacitance of Colloidal Photodoped ZnO Nanocrystals.
Brozek, Carl K; Hartstein, Kimberly H; Gamelin, Daniel R
2016-08-24
Colloidal semiconductor nanocrystals offer a unique opportunity to bridge molecular and bulk semiconductor redox phenomena. Here, potentiometric titration is demonstrated as a method for quantifying the Fermi levels and charging potentials of free-standing colloidal n-type ZnO nanocrystals possessing between 0 and 20 conduction-band electrons per nanocrystal, corresponding to carrier densities between 0 and 1.2 × 10(20) cm(-3). Potentiometric titration of colloidal semiconductor nanocrystals has not been described previously, and little precedent exists for analogous potentiometric titration of any soluble reductants involving so many electrons. Linear changes in Fermi level vs charge-carrier density are observed for each ensemble of nanocrystals, with slopes that depend on the nanocrystal size. Analysis indicates that the ensemble nanocrystal capacitance is governed by classical surface electrical double layers, showing no evidence of quantum contributions. Systematic shifts in the Fermi level are also observed with specific changes in the identity of the charge-compensating countercation. As a simple and contactless alternative to more common thin-film-based voltammetric techniques, potentiometric titration offers a powerful new approach for quantifying the redox properties of colloidal semiconductor nanocrystals.
Rodríguez-Torres, Maria del Pilar; Díaz-Torres, Luis Armando; Romero-Servin, Sergio
2014-01-01
Reactive and pharmaceutical-grade heparins were used as biologically compatible reducing and stabilizing agents to photochemically synthesize colloidal gold nanoparticles. Aggregates and anisotropic shapes were obtained photochemically under UV black-light lamp irradiation (λ = 366 nm). Heparin-functionalized gold nanoparticles were characterized by Scanning Electron Microscopy and UV-Vis spectroscopy. The negatively charged colloids were used for the Surface Enhanced Raman Spectroscopy (SERS) analysis of differently charged analytes (dyes). Measurements of pH were taken to inspect how the acidity of the medium affects the colloid-analyte interaction. SERS spectra were taken by mixing the dyes and the colloidal solutions without further functionalization or addition of any aggregating agent. PMID:25342319
Márquez-Islas, Roberto; Sánchez-Pérez, Celia; García-Valenzuela, Augusto
2014-02-01
We describe a method for obtaining the refractive index (RI), size, and concentration of nonabsorbing nanoparticles in suspension from relatively simple optical measurements. The method requires measuring the complex effective RI of two dilute suspensions of the particles in liquids of different refractive indices. We describe the theoretical basis of the proposed method and provide experimental results validating the procedure.
NASA Astrophysics Data System (ADS)
Antonopoulou, Evangelia; Rohmann-Shaw, Connor F.; Sykes, Thomas C.; Cayre, Olivier J.; Hunter, Timothy N.; Jimack, Peter K.
2018-03-01
Understanding the sedimentation behaviour of colloidal suspensions is crucial in determining their stability. Since sedimentation rates are often very slow, centrifugation is used to expedite sedimentation experiments. The effect of centrifugal acceleration on sedimentation behaviour is not fully understood. Furthermore, in sedimentation models, interparticle interactions are usually omitted by using the hard-sphere assumption. This work proposes a one-dimensional model for sedimentation using an effective maximum volume fraction, with an extension for sedimentation under centrifugal force. A numerical implementation of the model using an adaptive finite difference solver is described. Experiments with silica suspensions are carried out using an analytical centrifuge. The model is shown to be a good fit with experimental data for 480 nm spherical silica, with the effects of centrifugation at 705 rpm studied. A conversion of data to Earth gravity conditions is proposed, which is shown to recover Earth gravity sedimentation rates well. This work suggests that the effective maximum volume fraction accurately captures interparticle interactions and provides insights into the effect of centrifugation on sedimentation.
Unsteady sedimentation of flocculating non-Brownian suspensions
NASA Astrophysics Data System (ADS)
Zinchenko, Alexander
2017-11-01
Microstructural evolution and temporal dynamics of the sedimentation rate U(t) are studied for a monodisperse suspension of non-Brownian spherical particles subject to van der Waals attraction and electrostatic repulsion in the realistic range of colloidal parameters (Hamaker constant, surface potential, double layer thickness etc.). A novel economical high-order multipole algorithm is used to fully resolve hydrodynamical interactions in the dynamical simulations with up to 500 spheres in a periodic box and O(106) time steps, combined with geometry perturbation to incorporate lubrication and extend the solution to arbitrarily small particle separations. The total colloidal force near the secondary minimum often greatly exceeds the effective gravity/buoyancy force, resulting in the formation of strong but flexible bonds and large clusters as the suspension evolves from an initial well-mixed state of non-aggregated spheres. Ensemble averaging over many initial configurations is used to predict U(t) for particle volume fractions between 0.1 and 0.25. The results are fully convergent, system-size independent and cover a 2-2.5 fold growth of U(t) after a latency time.
Multi-scale kinetics of a field-directed colloidal phase transition.
Swan, James W; Vasquez, Paula A; Whitson, Peggy A; Fincke, E Michael; Wakata, Koichi; Magnus, Sandra H; De Winne, Frank; Barratt, Michael R; Agui, Juan H; Green, Robert D; Hall, Nancy R; Bohman, Donna Y; Bunnell, Charles T; Gast, Alice P; Furst, Eric M
2012-10-02
Polarizable colloids are expected to form crystalline equilibrium phases when exposed to a steady, uniform field. However, when colloids become localized this field-induced phase transition arrests and the suspension persists indefinitely as a kinetically trapped, percolated structure. We anneal such gels formed from magneto-rheological fluids by toggling the field strength at varied frequencies. This processing allows the arrested structure to relax periodically to equilibrium--colloid-rich, cylindrical columns. Two distinct growth regimes are observed: one in which particle domains ripen through diffusive relaxation of the gel, and the other where the system-spanning structure collapses and columnar domains coalesce apparently through field-driven interactions. There is a stark boundary as a function of magnetic field strength and toggle frequency distinguishing the two regimes. These results demonstrate how kinetic barriers to a colloidal phase transition are subverted through measured, periodic variation of driving forces. Such directed assembly may be harnessed to create unique materials from dispersions of colloids.
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.
NASA Astrophysics Data System (ADS)
Zaccone, Alessio; Gentili, Daniele; Wu, Hua; Morbidelli, Massimo
2010-04-01
The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.
Code of Federal Regulations, 2011 CFR
2011-10-01
..., charges, classifications, rules or regulations. 565.9 Section 565.9 Shipping FEDERAL MARITIME COMMISSION... Commission review, suspension and prohibition of rates, charges, classifications, rules or regulations. (a)(1..., charges, classifications, rules or regulations) from the Commission, each controlled carrier shall file a...
Code of Federal Regulations, 2010 CFR
2010-10-01
..., charges, classifications, rules or regulations. 565.9 Section 565.9 Shipping FEDERAL MARITIME COMMISSION... Commission review, suspension and prohibition of rates, charges, classifications, rules or regulations. (a)(1..., charges, classifications, rules or regulations) from the Commission, each controlled carrier shall file a...
Dynamic self-assembly and directed flow of rotating colloids in microchannels
NASA Astrophysics Data System (ADS)
Götze, Ingo O.; Gompper, Gerhard
2011-09-01
Nonequilibrium structure formation and dynamics in suspensions of superparamagnetic colloids driven by an external rotating magnetic field are studied by particle-based mesoscale hydrodynamics simulations in confined geometry. We address the fundamental question how the rotation of the colloids about their own axes can be converted into a translational motion by breaking the symmetry of the confining geometry. We study a two-dimensional system of colloids with short-range repulsive interactions, which mimics flow in shallow microchannels. In straight channels, we observe a two-way traffic but—for symmetry reasons—no net transport. However, by keeping some colloids fixed near one of the two walls, net transport can be achieved. This approach allows the control and switchability of the flow in complex microchannel networks. A minimal geometry that fulfills the requirement of broken symmetry are ring channels. We determine the translational velocity of the spinning colloids and study its dependence on the channel width for various median radii. We conclude that spinning colloids present a promising alternative for flow generation and control in microfluidic devices.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jadav, Mudra; Patel, Rajesh, E-mail: rjp@mkbhavuni.edu.in, E-mail: rpat7@yahoo.co
Here we present a technique using magnetic nanofluid to induce bidispersed suspension of nonmagnetic particles to assemble into colloidal chain, triangle, rectangle, ring-flower configurations. By changing the amplitude and direction of the magnetic field, we could tune the structure of nonmagnetic particles in magnetic nanofluid. The structures are assembled using magneto static interactions between effectively nonmagnetic particles dispersed in magnetizable magnetic nanofluid. The assembly of complex structures out of simple colloidal building blocks is of practical interest in photonic crystals and DNA biosensors.
NASA Astrophysics Data System (ADS)
Yethiraj, Anand
2010-03-01
External fields affect self-organization in Brownian colloidal suspensions in many different ways [1]. High-frequency time varying a.c. electric fields can induce effectively quasi-static dipolar inter-particle interactions. While dipolar interactions can provide access to multiple open equilibrium crystal structures [2] whose origin is now reasonably well understood, they can also give rise to competing interactions on short and long length scales that produce unexpected low-density ordered phases [3]. Farther from equilibrium, competing external fields are active in colloid spincoating. Drying colloidal suspensions on a spinning substrate produces a ``perfect polycrystal'' - tiny polycrystalline domains that exhibit long-range inter-domain orientational order [4] with resultant spectacular optical effects that are decoupled from single-crystallinity. High-speed movies of drying crystals yield insights into mechanisms of structure formation. Phenomena arising from multiple spatially- and temporally-varying external fields can give rise to further control of order and disorder, with potential application as patterned (photonic and magnetic) materials. [4pt] [1] A. Yethiraj, Soft Matter 3, 1099 (2007). [2] A. Yethiraj, A. van Blaaderen, Nature 421, 513 (2003). [3] A.K. Agarwal, A. Yethiraj, Phys. Rev. Lett ,102, 198301 (2009). [4] C. Arcos, K. Kumar, W. Gonz'alez-Viñas, R. Sirera, K. Poduska, A. Yethiraj, Phys. Rev. E ,77, 050402(R) (2008).
Liquid crystal-type assembly of native cellulose-glucuronoxylans extracted from plant cell wall.
Reis, D; Vian, B; Chanzy, H; Roland, J C
1991-01-01
In numerous plant cell walls, the cellulose microfibrils are arranged in a helicoidal pattern which has been considered as an analog to a cholesteric order. Here, we report on the spontaneous helicoidal organization which occurs in acellular conditions from aqueous suspensions of cellulose. The cellulosic mucilage of mature seeds of quince (Cydonia oblonga L) was studied both in situ (pre-release mucilage) and after water extraction and in in vitro re-assembly (prolonged high speed ultracentrifugation, further progressive dehydration and embedding in LR White methacrylate or hydrosoluble melamine resin). The cellulosic component was characterized by the use of cellobiohydrolase (CBH1) bound to colloidal gold, and the glucuronic acid residues of the xylan matrix were characterized by the use of cationised gold. Inside the seeds, the pre-release mucilage is mostly helicoidal, with the occurrence of more or less ordered domains, which indicate a fluid organization relevant to an actual liquid crystal state. Cytochemical tests revealed the tight association between cellulose and glucuronoxylans, the latter constituting a charged coat around each microfibril. Following the hydration of the seed, a cellulosic suspension was extracted in which microfibrils were totally dispersed. The progressive dehydration of the suspension gave rise to concentrated viscous drops. Ultrastructural observations revealed the occurrence of multidomain organization, from non-ordered to cholesteric-like regions, revealing that the mucilage is at the same time crystalline and liquid. This constitutes the first demonstration that liquid crystal type assemblies can arise from crystalline and biological cellulose in aqueous suspension. It strengthens the hypothesis that a transient liquid crystal state must occur during the cellulose ordering. The possible morphogenetic role of the glucuronoxylans in the cholesteric organization of the cellulose is discussed.
Deák, Ágota; Janovák, László; Tallósy, Szabolcs Péter; Bitó, Tamás; Sebők, Dániel; Buzás, Norbert; Pálinkó, István; Dékány, Imre
2015-02-17
Aqueous suspensions of spherical ZnMgAl-layered double hydroxides [LDH(sph)] and antibacterial silver nanoparticles (AgNPs) deposited on the lamellae of montmorillonite were used for the synthesis of composites, which behave like coherent gels at low pH (≲4.5) and incoherent sols at higher pH (≳4.5). The composition of the composite was chosen as LDH(sph)/Ag°-montm. = 25:75 wt % in order to ensure a sol-gel transition that can also be characterized by viscometry. This pH-sensitive heterocoagulated system consisting of oppositely charged colloid particles was suitable for the release of antimicrobial AgNPs immobilized on the clay lamellae via a pH-controlled gel-sol transition. The heterocoagulation process was also characterized by surface charge titration measurements. Spherical LDH/Ag°-montmorillonite composite samples were identified by X-ray diffraction (XRD) measurements. The morphological properties of the composites were studied, and the presence of the heterocoagulated structure was confirmed by scanning electron microscopy (SEM). The nanoscale structure of the LDH(sph)-Ag°-montmorillonite composite obtained was also verified by small-angle X-ray scattering (SAXS), and the rheological characteristics were studied at various pH values. The viscosity and yield value of the composite decreased by an order of magnitude upon increasing the pH from 3.0 to 5.5. The sol-gel transition of the composite suspension was reversible in the previously mentioned pH range.
Illustrating Chemical Concepts through Food Systems: Introductory Chemistry Experiments.
ERIC Educational Resources Information Center
Chambers, E., IV; Setser, C. S.
1980-01-01
Demonstrations involving foods that illustrate chemical concepts are described, including vaporization of liquids and Graham's law of diffusion, chemical reaction rates, adsorption, properties of solutions, colloidal dispersions, suspensions, and hydrogen ion concentration. (CS)
Powder agglomeration in a microgravity environment
NASA Technical Reports Server (NTRS)
Cawley, James D.
1994-01-01
This is the final report for NASA Grant NAG3-755 entitled 'Powder Agglomeration in a Microgravity Environment.' The research program included both two types of numerical models and two types of experiments. The numerical modeling included the use of Monte Carlo type simulations of agglomerate growth including hydrodynamic screening and molecular dynamics type simulations of the rearrangement of particles within an agglomerate under a gravitational field. Experiments included direct observation of the agglomeration of submicron alumina and indirect observation, using small angle light scattering, of the agglomeration of colloidal silica and aluminum monohydroxide. In the former class of experiments, the powders were constrained to move on a two-dimensional surface oriented to minimize the effect of gravity. In the latter, some experiments involved mixture of suspensions containing particles of opposite charge which resulted in agglomeration on a very short time scale relative to settling under gravity.
The Photo-Physics of Polythiophene Nanoparticles for Biological Applications.
Bargigia, Ilaria; Zucchetti, Elena; Srimath Kandada, Ajay Ram; Moreira, Miguel; Bossio, Caterina; Wong, Walter; Miranda, Paulo; Decuzzi, Paolo; Soci, Cesare; D'Andrea, Cosimo; Lanzani, Guglielmo
2018-05-01
In this work the photo-physics of poly(3-hexyltiophene) nanoparticles (NPs) is investigated in the context of their biological applications. The NPs made as colloidal suspensions in aqueous buffers present a distinct absorption band in the low energy region. Based on systematic analysis of absorption and transient absorption spectra taken under different pH conditions, this band is associated to charge transfer states generated by the polarization of loosely bound polymer chains and originated from complexes formed with electron withdrawing species. Importantly, the ground state depletion of these states upon photo-excitation is active even in the microsecond timescales, suggesting that they act as precursor states for long-living polarons which could be beneficial for cellular stimulation. Preliminary results of transient absorption microscopy of NPs internalized within the cells reveal the presence of long-living species, further substantiating their relevance in bio-interfaces. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Anions adsorption onto nanoparticles: effects on colloid stability and mobility in the environment
NASA Astrophysics Data System (ADS)
Missana, Tiziana; Benedicto, Ana; Mayordomo, Natalia; Alonso, Ursula
2013-04-01
Nanoparticles and colloids can enhance the contaminant transport in groundwater, if the contaminant is irreversibly adsorbed onto their surface; additionally colloids must be stable and mobile under the chemical conditions of the environment of interest. Colloid stability and mobility are factors directly related to the chemistry of the water, which determines the charge and size of the particles, but these colloidal properties can also be affected by the contaminant adsorption. This last point, which is potentially very relevant on the overall colloid-driven transport, is scarcely investigated. The evaluation of the stability of a colloidal system is generally carried out by measuring the aggregation kinetic after the change of a specific chemical condition, mainly pH or ionic strength of the aqueous solution. The effect of anion adsorption onto the stability of colloidal systems is mostly neglected. Parameters of the nanoparticles,as the point of zero charge (pH PCZ) or the isoelectric point (pH IEP) are determined with "inert" electrolytes and this might not be representative of their real behavior in natural systems. In this work, the effects of the Se(IV) (selenite) adsorption on alumina (Al2O3) nanoparticles have been analyzed. Selenite adsorption was studied in a wide range of pH (2-12) and ionic strengths (0.0005 - 0.1 M in NaClO4) and the effect of the adsorption on the main properties of the colloids (size and charge) were analyzed. Se adsorption on Al2O3 is almost independent of the ionic strength and decreases with increasing pH; sorption data were successfully fit by surface complexation modeling. Selenite adsorption (at medium-high surface occupancies) clearly affected the stability of Al2O3 colloids, with a clear shift of the isoelectric point towards more acid pH and enhancing colloid aggregation when the ionic strength increases. Considering the obtained results, the effect of anions in the chemical composition of natural water, frequently not accounted for in stability studies, will be discussed, as well as their implications on possible colloid-driven selenite transport in the environment.
Manipulating the Coffee-Ring Effect: Interactions at Work.
Anyfantakis, Manos; Baigl, Damien
2015-07-31
The evaporation of a drop of colloidal suspension pinned on a substrate usually results in a ring of particles accumulated at the periphery of the initial drop. Intense research has been devoted to understanding, suppressing and ultimately controlling this so-called coffee-ring effect (CRE). Although the crucial role of flow patterns in the CRE has been thoroughly investigated, the effect of interactions on this phenomenon has been largely neglected. This Concept paper reviews recent works in this field and shows that the interactions of colloids with (and at) liquid-solid and liquid-gas interfaces as well as bulk particle-particle interactions drastically affect the morphology of the deposit. General rules are established to control the CRE by tuning these interactions, and guidelines for the rational physicochemical formulation of colloidal suspensions capable of depositing particles in desirable patterns are provided. This opens perspectives for the reliable control of the CRE in real-world formulations and creates new paradigms for flexible particle patterning at all kinds of interfaces as well for the exploitation of the CRE as a robust and inexpensive diagnostic tool. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Choi, Young Joon; Jorshari, Razzi Movassaghi; Djilali, Ned
2015-03-10
Direct numerical simulations of the flow-nanoparticle interaction in a colloidal suspension are presented using an extended finite element method (XFEM) in which the dynamics of the nanoparticles is solved in a fully-coupled manner with the flow. The method is capable of accurately describing solid-fluid interfaces without the need of boundary-fitted meshes to investigate the dynamics of particles in complex flows. In order to accurately compute the high interparticle shear stresses and pressures while minimizing computing costs, an adaptive meshing technique is incorporated with the fluid-structure interaction algorithm. The particle-particle interaction at the microscopic level is modeled using the Lennard-Jones (LJ)more » potential and the corresponding potential parameters are determined by a scaling procedure. The study is relevant to the preparation of inks used in the fabrication of catalyst layers for fuel cells. In this paper, we are particularly interested in investigating agglomeration of the nanoparticles under external shear flow in a sliding bi-periodic Lees-Edwards frame. The results indicate that the external shear has a crucial impact on the structure formation of colloidal particles in a suspension.« less
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.
NASA Technical Reports Server (NTRS)
Tong, Penger
1996-01-01
In this paper we focus on the polymer-induced depletion attraction and its effect on colloidal sedimentation in colloid-polymer mixtures. We first report a small angle neutron scattering (SANS) study of the depletion effect in a mixture of hard-sphere-like colloid and non-adsorbing polymer. Then we present results of our recent sedimentation measurements in the same colloid-polymer mixture. A key parameter in controlling the sedimentation of heavy colloidal particles is the interparticle potential U(tau), which is the work required to bring two colloidal particles from infinity to a distance tau under a give solvent condition. This potential is known to affect the average settling velocity of the particles and experimentally one needs to have a way to continuously vary U(tau) in order to test the theory. The interaction potential U(tau) can be altered by adding polymer molecules into the colloidal suspension. In a mixture of colloid and non-adsorbing polymer, the potential U(tau) can develop an attractive well because of the depletion effect, in that the polymer chains are expelled from the region between two colloidal particles when their surface separation becomes smaller than the size of the polymer chains. The exclusion of polymer molecules from the space between the colloidal particles leads to an unbalanced osmotic pressure difference pushing the colloidal particles together, which results in an effective attraction between the two colloidal particles. The polymer-induced depletion attraction controls the phase stability of many colloid-polymer mixtures, which are directly of interest to industry.
Dimic-Misic, Katarina; Hummel, Michael; Paltakari, Jouni; Sixta, Herbert; Maloney, Thad; Gane, Patrick
2015-05-15
Suspensions of mineral pigment and cellulose fibrillar derivatives are materials regularly found in the forest products industries, particularly in paper and board production. Many manufacturing processes, including forming and coating employ flow geometries incorporating extensional flow. Traditionally, colloidal mineral pigment suspensions have been considered to show little to no non-linear behaviour in extensional viscosity. Additionally, recently, nanofibrillar materials, such as microfibrillar (MFC) and nanofibrillar cellulose (NFC), collectively termed MNFC, have been confirmed by their failure to follow the Cox-Merz rule to behave more as particulate material rather than showing polymeric rheological properties when dispersed in water. Such suspensions and their mixtures are currently intensively investigated to enable them to generate likely enhanced composite material properties. The processes frequently involve exposure to increasing levels of ionic strength, coming either from the weak solubility of pigments, such as calcium carbonate, or retained salts arising from the feed fibre source processing. By taking the simple case of polyacrylate stabilised calcium carbonate suspension and comparing the extensional viscosity as a function of post extension capillary-induced Hencky strain on a CaBER extensional rheometer over a range of increasing salt concentration, it has been shown that the regime of constriction changes as the classic DLVO double layer is progressively suppressed. This change is seen to lead to a characteristic double (bimodal) measured viscosity response for flocculated systems. With this novel characteristic established, more complex mixed suspensions of calcium carbonate, clay and MNFC have been studied, and the effects of fibrils versus flocculation identified and where possible separated. This technique is suggested to enable a better understanding of the origin of viscoelasticity in these important emerging water-based suspensions. Copyright © 2015 Elsevier Inc. All rights reserved.
Yang, Dingzheng; Yan, Bin; Xiang, Li; Xu, Haolan; Wang, Xiaogang; Zeng, Hongbo
2018-06-13
Understanding the surface properties and rheology of colloidal suspensions in the presence of polymer additives with high salinity are of great importance in formulating construction materials and optimizing process conditions in the mining and petroleum industry. In this work, the surface properties and rheology of a model spherical silica aqueous suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer at various salt concentrations have been investigated. Adsorption measurements using a Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) align well with zeta potential tests and show that polymer adsorption on silica surfaces is enhanced at high salinity (i.e., 3 M NaCl) than at low salinity (i.e., 1 mM NaCl) due to the suppression of the electrical double layer. Surface Forces Apparatus (SFA) measurements reveal that for interactions between two mica surfaces (the basal plane of which has a similar structure as silica) at a high polymer concentration (e.g., 2 wt%), steric repulsion dominates in 1 mM NaCl while bridging attraction is observed in 3 M NaCl. Surface force measurements agree with rheological results on silica suspensions with 0.5 to 2 wt% of PAA/PEO addition, which shows a significant decrease in yield stress in 1 mM NaCl due to steric repulsion but an insignificant variation in yield stress in 3 M NaCl due to attractive bridging interactions. This work provides useful information regarding the surface properties and rheological properties of comb-type polymer-mediated silica suspensions under different salinity conditions, with implications on designing and processing complex colloidal suspensions with polymer additives for various applications.
de Boer, F Y; Kok, R N U; Imhof, A; Velikov, K P
2018-04-18
Growing interest in using natural, biodegradable ingredients for food products leads to an increase in research for alternative sources of functional ingredients. One alternative is zein, a water-insoluble protein from corn. Here, a method to investigate the optical properties of white zein colloidal particles is presented in both diluted and concentrated suspensions. The particles are synthesized, after purification of zein, by anti-solvent precipitation. Mean particle diameters ranged from 35 to 135 nm based on dynamic light scattering. The value of these particles as white colorant is examined by measuring their optical properties. Dilute suspensions are prepared to measure the extinction cross section of individual particles and this was combined with Mie theory to determine a refractive index (RI) of 1.49 ± 0.01 for zein particles dispersed in water. This value is used to further model the optical properties of concentrated suspensions. To obtain full opacity of the suspension, comparable to 0.1-0.2 wt% suspensions of TiO2, concentrations of 2 to 3.3 wt% of zein particles are sufficient. The optimal size for maximal scattering efficiency is explored by modeling dilute and concentrated samples with RI's matching those of zein and TiO2 particles in water. The transport mean free path of light was determined experimentally and theoretically and the agreement between the transport mean free path calculated from the model and the measured value is better than 30%. Such particles have the potential to be an all-natural edible alternative for TiO2 as white colorant in wet food products.
Shang, Shenglong; Zhang, Qinghong; Wang, Hongzhi; Li, Yaogang
2017-01-01
A flexible, magnetic field induced structurally colored films with brilliant colors and high physical rigidity were reported in this article. Using an external magnetic field, the photocurable colloidal suspensions that containing superparamagnetic Fe 3 O 4 @C colloidal nanocrystal clusters (CNCs) could polymerize under UV light. After polymerization, the films with different colors (red, green, blue) were obtained. Through combination of suspensions which contains Fe 3 O 4 @C CNCs with different sizes, a series of multi-colored films were obtained. Moreover, these structural colors can be patterned easily by photolithography and various structural colored patterns were shown in the article. The structural colored patterns could conceal or display its color according to the changing of background which makes them hold significant potential applications for security materials. Copyright © 2016 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jiang, Tianying; Zukoski, Charles F., E-mail: czukoski@illinois.edu
2014-09-01
For decades, attempts have been made to understand the formation of colloidal glasses and gels by linking suspension mechanics to particle properties where details of size, shape, and spatial dependencies of pair potentials present a bewildering array of variables that can be manipulated to achieve observed properties. Despite the range of variables that control suspension properties, one consistent observation is the remarkably similarity of flow properties observed as particle properties are varied. Understanding the underlying origins of the commonality in those behaviors (e.g., shear-thinning with increasing stress, diverging zero shear rate viscosity with increasing volume fraction, development of a dynamicmore » yield stress plateau with increases in volume faction or strength of attraction, development of two characteristic relaxation times probed in linear viscoelasticity, the creation of a rubbery plateau modulus at high strain frequencies, and shear-thickening) remains a challenge. Recently, naïve mode coupling and dynamic localization theories have been developed to capture collective behavior giving rise to formation of colloidal glasses and gels. This approach characterizes suspension mechanics of strongly interacting particles in terms of sluggish long-range particle diffusion modulated by varying particle interactions and volume fraction. These theories capture the scaling of the modulus with the volume fraction and strength of interparticle attraction, the frequency dependence of the moduli at the onset of the gel/glass transition, together with the divergence of the zero shear rate viscosity and cessation of diffusivity for hard sphere systems as close packing is approached. In this study, we explore the generality of the predictions of dynamic localization theory for systems of particles composed of bimodal particle size distributions experiencing weak interactions. We find that the mechanical properties of these suspensions are well captured within the framework of dynamic localization theory and that suspension mechanics can be understood in terms of a dynamical potential barrier, the magnitude of which governs the zero shear rate viscosity, and onset of a dynamic yield stress plateau as volume fraction or strength of interaction is raised.« less
Lin, Binhua; Cui, Bianxiao; Xu, Xinliang; Zangi, Ronen; Diamant, Haim; Rice, Stuart A
2014-02-01
We report the results of experimental studies of the short-time-long-wavelength behavior of collective particle displacements in quasi-one-dimensional (q1D) and quasi-two-dimensional (q2D) colloid suspensions. Our results are reported via the q → 0 behavior of the hydrodynamic function H(q) that relates the effective collective diffusion coefficient D(e)(q), with the static structure factor S(q) and the self-diffusion coefficient of isolated particles D(0): H(q) ≡ D(e)(q)S(q)/D(0). We find an apparent divergence of H(q) as q → 0 with the form H(q) ∝ q(-γ) (1.7 < γ < 1.9) for both q1D and q2D colloid suspensions. Given that S(q) does not diverge as q → 0 we infer that D(e)(q) does. This behavior is qualitatively different from that of the three-dimensional H(q) and D(e)(q) as q → 0, and the divergence is of a different functional form from that predicted for the diffusion coefficient in one-component one-dimensional and two-dimensional fluids not subject to boundary conditions that define the dimensionality of the system. We provide support for the contention that the boundary conditions that define a confined system play a very important role in determining the long-wavelength behavior of the collective diffusion coefficient from two sources: (i) the results of simulations of H(q) and D(e)(q) in quasi-1D and quasi-2D systems and (ii) verification, using data from the work of Lin, Rice and Weitz [Phys. Rev. E 51, 423 (1995)], of the prediction by Bleibel et al., arXiv:1305.3715, that D(e)(q) for a monolayer of colloid particles constrained to lie in the interface between two fluids diverges as q(-1) as q → 0.
Restrepo, John F; Garcia-Sucerquia, Jorge
2013-01-01
The number of colloidal particles per unit of volume that can be imaged correctly with digital lensless holographic microscopy (DLHM) is determined numerically. Typical in-line DLHM holograms with controlled concentration are modeled and reconstructed numerically. By quantifying the ratio of the retrieved particles from the reconstructed hologram to the number of the seeding particles in the modeled intensity, the limit of concentration of the colloidal suspensions up to which DLHM can operate successfully is found numerically. A new shadow density parameter for spherical illumination is defined. The limit of performance of DLHM is determined from a graph of the shadow density versus the efficiency of the microscope.
Novel colloidal materials from functionalized polyoxometalates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Swenson, LaSalle; Orozco, Jose C.; Liu, Yuzi
Here, novel colloidal materials were prepared for the first time from the organo-functionalized Anderson structure polyoxometalate species [NaV IV 6O 6{(OCH 2CH 2) 2N(CH 2CH 2OH)} 6]Cl·H 2O and the mixed-addenda Keggin structure polyoxometalate, K 4(PVW 11O 40). The materials were characterized by SEM, TGA, FTIR and UV-vis spectroscopy. The colloidal materials are readily separated from suspension in the form of redistributable micrometer-scale monoliths, which may be considered a type of POM heterogenation. The monoliths are insoluble in low polarity media and lower aliphatic alcohols and readily form thin-films (δ < 100 um) by solvent casting.
Novel colloidal materials from functionalized polyoxometalates
Swenson, LaSalle; Orozco, Jose C.; Liu, Yuzi; ...
2017-07-13
Here, novel colloidal materials were prepared for the first time from the organo-functionalized Anderson structure polyoxometalate species [NaV IV 6O 6{(OCH 2CH 2) 2N(CH 2CH 2OH)} 6]Cl·H 2O and the mixed-addenda Keggin structure polyoxometalate, K 4(PVW 11O 40). The materials were characterized by SEM, TGA, FTIR and UV-vis spectroscopy. The colloidal materials are readily separated from suspension in the form of redistributable micrometer-scale monoliths, which may be considered a type of POM heterogenation. The monoliths are insoluble in low polarity media and lower aliphatic alcohols and readily form thin-films (δ < 100 um) by solvent casting.
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.
Colloidal systems and interfaces
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ross, S.; Morrison, E.D.
1988-01-01
This book is an excellent, four-part introductory text and sourcebook for those who want to acquire a quick background in , or brush up on, the physical properties and behavior of colloidal dispersions and interfaces. Part I covers properties of particles and techniques for determining particle size and surface area. Part II concentrates on the properties of interfaces, with brief subsections on insoluble monolayers, surface active solutes in aqueous and non-aqueous media, and the thermodynamics of adsorption at interfaces. Part III considers attractive and repulsive interactions, colloid stability (DLVO theory), and kinetics of coagulation. Part IV applies these concepts tomore » emulsions, foams, and suspensions. The sections on colloid rheology, interfacial tensions, Marangoni effects, and calculation of Hamaker constants are particularly good, as are Part IV and the numerous examples of practical applications used throughout the book to illustrate the concepts.« less
Effects of pH and cation adsorption on colloidal stability of graphene oxide in aquatic environments
NASA Astrophysics Data System (ADS)
Terracciano, Amalia
The presented doctoral research aims to improve the current understanding of the chemistry of Graphene Oxide Nanoparticles (GONPs) in common water systems. The widespread demand and future use of this nanomaterial in a broad range of different applications (i.e. biomedical, electronic, environmental) will certainly lead to its release in the environment with consequent exposure of ecosystems to graphene oxide (GO) toxicity. The described scenario demand a careful investigation and deep understanding of the environmental behavior and fate of GONPs, especially in water systems. Therefore this study focused on the investigation the effects of pH some of the most common water electrolytes (monovalent and divalent) and on GO colloidal stability. The interactions between the selected ions and the GO functional groups was also studied. The mobility of GO in porous media was first studied through filtrations tests that determine influence of ionic strength (IS) and solution composition on GO mobility. The GONPs showed to be completely retained in the porous media in presence of 3.5 mM of CaCl2 and in tap water while no retention was found for 10 mM of NaCl solution. The results indicated significant impact of divalent cations on the mobility of GO. Serial experiments were performed to quantify the adsorption of several cations (Na+, Ca2+ and Ba2+) on GO. The divalent cations showed to be strongly adsorbed on the GO surface with increasing pH and cation concentrations, while no significant sodium adsorption was detected. Raman spectroscopy and XPS analysis also showed strong differences in the typical spectra of GO, before and after adsorption of Ca2+ and Ba2+ which suggest chemical bond formation with the GO functional groups. The aggregation regime and the colloidal stability of the GO suspension in presence of selected electrolytes (Na+, Mg2+, Ca2+ and Ba2+) as function of pH was also extensively studied. The zeta potential, which is index of the stability of a colloidal suspension, was found to became more negative for GO in NaCl solutions for solution pH from 4 to 10 which is due to increased deprotonation of carboxyl (-COOH) and hydroxyl (-COH) groups on GO. Values of the zeta potential higher than +/-30 indicated increase stability of the colloidal suspension; however in presence of Ca2+ in solution, the zeta potential of GONPs become less negative (>-10 mV) with formation of aggregates which can be attributed to increased Ca2+ adsorption, especially at high pH. The increase adsorption will neutralize the negative surface charge to reduce electrostatic repulsion and promote aggregation. The same trend was found in presence of Ba2+ in solution. The critical coagulation concentration (CCC) of GO also showed to be strongly affected by Ca2+ and pH. The CCC value of GO remained at about 48 mM NaCl with increasing pH from 4.4 to 7 while it dramatically decreased from about 1.7 to 0.3 mM in CaCl2 solution with increasing pH. The results of this study suggest that pH and divalent cations, especially Ca2+ could significantly affect the colloidal stability of GONPs and therefore influence their mobility in the environment. Moreover the interactions between Ca2+ and Ba2+ and the GO nanosheets showed to be particularly strong which suggest inner-sphere complexation formation. The findings obtained from this doctoral research will contribute in improving the understanding of the fate and transport of the GONPs in aquatic environments and to develop more suitable models to predict its behavior.
Wette, Patrick; Klassen, Ina; Holland-Moritz, Dirk; Herlach, Dieter M; Schöpe, Hans Joachim; Lorenz, Nina; Reiber, Holger; Palberg, Thomas; Roth, Stephan V
2010-04-07
In titration experiments with NaOH, we have determined the full phase diagram of charged colloidal spheres in dependence on the particle density n, the particle effective charge Z(eff) and the concentration of screening electrolyte c using microscopy, light and ultrasmall angle x-ray scattering (USAXS). For sufficiently large n, the system crystallizes upon increasing Z(eff) at constant c and melts upon increasing c at only slightly altered Z(eff). In contrast to earlier work, equilibrium phase boundaries are consistent with a universal melting line prediction from computer simulation, if the elasticity effective charge is used. This charge accounts for both counterion condensation and many-body effects.
Characterization, origin and aggregation behavior of colloids in eutrophic shallow lake.
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.
Shear thickening in suspensions: the lubricated-to-frictional contact scenario
NASA Astrophysics Data System (ADS)
Morris, Jeffrey
2017-11-01
Suspensions of solid particles in viscous liquids can vary from low-viscosity liquids to wet granular materials or soft solids depending on the solids loading and the forces acting between particles. When the particles are very concentrated, these mixtures are ''dense suspensions.'' Dense suspensions often exhibit shear thickening, an increase in apparent viscosity as the shear rate is increased. In its most extreme form, order of magnitude increases in viscosity over such a narrow range in shear rate occur that the term discontinuous shear thickening (DST) is applied. DST is particularly striking as it occurs in the relatively simple case of nearly hard spheres in a Newtonian liquid, and is found to take place for submicron particles in colloidal dispersions to much larger particle corn starch dispersions. We focus on simulations of a recently developed ``lubricated-to-frictional'' rheology in which the interplay of viscous lubrication, repulsive surface forces, and contact friction between particle surfaces provides a scenario to explain DST. Our simulation method brings together elements of the discrete-element method from granular flow with a simplified Stokesian Dynamics, and can rationalize not only the abrupt change in properties with imposed shear rate (or shear stress), but also the magnitude of the change. The large change in properties is associated with the breakdown of lubricating films between particles, with activation of Coulomb friction between particles. The rate dependence is caused by the shearing forces driving particles to contact, overwhelming conservative repulsive forces between surfaces; the repulsive forces are representative of colloidal stabilization by surface charge or steric effects, e.g. due to adsorbed polymer. The results of simulation are compared to developments by other groups, including a number of experimental studies and a theory incorporating the same basic elements as the simulation. The comparison to experiments of the predictions of the lubricated-to-frictional rheology is generally good, but discrepancies demand some perspective on the strong simplifying assumptions in the model. Since contact is difficult to both establish and to characterize for surfaces between particles of micron scale or smaller, what is happening in the very close ``contacts'' is not clear, and how changes at this scale give rise to the large-scale force organization is yet to be established. The insight to the elements needed for the abrupt flow induced transition seen in DST thus suggests a need for consideration of both the microscopic physics of contact and the statistical physics governing the macroscopic properties. This work was supported in part by the NSF CBET program, Grant # 1605283.
NASA Astrophysics Data System (ADS)
Wang, Qing; Cheng, Tao; Wu, Yang
2014-12-01
Mineral colloids and humic substances often co-exist in subsurface environment and substantially influence uranium (U) transport. However, the combined effects of mineral colloids and humic substances on U transport are not clear. This study is aimed at quantifying U transport and elucidating geochemical processes that control U transport when both mineral colloids and humic acid (HA) are present. U-spiked solutions/suspensions were injected into water-saturated sand columns, and U and colloid concentrations in column effluent were monitored. We found that HA promoted U transport via (i) formation of aqueous U-HA complexes, and (ii) competition against aqueous U for surface sites on transport media. Illite colloids had no influence on U transport at pH 5 in the absence of HA due to low mobility of the colloids. At pH 9, U desorbed from mobile illite and the presence of illite decreased U transport. At pH 5, high U transport occurred when both illite colloids and HA were present, which was attributed to enhanced U adsorption to illite colloids via formation of ternary illite-HA-U surface complexes, and enhanced illite transport due to HA attachment to illite and transport media. This study demonstrates that the combined effects of mineral colloids and HA on contaminant transport is different from simple addition of the individual effect.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Triwibowo, J., E-mail: joko.triwibowo@lipi.go.id; Yuniarti, E.; Suharyadi, E.
2014-09-25
This research has been done on the synthesis of carbon coated LiFePO{sub 4} through sol-gel process. Carbon layer serves for improving electronic conductivity, while the variation of pH in the sol-gel process is intended to obtain the morphology of the material that may improve battery performance. LiFePO{sub 4}/C precursors are Li{sub 2}CO{sub 3}, NH{sub 4}H{sub 2}PO{sub 4} and FeC{sub 2}O{sub 4}.H{sub 2}O and citric acid. In the synthesis process, consisting of a colloidal suspension FeC{sub 2}O{sub 4}.H{sub 2}O and distilled water mixed with a colloidal suspension consisting of NH{sub 4}H{sub 2}PO{sub 4}, Li{sub 2}CO{sub 3}, and distilled water. Variations additionmore » of citric acid is used to control the pH of the gel formed by mixing two colloidal suspensions. Sol in this study had a pH of 5, 5.4 and 5.8. The obtained wet gel is further dried in the oven and then sintered at a temperature 700°C for 10 hours. The resulting material is further characterized by XRD to determine the phases formed. The resulting powder morphology is observed through SEM. Specific surface area of the powder was tested by BET, while the electronic conductivity characterized with EIS.« less
Rapid screening and species identification of E. coli, Listeria, and Salmonella by SERS technique
NASA Astrophysics Data System (ADS)
Liu, Yongliang; Chao, Kuanglin; Kim, Moon S.; Nou, Xiangwu
2008-04-01
Techniques for routine and rapid screening of the presence of foodborne bacteria are needed, and this study reports the feasibility of citrate-reduced silver colloidal SERS for identifying E. coli, Listeria, and Salmonella. Relative standard deviation (RSD) of SERS spectra from silver colloidal suspensions and ratios of P-O SERS peaks from small molecule (K3PO4) were used to assess the reproducibility, stability, and binding effectiveness of citrate-reduced silver colloids over batch and storage process. The results suggested the reproducibility of silver colloids over batch process and also stability and consistent binding effectiveness over 60-day storage period. Notably, although silver colloidal nanoparticles were stable for at least 90 days, their binding effectiveness began to decrease slightly after 60-day storage, with a binding reduction of about 12% at 90th day. Colloidal silver SERS, as demonstrated here, could be an important alternative technique in the rapid and simultaneous screening of the presence of three most outbreak bacteria due to the exclusive biomarkers, label-free and easy sampling attribute.
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.
Chen, Zhen; Zhao, Kong-Shuang; Guo, Lin; Feng, Cai-Hong
2007-04-28
Dielectric measurements were carried out on colloidal suspensions of palladium nanoparticle chains dispersed in poly(vinyl pyrrolidone)/ethylene glycol (PVP/EG) solution with different particle volume fractions, and dielectric relaxation with relaxation time distribution and small relaxation amplitude was observed in the frequency range from 10(5) to 10(7) Hz. By means of the method based on logarithmic derivative of the dielectric constant and a numerical Kramers-Kronig transform method, two dielectric relaxations were confirmed and dielectric parameters were determined from the dielectric spectra. The dielectric parameters showed a strong dependence on the volume fraction of palladium nanoparticle chain. Through analyzing limiting conductivity at low frequency, the authors found the conductance percolation phenomenon of the suspensions, and the threshold volume fraction is about 0.18. It was concluded from analyzing the dielectric parameters that the high frequency dielectric relaxation results from interfacial polarization and the low frequency dielectric relaxation is a consequence of counterion polarization. They also found that the dispersion state of the palladium nanoparticle chain in PVP/EG solution is dependent on the particle volume fraction, and this may shed some light on a better application of this kind of materials.
pH-dependent surface charging and points of zero charge. IV. Update and new approach.
Kosmulski, Marek
2009-09-15
The recently published points of zero charge (PZC) and isoelectric points (IEPs) of various materials are compiled to update the previous compilation [M. Kosmulski, Surface Charging and Points of Zero Charge, CRC Press, Boca Raton, FL, 2009]. Unlike in previous compilations by the same author [Chemical Properties of Material Surfaces, Dekker, New York, 2001; J. Colloid Interface Sci. 253 (2002) 77; J. Colloid Interface Sci. 275 (2004) 214; J. Colloid Interface Sci. 298 (2006) 730], the materials are sorted not only by the chemical formula, but also by specific product, that is, by brand name (commercially available materials), and by recipe (home-synthesized materials). This new approach indicated that the relatively consistent PZC/IEP reported in the literature for materials having the same chemical formula are due to biased choice of specimens to be studied. Specimens which have PZC/IEP close to the "recommended" value are selected more often than other specimens (PZC/IEP not reported before or PZC/IEP reported, but different from the "recommended" value). Thus, the previously published PZC/IEP act as a self-fulfilling prophecy.
Rheological signatures of gelation and effect of shear melting on aging colloidal suspension
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jatav, Shweta; Joshi, Yogesh M, E-mail: joshi@iitk.ac.in
2014-09-01
Colloidal suspensions that are out of thermodynamic equilibrium undergo physical aging wherein their structure evolves to lower the free energy. In aqueous suspension of Laponite, physical aging accompanies increases of elastic and viscous moduli as a function of time. In this work, we study temporal evolution of elastic and viscous moduli at different frequencies and observe that freshly prepared aqueous suspension of Laponite demonstrates identical rheological behavior reported for the crosslinking polymeric materials undergoing chemical gelation. Consequently at a certain time, tan δ is observed to be independent of frequency. However, for samples preserved under rest condition for longer duration beforemore » applying the shear melting, the liquid to solid transition subsequent to shear melting shows greater deviation from classical gelation. We also obtain continuous relaxation time spectra from the frequency dependence of viscous modulus. We observe that, with an increase in the rest time, continuous relaxation time spectrum shows gradual variation from negative slope, describing dominance of fast relaxation modes to positive slope representing dominance of slow relaxation modes. We propose that the deviation from gelation behavior for the shear melted suspensions originates from inability of shear melting to completely break the percolated structure thereby creating unbroken aggregates. The volume fraction of such unbroken aggregates increases with the rest time. For small rest times presence of fewer number of unbroken aggregates cause deviation from the classical gelation. On the other hand, at high rest times presence of greater fraction of unbroken aggregates subsequent to shear melting demonstrate dynamic arrest leading to inversion of relaxation time spectra.« less
Mykhaylyk, Olga; Sobisch, Titus; Almstätter, Isabella; Sanchez-Antequera, Yolanda; Brandt, Sabine; Anton, Martina; Döblinger, Markus; Eberbeck, Dietmar; Settles, Marcus; Braren, Rickmer; Lerche, Dietmar; Plank, Christian
2012-05-01
To optimize silica-iron oxide magnetic nanoparticles with surface phosphonate groups decorated with 25-kD branched polyethylenimine (PEI) for gene delivery. Surface composition, charge, colloidal stabilities, associations with adenovirus, magneto-tranduction efficiencies, cell internalizations, in vitro toxicities and MRI relaxivities were tested for the particles decorated with varying amounts of PEI. Moderate PEI-decoration of MNPs results in charge reversal and destabilization. Analysis of space and time resolved concentration changes during centrifugation clearly revealed that at >5% PEI loading flocculation gradually decreases and sufficient stabilization is achieved at >10%. The association with adenovirus occurred efficiently at levels over 5% PEI, resulting in the complexes stable in 50% FCS at a PEI-to-iron w/w ratio of ≥7%; the maximum magneto-transduction efficiency was achieved at 9-12% PEI. Primary silica iron oxide nanoparticles and those with 11.5% PEI demonstrated excellent r(2)* relaxivity values (>600 s(-1)(mM Fe)(-1)) for the free and cell-internalized particles. Surface decoration of the silica-iron oxide nanoparticles with a PEI-to-iron w/w ratio of 10-12% yields stable aqueous suspensions, allows for efficient viral gene delivery and labeled cell detection by MRI.
A Mussel-Derived One-Component Adhesive Coacervate
Wei, Wei; Tan, Yerpeng; Rodriguez, N. Martinez; Yu, Jing; Israelachvili, Jacob N.; Waite, J. Herbert
2013-01-01
Marine organisms process and deliver many of their underwater coatings and adhesives as complex fluids. In marine mussels, one such fluid, secreted during the formation of adhesive plaques, consists of a concentrated colloidal suspension of a mussel foot protein (mfp) known as Mfp-3S. Results of this study suggest that Mfp-3S becomes a complex fluid by a liquid-liquid phase separation from equilibrium solution at a pH and ionic strength reminiscent of conditions created by the mussel foot during plaque formation. The pH dependence of phase separation and its sensitivity indicate that inter/intra-molecular electrostatic interactions are partially responsible for driving the phase separation. Hydrophobic interactions between the nonpolar Mfp-3S proteins provide another important driving force for coacervation. As complex coacervation typically results from charge-charge interactions between polyanions and polycations, Mfp-3S is thus unique in being the only known protein that coacervates with itself. The Mfp-3S coacervate was shown to have an effective interfacial energy of ≤ 1 mJ/m2 which explains its tendency to spread over or engulf most surfaces. Of particular interest to biomedical applications is the extremely high adsorption capacity of coacervated Mfp-3S on hydroxyapatite. PMID:24060881
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.
Colloid-Colloid Hydrodynamic Interaction Around a Bend in a Quasi-One-Dimensional Channel
NASA Astrophysics Data System (ADS)
Liepold, Christopher; Zarcone, Ryan; Heumann, Tibor; Lin, Binhua; Rice, Stuart
We report a study of the correlation between a pair of particles in a colloid suspension in a bent quasi-one-dimensional (q1d) channel as a function of bend angle. As the bend angle becomes more acute, we observe an increasing depletion of particles in the vicinity of the bend and an increase in the nearest-neighbor separation in the pair correlation function for particles on opposite sides of the bend. Further, we observe that the peak value of D12, the coupling term in the pair diffusion tensor that characterizes the effect of the motion of particle 1 on particle 2, coincides with the first peak in the pair correlation function, and that the pair separation dependence of D12 mimics that of the pair correlation function. We show that the observed behavior is a consequence of the geometric constraints imposed by the single-file requirement that the particle centers lie on the centerline of the channel and the requirement that the hydrodynamic flow must follow the channel around the bend. We find that the correlation between a pair of particles in a colloidal suspension in a bent q1D channel has the same functional dependence on the pair correlation function as in a straight q1D channel when measured in a coordinate system that follows the centerline of the bent channel. NSF MRSEC (DMR-1420709), Dreyfus Foundation (SI-14-014).
Rouster, Paul; Pavlovic, Marko; Horváth, Endre; Forró, László; Dey, Sandwip K; Szilagyi, Istvan
2017-09-26
The colloidal stability of titanium oxide nanosheets (TNS) and nanowires (TiONW) was studied in the presence of protamine (natural polyelectrolyte) in aqueous dispersions, where the nanostructures possessed negative net charge, and the protamine was positively charged. Regardless of their shape, similar charging and aggregation behaviors were observed for both TNS and TiONW. Electrophoretic experiments performed at different protamine loadings revealed that the adsorption of protamine led to charge neutralization and charge inversion depending on the polyelectrolyte dose applied. Light scattering measurements indicated unstable dispersions once the surface charge was close to zero or slow aggregation below and above the charge neutralization point with negatively or positively charged nanostructures, respectively. These stability regimes were confirmed by the electron microscopy images taken at different polyelectrolyte loadings. The protamine dose and salt-dependent colloidal stability confirmed the presence of DLVO-type interparticle forces, and no experimental evidence was found for additional interactions (e.g., patch-charge, hydrophobic, or steric forces), which are usually present in similar polyelectrolyte-particle systems. These findings indicate that the polyelectrolyte adsorbs on the TNS and TiONW surfaces in a flat and extended conformation giving rise to the absence of surface heterogeneities. Therefore, protamine is an excellent biocompatible candidate to form smooth surfaces, for instance in multilayers composed of polyelectrolytes and particles to be used in biomedical applications.
Loeb, Jacques
1923-01-01
1. The effect of eight salts, NaCl, Na2SO4, Na4Fe(CN)6, CaCl2, LaCl3, ThCl4, and basic and acid fuchsin on the cataphoretic P.D. between solid particles and aqueous solutions was measured near the point of neutrality of water (pH 5.8). It was found that without the addition of electrolyte the cataphoretic P.D. between particles and water is very minute near the point of neutrality (pH 5.8), often less than 10 millivolts, if care is taken that the solutions are free from impurities. Particles which in the absence of salts have a positive charge in water near the point of neutrality (pH 5.8) are termed positive colloids and particles which have a negative charge under these conditions are termed negative colloids. 2. If care is taken that the addition of the salt does not change the hydrogen ion concentration of the solution (which in these experiments was generally pH 5.8) it can be said in general, that as long as the concentration of salts is not too high, the anions of the salt have the tendency to make the particles more negative (or less positive) and that cations have the opposite effect; and that both effects increase with the increasing valency of the ions. As soon as a maximal P.D. is reached, which varies for each salt and for each type of particles, a further addition of salt depresses the P.D. again. Aside from this general tendency the effects of salts on the P.D. are typically different for positive and negative colloids. 3. Negative colloids (collodion, mastic, Acheson's graphite, gold, and metal proteinates) are rendered more negative by low concentrations of salts with monovalent cation (e.g. Na) the higher the valency of the anion, though the difference in the maximal P.D. is slight for the monovalent Cl and the tetravalent Fe(CN)6 ions. Low concentrations of CaCl2 also make negative colloids more negative but the maximal P.D. is less than for NaCl; even LaCl3 increases the P.D. of negative particles slightly in low concentrations. ThCl4 and basic fuchsin, however, seem to make the negative particles positive even in very low concentrations. 4. Positive colloids (ferric hydroxide, calcium oxalate, casein chloride—the latter at pH 4.0) are practically not affected by NaCl, are rendered slightly negative by high concentrations of Na2SO4, and are rendered more negative by Na4Fe(CN)6 and acid dyes. Low concentrations of CaCl2 and LaCl3 increase the positive charge of the particles until a maximum is reached after which the addition of more salt depresses the P.D. again. 5. It is shown that alkalies (NaOH) act on the cataphoretic P.D. of both negative and positive particles as Na4Fe(CN)6 does at the point of neutrality. 6. Low concentrations of HCl raise the cataphoretic P.D. of particles of collodion, mastic, graphite, and gold until a maximum is reached, after which the P.D. is depressed by a further increase in the concentration of the acid. No reversal in the sign of charge of the particle occurs in the case of collodion, while if a reversal occurs in the case of mastic, gold, and graphite, the P.D. is never more than a few millivolts. When HCl changes the chemical nature of the colloid, e.g. when HCl is added to particles of amphoteric electrolytes like sodium gelatinate, a marked reversal will occur, on account of the transformation of the metal proteinate into a protein-acid salt. 7. A real reversal in the sign of charge of positive particles occurs, however, at neutrality if Na4Fe(CN)6 or an acid dye is added; and in the case of negative colloids when low concentrations of basic dyes or minute traces of ThCl4 are added. 8. Flocculation of the suspensions by salts occurs when the cataphoretic P.D. reaches a critical value which is about 14 millivolts for particles of graphite, gold, or mastic or denatured egg albumin; while for collodion particles it was about 16 millivolts. A critical P.D. of about 15 millivolts was also observed by Northrop and De Kruif for the flocculation of certain bacteria. PMID:19872064
NASA Astrophysics Data System (ADS)
Nägele, G.; Heinen, M.; Banchio, A. J.; Contreras-Aburto, C.
2013-11-01
Dynamic processes in dispersions of charged spherical particles are of importance both in fundamental science, and in technical and bio-medical applications. There exists a large variety of charged-particles systems, ranging from nanometer-sized electrolyte ions to micron-sized charge-stabilized colloids. We review recent advances in theoretical methods for the calculation of linear transport coefficients in concentrated particulate systems, with the focus on hydrodynamic interactions and electrokinetic effects. Considered transport properties are the dispersion viscosity, self- and collective diffusion coefficients, sedimentation coefficients, and electrophoretic mobilities and conductivities of ionic particle species in an external electric field. Advances by our group are also discussed, including a novel mode-coupling-theory method for conduction-diffusion and viscoelastic properties of strong electrolyte solutions. Furthermore, results are presented for dispersions of solvent-permeable particles, and particles with non-zero hydrodynamic surface slip. The concentration-dependent swelling of ionic microgels is discussed, as well as a far-reaching dynamic scaling behavior relating colloidal long- to short-time dynamics.
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
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.
Thermal diffusion behavior of hard-sphere suspensions.
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.
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
Brozek, Carl K; Zhou, Dongming; Liu, Hongbin; Li, Xiaosong; Kittilstved, Kevin R; Gamelin, Daniel R
2018-05-09
Colloidal ZnO semiconductor nanocrystals have previously been shown to accumulate multiple delocalized conduction-band electrons under chemical, electrochemical, or photochemical reducing conditions, leading to emergent semimetallic characteristics such as quantum plasmon resonances and raising prospects for application in multielectron redox transformations. Here, we demonstrate a dramatic enhancement in the capacitance of colloidal ZnO nanocrystals through aliovalent Fe 3+ -doping. Very high areal and volumetric capacitances (33 μF cm -2 , 233 F cm -3 ) are achieved in Zn 0.99 Fe 0.01 O nanocrystals that rival those of the best supercapacitors used in commercial energy-storage devices. The redox properties of these nanocrystals are probed by potentiometric titration and optical spectroscopy. These data indicate an equilibrium between electron localization by Fe 3+ dopants and electron delocalization within the ZnO conduction band, allowing facile reversible charge storage and removal. As "soluble supercapacitors", colloidal iron-doped ZnO nanocrystals constitute a promising class of solution-processable electronic materials with large charge-storage capacity attractive for future energy-storage applications.
Fuel-Mediated Transient Clustering of Colloidal Building Blocks.
van Ravensteijn, Bas G P; Hendriksen, Wouter E; Eelkema, Rienk; van Esch, Jan H; Kegel, Willem K
2017-07-26
Fuel-driven assembly operates under the continuous influx of energy and results in superstructures that exist out of equilibrium. Such dissipative processes provide a route toward structures and transient behavior unreachable by conventional equilibrium self-assembly. Although perfected in biological systems like microtubules, this class of assembly is only sparsely used in synthetic or colloidal analogues. Here, we present a novel colloidal system that shows transient clustering driven by a chemical fuel. Addition of fuel causes an increase in hydrophobicity of the building blocks by actively removing surface charges, thereby driving their aggregation. Depletion of fuel causes reappearance of the charged moieties and leads to disassembly of the formed clusters. This reassures that the system returns to its initial, equilibrium state. By taking advantage of the cyclic nature of our system, we show that clustering can be induced several times by simple injection of new fuel. The fuel-mediated assembly of colloidal building blocks presented here opens new avenues to the complex landscape of nonequilibrium colloidal structures, guided by biological design principles.
The role of ions in the self-healing behavior of soft particle suspensions
Scotti, Andrea; Gasser, Urs; Herman, Emily S.; Pelaez-Fernandez, Miguel; Han, Jun; Menzel, Andreas; Lyon, L. Andrew; Fernández-Nieves, Alberto
2016-01-01
Impurities in crystals generally cause point defects and can even suppress crystallization. This general rule, however, does not apply to colloidal crystals formed by soft microgel particles [Iyer ASJ, Lyon LA (2009) Angew Chem Int Ed 48:4562–4566], as, in this case, the larger particles are able to shrink and join the crystal formed by a majority of smaller particles. Using small-angle X-ray scattering, we find the limit in large-particle concentration for this spontaneous deswelling to persist. We rationalize our data in the context of those counterions that are bound to the microgel particles as a result of the electrostatic attraction exerted by the fixed charges residing on the particle periphery. These bound counterions do not contribute to the suspension osmotic pressure in dilute conditions, as they can be seen as internal degrees of freedom associated with each microgel particle. In contrast, at sufficiently high particle concentrations, the counterion cloud of each particle overlaps with that of its neighbors, allowing these ions to freely explore the space outside the particles. We confirm this scenario by directly measuring the osmotic pressure of the suspension. Because these counterions are then no longer bound, they create an osmotic pressure difference between the inside and outside of the microgels, which, if larger than the microgel bulk modulus, can cause deswelling, explaining why large, soft microgel particles feel the squeeze when suspended with a majority of smaller particles. We perform small-angle neutron scattering measurements to further confirm this remarkable behavior. PMID:27125854
Analogies Between Colloidal Sedimentation and Turbulent Convection at High Prandtl Numbers
NASA Technical Reports Server (NTRS)
Tong, P.; Ackerson, B. J.
1999-01-01
A new set of coarse-grained equations of motion is proposed to describe concentration and velocity fluctuations in a dilute sedimenting suspension of non-Brownian particles. With these equations, colloidal sedimentation is found to be analogous to turbulent convection at high Prandtl numbers. Using Kraichnan's mixing-length theory, we obtain scaling relations for the diffusive dissipation length delta(sub theta), the velocity variance delta u, and the concentration variance delta phi. The obtained scaling laws over varying particle radius alpha and volume fraction phi(sub ) are in excellent agreement with the recent experiment by Segre, Herbolzheimer, and Chaikin. The analogy between colloidal sedimentation and turbulent convection gives a simple interpretation for the existence of a velocity cut-off length, which prevents hydrodynamic dispersion coefficients from being divergent. It also provides a coherent framework for the study of sedimentation dynamics in different colloidal systems.
Stability diagram for dense suspensions of model colloidal Al2O3 particles in shear flow.
Hecht, Martin; Harting, Jens; Herrmann, Hans J
2007-05-01
In Al2O3 suspensions, depending on the experimental conditions, very different microstructures can be found, comprising fluidlike suspensions, a repulsive structure, and a clustered microstructure. For technical processing in ceramics, the knowledge of the microstructure is of importance, since it essentially determines the stability of a workpiece to be produced. To enlighten this topic, we investigate these suspensions under shear by means of simulations. We observe cluster formation on two different length scales: the distance of nearest neighbors and on the length scale of the system size. We find that the clustering behavior does not depend on the length scale of observation. If interparticle interactions are not attractive the particles form layers in the shear flow. The results are summarized in a stability diagram.
Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids
NASA Astrophysics Data System (ADS)
Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; Chave, Tony; Dumas, Thomas; Hennig, Christoph; Wiss, Thierry; Dieste Blanco, Oliver; Shuh, David K.; Tyliszcak, Tolek; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I.
2017-03-01
Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell.
Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids
Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; Chave, Tony; Dumas, Thomas; Hennig, Christoph; Wiss, Thierry; Dieste Blanco, Oliver; Shuh, David K.; Tyliszcak, Tolek; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I.
2017-01-01
Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell. PMID:28256635
Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids
Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; ...
2017-03-03
Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO 2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO 2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV)more » colloid. A comparative study of nanostructured PuO 2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO 2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO 2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO 2 cores and hydrolyzed Pu(IV) moieties at the surface shell.« less
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.
Activity statistics in a colloidal glass former: Experimental evidence for a dynamical transition
NASA Astrophysics Data System (ADS)
Abou, Bérengère; Colin, Rémy; Lecomte, Vivien; Pitard, Estelle; van Wijland, Frédéric
2018-04-01
In a dense colloidal suspension at a volume fraction below the glass transition, we follow the trajectories of an assembly of tracers over a large time window. We define a local activity, which quantifies the local tendency of the system to rearrange. We determine the statistics of the time integrated activity, and we argue that it develops a low activity tail that comes together with the onset of glassy-like behavior and heterogeneous dynamics. These rare events may be interpreted as the reflection of an underlying dynamic phase transition.
Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya
2015-01-01
Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles. PMID:25996055
Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya
2015-05-21
Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.
Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; ...
2015-05-21
Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions.more » We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. As a result, our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.« less
Active Colloids in Isotropic and Anisotropic Electrolytes
NASA Astrophysics Data System (ADS)
Peng, Chenhui
Electrically driven flows of fluids with respect to solid surfaces (electro-osmosis) and transport of particles in fluids (electrophoresis), collectively called electrokinetics, is a technologically important area of modern science. In this thesis, we study the electrokinetic phenomena in both isotropic and anisotropic fluids. A necessary condition of electrokinetics is separation of electric charges in space. In classic linear electrokinetics, with an isotropic electrolyte such as water, the charges are separated through dissociation of ionic groups at the solid-fluid interface; presence of the electric field is not required. In the nonlinear electrokinetics, the charges are separated with the assistance of the electric field. In the so-called induced-charge electro-osmosis (ICEO) the electric field separates charges near strongly polarizable surfaces such as metals. We establish the patterns of electro-osmotic velocities caused by nonlinear ICEO around an immobilized metallic and Janus (metallic-dielectric) spheres placed in water. In the case of the Janus particles, the flows are asymmetric, which results in pumping of water around the particle if it is immobilized, or in electrophoresis is the particle is free. When the isotropic electrolyte such as water is replaced with a LC electrolyte, the mechanism of the field-assisted charge separation becomes very different. Namely, the charges are separated at the director gradients, thanks to the anisotropy of electric conductivity and dielectric permittivity of the LC. These distortions can be created by the colloidal particles placed in the LC. We demonstrate the occurrence of nonlinear LC-enabled electro-osmosis (LCEO) by studying the flow patterns around colloidal spheres with different surface anchoring. LCEO velocities grow with the square of the electric field, which allows one to use an AC field to drive steady flows and to avoid electrode damage. Director distortions needed to trigger the LCEO can also be designed by surface-patterned modulated molecular orientation. The surface patterning is produced by photo-alignment. In the presence of an electric field, the spatially varying orientation induces space charges that trigger flows of the LC. The active patterned LC electrolyte converts the electric energy into the LC flows and transport of embedded particles of any type (fluid, solid, gaseous) along a predesigned trajectory, posing no limitation on the electric nature (charge, polarizability) of these particles and interfaces. The patterned LC electrolyte also induces persistent vortices of controllable rotation speed and direction that are quintessential for micro- and nanoscale mixing applications. The thesis also describes transport and placement of colloids by elasticity of a nematic LC with spatially varying molecular orientation. Colloidal particles in nematic environment are subject to the long-range elastic forces originating in the orientational order of the nematic. Gradients of the orientational order create an elastic energy landscape that drives the colloids into locations with preferred type of deformations. As an example, we demonstrate that colloidal spheres with perpendicular surface anchoring are driven into the regions of maximum splay, while spheres with tangential surface anchoring settle into the regions of bend. Elastic forces responsible for preferential placement are measured by exploring overdamped dynamics of the colloids. The results obtained in this thesis open new opportunities for design of materials and devices for micropumping, mixing, lab-on-a-chip and biosensing applications.
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.
Natural colloids are the dominant factor in the sedimentation of nanoparticles.
Quik, Joris T K; Stuart, Martien Cohen; Wouterse, Marja; Peijnenburg, Willie; Hendriks, A Jan; van de Meent, Dik
2012-05-01
Estimating the environmental exposure to manufactured nanomaterials is part of risk assessment. Because nanoparticles aggregate with each other (homoaggregation) and with other particles (heteroaggregation), the main route of the removal of most nanoparticles from water is aggregation, followed by sedimentation. The authors used water samples from two rivers in Europe, the Rhine and the Meuse. To distinguish between small (mainly natural organic matter [NOM]) particles and the remainder of the natural colloids present, both filtered and unfiltered river water was used to prepare the particle suspensions. The results show that the removal of nanoparticles from natural river water follows first-order kinetics toward a residual concentration. This was measured in river water with less than 1 mg L(-1) CeO(2) nanoparticles. The authors inferred that the heteroaggregation with or deposition onto the solid fraction of natural colloids was the main mechanism causing sedimentation in relation to homoaggregation. In contrast, the NOM fraction in filtered river water stabilized the residual nanoparticles against further sedimentation for up to 12 d. In 10 mg L(-1) and 100 mg L(-1) CeO(2) nanoparticle suspensions, homoaggregation is likely the main mechanism leading to sedimentation. The proposed model could form the basis for improved exposure assessment for nanomaterials. Copyright © 2012 SETAC.
NASA Astrophysics Data System (ADS)
Gurnon, Amanda Kate
The complex, nonlinear flow behavior of soft materials transcends industrial applications, smart material design and non-equilibrium thermodynamics. A long-standing, fundamental challenge in soft-matter science is establishing a quantitative connection between the deformation field, local microstructure and macroscopic dynamic flow properties i.e., the rheology. Soft materials are widely used in consumer products and industrial processes including energy recovery, surfactants for personal healthcare (e.g. soap and shampoo), coatings, plastics, drug delivery, medical devices and therapeutics. Oftentimes, these materials are processed by, used during, or exposed to non-equilibrium conditions for which the transient response of the complex fluid is critical. As such, designing new dynamic experiments is imperative to testing these materials and further developing micromechanical models to predict their transient response. Two of the most common classes of these soft materials stand as the focus of the present research; they are: solutions of polymer-like micelles (PLM or also known as wormlike micelles, WLM) and concentrated colloidal suspensions. In addition to their varied applications these two different classes of soft materials are also governed by different physics. In contrast, to the shear thinning behavior of the WLMs at high shear rates, the near hard-sphere colloidal suspensions are known to display increases, sometimes quite substantial, in viscosity (known as shear thickening). The stress response of these complex fluids derive from the shear-induced microstructure, thus measurements of the microstructure under flow are critical for understanding the mechanisms underlying the complex, nonlinear rheology of these complex fluids. A popular micromechanical model is reframed from its original derivation for predicting steady shear rheology of polymers and WLMs to be applicable to weakly nonlinear oscillatory shear flow. The validity, utility and limits of this constitutive model are tested by comparison with experiments on model WLM solutions. Further comparisons to the nonlinear oscillatory shear responses measured from colloidal suspensions establishes this analysis as a promising, quantitative method for understanding the underlying mechanisms responsible for the nonlinear dynamic response of complex fluids. A new experimental technique is developed to measure the microstructure of complex fluids during steady and transient shear flow using small-angle neutron scattering (SANS). The Flow-SANS experimental method is now available to the broader user communities at the NIST Center for Neutron Research, Gaithersburg, MD and the Institut Laue-Langevin, Grenoble, France. Using this new method, a model shear banding WLM solution is interrogated under steady and oscillatory shear. For the first time, the flow-SANS methods identify new metastable states for shear banding WLM solutions, thus establishing the method as capable of probing new states not accessible using traditional steady or linear oscillatory shear methods. The flow-induced three-dimensional microstructure of a colloidal suspension under steady and dynamic oscillatory shear is also measured using these rheo- and flow-SANS methods. A new structure state is identified in the shear thickening regime that proves critical for defining the "hydrocluster" microstructure state of the suspension that is responsible for shear thickening. For both the suspensions and the WLM solutions, stress-SANS rules with the measured microstructures define the individual stress components arising separately from conservative and hydrodynamic forces and these are compared with the macroscopic rheology. Analysis of these results defines the crucial length- and time-scales of the transient microstructure response. The novel dynamic microstructural measurements presented in this dissertation provide new insights into the complexities of shear thickening and shear banding flow phenomena, which are effects observed more broadly across many different types of soft materials. Consequently, the microstructure-rheology property relationships developed for these two classes of complex fluids will aid in the testing and advancement of micromechanical constitutive model development, smart material design, industrial processing and fundamental non-equilibrium thermodynamic research of a broad range of soft materials.
Farber, Paulo Luiz; Hochman, Bernardo; Furtado, Fabianne; Ferreira, Lydia Masako
2014-02-01
The role of endogenous electric fields in wound healing is still not fully understood. Electric fields are of fundamental importance in various biological processes, ranging from embryonic development to disease progression, as described by many investigators in the last century. This hypothesis brings together some relevant literature on the importance of electric fields in physiology and pathology, the theory of biologically closed electric circuits, skin battery (a phenomenon that occurs after skin injury and seems to be involved in tissue repair), the relationship between electric charge and interstitial exclusion, and how skin tissues can be regarded as colloidal systems. The importance of electric charges, as established in the early works on the subject and the relevance of zeta potential and colloid stability are also analyzed, and together bring a new light for the physics involved in the wound repair of all the body tissues. Copyright © 2013 Elsevier Ltd. All rights reserved.
Mechanisms for Non-Linear Optical Behaviour in Molecular Fluids
NASA Astrophysics Data System (ADS)
McEwan, Kenneth J.
Available from UMI in association with The British Library. Requires signed TDF. This thesis describes a study of the non-linear optical mechanisms that allow high power laser radiation to interact and change the optical properties of fluid based media. Attention is focused on understanding the finite time-scale of the microscopic response and its influence on the experimental observation. Two classes of material are studied: liquid crystalline fluids in their isotropic phase and suspensions of particles capable of absorbing the laser radiation. In the former case a quantitative description of the optical transients seen in two experiments, degenerate four wave mixing and "z-scan" (self-focusing), is obtained. This description is based upon an analysis of refractive index changes associated with laser-induced molecular reorientation and with thermal effects, for molecules that absorb the laser radiation. Material parameters for a large range of nematogens are obtained by applying this description to experimental data. In the absorbing colloidal suspensions a novel mechanism for degenerate four wave mixing is identified and studied. The experimental results are suggestive of a mechanism in which vapour bubbles nucleate explosively around the colloidal particles and drive a coherent sound -wave excitation of the fluid. Theoretical studies confirm that rapid bubble nucleation is possible by a process of spinodal decomposition under the experimental conditions and it is shown that this mechanism can be expected to give rise to transient behaviour of the type observed. Finally laser-induced refractive index changes in a colloidal suspension in a solid matrix are studied. The dynamics of the formation of refractive index gratings is examined and correlated with microscopically observed structural changes in the matrix. ftn*Funded by DRA, Electronics Division (formerly RSRE).
Chattopadhyay, Ankur; Rani, Poonam; Srivastava, Rajendra; Dhar, Purbarun
2018-06-01
The present article discusses the typical influence of grafted conducting polymers in the mesoscale pores of dielectric particles on the static and dynamic electrorheology and electro-viscoelastic behavior of corresponding colloids. Nanocrystalline meso-nanoporous zeolite has been prepared by chemical synthesis and subsequently polyaniline (PANI) coating has been implemented. Electrorheological (ER) suspensions have been formed by dispersing the nanoparticles in silicone oil and their viscoelastic behaviors are examined to understand the nature of such complex colloidal systems under electric fields. PANI-Zeolite ER fluids demonstrate higher static electroviscous effects and yield stress potential than untreated Zeolite, typically studied in literature. Transient electro-viscous characterizations show a stable and negligible hysteresis behavior when both the fluids are exposed to constant as well as time varying electric field intensities. Further oscillatory shear experiments of frequency and strain sweeps exhibit predominant elastic behavior in case of Zeolite based ER suspensions as compared to PANI systems. Detailed investigations reveal Zeolite based ER suspensions display enhanced relative yielding as well as electro-viscoelastic stability than the PANI-Zeolite. The steady state viscous behaviors are scaled against the non-dimensional Mason number to model the system behavior for both fluids. Experimental data of flow behaviors of both the ER fluids are compared with semi-classical models and it is found that the CCJ model possesses a closer proximity than traditional Bingham model, thereby revealing the fluids to be generic pseudo-linear fluids. The present article reveals that while the PANI based fluids are typically hailed superior in literature, it is only restricted to steady shear utilities. In case of dynamic and oscillatory systems, the traditional Zeolite based fluids exhibit superior ER caliber. Copyright © 2018 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Dave, Kashyap; Dhayal, Marshal
2017-02-01
A hydrosol approach developed to synthesize fluorescence quenched fluorescein isothiocyanate (FITC) functionalized colloidal suspension of graphene oxide nanoparticles (GONP). UV-vis spectroscopic measurements showed characteristic peak at 236 nm and 300 nm due to pi-pi* interaction in Cdbnd C and n-pi* transition in Cdbnd O bond of GONP, respectively. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra showed reduced intensity of 1429 cm-1 IR band of GONP due to the electrostatic and pi-pi interactions of FITC with GONP in FITC-GONP. ATR-FTIR spectra of different amino acid co-functionalised FITC-GONP showed an increase in the FTIR band intensity at 1429 cm-1 which was significantly reduced due to electrostatic/pi-pi interactions of FITC with GONP in the absence of the amino acids. A peak at 1084 cm-1 in ATR-FTIR spectra appears which confirms the interaction between amine group of amino acids and sbnd COO- groups at GONP surface. The FITC interaction with GONP lead to fluorescence resonance energy transfers (FRET) and resulted in a liner decrease in the FITC fluorescence with an increase of GONP concentration. An increase in the reappearance of FITC fluorescence observed while the amino acid concentration was increased in co-functionalised FITC-GONP. The quantified amount of reappeared fluorescence of FITC in amino acid co-functionalised FITC-GONP depends on the concentration, polar and non-polar nature of amino acids. The reappearance of FITC from the surface of FITC-GONP with the addition of amino acid was found to be consistent with the organic substitute, size of amino acids and their functionalities. Therefore, FRET based method using FITC-GONP colloidal suspension may have potential application in determining the binding nature of biomolecules with GONP for biomedical applications.
Controllable Nanoparticle Assembly and Actuation with Modified Dipole Potentials in Simulation
NASA Astrophysics Data System (ADS)
Dempster, Joshua
Science at the nanoscale poses several recurring difficulties. How can we control the assembly of objects too small for direct manipulation to be practical? How can we extend that control to in vivo systems so we can make use of nanotechnology in medicine? And how can we recreate the extraordinary capacities of Nature: healing, replication, growth, adaptation, self-regulation? One of the most powerful tools for addressing these challenges is the simple, familiar dipole moment. Since their debut as fuel control devices at NASA in the early sixties, possible applications for dipole suspensions have grown to areas far beyond what their creators envisioned. A multitude of ambitious new medical and mechanical applications make use of dipolar colloids. Dipoles are attractive from a practical standpoint because one can use fields to control not just their orientation and location, but also their mutual interactions. From a physical standpoint, dipoles are compelling as an exceptionally simple form of symmetry-breaking that leads to a variety of complex phenomena. This thesis studies the assembly and control of spherical colloids with a dipolar interaction modified by additional conditions using simulations. Three cases are examined in detail. The first is the case of an electrical dipole moment created by regions of opposite charge density on the surface of a colloid. Here the dipole potential is modified by strong screening. Such a system is interesting as a model for certain proteins in a high-salt solution and suggests possible uses for inverse Janus colloids. The resulting phases have little resemblance to the usual dipole phases and can be controlled with small quantities of homogeneously charged particles. In the second case, superparamagnetic dipoles are linked into chains. Such chains have been realized in a wide variety of experimental schemes. A general theory is developed for the equilibrium shapes of the chains in a precessing field when their endpoints are fixed. This theory reveals that the chains are good candidates for contracting muscles in microscopic devices with a conveniently harmonic form for their potentials. Ensembles of free chains can be put to more elaborate uses. To illustrate, a regime is designed that spins the chains into a self-healing cross-linked gel. Finally, we will turn to self-replication. Decorating a permanent dipole with a single permanent binding site is enough to enable self-replication using dimers as the template. A periodic magnetic drive provides the energy to drive replication. Several theoretical principles regarding the statistics of linear self-replicators are deduced and used to optimize the dipole replicating system.
Rheology of dense suspensions of non colloidal particles
NASA Astrophysics Data System (ADS)
Guazzelli, Élisabeth
2017-06-01
Dense suspensions are materials with broad applications both in industrial processes (e.g. waste disposal, concrete, drilling muds, metalworking chip transport, and food processing) and in natural phenomena (e.g. flows of slurries, debris, and lava). Despite its long research history and its practical relevance, the mechanics of dense suspensions remain poorly understood. The major difficulty is that the grains interact both by hydrodynamic interactions through the liquid and by mechanical contact. These systems thus belong to an intermediate regime between pure suspensions and granular flows. We show that we can unify suspension and granular rheology under a common framework by transferring the frictional approach of dry granular media to wet suspensions of spherical particles. We also discuss non-Newtonian behavior such as normal-stress differences and shear-induced migration. Beyond the classical problem of dense suspension of hard spheres which is far from being completely resolved, there are also entirely novel avenues of study concerning more complex mixtures of particles and fluids such as those involving other types of particles (e.g. fibers) or non-Newtonian fluids that we will also address.
Colloid transport in porous media: impact of hyper-saline solutions.
Magal, Einat; Weisbrod, Noam; Yechieli, Yoseph; Walker, Sharon L; Yakirevich, Alexander
2011-05-01
The transport of colloids suspended in natural saline solutions with a wide range of ionic strengths, up to that of Dead Sea brines (10(0.9) M) was explored. Migration of microspheres through saturated sand columns of different sizes was studied in laboratory experiments and simulated with mathematical models. Colloid transport was found to be related to the solution salinity as expected. The relative concentration of colloids at the columns outlet decreased (after 2-3 pore volumes) as the solution ionic strength increased until a critical value was reached (ionic strength > 10(-1.8) M) and then remained constant above this level of salinity. The colloids were found to be mobile even in the extremely saline brines of the Dead Sea. At such high ionic strength no energetic barrier to colloid attachment was presumed to exist and colloid deposition was expected to be a favorable process. However, even at these salinity levels, colloid attachment was not complete and the transport of ∼ 30% of the colloids through the 30-cm long columns was detected. To further explore the deposition of colloids on sand surfaces in Dead Sea brines, transport was studied using 7-cm long columns through which hundreds of pore volumes were introduced. The resulting breakthrough curves exhibited a bimodal shape whereby the relative concentration (C/C(0)) of colloids at the outlet rose to a value of 0.8, and it remained relatively constant (for the ∼ 18 pore volumes during which the colloid suspension was flushed through the column) and then the relative concentration increased to a value of one. The bimodal nature of the breakthrough suggests different rates of colloid attachment. Colloid transport processes were successfully modeled using the limited entrapment model, which assumes that the colloid attachment rate is dependent on the concentration of the attached colloids. Application of this model provided confirmation of the colloid aggregation and their accelerated attachment during transport through soil in high salinity solution. Copyright © 2011 Elsevier Ltd. All rights reserved.
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, fd, 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×fd. 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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dobson, E.L.; Gofman, J.W.; Jones, H.B.
Several workers have shown that certain colloidally dispered materials are removed from the blood stream by the liver and spleen. Jones, Wrobel, and Lyons have utilized suspensions of anhydrous chromic phosphate for the selective irradiation of the liver and spleen with p{sup 32} beta particles. Gersh demonstrated that colloidal calcium phosphate is taken up by the liver and spleen. He stressed the failure of bone marrow phagocytes to take up this colloid in rats and dogs (though he referred to possible uptake in the marrow of rabbits under special conditions), and commented on the relative 'refractoriness' in general of themore » bono marrow as compared with liver and spleen with respect to the uptake of colloidal dyes from the blood stream. Some histological data indicate that 'Thorotrast' (a colloidal thorium dioxide preparation) is deposited in the bone marrow as well as in the liver and spleen, but no quantitative data as to the relative distribution are available. In the preceding communication the methods for the preparation of colloids incorporating radioisotopes of yttrium, columbium, and zirconium were given. The present studies are concerned with the localization of such colloids primarily in the bone marrow or primarily in the spleen and liver, with an analysis of some of the factors which may be responsible for differences in localization.« less
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.
Depinning and heterogeneous dynamics of colloidal crystal layers under shear flow
NASA Astrophysics Data System (ADS)
Gerloff, Sascha; Klapp, Sabine H. L.
2016-12-01
Using Brownian dynamics (BD) simulations and an analytical approach we investigate the shear-induced, nonequilibrium dynamics of dense colloidal suspensions confined to a narrow slit-pore. Focusing on situations where the colloids arrange in well-defined layers with solidlike in-plane structure, the confined films display complex, nonlinear behavior such as collective depinning and local transport via density excitations. These phenomena are reminiscent of colloidal monolayers driven over a periodic substrate potential. In order to deepen this connection, we present an effective model that maps the dynamics of the shear-driven colloidal layers to the motion of a single particle driven over an effective substrate potential. This model allows us to estimate the critical shear rate of the depinning transition based on the equilibrium configuration, revealing the impact of important parameters, such as the slit-pore width and the interaction strength. We then turn to heterogeneous systems where a layer of small colloids is sheared with respect to bottom layers of large particles. For these incommensurate systems we find that the particle transport is dominated by density excitations resembling the so-called "kink" solutions of the Frenkel-Kontorova (FK) model. In contrast to the FK model, however, the corresponding "antikinks" do not move.
Living Clusters and Crystals from Low-Density Suspensions of Active Colloids
NASA Astrophysics Data System (ADS)
Mognetti, B. M.; Šarić, A.; Angioletti-Uberti, S.; Cacciuto, A.; Valeriani, C.; Frenkel, D.
2013-12-01
Recent studies aimed at investigating artificial analogs of bacterial colonies have shown that low-density suspensions of self-propelled particles confined in two dimensions can assemble into finite aggregates that merge and split, but have a typical size that remains constant (living clusters). In this Letter, we address the problem of the formation of living clusters and crystals of active particles in three dimensions. We study two systems: self-propelled particles interacting via a generic attractive potential and colloids that can move toward each other as a result of active agents (e.g., by molecular motors). In both cases, fluidlike “living” clusters form. We explain this general feature in terms of the balance between active forces and regression to thermodynamic equilibrium. This balance can be quantified in terms of a dimensionless number that allows us to collapse the observed clustering behavior onto a universal curve. We also discuss how active motion affects the kinetics of crystal formation.
Roughness-dependent tribology effects on discontinuous shear thickening
Hsu, Chiao-Peng; Ramakrishna, Shivaprakash N.; Zanini, Michele; Spencer, Nicholas D.
2018-01-01
Surface roughness affects many properties of colloids, from depletion and capillary interactions to their dispersibility and use as emulsion stabilizers. It also impacts particle–particle frictional contacts, which have recently emerged as being responsible for the discontinuous shear thickening (DST) of dense suspensions. Tribological properties of these contacts have been rarely experimentally accessed, especially for nonspherical particles. Here, we systematically tackle the effect of nanoscale surface roughness by producing a library of all-silica, raspberry-like colloids and linking their rheology to their tribology. Rougher surfaces lead to a significant anticipation of DST onset, in terms of both shear rate and solid loading. Strikingly, they also eliminate continuous thickening. DST is here due to the interlocking of asperities, which we have identified as “stick–slip” frictional contacts by measuring the sliding of the same particles via lateral force microscopy (LFM). Direct measurements of particle–particle friction therefore highlight the value of an engineering-tribology approach to tuning the thickening of suspensions. PMID:29717043
Transparent arrays of silver nanowire rings driven by evaporation of sessile droplets
NASA Astrophysics Data System (ADS)
Wang, Xiaofeng; Kang, Giho; Seong, Baekhoon; Chae, Illkyeong; Teguh Yudistira, Hadi; Lee, Hyungdong; Kim, Hyunggun; Byun, Doyoung
2017-11-01
A coffee-ring pattern can be yielded on the three-phase contact line following evaporation of sessile droplets with suspended insoluble solutes, such as particles, DNA molecules, and mammalian cells. The formation of such coffee-ring, together with their suppression has been applied in printing and coating technologies. We present here an experimental study on the assembly of silver nanowires inside an evaporating droplet of a colloidal suspension. The effects of nanowire length and concentration on coffee-ring formation of the colloidal suspension were investigated. Several sizes of NWs with an aspect ratio between 50 and 1000 were systematically investigated to fabricate coffee-ring patterns. Larger droplets containing shorter nanowires formed clearer ring deposits after evaporation. An order-to-disorder transition of the nanowires’ alignment was found inside the rings. A printing technique with the evaporation process enabled fabrication of arrays of silver nanowire rings. We could manipulate the patterns silver nanowire rings, which might be applied to the transparent and flexible electrode.
Roughness-dependent tribology effects on discontinuous shear thickening.
Hsu, Chiao-Peng; Ramakrishna, Shivaprakash N; Zanini, Michele; Spencer, Nicholas D; Isa, Lucio
2018-05-15
Surface roughness affects many properties of colloids, from depletion and capillary interactions to their dispersibility and use as emulsion stabilizers. It also impacts particle-particle frictional contacts, which have recently emerged as being responsible for the discontinuous shear thickening (DST) of dense suspensions. Tribological properties of these contacts have been rarely experimentally accessed, especially for nonspherical particles. Here, we systematically tackle the effect of nanoscale surface roughness by producing a library of all-silica, raspberry-like colloids and linking their rheology to their tribology. Rougher surfaces lead to a significant anticipation of DST onset, in terms of both shear rate and solid loading. Strikingly, they also eliminate continuous thickening. DST is here due to the interlocking of asperities, which we have identified as "stick-slip" frictional contacts by measuring the sliding of the same particles via lateral force microscopy (LFM). Direct measurements of particle-particle friction therefore highlight the value of an engineering-tribology approach to tuning the thickening of suspensions. Copyright © 2018 the Author(s). Published by PNAS.
NASA Astrophysics Data System (ADS)
Salim, Evan T.; Admon Saimon, Jehan; Abood, Marwa K.; Fakhri, Makram A.
2017-10-01
This work presents the successful preparation of niobium pentoxide micro structures thin films at room temperature. A chemical colloidal suspension was deposited employing Spin coating method. Nb2O5 thin films were prepared at two different thicknesses before and after ultrasonic vibration processes. Optical, structural, and morphological properties were studied. An enhanced crystalline structure with bigger grain size at both thicknesses was obtained after ultrasonic process; this was ensured by SEM results. The energy gap of the prepared films was estimated and found to be about (2.81, 2.42) eV for (T1 = 325 nm) and (2.59, 2.32) eV at the second thickness (T2 = 425 nm). The I-V characteristic study of prepared heterojunction on silicon substrate show an increase in the rectification ratio after the ultrasonic vibrational process for both thicknesses.
Li, Yuelin; Jiang, Zhang; Lin, Xiao -Min; ...
2015-01-30
Many potential industrial, medical, and environmental applications of metal nanorods rely on the physics and resultant kinetics and dynamics of the interaction of these particles with light. We report a surprising kinetics transition in the global melting of femtosecond laser-driven gold nanorod aqueous colloidal suspension. At low laser intensity, the melting exhibits a stretched exponential kinetics, which abruptly transforms into a compressed exponential kinetics when the laser intensity is raised. It is found the relative formation and reduction rate of intermediate shapes play a key role in the transition. Supported by both molecular dynamics simulations and a kinetic model, themore » behavior is traced back to the persistent heterogeneous nature of the shape dependence of the energy uptake, dissipation and melting of individual nanoparticles. These results could have significant implications for various applications such as water purification and electrolytes for energy storage that involve heat transport between metal nanorod ensembles and surrounding solvents.« less
[MAXIMUM SINGLE DOSE OF COLLOIDAL SILVER NEGATIVELY AFFECTS ERYTHROPOIESIS IN VITRO].
Tishevskayal, N V; Zakharovl, Y M; Bolotovl, A A; Arkhipenko, Yu V; Sazontova, T G
2015-01-01
Erythroblastic islets (EI) of rat bone marrow were cultured for 24 h in the presence of silver nanoparticles (1.07 · 10(-4) mg/ml; 1.07 · 10(-3) mg/ml; and 1.07 · 10(-2) mg/mL). The colloidal silver at 1.07 · 10(-3) mg/ml concentration inhibited the formation of new Elby disrupting contacts of bone marrow macrophages with CFU-E (erythropoiesis de novo) by 65.3% (p < 0.05). Colloidal silver nanoparticles suppressed the reconstruction of erythropoiesis and inhibited the formation of new EI by disrupting contacts of CFU-E and central macrophages with matured erythroidal "crown" (erythropoiesis de repeto). The colloidal silver concentration of 1.07 · 10(-3) mg/ml in the culture medium also reduced the number of self-reconstructing EI by 67.5% (p <0.05), whereas 1.07 · 10(-2) mg/ml colloidal silver reduced this value by 93.7% (p < 0.05). Silver nanoparticles retarded maturation of erythroid cells at the stage of oxiphylic normoblast denucleation: 1.07 · 10(-3) mg/ml colloidal silver increased the number of mature El by 53% (p < 0.05). The retardation of erythropoiesis by colloidal silver in concentration equivalent to the maximum single dose is related to the effect of silver nanoparticles rather than glycerol present in the colloidal suspension.
Simulations to Predict the Phase Behavior and Structure of Multipolar Colloidal Particles
NASA Astrophysics Data System (ADS)
Rutkowski, David Matthew
Colloidal particles with anisotropic charge distributions can assemble into a number of interesting structures including chains, lattices and micelles that could be useful in biotechnology, optics and electronics. The goal of this work is to understand how the properties of the colloidal particles, such as their charge distribution or shape, affect the selfassembly and phase behavior of collections of such particles. The specific aim of this work is to understand how the separation between a pair of oppositely signed charges affects the phase behavior and structure of assemblies of colloidal particles. To examine these particles, we have used both discontinuous molecular dynamics (DMD) and Monte Carlo (MC) simulation techniques. In our first study of colloidal particles with finite charge separation, we simulate systems of 2-D colloidal rods with four possible charge separations. Our simulations show that the charge separation does indeed have a large effect on the phase behavior as can be seen in the phase diagrams we construct for these four systems in the area fraction-reduced temperature plane. The phase diagrams delineate the boundaries between isotropic fluid, string-fluid and percolated fluid for all systems considered. In particular, we find that coarse gel-like structures tend to form at large charge separations while denser aggregates form at small charge separations, suggesting a route to forming low volume gels by focusing on systems with large charge separations. Next we examine systems of circular particles with four embedded charges of alternating sign fixed to a triangular lattice. This system is found to form a limit periodic structure, a theoretical structure with an infinite number of phase transitions, under specific conditions. The limit-periodic structure only forms when the rotation of the particles in the system is restricted to increments of pi/3. When the rotation is restricted to increments of th/6 or the rotation is continuous, related structures form including a striped phase and a phase with nematic order. Neither the distance from the point charges to the center of the particle nor the angle between the charges influences whether the system forms a limit-periodic structure, suggesting that point quadrupoles may also be able to form limit-periodic structures. Results from these simulations will likely aid in the quest to find an experimental realization of a limit-periodic structure. Next we examine the effect of charge separation on the self-assembly of systems of 2-D colloidal particles with off-center extended dipoles. We simulate systems with both small and large charge separations for a set of displacements of the dipole from the particle center. Upon cooling, these particles self-assemble into closed, cyclic structures at large displacements including dimers, triangular shapes and square shapes, and chain-like structures at small displacements. At extremely low temperatures, the cyclic structures form interesting lattices with particles of similar chirality grouped together. Results from this work could aid in the experimental construction of open lattice-like structures that could find use in photonic applications. Finally, we present work in collaboration with Drs. Bhuvnesh Bharti and Orlin Velev in which we investigate how the surface coverage affects the self-assembly of systems of Janus particles coated with both an iron oxide and fatty acid chain layer. We model these particles by decorating a sphere with evenly dispersed points that interact with points on other spheres through square-well interactions. The interactions are designed to mimic specific coverage values for the iron oxide/fatty acid chain layer. Structures similar to those found in experiment form readily in the simulations. The number of clusters formed as a function of surface coverage agrees well with experiment. The aggregation behavior of these novel particles can therefore, be described by a relatively simple model.
NASA Astrophysics Data System (ADS)
Faisal, Mahtab
Much research efforts have been devoted in developing new synthetic approaches for fluorescent silica nanoparticles (FSNPs) due to their potential high-technological applications. However, light emissions from most of the FSNPs prepared so far have been rather weak. This is due to the emission quenching caused by the aggregation of fluorophores in the solid state. We have observed a novel phenomenon of aggregation-induced emission (AIE): a series of propeller-shaped molecules such as tetraphenylethene (TPE) and silole are induced to emit efficiently by aggregate formation. Thus, they are ideal fluorophors for the construction of FSNPs and my thesis work focuses on the synthesis of silica nanoparticles containing these luminogens and magnetic nanostructures. Highly emissive FSNPs with core-shell structures are fabricated by surfactant-free sol-gel reactions of tetraphenylethene- (TPE) and silole-functionalized siloxanes followed by the reactions with tetraethoxysilane. The FSNPs are uniformly sized, surface-charged and colloidally stable. The diameters of the FSNPs are tunable in the range of 45--295 nm by changing the reaction conditions. Whereas their TPE and silole precursors are non-emissive, the FSNPs emit strong visible lights, thanks to the novel aggregation-induced emission characteristics of the TPE and silole aggregates in the hybrid nanoparticles. The FSNPs pose no toxicity to living cells and can be utilized to selectively image cytoplasm of HeLa cells. Applying the same tool in the presence of citrate-coated magnetite nanoparticles, uniform magnetic fluorescent silica nanoparticles (MFSNPs) with smooth surfaces are fabricated. These particles exhibit appreciable surface charges and hence good colloidal stability. They are superparamagnetic, exhibiting no hysteresis at room temperature. UV irradiation of a suspension of MFSNPs in ethanol gives strong blue and green emissions. The MFSNPs can selectively stain the cytoplasmic regions of the living cells. Sol-gel reaction in the presence of (3-aminopropyl)triethoxysilane has generated MFSNP-NH2 with numerous amino functionalities decorated on the surfaces, enabling them to immobilize bovine serum albumin efficiently. FSNPs with strong light emissions are facilely fabricated by thio-click chemistry, Cu(I)-catalyzed 1,3-dipolar cycloaddition, and sol-gel reaction. The FSNPs are characterized by SEM, TEM, IR, PL, and zeta potential analyses. They are uniformly sized with smooth surfaces. Upon photoexcitation, the FSNPs emit strong visible lights with fluorescence quantum yields up to 25.5%. Sugar-functionalized fluorescent silica nanoparticles are facilely fabricated by click reaction of azide-modified FSNPs with sugar- containing phenylacetylene catalyzed by Cu(PPh3)3Br in THF. The nanoparticles are uniformly sized and emit efficient light upon photoexcitation. They can function as fluorescent visualizers for intracellular imaging and can target specific cancer cells. Folic acid-functionalized fluorescent silica nanoparticles are facilely fabricated by surface functionalization of FSNPs with folic acid. The nanoparticles are spherical in shape. They possess high zeta potentials and hence exhibit excellent colloidal stability. UV irradiation of suspensions of the nanoparticles in ethanol gives strong blue and green emissions at 465 and 490 nm with absolute fluorescence quantum yields up to 47%. Carboxylic acid and thiol-functionalized fluorescent silica nanoparticles (FSNP-COOH and FSNP-SH) with uniform particle sizes, narrow size distributions, and smooth surface morphologies are fabricated. The nanoparticles possess high surface charges and exhibit strong light emissions upon photoexcitation. They can adsorb lysozyme strongly on their surfaces and for 5 mg of FSNP-COOH and FSNP-SH, they can take 209 and 86 mug of lysozyme. Thus, they are potential carriers for protein and fluorescent probes or biosensors for an array of biological applications.
Dynamic self-assembly of charged colloidal strings and walls in simple fluid flows.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Ning
Independent of the methods of nuclear waste disposal, the degradation of packaging materials could lead to mobilization and transport of radionuclides into the geosphere. This process can be significantly accelerated due to the association of radionuclides with the backfill materials or mobile colloids in groundwater. The transport of these colloids is complicated by the inherent coupling of physical and chemical heterogeneities (e.g., pore space geometry, grain size, charge heterogeneity, and surface hydrophobicity) in natural porous media that can exist on the length scale of a few grains. In addition, natural colloids themselves are often heterogeneous in their surface properties (e.g.,more » clay platelets possess opposite charges on the surface and along the rim). Both physical and chemical heterogeneities influence the transport and retention of radionuclides under various groundwater conditions. However, the precise mechanisms how these coupled heterogeneities influence colloidal transport are largely elusive. This knowledge gap is a major source of uncertainty in developing accurate models to represent the transport process and to predict distribution of radionuclides in the geosphere.« less
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).
Multipole Plasmon Resonances in Gold Nanorods
Payne, Emma Kathryn; Shuford, Kevin L.; Park, Sungho; Schatz, George C.
2011-01-01
The optical properties of gold rods electrochemically deposited in anodic aluminum oxide templates have been investigated. Homogeneous suspensions of rods with average diameter of 85 nm and varying lengths of 96, 186, 321, 465, 495, 578, 641, 735, and 1175 nm were fabricated. The purity and dimensions of these rod nanostructures allowed us to observe higher order multipole resonances for the first time in a colloidal suspension. The experimental optical spectra agree with discrete dipole approximation calculations that have been modeled from the dimensions of the gold nanorods. PMID:16471797
Impact-induced solidlike behavior and elasticity in concentrated colloidal suspensions
NASA Astrophysics Data System (ADS)
Chu, Baojin; Salem, David R.
2017-10-01
Modified drop weight impact tests were performed on Si O2 -ethylene glycol concentrated suspensions. Counterintuitive impact-induced solidlike behavior and elasticity, causing significant deceleration and rebound of the impactor, were observed. We provide evidence that the observed large deceleration force on the impactor mainly originates from the hydrodynamic force, and that the elasticity arises from the short-range repulsive force of a solvation layer on the particle surface. This study presents key experimental results to help understand the mechanisms underlying various stress-induced solidification phenomena.
Coupled factors influencing detachment of nano- and micro-sized particles from primary minima.
Shen, Chongyang; Lazouskaya, Volha; Jin, Yan; Li, Baoguo; Ma, Zhiqiang; Zheng, Wenjuan; Huang, Yuanfang
2012-06-01
This study examined the detachments of nano- and micro-sized colloids from primary minima in the presence of cation exchange by laboratory column experiments. Colloids were initially deposited in columns packed with glass beads at 0.2 M CaCl(2) in the primary minima of Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energies. Then, the columns were flushed with NaCl solutions with different ionic strengths (i.e., 0.001, 0.01, 0.1 and 0.2 M). Detachments were observed at all ionic strengths and were particularly significant for the nanoparticle. The detachments increased with increasing electrolyte concentration for the nanoparticle whereas increased from 0.001 M to 0.01 M and decreased with further increasing electrolyte concentration for the micro-sized colloid. The observations were attributed to coupled influence of cation exchange, short-range repulsion, surface roughness, surface charge heterogeneity, and deposition in the secondary minima. The detachments of colloids from primary minima challenge the common belief that colloid interaction in primary minimum is irreversible and resistant to disturbance in solution ionic strength and composition. Although the significance of surface roughness, surface charge heterogeneity, and secondary minima on colloid deposition has been widely recognized, our study implies that they also play important roles in colloid detachment. Whereas colloid detachment is frequently associated with decrease of ionic strength, our results show that increase of ionic strength can also cause detachment due to influence of cation exchange. Copyright © 2012 Elsevier B.V. All rights reserved.
Nano-colloid electrophoretic transport: Fully explicit modelling via dissipative particle dynamics
NASA Astrophysics Data System (ADS)
Hassanzadeh Afrouzi, Hamid; Farhadi, Mousa; Sedighi, Kurosh; Moshfegh, Abouzar
2018-02-01
In present study, a novel fully explicit approach using dissipative particle dynamics (DPD) method is introduced for modelling electrophoretic transport of nano-colloids in an electrolyte solution. Slater type charge smearing function included in 3D Ewald summation method is employed to treat electrostatic interaction. Moreover, capability of different thermostats are challenged to control the system temperature and study the dynamic response of colloidal electrophoretic mobility under practical ranges of external electric field in nano scale application (0.072 < E < 0.361 v / nm) covering non-linear response regime, and ionic salt concentration (0.049 < SC < 0.69 [M]) covering weak to strong Debye screening of the colloid. The effect of different colloidal repulsions are then studied on temperature, reduced mobility and zeta potential which is computed based on charge distribution within the spherical colloidal EDL. System temperature and electrophoretic mobility both show a direct and inverse relationship respectively with electric field and colloidal repulsion. Mobility declining with colloidal repulsion reaches a plateau which is a relatively constant value at each electrolyte salinity for Aii > 600 in DPD units regardless of electric field intensity. Nosé-Hoover-Lowe-Andersen and Lowe-Andersen thermostats are found to function more effectively under high electric fields (E > 0.145 [ v / nm ]) while thermal equilibrium is maintained. Reasonable agreements are achieved by benchmarking the radial distribution function with available electrolyte structure modellings, as well as comparing reduced mobility against conventional Smoluchowski and Hückel theories, and numerical solution of Poisson-Boltzmann equation.
Fujita, Yosuke; Kobayashi, Motoyoshi
2016-07-01
We have studied the transport of colloidal silica in various degrees of a water-saturated Toyoura sand column, because silica particles are widely used as catalyst carriers and abrasive agents, and their toxicity is reported recently. Since water-silica, water-sand, and air-water interfaces have pH-dependent negative charges, the magnitude of surface charge was controlled by changing the solution pH. The results show that, at high pH conditions (pH 7.4), the deposition of colloidal silica to the sand surface is interrupted and the silica concentration at the column outlet immediately reaches the input concentration in saturated conditions. In addition, the relative concentration of silica at the column outlet only slightly decreases to 0.9 with decreasing degrees of water saturation to 38%, because silica particles are trapped in straining regions in the soil pore and air-water interface. On the other hand, at pH 5 conditions (low pH), where sand and colloid have less charge, reduced repulsive forces result in colloidal silica attaching onto the sand in saturated conditions. The deposition amount of silica particles remarkably increases with decreasing degrees of water saturation to 37%, which is explained by more particles being retained in the sand column associated with the air-water interface. In conclusion, at higher pH, the mobility of silica particles is high, and the air-water interface is inactive for the deposition of silica. On the other hand, at low pH, the deposition amount increases with decreasing water saturation, and the particle transport is inhibited. Copyright © 2016 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dylla-Spears, R.; Wong, L.; Shen, N.
Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption tomore » measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles—far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface.« less
Retention of Aqu/C60 Nanoparticles on Quartz Surfaces
Studies have shown that C60 fullerene can form stable suspensions of colloidal sized particles in water resulting in C60 aqueous concentrations many orders of magnitude above C60’s aqueous solubility. These studies have raised concern over the mobility and distribution of fuller...
Nanodiamond in Colloidal Suspension: Electrophoresis; Other Observations
NASA Technical Reports Server (NTRS)
Meshik, A. P.; Pravdivtseva, O. V.; Hohenberg, C. M.
2002-01-01
Selective laser extraction has demonstrated that meteoritic diamonds may consist of subpopulations with different optical absorption properties, but it is not clear what makes them optically different. More work is needed to understand the mechanism for selective laser extraction. Additional information is contained in the original extended abstract.
A novel green approach for the preparation of cellulose nanowhiskers from white coir.
Nascimento, Diego M; Almeida, Jessica S; Dias, Amanda F; Figueirêdo, Maria Clea B; Morais, João Paulo S; Feitosa, Judith P A; de F Rosa, Morsyleide
2014-09-22
The aim of this work was to optimize the extraction of cellulose nanowhiskers (CNW) from unripe coconut husk fibers (CHF). The CHF was delignified using organosolv process, followed by alkaline bleaching (5% (w/w) H2O2+4% (w/w) NaOH; 50°C, 90 min). The CHF was subsequently hydrolyzed with 30% (v/v) sulfuric acid (60°C, 360 min). The process yielded a partially delignified acetosolv cellulose pulp and acetic black liquor, from which the lignin was recovered. The CNW from the acetosolv pulp exhibited an average length of 172±88 nm and a diameter of 8±3 nm, (aspect ratio of 22±8). The surface charge of the CNW was -33 mV, indicating a stable aqueous colloidal suspension. The nanocrystals presented physical characteristics close to those extracted from cellulose pulp made by CHF chlorine-pulping. This approach offers the additional advantage of extracting the lignin as an alternative to eradication. Copyright © 2014 Elsevier Ltd. All rights reserved.
Ovalle-Serrano, S A; Gómez, F N; Blanco-Tirado, C; Combariza, M Y
2018-06-01
Fique fibers are extracted from Furcraea spp. leaves, with 5% average mass yield, using mechanical decortication. Juice, pulp and tow, the by-products of this process, amount 95% of the leaf weight and are considered waste. We extracted cellulose nanofibrils (CNF) from Fique tow, via ultrasound-assisted TEMPO followed by mechanical disintegration with sonication. Fique CNF exhibit diameters around 100 nm, degree of oxidation (DO) of 0.27 and surface charge density (σ) of 1.6 mmol/g. Fique CNF aqueous suspensions show optical birefringence and high colloidal stability due to a high ζ potential (-53 mV). The morphology, chemical structure, crystallinity and phase transitions of Fique CNF were studied using FESEM, IR-ATR, XRD and TGA. We observed that the delignification pretreatment and the TEMPO reaction assisted by ultrasound significantly increase Fique CNF σ and ζ potential, in contrast with the oxidation carried out without ultrasound or with raw (lignified) tow. Copyright © 2018 Elsevier Ltd. All rights reserved.
Dhanasekaran, Madhumitha; Dhathathreyan, Aruna
2017-08-01
This work examines fibro-proliferation through interaction of myoglobin (Mb), a globular protein with collagen, an extracellular matrix fibrous protein. Designed colloids of Mb at pH 4.5 and 7.5 have been mixed with collagen solution at pH 7.5 and 4.5 in different concentrations altering their surface charges. For the Mb colloids, 100-200nm sizes have been measured from Transmission electron micrographs and zeta sizer. CD spectra shows a shift to beta sheet like structure for the protein in the colloids. Interaction at Mb/Collagen interface studied using Dilational rheology, Quartz crystal microbalance with dissipation and Differential Scanning calorimetry show that the perturbation is not only by the charge compensation arising from the difference in pH of the colloids and collagen, but also by the organized assembly of collagen at that particular pH. Results demonstrate that positive Mb colloids at pH 4.5, having more% of entrained water stabilize the collagen fibrils (pH 7.5) around them. Ensuing dehydration leads to effective cross-linking and inherently anisotropic growth of fibrils/fibres of collagen. In the case of Mb colloids at pH 7.5, the fibril formation seems to supersede the clustering of Mb suggesting that the fibro-proliferation is both pH and hydrophilic-hydrophobic balance dependent at the interface. Copyright © 2017 Elsevier B.V. All rights reserved.
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).
NASA Astrophysics Data System (ADS)
Wu, Ling; Nishi, Hiroyasu; Tatsuma, Tetsu
2015-10-01
Photoelectrodes based on plasmonic Au semishell (or halfshell) arrays are developed. A colloidal crystal consisting of SiO2@TiO2 core-shell particles is prepared on a TiO2-coated transparent electrode. A Au semishell (or halfshell) array is deposited by sputtering or evaporation on the colloidal crystal. An electrode with the semishell (or halfshell) array exhibits negative photopotential shifts and anodic photocurrents under visible light at 500-800 nm wavelengths in an aqueous electrolyte containing an electron donor. In particular, hydroquinone and ethanol are good electron donors. The photocurrents can be explained in terms of plasmon-induced charge separation at the Au-TiO2 interface.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Ling; Nishi, Hiroyasu; Tatsuma, Tetsu, E-mail: tatsuma@iis.u-tokyo.ac.jp
2015-10-01
Photoelectrodes based on plasmonic Au semishell (or halfshell) arrays are developed. A colloidal crystal consisting of SiO{sub 2}@TiO{sub 2} core-shell particles is prepared on a TiO{sub 2}-coated transparent electrode. A Au semishell (or halfshell) array is deposited by sputtering or evaporation on the colloidal crystal. An electrode with the semishell (or halfshell) array exhibits negative photopotential shifts and anodic photocurrents under visible light at 500-800 nm wavelengths in an aqueous electrolyte containing an electron donor. In particular, hydroquinone and ethanol are good electron donors. The photocurrents can be explained in terms of plasmon-induced charge separation at the Au-TiO{sub 2} interface.
A Colloidal-Quantum-Dot-Based Self-Charging System via the Near-Infrared Band.
Baek, Se-Woong; Cho, Jungmin; Kim, Joo-Seong; Kim, Changjo; Na, Kwangmin; Lee, Sang-Hoon; Jun, Sunhong; Song, Jung Hoon; Jeong, Sohee; Choi, Jang Wook; Lee, Jung-Yong
2018-05-11
A novel self-charging platform is proposed using colloidal-quantum-dot (CQD) photovoltaics (PVs) via the near-infrared (NIR) band for low-power electronics. Low-bandgap CQDs can convert invisible NIR light sources to electrical energy more efficiently than wider spectra because of reduced thermalization loss. This energy-conversion strategy via NIR photons ensures an enhanced photostability of the CQD devices. Furthermore, the NIR wireless charging system can be concealed using various colored and NIR-transparent fabric or films, providing aesthetic freedom. Finally, an NIR-driven wireless charging system is demonstrated for a wearable healthcare bracelet by integrating a CQD PVs receiver with a flexible lithium-ion battery and entirely embedding them into a flexible strap, enabling permanent self-charging without detachment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Ceramic membranes with enhanced thermal stability
Anderson, Marc A.; Xu, Qunyin; Bischoff, Brian L.
1993-01-01
A method of creating a ceramic membrane with enhanced thermal stability is disclosed. The method involves combining quantities of a first metal alkoxide with a second metal, the quantities selected to give a preselected metal ratio in the resultant membrane. A limited amount of water and acid is added to the combination and stirred until a colloidal suspension is formed. The colloid is dried to a gel, and the gel is fired at a temperature greater than approximately 400.degree. C. The porosity and surface area of ceramic membranes formed by this method are not adversely affected by this high temperature firing.
Shear Induced Structural Relaxation in a Supercooled Colloidal Liquid
NASA Astrophysics Data System (ADS)
Chen, Dandan; Semwogerere, Denis; Weeks, Eric R.
2009-11-01
Amorphous materials include many common products we use everyday, such as window glass, moisturizer, shaving cream and peanut butter. These materials have liquid-like disordered structure, but keep their shapes like a solid. The rheology of dense amorphous materials under large shear strain is not fully understood, partly due to the difficulty of directly viewing the microscopic details of such materials. We use a colloidal suspension to simulate amorphous materials, and study the shear- induced structural relaxation with fast confocal microscopy. We quantify the plastic rearrangements of the particles using standard analysis techniques based on the motion of the particles.
Cellulose nanocrystals with tunable surface charge for nanomedicine
NASA Astrophysics Data System (ADS)
Hosseinidoust, Zeinab; Alam, Md Nur; Sim, Goeun; Tufenkji, Nathalie; van de Ven, Theo G. M.
2015-10-01
Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge.Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge. Electronic supplementary information (ESI) available: Additional results are presented in the ESI in Fig. S1 through S4. See DOI: 10.1039/c5nr02506k
NASA Astrophysics Data System (ADS)
Goltz, Douglas; Boileau, Michael; Reinfelds, Gundars
2003-07-01
When high current (1-10 A cm -2) is applied between two conductive samples (metals) in aqueous solution, electroerosion occurs on the surface as a result of electrolysis and possibly collisions of dissolved ions with the metal surface. The power supply for the electroerosion apparatus in this work was a modified spark source unit. Current could be varied in intervals of 2.5, 5 and 10 A in either half-wave (unipolar) or full-wave (bipolar) output. The electroeroded metal forms a colloidal suspension in aqueous solution with particle sizes of the order of 1-10 μm and possibly larger. The suspension is readily dissolved using a small amount (100 μl) of concentrated acid (HCl or HNO 3) prior to analysis. Electroerosion of steel and brass in aqueous solution is described both for rapid sample dissolution and as a solid sampling approach for ICP-MS. Some of the electroerosion properties described in this paper include rates of erosion as a function of gap between the conductive samples and solution conductivity. Rates of electroerosion decreased from 120 to 30 μg s -1 as the gap was increased from 2 to 5 mm. Rates of electroerosion also increased significantly from 200 to 1000 μg s -1 as the conductivity of the electroerosion solution increased from 0.01 to 0.05 M NaCl. Interfacing the electroerosion apparatus to an ICP-MS was straight forward, as no special equipment was required. Therefore, the electroerosion apparatus can be used for rapid 'on-line' sample dissolution prior to introduction into an ICP. ICP-MS time profiles of selected metals in stainless steel 308L illustrate the behavior of 52Cr +, 55Mn + and 60Ni + during a typical electroerosion cycle. Aspiration of the colloidal suspension into the ICP did not appear to load the plasma significantly, however, all of the metals produced noisy signals (±10%). A glass concentric nebulizer was used without clogging, so it is likely that the heterogeneous nature of the colloidal suspension caused this effect.
NASA Astrophysics Data System (ADS)
Dittrich, T. M.; Boukhalfa, H.; Reimus, P. W.
2014-12-01
The objective of this study was to investigate and quantify the effects of desorption kinetics and colloid transport on radionuclides with different sorption affinities. We focused on quantifying transport mechanisms important for upscaling in time and distance. This will help determine the long-term fate and transport of radionuclides to aid in risk assessments. We selected a fractured/weathered granodiorite at the Grimsel Test Site (GTS) in Switzerland as a model crystalline rock repository system because the system has been thoroughly studied and field experiments involving radionuclides have already been conducted. Working on this system provides a unique opportunity to compare lab experiments with field-scale observations. Weathered fracture fill material (FFM) and bentonite used as backfill at the GTS were characterized (e.g., BET, SEM/EDS, QXRD), and batch and breakthrough column experiments were conducted. Solutions were prepared in synthetic groundwaters that matched the natural water chemistry. FFM samples were crushed, rinsed, sieved (150-355 μm), and equilibrated with synthetic groundwater. Bentonite was crushed, sodium-saturated, equilibrated with synthetic groundwater, and settled to yield a stable suspension. Suspensions were equilibrated with Am, Cs, or Pu. All experiments were conducted with Teflon®materials to limit sorption to system components. After radionuclide/colloid injections reached stability, radionuclide-free solutions were injected to observe the desorption and release behavior. Aliquots of effluent were measured for pH, colloid concentration, and total and dissolved radionuclides. Unanalyzed effluent from the first column was then injected through a second column of fresh material. The process was repeated for a third column and the results of all three breakthrough curves were modeled with a multi-site/multi-rate MATLAB code to elucidate the sorption rate coefficients and binding site densities of the bentonite colloids and fracture fill material. Nearly 50% of the sorbed Am was exchanged from the colloids to the fracture filling material in each of the three columns; whereas, less Cs and Pu was desorbed with each pass through a new column. Using a two-site kinetic model allowed for interrogation of desorption rates and dominant transport parameters.
Pilot scale application of nanosized iron oxides as electron acceptors for bioremediation
NASA Astrophysics Data System (ADS)
Bosch, Julian; Fritzsche, Andreas; Frank-Fahle, Beatrice; Lüders, Tilmann; Höss, Sebastian; Eisenmann, Heinrich; Held, Thomas; Totsche, Kai U.; Meckenstock, Rainer U.
2014-05-01
Microbial reduction of ferric iron is a major biogeochemical process in groundwater aquifer ecosystems and often associated with the degradation of organic contaminants, as bacteria couple iron reduction to the oxidation reduced carbon like e.g. BTEX. Yet in general the low bioavailability of natural iron oxides limits microbial reduction rates. However, nanosized iron oxides have an unequally enhanced bioavailability and reactivity compared to their respective bulk, macro-sized, and more crystalline materials. At the same time, nanosized iron oxides can be produced in stable colloidal suspensions, permitting efficient injections into contaminated aquifers. We examined the reactivity of nanosized synthetic colloidal iron oxides in microbial iron reduction. Application of colloidal nanoparticles led to a strong and sustainable enhancement of microbial reaction rates in batch experiments and sediment columns. Toluene oxidation was increased five-fold as compared to bulk, non-colloidal ferrihydrite as electron acceptor. Furthermore, we developed a unique approach for custom-tailoring the subsurface mobility of these particles after being injected into a contaminant plume. In a field pilot application, we injected 18 m3 of an iron oxide nanoparticle solution into a BTEX contaminated aquifer with a maximum excess pressure as low as 0.2 bar. The applied suspension showed a superior subsurface mobility, creating a reactive zone of 4 m height (corresponding to the height of the confined aquifer) and 6 m in diameter. Subsequent monitoring of BTEX, microbial BTEX degradation metabolites, ferrous iron generation, stable isotopes fractionation, microbial populations, and methanogenesis demonstrated the strong impact of our approach. Mathematic processed X-ray diffractograms and FTIR spectra provided a semi-quantitatively estimate of the long-term fate of the iron oxide colloids in the aquifer. Potential environmental risks of the injection itself were monitored with ecotoxicological investigations. Our data suggest that the injection of ferric iron nanoparticles as electron acceptors into contaminated aquifers for the enhancement of microbial contaminant degradation might develop into a novel bioremediation strategy.
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
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
Flocking ferromagnetic colloids
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
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
Crystallography of ordered colloids using optical microscopy. 2. Divergent-beam technique.
Rogers, Richard B; Lagerlöf, K Peter D
2008-04-10
A technique has been developed to extract quantitative crystallographic data from randomly oriented colloidal crystals using a divergent-beam approach. This technique was tested on a series of diverse experimental images of colloidal crystals formed from monodisperse suspensions of sterically stabilized poly-(methyl methacrylate) spheres suspended in organic index-matching solvents. Complete sets of reciprocal lattice basis vectors were extracted in all but one case. When data extraction was successful, results appeared to be accurate to about 1% for lattice parameters and to within approximately 2 degrees for orientation. This approach is easier to implement than a previously developed parallel-beam approach with the drawback that the divergent-beam approach is not as robust in certain situations with random hexagonal close-packed crystals. The two techniques are therefore complimentary to each other, and between them it should be possible to extract quantitative crystallographic data with a conventional optical microscope from any closely index-matched colloidal crystal whose lattice parameters are compatible with visible wavelengths.
Mahmoud, Nouf N; Alkilany, Alaaldin M; Khalil, Enam A; Al-Bakri, Amal G
2017-01-01
The antibacterial activity of gold nanorod (GNR) suspensions of different surface functionalities was investigated against standard strains of Staphylococcus aureus and Propionibacterium acnes , taking into consideration two commonly "overlooked" factors: the colloidal stability of GNR suspensions upon mixing with bacterial growth media and the possible contribution of "impurities/molecules" in GNR suspensions to the observed antibacterial activity. The results demonstrated that cationic polyallylamine hydrochloride (PAH)-GNR were severely aggregated when exposed to bacterial growth media compared to other GNR suspensions. In addition, the free cetyltrimethylammonium bromide (CTAB) present in GNR suspensions is most likely the origin of the observed antibacterial activity. However, the antibacterial activity of GNR themselves could not be excluded. Probing these two critical control studies prevents misinterpretations and artifacts of the antibacterial activity of nanoparticles. Unfortunately, these practices are usually ignored in the published studies and may explain the significant conflicting results. In addition, this study indicates that GNR could be a promising candidate for the treatment of skin follicular diseases such as acne vulgaris.
Winuprasith, Thunnalin; Suphantharika, Manop; McClements, David Julian; He, Lili
2014-02-15
In this work, we investigated the conformational changes of a globular protein (β-lactoglobulin, β-lg) coated on the surface of 200 nm gold nanoparticles (GNPs) using a number of analytical techniques: dynamic light scattering (DLS); particle electrophoresis (ζ-potential); localized surface plasmon resonance (LSPR) spectroscopy; transmission electron microscopy (TEM); and surface-enhanced Raman scattering (SERS). The β-lg (pH 3) concentration had a pronounced effect on the aggregation and surface charge of β-lg-coated GNPs. The surface charge of GNPs changed from negative to positive as increasing amounts of β-lg molecule were added, indicating that the globular protein molecules adsorbed to the surfaces of the particles. Extensive particle aggregation occurred when β-lg did not saturate the GNP surfaces, which was attributed to electrostatic bridging flocculation. Modifications in LSPR and SERS spectra after addition of β-lg to the GNP suspensions supported the adsorption of β-lg to the particle surfaces. Moreover, SERS highlighted the importance of a number of specific molecular groups in the binding interaction, and suggested conformational changes of the globular protein after adsorption. This research provides useful information for characterizing and understanding the interactions between globular proteins and colloidal particles. Copyright © 2013 Elsevier Inc. All rights reserved.
Spanhel, Lubomir; Anderson, Marc A.
1992-07-07
A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.
Spanhel, Lubomir; Anderson, Marc A.
1991-10-22
A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.
Using Asymmetric Flow Field-Flow Fractionation (AF4) to Determine C60 Colloidal Size Distributions
The formation of aqueous fullerene suspensions by solvent exchange, sonication, or extended mixing in water is widely reported. Commonly used methods for determining the size of these aggregates rely on static and dynamic light scattering, electron microscopy (EM), or atomic forc...
THE EFFECT OF PH AND DISSOLVED INORGANIC CARBON ON THE PROPERTIES OF IRON COLLOIDAL SUSPENSIONS
Discolored water resulting from suspended iron particles is a relatively common drinking water consumer complaint. These particles result from the oxygenation of Fe(II), and this study shows that pH and dissolved inorganic carbon (DIC) have important effects on their properties....
Large scale structures in liquid crystal/clay colloids
NASA Astrophysics Data System (ADS)
van Duijneveldt, Jeroen S.; Klein, Susanne; Leach, Edward; Pizzey, Claire; Richardson, Robert M.
2005-04-01
Suspensions of three different clays in K15, a thermotropic liquid crystal, have been studied by optical microscopy and small angle x-ray scattering. The three clays were claytone AF, a surface treated natural montmorillonite, laponite RD, a synthetic hectorite, and mined sepiolite. The claytone and laponite were sterically stabilized whereas sepiolite formed a relatively stable suspension in K15 without any surface treatment. Micrographs of the different suspensions revealed that all three suspensions contained large scale structures. The nature of these aggregates was investigated using small angle x-ray scattering. For the clays with sheet-like particles, claytone and laponite, the flocs contain a mixture of stacked and single platelets. The basal spacing in the stacks was independent of particle concentration in the suspension and the phase of the solvent. The number of platelets in the stack and their percentage in the suspension varied with concentration and the aspect ratio of the platelets. The lath shaped sepiolite did not show any tendency to organize into ordered structures. Here the aggregates are networks of randomly oriented single rods.
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.
NASA Astrophysics Data System (ADS)
Suciu, B.; Tomioka, T.
2016-09-01
Yaw damper represents a major source of excitation for flexural vibration of the railway carbody. In order to reduce transmissibility of such undesired excitation, yaw damper should allow for large force transmission at low working frequencies, but should behave as vibration isolator at high working frequencies. Unfortunately, the yaw oil damper (OD), which is nowadays in service, has poor intrinsic elastic capabilities and provides damping forces varying as a power function versus the piston speed. Since colloidal damper (CD) has intrinsic elastic capabilities and larger damping forces at lower excitation frequencies, it occurs as an attractive alternative solution to traditional yaw dampers. In this work, a yaw CD destined to carbody suspension of a bullet train was designed and manufactured; then, its dynamic characteristics, produced by both the frictional and colloidal effects, were evaluated from the experimental results, obtained during horizontal vibration tests, performed on a ball-screw shaker. Compared to the corresponding classical yaw OD, the trial yaw CD allowed for: weight reduction of 31.6%; large damping force, dissipated energy and spring constant at long piston stroke under low excitation frequency; low damping force, dissipated energy and spring constant at short piston stroke under high excitation frequency. Elastic properties were justified by introducing a model for the spring constant that included the effect of pore size distribution.
Fabricating TiO2 nanocolloids by electric spark discharge method at normal temperature and pressure.
Tseng, Kuo-Hsiung; Chang, Chaur-Yang; Chung, Meng-Yun; Cheng, Ting-Shou
2017-11-17
In this study, TiO 2 nanocolloids were successfully fabricated in deionized water without using suspending agents through using the electric spark discharge method at room temperature and under normal atmospheric pressure. This method was exceptional because it did not create nanoparticle dispersion and the produced colloids contained no derivatives. The proposed method requires only traditional electrical discharge machines (EDMs), self-made magnetic stirrers, and Ti wires (purity, 99.99%). The EDM pulse on time (T on ) and pulse off time (T off ) were respectively set at 50 and 100 μs, 100 and 100 μs, 150 and 100 μs, and 200 and 100 μs to produce four types of TiO 2 nanocolloids. Zetasizer analysis of the nanocolloids showed that a decrease in T on increased the suspension stability, but there were no significant correlations between T on and particle size. Colloids produced from the four production configurations showed a minimum particle size between 29.39 and 52.85 nm and a zeta-potential between -51.2 and -46.8 mV, confirming that the method introduced in this study can be used to produce TiO 2 nanocolloids with excellent suspension stability. Scanning electron microscopy with energy dispersive spectroscopy also indicated that the TiO 2 colloids did not contain elements other than Ti and oxygen.
NASA Astrophysics Data System (ADS)
Hartman, John; Kirby, Brian
2017-03-01
Nanoparticle tracking analysis, a multiprobe single particle tracking technique, is a widely used method to quickly determine the concentration and size distribution of colloidal particle suspensions. Many popular tools remove non-Brownian components of particle motion by subtracting the ensemble-average displacement at each time step, which is termed dedrifting. Though critical for accurate size measurements, dedrifting is shown here to introduce significant biasing error and can fundamentally limit the dynamic range of particle size that can be measured for dilute heterogeneous suspensions such as biological extracellular vesicles. We report a more accurate estimate of particle mean-square displacement, which we call decorrelation analysis, that accounts for correlations between individual and ensemble particle motion, which are spuriously introduced by dedrifting. Particle tracking simulation and experimental results show that this approach more accurately determines particle diameters for low-concentration polydisperse suspensions when compared with standard dedrifting techniques.
Surface grafting of cellulose nanocrystals with poly(ethylene oxide) in aqueous media.
Kloser, Elisabeth; Gray, Derek G
2010-08-17
Aqueous suspensions of poly(ethylene oxide)-grafted nanocrystalline cellulose (PEO-grafted NCC) were prepared in order to achieve steric instead of electrostatic stabilization. A two-step process was employed: in the first step NCC suspensions prepared by sulfuric acid hydrolysis were desulfated with sodium hydroxide, and in the second step the surfaces of the crystals were functionalized with epoxy-terminated poly(ethylene oxide) (PEO epoxide) under alkaline conditions. The PEO-grafted samples were analyzed by conductometric titration, ATR-IR, solid-state NMR, MALDI-TOF MS, SEC MALLS, and AFM. The covalent nature of the linkage was confirmed by weight increase and MALDI-TOF analysis. The PEO-grafted cellulose nanocrystals (CNCs) formed a stable colloidal suspension that remained well dispersed, while the desulfated nanoparticles aggregated and precipitated. Upon concentration of the PEO-grafted aqueous NCC suspension, a chiral nematic phase was observed.
Lin, Jianfeng; Dang, Haijun; Xie, Jinchuan; Zhou, Guoqing; Li, Mei; Zhang, Jihong
2015-09-01
Traditional sorption experiments commonly treat the colloidal species of low-solubility contaminants as immobile species when separated by centrifugation or ultrafiltration. This study shows that, from a viewpoint of a three-phase system, the mobile Pu species, especially the colloidal species, play an important role in Pu partitioning in water-granite and water-α-FeOOH systems. A new distribution coefficient term Ks/(d+c) was defined to take the mobile colloidal species into consideration, and it differs to the traditional distribution coefficient Ks/d by orders of magnitude in the water-granite and water-α-FeOOH systems. This term, Ks/(d+c), can quantitatively describe Pu partitioning in the suspension, in particular the fraction of mobile species that dominate Pu migration in the environment. The effects of ionic strength (I) and pH on the Pu partitioning in water-granite and water-α-FeOOH systems are well interpreted with respect to the zeta potential change of granite grains, α-FeOOH colloid particles and polymeric Pu. It is concluded that the presence of the α-FeOOH colloid with a low concentration (<10 mg L(-1)) is favorable for the stability of colloidal Pu and leads to large proportion of mobile Pu, especially colloid-associated Pu, which will migrate much faster than dissolved Pu in groundwater.
NASA Astrophysics Data System (ADS)
Chen, Xiaomin; Gu, Huaimin; Shen, Gaoshan; Dong, Xiao; Kang, Jian
2010-06-01
The surface enhanced Raman scattering (SERS) of caffeine on borohydride-reduced silver colloids system under different aqueous solution environment has been studied in this paper. The relative intensity of SERS of caffeine significantly varies with different concentrations of sodium chloride and silver particles. However, at too high or too low concentration of sodium chloride and silver particle, the enhancement of SERS spectra is not evident. The SERS spectra of caffeine suggest that the contribution of the charge transfer mechanism to SERS may be dominant. The chloride ions can significantly enhance the efficiency of SERS, while the enhancement is selective, as the efficiency in charge transfer enhancement is higher than in electromagnetic enhancement. Therefore, it can be concluded that the active site of chloride ion locates on the bond between the caffeine and the silver surface. In addition, the SERS spectra of caffeine on borohydride-reduced and citrate-reduced silver colloids are different, which may be due to different states caffeine adsorbed on silver surface under different silver colloids.
Mora-Sero, Ivan; Bertoluzzi, Luca; Gonzalez-Pedro, Victoria; Gimenez, Sixto; Fabregat-Santiago, Francisco; Kemp, Kyle W; Sargent, Edward H; Bisquert, Juan
2013-01-01
Colloidal quantum dot solar cells achieve spectrally selective optical absorption in a thin layer of solution-processed, size-effect tuned, nanoparticles. The best devices built to date have relied heavily on drift-based transport due to the action of an electric field in a depletion region that extends throughout the thickness of the quantum dot layer. Here we study for the first time the behaviour of the best-performing class of colloidal quantum dot films in the absence of an electric field, by screening using an electrolyte. We find that the action of selective contacts on photovoltage sign and amplitude can be retained, implying that the contacts operate by kinetic preferences of charge transfer for either electrons or holes. We develop a theoretical model to explain these experimental findings. The work is the first to present a switch in the photovoltage in colloidal quantum dot solar cells by purposefully formed selective contacts, opening the way to new strategies in the engineering of colloidal quantum dot solar cells.
Elementary sulfur in effluent from denitrifying sulfide removal process as adsorbent for zinc(II).
Chen, Chuan; Zhou, Xu; Wang, Aijie; Wu, Dong-hai; Liu, Li-hong; Ren, Nanqi; Lee, Duu-Jong
2012-10-01
The denitrifying sulfide removal (DSR) process can simultaneously convert sulfide, nitrate and organic compounds into elementary sulfur (S(0)), di-nitrogen gas and carbon dioxide, respectively. However, the S(0) formed in the DSR process are micro-sized colloids with negatively charged surface, making isolation of S(0) colloids from other biological cells and metabolites difficult. This study proposed the use of S(0) in DSR effluent as a novel adsorbent for zinc removal from wastewaters. Batch and continuous tests were conducted for efficient zinc removal with S(0)-containing DSR effluent. At pH<7.5, removal rates of zinc(II) were increased with increasing pH. The formed S(0) colloids carried negative charge onto which zinc(II) ions could be adsorbed via electrostatic interactions. The zinc(II) adsorbed S(0) colloids further enhanced coagulation-sedimentation efficiency of suspended solids in DSR effluents. The DSR effluent presents a promising coagulant for zinc(II) containing wastewaters. Copyright © 2012 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Burtsev, Vasilii; Marchuk, Valentina; Kugaevskiy, Artem; Guselnikova, Olga; Elashnikov, Roman; Miliutina, Elena; Postnikov, Pavel; Svorcik, Vaclav; Lyutakov, Oleksiy
2018-03-01
Nano-spheres lithography is actually considered as a powerful tool to manufacture various periodic structures with a wide potential in the field of nano- and micro-fabrication. However, during self-assembling of colloid microspheres, various defects and mismatches can appear. In this work the size and quality of single-domains of closed-packed polystyrene (PS), grown up on thin Au layers modified by hydrophilic or hydrophobic functional groups via diazonium chemistry was studied. The effects of the surface modification on the quality and single-domain size of polystyrene (PS) microspheres array were investigated and discussed. Modified surfaces were characterized using the AFM and wettability tests. PS colloidal suspension was deposited using the drop evaporation method. Resulted PS microspheres array was characterized using the SEM, AFM and confocal microscopy technique.
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.
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.
Guerrero-García, Guillermo Iván; González-Tovar, Enrique; Chávez-Páez, Martín; Kłos, Jacek; Lamperski, Stanisław
2017-12-20
The spatial extension of the ionic cloud neutralizing a charged colloid or an electrode is usually characterized by the Debye length associated with the supporting charged fluid in the bulk. This spatial length arises naturally in the linear Poisson-Boltzmann theory of point charges, which is the cornerstone of the widely used Derjaguin-Landau-Verwey-Overbeek formalism describing the colloidal stability of electrified macroparticles. By definition, the Debye length is independent of important physical features of charged solutions such as the colloidal charge, electrostatic ion correlations, ionic excluded volume effects, or specific short-range interactions, just to mention a few. In order to include consistently these features to describe more accurately the thickness of the electrical double layer of an inhomogeneous charged fluid in planar geometry, we propose here the use of the capacitive compactness concept as a generalization of the compactness of the spherical electrical double layer around a small macroion (González-Tovar et al., J. Chem. Phys. 2004, 120, 9782). To exemplify the usefulness of the capacitive compactness to characterize strongly coupled charged fluids in external electric fields, we use integral equations theory and Monte Carlo simulations to analyze the electrical properties of a model molten salt near a planar electrode. In particular, we study the electrode's charge neutralization, and the maximum inversion of the net charge per unit area of the electrode-molten salt system as a function of the ionic concentration, and the electrode's charge. The behaviour of the associated capacitive compactness is interpreted in terms of the charge neutralization capacity of the highly correlated charged fluid, which evidences a shrinking/expansion of the electrical double layer at a microscopic level. The capacitive compactness and its first two derivatives are expressed in terms of experimentally measurable macroscopic properties such as the differential and integral capacity, the electrode's surface charge density, and the mean electrostatic potential at the electrode's surface.
Cai, Li; Peng, Shengnan; Wu, Dan; Tong, Meiping
2016-01-01
Colloids (non-biological and biological) with different sizes are ubiquitous in natural environment. The investigations regarding the influence of different-sized colloids on the transport and deposition behaviors of engineered-nanoparticles in porous media yet are still largely lacking. This study investigated the effects of different-sized non-biological and biological colloids on the transport of titanium dioxide nanoparticles (nTiO2) in quartz sand under both electrostatically favorable and unfavorable conditions. Fluorescent carboxylate-modified polystyrene latex microspheres (CML) with sizes of 0.2-2 μm were utilized as model non-biological colloids, while Gram-negative Escherichia coli (∼ 1 μm) and Gram-positive Bacillus subtilis (∼ 2 μm) were employed as model biological colloids. Under the examined solution conditions, both breakthrough curves and retained profiles of nTiO2 with different-sized CML particles/bacteria were similar as those without colloids under favorable conditions, indicating that the copresence of model colloids in suspensions had negligible effects on the transport and deposition of nTiO2 under favorable conditions. In contrast, higher breakthrough curves and lower retained profiles of nTiO2 with CML particles/bacteria relative to those without copresent colloids were observed under unfavorable conditions. Clearly, the copresence of model colloids increased the transport and decreased the deposition of nTiO2 in quartz sand under unfavorable conditions (solution conditions examined in present study). Both competition of deposition sites on quartz sand surfaces and the enhanced stability/dispersion of nTiO2 induced by copresent colloids were found to be responsible for the increased nTiO2 transport with colloids under unfavorable conditions. Moreover, the smallest colloids had the highest coverage on sand surface and most significant dispersion effect on nTiO2, resulting in the greatest nTiO2 transport. Copyright © 2015. Published by Elsevier Ltd.
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.
NASA Astrophysics Data System (ADS)
Viazzi, Céline; Rouessac, Vincent; Lenormand, Pascal; Julbe, Anne; Ansart, Florence; Guizard, Christian
2011-03-01
Sol-gel routes are often investigated and adapted to prepare, by suitable chemical modifications, submicronic powders and derived materials with controlled morphology, which cannot be obtained by conventional solid state chemistry paths. Wet chemistry methods provide attractive alternative routes because mixing of species occurs at the atomic scale. In this paper, ultrafine powders were prepared by a novel synthesis method based on the sol-gel process and were dispersed into suspensions before processing. This paper presents new developments for the preparation of functional materials like yttria-stabilized-zirconia (YSZ, 8% Y2O3) used as electrolyte for solid oxide fuel cells. YSZ thick films were coated onto porous Ni-YSZ substrates using a suspension with an optimized formulation deposited by either a dip-coating or a spin-coating process. The suspension composition is based on YSZ particles encapsulated by a zirconium alkoxide which was added with an alkoxide derived colloidal sol. The in situ growth of these colloids increases significantly the layer density after an appropriated heat treatment. The derived films were continuous, homogeneous and around 20 μm thick. The possible up-scaling of this process has been also considered and the suitable processing parameters were defined in order to obtain, at an industrial scale, homogeneous, crack-free, thick and adherent films after heat treatment at 1400 °C.
Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions
Vodnala, Preeti; Karunaratne, Nuwan; Lurio, Laurence; ...
2018-02-02
The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f(q,τ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids.
Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vodnala, Preeti; Karunaratne, Nuwan; Lurio, Laurence
The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f(q,τ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids.
Hansen, R.S.; Minturn, R.E.
1958-02-25
This patent deals with a method of preparing actinide metal oxides of a very fine particle size and of forming stable suspensions therefrom. The process consists of dissolving the nitrate of the actinide element in a combustible organic solvent, converting the solution obtained into a spray, and igniting the spray whereby an oxide powder is obtained. The oxide powder is then slurried in an aqueous soiution of a substance which is adsorbable by said oxides, dspersed in a colloid mill whereby a suspension is obtained, and electrodialyzed until a low spectiic conductance is reached.
Hard-sphere-like dynamics in highly concentrated alpha-crystallin suspensions
NASA Astrophysics Data System (ADS)
Vodnala, Preeti; Karunaratne, Nuwan; Lurio, Laurence; Thurston, George M.; Vega, Michael; Gaillard, Elizabeth; Narayanan, Suresh; Sandy, Alec; Zhang, Qingteng; Dufresne, Eric M.; Foffi, Giuseppe; Grybos, Pawel; Kmon, Piotr; Maj, Piotr; Szczygiel, Robert
2018-02-01
The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f (q ,τ ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids.
Angle-Resolved Second-Harmonic Light Scattering from Colloidal Particles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, N.; Angerer, W. E.; Yodh, A. G.
2001-09-03
We report angle-resolved second-harmonic generation (SHG) measurements from suspensions of centrosymmetric micron-size polystyrene spheres with surface-adsorbed dye (malachite green). The second-harmonic scattering profiles differ qualitatively from linear light scattering profiles of the same particles. We investigated these radiation patterns using several polarization configurations and particle diameters. We introduce a simple Rayleigh-Gans-Debye model to account for the SHG scattering anisotropy. The model compares favorably with our experimental data. Our measurements suggest scattering anisotropy may be used to isolate particle nonlinear optics from other bulk nonlinear optical effects in suspension.
The role of silica colloids on facilitated cesium transport through glass bead columns and modeling
NASA Astrophysics Data System (ADS)
Noell, Alan L.; Thompson, Joseph L.; Corapcioglu, M. Yavuz; Triay, Inés R.
1998-05-01
Groundwater colloids can act as a vector which enhances the migration of contaminants. While sorbed to mobile colloids, contaminants can be held in the aqueous phase which prevents them from interacting with immobile aquifer surfaces. In this study, an idealized laboratory set-up was used to examine the influence of amorphous silica colloids on the transport of cesium. Synthetic groundwater and saturated glass bead columns were used to minimize the presence of natural colloidal material. The columns were assembled in replicate, some packed with 150-210 μm glass bead and others packed with 355-420 μm glass beads. The colloids used in these experiments were 100 nm amorphous silica colloids from Nissan Chemical Company. In the absence of these colloids, the retardation factor for cesium was 8.0 in the 150-210 μm glass bead columns and 3.6 in the 355-420 μm glass bead columns. The influence of anthropogenic colloids was tested by injecting 0.09 pore volume slugs of an equilibrated suspension of cesium and colloids into the colloid-free columns. Although there was little noticeable facilitation in the smaller glass bead columns, there was a slight reduction in the retardation of cesium in the larger glass bead columns. This was attributed to cesium having less of a retention time in the larger glass bead columns. When cesium was injected into columns with a constant flux of colloids, the retardation of cesium was reduced by 14-32% in the 150-210 μm glass bead columns and by 38-51% in the 355-420 μm glass bead columns. A model based on Corapcioglu and Jiang (1993) [Corapcioglu, M.Y., Jiang, S., 1993. Colloid-facilitated groundwater contaminant transport, Water Resour. Res., 29 (7) 2215-2226] was compared with the experimental elution data. When equilibrium sorption expressions were used and the flux of colloids through the glass bead columns was constant, the colloid facilitated transport of cesium was able to be described using an effective retardation coefficient. Fully kinetic simulations, however, more accurately described the colloid facilitated transport of cesium.
The impact of capping agents and environmental conditions (pH, ionic strength, and background electrolytes) on surface charge and aggregation potential of silver nanoparticles (AgNPs) suspensions were investigated. Capping agents are chemicals used in the synthesis of nanopartic...
Teh, Lay K; Yan, Qingfeng; Wong, Chee C
2009-04-01
We develop a new method to fabricate suspended sheets of nanocrystals (NCs) on porous surfaces. The method relies on the resistance of an aqueous suspension droplet to infiltrate a porous network; hence, the method is named anti-infiltration. The process works by combining fluid dynamics of a liquid droplet during impact/absorption onto a porous surface with the convective self-assembly of NCs. The immobilization of the liquid droplet edge due to the self-assembly of NCs at the meniscus is harnessed to halt the lateral spreading of the droplet and, consequently, the capillary penetration of the liquid immediately after droplet impact. Further capillary penetration of the liquid is drastically reduced because of the competition between capillary forces and convective losses as well as the rapid occlusion of the pores as soon as a continuous NC film has formed upon evaporation of the suspension. This method holds promise for a wide variety of optoelectronic, sensing, and separation membrane applications. As an example, we demonstrate that these suspended NC layers are suitable candidates as planar defects embedded within a colloidal photonic crystal.
Exploration and characterization of new synthesis methods for C60 colloidal suspensions in water
NASA Astrophysics Data System (ADS)
Hilburn, Martha E.
Buckminsterfullerene, C60, has been used in the production of several commercial products from badminton racquets and lubricants for their mechanical properties to cosmetics and even dietary supplements for their "antioxidant" properties. Multi-ton production of C60 began in 2003 encouraging serious consideration of its fate in the environment in the case of an accidental release or improper disposal. Although C60 is practically insoluble in water, it readily forms stable aqueous colloidal suspensions (termed nC60) through solvent exchange methods or long-term vigorous stirring in water. Two new solvent exchange methods for synthesizing nC60 are presented. These methods combine key advantages of multiple existing synthesis methods including high yield, narrow particle size distribution, short synthesis time, and an absence of solvents such as tetrahydrofuran that have historically caused problems in laboratory synthesized aggregates. The resulting samples are attractive candidates for use in controlled environmental impact, biological, and toxicity studies. An improved method for quantifying residual solvents in nC60 samples utilizing solid phase micro extraction gas chromatography mass spectrometry (SPME-GC-MS) is also discussed.
Transport coefficients and mechanical response in hard-disk colloidal suspensions
NASA Astrophysics Data System (ADS)
Zhang, Bo-Kai; Li, Jian; Chen, Kang; Tian, Wen-De; Ma, Yu-Qiang
2016-11-01
We investigate the transport properties and mechanical response of glassy hard disks using nonlinear Langevin equation theory. We derive expressions for the elastic shear modulus and viscosity in two dimensions on the basis of thermal-activated barrier-hopping dynamics and mechanically accelerated motion. Dense hard disks exhibit phenomena such as softening elasticity, shear-thinning of viscosity, and yielding upon deformation, which are qualitatively similar to dense hard-sphere colloidal suspensions in three dimensions. These phenomena can be ascribed to stress-induced “landscape tilting”. Quantitative comparisons of these phenomena between hard disks and hard spheres are presented. Interestingly, we find that the density dependence of yield stress in hard disks is much more significant than in hard spheres. Our work provides a foundation for further generalizing the nonlinear Langevin equation theory to address slow dynamics and rheological behavior in binary or polydisperse mixtures of hard or soft disks. Project supported by the National Basic Research Program of China (Grant No. 2012CB821500) and the National Natural Science Foundation of China (Grant Nos. 21374073 and, 21574096).
Xie, Qingguang; Harting, Jens
2018-05-08
The deposition of particles on a substrate by drying a colloidal suspension droplet is at the core of applications ranging from traditional printing on paper to printable electronics or photovoltaic devices. The self-pinning induced by the accumulation of particles at the contact line plays an important role in the formation of a deposit. In this article, we investigate, both numerically and theoretically, the effect of friction between the particles and the substrate on the deposition pattern. Without friction, the contact line shows a stick-slip behavior and a dotlike deposit is left after the droplet is evaporated. By increasing the friction force, we observe a transition from a dotlike to a ringlike deposit. We propose a theoretical model to predict the effective radius of the particle deposit as a function of the friction force. Our theoretical model predicts a critical friction force when self-pinning happens and the effective radius of deposit increases with increasing friction force, confirmed by our simulation results. Our results can find implications for developing active control strategies for the deposition of drying droplets.
Bacterial Flagella as a Model Rigid Rod of Tunable Shape
NASA Astrophysics Data System (ADS)
Schwenger, Walter; Yardimci, Sevim; Gibaud, Thomas; Snow, Henry; Urbach, Jeff; Dogic, Zvonimir
In this research, we study the physical properties of suspensions of bacterial flagella from Salmonella typhimurium prepared in a variety of rigid polymorphic shapes. Flagella act as a rigid colloidal particle that can exhibit non-trivial geometry including helices of varying dimensions, straight rods, or a combination of the two in the same filament. By controlling the conditions in which flagella are prepared, the polymorphic shape assumed by the filament can be controlled. Utilizing different polymorphic shapes, we combine results from optical microscopy observations of single filaments with bulk rheological measurements to help understand the role that constituent colloidal geometry plays in complex bulk behavior.
NASA Astrophysics Data System (ADS)
Kȩdzierski, Marcin; Wajnryb, Eligiusz
2011-10-01
Self-diffusion of colloidal particles confined to a cylindrical microchannel is considered theoretically and numerically. Virial expansion of the self-diffusion coefficient is performed. Two-body and three-body hydrodynamic interactions are evaluated with high precision using the multipole method. The multipole expansion algorithm is also used to perform numerical simulations of the self-diffusion coefficient, valid for all possible particle packing fractions. Comparison with earlier results shows that the widely used method of reflections is insufficient for calculations of hydrodynamic interactions even for small packing fractions and small particles radii, contrary to the prevalent opinion.
Paramagnetic colloids: Chaotic routes to clusters and molecules
NASA Astrophysics Data System (ADS)
Abdi, Hamed; Soheilian, Rasam; Erb, Randall M.; Maloney, Craig E.
2018-03-01
We present computer simulations and experiments on dilute suspensions of superparamagnetic particles subject to rotating magnetic fields. We focus on chains of four particles and their decay routes to stable structures. At low rates, the chains track the external field. At intermediate rates, the chains break up but perform a periodic (albeit complex) motion. At sufficiently high rates, the chains generally undergo chaotic motion at short times and decay to either closely packed clusters or more dispersed, colloidal molecules at long times. We show that the transition out of the chaotic states can be described as a Poisson process in both simulation and experiment.
Photoelastic colloidal gel for a high-sensitivity strain sensor.
Pan, Hui; Chen, Zhixin; Zhu, Shenmin; Jiang, Chun; Zhang, Di
2018-04-27
Nanoparticles, having the ability to self-assemble into an ordered structure in their suspensions, analogous to liquid crystals, have attracted extensive attention. Herein, we report a new type of colloidal gel with an ordered crystal structure assembled from 1D and 2D nanoparticles. The material has high elasticity and, more interestingly, it shows significant photoelasticity. Its refractive index can be tuned under external stress and exhibits an ultra-wide dynamic range (Δn) of the order of 10 -2 . Due to the large Δn, the material shows an extremely high strain sensibility of 720 nm/ε, an order of magnitude higher than the reported ones.
A Silicon Nanocrystal Schottky Junction Solar Cell produced from Colloidal Silicon Nanocrystals
2010-01-01
Solution-processed semiconductors are seen as a promising route to reducing the cost of the photovoltaic device manufacture. We are reporting a single-layer Schottky photovoltaic device that was fabricated by spin-coating intrinsic silicon nanocrystals (Si NCs) from colloidal suspension. The thin-film formation process was based on Si NCs without any ligand attachment, exchange, or removal reactions. The Schottky junction device showed a photovoltaic response with a power conversion efficiency of 0.02%, a fill factor of 0.26, short circuit-current density of 0.148 mA/cm2, and open-circuit voltage of 0.51 V. PMID:20676200
Photoelastic colloidal gel for a high-sensitivity strain sensor
NASA Astrophysics Data System (ADS)
Pan, Hui; Chen, Zhixin; Zhu, Shenmin; Jiang, Chun; Zhang, Di
2018-04-01
Nanoparticles, having the ability to self-assemble into an ordered structure in their suspensions, analogous to liquid crystals, have attracted extensive attention. Herein, we report a new type of colloidal gel with an ordered crystal structure assembled from 1D and 2D nanoparticles. The material has high elasticity and, more interestingly, it shows significant photoelasticity. Its refractive index can be tuned under external stress and exhibits an ultra-wide dynamic range (Δn) of the order of 10-2. Due to the large Δn, the material shows an extremely high strain sensibility of 720 nm/ɛ, an order of magnitude higher than the reported ones.
Chain Dynamics in Magnetorheological Suspensions
NASA Technical Reports Server (NTRS)
Gast, A. P.; Furst, E. M.
1999-01-01
Magnetorheological (MR) suspensions are composed of colloidal particles which acquire dipole moments when subjected to an external magnetic field. At sufficient field strengths and concentrations, the dipolar particles rapidly aggregate to form long chains. Subsequent lateral cross-linking of the dipolar chains is responsible for a rapid liquid-to-solid-like rheological transition. The unique, magnetically-activated rheological properties of MR suspensions make them ideal for interfacing mechanical systems to electronic controls. Additionally, the ability to experimentally probe colloidal suspensions interacting through tunable anisotropic potentials is of fundamental interest. Our current experimental work has focused on understanding the fluctuations of dipolar chains. It has been proposed by Halsey and Toor (HT) that the strong Landau-Peierls thermal fluctuations of dipolar chains could be responsible for long-range attractions between chains. Such interactions will govern the long-time relaxation of MR suspensions. We have synthesized monodisperse neutrally buoyant MR suspensions by density matching stabilized ferrofluid emulsion droplets with D2O. This allows us to probe the dynamics of the dipolar chains using light scattering without gravitational, interfacial, and polydispersity effects to resolve the short-wavelength dynamics of the dipolar chains. We used diffusing wave spectroscopy to measure these dynamics. The particle displacements at short times that show an independence to the field strength, but at long times exhibit a constrained, sub-diffusive motion that slows as the dipole strength is increased. The experiments are in good qualitative agreement with Brownian dynamics simulations of dipolar chains. Although there have been several important and detailed studies of the structure and interactions in MR suspensions, there has not been conclusive evidence that supports or contradicts the HT model prediction that long-range interactions exist between fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead-spring systems. These chains form the basis for our current experiments with optical traps.
Carey, Graham H; Levina, Larissa; Comin, Riccardo; Voznyy, Oleksandr; Sargent, Edward H
2015-06-03
Through a combination of chemical and mutual dot-to-dot surface passivation, high-quality colloidal quantum dot solids are fabricated. The joint passivation techniques lead to a record diffusion length for colloidal quantum dots of 230 ± 20 nm. The technique is applied to create thick photovoltaic devices that exhibit high current density without losing fill factor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Piacenza, Elena; Presentato, Alessandro; Turner, Raymond J
2018-02-25
In the last 15 years, the exploitation of biological systems (i.e. plants, bacteria, mycelial fungi, yeasts, and algae) to produce metal(loid) (Me)-based nanomaterials has been evaluated as eco-friendly and a cost-effective alternative to the chemical synthesis processes. Although the biological mechanisms of biogenic Me-nanomaterial (Bio-Me-nanomaterials) production are not yet completely elucidated, a key advantage of such bio-nanostructures over those chemically synthesized is related to their natural thermodynamic stability, with several studies ascribed to the presence of an organic layer surrounding these Bio-Me-nanostructures. Different macromolecules (e.g. proteins, peptides, lipids, DNA, and polysaccharides) or secondary metabolites (e.g. flavonoids, terpenoids, glycosides, organic acids, and alkaloids) naturally produced by organisms have been indicated as main contributors to the stabilization of Bio-Me-nanostructures. Nevertheless, the chemical-physical mechanisms behind the ability of these molecules in providing stability to Bio-Me-nanomaterials are unknown. In this context, transposing the stabilization theory of chemically synthesized Me-nanomaterials (Ch-Me-nanomaterials) to biogenic materials can be used towards a better comprehension of macromolecules and secondary metabolites role as stabilizing agents of Bio-Me-nanomaterials. According to this theory, nanomaterials are generally featured by high thermodynamic instability in suspension, due to their high surface area and surface energy. This feature leads to the necessity to stabilize chemical nanostructures, even during or directly after their synthesis, through the development of (i) electrostatic, (ii) steric, or (iii) electrosteric interactions occurring between molecules and nanomaterials in suspension. Based on these three mechanisms, this review is focused on parallels between the stabilization of biogenic or chemical nanomaterials, suggesting which chemical-physical mechanisms may be involved in the natural stability of Bio-Me-nanomaterials. As a result, macromolecules such as DNA, polyphosphates and proteins may electrostatically interact with Bio-Me-nanomaterials in suspension through their charged moieties, showing the same properties of counterions in Ch-Me-nanostructure suspensions. Since several biomolecules (e.g. neutral lipids, nonionic biosurfactants, polysaccharides, and secondary metabolites) produced by metal(loid)-grown organisms can develop similar steric hindrance as compared to nonionic amphiphilic surfactants and block co-polymers generally used to sterically stabilize Ch-Me-nanomaterials. These biomolecules, most likely, are involved in the development of steric stabilization, because of their bulky structures. Finally, charged lipids and polysaccharides, ionic biosurfactants or proteins with amphiphilic properties can exert a dual effect (i.e. electrostatic and steric repulsion interactions) in the contest of Bio-Me-nanomaterials, leading to the high degree of stability observed.
Smectite clay--inorganic nanoparticle mixed suspensions: phase behaviour and rheology.
Bailey, Louise; Lekkerkerker, Henk N W; Maitland, Geoffrey C
2015-01-14
Smectite clay minerals and their suspensions have long been of both great scientific and applications interest and continue to display a remarkable range of new and interesting behaviour. Recently there has been an increasing interest in the properties of mixed suspensions of such clays with nanoparticles of different size, shape and charge. This review aims to summarize the current status of research in this area focusing on phase behaviour and rheological properties. We will emphasize the rich range of data that has emerged for these systems and the challenges they present for future investigations. The review starts with a brief overview of the behaviour and current understanding of pure smectite clays and their suspensions. We then cover the work on smectite clay-inorganic nanoparticle mixed suspensions according to the shape and charge of the nanoparticles - spheres, rods and plates either positively or negatively charged. We conclude with a summary of the overarching trends that emerge from these studies and indicate where gaps in our understanding need further research for better understanding the underlying chemistry and physics.
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.
Does water content or flow rate control colloid transport in unsaturated porous media?
Knappenberger, Thorsten; Flury, Markus; Mattson, Earl D; Harsh, James B
2014-04-01
Mobile colloids can play an important role in contaminant transport in soils: many contaminants exist in colloidal form, and colloids can facilitate transport of otherwise immobile contaminants. In unsaturated soils, colloid transport is, among other factors, affected by water content and flow rate. Our objective was to determine whether water content or flow rate is more important for colloid transport. We passed negatively charged polystyrene colloids (220 nm diameter) through unsaturated sand-filled columns under steady-state flow at different water contents (effective water saturations Se ranging from 0.1 to 1.0, with Se = (θ - θr)/(θs - θr)) and flow rates (pore water velocities v of 5 and 10 cm/min). Water content was the dominant factor in our experiments. Colloid transport decreased with decreasing water content, and below a critical water content (Se < 0.1), colloid transport was inhibited, and colloids were strained in water films. Pendular ring and water film thickness calculations indicated that colloids can move only when pendular rings are interconnected. The flow rate affected retention of colloids in the secondary energy minimum, with less colloids being trapped when the flow rate increased. These results confirm the importance of both water content and flow rate for colloid transport in unsaturated porous media and highlight the dominant role of water content.
Buitenhuis, Johan
2012-09-18
The electrophoretic mobility of rodlike fd viruses is measured and compared to theory, with the theoretical calculations performed according to Stigter (Stigter, D. Charged Colloidal Cylinder with a Gouy Double-Layer. J. Colloid Interface Sci. 1975, 53, 296-306. Stigter, D. Electrophoresis of Highly Charged Colloidal Cylinders in Univalent Salt- Solutions. 1. Mobility in Transverse Field. J. Phys. Chem. 1978, 82, 1417-1423. Stigter, D. Electrophoresis of Highly Charged Colloidal Cylinders in Univalent Salt Solutions. 2. Random Orientation in External Field and Application to Polyelectrolytes. J. Phys. Chem. 1978, 82, 1424-1429. Stigter, D. Theory of Conductance of Colloidal Electrolytes in Univalent Salt Solutions. J. Phys. Chem. 1979, 83, 1663-1670), who describes the electrophoretic mobility of infinite cylinders including relaxation effects. Using the dissociation constants of the ionizable groups on the surfaces of the fd viruses, we can calculate the mobility without any adjustable parameter (apart from the possible Stern layer thickness). In addition, the approximation in the theoretical description of Stigter (and others) of using a model of infinitely long cylinders, which consequently is independent of the aspect ratio, is examined by performing more elaborate numerical calculations for finite cylinders. It is shown that, although the electrophoretic mobility of cylindrical particles in the limit of low ionic strength depends on the aspect ratio much more than "end effects", at moderate and high ionic strengths the finite and infinite cylinder models differ only to a degree that can be attributed to end effects. Furthermore, the range of validity of the Stokes regime is systematically calculated.
Fast microbial reduction of ferrihydrite colloids from a soil effluent
NASA Astrophysics Data System (ADS)
Fritzsche, Andreas; Bosch, Julian; Rennert, Thilo; Heister, Katja; Braunschweig, Juliane; Meckenstock, Rainer U.; Totsche, Kai U.
2012-01-01
Recent studies on the microbial reduction of synthetic iron oxide colloids showed their superior electron accepting property in comparison to bulk iron oxides. However, natural colloidal iron oxides differ in composition from their synthetic counterparts. Besides a potential effect of colloid size, microbial iron reduction may be accelerated by electron-shuttling dissolved organic matter (DOM) as well as slowed down by inhibitors such as arsenic. We examined the microbial reduction of OM- and arsenic-containing ferrihydrite colloids. Four effluent fractions were collected from a soil column experiment run under water-saturated conditions. Ferrihydrite colloids precipitated from the soil effluent and exhibited stable hydrodynamic diameters ranging from 281 (±146) nm in the effluent fraction that was collected first and 100 (±43) nm in a subsequently obtained effluent fraction. Aliquots of these oxic effluent fractions were added to anoxic low salt medium containing diluted suspensions of Geobacter sulfurreducens. Independent of the initial colloid size, the soil effluent ferrihydrite colloids were quickly and completely reduced. The rates of Fe2+ formation ranged between 1.9 and 3.3 fmol h-1 cell-1, and are in the range of or slightly exceeding previously reported rates of synthetic ferrihydrite colloids (1.3 fmol h-1 cell-1), but greatly exceeding previously known rates of macroaggregate-ferrihydrite reduction (0.07 fmol h-1 cell-1). The inhibition of microbial Fe(III) reduction by arsenic is unlikely or overridden by the concurrent enhancement induced by soil effluent DOM. These organic species may have increased the already high intrinsic reducibility of colloidal ferrihydrite owing to quinone-mediated electron shuttling. Additionally, OM, which is structurally associated with the soil effluent ferrihydrite colloids, may also contribute to the higher reactivity due to increasing solubility and specific surface area of ferrihydrite. In conclusion, ferrihydrite colloids from soil effluents can be considered as highly reactive electron acceptors in anoxic environments.
Colloid transport in model fracture filling materials
NASA Astrophysics Data System (ADS)
Wold, S.; Garcia-Garcia, S.; Jonsson, M.
2010-12-01
Colloid transport in model fracture filling materials Susanna Wold*, Sandra García-García and Mats Jonsson KTH Chemical Science and Engineering Royal Institute of Technology, SE-100 44 Stockholm, Sweden *Corresponding author: E-mail: wold@kth.se Phone: +46 8 790 6295 In colloid transport in water-bearing fractures, the retardation depends on interactions with the fracture surface by sorption or filtration. These mechanisms are difficult to separate. A rougher surface will give a larger area available for sorption, and also when a particle is physically hindered, it approaches the surface and enables further sorption. Sorption can be explained by electrostatics were the strongest sorption on minerals always is observed at pH below pHpzc (Filby et al., 2008). The adhesion of colloids to mineral surfaces is related to the surface roughness according to a recent study (Darbha et al., 2010). There is a large variation in the characteristics of water-bearing fractures in bedrock in terms of aperture distribution, flow velocity, surface roughness, mineral distributions, presence of fracture filling material, and biological and organic material, which is hard to implement in modeling. The aim of this work was to study the transport of negatively charged colloids in model fracture filling material in relation to flow, porosity, mineral type, colloid size, and surface charge distribution. In addition, the impact on transport of colloids of mixing model fracture filling materials with different retention and immobilization capacities, determined by batch sorption experiments, was investigated. The transport of Na-montmorillonite colloids and well-defined negatively charged latex microspheres of 50, 100, and 200 nm diameter were studied in either columns containing quartz or quartz mixed with biotite. The ionic strength in the solution was exclusively 0.001 and pH 6 or 8.5. The flow rates used were 0.002, 0.03, and 0.6 mL min-1. Sorption of the colloids on the model fracture minerals was studied prior to the transport experiments under the same conditions. By varying the amount of solid substrate, it was possible to determine an interaction constant from a linear expression. Complementary zeta potential measurements and scanning electron microscopy (SEM) imaging were performed to examine the mineral surfaces after exposure to colloids. In experiments with low flow rates the retention of the colloids in the transport experiments were attributed to the interaction constants including both physical filtration and sorption. At higher flow rate the interactions between colloids and mineral surfaces were also significant but not as pronounced. Immobilization and retardation of the colloids were reflected by the interaction constants, which included both an irreversible and a reversible component of physical filtration and sorption. References Darbha, G.K., Schaefer, T., Heberling, F., Lüttge, A. and Fisher, C. 2010. Retention of Latex Colloids on Calcite as a Function of Surface Roughness and Topography. Langmuir, 26(7), 4743-4752. Filby, A., Plaschke, M., Geckeis, H., Fanghänel, Th. 2008. Interaction of latex colloids with mineral surfaces and Grimsel granodiorite. J. Contam. Hydrol., 102, 273-284.
Ramirez-Dorronsoro, Juan-Carlos; Jacko, Robert B; Kildsig, Dane O
2006-01-01
The purpose of this study was to develop an instrument (the Purdue instrument) and the corresponding methodologies to measure the electrostatic charge development (chargeability) of dry powders when they are in dynamic contact with stainless steel surfaces. The system used an inductive noncontact sensor located inside an aluminum Faraday cage and was optimized to measure the charging capabilities of a fixed volume of powder (0.5 cc). The chargeability of 5,5-diphenyl-hydantoin, calcium sulfate dihydrate, cimetidine, 3 grades of colloidal silicon dioxide, magnesium stearate, 4 grades of microcrystalline cellulose, salicylic acid, sodium carbonate, sodium salicylate, spray-dried lactose, and sulfinpyrazone were tested at 4 linear velocities, and the particle size distribution effect was assessed for 3 different grades of colloidal silicon dioxide and 4 different grades of microcrystalline cellulose. The chargeability values exhibited a linear relationship for the range of velocities studied, with colloidal silicon dioxide exhibiting the maximum negative chargeability and with spray-dried lactose being the only compound to exhibit positive chargeability. The instrument sensitivity was improved by a factor of 2 over the first generation version, and the electrostatic charge measurements were reproducible with relative standard deviations ranging from nondetectable to 33.7% (minimum of 3 replicates). These results demonstrate the feasibility of using the Purdue instrument to measure the electrostatic charge control capabilities of pharmaceutical dry powders with a reasonable level of precision.
Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sodipo, Bashiru Kayode; Azlan, Abdul Aziz; Innovation
2015-04-24
Superparamagnetic iron oxide nanoparticles (SPION)/Silica composite nanoparticles were prepared by ultrasonically irradiating colloidal suspension of silica and SPION mixture. Both silica and SPION were synthesized independently via co-precipitation and sol-gel method, respectively. Their mixtures were sonicated at different pH between 3 and 5. Electrophoresis measurement and other physicochemical analyses of the products demonstrate that at lower pH SPION was found incorporated into the silica. However, at pH greater than 4, SPION was unstable and unable to withstand the turbulence flow and shock wave from the ultrasonic field. Results suggest that the formation of the SPION/silica composite nanoparticles is strongly relatedmore » to the inelastic collision induced by ultrasonic irradiation. More so, the formation the composite nanoparticles via the ultrasonic field are dependent on the zeta potential and colloidal stability of the particles.« less
Tien, Der-Chi; Tseng, Kuo-Hsiung; Liao, Chih-Yu; Tsung, Tsing-Tshih
2008-10-01
Nanoscale techniques for silver production may assist the resurgence of the medical use of silver, especially given that pathogens are showing increasing resistance to antibiotics. Traditional chemical synthesis methods for colloidal silver (CS) may lead to the presence of toxic chemical species or chemical residues, which may inhibit the effectiveness of CS as an antibacterial agent. To counter these problems a spark discharge system (SDS) was used to fabricate a suspension of colloidal silver in deionized water with no added chemical surfactants. SDS-CS contains both metallic silver nanoparticles (Ag(0)) and ionic silver forms (Ag(+)). The antimicrobial affect of SDS-CS on Staphylococcus aureus was studied. The results show that CS solutions with an ionic silver concentration of 30 ppm or higher are strong enough to destroy S. aureus. In addition, it was found that a solution's antimicrobial potency is directly related to its level of silver ion concentration.
Mesoscale Particle-Based Model of Electrophoretic Deposition
Giera, Brian; Zepeda-Ruiz, Luis A.; Pascall, Andrew J.; ...
2016-12-20
In this paper, we present and evaluate a semiempirical particle-based model of electrophoretic deposition using extensive mesoscale simulations. We analyze particle configurations in order to observe how colloids accumulate at the electrode and arrange into deposits. In agreement with existing continuum models, the thickness of the deposit increases linearly in time during deposition. Resulting colloidal deposits exhibit a transition between highly ordered and bulk disordered regions that can give rise to an appreciable density gradient under certain simulated conditions. The overall volume fraction increases and falls within a narrow range as the driving force due to the electric field increasesmore » and repulsive intercolloidal interactions decrease. We postulate ordering and stacking within the initial layer(s) dramatically impacts the microstructure of the deposits. Finally, we find a combination of parameters, i.e., electric field and suspension properties, whose interplay enhances colloidal ordering beyond the commonly known approach of only reducing the driving force.« less
Unity quantum yield of photogenerated charges and band-like transport in quantum-dot solids.
Talgorn, Elise; Gao, Yunan; Aerts, Michiel; Kunneman, Lucas T; Schins, Juleon M; Savenije, T J; van Huis, Marijn A; van der Zant, Herre S J; Houtepen, Arjan J; Siebbeles, Laurens D A
2011-09-25
Solid films of colloidal quantum dots show promise in the manufacture of photodetectors and solar cells. These devices require high yields of photogenerated charges and high carrier mobilities, which are difficult to achieve in quantum-dot films owing to a strong electron-hole interaction and quantum confinement. Here, we show that the quantum yield of photogenerated charges in strongly coupled PbSe quantum-dot films is unity over a large temperature range. At high photoexcitation density, a transition takes place from hopping between localized states to band-like transport. These strongly coupled quantum-dot films have electrical properties that approach those of crystalline bulk semiconductors, while retaining the size tunability and cheap processing properties of colloidal quantum dots.
NASA Astrophysics Data System (ADS)
Su, Yu; Swan, James W.; Zia, Roseanna N.
2017-03-01
Accurate modeling of particle interactions arising from hydrodynamic, entropic, and other microscopic forces is essential to understanding and predicting particle motion and suspension behavior in complex and biological fluids. The long-range nature of hydrodynamic interactions can be particularly challenging to capture. In dilute dispersions, pair-level interactions are sufficient and can be modeled in detail by analytical relations derived by Jeffrey and Onishi [J. Fluid Mech. 139, 261-290 (1984)] and Jeffrey [Phys. Fluids A 4, 16-29 (1992)]. In more concentrated dispersions, analytical modeling of many-body hydrodynamic interactions quickly becomes intractable, leading to the development of simplified models. These include mean-field approaches that smear out particle-scale structure and essentially assume that long-range hydrodynamic interactions are screened by crowding, as particle mobility decays at high concentrations. Toward the development of an accurate and simplified model for the hydrodynamic interactions in concentrated suspensions, we recently computed a set of effective pair of hydrodynamic functions coupling particle motion to a hydrodynamic force and torque at volume fractions up to 50% utilizing accelerated Stokesian dynamics and a fast stochastic sampling technique [Zia et al., J. Chem. Phys. 143, 224901 (2015)]. We showed that the hydrodynamic mobility in suspensions of colloidal spheres is not screened, and the power law decay of the hydrodynamic functions persists at all concentrations studied. In the present work, we extend these mobility functions to include the couplings of particle motion and straining flow to the hydrodynamic stresslet. The couplings computed in these two articles constitute a set of orthogonal coupling functions that can be utilized to compute equilibrium properties in suspensions at arbitrary concentration and are readily applied to solve many-body hydrodynamic interactions analytically.
Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface
Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.
2009-01-01
Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599
Mechanisms of polyelectrolyte enhanced surfactant adsorption at the air-water interface.
Stenger, Patrick C; Palazoglu, Omer A; Zasadzinski, Joseph A
2009-05-01
Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids.
NASA Astrophysics Data System (ADS)
Zia, Roseanna N.; Swan, James W.; Su, Yu
2015-12-01
The formulation of detailed models for the dynamics of condensed soft matter including colloidal suspensions and other complex fluids requires accurate description of the physical forces between microstructural constituents. In dilute suspensions, pair-level interactions are sufficient to capture hydrodynamic, interparticle, and thermodynamic forces. In dense suspensions, many-body interactions must be considered. Prior analytical approaches to capturing such interactions such as mean-field approaches replace detailed interactions with averaged approximations. However, long-range coupling and effects of concentration on local structure, which may play an important role in, e.g., phase transitions, are smeared out in such approaches. An alternative to such approximations is the detailed modeling of hydrodynamic interactions utilizing precise couplings between moments of the hydrodynamic traction on a suspended particle and the motion of that or other suspended particles. For two isolated spheres, a set of these functions was calculated by Jeffrey and Onishi [J. Fluid Mech. 139, 261-290 (1984)] and Jeffrey [J. Phys. Fluids 4, 16-29 (1992)]. Along with pioneering work by Batchelor, these are the touchstone for low-Reynolds-number hydrodynamic interactions and have been applied directly in the solution of many important problems related to the dynamics of dilute colloidal dispersions [G. K. Batchelor and J. T. Green, J. Fluid Mech. 56, 375-400 (1972) and G. K. Batchelor, J. Fluid Mech. 74, 1-29 (1976)]. Toward extension of these functions to concentrated systems, here we present a new stochastic sampling technique to rapidly calculate an analogous set of mobility functions describing the hydrodynamic interactions between two hard spheres immersed in a suspension of arbitrary concentration, utilizing accelerated Stokesian dynamics simulations. These mobility functions provide precise, radially dependent couplings of hydrodynamic force and torque to particle translation and rotation, for arbitrary colloid volume fraction ϕ. The pair mobilities (describing entrainment of one particle by the disturbance flow created by another) decay slowly with separation distance: as 1/r, for volume fractions 0.05 ≤ ϕ ≤ 0.5. For the relative mobility, we find an initially rapid growth as a pair separates, followed by a slow, 1/r growth. Up to ϕ ≤ 0.4, the relative mobility does not reached the far-field value even beyond separations of many particle sizes. In the case of ϕ = 0.5, the far-field asymptote is reached but only at a separation of eight radii and after a slow 1/r growth. At these higher concentrations, the coefficients also reveal liquid-like structural effects on pair mobility at close separations. These results confirm that long-range many-body hydrodynamic interactions are an essential part of the dynamics of concentrated systems and that care must be taken when applying renormalization schemes.
Zia, Roseanna N; Swan, James W; Su, Yu
2015-12-14
The formulation of detailed models for the dynamics of condensed soft matter including colloidal suspensions and other complex fluids requires accurate description of the physical forces between microstructural constituents. In dilute suspensions, pair-level interactions are sufficient to capture hydrodynamic, interparticle, and thermodynamic forces. In dense suspensions, many-body interactions must be considered. Prior analytical approaches to capturing such interactions such as mean-field approaches replace detailed interactions with averaged approximations. However, long-range coupling and effects of concentration on local structure, which may play an important role in, e.g., phase transitions, are smeared out in such approaches. An alternative to such approximations is the detailed modeling of hydrodynamic interactions utilizing precise couplings between moments of the hydrodynamic traction on a suspended particle and the motion of that or other suspended particles. For two isolated spheres, a set of these functions was calculated by Jeffrey and Onishi [J. Fluid Mech. 139, 261-290 (1984)] and Jeffrey [J. Phys. Fluids 4, 16-29 (1992)]. Along with pioneering work by Batchelor, these are the touchstone for low-Reynolds-number hydrodynamic interactions and have been applied directly in the solution of many important problems related to the dynamics of dilute colloidal dispersions [G. K. Batchelor and J. T. Green, J. Fluid Mech. 56, 375-400 (1972) and G. K. Batchelor, J. Fluid Mech. 74, 1-29 (1976)]. Toward extension of these functions to concentrated systems, here we present a new stochastic sampling technique to rapidly calculate an analogous set of mobility functions describing the hydrodynamic interactions between two hard spheres immersed in a suspension of arbitrary concentration, utilizing accelerated Stokesian dynamics simulations. These mobility functions provide precise, radially dependent couplings of hydrodynamic force and torque to particle translation and rotation, for arbitrary colloid volume fraction ϕ. The pair mobilities (describing entrainment of one particle by the disturbance flow created by another) decay slowly with separation distance: as 1/r, for volume fractions 0.05 ≤ ϕ ≤ 0.5. For the relative mobility, we find an initially rapid growth as a pair separates, followed by a slow, 1/r growth. Up to ϕ ≤ 0.4, the relative mobility does not reached the far-field value even beyond separations of many particle sizes. In the case of ϕ = 0.5, the far-field asymptote is reached but only at a separation of eight radii and after a slow 1/r growth. At these higher concentrations, the coefficients also reveal liquid-like structural effects on pair mobility at close separations. These results confirm that long-range many-body hydrodynamic interactions are an essential part of the dynamics of concentrated systems and that care must be taken when applying renormalization schemes.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zia, Roseanna N., E-mail: zia@cbe.cornell.edu; Su, Yu; Swan, James W.
2015-12-14
The formulation of detailed models for the dynamics of condensed soft matter including colloidal suspensions and other complex fluids requires accurate description of the physical forces between microstructural constituents. In dilute suspensions, pair-level interactions are sufficient to capture hydrodynamic, interparticle, and thermodynamic forces. In dense suspensions, many-body interactions must be considered. Prior analytical approaches to capturing such interactions such as mean-field approaches replace detailed interactions with averaged approximations. However, long-range coupling and effects of concentration on local structure, which may play an important role in, e.g., phase transitions, are smeared out in such approaches. An alternative to such approximations ismore » the detailed modeling of hydrodynamic interactions utilizing precise couplings between moments of the hydrodynamic traction on a suspended particle and the motion of that or other suspended particles. For two isolated spheres, a set of these functions was calculated by Jeffrey and Onishi [J. Fluid Mech. 139, 261–290 (1984)] and Jeffrey [J. Phys. Fluids 4, 16–29 (1992)]. Along with pioneering work by Batchelor, these are the touchstone for low-Reynolds-number hydrodynamic interactions and have been applied directly in the solution of many important problems related to the dynamics of dilute colloidal dispersions [G. K. Batchelor and J. T. Green, J. Fluid Mech. 56, 375–400 (1972) and G. K. Batchelor, J. Fluid Mech. 74, 1–29 (1976)]. Toward extension of these functions to concentrated systems, here we present a new stochastic sampling technique to rapidly calculate an analogous set of mobility functions describing the hydrodynamic interactions between two hard spheres immersed in a suspension of arbitrary concentration, utilizing accelerated Stokesian dynamics simulations. These mobility functions provide precise, radially dependent couplings of hydrodynamic force and torque to particle translation and rotation, for arbitrary colloid volume fraction ϕ. The pair mobilities (describing entrainment of one particle by the disturbance flow created by another) decay slowly with separation distance: as 1/r, for volume fractions 0.05 ≤ ϕ ≤ 0.5. For the relative mobility, we find an initially rapid growth as a pair separates, followed by a slow, 1/r growth. Up to ϕ ≤ 0.4, the relative mobility does not reached the far-field value even beyond separations of many particle sizes. In the case of ϕ = 0.5, the far-field asymptote is reached but only at a separation of eight radii and after a slow 1/r growth. At these higher concentrations, the coefficients also reveal liquid-like structural effects on pair mobility at close separations. These results confirm that long-range many-body hydrodynamic interactions are an essential part of the dynamics of concentrated systems and that care must be taken when applying renormalization schemes.« less
Passive colloids work together to become Active
NASA Astrophysics Data System (ADS)
Kandula, Hima Nagamanasa; Wang, Wei; Zhang, Jie; Wu, Huanxin; Han, Ming; Luijten, Erik; Granick, Steve
In recent years there is growing body of research to design self-propelled colloids to gain insights into non-equilibrium systems including living matter. While most active colloids developed hitherto entail prefabrication of Janus colloids and possess single fixed active site, we present one simple system where active colloids are formed in-situ naturally with multiple active sites and are reversible as well as reconfigurable. A binary mixture of Brownian colloids which have opposite polarizations when subjected to an AC electric field spontaneously assemble into clusters which are propelled by asymmetric induced charge electro osmosis. We find that tuning the relative sizes of the two species allows for the control over the number of active sites. More interestingly, the patches are dynamic enabling reconfiguration of the active cluster. Consequently, the clusters are active not only in motion but also in their structure.
Ferraris, Sara; Cazzola, Martina; Peretti, Veronica; Stella, Barbara; Spriano, Silvia
2018-01-01
Surface properties of biomaterials (e.g., roughness, chemical composition, charge, wettability, and hydroxylation degree) are key features to understand and control the complex interface phenomena that happens upon contact with physiological fluids. Numerous physico-chemical techniques can be used in order to investigate in depth these crucial material features. Among them, zeta potential measurements are widely used for the characterization of colloidal suspensions, but actually poorly explored in the study of solid surfaces, even if they can give significant information about surface charge in function of pH and indirectly about surface functional groups and reactivity. The aim of the present research is application of zeta potential measurements of solid surfaces for the in vitro testing of biomaterials. In particular, bare and surface modified Ti6Al4V samples have been compared in order to evaluate their isoelectric points (IEPs), surface charge at physiological pH, in vitro bioactivity [in simulated body fluid (SBF)] and protein absorption. Zeta potential titration was demonstrated as a suitable technique for the surface characterization of surface treated Ti6Al4V substrates. Significant shift of the isoelectric point was recorded after a chemical surface treatment (because of the exposition of hydroxyl groups), SBF soaking (because of apatite precipitation IEP moves close to apatite one) and protein absorption (IEP moves close to protein ones). Moreover, the shape of the curve gives information about exposed functional groups (e.g., a plateau in the basic range appears due to the exposition of acidic OH groups and in the acidic range due to exposition of basic NH2 groups). PMID:29868575
Harikrishnan, A R; Dhar, Purbarun; Agnihotri, Prabhat K; Gedupudi, Sateesh; Das, Sarit Kumar
2017-06-22
Even though there are quite large studies on wettability of aqueous surfactants and a few studies on effects of nanoparticles on wettability of colloids, to the best of authors' knowledge, there is no study reported on the combined effect of surfactant and nanoparticles in altering the wettability. The present study, for the first time, reports an extensive experimental and theoretical study on the combined effect of surfactants and nanoparticles on the wettability of complex fluids such as nanocolloids on different substrates, ranging from hydrophilic with a predominantly polar surface energy component (silicon wafer and glass) to near hydrophobic range with a predominantly dispersive component of surface energy (aluminum and copper substrates). Systematically planned experiments are carried out to segregate the contributing effects of surfactants, particles, and combined particle and surfactants in modulating the wettability. The mechanisms and the governing parameters behind the interactions of nanocolloids alone and of surfactant capped nanocolloids with different surfaces are found to be grossly different. The article, for the first time, also analyzes the interplay of the nature of surfaces, surfactant and particle concentrations on contact angle, and contact angle hysteresis (CAH) of particle and surfactant impregnated colloidal suspensions. In the case of nanoparticle suspensions, the contact angle is observed to decrease for the hydrophobic system and increase for the hydrophilic systems considered. On the contrary, the combined particle and surfactant colloidal system shows a quasi-unique wetting behavior of decreasing contact angle with particle concentration on all substrates. Also interestingly, the combined particle surfactant system at all particle concentrations shows a wetting angle much lower than that of the only-surfactant case at the same surfactant concentration. Such counterintuitive observations have been explained based on the near-surface interactivity of the particle, fluid, and surfactant molecules based on effective slip length considerations. The CAH analyses of colloidal suspensions at varying surfactant and particle concentrations reveal in-depth physical insight into contact line pinning, and a unique novel relationship is established between the contact angle and differential energy for distorting the instantaneous contact angle for a pinned sessile droplet. A detailed theoretical analysis of the governing parameters influencing the wettability has been presented invoking the principles of DLVO (Derjaguin-Landau-Verwey-Overbeek), surface energy and interaction parameters influencing at the molecular scale, and the theoretical framework is found to support the experimental observations.
Rogers, Kim R; Navratilova, Jana; Stefaniak, Aleksandr; Bowers, Lauren; Knepp, Alycia K; Al-Abed, Souhail R; Potter, Phillip; Gitipour, Alireza; Radwan, Islam; Nelson, Clay; Bradham, Karen D
2018-04-01
Given the potential for human exposure to silver nanoparticles from spray disinfectants and dietary supplements, we characterized the silver-containing nanoparticles in 22 commercial products that advertised the use of silver or colloidal silver as the active ingredient. Characterization parameters included: total silver, fractionated silver (particulate and dissolved), primary particle size distribution, hydrodynamic diameter, particle number, and plasmon resonance absorbance. A high degree of variability between claimed and measured values for total silver was observed. Only 7 of the products showed total silver concentrations within 20% of their nominally reported values. In addition, significant variations in the relative percentages of particulate vs. soluble silver were also measured in many of these products reporting to be colloidal. Primary silver particle size distributions by transmission electron microscopy (TEM) showed two populations of particles - smaller particles (<5nm) and larger particles between 20 and 40nm. Hydrodynamic diameter measurements using nanoparticle tracking analysis (NTA) correlated well with TEM analysis for the larger particles. Z-average (Z-Avg) values measured using dynamic light scattering (DLS); however, were typically larger than both NTA or TEM particle diameters. Plasmon resonance absorbance signatures (peak absorbance at around 400nm indicative of metallic silver nanoparticles) were only noted in 4 of the 9 yellow-brown colored suspensions. Although the total silver concentrations were variable among products, ranging from 0.54mg/L to 960mg/L, silver containing nanoparticles were identified in all of the product suspensions by TEM. Published by Elsevier B.V.
Self-assembly of resins and asphaltenes facilitates asphaltene dissolution by an organic acid.
Hashmi, Sara M; Firoozabadi, Abbas
2013-03-15
Asphaltene precipitation occurs in petroleum fluids under certain unfavorable conditions, but can be controlled by tuning composition. Aromatic solvents in large quantities can prevent precipitation entirely and can dissolve already precipitated asphaltenes. Some polymeric surfactants can dissolve asphaltenes when added at much lower concentrations than required by aromatic solvents. Other dispersants can truncate asphaltene precipitation at the sub-micron length scale, creating stable colloidal asphaltene dispersants. One particular asphaltene dispersant, dodecylbenzene sulfonic acid (DBSA), can do both, namely: (1) stabilize asphaltene colloids and (2) dissolve asphaltenes to the molecular scale. Acid-base interactions are responsible for the efficiency of DBSA in dissolving asphaltenes compared to aromatic solvents. However, many details remain to be quantified regarding the action of DBSA on asphaltenes, including the effect of petroleum fluid composition. For instance, resins, naturally amphiphilic components of petroleum fluids, can associate with asphaltenes, but it is unknown whether they cooperate or compete with DBSA. Similarly, the presence of metals is known to hinder asphaltene dissolution by DBSA, but its effect on colloidal asphaltene stabilization has yet to be considered. We introduce the concepts of cooperativity and competition between petroleum fluid components and DBSA in stabilizing and dissolving asphaltenes. Notably, we find that resins cooperatively interact with DBSA in dissolving asphaltenes. We use UV-vis spectroscopy to investigate the interactions responsible for the phase transitions between unstable suspensions, stable suspensions, and molecular solutions of asphaltenes. Copyright © 2012 Elsevier Inc. All rights reserved.
Aggregation of montmorillonite and organic matter in aqueous media containing artificial seawater.
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.
NASA Astrophysics Data System (ADS)
Zhang, Rui; Schweizer, Kenneth S.
2012-04-01
We generalize the microscopic naïve mode coupling and nonlinear Langevin equation theories of the coupled translation-rotation dynamics of dense suspensions of uniaxial colloids to treat the effect of applied stress on shear elasticity, cooperative cage escape, structural relaxation, and dynamic and static yielding. The key concept is a stress-dependent dynamic free energy surface that quantifies the center-of-mass force and torque on a moving colloid. The consequences of variable particle aspect ratio and volume fraction, and the role of plastic versus double glasses, are established in the context of dense, glass-forming suspensions of hard-core dicolloids. For low aspect ratios, the theory provides a microscopic basis for the recently observed phenomenon of double yielding as a consequence of stress-driven sequential unlocking of caging constraints via reduction of the distinct entropic barriers associated with the rotational and translational degrees of freedom. The existence, and breadth in volume fraction, of the double yielding phenomena is predicted to generally depend on both the degree of particle anisotropy and experimental probing frequency, and as a consequence typically occurs only over a window of (high) volume fractions where there is strong decoupling of rotational and translational activated relaxation. At high enough concentrations, a return to single yielding is predicted. For large aspect ratio dicolloids, rotation and translation are always strongly coupled in the activated barrier hopping event, and hence for all stresses only a single yielding process is predicted.
Omega-3 fatty acids incorporated colloidal systems for the delivery of Angelica gigas Nakai extract.
Lee, Jeong-Jun; Park, Ju-Hwan; Lee, Jae-Young; Jeong, Jae Young; Lee, Song Yi; Yoon, In-Soo; Kang, Wie-Soo; Kim, Dae-Duk; Cho, Hyun-Jong
2016-04-01
Omega-3 (ω-3) fish oil-enriched colloidal systems were developed for the oral delivery of Angelica gigas Nakai (AGN) extract (ext). By constructing a pseudo-ternary phase diagram, the composition of oil-in-water (o/w) microemulsion (ME) systems based on ω-3 (oil), Labrasol (surfactant), and water was determined. AGN ext was dissolved into the ME system and d-α-tocopherol polyethylene glycol 1000 succinate (TPGS) was added to the ME formulation in order to enhance the mucosal absorption of the pharmacologically active ingredients in the AGN ext. The droplet size of AGN-loaded MEs was 205-277 nm and their morphology was spherical. The release of major components of AGN, decursin (D) and decursinol angelate (DA), from ME formulations in pH 1.2 and 6.8 buffers was significantly greater (P<0.05) than that from the AGN suspension group. The pharmacokinetic properties of AGN-loaded MEs in rats were evaluated by measuring decursinol (DOH) concentrations in plasma after oral administration. TPGS-included ME (F2) resulted in significantly greater (P<0.05) systemic exposure of DOH than that with ME without TPGS (F1), AGN ext+TPGS, and AGN in suspension. Severe toxicity of F1 and F2 on the intestinal epithelium was not observed by histological staining. The colloidal carriers described herein are promising delivery systems for oral administration of AGN ext. Copyright © 2015 Elsevier B.V. All rights reserved.
Colloidal spray method for low cost thin coating deposition
Pham, Ai-Quoc; Glass, Robert S.; Lee, Tae H.
2005-01-25
A dense or porous coating of material is deposited onto a substrate by forcing a colloidal suspension through an ultrasonic nebulizer and spraying a fine mist of particles in a carrier medium onto a sufficiently heated substrate. The spraying rate is essentially matched to the evaporation rate of the carrier liquid from the substrate to produce a coating that is uniformly distributed over the surface of the substrate. Following deposition to a sufficient coating thickness, a single sintering step may be used to produce a dense ceramic coating. Using this method, coatings ranging in thickness from about one to several hundred microns can be obtained. By using a plurality of compounds in the colloidal suspension, coatings of mixed composition can be obtained. By using a plurality of solutions and separate pumps and a single or multiple ultrasonic nebulizer(s), and varying the individual pumping rates and/or the concentrations of the solutions, a coating of mixed and discontinuously graded (e.g., stepped) or continuously graded layers may be obtained. This method is particularly useful for depositing ceramic coatings. Dense ceramic coating materials on porous substrates are useful in providing improved electrode performance in devices such as high power density solid oxide fuel cells. Dense ceramic coatings obtained by the invention are also useful for gas turbine blade coatings, sensors, steam electrolyzers, etc. The invention has general use in preparation of systems requiring durable and chemically resistant coatings, or coatings having other specific chemical or physical properties.
Colloidal spray method for low cost thin coating deposition
Pham, Ai-Quoc; Glass, Robert S.; Lee, Tae H.
2002-01-01
A dense or porous coating of material is deposited onto a substrate by forcing a colloidal suspension through an ultrasonic nebulizer and spraying a fine mist of particles in a carrier medium onto a sufficiently heated substrate. The spraying rate is essentially matched to the evaporation rate of the carrier liquid from the substrate to produce a coating that is uniformly distributed over the surface of the substrate. Following deposition to a sufficient coating thickness, a single sintering step may be used to produce a dense ceramic coating. Using this method, coatings ranging in thickness from about one to several hundred microns can be obtained. By using a plurality of compounds in the colloidal suspension, coatings of mixed composition can be obtained. By using a plurality of solutions and separate pumps and a single or multiple ultrasonic nebulizer(s), and varying the individual pumping rates and/or the concentrations of the solutions, a coating of mixed and discontinuously graded (e.g., stepped) or continuously graded layers may be obtained. This method is particularly useful for depositing ceramic coatings. Dense ceramic coating materials on porous substrates are useful in providing improved electrode performance in devices such as high power density solid oxide fuel cells. Dense ceramic coatings obtained by the invention are also useful for gas turbine blade coatings, sensors, steam electrolyzers, etc. The invention has general use in preparation of systems requiring durable and chemically resistant coatings, or coatings having other specific chemical or physical properties.
Christidis, G.E.; Blum, A.E.; Eberl, D.D.
2006-01-01
The influence of layer charge and charge distribution of dioctahedral smectites on the rheological and swelling properties of bentonites is examined. Layer charge and charge distribution were determined by XRD using the LayerCharge program [Christidis, G.E., Eberl, D.D., 2003. Determination of layer charge characteristics of smectites. Clays Clay Miner. 51, 644-655.]. The rheological properties were determined, after sodium exchange using the optimum amount of Na2CO3, from free swelling tests. Rheological properties were determined using 6.42% suspensions according to industrial practice. In smectites with layer charges of - 0.425 to - 0.470 per half formula unit (phfu), layer charge is inversely correlated with free swelling, viscosity, gel strength, yield strength and thixotropic behaviour. In these smectites, the rheological properties are directly associated with the proportion of low charge layers. By contrast, in low charge and high charge smectites there is no systematic relation between layer charge or the proportion of low charge layers and rheological properties. However, low charge smectites yield more viscous suspensions and swell more than high charge smectites. The rheological properties of bentonites also are affected by the proportion of tetrahedral charge (i.e. beidellitic charge), by the existence of fine-grained minerals having clay size, such as opal-CT and to a lesser degree by the ionic strength and the pH of the suspension. A new method for classification of smectites according to the layer charge based on the XRD characteristics of smecites is proposed, that also is consistent with variations in rheological properties. In this classification scheme the term smectites with intermediate layer charge is proposed. ?? 2006 Elsevier B.V. All rights reserved.
NASA Technical Reports Server (NTRS)
Zhu, Ji-Xiang; Chaikin, P. M.; Li, Min; Russel, W. B.; Ottewill, R. H.; Rogers, R.; Meyer, W. V.
1998-01-01
Classical hard spheres have long served as a paradigm for our understanding of the structure of liquids, crystals, and glasses and the transitions between these phases. Ground-based experiments have demonstrated that suspensions of uniform polymer colloids are near-ideal physical realizations of hard spheres. However, gravity appears to play a significant and unexpected role in the formation and structure of these colloidal crystals. In the microgravity environment of the Space Shuttle, crystals grow purely via random stacking of hexagonal close-packed planes, lacking any of the face-centered cubic (FCC) component evident in crystals grown in 1 g beyond melting and allowed some time to settle. Gravity also masks 33-539 the natural growth instabilities of the hard sphere crystals which exhibit striking dendritic arms when grown in microgravity. Finally, high volume fraction "glass" samples which fail to crystallize after more than a year in 1 g begin nucleation after several days and fully crystallize in less than 2 weeks on the Space Shuttle.
Colloid-colloid hydrodynamic interaction around a bend in a quasi-one-dimensional channel.
Liepold, Christopher; Zarcone, Ryan; Heumann, Tibor; Rice, Stuart A; Lin, Binhua
2017-07-01
We report a study of how a bend in a quasi-one-dimensional (q1D) channel containing a colloid suspension at equilibrium that exhibits single-file particle motion affects the hydrodynamic coupling between colloid particles. We observe both structural and dynamical responses as the bend angle becomes more acute. The structural response is an increasing depletion of particles in the vicinity of the bend and an increase in the nearest-neighbor separation in the pair correlation function for particles on opposite sides of the bend. The dynamical response monitored by the change in the self-diffusion [D_{11}(x)] and coupling [D_{12}(x)] terms of the pair diffusion tensor reveals that the pair separation dependence of D_{12} mimics that of the pair correlation function just as in a straight q1D channel. We show that the observed behavior is a consequence of the boundary conditions imposed on the q1D channel: both the single-file motion and the hydrodynamic flow must follow the channel around the bend.
Hafner, Anita; Lovrić, Jasmina; Voinovich, Dario; Filipović-Grcić, Jelena
2009-11-03
In this study, the potential of lecithin/chitosan nanoparticles (NPs) as a mucoadhesive colloidal nanosystem for transmucosal delivery of melatonin was investigated. The size, zeta potential and melatonin loading of the lecithin/chitosan NPs were investigated as a function of lecithin type (Lipoid S45, S75 and S100) and chitosan content in the preparation. The NPs were characterised by mean diameter and zeta potential ranging between 121.6 and 347.5 nm, and 7.5 and 32.7 mV, respectively, and increasing with lecithin-negative charge and chitosan content in the preparation. Melatonin loadings were up to 7.1%. All NPs were characterised by prolonged release profiles with an initial burst (approximately 25%), followed by a slow release phase. Approximately 60-70% of melatonin was released in 4h. The permeability of melatonin was investigated using Caco-2 cells as an in vitro model of the epithelial barrier. Melatonin permeability from an NP suspension prepared with Lipoid S45 lecithin and a lecithin-to-chitosan weight ratio (L/C) of 20:1 (sample C2) was significantly improved compared to the permeability of melatonin from the solution (P<0.001) and from all other NPs investigated (P<0.05). The results obtained by the cell viability studies (MTT and LDH leakage assays) showed that C2 NP suspension did not induce plasma membrane damage or decrease cell viability and could be safely applied to Caco-2 cells in the concentration range tested (<400 microg/ml).
Roll-to-roll light directed electrophoretic deposition system and method
Pascall, Andrew J.; Kuntz, Joshua
2017-06-06
A roll-to-roll light directed electrophoretic deposition system and method advances a roll of a flexible electrode web substrate along a roll-to-roll process path, where a material source is positioned to provide on the flexible electrode web substrate a thin film colloidal dispersion of electrically charged colloidal material dispersed in a fluid. A counter electrode is also positioned to come in contact with the thin film colloidal dispersion opposite the flexible electrode web substrate, where one of the counter electrode and the flexible electrode web substrate is a photoconductive electrode. A voltage source is connected to produce an electric potential between the counter electrode and the flexible electrode web substrate to induce electrophoretic deposition on the flexible electrode web substrate when the photoconductive electrode is rendered conductive, and a patterned light source is arranged to illuminate the photoconductive electrode with a light pattern and render conductive illuminated areas of the photoconductive electrode so that a patterned deposit of the electrically charged colloidal material is formed on the flexible electrode web substrate.
NASA Astrophysics Data System (ADS)
Kluijtmans, Sebastiaan G. J. M.; de Hoog, Els H. A.; Philipse, Albert P.
1998-05-01
The influence of charge on diffusion in porous media was studied for fluorescent colloidal silica spheres diffusing in a porous glass medium. The bicontinuous porous silica glasses were optically matched with an organic solvent mixture in which both glass and tracers are negatively charged. Using fluorescence recovery after photobleaching, the long-time self-diffusion coefficient DSL of the confined silica particles was monitored in situ as a function of the ionic strength and particle to pore size ratio. At high salt concentration DSL reaches a relatively high plateau value, which depends on the particle to pore size ratio. This plateau value is unexpectedly higher than the value found for uncharged silica spheres in these porous glasses, but still significantly smaller than the free particle bulk diffusion coefficient of the silica spheres. At low salt concentration DSL reduces markedly, up to the point where colloids are nearly immobilized. This peculiar retardation probably originates from potential traps and barriers at pore intersections due to deviations from cylinder symmetry in the double layer interactions between tracers and pore walls. This indicates that diffusion of charged particles in tortuous porous media may be very different from transport in long capillaries without such intersections.
Order and gelation of cellulose nanocrystal suspensions: an overview of some issues
NASA Astrophysics Data System (ADS)
Gray, Derek G.
2017-12-01
Cellulose nanocrystals (CNCs) are polydisperse rod-shaped particles of crystalline cellulose I, typically prepared by sulfuric acid hydrolysis of natural cellulose fibres to give aqueous colloidal suspensions stabilized by sulfate half-ester groups. Sufficiently dilute suspensions are isotropic fluids, but as the concentration of CNC in water is increased, a critical concentration is reached where a spontaneously ordered phase is observed. The (equilibrium) phase separation of the ordered chiral nematic phase is in competition with a tendency of the CNC suspension to form a gel. Qualitatively, factors that reduce the stability of the CNC suspension favour the onset of gelation. The chiral nematic structure is preserved, at least partially, when the suspension dries. Solid chiral nematic films of cellulose are of interest for their optical and templating properties, but the preparation of the films requires improvement. The processes that govern the formation of solid chiral nematic films from CNC suspensions include phase separation, gelation and also the effects of shear on CNC orientation during evaporation. Some insight into these processes is provided by polarized light microscopy, which indicates that the relaxation of shear-induced orientation to give a chiral nematic structure may occur via an intermediate twist-bend state. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.
Surface chemical effects on colloid stability and transport through natural porous media
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.
Saito, Shuntaro; Hasegawa, Jun; Kobayashi, Naoki; Tomitsuka, Toshiaki; Uchiyama, Susumu; Fukui, Kiichi
2013-05-01
To develop a general strategy for optimizing monoclonal antibody (MAb) formulations. Colloidal stabilities of four representative MAbs solutions were assessed based on the second virial coefficient (B 2) at 20°C and 40°C, and net charges at different NaCl concentrations, and/or in the presence of sugars. Conformational stabilities were evaluated from the unfolding temperatures. The aggregation propensities were determined at 40°C and after freeze-thawing. The electrostatic potential of antibody surfaces was simulated for the development of rational formulations. Similar B 2 values were obtained at 20°C and 40°C, implying little dependence on temperature. B 2 correlated quantitatively with aggregation propensities at 40°C. The net charge partly correlated with colloidal stability. Salts stabilized or destabilized MAbs, depending on repulsive or attractive interactions. Sugars improved the aggregation propensity under freeze-thaw stress through improved conformational stability. Uneven and even distributions of potential surfaces were attributed to attractive and strong repulsive electrostatic interactions. Assessment of colloidal stability at the lowest ionic strength is particularly effective for the development of formulations. If necessary, salts are added to enhance the colloidal stability. Sugars further improved aggregation propensities by enhancing conformational stability. These behaviors are rationally predictable according to the surface potentials of MAbs.
Trauscht, Jacob; Pazmino, Eddy; Johnson, William P
2015-09-01
Despite several decades of research there currently exists no mechanistic theory to predict colloid attachment in porous media under environmental conditions where colloid-collector repulsion exists (unfavorable conditions for attachment). It has long been inferred that nano- to microscale surface heterogeneity (herein called discrete heterogeneity) drives colloid attachment under unfavorable conditions. Incorporating discrete heterogeneity into colloid-collector interaction calculations in particle trajectory simulations predicts colloid attachment under unfavorable conditions. As yet, discrete heterogeneity cannot be independently measured by spectroscopic or other approaches in ways directly relevant to colloid-surface interaction. This, combined with the fact that a given discrete heterogeneity representation will interact differently with differently sized colloids as well as different ionic strengths for a given sized colloid, suggests a strategy to back out representative discrete heterogeneity by a comparison of simulations to experiments performed across a range of colloid size, solution IS, and fluid velocity. This has recently been performed for interaction of carboxylate-modified polystyrene latex (CML) microsphere attachment to soda lime glass at pH 6.7 with NaCl electrolyte. However, extension to other surfaces, pH values, and electrolytes is needed. For this reason, the attachment of CML (0.25, 1.1, and 2.0 μm diameters) from aqueous suspension onto a variety of unfavorable mineral surfaces (soda lime glass, muscovite, and albite) was examined for pH values of 6.7 and 8.0), fluid velocities (1.71 × 10(-3) and 5.94 × 10(-3) m s(-1)), IS (6.0 and 20 mM), and electrolytes (NaCl, CaSO4, and multivalent mixtures). The resulting representative heterogeneities (heterodomain size and surface coverage, where heterodomain refers to nano- to microscale attractive domains) yielded colloid attachment predictions that were compared to predictions from existing applicable semiempirical expressions in order to examine the strengths and weaknesses of the discrete heterogeneity approach and opportunities for improvement.
Technology utilization program report
NASA Technical Reports Server (NTRS)
1974-01-01
The application of aerospace technology to the solution of public health and industrial problems is reported. Data cover: (1) development of an externally rechargeable cardiac pacemaker, (2) utilization of ferrofluids-colloidal suspensions of ferrite particles - in the efficient separation of nonferrous metals as Ni, Zn, Cu, and Al from shredded automobile scrap, and (3) development of a breathing system for fire fighters.
Electrohydrodynamic simulation of an electrospray in a colloid thruster
NASA Astrophysics Data System (ADS)
Jugroot, Manish; Forget, Martin; Malardier-Jugroot, Cecile
2012-02-01
A precise understanding of electrosprays is highly interesting as the complexity of micro-technology (such as nano-material processing, spacecraft propulsion and mass-spectrometers) systems increases. A multi-component CFD-based model coupling fluid dynamics, charged species dynamics and electric field is developed. The simulations describe the charged fluid interface with emphasis on the Taylor cone formation and cone-jet transition under the effect of a electric field. The goal is to recapture this transition from a rounded liquid interface into a Taylor cone from an initial uniform distribution, without making assumptions on the behaviour, geometry or charge distribution of the system. The time evolution of the interface highlights the close interaction among space charge, coulombic forces and the surface tension, which appear as governing and competing processes in the transition. The results from the coupled formalism provide valuable insights on the physical phenomena and will be applied to a colloid thruster for small spacecrafts.
High charge-carrier mobility enables exploitation of carrier multiplication in quantum-dot films
Sandeep, C. S. Suchand; Cate, Sybren ten; Schins, Juleon M.; Savenije, Tom J.; Liu, Yao; Law, Matt; Kinge, Sachin; Houtepen, Arjan J.; Siebbeles, Laurens D. A.
2013-01-01
Carrier multiplication, the generation of multiple electron–hole pairs by a single photon, is of great interest for solar cells as it may enhance their photocurrent. This process has been shown to occur efficiently in colloidal quantum dots, however, harvesting of the generated multiple charges has proved difficult. Here we show that by tuning the charge-carrier mobility in quantum-dot films, carrier multiplication can be optimized and may show an efficiency as high as in colloidal dispersion. Our results are explained quantitatively by the competition between dissociation of multiple electron–hole pairs and Auger recombination. Above a mobility of ~1 cm2 V−1 s−1, all charges escape Auger recombination and are quantitatively converted to free charges, offering the prospect of cheap quantum-dot solar cells with efficiencies in excess of the Shockley–Queisser limit. In addition, we show that the threshold energy for carrier multiplication is reduced to twice the band gap of the quantum dots. PMID:23974282
Xu, Xingsheng; Li, Xingyun
2015-01-01
We investigate the photoluminescence (PL) spectra and the time-resolved PL decay process from colloidal quantum dots on SiN/SiO2 wet etched via BOE (HF:NH4F:H2O). The spectrum displays multi-peak shapes that vary with irradiation time. The evolution of the spectral peaks with irradiation time and collection angle demonstrates that the strong coupling of the charged-exciton emission to the leaky modes of the SiN/SiO2 slab waveguide predominantly produces short-wavelength spectral peaks, resulting in multi-peak spectra. We conclude that BOE etching enhances the charged-exciton emission efficiency and its contribution to the total emission compared with the unetched case. BOE etching smoothes the electron confinement potential, thus decreasing the Auger recombination rate. Therefore, the charged-exciton emission efficiency is high, and the charged-exciton-polariton emission can be further enhanced through strong coupling to the leaky mode of the slab waveguide. PMID:25988709
Dynamic Colloidal Molecules Maneuvered by Light-Controlled Janus Micromotors.
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.
Shear thinning in soft particle suspensions
NASA Astrophysics Data System (ADS)
Voudouris, Panayiotis; van der Zanden, Berco; Florea, Daniel; Fahimi, Zahra; Wyss, Hans
2012-02-01
Suspensions of soft deformable particles are encountered in a wide range of food and biological materials. Examples are biological cells, micelles, vesicles or microgel particles. While the behavior of suspenions of hard spheres - the classical model system of colloid science - is reasonably well understood, a full understanding of these soft particle suspensions remains elusive. The relation between single particle properties and macroscopic mechanical behavior still remains poorly understood in these materials. Here we examine the surprising shear thinning behavior that is observed in soft particle suspensions as a function of particle softness. We use poly-N-isopropylacrylamide (p-NIPAM) microgel particles as a model system to study this effect in detail. These soft spheres show significant shear thinning even at very large Peclet numbers, where this would not be observed for hard particles. The degree of shear thinning is directly related to the single particle elastic properties, which we characterize by the recently developed Capillary Micromechanics technique. We present a simple model that qualitatively accounts for the observed behavior.
Patsahan, O; Ciach, A
2012-09-01
Effects of size and charge asymmetry between oppositely charged ions or particles on spatial inhomogeneities are studied for a large range of charge and size ratios. We perform a stability analysis of the primitive model of ionic systems with respect to periodic ordering using the collective variables-based theory. We extend previous studies [Ciach et al., Phys. Rev. E 75, 051505 (2007)] in several ways. First, we employ a nonlocal approximation for the reference hard-sphere fluid which leads to the Percus-Yevick pair direct correlation functions for the uniform case. Second, we use the Weeks-Chandler-Anderson regularization scheme for the Coulomb potential inside the hard core. We determine the relevant order parameter connected with the periodic ordering and analyze the character of the dominant fluctuations along the λ lines. We show that the above-mentioned modifications produce large quantitative and partly qualitative changes in the phase diagrams obtained previously. We discuss possible scenarios of the periodic ordering for the whole range of size and charge ratios of the two ionic species, covering electrolytes, ionic liquids, charged globular proteins or nanoparticles in aqueous solutions, and charge-stabilized colloids.
Hu, Yi; Cheng, Xuanhong; Daniel Ou-Yang, H
2013-01-01
Fluorescence correlation spectroscopy (FCS) is one of the most sensitive methods for enumerating low concentration nanoparticles in a suspension. However, biological nanoparticles such as viruses often exist at a concentration much lower than the FCS detection limit. While optically generated trapping potentials are shown to effectively enhance the concentration of nanoparticles, feasibility of FCS for enumerating field-enriched nanoparticles requires understanding of the nanoparticle behavior in the external field. This paper reports an experimental study that combines optical trapping and FCS to examine existing theoretical predictions of particle concentration. Colloidal suspensions of polystyrene (PS) nanospheres and HIV-1 virus-like particles are used as model systems. Optical trapping energies and statistical analysis are used to discuss the applicability of FCS for enumerating nanoparticles in a potential well produced by a force field.
Effective temperatures and the breakdown of the Stokes-Einstein relation for particle suspensions.
Mendoza, Carlos I; Santamaría-Holek, I; Pérez-Madrid, A
2015-09-14
The short- and long-time breakdown of the classical Stokes-Einstein relation for colloidal suspensions at arbitrary volume fractions is explained here by examining the role that confinement and attractive interactions play in the intra- and inter-cage dynamics executed by the colloidal particles. We show that the measured short-time diffusion coefficient is larger than the one predicted by the classical Stokes-Einstein relation due to a non-equilibrated energy transfer between kinetic and configuration degrees of freedom. This transfer can be incorporated in an effective kinetic temperature that is higher than the temperature of the heat bath. We propose a Generalized Stokes-Einstein relation (GSER) in which the effective temperature replaces the temperature of the heat bath. This relation then allows to obtain the diffusion coefficient once the viscosity and the effective temperature are known. On the other hand, the temporary cluster formation induced by confinement and attractive interactions of hydrodynamic nature makes the long-time diffusion coefficient to be smaller than the corresponding one obtained from the classical Stokes-Einstein relation. Then, the use of the GSER allows to obtain an effective temperature that is smaller than the temperature of the heat bath. Additionally, we provide a simple expression based on a differential effective medium theory that allows to calculate the diffusion coefficient at short and long times. Comparison of our results with experiments and simulations for suspensions of hard and porous spheres shows an excellent agreement in all cases.
The role of water in slip casting
NASA Technical Reports Server (NTRS)
Mccauley, R. A.; Phelps, G. W.
1984-01-01
Slips and casting are considered in terms of physical and colloidal chemistry. Casting slips are polydisperse suspensions of lyophobic particles in water, whose degree of coagulation is controlled by interaction of flocculating and deflocculating agents. Slip casting rate and viscosity are functions of temperature. Slip rheology and response to deflocculating agents varies significantly as the kinds and amounts of colloid modifiers change. Water is considered as a raw material. Various concepts of water/clay interactions and structures are discussed. Casting is a de-watering operation in which water moves from slip to cast to mold in response to a potential energy termed moisture stress. Drying is an evaporative process from a free water surface.
Brownian versus Newtonian devitrification of hard-sphere glasses
NASA Astrophysics Data System (ADS)
Montero de Hijes, Pablo; Rosales-Pelaez, Pablo; Valeriani, Chantal; Pusey, Peter N.; Sanz, Eduardo
2017-08-01
In a recent molecular dynamics simulation work it has been shown that glasses composed of hard spheres crystallize via cooperative, stochastic particle displacements called avalanches [E. Sanz et al., Proc. Natl. Acad. Sci. USA 111, 75 (2014), 10.1073/pnas.1308338110]. In this Rapid Communication we investigate if such a devitrification mechanism is also present when the dynamics is Brownian rather than Newtonian. The research is motivated in part by the fact that colloidal suspensions, an experimental realization of hard-sphere systems, undergo Brownian motion. We find that Brownian hard-sphere glasses do crystallize via avalanches with very similar characteristics to those found in the Newtonian case. We briefly discuss the implications of these findings for experiments on colloids.
Location on chitin in the cyst wall of Entamoeba invadens with colloidal gold tracers.
Arroyo-Begovich, A; Cárabez-Trejo, A
1982-04-01
Chitin was located in the cyst wall of Entamoeba invadens with colloidal gold-linked wheat germ agglutinin. Cysts stained differentially from trophozoites when encysting cultures were treated with the gold tracer; cysts acquired a wine-red coloration while, in general trophozoites remained unstained. Observation of cells with the electron microscope revealed that the tracer particles were bound specifically to the walls of the surface of the cyst when cells were exposed in suspension, and to the cyst wall cross-section, when cells were exposed to the tracer in thin section, indicating that chitin fibers were distributed on the surface as well as throughout the matrix of the cyst wall.
NASA Astrophysics Data System (ADS)
Fu, Yanan; Xie, Honglan; Deng, Biao; Du, Guohao; Xiao, Tiqiao
2017-06-01
The floatage self-assembly method was introduced with mixed solvent as the medium of polystyrene sphere suspension to fabricate the colloidal crystal. The three dimensional (3D) void system of the colloidal crystal was noninvasively characterized by synchrotron radiation phase-contrast computed tomography, and the quantitative image analysis was implemented aiming to the polystyrene sphere colloidal crystal. Comparing with gravity sedimentation method, the three samples fabricated from floatage self-assembly with mixed solvents have the lowest porosity, and when ethylene glycol and water were mixed with ratio of 1:1, the lowest porosity of 27.49% could be achieved, that has been very close to the minimum porosity of ordered 3D monodisperse sphere array (26%). In single slices, the porosities and fractal dimension for the voids were calculated. The results showed that two factors would significantly influence the porosity of the whole colloidal crystal: the first deposited sphere layer's orderliness and the sedimentation speed of the spheres. The floatage self-assembly could induce a stable close-packing process, resulted from the powerful nucleation force-lateral capillary force coupled with the mixed solvent to regulate the floating upward speed for purpose of matching the assembly rate.
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.
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
Adsorption of reovirus by minerals and soils.
Moore, R S; Taylor, D H; Reddy, M M; Sturman, L S
1982-01-01
Adsorption of [35S]methionine-labeled reovirus by 30 dry soils, minerals, and finely ground rocks suspended in synthetic freshwater at pH 7 was investigated to determine the conditions necessary for optimum virus removal during land application of wastewaters. All of the minerals and soils studied were excellent adsorbents of reovirus, with greater than 99% of the virus adsorbed after 1 h at 4 degrees C. Thereafter, virus remaining in suspension was significantly inactivated, and within 24 h a three to five log10 reduction in titer occurred. The presence of divalent cations, i.e., Ca2+ and Mg2+, in synthetic freshwater enhanced removal, whereas soluble organic matter decreased the amount of virus adsorbed in secondary effluent. The amount of virus adsorbed by these substrates was inversely correlated with the amount of organic matter, capacity to adsorb cationic polyelectrolyte, and electrophoretic mobility. Adsorption increased with increasing available surface area, as suspended infectivity was reduced further by the more finely divided substrates. However, the organic content of the soils reduced the level of infectious virus adsorbed below that expected from surface area measurements alone. The inverse correlation between virus adsorption and substrate capacity for cationic polyelectrolyte indicates that the adsorption of infectious reovirus particles is predominately a charged colloidal particle-charged surface interaction. Thus, adsorption of polyelectrolyte may be useful in predicting the fate of viruses during land application of sewage effluents and sludges. PMID:7149717
An anisotropic hydrogel with electrostatic repulsion between cofacially aligned nanosheets
NASA Astrophysics Data System (ADS)
Liu, Mingjie; Ishida, Yasuhiro; Ebina, Yasuo; Sasaki, Takayoshi; Hikima, Takaaki; Takata, Masaki; Aida, Takuzo
2015-01-01
Machine technology frequently puts magnetic or electrostatic repulsive forces to practical use, as in maglev trains, vehicle suspensions or non-contact bearings. In contrast, materials design overwhelmingly focuses on attractive interactions, such as in the many advanced polymer-based composites, where inorganic fillers interact with a polymer matrix to improve mechanical properties. However, articular cartilage strikingly illustrates how electrostatic repulsion can be harnessed to achieve unparalleled functional efficiency: it permits virtually frictionless mechanical motion within joints, even under high compression. Here we describe a composite hydrogel with anisotropic mechanical properties dominated by electrostatic repulsion between negatively charged unilamellar titanate nanosheets embedded within it. Crucial to the behaviour of this hydrogel is the serendipitous discovery of cofacial nanosheet alignment in aqueous colloidal dispersions subjected to a strong magnetic field, which maximizes electrostatic repulsion and thereby induces a quasi-crystalline structural ordering over macroscopic length scales and with uniformly large face-to-face nanosheet separation. We fix this transiently induced structural order by transforming the dispersion into a hydrogel using light-triggered in situ vinyl polymerization. The resultant hydrogel, containing charged inorganic structures that align cofacially in a magnetic flux, deforms easily under shear forces applied parallel to the embedded nanosheets yet resists compressive forces applied orthogonally. We anticipate that the concept of embedding anisotropic repulsive electrostatics within a composite material, inspired by articular cartilage, will open up new possibilities for developing soft materials with unusual functions.
An anisotropic hydrogel with electrostatic repulsion between cofacially aligned nanosheets.
Liu, Mingjie; Ishida, Yasuhiro; Ebina, Yasuo; Sasaki, Takayoshi; Hikima, Takaaki; Takata, Masaki; Aida, Takuzo
2015-01-01
Machine technology frequently puts magnetic or electrostatic repulsive forces to practical use, as in maglev trains, vehicle suspensions or non-contact bearings. In contrast, materials design overwhelmingly focuses on attractive interactions, such as in the many advanced polymer-based composites, where inorganic fillers interact with a polymer matrix to improve mechanical properties. However, articular cartilage strikingly illustrates how electrostatic repulsion can be harnessed to achieve unparalleled functional efficiency: it permits virtually frictionless mechanical motion within joints, even under high compression. Here we describe a composite hydrogel with anisotropic mechanical properties dominated by electrostatic repulsion between negatively charged unilamellar titanate nanosheets embedded within it. Crucial to the behaviour of this hydrogel is the serendipitous discovery of cofacial nanosheet alignment in aqueous colloidal dispersions subjected to a strong magnetic field, which maximizes electrostatic repulsion and thereby induces a quasi-crystalline structural ordering over macroscopic length scales and with uniformly large face-to-face nanosheet separation. We fix this transiently induced structural order by transforming the dispersion into a hydrogel using light-triggered in situ vinyl polymerization. The resultant hydrogel, containing charged inorganic structures that align cofacially in a magnetic flux, deforms easily under shear forces applied parallel to the embedded nanosheets yet resists compressive forces applied orthogonally. We anticipate that the concept of embedding anisotropic repulsive electrostatics within a composite material, inspired by articular cartilage, will open up new possibilities for developing soft materials with unusual functions.
Interaction of two cylinders in shear flow at low Wi
NASA Astrophysics Data System (ADS)
Brown, M. J.; Leal, L. G.
2001-11-01
Experiments [Lyon et al., 2001; Boussima et al., 1996; Michelle et al., 1977] have shown that non-Brownian, non-Colloidal, and charge-neutral particles, when suspended in viscoelastic media and subjected to shear, will aggregate and flow-align above a critical shear rate Wi O(10). Giesekus [1978] proposed a mechanism for aggregation based on the attractive hoop thrusts about two particles in viscoelastic flow. This pairwise mechanism of attraction is borne out in studies of sedimenting particles [Feng & Joseph, 1996; Joseph et al., 1994], and seems a valid explanation for the aggregation observed in sedimenting suspensions over all Wi > Re [Joseph et al., 1994; Phillips, 1996.] Consideration of the flow around two particles in shear would lead one to expect attraction by this hoop thrust mechanism as well. However, it remains unclear why shear-induced aggregation only occurs above a critical Wi. A first step in understanding this criticality is to establish the low Wi behavior of two particles in shear. In this talk, we report on the interaction of two freely-mobile cylinders as predicted by an n-th order fluid computation.