Driving morphological changes in magnetic nanoparticle structures through the application of acoustic waves and magnetic fields

NASA Astrophysics Data System (ADS)

Huang, Ann; Miansari, Morteza; Friend, James

The growing interest in acoustic manipulation of particles in micro to nanofluidics using surface acoustic waves (SAW), together with the many applications of magnetic nanoparticles-whether individual or in arrays-underpins our discovery of how these forces can be used to rapidly, easily, and irreversibly form 1D chains and 2D films. These films and chains are currently difficult to produce yet offer many advantages over individual nanoparticles in suspension. Making use of the scale of the structures formed, 10-9 to 10-5 m, and by taking a balance of the relevant external and interparticle forces, the underlying mechanisms responsible for the phenomena become apparent. For 1D chains, the magnetic field alone is sufficient, though applying an acoustic field drives a topology change from loosely connected chains to loops of 10 -100 particles. Adding the acoustic field drives a transition from these looped structures to dense 2D arrays via interparticle Bjerknes forces. Inter-particle drainage of the surrounding fluid leaves these structures intact after removal of the externally applied forces. Clear morphology transitions are present and depend on the relative amplitude of the incident Brownian, Bjerknes, and magnetic forces. UCSD: Frontiers of Innovation Scholars Program (U-1024).

Force-chain evolution in a two-dimensional granular packing compacted by vertical tappings

NASA Astrophysics Data System (ADS)

Iikawa, Naoki; Bandi, M. M.; Katsuragi, Hiroaki

2018-03-01

We experimentally study the statistics of force-chain evolution in a vertically-tapped two-dimensional granular packing by using photoelastic disks. In this experiment, the tapped granular packing is gradually compacted. During the compaction, the isotropy of grain configurations is quantified by measuring the deviator anisotropy derived from fabric tensor, and then the evolution of force-chain structure is quantified by measuring the interparticle forces and force-chain orientational order parameter. As packing fraction increases, the interparticle force increases and finally saturates to an asymptotic value. Moreover, the grain configurations and force-chain structures become isotropically random as the tapping-induced compaction proceeds. In contrast, the total length of force chains remains unchanged. From the correlations of those parameters, we find two relations: (i) a positive correlation between the isotropy of grain configurations and the disordering of force-chain orientations, and (ii) a negative correlation between the increasing of interparticle forces and the disordering of force-chain orientations. These relations are universally held regardless of the mode of particle motions with or without convection.

The effects of intraparticle and interparticle interactions on the magnetic hysteresis loop of frozen suspensions of bionized nanoferrite particles

NASA Astrophysics Data System (ADS)

Boekelheide, Zoe; Gruettner, Cordula; Dennis, Cindi

Bionized nano-ferrite (iron oxide/dextran) nanoparticles have been shown to have a large heating response in an alternating magnetic field, making them very promising for applications in magnetic nanoparticle hyperthermia cancer treatment. Magnetic hysteresis loop measurements of these particles provide insight into the magnetic reversal behavior of these particles, and thus their heating response. Measurements have been performed on frozen suspensions of nanoparticles dispersed in H2O, which have been frozen in a range of applied fields in order to tune the interparticle dipolar interactions through formation of linear chains. These experimental results are compared with micromagnetic models of both monolithic (single-domain) and internally structured (multi-grain) particles. It is found that the internal structure of the nanoparticles, which are made up of parallelepiped-shaped grains, is important for describing the magnetic reversal behavior of the particles and the resulting shape of the hysteresis loops. In addition to this, interparticle interactions between particles in a linear chain modify the reversal behavior and thus the shape of the hysteresis loop.

Self-Assembly of DNA-Coated Particles: Experiment, Simulation and Theory

NASA Astrophysics Data System (ADS)

Song, Minseok

The bottom-up assembly of material architectures with tunable complexity, function, composition, and structure is a long sought goal in rational materials design. One promising approach aims to harnesses the programmability and specificity of DNA hybridization in order to direct the assembly of oligonucleotide-functionalized nano- and micro-particles by tailoring, in part, interparticle interactions. DNA-programmable assembly into three-dimensionally ordered structures has attracted extensive research interest owing to emergent applications in photonics, plasmonics and catalysis and potentially many other areas. Progress on the rational design of DNA-mediated interactions to create useful two-dimensional structures (e.g., structured films), on the other hand, has been rather slow. In this thesis, we establish strategies to engineer a diversity of 2D crystalline arrangements by designing and exploiting DNA-programmable interparticle interactions. We employ a combination of simulation, theory and experiments to predict and confirm accessibility of 2D structural diversity in an effort to establish a rational approach to 2D DNA-mediated particle assembly. We start with the experimental realization of 2D DNA-mediated assembly by decorating micron-sized silica particles with covalently attached single-stranded DNA through a two-step reaction. Subsequently, we elucidate sensitivity and ultimate controllability of DNA-mediated assembly---specifically the melting transition from dispersed singlet particles to aggregated or assembled structures---through control of the concentration of commonly employed nonionic surfactants. We relate the observed tunability to an apparent coupling with the critical micelle temperature in these systems. Also, both square and hexagonal 2D ordered particle arrangements are shown to evolve from disordered aggregates under appropriate annealing conditions defined based upon pre-established melting profiles. Subsequently, the controlled mixing of complementary ssDNA functionality on individual particles ('multi-flavoring') as opposed to functionalization of particles with the same type of ssDNA ('uni-flavoring') is explored as a possible design handle for tuning interparticle interactions and, thereby, accessing diverse structures. We employ a combination of simulations, theory, and experimental validation toward establishing 'multi-flavoring' as a rational design strategy. Firstly, MD simulations are carried out using effective pair potentials to describe interparticle interactions that are representative of different degrees of ssDNA 'multi-flavoring'. These simulations reveal the template-free assembly of a diversity of 2D crystal polymorphs that is apparently tunable by controlling the relative attractive strengths between like and unlike functionalized particles. The resulting phase diagrams predict conditions (i.e., strengths of relative interparticle interactions) for obtaining crystalline phases with lattice symmetries ranging among square, alternating string hexagonal, random hexagonal, rhombic, honeycomb, and even kagome. Finally, these model findings are translated to experiments, in which binary microparticles are decorated with a tailored mixture of two different complementary ssDNA strands as a straight-forward means to realize tunable particle interactions. Guided by simple statistical mechanics and the detailed MD simulations, 'multi-flavoring' and control of solution phase particle stoichiometry resulted in experimental realization of structurally diverse 2D microparticle assemblies consistent with predictions, such as square, pentagonal and hexagonal lattices (honeycomb, kagome). The combined simulation, theory, and experimental findings reveal how control of interparticle interactions via DNA-functionalized particle "multi-flavoring" can lead to an even wider range of accessible colloidal crystal structures. The 2D experiments coupled with the model predictions may be used to provide new fundamental insight into nano- or microparticle assembly in three dimensions.

Interparticle spacing and structural ordering in superlattice PbS nanocrystal solids undergoing ligand exchange

DOE PAGES

Weidman, Mark C.; Yager, Kevin G.; Tisdale, William A.

2014-12-12

Controlling the interparticle spacing in quantum dot (QD) thin films is the most readily accessible way to control transport rates between neighboring QDs and a critical component of device optimization. Here, we use X-ray scattering measurements to accurately measure the interparticle spacing in films of highly monodisperse lead sulfide (PbS) QDs that have undergone a variety of device-relevant ligand exchanges. We tabulate these values for use in simulations and data analysis. We find that monothiol and dithiol ligand species typically result in interparticle spacing values that are equal to the length of a single monothiol or dithiol ligand. Additionally, wemore » find that spin-coating a thick film of QDs followed by a long-duration ligand exchange results in a more complete ligand exchange than spin-coating many thin layers with short-duration ligand exchanges in between. The former method also preserves a remarkable degree of the long-range ordering that was present in the film prior to ligand exchange. These results shed light on ways to produce highly-ordered QD solids with compact and functional ligands, which could lead to enhanced interdot coupling and transport phenomena.« less

A microsphere assembly method with laser microwelding for fabrication of three-dimensional periodic structures

NASA Astrophysics Data System (ADS)

Takagi, Kenta; Omote, Masanori; Kawasaki, Akira

2010-03-01

The orderly build-up of monosized microspheres with sizes of hundreds of micrometres enabled us to develop three-dimensional (3D) photonic crystal devices for terahertz electromagnetic waves. We designed and manufactured an original 3D particle assembly system capable of fabricating arbitrary periodic structures from these spherical particles. This method employs a pick-and-place assembling approach with robotic manipulation and interparticle laser microwelding in order to incorporate a contrivance for highly accurate arraying: an operation that compensates the size deviation of raw monosized particles. Pre-examination of particles of various materials revealed that interparticle laser welding must be achieved with local melting by suppressing heat diffusion from the welding area. By optimizing the assembly conditions, we succeeded in fabricating an accurate periodic structure with a diamond lattice from 400 µm polyethylene composite particles. This structure demonstrated a photonic bandgap in the terahertz frequency range.

Functional liquid structures by emulsification of graphene and other two-dimensional nanomaterials.

PubMed

Large, Matthew J; Ogilvie, Sean P; Meloni, Manuela; Amorim Graf, Aline; Fratta, Giuseppe; Salvage, Jonathan; King, Alice A K; Dalton, Alan B

2018-01-25

Pickering emulsions stabilised with nanomaterials provide routes to a range of functional macroscopic assemblies. We demonstrate the formation and properties of water-in-oil emulsions prepared through liquid-phase exfoliation of graphene. Due to the functional nature of the stabiliser, the emulsions exhibit conductivity due to inter-particle tunnelling. We demonstrate a strain sensing application with a large gauge factor of ∼40; the highest reported in a liquid. Our methodology can be applied to other two-dimensional layered materials opening up applications such as energy storage materials, and flexible and printable electronics.

Quantum dynamical simulations of local field enhancement in metal nanoparticles.

PubMed

Negre, Christian F A; Perassi, Eduardo M; Coronado, Eduardo A; Sánchez, Cristián G

2013-03-27

Field enhancements (Γ) around small Ag nanoparticles (NPs) are calculated using a quantum dynamical simulation formalism and the results are compared with electrodynamic simulations using the discrete dipole approximation (DDA) in order to address the important issue of the intrinsic atomistic structure of NPs. Quite remarkably, in both quantum and classical approaches the highest values of Γ are located in the same regions around single NPs. However, by introducing a complete atomistic description of the metallic NPs in optical simulations, a different pattern of the Γ distribution is obtained. Knowing the correct pattern of the Γ distribution around NPs is crucial for understanding the spectroscopic features of molecules inside hot spots. The enhancement produced by surface plasmon coupling is studied by using both approaches in NP dimers for different inter-particle distances. The results show that the trend of the variation of Γ versus inter-particle distance is different for classical and quantum simulations. This difference is explained in terms of a charge transfer mechanism that cannot be obtained with classical electrodynamics. Finally, time dependent distribution of the enhancement factor is simulated by introducing a time dependent field perturbation into the Hamiltonian, allowing an assessment of the localized surface plasmon resonance quantum dynamics.

An integrated study of thermal treatment effects on the microstructure and magnetic properties of Zn-ferrite nanoparticles

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

Antic, Bratislav; Perovic, Marija; Kremenovic, Aleksandar

2015-09-30

The evolution of the magnetic state, crystal structure and microstructure parameters of nanocrystalline zinc–ferrite, tuned by thermal annealing of ~4 nm nanoparticles, was systematically studied by complementary characterization methods. Structural analysis of neutron and synchrotron x-ray radiation data revealed a mixed cation distribution in the nanoparticle samples, with the degree of inversion systematically decreasing from 0.25 in an as-prepared nanocrystalline sample to a non-inverted spinel structure with a normal cation distribution in the bulk counterpart. The results of DC magnetization and Mossbauer spectroscopy experiments indicated a superparamagnetic relaxation in ~4 nm nanoparticles, albeit with different freezing temperatures T f ofmore » 27.5 K and 46 K, respectively. The quadrupole splitting parameter decreases with the annealing temperature due to cation redistribution between the tetrahedral and octahedral sites of the spinel structure and the associated defects. DC magnetization measurements indicated the existence of significant interparticle interactions among nanoparticles (‘superspins’). Additional confirmation for the presence of interparticle interactions was found from the fit of the T f(H) dependence to the AT line, from which a value of the anisotropy constant of K eff = 5.6 × 10 5 erg cm -3 was deduced. Further evidence for strong interparticle interactions was found from AC susceptibility measurements, where the frequency dependence of the freezing temperature T f(ƒ) was satisfactory described by both Vogel–Fulcher and dynamic scaling theory, both applicable for interacting systems. The parameters obtained from these fits suggest collective freezing of magnetic moments at T f .« less

Structural control of nonlinear optical absorption and refraction in dense metal nanoparticle arrays.

PubMed

Kohlgraf-Owens, Dana C; Kik, Pieter G

2009-08-17

The linear and nonlinear optical properties of a composite containing interacting spherical silver nanoparticles embedded in a dielectric host are studied as a function of interparticle separation using three dimensional frequency domain simulations. It is shown that for a fixed amount of metal, the effective third-order nonlinear susceptibility of the composite chi((3))(omega) can be significantly enhanced with respect to the linear optical properties, due to a combination of resonant surface plasmon excitation and local field redistribution. It is shown that this geometry-dependent susceptibility enhancement can lead to an improved figure of merit for nonlinear absorption. Enhancement factors for the nonlinear susceptibility of the composite are calculated, and the complex nature of the enhancement factors is discussed.

Small-angle neutron scattering study of the short-range organization of dispersed CsNi[Cr(CN){sub 6}] nanoparticles

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

Ridier, Karl; Gillon, Béatrice; André, Gilles

2015-09-21

Prussian blue analogues magnetic nanoparticles (of radius R{sub 0} = 2.4–8.6 nm) embedded in PVP (polyvinylpyrrolidone) or CTA{sup +} (cetyltrimethylammonium) matrices have been studied using neutron diffraction and small angle neutron scattering (SANS) at several concentrations. For the most diluted particles in neutral PVP, the SANS signal is fully accounted for by a “single-particle” spherical form factor with no structural correlations between the nanoparticles and with radii comparable to those inferred from neutron diffraction. For higher concentration in PVP, structural correlations modify the SANS signal with the appearance of a structure factor peak, which is described using an effective “mean-field” model. A newmore » length scale R{sup * }≈ 3R{sub 0}, corresponding to an effective repulsive interaction radius, is evidenced in PVP samples. In CTA{sup +}, electrostatic interactions play a crucial role and lead to a dense layer of CTA{sup +} around the nanoparticles, which considerably alter the SANS patterns as compared to PVP. The SANS data of nanoparticles in CTA{sup +} are best described by a core-shell model without visible inter-particle structure factor.« less

Photovoltaic properties of high efficiency plastic dye-sensitized solar cells employing interparticle binding agent "nanoglue".

PubMed

Li, Yuelong; Yoo, Kicheon; Lee, Doh-Kwon; Kim, Jin Young; Kim, Honggon; Kim, Bongsoo; Ko, Min Jae

2013-06-07

An interparticle binding agent, or nanoglue, was synthesized by a sol-gel process, which facilitated the preparation of well-interconnected TiO2 electrodes at low-temperatures for plastic dye-sensitized solar cells. The viscosity of the nanoglue-based pastes was seven times higher than that obtained in pastes without any nanoglue. The increased viscosity was sufficiently high enough for coating thick films to fabricate TiO2 electrodes. The structural and photovoltaic properties of the films were extensively investigated by varying the amounts of nanoglue. A reduced pore size and greatly enhanced surface area were observed in the nanoglue-based films. Improved interparticle connectivity, resulting in faster electron transport, was confirmed by photocurrent transient spectroscopy and electrochemical impedance measurements of the nanoglue-based films. The electron diffusion length and charge collection efficiency were also enhanced in these nanoglue-based films. A maximum conversion efficiency of 5.43% was achieved in films containing 20 wt% nanoglue fabricated on a plastic substrate under one-sun illumination, even without any additional treatment.

The opposition and tilt effects of Saturn’s rings from HST observations

NASA Astrophysics Data System (ADS)

Salo, Heikki; French, Richard G.

2010-12-01

The two major factors contributing to the opposition brightening of Saturn's rings are (i) the intrinsic brightening of particles due to coherent backscattering and/or shadow hiding on their surfaces, and (ii) the reduced interparticle shadowing when the solar phase angle α → 0°. We utilize the extensive set of Hubble Space Telescope observations (Cuzzi, J.N., French, R.G., Dones, L. [2002]. Icarus 158, 199-223) for different elevation angles B and wavelengths λ to disentangle these contributions. We assume that the intrinsic contribution is independent of B, so that any B dependence of the phase curves is due to interparticle shadowing, which must also act similarly for all λ's. Our study complements that of Poulet et al. (Poulet, F., Cuzzi, J.N., French, R.G., Dones, L. [2002]. Icarus 158, 224), who used a subset of data for a single B ˜ 10°, and the French et al. (French, R.G., Verbiscer, A., Salo, H., McGhee, C.A., Dones, L. [2007b] PASP 119, 623-642) study for the B ˜ 23° data set that included exact opposition. We construct a grid of dynamical/photometric simulation models, with the method of Salo and Karjalainen (Salo and Karjalainen [2003]. Icarus 164, 428-460), and use these simulations to fit the elevation-dependent part of opposition brightening. Eliminating the modeled interparticle component yields the intrinsic contribution to the opposition effect: for the B and A rings it is almost entirely due to coherent backscattering; for the C ring, an intraparticle shadow hiding contribution may also be present. Based on our simulations, the width of the interparticle shadowing effect is roughly proportional to B. This follows from the observation that as B decreases, the scattering is primarily from the rarefied low filling factor upper ring layers, whereas at larger B's the dense inner parts are visible. Vertical segregation of particle sizes further enhances this effect. The elevation angle dependence of interparticle shadowing also explains most of the B ring tilt effect (the increase of brightness with elevation). From comparison of the magnitude of the tilt effect at different filters, we show that multiple scattering can account for at most a 10% brightness increase as B → 26°, whereas the remaining 20% brightening is due to a variable degree of interparticle shadowing. The negative tilt effect of the middle A ring is well explained by the the same self-gravity wake models that account for the observed A ring azimuthal brightness asymmetry (Salo, H., Karjalainen, R., French, R.G. [2004]. Icarus 170, 70-90; French, R.G., Salo, H., McGhee, C.A., Dones, L. [2007]. Icarus 189, 493-522).

Interparticle interaction effects on magnetic behaviors of hematite (α-Fe2O3) nanoparticles

NASA Astrophysics Data System (ADS)

Can, Musa Mutlu; Fırat, Tezer; Özcan, Şadan

2011-07-01

The interparticle magnetic interactions of hematite (α-Fe2O3) nanoparticles were investigated by temperature and magnetic field dependent magnetization curves. The synthesis were done in two steps; milling metallic iron (Fe) powders in pure water (H2O), known as mechanical milling technique, and annealing at 600 °C. The crystal and molecular structure of prepared samples were determined by X-ray powder diffraction (XRD) spectra and Fourier transform infrared (FTIR) spectra results. The average particle sizes and the size distributions were figured out using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The magnetic behaviors of α-Fe2O3 nanoparticles were analyzed with a vibrating sample magnetometer (VSM). As a result of the analysis, it was observed that the prepared α-Fe2O3 nanoparticles did not perform a sharp Morin transition (the characteristic transition of α-Fe2O3) due to lack of unique particle size distribution. However, the transition can be observed in the wide temperature range as “a continuously transition”. Additionally, the effect of interparticle interaction on magnetic behavior was determined from the magnetization versus applied field (σ(M)) curves for 26±2 nm particles, dispersed in sodium oxalate matrix under ratios of 200:1, 300:1, 500:1 and 1000:1. The interparticle interaction fields, recorded at 5 K to avoid the thermal interactions, were found as ∼1082 Oe for 26±2 nm particles.

Study of Electron Gas on a Neutron-Rich Nuclear Pasta

NASA Astrophysics Data System (ADS)

Ramirez-Homs, Enrique

This study used a classical molecular dynamics model to observe the role of electron gas on the formation of nuclear structures at subsaturation densities (rho < 0.015 fm-3) and low temperatures (T < 1MeV ). The simulations were performed by varying the Coulomb interaction strength on systems of isospin symmetric and asymmetric matter with periodic boundary conditions. The effect was quantified on the fragment size multiplicity, the inter-particle distance, the isospin content of the clusters, the nucleon mobility and cluster persistence, and on the nuclear structure shapes. The existence of the nuclear pasta structures was observed even with the absence of the Coulomb interaction but with a modication of the shapes formed. It was found that the presence of the electron gas tends to distribute matter more evenly, forms less compact objects, decreases the isospin content of clusters, modies the nucleon mobility, reduces the persistence and the fragment size multiplicity, but does not alter the inter-particle distance in clusters. The degree of these effects also varied on the nuclear structures and depended on their isospin content, temperature, and density.

Programming the Assembly of Unnatural Materials with Nucleic Acids

NASA Astrophysics Data System (ADS)

Mirkin, Chad

Nature directs the assembly of enormously complex and highly functional materials through an encoded class of biomolecules, nucleic acids. The establishment of a similarly programmable code for the construction of synthetic, unnatural materials would allow researchers to impart functionality by precisely positioning all material components. Although it is exceedingly difficult to control the complex interactions between atomic and molecular species in such a manner, interactions between nanoscale components can be directed through the ligands attached to their surface. Our group has shown that nucleic acids can be used as highly programmable surface ligands to control the spacing and symmetry of nanoparticle building blocks in structurally sophisticated and functional materials. These nucleic acids function as programmable ``bonds'' between nanoparticle ``atoms,'' analogous to a nanoscale genetic code for assembling materials. The sequence and length tunability of nucleic acid bonds has allowed us to define a powerful set of design rules for the construction of nanoparticle superlattices with more than 30 unique lattice symmetries, tunable defect structures and interparticle spacings, and several well-defined crystal habits. Further, the nature of the nucleic acid bond enables an additional level of structural control: temporal regulation of dynamic material response to external biomolecular and chemical stimuli. This control allows for the reversible transformation between thermodynamic states with different crystal symmetries, particle stoichiometries, thermal stabilities, and interparticle spacings on demand. Notably, our unique genetic approach affords functional nanoparticle architectures that, among many other applications, can be used to systematically explore and manipulate optoelectronic material properties, such as tunable interparticle plasmonic interactions, microstructure-directed energy emission, and coupled plasmonic and photonic modes.

Roles of additives and surface control in slurry atomization

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

Tsai, S.C.

1990-01-01

This report focuses on the effects of interparticle forces on the rheology and airblast atomization of micronized coal water slurry (CWS). We found that the CWS flow behavior index is determined by the relative importance of the interparticle van der Waals attraction and the interparticle electrostatic repulsion. The former intensifies as the Hamaker constant increases and the interparticle distance reduces while the latter increases as the particle surface charge density increases. The interparticle attraction causes particle aggregation, which breaks down at high shear rates, and thus leads to slurry pseudoplastic behavior. In contrast, the interparticle repulsion prevents particle aggregation andmore » thus leads to Newtonian behavior. Both atomized at low atomizing air pressures (less than 270 kPa) using twin-fluid jet atomizers of various distributor designs. We found that the atomized drop sizes of micronized coal water slurries substantially decrease as the atomizing air pressure exceeds a threshold value. The effects of coal volume fraction, coal particle surface charge, liquid composition and liquid viscosity on slurry atomization can be accounted for by their effects on slurry rheology. 26 refs.« less

Simulation and Implementation of a Morphology-Tuned Gold Nano-Islands Integrated Plasmonic Sensor

PubMed Central

Ozhikandathil, Jayan; Packirisamy, Muthukumaran

2014-01-01

This work presents simulation, analysis and implementation of morphology tuning of gold nano-island structures deposited by a novel convective assembly technique. The gold nano-islands were simulated using 3D Finite-Difference Time-Domain (FDTD) techniques to investigate the effect of morphological changes and adsorption of protein layers on the localized surface plasmon resonance (LSPR) properties. Gold nano-island structures were deposited on glass substrates by a novel and low-cost convective assembly process. The structure formed by an uncontrolled deposition method resulted in a nano-cluster morphology, which was annealed at various temperatures to tune the optical absorbance properties by transforming the nano-clusters to a nano-island morphology by modifying the structural shape and interparticle separation distances. The dependence of the size and the interparticle separation distance of the nano-islands on the LSPR properties were analyzed in the simulation. The effect of adsorption of protein layer on the nano-island structures was simulated and a relation between the thickness and the refractive index of the protein layer on the LSPR peak was presented. Further, the sensitivity of the gold nano-island integrated sensor against refractive index was computed and compared with the experimental results. PMID:24932868

Electron tomography provides a direct link between the Payne effect and the inter-particle spacing of rubber composites

PubMed Central

Staniewicz, Lech; Vaudey, Thomas; Degrandcourt, Christophe; Couty, Marc; Gaboriaud, Fabien; Midgley, Paul

2014-01-01

Rubber-filler composites are a key component in the manufacture of tyres. The filler provides mechanical reinforcement and additional wear resistance to the rubber, but it in turn introduces non-linear mechanical behaviour to the material which most likely arises from interactions between the filler particles, mediated by the rubber matrix. While various studies have been made on the bulk mechanical properties and of the filler network structure (both imaging and by simulations), there presently does not exist any work directly linking filler particle spacing and mechanical properties. Here we show that using STEM tomography, aided by a machine learning image analysis procedure, to measure silica particle spacings provides a direct link between the inter-particle spacing and the reduction in shear modulus as a function of strain (the Payne effect), measured using dynamic mechanical analysis. Simulations of filler network formation using attractive, repulsive and non-interacting potentials were processed using the same method and compared with the experimental data, with the net result being that an attractive inter-particle potential is the most accurate way of modelling styrene-butadiene rubber-silica composite formation. PMID:25487130

Improved dual-porosity models for petrophysical analysis of vuggy reservoirs

NASA Astrophysics Data System (ADS)

Wang, Haitao

2017-08-01

A new vug interconnection, isolated vug (IVG), was investigated through resistivity modeling and the dual-porosity model for connected vug (CVG) vuggy reservoirs was tested. The vuggy models were built by pore-scale modeling, and their electrical resistivity was calculated by the finite difference method. For CVG vuggy reservoirs, the CVG reduced formation factors and increased the porosity exponents, and the existing dual-porosity model failed to match these results. Based on the existing dual-porosity model, a conceptual dual-porosity model for CVG was developed by introducing a decoupled term to reduce the resistivity of the model. For IVG vuggy reservoirs, IVG increased the formation factors and porosity exponents. The existing dual-porosity model succeeded due to accurate calculation of the formation factors of the deformed interparticle porous media caused by the insertion of the IVG. Based on the existing dual-porosity model, a new porosity model for IVG vuggy reservoirs was developed by simultaneously recalculating the formation factors of the altered interparticle pore-scale models. The formation factors and porosity exponents from the improved and extended dual-porosity models for CVG and IVG vuggy reservoirs well matched the simulated formation factors and porosity exponents. This work is helpful for understanding the influence of connected and disconnected vugs on resistivity factors—an issue of particular importance in carbonates.

Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering.

PubMed

Ho, Tuan Anh; Greathouse, Jeffery A; Wang, Yifeng; Criscenti, Louise J

2017-11-10

The porosity of clay aggregates is an important property governing chemical reactions and fluid flow in low-permeability geologic formations and clay-based engineered barrier systems. Pore spaces in clays include interlayer and interparticle pores. Under compaction and dewatering, the size and geometry of such pore spaces may vary significantly (sub-nanometer to microns) depending on ambient physical and chemical conditions. Here we report a molecular dynamics simulation method to construct a complex and realistic clay-like nanoparticle aggregate with interparticle pores and grain boundaries. The model structure is then used to investigate the effect of dewatering and water content on micro-porosity of the aggregates. The results suggest that slow dewatering would create more compact aggregates compared to fast dewatering. Furthermore, the amount of water present in the aggregates strongly affects the particle-particle interactions and hence the aggregate structure. Detailed analyses of particle-particle and water-particle interactions provide a molecular-scale view of porosity and texture development of the aggregates. The simulation method developed here may also aid in modeling the synthesis of nanostructured materials through self-assembly of nanoparticles.

Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering

DOE PAGES

Ho, Tuan Anh; Greathouse, Jeffery A.; Wang, Yifeng; ...

2017-11-10

The porosity of clay aggregates is an important property governing chemical reactions and fluid flow in low-permeability geologic formations and clay-based engineered barrier systems. Pore spaces in clays include interlayer and interparticle pores. Under compaction and dewatering, the size and geometry of such pore spaces may vary significantly (sub-nanometer to microns) depending on ambient physical and chemical conditions. Here we report a molecular dynamics simulation method to construct a complex and realistic clay-like nanoparticle aggregate with interparticle pores and grain boundaries. The model structure is then used to investigate the effect of dewatering and water content on micro-porosity of themore » aggregates. The results suggest that slow dewatering would create more compact aggregates compared to fast dewatering. Furthermore, the amount of water present in the aggregates strongly affects the particle-particle interactions and hence the aggregate structure. Detailed analyses of particle-particle and water-particle interactions provide a molecular-scale view of porosity and texture development of the aggregates. The simulation method developed here may also aid in modeling the synthesis of nanostructured materials through self-assembly of nanoparticles.« less

Elastic properties of magnetorheological elastomer: description with the two-particle mesoscopic model

NASA Astrophysics Data System (ADS)

Biller, A. M.; Stolbov, O. V.; Raikher, Yu L.

2017-06-01

A pair of magnetizable solid particles embedded in a cylinder made of high-elasticity material is considered as a model of a mesoscopic structure element of a magnetorheological elastomer. An applied magnetic field induces ponderomotive interaction of the particles making them to move relative to one another so as to balance the counteracting magnetic and elastic forces. In a certain parameter range, the system exhibits bistability due to which under the increase / decrease of the field, the interparticle distance changes in a hysteretic manner. This behavior has a significant effect on the ability of the mesoscopic element to resist external load. Using the developed two-particle model prone to the magnetomechanical hysteresis, we extend it to the case of a virtually macroscopic sample presenting the latter as a superposition of such elements with distributed interparticle distances. In spite of its simplicity, this scheme in a generally correct way describes the field-induced changes of the internal structure and elastic modulus of the magnetorheological composites.

Structural diversity in binary superlattices self-assembled from polymer-grafted nanocrystals

DOE PAGES

Ye, Xingchen; Zhu, Chenhui; Ercius, Peter; ...

2015-12-02

Multicomponent nanocrystal superlattices represent an interesting class of material that derives emergent properties from mesoscale structure, yet their programmability can be limited by the alkyl-chain-based ligands decorating the surfaces of the constituent nanocrystals. Polymeric ligands offer distinct advantages, as they allow for more precise tuning of the effective size and ‘interaction softness’ through changes to the polymer’s molecular weight, chemical nature, architecture, persistence length and surrounding solvent. Here we show the formation of 10 different binary nanocrystal superlattices (BNSLs) with both two- and three-dimensional order through independent adjustment of the core size of spherical nanocrystals and the molecular weight ofmore » densely grafted polystyrene ligands. These polymer-brush-based ligands introduce new energetic contributions to the interparticle potential that stabilizes various BNSL phases across a range of length scales and interparticle spacings. In conclusion, our study opens the door for nanocrystals to become modular elements in the design of functional particle brush solids with controlled nanoscale interfaces and mesostructures.« less

Percolation, phase separation, and gelation in fluids and mixtures of spheres and rods

NASA Astrophysics Data System (ADS)

Jadrich, Ryan; Schweizer, Kenneth S.

2011-12-01

The relationship between kinetic arrest, connectivity percolation, structure and phase separation in protein, nanoparticle, and colloidal suspensions is a rich and complex problem. Using a combination of integral equation theory, connectivity percolation methods, naïve mode coupling theory, and the activated dynamics nonlinear Langevin equation approach, we study this problem for isotropic one-component fluids of spheres and variable aspect ratio rigid rods, and also percolation in rod-sphere mixtures. The key control parameters are interparticle attraction strength and its (short) spatial range, total packing fraction, and mixture composition. For spherical particles, formation of a homogeneous one-phase kinetically stable and percolated physical gel is predicted to be possible, but depends on non-universal factors. On the other hand, the dynamic crossover to activated dynamics and physical bond formation, which signals discrete cluster formation below the percolation threshold, almost always occurs in the one phase region. Rods more easily gel in the homogeneous isotropic regime, but whether a percolation or kinetic arrest boundary is reached first upon increasing interparticle attraction depends sensitively on packing fraction, rod aspect ratio and attraction range. Overall, the connectivity percolation threshold is much more sensitive to attraction range than either the kinetic arrest or phase separation boundaries. Our results appear to be qualitatively consistent with recent experiments on polymer-colloid depletion systems and brush mediated attractive nanoparticle suspensions.

High precision and high yield fabrication of dense nanoparticle arrays onto DNA origami at statistically independent binding sites

NASA Astrophysics Data System (ADS)

Takabayashi, Sadao; Klein, William P.; Onodera, Craig; Rapp, Blake; Flores-Estrada, Juan; Lindau, Elias; Snowball, Lejmarc; Sam, Joseph T.; Padilla, Jennifer E.; Lee, Jeunghoon; Knowlton, William B.; Graugnard, Elton; Yurke, Bernard; Kuang, Wan; Hughes, William L.

2014-10-01

High precision, high yield, and high density self-assembly of nanoparticles into arrays is essential for nanophotonics. Spatial deviations as small as a few nanometers can alter the properties of near-field coupled optical nanostructures. Several studies have reported assemblies of few nanoparticle structures with controlled spacing using DNA nanostructures with variable yield. Here, we report multi-tether design strategies and attachment yields for homo- and hetero-nanoparticle arrays templated by DNA origami nanotubes. Nanoparticle attachment yield via DNA hybridization is comparable with streptavidin-biotin binding. Independent of the number of binding sites, >97% site-occupation was achieved with four tethers and 99.2% site-occupation is theoretically possible with five tethers. The interparticle distance was within 2 nm of all design specifications and the nanoparticle spatial deviations decreased with interparticle spacing. Modified geometric, binomial, and trinomial distributions indicate that site-bridging, steric hindrance, and electrostatic repulsion were not dominant barriers to self-assembly and both tethers and binding sites were statistically independent at high particle densities.High precision, high yield, and high density self-assembly of nanoparticles into arrays is essential for nanophotonics. Spatial deviations as small as a few nanometers can alter the properties of near-field coupled optical nanostructures. Several studies have reported assemblies of few nanoparticle structures with controlled spacing using DNA nanostructures with variable yield. Here, we report multi-tether design strategies and attachment yields for homo- and hetero-nanoparticle arrays templated by DNA origami nanotubes. Nanoparticle attachment yield via DNA hybridization is comparable with streptavidin-biotin binding. Independent of the number of binding sites, >97% site-occupation was achieved with four tethers and 99.2% site-occupation is theoretically possible with five tethers. The interparticle distance was within 2 nm of all design specifications and the nanoparticle spatial deviations decreased with interparticle spacing. Modified geometric, binomial, and trinomial distributions indicate that site-bridging, steric hindrance, and electrostatic repulsion were not dominant barriers to self-assembly and both tethers and binding sites were statistically independent at high particle densities. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03069a

Inverse Photonic Glasses by Packing Bidisperse Hollow Microspheres with Uniform Cores.

PubMed

Kim, Seung-Hyun; Magkiriadou, Sofia; Rhee, Do Kyung; Lee, Doo Sung; Yoo, Pil J; Manoharan, Vinothan N; Yi, Gi-Ra

2017-07-19

A major fabrication challenge is producing disordered photonic materials with an angle-independent structural red color. Theoretical work has shown that such a color can be produced by fabricating inverse photonic glasses with monodisperse, nontouching voids in a silica matrix. Here, we demonstrate a route toward such materials and show that they have an angle-independent red color. We first synthesize monodisperse hollow silica particles with precisely controlled shell thickness and then make glassy colloidal structures by mixing two types of hollow particles with the same core size and different shell thicknesses. We then infiltrate the interstices with index-matched polymers, producing disordered porous materials with uniform, nontouching air voids. This procedure allows us to control the light-scattering form factor and structure factor of these porous materials independently, which is not possible to do in photonic glasses consisting of packed solid particles. The structure factor can be controlled by the shell thickness, which sets the distance between pores, whereas the pore size determines the peak wave vector of the form factor, which can be set below the visible range to keep the main structural color pure. By using a binary mixture of 246 and 268 nm hollow silica particles with 180 nm cores in an index-matched polymer matrix, we achieve angle-independent red color that can be tuned by controlling the shell thickness. Importantly, the width of the reflection peak can be kept constant, even for larger interparticle distances.

Interparticle interactions mediated superspin glass to superferromagnetic transition in Ni-bacterial cellulose aerogel nanocomposites

NASA Astrophysics Data System (ADS)

Thiruvengadam, V.; Vitta, Satish

2016-06-01

The interparticle interactions in the magnetic nanocomposites play a dominant role in controlling phase transitions: superparamagnetic to superspin glass and to superferromagnetic. These interactions can be tuned by controlling the size and number density of nanoparticles. The aerogel composites, 0.3Ni-BC and 0.7Ni-BC, consisting of Ni nanoparticles distributed in the bacterial cellulose have been used as a model system to study these interactions. Contrary to conventional approach, size of Ni-nanoparticles is not controlled and allowed to form naturally in bacterial cellulose template. The uncontrolled growth of Ni results in the formation of nanoparticles with 3 different size distributions - <10 nm particles along the length of fibrils, 50 nm particles in the intermediate spaces between the fibrils, and >100 nm particles in voids formed by reticulate structure. At room temperature, the composites exhibit a weakly ferromagnetic behaviour with a coercivity of 40 Oe, which increases to 160 Oe at 10 K. The transition from weakly ferromagnetic state to superferromagnetic state at low temperatures is mediated by the superspin glass state at intermediate temperatures via the interparticle interactions aided by nanoparticles present along the length of fibres. A temperature dependent microstructural model has been developed to understand the magnetic behaviour of nanocomposite aerogels.

Vibrational properties of quasi-two-dimensional colloidal glasses with varying interparticle attraction.

PubMed

Gratale, Matthew D; Ma, Xiaoguang; Davidson, Zoey S; Still, Tim; Habdas, Piotr; Yodh, A G

2016-10-01

We measure the vibrational modes and particle dynamics of quasi-two-dimensional colloidal glasses as a function of interparticle interaction strength. The interparticle attractions are controlled via a temperature-tunable depletion interaction. Specifically, the interparticle attraction energy is increased gradually from a very small value (nearly hard-sphere) to moderate strength (∼4k_{B}T), and the variation of colloidal particle dynamics and vibrations are concurrently probed. The particle dynamics slow monotonically with increasing attraction strength, and the particle motions saturate for strengths greater than ∼2k_{B}T, i.e., as the system evolves from a nearly repulsive glass to an attractive glass. The shape of the phonon density of states is revealed to change with increasing attraction strength, and the number of low-frequency modes exhibits a crossover for glasses with weak compared to strong interparticle attraction at a threshold of ∼2k_{B}T. This variation in the properties of the low-frequency vibrational modes suggests a new means for distinguishing between repulsive and attractive glass states.

Bringing life to soil physical processes

NASA Astrophysics Data System (ADS)

Hallett, P. D.

2013-12-01

When Oklahoma's native prairie grass roots were replaced by corn, the greatest environmental (and social) disaster ever to hit America ensued. The soils lost structure, physical binding by roots was annihilated and when drought came the Great Dust Bowl commenced. This form of environmental disaster has repeated over history and although not always apparent, similar processes drive the degradation of seemingly productive farmland and forests. But just as negative impacts on biology are deleterious to soil physical properties, positive impacts could reverse these trends. In finding solutions to soil sustainability and food security, we should be able to exploit biological processes to improve soil physical properties. This talk will focus on a quantitative understanding of how biology changes soil physical behaviour. Like the Great Dust Bowl, it starts with reinforcement mechanisms by plant roots. We found that binding of soil by cereal (barley) roots within 5 weeks of planting can more than double soil shear strength, with greater plant density causing greater reinforcement. With time, however, the relative impact of root reinforcement diminishes due to root turnover and aging of the seedbed. From mechanical tests of individual roots, reasonable predictions of reinforcement by tree roots are possible with fibre bundle models. With herbaceous plants like cereals, however, the same parameters (root strength, stiffness, size and distribution) result in a poor prediction. We found that root type, root age and abiotic factors such as compaction and waterlogging affect mechanical behaviour, further complicating the understanding and prediction of root reinforcement. For soil physical stability, the interface between root and soil is an extremely important zone in terms of resistance of roots to pull-out and rhizosphere formation. Compounds analogous to root exudates have been found with rheological tests to initially decrease the shear stress where wet soils flow, but after decomposition of these exudates by microbes the shear stress increases. This suggests an initial dispersion, followed by aggregation of the soil, which explains the structural arrangement of soil particles in the rhizosphere observed by microscopy. Dispersion of soil minerals in the root zone is important to release bound nutrients from mineral surfaces. Using fracture mechanics we measured large impacts of biological exudates on the toughness and interparticle bond energy of soils. Now novel tests are being developed to quantify interparticle bonding by biological exudates on single and multiple particle contacts, including mechanical test specimens that can be inoculated with specific bacteria or fungi. This will allow for clay mineralogy, water potential and solution chemistry impacts on interparticle bonding to be quantified directly. Wettability experiments with the same samples measure hydrological properties such as contact angle. Basic information from these tests will help explain biological processes that drive soil structure formation and stabilisation, providing data for models of soil structure dynamics.

Importance of the DNA “bond” in programmable nanoparticle crystallization

PubMed Central

Macfarlane, Robert J.; Thaner, Ryan V.; Brown, Keith A.; Zhang, Jian; Lee, Byeongdu; Nguyen, SonBinh T.; Mirkin, Chad A.

2014-01-01

If a solution of DNA-coated nanoparticles is allowed to crystallize, the thermodynamic structure can be predicted by a set of structural design rules analogous to Pauling’s rules for ionic crystallization. The details of the crystallization process, however, have proved more difficult to characterize as they depend on a complex interplay of many factors. Here, we report that this crystallization process is dictated by the individual DNA bonds and that the effect of changing structural or environmental conditions can be understood by considering the effect of these parameters on free oligonucleotides. Specifically, we observed the reorganization of nanoparticle superlattices using time-resolved synchrotron small-angle X-ray scattering in systems with different DNA sequences, salt concentrations, and densities of DNA linkers on the surface of the nanoparticles. The agreement between bulk crystallization and the behavior of free oligonucleotides may bear important consequences for constructing novel classes of crystals and incorporating new interparticle bonds in a rational manner. PMID:25298535

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

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Urich, Matthew

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

Modeling the evolution of lithium-ion particle contact distributions using a fabric tensor approach

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

Stershic, A. J.; Simunovic, S.; Nanda, J.

2015-08-25

Electrode microstructure and processing can strongly influence lithium-ion battery performance such as capacity retention, power, and rate. Battery electrodes are multi-phase composite structures wherein conductive diluents and binder bond active material to a current collector. The structure and response of this composite network during repeated electrochemical cycling directly affects battery performance characteristics. We propose the fabric tensor formalism for describing the structure and evolution of the electrode microstructure. Fabric tensors are directional measures of particulate assemblies based on inter-particle connectivity, relating to the structural and transport properties of the electrode. Fabric tensor analysis is applied to experimental data-sets for positivemore » electrode made of lithium nickel manganese cobalt oxide, captured by X-ray tomography for several compositions and consolidation pressures. We show that fabric tensors capture the evolution of inter-particle contact distribution and are therefore good measures for the internal state of and electronic transport within the electrode. The fabric tensor analysis is also applied to Discrete Element Method (DEM) simulations of electrode microstructures using spherical particles with size distributions from the tomography. Furthermore, these results do not follow the experimental trends, which indicates that the particle size distribution alone is not a sufficient measure for the electrode microstructures in DEM simulations.« less

Experimental measurement of interparticle acoustic radiation force in the Rayleigh limit

NASA Astrophysics Data System (ADS)

Mohapatra, Abhishek Ray; Sepehrirahnama, Shahrokh; Lim, Kian-Meng

2018-05-01

Acoustophoresis is a form of contact-free particle manipulation in microfluidic devices. The precision of manipulation can be enhanced with better understanding of the acoustic radiation force. In this paper we present the measurements of interparticle radiation force between a pair of polystyrene beads in the Rayleigh limit. The study is conducted for three different sizes of beads and the experimental results are of the same order of magnitude when compared with theoretical predictions. However, the experimental values are larger than the theoretical values. The trend of a decrease in the magnitude of the interparticle radiation force with decreasing particle size and increasing center-to-center distance between the particles is also observed experimentally. The experiments are conducted in the specific scenario where the pair of beads are in close proximity, but not in contact with each other, and the beads are approaching the pressure nodal plane with the center-to-center line aligned perpendicular to the incident wave. This scenario minimizes the presence of the primary radiation force, allowing accurate measurement of the interparticle force. The attractive nature of the interparticle force is observed, consistent with theoretical predictions.

Nanoscale Interparticle Distance within Dimers in Solution Measured by Light Scattering

PubMed Central

2017-01-01

We demonstrate a novel approach to quantify the interparticle distance in colloidal dimers using Mie scattering. The interparticle distance is varied in a controlled way by changing the ionic strength of the solution and the magnetic attraction between the particles. The measured scaling behavior is interpreted using an energy–distance model that includes the repulsive electrostatic and attractive magnetic interactions. The center-to-center distances of particles with a 525 nm radius can be determined with a root-mean-square accuracy of 12 nm. The data show that the center-to-center distance is larger by 83 nm compared to perfect spheres. The underlying distance offset can be attributed to repulsion by charged protrusions caused by particle surface roughness. The measurement method accurately quantifies interparticle distances that can be used to study cluster formation and colloid aggregation in complex systems, e.g., in biosensing applications. PMID:29183122

Strain induced plasmon tuning in planar square-shaped aluminum nanoparticles array

NASA Astrophysics Data System (ADS)

Mokkath, Junais Habeeb

2018-06-01

Metal nanoparticle aggregate is an exciting platform for manipulating light-matter interactions at the nanoscale, thanks to the optically driven free electrons couple electrically across the inter-particle gap region. We use time dependent density functional theory calculations to investigate the optical response modulations in planar square-shaped aluminum nanoparticles array via morphology deformation (varying the inter-particle gap distance in the range of 2-20 Å) separately along one and two directions. We report the surprising observation that irrespective of the different morphology deformations, there exists a unique inter-particle gap distance of 12 Å for which, a maximum optical field enhancement can be achieved. We remark that plasmonic interaction between metal nanoparticles in an aggregate is controlled to a large extent by the size of the inter-particle gap distance. We believe that our quantum mechanical calculations will inspire and contribute to the design, control, and exploitation of aluminum based plasmonic devices.

Formation of Aluminum Particles with Shell Morphology during Pressureless Spark Plasma Sintering of Fe–Al Mixtures: Current-Related or Kirkendall Effect?

PubMed Central

Dudina, Dina V.; Bokhonov, Boris B.; Mukherjee, Amiya K.

2016-01-01

A need to deeper understand the influence of electric current on the structure and properties of metallic materials consolidated by Spark Plasma Sintering (SPS) stimulates research on inter-particle interactions, bonding and necking processes in low-pressure or pressureless conditions as favoring technique-specific local effects when electric current passes through the underdeveloped inter-particle contacts. Until now, inter-particle interactions during pressureless SPS have been studied mainly for particles of the same material. In this work, we focused on the interactions between particles of dissimilar materials in mixtures of micrometer-sized Fe and Al powders forming porous compacts during pressureless SPS at 500–650 °C. Due to the chemical interaction between Al and Fe, necks of conventional shape did not form between the dissimilar particles. At the early interaction stages, the Al particles acquired shell morphology. It was shown that this morphology change was not related to the influence of electric current but was due to the Kirkendall effect in the Fe–Al system and particle rearrangement in a porous compact. No experimental evidence of melting or melt ejection during pressureless SPS of the Fe–Al mixtures or Fe and Al powders sintered separately was observed. Porous FeAl-based compacts could be obtained from Fe-40at.%Al mixtures by pressureless SPS at 650 °C. PMID:28773498

Surface morphology of a modified ballistic deposition model.

PubMed

Banerjee, Kasturi; Shamanna, J; Ray, Subhankar

2014-08-01

The surface and bulk properties of a modified ballistic deposition model are investigated. The deposition rule interpolates between nearest- and next-nearest-neighbor ballistic deposition and the random deposition models. The stickiness of the depositing particle is controlled by a parameter and the type of interparticle force. Two such forces are considered: Coulomb and van der Waals type. The interface width shows three distinct growth regions before eventual saturation. The rate of growth depends more strongly on the stickiness parameter than on the type of interparticle force. However, the porosity of the deposits is strongly influenced by the interparticle force.

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

DOE PAGES

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; ...

2017-11-13

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

PubMed Central

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; Yang, Lin; Yoshimura, Hideyuki; Miettinen, Heini M.; LaFrance, Ben; Patterson, Dustin P.; Schwarz, Benjamin; Karty, Jonathan A.; Prevelige, Peter E.; Lee, Byeongdu; Douglas, Trevor

2018-01-01

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy; the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from an amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles, and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. This study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales, and exhibits properties and function that arise from the interaction between individual building blocks. PMID:29131580

Effects of Pt and ionomer ratios on the structure of catalyst layer: A theoretical model for polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Ishikawa, H.; Sugawara, Y.; Inoue, G.; Kawase, M.

2018-01-01

The 3D structure of the catalyst layer (CL) in the polymer electrolyte fuel cell (PEFC) is modeled with a Pt/carbon (Pt/C) ratio of 0.4-2.3 and ionomer/carbon (i/C) ratio of 0.5-1.5, and the structural properties are evaluated by numerical simulation. The models are constructed by mimicking the actual shapes of Pt particles and carbon aggregates, as well as the ionomer adhesion in real CLs. CLs with different compositions are characterized by structural properties such as Pt inter-particle distance, ionomer coating thickness, pore size distribution, tortuosity, and ionomer coverage on Pt. The results for Pt/C = 1.0, i/C = 1.0 with Pt loading of 0.3 mg cm-2 and 50% porosity are validated against measured data for CLs with the same composition. With increasing i/C ratio, the smaller pores disappear and the number of isolated pores increases; while the ionomer connection and its coverage on Pt are significantly enhanced at i/C ∼1.0. With increasing Pt/C ratio, the Pt inter-particle distance decreases as the particles connect with each other. The tortuosity of the pores and the ionomer exhibits a trade-off relation depending on the ionomer volume. Further CL design concepts to optimize both O2 diffusion and H+ conduction are discussed.

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

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

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

Direct Measurement of Interparticle Forces of Titan Aerosol Analogs ("Tholin") Using Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Yu, Xinting; Hörst, Sarah M.; He, Chao; McGuiggan, Patricia; Bridges, Nathan T.

2017-12-01

To understand the origin of the dunes on Titan, it is important to investigate the material properties of Titan's organic sand particles on Titan. The organic sand may behave distinctively compared to the quartz/basaltic sand on terrestrial planets (Earth, Venus, and Mars) due to differences in interparticle forces. We measured the surface energy (through contact angle measurements) and elastic modulus (through Atomic Force Microscopy) of the Titan aerosol analog (tholin). We find that the surface energy of a tholin thin film is about 70.9 mN/m, and its elastic modulus is about 3.0 GPa (similar to hard polymers like PMMA and polystyrene). For two 20 μm diameter particles, the theoretical cohesion force is therefore 3.3 μN. We directly measured interparticle forces for relevant materials: tholin particles are 0.8 ± 0.6 μN, while the interparticle cohesion between walnut shell particles (a typical model materials for the Titan Wind Tunnel, TWT) is only 0.4 ± 0.1 μN. The interparticle cohesion forces are much larger for tholins and presumably Titan sand particles than materials used in the TWT. This suggests that we should increase the interparticle force in both analog experiments (TWT) and threshold models to correctly translate the results to real Titan conditions. The strong cohesion of tholins may also inform us how the small aerosol particles (˜1 μm) in Titan's atmosphere are transformed into large sand particles (˜200 μm). It may also support the cohesive sand formation mechanism suggested by Rubin and Hesp (2009), where only unidirectional wind is needed to form linear dunes on Titan.

Saltation threshold on Mars - The effect of interparticle force, surface roughness, and low atmospheric density. [from wind-tunnel experiments

NASA Technical Reports Server (NTRS)

Iversen, J. D.; White, B. R.; Pollack, J. B.; Greeley, R.

1976-01-01

Results are reported for wind-tunnel experiments performed to determine the threshold friction speed of particles with different densities. Experimentally determined threshold speeds are plotted as a function of particle diameter and in terms of threshold parameter vs particle friction Reynolds number. The curves are compared with those of previous experiments, and an A-B curve is plotted to show differences in threshold speed due to differences in size distributions and particle shapes. Effects of particle diameter are investigated, an expression for threshold speed is derived by considering the equilibrium forces acting on a single particle, and other approximately valid expressions are evaluated. It is shown that the assumption of universality of the A-B curve is in error at very low pressures for small particles and that only predictions which take account of both Reynolds number and effects of interparticle forces yield reasonable agreement with experimental data. Effects of nonerodible surface roughness are examined, and threshold speeds computed with allowance for this factor are compared with experimental values. Threshold friction speeds on Mars are then estimated for a surface pressure of 5 mbar, taking into account all the factors considered.

Direct Measurements of Surface Energy, Elastic Modulus and Interparticle Forces of Titan Aerosol Analog (`Tholin') Using Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Yu, X.; Horst, S. M.; He, C.; McGuiggan, P.; Bridges, N. T.

2017-12-01

To understand the origin of the dunes on Titan, it is important to investigate the material properties of the sand particles on Titan, which are mainly made of organics deposited from the atmosphere [1]. The organic sand may behave differently compared to the quartz/basaltic sand on terrestrial planets (Earth, Venus, Mars) in terms of interparticle forces. We measured the surface energy (through contact angle measurements) and elastic modulus (through Atomic Force Microscopy, AFM) of Titan aerosol analog (tholins) produced in our lab. Tholins may be compositionally similar to sand on Titan. We directly measured the interparticle forces between a tholin particle adhered to an AFM cantilver and tholin particles on a substrate. We also measured the properties of walnut shells, a typical material used in the Titan Wind Tunnel (TWT, [2, 3]). We find the surface energy of a tholin thin film is about 70.9 mN/m and its elastic modulus is about 3.5 GPa (similar to hard polymers like PMMA and polystyrene). We used the two measured material properties of tholin to calculate its interparticle cohesion assuming simple sphere-sphere geometry [4]. For two 20 µm particles, the theoretical cohesion force is about 6682 nN. Under dry nitrogen (RH<1%), the directly measured interparticle forces using AFM was approximately 4000 nN, which is smaller than theoretical predictions but still relatively strong under dry conditions. The interparticle cohesion between walnut shell particles is only 200 nN, which is much lower than between tholin particles. The key finding of this study is that the interparticle cohesion forces are much larger for tholins and presumably Titan sand particles than for terrestrial sand and materials used in the wind tunnel. This suggests we should increase the interparticle force in both analog experiments (TWT) and threshold models (e.g. [5]) to correctly translate the results to real Titan conditions. The strong cohesion of tholins may also inform us how the small aerosol particles ( 1 µm) in Titan's atmosphere are transformed into large sand particles ( 200 µm). References: [1] J. W. Barnes et al. Icarus, 195, 400, 2008. [2] D. M. Burr, et al. Nat., 517, 60, 2015. [3] X. Yu et al., Icarus, 297, 97, 2017. [4] K. L. Johnson et al., Proc. R. Soc. Lond., A 324, 301, 1971. [5] Y. Shao & H. Lu, J. Geophys. Res., 105, 22437, 2000.

Microstructure, Mechanical Properties, and Two-Body Abrasive Wear Behavior of Cold-Sprayed 20 vol.% Cubic BN-NiCrAl Nanocomposite Coating

NASA Astrophysics Data System (ADS)

Luo, Xiao-Tao; Yang, Er-Juan; Shang, Fu-Lin; Yang, Guan-Jun; Li, Chen-Xin; Li, Chang-Jiu

2014-10-01

20 vol.% cubic boron nitride (cBN) dispersoid reinforced NiCrAl matrix nanocomposite coating was prepared by cold spray using mechanically alloyed nanostructured composite powders. The as-sprayed nanocomposite coating was annealed at a temperature of 750 °C to enhance the inter-particle bonding. Microstructure of spray powders and coatings was characterized. Vickers microhardness of the coatings was measured. Two-body abrasive wear behavior of the coatings was examined on a pin-on-disk test. It was found that, in mechanically alloyed composite powders, nano-sized and submicro-sized cBN particles are uniformly distributed in nanocrystalline NiCrAl matrix. Dense coating was deposited by cold spray at a gas temperature of 650 °C with the same phases and grain size as those of the starting powder. Vickers hardness test yielded a hardness of 1063 HV for the as-sprayed 20 vol.% cBN-NiCrAl coating. After annealed at 750 °C for 5 h, unbonded inter-particle boundaries were partially healed and evident grain growth of nanocrystalline NiCrAl was avoided. Wear resistance of the as-sprayed 20 vol.% cBN-NiCrAl nanocomposite coating was comparable to the HVOF-sprayed WC-12Co coating. Annealing of the nanocomposite coating resulted in the improvement of wear resistance by a factor of ~33% owing to the enhanced inter-particle bonding. Main material removal mechanisms during the abrasive wear are also discussed.

Direction-specific interaction forces underlying zinc oxide crystal growth by oriented attachment

DOE PAGES

Zhang, X.; Shen, Z.; Liu, J.; ...

2017-10-10

Here, crystallization by particle attachment is impacting our understanding of natural mineralization processes and holds promise for novel materials design. When particles assemble in crystallographic registry, expulsion of the intervening solvent and particle coalescence is enabled by near-perfect co-alignment via interparticle forces that remain poorly quantified. Here we report measurement and simulation of these nanoscale aligning forces for the ZnO(0001)-ZnO(000¯1) system in aqueous solution. Dynamic force spectroscopy using nanoengineered single crystal probes reveals an attractive force with 60o rotational periodicity. Calculated distance and orientation-dependent potentials of mean force show several attractive free energy wells distinguished by numbers of intervening watermore » layers, which reach a minimum when aligned. The calculated activation energy to separate the attractively bound solvated interfaces perfectly reproduces the measured 60o periodicity, revealing the key role of intervening water structuring as a basis to generate the interparticle torque that completes alignment and enables coalescence.« less

Direction-specific interaction forces underlying zinc oxide crystal growth by oriented attachment

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

Zhang, X.; Shen, Z.; Liu, J.

Here, crystallization by particle attachment is impacting our understanding of natural mineralization processes and holds promise for novel materials design. When particles assemble in crystallographic registry, expulsion of the intervening solvent and particle coalescence is enabled by near-perfect co-alignment via interparticle forces that remain poorly quantified. Here we report measurement and simulation of these nanoscale aligning forces for the ZnO(0001)-ZnO(000¯1) system in aqueous solution. Dynamic force spectroscopy using nanoengineered single crystal probes reveals an attractive force with 60o rotational periodicity. Calculated distance and orientation-dependent potentials of mean force show several attractive free energy wells distinguished by numbers of intervening watermore » layers, which reach a minimum when aligned. The calculated activation energy to separate the attractively bound solvated interfaces perfectly reproduces the measured 60o periodicity, revealing the key role of intervening water structuring as a basis to generate the interparticle torque that completes alignment and enables coalescence.« less

An investigation of localised surface plasmon resonance (LSPR) of Ag nanoparticles produced by pulsed laser deposition (PLD) technique

NASA Astrophysics Data System (ADS)

Gezgin, Serap Yiǧit; Kepceoǧlu, Abdullah; Kılıç, Hamdi Şükür

2017-02-01

Noble metal nano-structures such as Ag, Cu, Au are used commonly to increase power conversion efficiency of the solar cell by using their surface plasmons. The plasmonic metal nanoparticles of Ag among others that have strong LSPR in near UV range. They increase photon absorbance via embedding in the active semiconductor of the solar cell. Thin films of Ag are grown in the desired particle size and interparticle distance easily and at low cost by PLD technique. Ag nanoparticle thin films were grown on micro slide glass at 25-36 mJ laser pulse energies under by PLD using ns-Nd:YAG laser. The result of this work have been presented by carrying out UV-VIS and AFM analysis. It was concluded that a laser energy increases, the density and size of Ag-NPs arriving on the substrate increases, and the interparticle distance was decreases. Therefore, LSPR wavelength shifts towards to longer wavelength region.

From tunable core-shell nanoparticles to plasmonic drawbridges: Active control of nanoparticle optical properties

PubMed Central

Byers, Chad P.; Zhang, Hui; Swearer, Dayne F.; Yorulmaz, Mustafa; Hoener, Benjamin S.; Huang, Da; Hoggard, Anneli; Chang, Wei-Shun; Mulvaney, Paul; Ringe, Emilie; Halas, Naomi J.; Nordlander, Peter; Link, Stephan; Landes, Christy F.

2015-01-01

The optical properties of metallic nanoparticles are highly sensitive to interparticle distance, giving rise to dramatic but frequently irreversible color changes. By electrochemical modification of individual nanoparticles and nanoparticle pairs, we induced equally dramatic, yet reversible, changes in their optical properties. We achieved plasmon tuning by oxidation-reduction chemistry of Ag-AgCl shells on the surfaces of both individual and strongly coupled Au nanoparticle pairs, resulting in extreme but reversible changes in scattering line shape. We demonstrated reversible formation of the charge transfer plasmon mode by switching between capacitive and conductive electronic coupling mechanisms. Dynamic single-particle spectroelectrochemistry also gave an insight into the reaction kinetics and evolution of the charge transfer plasmon mode in an electrochemically tunable structure. Our study represents a highly useful approach to the precise tuning of the morphology of narrow interparticle gaps and will be of value for controlling and activating a range of properties such as extreme plasmon modulation, nanoscopic plasmon switching, and subnanometer tunable gap applications. PMID:26665175

Nanoparticle Superlattices: The Roles of Soft Ligands

PubMed Central

Si, Kae Jye; Chen, Yi; Shi, Qianqian

2017-01-01

Abstract Nanoparticle superlattices are periodic arrays of nanoscale inorganic building blocks including metal nanoparticles, quantum dots and magnetic nanoparticles. Such assemblies can exhibit exciting new collective properties different from those of individual nanoparticle or corresponding bulk materials. However, fabrication of nanoparticle superlattices is nontrivial because nanoparticles are notoriously difficult to manipulate due to complex nanoscale forces among them. An effective way to manipulate these nanoscale forces is to use soft ligands, which can prevent nanoparticles from disordered aggregation, fine‐tune the interparticle potential as well as program lattice structures and interparticle distances – the two key parameters governing superlattice properties. This article aims to review the up‐to‐date advances of superlattices from the viewpoint of soft ligands. We first describe the theories and design principles of soft‐ligand‐based approach and then thoroughly cover experimental techniques developed from soft ligands such as molecules, polymer and DNA. Finally, we discuss the remaining challenges and future perspectives in nanoparticle superlattices. PMID:29375958

Correlated Optical Spectroscopy and Transmission Electron Microscopy of Individual Hollow Nanoparticles and their Dimers

PubMed Central

Yang, Linglu; Yan, Bo; Reinhard, Björn M.

2009-01-01

The optical spectra of individual Ag-Au alloy hollow particles were correlated with the particles’ structures obtained by transmission electron microscopy (TEM). The TEM provided direct experimental access to the dimension of the cavity, thickness of the metal shell, and the interparticle distance of hollow particle dimers with high spatial resolution. The analysis of correlated spectral and structural information enabled the quantification of the influence of the core-shell structure on the resonance energy, plasmon lifetime, and plasmon coupling efficiency. Electron beam exposure during TEM inspection was observed to affect plasmon wavelength and lifetime, making optical inspection prior to structural characterization mandatory. PMID:19768108

Effect of long-range repulsive Coulomb interactions on packing structure of adhesive particles.

PubMed

Chen, Sheng; Li, Shuiqing; Liu, Wenwei; Makse, Hernán A

2016-02-14

The packing of charged micron-sized particles is investigated using discrete element simulations based on adhesive contact dynamic model. The formation process and the final obtained structures of ballistic packings are studied to show the effect of interparticle Coulomb force. It is found that increasing the charge on particles causes a remarkable decrease of the packing volume fraction ϕ and the average coordination number 〈Z〉, indicating a looser and chainlike structure. Force-scaling analysis shows that the long-range Coulomb interaction changes packing structures through its influence on particle inertia before they are bonded into the force networks. Once contact networks are formed, the expansion effect caused by repulsive Coulomb forces are dominated by short-range adhesion. Based on abundant results from simulations, a dimensionless adhesion parameter Ad*, which combines the effects of the particle inertia, the short-range adhesion and the long-range Coulomb interaction, is proposed and successfully scales the packing results for micron-sized particles within the latest derived adhesive loose packing (ALP) regime. The structural properties of our packings follow well the recent theoretical prediction which is described by an ensemble approach based on a coarse-grained volume function, indicating some kind of universality in the low packing density regime of the phase diagram regardless of adhesion or particle charge. Based on the comprehensive consideration of the complicated inter-particle interactions, our findings provide insight into the roles of short-range adhesion and repulsive Coulomb force during packing formation and should be useful for further design of packings.

Nanoparticle heterodimers: The role of size and interparticle gap distance on the optical response

NASA Astrophysics Data System (ADS)

Mokkath, Junais Habeeb

2018-05-01

Composite plasmonic nanostructures with controlled size, shape and relative arrangement is a subject of significant current research interest. Much of this is stimulated by the prospects by generating enormous near-field enhancements of the surface and interparticle gap regions for potential applications in surface-enhanced spectroscopies. In this manuscript, using time-dependent density functional theory (TDDFT) calculations, we investigate how the optical response in size matched homodimers and size mismatched heterodimers composed of Aluminum modify while varying the size and interparticle gap distances in the sub-nanometer range. Both systems show interesting optical response evolution. In particular, the size mismatched heterodimers show even more complex optical response evolution due to a symmetry-breaking in the system.

Impact of self-assembled surfactant structures on rheology of concentrated nanoparticle dispersions.

PubMed

Zaman, A A; Singh, P; Moudgil, B M

2002-07-15

Rheological behavior of surfactant-stabilized colloidal dispersions of silica particles under extreme conditions (low pH, high ionic strength) has been investigated in relation to interparticle forces and stability of the dispersion. The surfactant used as the dispersing agent was C(12)TAB, a cationic surfactant. Stability analysis through turbidity measurements indicated that there is a sharp increase in the stability of the dispersion when the surfactant concentration is in the range of 8 to 10 mM in the system. The state of the dispersion changes from an unstable regime to a stable regime above a critical concentration of C(12)TAB in the system. In the case of interaction forces measured between the silica substrate and AFM tip, no repulsive force was observed up to a surfactant concentration of 8 mM and a transition from no repulsive forces to steric repulsive forces occurred between 8 and 10 mM. Rheological measurements as a function of C(12)TAB concentration indicated a significant decrease in the viscosity and linear viscoelastic functions of the dispersion over the same range of surfactant concentration (8 to 10 mM C(12)TAB), showing a strong correlation between the viscosity behavior, interparticle forces, and structure development in the dispersion.

Fano resonance assisting plasmonic circular dichroism from nanorice heterodimers for extrinsic chirality

NASA Astrophysics Data System (ADS)

Hu, Li; Huang, Yingzhou; Fang, Liang; Chen, Guo; Wei, Hua; Fang, Yurui

2015-11-01

In this work, the circular dichroisms (CD) of nanorice heterodimers consisting of two parallel arranged nanorices with the same size but different materials are investigated theoretically. Symmetry-breaking is introduced by using different materials and oblique incidence to achieve strong CD at the vicinity of Fano resonance peaks. We demonstrate that all Au-Ag heterodimers exhibit multipolar Fano resonances and strong CD effect. A simple quantitative analysis shows that the structure with larger Fano asymmetry factor has stronger CD. The intensity and peak positions of the CD effect can be flexibly tuned in a large range by changing particle size, shape, the inter-particle distance and surroundings. Furthermore, CD spectra exhibit high sensitivity to ambient medium in visible and near infrared regions. Our results here are beneficial for the design and application of high sensitive CD sensors and other related fields.

Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: Isotherms, kinetics, thermodynamics and process mechanism.

PubMed

Badawi, M A; Negm, N A; Abou Kana, M T H; Hefni, H H; Abdel Moneem, M M

2017-06-01

Chitosan was reacted by tannic acid to obtain three modified chitosan biopolymer. Their chemical structures were characterized by FTIR and elemental analysis. The prepared biopolymers were used to adsorb Al(III) and Pb(II) metal ions from industrial wastewater. The factors affecting the adsorption process were biosorbent amount, initial concentration of metal ion and pH of the medium. The adsorption efficiency increased considerably with the increase of the biosorbent amount and pH of the medium. The adsorption process of biosorbent on different metal ions was fitted by Freundlich adsorption model. The adsorption kinetics was followed Pseudo-second-order kinetic model. The adsorption process occurred according to diffusion mechanism which was confirmed by the interparticle diffusion model. The modified biopolymers were efficient biosorbents for removal of Pb(II) and Al(III) metal ions from the medium. Copyright © 2017 Elsevier B.V. All rights reserved.

Gelation under shear

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

Butler, B.D.; Hanley, H.J.M.; Straty, G.C.

An experimental small angle neutron scattering (SANS) study of dense silica gels, prepared from suspensions of 24 nm colloidal silica particles at several volume fractions {theta} is discussed. Provided that {theta}{approx_lt}0.18, the scattered intensity at small wave vectors q increases as the gelation proceeds, and the structure factor S(q, t {yields} {infinity}) of the gel exhibits apparent power law behavior. Power law behavior is also observed, even for samples with {theta}>0.18, when the gel is formed under an applied shear. Shear also enhances the diffraction maximum corresponding to the inter-particle contact distance of the gel. Difficulties encountered when trying tomore » interpret SANS data from these dense systems are outlined. Results of computer simulations intended to mimic gel formation, including computations of S(q, t), are discussed. Comments on a method to extract a fractal dimension characterizing the gel are included.« less

Self-Assembled Framework Enhances Electronic Communication of Ultrasmall-Sized Nanoparticles for Exceptional Solar Hydrogen Evolution

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

Li, Xu-Bing; Gao, Yu-Ji; Wang, Yang

Colloidal quantum dots (QDs) have demonstrated great promise in artificial photosynthesis. However, the ultrasmall size hinders its controllable and effective interaction with cocatalysts. To improve the poor interparticle electronic communication between free QD and cocatalyst, we design here a self-assembled architecture of nanoparticles, QDs and Ptnanoparticles, simply jointed together by molecular polyacrylate to greatly enhance the rate and efficiency of interfacial electron transfer (ET). The enhanced interparticle electronic communication is confirmed by femtosecond transient absorption spectroscopy and X-ray transient absorption. Taking advantage of the enhanced interparticle ET with a time scale of ~65 ps, 5.0 mL assembled CdSe/CdS QDs/cocatalysts solutionmore » produces 94 ± 1.5 mL (4183 ± 67 µmol) molecular H 2 in 8 h, giving rise to an internal quantum yield of ~65% in the first 30 min and a total turnover number of >16,400,000 per Pt-nanoparticle. This study demonstrates that self-assembly is a promising way to improve the sluggish kinetics of interparticle ET process, which is the key step for advanced H 2 photosynthesis.« less

Self-Assembled Framework Enhances Electronic Communication of Ultrasmall-Sized Nanoparticles for Exceptional Solar Hydrogen Evolution

DOE PAGES

Li, Xu-Bing; Gao, Yu-Ji; Wang, Yang; ...

2017-03-10

Colloidal quantum dots (QDs) have demonstrated great promise in artificial photosynthesis. However, the ultrasmall size hinders its controllable and effective interaction with cocatalysts. To improve the poor interparticle electronic communication between free QD and cocatalyst, we design here a self-assembled architecture of nanoparticles, QDs and Ptnanoparticles, simply jointed together by molecular polyacrylate to greatly enhance the rate and efficiency of interfacial electron transfer (ET). The enhanced interparticle electronic communication is confirmed by femtosecond transient absorption spectroscopy and X-ray transient absorption. Taking advantage of the enhanced interparticle ET with a time scale of ~65 ps, 5.0 mL assembled CdSe/CdS QDs/cocatalysts solutionmore » produces 94 ± 1.5 mL (4183 ± 67 µmol) molecular H 2 in 8 h, giving rise to an internal quantum yield of ~65% in the first 30 min and a total turnover number of >16,400,000 per Pt-nanoparticle. This study demonstrates that self-assembly is a promising way to improve the sluggish kinetics of interparticle ET process, which is the key step for advanced H 2 photosynthesis.« less

The dendritic effect and magnetic permeability in dendron coated nickel and manganese zinc ferrite nanoparticles.

PubMed

Jishkariani, Davit; Lee, Jennifer D; Yun, Hongseok; Paik, Taejong; Kikkawa, James M; Kagan, Cherie R; Donnio, Bertrand; Murray, Christopher B

2017-09-28

The collective magnetic properties of nanoparticle (NP) solid films are greatly affected by inter-particle dipole-dipole interactions and therefore the proximity of the neighboring particles. In this study, a series of dendritic ligands (generations 0 to 3, G0-G3) have been designed and used to cover the surface of magnetic NPs to control the spacings between the NP components in single lattices. The dendrons of different generations introduced here were based on the 2,2-bis(hydroxymethyl)propionic acid (Bis-MPA) scaffold and equipped with an appropriate surface binding group at one end and several fatty acid segments at the other extremity. The surface of the NPs was then modified by partial ligand exchange between the primary stabilizing surfactants and the new dendritic wedges. It was shown that this strategy permitted very precise tuning of inter-particle spacings in the range of 2.9-5.0 nm. As expected, the increase in the inter-particle spacings reduced the dipole-dipole interactions between magnetic NPs and therefore allowed changes in their magnetic permeability. The dendron size and inter-particle distance dependence was studied to reveal the dendritic effect and identify the optimal geometry and generation.

Development and testing of a unique carousel wind tunnel to experimentally determine the effect of gravity and the interparticle force on the physics of wind-blown particles

NASA Technical Reports Server (NTRS)

Leach, R. N.; Greeley, Ronald; White, Bruce R.; Iversen, James D.

1987-01-01

In the study of planetary aeolian processes the effect of gravity is not readily modeled. Gravity appears in the equations of particle motion along with the interparticle forces but the two are not separable. A wind tunnel that perimits multiphase flow experiments with wind blown particles at variable gravity was built and experiments were conducted at reduced gravity. The equations of particle motion initiation (saltation threshold) with variable gravity were experimentally verified and the interparticle force was separated. A uniquely design Carousel Wind Tunnel (CWT) allows for the long flow distance in a small sized tunnel since the test section if a continuous loop and develops the required turbulent boundary layer. A prototype model of the tunnel where only the inner drum rotates was built and tested in the KC-135 Weightless Wonder 4 zero-g aircraft. Future work includes further experiments with walnut shell in the KC-135 which sharply graded particles of widely varying median sizes including very small particles to see how interparticle force varies with particle size, and also experiments with other aeolian material.

Bioassay using blocking temperature: Interparticle interactions between biofunctionalized magnetic nanoparticles conjugated with biotargets

NASA Astrophysics Data System (ADS)

Wang, C. Y.; Yang, T. W.; Shen, D.; Chen, K. L.; Chen, J. M.; Liao, S. H.; Chieh, J. J.; Yang, H. C.; Wang, L. M.

2017-03-01

This paper reports a bioassay of alpha-fetoprotein (AFP) concentration achieved via the measurement of blocking temperature (TB). Biofunctionalized magnetic nanoparticles (BMNs) consisting of anti-alpha-fetoprotein coated onto dextran-coated magnetic nanoparticles composed of Fe3O4 were prepared and then conjugated with AFP biotargets. It was found that both the saturation magnetization and value of TB increased with the concentration of the associated AFP. Furthermore, the dependence of TB of the samples on magnetic field agreed with the interparticle interaction model. Thus, this study demonstrated a platform to detect biomarkers by characterizing TB with a sensitivity limit of 20 ppb of AFP. The promising results obtained for this bioassay can be attributed to the interparticle interactions and Néel motions of magnetic moments in the BMNs.

Evolution of network architecture in a granular material under compression

NASA Astrophysics Data System (ADS)

Bassett, Danielle

As a granular material is compressed, the particles and forces within the system arrange to form complex and heterogeneous collective structures. However, capturing and characterizing the dynamic nature of the intrinsic inhomogeneity and mesoscale architecture of granular systems can be challenging. Here, we utilize multilayer networks as a framework for directly quantifying the evolution of mesoscale architecture in a compressed granular system. We examine a quasi-two-dimensional aggregate of photoelastic disks, subject to biaxial compressions through a series of small, quasistatic steps. Treating particles as network nodes and inter-particle forces as network edges, we construct a multilayer network for the system by linking together the series of static force networks that exist at each strain step. We then extract the inherent mesoscale structure from the system by using a generalization of community detection methods to multilayer networks, and we define quantitative measures to characterize the reconfiguration and evolution of this structure throughout the compression process. To test the sensitivity of the network model to particle properties, we examine whether the method can distinguish a subsystem of low-friction particles within a bath of higher-friction particles. We find that this can be done by considering the network of tangential forces, and that the community structure is better able to separate the subsystem than consideration of the local inter-particle forces alone. The results discussed throughout this study suggest that these novel network science techniques may provide a direct way to compare and classify data from systems under different external conditions or with different physical makeup. National Science Foundation (BCS-1441502, PHY-1554488, and BCS-1631550).

Hierarchical self-assembly of nanoparticles in polymer matrix and the nature of the interparticle interaction

NASA Astrophysics Data System (ADS)

Lin, Yu-Chiao; Chen, Chun-Yu; Chen, Hsin-Lung; Hashimoto, Takeji; Chen, Show-An; Li, Yen-Cheng

2015-06-01

Using small angle X-ray scattering (SAXS), we elucidated the spatial organization of palladium (Pd) nanoparticles (NPs) in the polymer matrix of poly(2-vinylpyridine) (P2VP) and the nature of inter-nanoparticle interactions, where the NPs were synthesized in the presence of P2VP by the reduction of palladium acetylacetonate (Pd(acac)2). The experimental SAXS profiles were analysed on the basis of a hierarchical structure model considering the following two types of interparticle potential: (i) hard-core repulsion only (i.e., the hard-sphere interaction) and (ii) hard-core repulsion together with an attractive potential well (i.e., the sticky hard-sphere interaction). The corresponding theoretical scattering functions, which were used for analysing the experimental SAXS profiles, were obtained within the context of the Percus-Yevick closure and the Ornstein-Zernike equation in the fundamental liquid theory. The analyses revealed that existence of the attractive potential well is indispensable to account for the experimental SAXS profiles. Moreover, the morphology of the hybrids was found to be characterized by a hierarchical structure with three levels, where about six primary NPs with the diameter of ca. 1.8 nm (level one) formed local clusters (level two), and these clusters aggregated to build up a large-scale mass-fractal structure (level three) with the fractal dimension of ca. 2.3. The scattering function developed here is of general use for quantitatively characterizing the morphological structures of polymer/NP hybrids and, in particular, for exploring the interaction potential of the NPs on the basis of the fundamental liquid theory.

Boson peak, heterogeneity and intermediate-range order in binary SiO2-Al2O3 glasses.

PubMed

Ando, Mariana F; Benzine, Omar; Pan, Zhiwen; Garden, Jean-Luc; Wondraczek, Katrin; Grimm, Stephan; Schuster, Kay; Wondraczek, Lothar

2018-03-29

In binary aluminosilicate liquids and glasses, heterogeneity on intermediate length scale is a crucial factor for optical fiber performance, determining the lower limit of optical attenuation and Rayleigh scattering, but also clustering and precipitation of optically active dopants, for example, in the fabrication of high-power laser gain media. Here, we consider the low-frequency vibrational modes of such materials for assessing structural heterogeneity on molecular scale. We determine the vibrational density of states VDoS g(ω) using low-temperature heat capacity data. From correlation with low-frequency Raman spectroscopy, we obtain the Raman coupling coefficient. Both experiments allow for the extraction of the average dynamic correlation length as a function of alumina content. We find that this value decreases from about 3.9 nm to 3.3 nm when mildly increasing the alumina content from zero (vitreous silica) to 7 mol%. At the same time, the average inter-particle distance increases slightly due to the presence of oxygen tricluster species. In accordance with Loewensteinian dynamics, this proves that mild alumina doping increases structural homogeneity on molecular scale.

Identification of Mott insulators and Anderson insulators in self-assembled gold nanoparticles thin films

NASA Astrophysics Data System (ADS)

Jiang, Cheng-Wei; Ni, I.-Chih; Tzeng, Shien-Der; Wu, Cen-Shawn; Kuo, Watson

2014-05-01

How the interparticle tunnelling affects the charge conduction of self-assembled gold nanoparticles is studied by three means: tuning the tunnel barrier width by different molecule modification and by substrate bending, and tuning the barrier height by high-dose electron beam exposure. All approaches indicate that the metal-Mott insulator transition is governed predominantly by the interparticle coupling strength, which can be quantified by the room temperature sheet resistance. The Hubbard gap, following the prediction of quantum fluctuation theory, reduces to zero rapidly as the sheet resistance decreases to the quantum resistance. At very low temperature, the fate of devices near the Mott transition depends on the strength of disorder. The charge conduction is from nearest-neighbour hopping to co-tunnelling between nanoparticles in Mott insulators whereas it is from variable-range hopping through charge puddles in Anderson insulators. When the two-dimensional nanoparticle network is under a unidirectional strain, the interparticle coupling becomes anisotropic so the average sheet resistance is required to describe the charge conduction.How the interparticle tunnelling affects the charge conduction of self-assembled gold nanoparticles is studied by three means: tuning the tunnel barrier width by different molecule modification and by substrate bending, and tuning the barrier height by high-dose electron beam exposure. All approaches indicate that the metal-Mott insulator transition is governed predominantly by the interparticle coupling strength, which can be quantified by the room temperature sheet resistance. The Hubbard gap, following the prediction of quantum fluctuation theory, reduces to zero rapidly as the sheet resistance decreases to the quantum resistance. At very low temperature, the fate of devices near the Mott transition depends on the strength of disorder. The charge conduction is from nearest-neighbour hopping to co-tunnelling between nanoparticles in Mott insulators whereas it is from variable-range hopping through charge puddles in Anderson insulators. When the two-dimensional nanoparticle network is under a unidirectional strain, the interparticle coupling becomes anisotropic so the average sheet resistance is required to describe the charge conduction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06627d

Recognition-Mediated Assembly of Quantum Dot Polymer Conjugates with Controlled Morphology

PubMed Central

Nandwana, Vikas; Subramani, Chandramouleeswaran; Eymur, Serkan; Yeh, Yi-Cheun; Tonga, Gulen Yesilbag; Tonga, Murat; Jeong, Youngdo; Yang, Boqian; Barnes, Michael D.; Cooke, Graeme; Rotello, Vincent M.

2011-01-01

We have demonstrated a polymer mediated “bricks and mortar” method for the self-assembly of quantum dots (QDs). This strategy allows QDs to self-assemble into structured aggregates using complementary three-point hydrogen bonding. The resulting nanocomposites have distinct morphologies and inter-particle distances based on the ratio between QDs and polymer. Time resolved photoluminescence measurements showed that the optical properties of the QDs were retained after self-assembly. PMID:22016664

Elastohydrodynamic lubrication in point contact on the surfaces of particle-reinforced composite

NASA Astrophysics Data System (ADS)

Chen, Keying; Zeng, Liangcai; Wu, Zhenpeng; Zheng, Feilong

2018-04-01

Appreciable friction and serious wear are common challenges in the operation of advanced manufacturing equipment, and friction pairs may be susceptible to damage even with oil lubrication when point contact exists. In this study, a type of particle-reinforced composite material is introduced for one of the components of a heavy-load contact pair, and the performance improvement of elastohydrodynamic lubrication (EHL) is analyzed considering the rheological properties of non-Newtonian fluids. The Ree-Eyring EHL model is used considering the surface of the particle-reinforced composite, in which the film thickness includes the particle-induced elastic deformation. The problem of inclusions with different eigenstrains is solved by using Galerkin vectors. The influences of particle properties, size, burial depth, and interparticle distance on point-contact EHL are investigated. Furthermore, using several cases, the structural parameters of the particles in the composites are optimized, and an appropriate parameter range is obtained with the goal of reducing friction. Finally, the results for the EHL traction coefficient demonstrate that appropriate particle properties, size, burial depth, and interparticle distance can effectively reduce the traction coefficient in heavy-load contact.

Controlling coulomb interactions in infrared stereometamaterials for unity light absorption

NASA Astrophysics Data System (ADS)

Mudachathi, Renilkumar; Moritake, Yuto; Tanaka, Takuo

2018-05-01

We investigate the influence of near field interactions between the constituent 3D split ring resonators on the absorbance and resonance frequency of a stereo metamaterial based perfect light absorber. The experimental and theoretical analyses reveal that the magnetic resonance red shifts and broadens for both the decreasing vertical and lateral separations of the constituents within the metamaterial lattice, analogous to plasmon hybridization. The strong interparticle interactions for higher density reduce the effective cross-section per resonator, which results in weak light absorption observed in both experimental and theoretical analyses. The red shift of the magnetic resonance with increasing lattice density is an indication of the dominating electric dipole interactions and we analyzed the metamaterial system in an electrostatic point of view to explain the observed resonance shift and decreasing absorption peak. From these analyses, we found that the fill factor introduces two competing factors determining the absorption efficiency such as coulomb interactions between the constituent resonators and their number density in a given array structure. We predicted unity light absorption for a fill factor of 0.17 balancing these two opposing factors and demonstrate an experimental absorbance of 99.5% at resonance with our 3D device realized using residual stress induced bending of 2D patterns.

Direct Visualization of Planar Assembly of Plasmonic Nanoparticles Adjacent to Electrodes in Oscillatory Electric Fields.

PubMed

Ferrick, Adam; Wang, Mei; Woehl, Taylor J

2018-05-29

Electric field-directed assembly of colloidal nanoparticles (NPs) has been widely adopted for fabricating functional thin films and nanostructured surfaces. While first-order electrokinetic effects on NPs are well-understood in terms of classical models, effects of second-order electrokinetics that involve induced surface charge are still poorly understood. Induced charge electroosmotic phenomena, such as electrohydrodynamic (EHD) flow, have long been implicated in electric field-directed NP assembly with little experimental basis. Here, we use in situ dark-field optical microscopy and plasmonic NPs to directly observe the dynamics of planar assembly of colloidal NPs adjacent to a planar electrode in low-frequency (<1 kHz) oscillatory electric fields. We exploit the change in plasmonic NP color resulting from interparticle plasmonic coupling to visualize the assembly dynamics and assembly structure of silver NPs. Planar assembly of NPs is unexpected because of strong electrostatic repulsion between NPs and indicates that there are strong attractive interparticle forces oriented perpendicular to the electric field direction. A parametric investigation of the voltage- and frequency-dependent phase behavior reveals that planar NP assembly occurs over a narrow frequency range below which irreversible ballistic deposition occurs. Two key experimental observations are consistent with EHD flow-induced NP assembly: (1) NPs remain mobile during assembly and (2) electron microscopy observations reveal randomly close-packed planar assemblies, consistent with strong interparticle attraction. We interpret planar assembly in terms of EHD fluid flow and develop a scaling model that qualitatively agrees with the measured phase regions. Our results are the first direct in situ observations of EHD flow-induced NP assembly and shed light on long-standing unresolved questions concerning the formation of NP superlattices during electric field-induced NP deposition.

Systematic investigation of the SERS efficiency and SERS hotspots in gas-phase deposited Ag nanoparticle assemblies.

PubMed

He, L B; Wang, Y L; Xie, X; Han, M; Song, F Q; Wang, B J; Cheng, W L; Xu, H X; Sun, L T

2017-02-15

Gas-phase deposited Ag nanoparticle assemblies are one of the most commonly used plasmonic substrates benefiting from their remarkable advantages such as clean particle surface, tunable particle density, available inter-particle gaps, low-cost and scalable fabrication, and excellent industry compatibility. However, their performance efficiencies are difficult to optimize due to the lack of knowledge of the hotspots inside their structures. We here report a design of delicate rainbow-like Ag nanoparticle assemblies, based on which the hotspots can be revealed through a combinatorial approach. The findings show that the hotspots in gas-phase deposited Ag nanoparticle assemblies are uniquely entangled by the excitation energy and specific inter-particle gaps, differing from the matching conditions in periodic arrays. For Ag nanoparticle assemblies deposited on Formvar-filmed substrates, the mean particle size is maintained around 10 nm, while the particle density can be widely tuned. The one possessing the highest SERS efficiency (under 473 nm excitation) have a particle number density of around 7100 μm -2 . Gaps with an inter-particle spacing of around 3 nm are found to serve as SERS hotspots, and these hotspots contribute to 68% of the overall SERS intensity. For Ag nanoparticle assemblies fabricated on carbon-filmed substrates, the mean particle size can be feasibly tuned. The one possessing the highest SERS efficiency under 473 nm excitation has a particle number density of around 460 μm -2 and a mean particle size of around 42.1 nm. The construction of Ag-analyte-Ag sandwich-like nanoparticle assemblies by a two-step-deposition method slightly improves the SERS efficiency when the particle number density is low, but suppresses the SERS efficiency when the particle number density is high.

Discrete Element Method Simulations of the Inter-Particle Contact Parameters for the Mono-Sized Iron Ore Particles.

PubMed

Li, Tongqing; Peng, Yuxing; Zhu, Zhencai; Zou, Shengyong; Yin, Zixin

2017-05-11

Aiming at predicting what happens in reality inside mills, the contact parameters of iron ore particles for discrete element method (DEM) simulations should be determined accurately. To allow the irregular shape to be accurately determined, the sphere clump method was employed in modelling the particle shape. The inter-particle contact parameters were systematically altered whilst the contact parameters between the particle and wall were arbitrarily assumed, in order to purely assess its impact on the angle of repose for the mono-sized iron ore particles. Results show that varying the restitution coefficient over the range considered does not lead to any obvious difference in the angle of repose, but the angle of repose has strong sensitivity to the rolling/static friction coefficient. The impacts of the rolling/static friction coefficient on the angle of repose are interrelated, and increasing the inter-particle rolling/static friction coefficient can evidently increase the angle of repose. However, the impact of the static friction coefficient is more profound than that of the rolling friction coefficient. Finally, a predictive equation is established and a very close agreement between the predicted and simulated angle of repose is attained. This predictive equation can enormously shorten the inter-particle contact parameters calibration time that can help in the implementation of DEM simulations.

Investigating the settling dynamics of cohesive silt particles with particle-resolving simulations

NASA Astrophysics Data System (ADS)

Sun, Rui; Xiao, Heng; Sun, Honglei

2018-01-01

The settling of cohesive sediment is ubiquitous in aquatic environments, and the study of the settling process is important for both engineering and environmental reasons. In the settling process, the silt particles show behaviors that are different from non-cohesive particles due to the influence of inter-particle cohesive force. For instance, the flocs formed in the settling process of cohesive silt can loosen the packing, and thus the structural densities of cohesive silt beds are much smaller than that of non-cohesive sand beds. While there is a consensus that cohesive behaviors depend on the characteristics of sediment particles (e.g., Bond number, particle size distribution), little is known about the exact influence of these characteristics on the cohesive behaviors. In addition, since the cohesive behaviors of the silt are caused by the inter-particle cohesive forces, the motions of and the contacts among silt particles should be resolved to study these cohesive behaviors in the settling process. However, studies of the cohesive behaviors of silt particles in the settling process based on particle-resolving approach are still lacking. In the present work, three-dimensional settling process is investigated numerically by using CFD-DEM (Computational Fluid Dynamics-Discrete Element Method). The inter-particle collision force, the van der Waals force, and the fluid-particle interaction forces are considered. The numerical model is used to simulate the hindered settling process of silt based on the experimental setup in the literature. The results obtained in the simulations, including the structural densities of the beds, the characteristic lines, and the particle terminal velocity, are in good agreement with the experimental observations in the literature. To the authors' knowledge, this is the first time that the influences of non-dimensional Bond number and particle polydispersity on the structural densities of silt beds have been investigated separately. The results demonstrate that the cohesive behavior of silt in the settling process is attributed to both the cohesion among silt particles themselves and the particle polydispersity. To guide to the macro-scale modeling of cohesive silt sedimentation, the collision frequency functions obtained in the numerical simulations are also presented based on the micromechanics of particles. The results obtained by using CFD-DEM indicate that the binary collision theory over-estimated the particle collision frequency in the flocculation process at high solid volume fraction.

Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite

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

Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan

2016-04-06

Variable-temperature X-ray diffraction and 2H NMR spectroscopy of the smectite mineral, hectorite, containing interlayer Na +, K +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Pb 2+ equilibrated at 43% relative humidity (RH) and mixed with 2H 2O to form a paste provide a comprehensive picture of the structural environments and dynamics of interlayer 2H 2O and the relationships of these properties to interlayer hydration state, the hydration energy and polarizability of the cation, temperature, and the formation of ice-1h in the interparticle pores. The variation in basal spacing shown by the XRD data correlates well with themore » 2H NMR behavior, and the XRD data show for the first time in hectorites that crystallization of interparticle ice-1h causes a decrease in the interlayer spacing, likely due to removal of interlayer 2H 2O. The variation of the 2H NMR behavior of all the samples with decreasing temperature reflects decreasing frequencies of motion for the rotation of the 2H 2O molecules around their dipoles, reorientation of the 2H 2O molecules, and exchange of the 2H 2O molecules between interlayer sites coordinated to and not coordinated to the cations.« less

High-temperature crystallization of nanocrystals into three-dimensional superlattices.

PubMed

Wu, Liheng; Willis, Joshua J; McKay, Ian Salmon; Diroll, Benjamin T; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J

2017-08-10

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.

High-temperature crystallization of nanocrystals into three-dimensional superlattices

NASA Astrophysics Data System (ADS)

Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; Diroll, Benjamin T.; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J.

2017-08-01

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.

Experimental study on inter-particle acoustic forces.

PubMed

Garcia-Sabaté, Anna; Castro, Angélica; Hoyos, Mauricio; González-Cinca, Ricard

2014-03-01

A method for the experimental measurement of inter-particle forces (secondary Bjerknes force) generated by the action of an acoustic field in a resonator micro-channel is presented. The acoustic radiation force created by an ultrasonic standing wave moves suspended particles towards the pressure nodes and the acoustic pressure induces particle volume oscillations. Once particles are in the levitation plane, transverse and secondary Bjerknes forces become important. Experiments were carried out in a resonator filled with a suspension composed of water and latex particles of different size (5-15 μm) at different concentrations. Ultrasound was generated by means of a 2.5 MHz nominal frequency transducer. For the first time the acoustic force generated by oscillating particles acting on other particles has been measured, and the critical interaction distance in various cases has been determined. Inter-particle forces on the order of 10(-14) N have been measured by using this method.

Longitudinal domain wall formation in elongated assemblies of ferromagnetic nanoparticles

PubMed Central

Varón, Miriam; Beleggia, Marco; Jordanovic, Jelena; Schiøtz, Jakob; Kasama, Takeshi; Puntes, Victor F.; Frandsen, Cathrine

2015-01-01

Through evaporation of dense colloids of ferromagnetic ~13 nm ε-Co particles onto carbon substrates, anisotropic magnetic dipolar interactions can support formation of elongated particle structures with aggregate thicknesses of 100–400 nm and lengths of up to some hundred microns. Lorenz microscopy and electron holography reveal collective magnetic ordering in these structures. However, in contrast to continuous ferromagnetic thin films of comparable dimensions, domain walls appear preferentially as longitudinal, i.e., oriented parallel to the long axis of the nanoparticle assemblies. We explain this unusual domain structure as the result of dipolar interactions and shape anisotropy, in the absence of inter-particle exchange coupling. PMID:26416297

Dynamics of dissipative self-assembly of particles interacting through oscillatory forces

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

Tagliazucchi, M.; Szleifer, I.

Dissipative self-assembly is the formation of ordered structures far from equilibrium, which continuously uptake energy and dissipate it into the environment. Due to its dynamical nature, dissipative self-assembly can lead to new phenomena and possibilities of self-organization that are unavailable to equilibrium systems. Understanding the dynamics of dissipative self-assembly is required in order to direct the assembly to structures of interest. In the present work, Brownian dynamics simulations and analytical theory were used to study the dynamics of self-assembly of a mixture of particles coated with weak acids and bases under continuous oscillations of the pH. The pH of themore » system modulates the charge of the particles and, therefore, the interparticle forces oscillate in time. This system produces a variety of self-assembled structures, including colloidal molecules, fibers and different types of crystalline lattices. The most important conclusions of our study are: (i) in the limit of fast oscillations, the whole dynamics (and not only those at the non-equilibrium steady state) of a system of particles interacting through time-oscillating interparticle forces can be described by an effective potential that is the time average of the time-dependent potential over one oscillation period; (ii) the oscillation period is critical to determine the order of the system. In some cases the order is favored by very fast oscillations while in others small oscillation frequencies increase the order. In the latter case, it is shown that slow oscillations remove kinetic traps and, thus, allow the system to evolve towards the most stable non-equilibrium steady state.« less

Discrete Element Method Simulations of the Inter-Particle Contact Parameters for the Mono-Sized Iron Ore Particles

PubMed Central

Li, Tongqing; Peng, Yuxing; Zhu, Zhencai; Zou, Shengyong; Yin, Zixin

2017-01-01

Aiming at predicting what happens in reality inside mills, the contact parameters of iron ore particles for discrete element method (DEM) simulations should be determined accurately. To allow the irregular shape to be accurately determined, the sphere clump method was employed in modelling the particle shape. The inter-particle contact parameters were systematically altered whilst the contact parameters between the particle and wall were arbitrarily assumed, in order to purely assess its impact on the angle of repose for the mono-sized iron ore particles. Results show that varying the restitution coefficient over the range considered does not lead to any obvious difference in the angle of repose, but the angle of repose has strong sensitivity to the rolling/static friction coefficient. The impacts of the rolling/static friction coefficient on the angle of repose are interrelated, and increasing the inter-particle rolling/static friction coefficient can evidently increase the angle of repose. However, the impact of the static friction coefficient is more profound than that of the rolling friction coefficient. Finally, a predictive equation is established and a very close agreement between the predicted and simulated angle of repose is attained. This predictive equation can enormously shorten the inter-particle contact parameters calibration time that can help in the implementation of DEM simulations. PMID:28772880

Surface Plasmon Damping Quantified with an Electron Nanoprobe

PubMed Central

Bosman, Michel; Ye, Enyi; Tan, Shu Fen; Nijhuis, Christian A.; Yang, Joel K. W.; Marty, Renaud; Mlayah, Adnen; Arbouet, Arnaud; Girard, Christian; Han, Ming-Yong

2013-01-01

Fabrication and synthesis of plasmonic structures is rapidly moving towards sub-nanometer accuracy in control over shape and inter-particle distance. This holds the promise for developing device components based on novel, non-classical electro-optical effects. Monochromated electron energy-loss spectroscopy (EELS) has in recent years demonstrated its value as a qualitative experimental technique in nano-optics and plasmonic due to its unprecedented spatial resolution. Here, we demonstrate that EELS can also be used quantitatively, to probe surface plasmon kinetics and damping in single nanostructures. Using this approach, we present from a large (>50) series of individual gold nanoparticles the plasmon Quality factors and the plasmon Dephasing times, as a function of energy/frequency. It is shown that the measured general trend applies to regular particle shapes (rods, spheres) as well as irregular shapes (dendritic, branched morphologies). The combination of direct sub-nanometer imaging with EELS-based plasmon damping analysis launches quantitative nanoplasmonics research into the sub-nanometer realm. PMID:23425921

Asymmetric van der Waals Forces Drive Orientation of Compositionally Anisotropic Nanocylinders within Smectic Arrays: Experiment and Simulation

PubMed Central

Smith, Benjamin D.; Fichthorn, Kristen A.; Kirby, David J.; Quimby, Lisa M.; Triplett, Derek A.; González, Pedro; Hernández, Darimar; Keating, Christine D.

2014-01-01

Understanding how micro- and nanoparticles interact is important for achieving bottom-up assembly of desired structures. Here, we examine the self-assembly of two-component, compositionally asymmetric nanocylinders that sediment from solution onto a solid surface. These particles spontaneously formed smectic arrays. Within the rows of an array, nanocylinders tended to assemble such that neighboring particles had the same orientation of their segments. As a probe of interparticle interactions, we classified nanocylinder alignments by measuring the segment orientations of many sets of neighboring particles. Monte Carlo simulations incorporating an exact expression for the van der Waals (vdW) energy indicate that differences in the vdW interactions, even when small, are the key factor in producing observed segment alignment. These results point to asymmetrical vdW interactions as a potentially powerful means of controlling orientation in multicomponent cylinder arrays, and suggest that designing for these interactions could yield new ways to control self-assembly. PMID:24308771

Investigation of structural, morphological, luminescent and thermal properties of combusted aluminium-based iron oxide

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

Shinde, S.S.; Rajpure, K.Y., E-mail: rajpure@yahoo.co

Nanocomposites of aluminium integrated hematite {alpha}-Fe{sub 2}O{sub 3} are synthesized by combustion route using aqueous solutions of AR grade ferric trichloride and aluminium nitrate as precursors. The influence of aluminium incorporation on to the morphology, XPS, photoluminescence and thermal properties has been investigated. The FESEM and AFM micrographs depict that the samples are compact and have homogeneously distributed grains of varying sizes ({approx}20-60 nm). Chemical composition and valence states of constituent elements in hematite are analyzed by XPS. In room temperature photoluminescence (PL) study, we observed strong violet emission around 436 nm without any deep-level emission and a small PLmore » FWHM indicating that the concentrations of defects are responsible for deep-level emissions. The specific heat and thermal conductivity study shows the phonon conduction behavior is dominant. We studied interparticle interactions using complex impedance spectroscopy. We report a new potential candidate for its possible applications in optoelectronics and magnetic devices. -- Graphical abstract: Frequency and temperature dependent interparticle interactions like grains, grain boundary effects using complex impedance spectroscopy of pure and 10 at% Al:Fe{sub 2}O{sub 3} have been studied. Display Omitted« less

Effective interactions and dynamics of small passive particles in an active bacterial medium

NASA Astrophysics Data System (ADS)

Semeraro, Enrico F.; Devos, Juliette M.; Narayanan, Theyencheri

2018-05-01

This article presents an investigation of the interparticle interactions and dynamics of submicron silica colloids suspended in a bath of motile Escherichia coli bacteria. The colloidal microstructure and dynamics were probed by ultra-small-angle x-ray scattering and multi-speckles x-ray photon correlation spectroscopy, respectively. Both static and hydrodynamic interactions were obtained for different colloid volume fractions and bacteria concentrations as well as when the interparticle interaction potential was modified by the motility buffer. Results suggest that motile bacteria reduce the effective attractive interactions between passive colloids and enhance their dynamics at high colloid volume fractions. The enhanced dynamics under different static interparticle interactions can be rationalized in terms of an effective viscosity of the medium and unified by means of an empirical effective temperature of the system. While the influence of swimming bacteria on the colloid dynamics is significantly lower for small particles, the role of motility buffer on the static and dynamic interactions becomes more pronounced.

Fluctuation-induced transport of two coupled particles: effect of the interparticle interaction.

PubMed

Makhnovskii, Yurii A; Rozenbaum, Viktor M; Sheu, Sheh-Yi; Yang, Dah-Yen; Trakhtenberg, Leonid I; Lin, Sheng Hsien

2014-06-07

We consider a system of two coupled particles fluctuating between two states, with different interparticle interaction potentials and particle friction coefficients. An external action drives the interstate transitions that induces reciprocating motion along the internal coordinate x (the interparticle distance). The system moves unidirectionally due to rectification of the internal motion by asymmetric friction fluctuations and thus operates as a dimeric motor that converts input energy into net movement. We focus on how the law of interaction between the particles affects the dimer transport and, in particular, the role of thermal noise in the motion inducing mechanism. It is argued that if the interaction potential behaves at large distances as x(α), depending on the value of the exponent α, the thermal noise plays a constructive (α > 2), neutral (α = 2), or destructive (α < 2) role. In the case of α = 1, corresponding piecewise linear potential profiles, an exact solution is obtained and discussed in detail.

Tunable Quantum Dot Solids: Impact of Interparticle Interactions on Bulk Properties

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

Sinclair, Michael B.; Fan, Hongyou; Brener, Igal

2015-09-01

QD-solids comprising self-assembled semiconductor nanocrystals such as CdSe are currently under investigation for use in a wide array of applications including light emitting diodes, solar cells, field effect transistors, photodetectors, and biosensors. The goal of this LDRD project was develop a fundamental understanding of the relationship between nanoparticle interactions and the different regimes of charge and energy transport in semiconductor quantum dot (QD) solids. Interparticle spacing was tuned through the application of hydrostatic pressure in a diamond anvil cell, and the impact on interparticle interactions was probed using x-ray scattering and a variety of static and transient optical spectroscopies. Duringmore » the course of this LDRD, we discovered a new, previously unknown, route to synthesize semiconductor quantum wires using high pressure sintering of self-assembled quantum dot crystals. We believe that this new, pressure driven synthesis approach holds great potential as a new tool for nanomaterials synthesis and engineering.« less

Protein structure and interactions in the solid state studied by small-angle neutron scattering.

PubMed

Curtis, Joseph E; McAuley, Arnold; Nanda, Hirsh; Krueger, Susan

2012-01-01

Small-angle neutron scattering (SANS) is uniquely qualified to study the structure of proteins in liquid and solid phases that are relevant to food science and biotechnological applications. We have used SANS to study a model protein, lysozyme, in both the liquid and water ice phases to determine its gross-structure, interparticle interactions and other properties. These properties have been examined under a variety of solution conditions before, during, and after freezing. Results for lysozyme at concentrations of 50 mg mL(-1) and 100 mg mL(-1), with NaCl concentrations of 0.4 M and 0 M, respectively, both in the liquid and frozen states, are presented and implications for food science are discussed.

High-temperature crystallization of nanocrystals into three-dimensional superlattices

DOE PAGES

Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; ...

2017-07-31

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single-and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) ofmore » micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. In conclusion, the rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.« less

Sequential programmable self-assembly: Role of cooperative interactions

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

Jonathan D. Halverson; Tkachenko, Alexei V.

Here, we propose a general strategy of “sequential programmable self-assembly” that enables a bottom-up design of arbitrary multi-particle architectures on nano- and microscales. We show that a naive realization of this scheme, based on the pairwise additive interactions between particles, has fundamental limitations that lead to a relatively high error rate. This can be overcome by using cooperative interparticle binding. The cooperativity is a well known feature of many biochemical processes, responsible, e.g., for signaling and regulations in living systems. Here we propose to utilize a similar strategy for high precision self-assembly, and show that DNA-mediated interactions provide a convenientmore » platform for its implementation. In particular, we outline a specific design of a DNA-based complex which we call “DNA spider,” that acts as a smart interparticle linker and provides a built-in cooperativity of binding. We demonstrate versatility of the sequential self-assembly based on spider-functionalized particles by designing several mesostructures of increasing complexity and simulating their assembly process. This includes a number of finite and repeating structures, in particular, the so-called tetrahelix and its several derivatives. Due to its generality, this approach allows one to design and successfully self-assemble virtually any structure made of a “GEOMAG” magnetic construction toy, out of nanoparticles. According to our results, once the binding cooperativity is strong enough, the sequential self-assembly becomes essentially error-free.« less

Sequential programmable self-assembly: Role of cooperative interactions

DOE PAGES

Jonathan D. Halverson; Tkachenko, Alexei V.

2016-03-04

Here, we propose a general strategy of “sequential programmable self-assembly” that enables a bottom-up design of arbitrary multi-particle architectures on nano- and microscales. We show that a naive realization of this scheme, based on the pairwise additive interactions between particles, has fundamental limitations that lead to a relatively high error rate. This can be overcome by using cooperative interparticle binding. The cooperativity is a well known feature of many biochemical processes, responsible, e.g., for signaling and regulations in living systems. Here we propose to utilize a similar strategy for high precision self-assembly, and show that DNA-mediated interactions provide a convenientmore » platform for its implementation. In particular, we outline a specific design of a DNA-based complex which we call “DNA spider,” that acts as a smart interparticle linker and provides a built-in cooperativity of binding. We demonstrate versatility of the sequential self-assembly based on spider-functionalized particles by designing several mesostructures of increasing complexity and simulating their assembly process. This includes a number of finite and repeating structures, in particular, the so-called tetrahelix and its several derivatives. Due to its generality, this approach allows one to design and successfully self-assemble virtually any structure made of a “GEOMAG” magnetic construction toy, out of nanoparticles. According to our results, once the binding cooperativity is strong enough, the sequential self-assembly becomes essentially error-free.« less

Simulation study of charged nanoparticles confined in a rectangular tube with discrete wall charges.

PubMed

Yuet, Pak K

2006-03-28

The development of novel nanomaterials has been a subject of intense interest in recent years. An interesting structure among these materials is the so-called "pea pods" (i.e., nanoparticles confined in nanotubes). To facilitate the development and commercialization of these materials, it is important that we have an in-depth understanding of their behavior. The study of confined charged particles is particularly challenging because of the long-ranged nature of electrostatic interaction, and both interparticle and particle-confinement interactions are likely to play a role in determining the system behavior. The primary objective of this study is to develop a better understanding of the behavior of charged nanoparticles in a charged tubular confinement using Monte Carlo simulation, with particular focus on the effect of electrostatic interactions on the structure of the particles. Simulation results have shown that (i) the structuring of confined particles is associated with the asymmetry of the long-ranged interaction and (ii) factors such as confinement geometry and particle charge and size asymmetry can be manipulated to produce different particle structures. The present study represents the first step in an attempt to gain further insight into the behavior of confined nanosystems, with the ultimate objective of exploiting these characteristics, particularly the interactions between the confined particles and their external environment, in developing novel nanomaterials.

Simulation of Liquid Droplet in Air and on a Solid Surface

NASA Astrophysics Data System (ADS)

Launglucknavalai, Kevin

Although multiphase gas and liquid phenomena occurs widely in engineering problems, many aspects of multiphase interaction like within droplet dynamics are still not quantified. This study aims to qualify the Lattice Boltzmann (LBM) Interparticle Potential multiphase computational method in order to build a foundation for future multiphase research. This study consists of two overall sections. The first section in Chapter 2 focuses on understanding the LBM method and Interparticle Potential model. It outlines the LBM method and how it relates to macroscopic fluid dynamics. The standard form of LBM is obtained. The perturbation solution obtaining the Navier-Stokes equations from the LBM equation is presented. Finally, the Interparticle Potential model is incorporated into the numerical LBM method. The second section in Chapter 3 presents the verification and validation cases to confirm the behavior of the single-phase and multiphase LBM models. Experimental and analytical results are used briefly to compare with numerical results when possible using Poiseuille channel flow and flow over a cylinder. While presenting the numerical results, practical considerations like converting LBM scale variables to physical scale variables are considered. Multiphase results are verified using Laplaces law and artificial behaviors of the model are explored. In this study, a better understanding of the LBM method and Interparticle Potential model is gained. This allows the numerical method to be used for comparison with experimental results in the future and provides a better understanding of multiphase physics overall.

Roles of additives and surface control in slurry atomization. Final project report

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

Tsai, S.C.

1992-12-31

This project studies the rheology and airblast atomization of micronized coal slurries. Its major objectives are (1) to promote further understanding of the mechanisms and the roles of additives in airblast atomization of coal water slurry (CWS), and (2) to investigate the impacts of coal particle surface properties and interparticle forces on CWS rheology. We have found that the flow behavior index (n) of a suspension (or slurry) is determined by the relative importance of the interparticle van der Waals attraction and the interparticle electrostatic repulsion. The interparticle attraction, measured by the Hamaker constant scaled to the thermal energy atmore » 25{degrees}C (A/kT), causes particle aggregation, which breaks down at high shear rates, and thus leads to slurry pseudoplastic behavior (n< 1). At a constant particle volume fraction and surface charge density (qualitatively measured by the zeta potential in deionized water), n decreases linearly as A/kT increases. The relative viscosity of the pseudoplastic suspension with respect to that of the suspending liquid is found to be independent of particle density and correlate well with the particle Peclet number which equals the particle diffusional relaxation time multiplied by shear rate. Specifically, the relative viscosities of the pseudoplastic glycerol/water coal slurry and the ethylene glycol/glycerol sand slurry, at same volume fractions as well as similar particle size distributions and liquid viscosities, as functions of the particle Peclet number fall along the same line.« less

Roles of additives and surface control in slurry atomization

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

Tsai, S.C.

1992-01-01

This project studies the rheology and airblast atomization of micronized coal slurries. Its major objectives are (1) to promote further understanding of the mechanisms and the roles of additives in airblast atomization of coal water slurry (CWS), and (2) to investigate the impacts of coal particle surface properties and interparticle forces on CWS rheology. We have found that the flow behavior index (n) of a suspension (or slurry) is determined by the relative importance of the interparticle van der Waals attraction and the interparticle electrostatic repulsion. The interparticle attraction, measured by the Hamaker constant scaled to the thermal energy atmore » 25[degrees]C (A/kT), causes particle aggregation, which breaks down at high shear rates, and thus leads to slurry pseudoplastic behavior (n< 1). At a constant particle volume fraction and surface charge density (qualitatively measured by the zeta potential in deionized water), n decreases linearly as A/kT increases. The relative viscosity of the pseudoplastic suspension with respect to that of the suspending liquid is found to be independent of particle density and correlate well with the particle Peclet number which equals the particle diffusional relaxation time multiplied by shear rate. Specifically, the relative viscosities of the pseudoplastic glycerol/water coal slurry and the ethylene glycol/glycerol sand slurry, at same volume fractions as well as similar particle size distributions and liquid viscosities, as functions of the particle Peclet number fall along the same line.« less

Effect of Young's Modulus and Surface Roughness on the Inter-Particle Friction of Granular Materials.

PubMed

Sandeep, Chitta Sai; Senetakis, Kostas

2018-01-31

In the study we experimentally examine the influence of elastic properties and surface morphology on the inter-particle friction of natural soil grains. The experiments are conducted with a custom-built micromechanical apparatus and the database is enhanced by testing engineered-reference grains. Naturally-occurring geological materials are characterized by a wide spectrum of mechanical properties (e.g., Young's modulus) and surface morphology (e.g., roughness), whereas engineered grains have much more consistent characteristics. Comparing to engineered materials, geological materials are found to display more pronounced initial plastic behavior during compression. Under the low normal load range applied in the study, between 1 and 5 N, we found that the frictional force is linearly correlated with the applied normal load, but we acknowledge that the data are found more scattered for natural soil grains, especially for rough and weathered materials which have inconsistent characteristics. The inter-particle coefficient of friction is found to be inversely correlated with the Young's modulus and the surface roughness. These findings are important in geophysical and petroleum engineering contents, since a number of applications, such as landslides and granular flows, hydraulic fracturing using proppants, and weathering process of cliffs, among others, can be simulated using discrete numerical methods. These methods employ contact mechanics properties at the grain scale and the inter-particle friction is one of these critical components. It is stressed in our study that friction is well correlated with the elastic and morphological characteristics of the grains.

Evolution of network architecture in a granular material under compression

NASA Astrophysics Data System (ADS)

Papadopoulos, Lia; Puckett, James G.; Daniels, Karen E.; Bassett, Danielle S.

2016-09-01

As a granular material is compressed, the particles and forces within the system arrange to form complex and heterogeneous collective structures. Force chains are a prime example of such structures, and are thought to constrain bulk properties such as mechanical stability and acoustic transmission. However, capturing and characterizing the evolving nature of the intrinsic inhomogeneity and mesoscale architecture of granular systems can be challenging. A growing body of work has shown that graph theoretic approaches may provide a useful foundation for tackling these problems. Here, we extend the current approaches by utilizing multilayer networks as a framework for directly quantifying the progression of mesoscale architecture in a compressed granular system. We examine a quasi-two-dimensional aggregate of photoelastic disks, subject to biaxial compressions through a series of small, quasistatic steps. Treating particles as network nodes and interparticle forces as network edges, we construct a multilayer network for the system by linking together the series of static force networks that exist at each strain step. We then extract the inherent mesoscale structure from the system by using a generalization of community detection methods to multilayer networks, and we define quantitative measures to characterize the changes in this structure throughout the compression process. We separately consider the network of normal and tangential forces, and find that they display a different progression throughout compression. To test the sensitivity of the network model to particle properties, we examine whether the method can distinguish a subsystem of low-friction particles within a bath of higher-friction particles. We find that this can be achieved by considering the network of tangential forces, and that the community structure is better able to separate the subsystem than a purely local measure of interparticle forces alone. The results discussed throughout this study suggest that these network science techniques may provide a direct way to compare and classify data from systems under different external conditions or with different physical makeup.

Extrinsic extinction cross-section in the multiple acoustic scattering by fluid particles

NASA Astrophysics Data System (ADS)

Mitri, F. G.

2017-04-01

Cross-sections (and their related energy efficiency factors) are physical parameters used in the quantitative analysis of different phenomena arising from the interaction of waves with a particle (or multiple particles). Earlier works with the acoustic scattering theory considered such quadratic (i.e., nonlinear) quantities for a single scatterer, although a few extended the formalism for a pair of scatterers but were limited to the scattering cross-section only. Therefore, the standard formalism applied to viscous particles is not suitable for the complete description of the cross-sections and energy balance of the multiple-particle system because both absorption and extinction phenomena arise during the multiple scattering process. Based upon the law of the conservation of energy, this work provides a complete comprehensive analysis for the extrinsic scattering, absorption, and extinction cross-sections (i.e., in the far-field) of a pair of viscous scatterers of arbitrary shape, immersed in a nonviscous isotropic fluid. A law of acoustic extinction taking into consideration interparticle effects in wave propagation is established, which constitutes a generalized form of the optical theorem in multiple scattering. Analytical expressions for the scattering, absorption, and extinction cross-sections are derived for plane progressive waves with arbitrary incidence. The mathematical expressions are formulated in partial-wave series expansions in cylindrical coordinates involving the angle of incidence, the addition theorem for the cylindrical wave functions, and the expansion coefficients of the scatterers. The analysis shows that the multiple scattering cross-section depends upon the expansion coefficients of both scatterers in addition to an interference factor that depends on the interparticle distance. However, the extinction cross-section depends on the expansion coefficients of the scatterer located in a particular system of coordinates, in addition to the interference term. Numerical examples illustrate the analysis for two viscous fluid circular cylindrical cross-sections immersed in a non-viscous fluid. Computations for the (non-dimensional) scattering, absorption, and extinction cross-section factors are performed with particular emphasis on varying the angle of incidence, the interparticle distance, and the sizes, and the physical properties of the particles. A symmetric behavior is observed for the dimensionless multiple scattering cross-section, while asymmetries arise for both the dimensionless absorption and extinction cross-sections with respect to the angle of incidence. The present analysis provides a complete analytical and computational method for the prediction of cross-section and energy efficiency factors in multiple acoustic scattering of plane waves of arbitrary incidence by a pair of scatterers. The results can be used as a priori information in the direct or inverse characterization of multiple scattering systems such as acoustically engineered fluid metamaterials with reconfigurable periodicities, cloaking devices, liquid crystals, and other applications.

Preparation of flexible TiO2 photoelectrodes for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Li, Wen-Ren; Wang, Hsiu-Hsuan; Lin, Chia-Feng; Su, Chaochin

2014-09-01

Dye-sensitized solar cells (DSSCs) based on nanocrystalline TiO2 photoelectrodes on indium tin oxide (ITO) coated polymer substrates have drawn great attention due to its lightweight, flexibility and advantages in commercial applications. However, the thermal instability of polymer substrates limits the process temperature to below 150 °C. In order to assure high and firm interparticle connection between TiO2 nanocrystals (TiO2-NC) and polymer substrates, the post-treatment of flexible TiO2 photoelectrodes (F-TiO2-PE) by mechanical compression was employed. In this work, Degussa P25 TiO2-NC was mixed with tert-butyl alcohol and DI-water to form TiO2 paste. F-TiO2-PE was then prepared by coating the TiO2 paste onto ITO coated polyethylene terephthalate (PET) substrate using doctor blade followed by low temperature sintering at 120 °C for 2 hours. To study the effect of mechanical compression, we applied 50 and 100 kg/cm2 pressure on TiO2/PET to complete the fabrication of F-TiO2-PE. The surface morphology of F-TiO2-PE was characterized using scanning electron microscopy. The resultant F-TiO2-PE sample exhibited a smooth, crack-free structure indicating the great improvement in the interparticle connection of TiO2-NC. Increase of compression pressure could lead to the increase of DSSC photoconversion efficiency. The best photoconversion efficiency of 4.19 % (open circuit voltage (Voc) = 0.79 V, short-circuit photocurrent density (Jsc) = 7.75 mA/cm2, fill factor (FF) = 0.68) was obtained for the F-TiO2-PE device, which showed great enhancement compared with the F-TiO2-PE cell without compression treatment. The effect of compression in DSSC performance was vindicated by the electrochemical impedance spectroscopy measurement.

LETTER TO THE EDITOR: Backbones of traffic jams

NASA Astrophysics Data System (ADS)

Shikhar Gupta, Himadri; Ramaswamy, Ramakrishna

1996-11-01

We study the jam phase of the deterministic traffic model in two dimensions. Within the jam phase, there is a phase transition, from a self-organized jam (formed by initial synchronization followed by jamming), to a random-jam structure. The backbone of the jam is defined and used to analyse self-organization in the jam. The fractal dimension and interparticle correlations on the backbone indicate a continous phase transition at density 0305-4470/29/21/003/img1 with critical exponent 0305-4470/29/21/003/img2, which are characterized through simulations.

Nanoparticle Superlattice Engineering with DNA

NASA Astrophysics Data System (ADS)

Macfarlane, Robert J.; Lee, Byeongdu; Jones, Matthew R.; Harris, Nadine; Schatz, George C.; Mirkin, Chad A.

2011-10-01

A current limitation in nanoparticle superlattice engineering is that the identities of the particles being assembled often determine the structures that can be synthesized. Therefore, specific crystallographic symmetries or lattice parameters can only be achieved using specific nanoparticles as building blocks (and vice versa). We present six design rules that can be used to deliberately prepare nine distinct colloidal crystal structures, with control over lattice parameters on the 25- to 150-nanometer length scale. These design rules outline a strategy to independently adjust each of the relevant crystallographic parameters, including particle size (5 to 60 nanometers), periodicity, and interparticle distance. As such, this work represents an advance in synthesizing tailorable macroscale architectures comprising nanoscale materials in a predictable fashion.

Pushing, pulling and electromagnetic radiation force cloaking by a pair of conducting cylindrical particles

NASA Astrophysics Data System (ADS)

Mitri, F. G.

2018-02-01

The present analysis shows that two conducting cylindrical particles illuminated by an axially-polarized electric field of plane progressive waves at arbitrary incidence will attract, repel or become totally cloaked (i.e., invisible to the transfer of linear momentum carried by the incident waves), depending on their sizes, the interparticle distance as well as the angle of incidence of the incident field. Based on the rigorous multipole expansion method and the translational addition theorem of cylindrical wave functions, the electromagnetic (EM) radiation forces arising from multiple scattering effects between a pair of perfectly conducting cylindrical particles of circular cross-sections are derived and computed. An effective incident field on a particular particle is determined first, and used subsequently with its corresponding scattered field to derive the closed-form analytical expressions for the radiation force vector components. The mathematical expressions for the EM radiation force components (i.e. longitudinal and transverse) are exact, and have been formulated in partial-wave series expansions in cylindrical coordinates involving the angle of incidence, the interparticle distance and the expansion coefficients. Numerical examples illustrate the analysis for two perfectly conducting circular cylinders in a homogeneous nonmagnetic medium of wave propagation. The computations for the dimensionless radiation force functions are performed with particular emphasis on varying the angle of incidence, the interparticle distance, and the sizes of the particles. Depending on the interparticle distance and angle of incidence, the cylinders yield total neutrality (or invisibility); they experience no force and become unresponsive to the transfer of the EM linear momentum due to multiple scattering cancellation effects. Moreover, pushing or pulling EM forces between the two cylinders arise depending on the interparticle distance, the angle of incidence and their size parameters. This study provides a complete analytical method and computations for the longitudinal and transverse radiation force components in the multiple scattering of EM plane progressive waves with potential applications in particle manipulation, optically-engineered metamaterials with reconfigurable periodicities and cloaking devices to name a few examples.

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

Polemi, A.; Shuford, K. L.

We investigate the use of a Fabry-Perot dielectric structure combined with differently shaped nanoparticles for Surface Enhanced Raman Scattering. In particular, we show how an ideal two-layer Fabry-Perot configuration enhances the local surface field of silver nanoparticles positioned on the surface of the structure. We develop the concept using disc dimers and then extend the discussion to bowtie nanoparticles. The structure is excited by a single emitter, which couples to the nanoparticles through the dielectric layers, producing a wide aperture field that can be used to excite multiple dimers. We show how an array of nanoparticles can be properly arrangedmore » in order to increase the total scattering signal generated from the structure. The layered geometry produces robust field properties in between nanoparticles, making the overall sensing characteristics less sensitive to the interparticle seperation distance and incident polarization.« less

Dusty plasma in a glow discharge in helium in temperature range of 5–300 K

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

Samoilov, I. S.; Baev, V. P.; Timofeev, A. V., E-mail: timofeevalvl@gmail.com

2017-03-15

Dusty plasma structures in glow discharge in helium in the temperature range of 5–300 K are investigated experimentally. We have described the experimental setup that makes it possible to continuously vary the temperature regime. The method for experimental data processing has been described. We have measured interparticle distances in the temperature range of 9–295 K and compared them with the Debye radius. We indicate the ranges of variations in experimental parameters in which plasma–dust structures are formed and various types of their behavior are manifested (rotation, vibrations of structures, formation of vertical linear chains, etc.). The applicability of the Yukawamore » potential to the description of the structural properties of a dusty plasma in the experimental conditions is discussed.« less

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

Ballouz, Ronald-Louis; Richardson, Derek C.; Morishima, Ryuji

We study the B ring’s complex optical depth structure. The source of this structure may be the complex dynamics of the Keplerian shear and the self-gravity of the ring particles. The outcome of these dynamic effects depends sensitively on the collisional and physical properties of the particles. Two mechanisms can emerge that dominate the macroscopic physical structure of the ring: self-gravity wakes and viscous overstability. Here we study the interplay between these two mechanisms by using our recently developed particle collision method that allows us to better model the inter-particle contact physics. We find that for a constant ring surfacemore » density and particle internal density, particles with rough surfaces tend to produce axisymmetric ring features associated with the viscous overstability, while particles with smoother surfaces produce self-gravity wakes.« less

Sensing Properties of a Fabry-Perot Dielectric Structure and Dimer Nanoparticles

DOE PAGES

Polemi, A.; Shuford, K. L.

2012-01-01

We investigate the use of a Fabry-Perot dielectric structure combined with differently shaped nanoparticles for Surface Enhanced Raman Scattering. In particular, we show how an ideal two-layer Fabry-Perot configuration enhances the local surface field of silver nanoparticles positioned on the surface of the structure. We develop the concept using disc dimers and then extend the discussion to bowtie nanoparticles. The structure is excited by a single emitter, which couples to the nanoparticles through the dielectric layers, producing a wide aperture field that can be used to excite multiple dimers. We show how an array of nanoparticles can be properly arrangedmore » in order to increase the total scattering signal generated from the structure. The layered geometry produces robust field properties in between nanoparticles, making the overall sensing characteristics less sensitive to the interparticle seperation distance and incident polarization.« less

Linking initial microstructure and local response during quasistatic granular compaction

DOE PAGES

Hurley, R. C.; Lind, J.; Pagan, D. C.; ...

2017-07-24

In this study, we performed experiments combining three-dimensional x-ray diffraction and x-ray computed tomography to explore the relationship between microstructure and local force and strain during quasistatic granular compaction. We found that initial void space around a grain and contact coordination number before compaction can be used to predict regions vulnerable to above-average local force and strain at later stages of compaction. We also found correlations between void space around a grain and coordination number, and between grain stress and maximum interparticle force, at all stages of compaction. Finally, we observed grains that fracture to have an above-average initial localmore » void space and a below-average initial coordination number. In conclusion, our findings provide (1) a detailed description of microstructure evolution during quasistatic granular compaction, (2) an approach for identifying regions vulnerable to large values of strain and interparticle force, and (3) methods for identifying regions of a material with large interparticle forces and coordination numbers from measurements of grain stress and local porosity.« less

Rheological Properties of Automorphic and Semihydromorphic Cryometamorphic Northern Taiga Soils in Northeastern European Russia (Komi Republic)

NASA Astrophysics Data System (ADS)

Kholopov, Yu. V.; Khaidapova, D. D.; Lapteva, E. M.

2018-04-01

Soil pastes at the water content corresponding to the maximum swelling of samples from different genetic horizons of cryometamorphic soils―surface-gleyic iron-illuvial svetlozem (Folic Albic Stagnosol) and peaty and peat humus-impregnated gleyic svetlozems (Histic Gleyic Stagnosols)―have been studied with an MCR-302 modular rheometer (Anton Paar, Austria). It has been found that the strongest interparticle bonds are formed in the horizons of cryometamorphic soils characterized by high contents of humic substances and organomineral Al-Fe-humus compounds. These are horizons of podzol microprofile (Eg and BHF) in iron-illuvial svetlozem and a humus-impregnated horizon (ELhi,g) in peaty and peat svetlozems. Organomineral Al-Fe-humus compounds, as well as the seasonal freezing of soils, determine the elastic-brittle character of interparticle interactions. The contents of clay fractions, exchangeable bases, and organic and organomineral substances impart viscoelastic properties to these contacts. An enhancement of elastic-brittle properties of soil is observed under the impact of gleying and freezing. The threefold decrease of the structural interaction parameter (∫ Z) when going from automorphic to semihydromorphic conditions indicates a decrease in the resistance of peaty and peat svetlozems to mechanical loads under increasing hydromorphism compared to iron-illuvial svetlozems.

Optimization of stress relief heat treatment of PHWR pressure tubes (Zr 2.5Nb alloy)

NASA Astrophysics Data System (ADS)

Choudhuri, Gargi; Srivastava, D.; Gurumurthy, K. R.; Shah, B. K.

2008-12-01

The micro-structure of cold worked Zr-2.5%Nb pressure tube material consists of elongated grains of α-zirconium enclosed by a thin film of β-zirconium phase. This β-Zr phase is unstable and on heating, progressively decomposes to α-Zr phase and β-phase enriched with Nb and ultimately form β Nb. Meta-stable ω-phase precipitates as an intermediate step during decomposition depending on the heat treatment schedule, β→α+β→α+ω+β→α+β→α+β Morphological changes occur in the β-zirconium phase during the decomposition. The continuous ligaments of β Zr phase turn into a discontinuous array of particles followed by globulization of the β-phase. The morphological changes impose a significant effect on the creep rate and on the delayed hydride cracking velocity due to reduction in the hydrogen diffusion coefficient in α Zr. If the continuity of β-phase is disrupted by heat treatment, the effective diffusion coefficient decreases with a concomitant reduction in DHC velocity. The pressure tubes for the Indian PHWRs are made by a process of hot extrusion followed by cold pilgering in two stages and an intermediate annealing. Autoclaving at 400 °C for 36 h ensures stress relieving of the finished tubes. In the present studies, autoclaving duration at 400 °C was varied from 24 h to 96 h at 12 h-steps and the micro-structural changes in the β-phase were observed by TEM. Dislocation density, hardness and the micro-structural features such as thickness of β-phase, inter-particle spacing and volume fraction of the phases were measured at each stage. Autoclaving for a longer duration was found to change the morphology of β-phase and increase the inter-particle spacing. Progressive changes in the aspect ratio of the β-phase and their size and distribution are documented and reported. These micro-structural modifications are expected to decrease DHC velocity during reactor operation.

Electron tomography and nano-diffraction enabling the investigation of individual magnetic nanoparticles inside fibers of MR visible implants

NASA Astrophysics Data System (ADS)

Slabu, I.; Wirch, N.; Caumanns, T.; Theissmann, R.; Krüger, M.; Schmitz-Rode, T.; Weirich, T. E.

2017-08-01

Superparamagnetic iron oxide nanoparticles (SPIONPs) incorporated into the base material of implants are used as contrast agents in magnetic resonance imaging for the delineation of the implants from the surrounding tissue. However, the delineation quality is strongly related to the structural characteristics of the incorporated SPIONPs and their interparticle interaction as well as their interaction with the polymer matrix of the implant. Consequently, a profound knowledge of the formation of aggregates inside the polymer matrix, which are responsible for strong interparticle interactions, and of their structural characteristics, is required for controlling the magnetic resonance image quality of the implants. In this work, transmission electron microscopy methods such as electron tomography and nano-electron diffraction were used to depict SPIONP aggregates inside the melt-spin polyvinylidene fluoride fibers used for the assembly of implants and to determine the crystal structure of individual nanocrystals inside these aggregates, respectively. Using these techniques it was possible for the first time to characterize the aggregates inside the fibers of implants and to validate the magnetization measurements that have been previously used to assess the interaction phenomena inside the fibers of implants. With electron tomography, inhomogeneously sized distributed aggregates were delineated and 3D models of these aggregates were constructed. Furthermore, the distribution of the aggregates inside the fibers was verified by means of magnetic force microscopy. With nano-diffraction measurements, the SPIONP crystal structure inside the fibers of the implant could not be clearly assigned to that of magnetite (Fe3O4) or maghemite (γ-Fe2O3). Therefore, additional electron energy loss spectroscopy measurements were performed, which revealed the presence of both phases of Fe3O4 and γ-Fe2O3, probably caused by oxidation processes during the manufacture of the fibers by melt-spinning.

Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip

NASA Astrophysics Data System (ADS)

Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

2017-03-01

This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7 × 108) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8 × 109) was 2.5 times greater than the experimental enhancement factor (1.1 × 109). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9 × 1011), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

Phase transitions, interparticle correlations, and elementary processes in dense plasmas

NASA Astrophysics Data System (ADS)

Ichimaru, Setsuo

2017-12-01

Astrophysical dense plasmas are those we find in the interiors, surfaces, and outer envelopes of stellar objects such as neutron stars, white dwarfs, the Sun, and giant planets. Condensed plasmas in the laboratory settings include those in ultrahigh-pressure metal-physics experiments undertaken for realization of metallic hydrogen. We review basic physics issues studied in the past 60 some years on the phase transitions, the interparticle correlations, and the elementary processes in dense plasmas, through survey on scattering of electromagnetic waves, equations of state, phase diagrams, transport processes, stellar and planetary magnetisms, and thermo- and pycnonuclear reactions.

Structure organization and magnetic properties of microscale ferrogels: The effect of particle magnetic anisotropy

NASA Astrophysics Data System (ADS)

Ryzhkov, Aleksandr V.; Melenev, Petr V.; Balasoiu, Maria; Raikher, Yuriy L.

2016-08-01

The equilibrium structure and magnetic properties of a ferrogel object of small size (microferrogel(MFG)) are investigated by coarse-grained molecular dynamics. As a generic model of a microferrogel (MFG), a sample with a lattice-like mesh is taken. The solid phase of the MFG consists of magnetic (e.g., ferrite) nanoparticles which are mechanically linked to the mesh making some part of its nodes. Unlike previous models, the finite uniaxial magnetic anisotropy of the particles, as it is the case for real ferrogels, is taken into account. For comparison, two types of MFGs are considered: MFG-1, which dwells in virtually non-aggregated state independently of the presence of an external magnetic field, and MFG-2, which displays aggregation yet under zero field. The structure states of the samples are analyzed with the aid of angle-resolved radial distribution functions and cluster counts. The results reveal the crucial role of the matrix elasticity on the structure organization as well as on magnetization of both MFGs. The particle anisotropy, which plays insignificant role in MFG-1 (moderate interparticle magnetodipole interaction), becomes an important factor in MFG-2 (strong interaction). There, the restrictions imposed on the particle angular freedom by the elastic matrix result in notable diminution of the particle chain lengths as well as the magnetization of the sample. The approach proposed enables one to investigate a large variety of MFGs, including those of capsule type and to purposefully choose the combination of their magnetoelastic parameters.

Angle-adjustable density field formulation for the modeling of crystalline microstructure

NASA Astrophysics Data System (ADS)

Wang, Zi-Le; Liu, Zhirong; Huang, Zhi-Feng

2018-05-01

A continuum density field formulation with particle-scale resolution is constructed to simultaneously incorporate the orientation dependence of interparticle interactions and the rotational invariance of the system, a fundamental but challenging issue in modeling the structure and dynamics of a broad range of material systems across variable scales. This generalized phase field crystal-type approach is based upon the complete expansion of particle direct correlation functions and the concept of isotropic tensors. Through applications to the modeling of various two- and three-dimensional crystalline structures, our study demonstrates the capability of bond-angle control in this continuum field theory and its effects on the emergence of ordered phases, and provides a systematic way of performing tunable angle analyses for crystalline microstructures.

Optimally designed gold nanorattles with strong built-in hotspots and weak polarization dependence

NASA Astrophysics Data System (ADS)

Zhang, Xuemin; Wang, Tieqiang; Li, Yunong; Fu, Yu; Guo, Lei

2017-12-01

Localized electromagnetic fields generated by interparticle plasmon coupling suffer greatly from nonreproducibility because they are extremely sensitive to the nanoparticle aggregation status and the incident polarization. Here, we synthesize gold nanorattles that exhibit inherent aggregation-insensitive hotspots due to the intraparticle core-shell plasmon coupling, and investigate the structural effect on the intraparticle coupling strength and its polarization dependence. Through optimizing the structural parameters, we successfully synthesize gold nanorattles with strong built-in hotspots and weak polarization dependence. These aggregation-insensitive and weakly polarization-dependent hotspots make the Raman enhancement from nanorattle aggregates show an unusual weak dependence on the particle aggregation status, which therefore affords the opportunity to fabricate uniform and reproducible surface enhanced Raman scattering substrates.

The effect of magnetic nanoparticle concentration on the structure organisation of a microferrogel

NASA Astrophysics Data System (ADS)

Ryzhkov, A. V.; Melenev, P. V.; Balasoiu, M.; Raikher, Yu L.

2018-03-01

Coarse-grained molecular dynamics simulation is applied to study the structural response of micro-sized magnetopolymer objects – microferrogels (MFG). The results for MFGs with different magnetic properties and concentrations of magnetic filler nanoparticles are analysed to detect the transition between non-aggregated configurations and the states with pronounced chains. The nanoparticles are assumed to be either magnetically isotropic or to possess infinite magnetic anisotropy. It is shown that, depending on the type of the particle anisotropy, an applied field in rather different ways affects the MFG structure and shape. Diagrams describing the degree of aggregation as a function of the parameter of the interparticle magnetodipolar interaction and concentration are presented. In particular, it is found that in the case of infinitely anisotropic nanoparticles the aggregation transitions undergoes via a non-trivial scenario. The effect of the structure transformations on the volume change of the MFG objects is studied as well.

The origin of facet selectivity and alignment in anatase TiO 2 nanoparticles in electrolyte solutions: implications for oriented attachment in metal oxides

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

Sushko, M. L.; Rosso, K. M.

Atomic-to-mesoscale simulations were used to reveal the origin of oriented attachment between anatase TiO2 nanoparticles in aqueous HCl solutions. Analysis of the distance and pH dependence of interparticle interactions demonstrates that ion correlation forces are responsible for facet-specific attraction and rotation into lattice co-alignment at long-range. These forces give rise to a metastable solvent separated capture minimum on the disjoining pressure-distance curve, with the barrier to attachment largely due to steric hydration forces from structured intervening solvent.

Annealing cycles and the self-organization of functionalized colloids

NASA Astrophysics Data System (ADS)

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

2018-01-01

The self-assembly of functionalized (patchy) particles with directional interactions into target structures is still a challenge, despite the significant experimental advances in their synthesis. Self-assembly pathways are typically characterized by high energy barriers that hinder access to stable (equilibrium) structures. A possible strategy to tackle this challenge is to perform annealing cycles. By periodically switching on and off the inter-particle bonds, one expects to smooth-out the kinetic pathways and favor the assembly of targeted structures. Preliminary results have shown that the efficiency of annealing cycles depends strongly on their frequency. Here, we study numerically how this frequency-dependence scales with the strength of the directional interactions (size of the patch σ). We use analytical arguments to show that the scaling results from the statistics of a random walk in configurational space.

"Hypothetical" Heavy Particles Dynamics in LES of Turbulent Dispersed Two-Phase Channel Flow

NASA Technical Reports Server (NTRS)

Gorokhovski, M.; Chtab, A.

2003-01-01

The extensive experimental study of dispersed two-phase turbulent flow in a vertical channel has been performed in Eaton's research group in the Mechanical Engineering Department at Stanford University. In Wang & Squires (1996), this study motivated the validation of LES approach with Lagrangian tracking of round particles governed by drag forces. While the computed velocity of the flow have been predicted relatively well, the computed particle velocity differed strongly from the measured one. Using Monte Carlo simulation of inter-particle collisions, the computation of Yamamoto et al. (2001) was specifically performed to model Eaton's experiment. The results of Yamamoto et al. (2001) improved the particle velocity distribution. At the same time, Vance & Squires (2002) mentioned that the stochastic simualtion of inter-particle collisions is too expensive, requiring significantly more CPU resources than one needs for the gas flow computation. Therefore, the need comes to account for the inter-particle collisions in a simpler and still effective way. To present such a model in the framework of LES/Lagrangian particle approach, and to compare the calculated results with Eaton's measurement and modeling of Yamamoto is the main objective of the present paper.

Interparticle collision of natural sediment grains in water

USGS Publications Warehouse

Schmeeckle, Mark W.; Nelson, Jonathan M.; Pitlick, John; Bennett, James P.

2001-01-01

Elastohydrodynamic theory and measurements of particle impacts on an inclined glass plane in water are used to investigate the mechanics of interparticle collisions in sediment‐transporting flows. A collision Stokes number is proposed as a measure of the momentum of an interparticle collision versus the viscous pressure force in the interstitial gap between colliding particles. The viscous pressure force opposes motion of the particles on approach and rebound. A Stokes number of between 39 and 105 is estimated as the critical range below which particle impacts are completely viscously damped and above which impacts are partially elastic. The critical Stokes number is shown to roughly coincide with the Bagnold number transition between macroviscous and grain inertial debris flows and the transition between damped and partially elastic bed load transport saltation impacts. The nonspherical nature of natural particles significantly alters the motion of the center of mass after a partially elastic collision. The normal to the point of contact between the particles does not necessarily go through the center of mass. Thus normal rebound of the center of mass may not occur. A model of particle motion after rebound for particles of arbitrary shape, conserving both linear and angular momentum, is proposed.

Mapping the exciton diffusion in semiconductor nanocrystal solids.

PubMed

Kholmicheva, Natalia; Moroz, Pavel; Bastola, Ebin; Razgoniaeva, Natalia; Bocanegra, Jesus; Shaughnessy, Martin; Porach, Zack; Khon, Dmitriy; Zamkov, Mikhail

2015-03-24

Colloidal nanocrystal solids represent an emerging class of functional materials that hold strong promise for device applications. The macroscopic properties of these disordered assemblies are determined by complex trajectories of exciton diffusion processes, which are still poorly understood. Owing to the lack of theoretical insight, experimental strategies for probing the exciton dynamics in quantum dot solids are in great demand. Here, we develop an experimental technique for mapping the motion of excitons in semiconductor nanocrystal films with a subdiffraction spatial sensitivity and a picosecond temporal resolution. This was accomplished by doping PbS nanocrystal solids with metal nanoparticles that force the exciton dissociation at known distances from their birth. The optical signature of the exciton motion was then inferred from the changes in the emission lifetime, which was mapped to the location of exciton quenching sites. By correlating the metal-metal interparticle distance in the film with corresponding changes in the emission lifetime, we could obtain important transport characteristics, including the exciton diffusion length, the number of predissociation hops, the rate of interparticle energy transfer, and the exciton diffusivity. The benefits of this approach to device applications were demonstrated through the use of two representative film morphologies featuring weak and strong interparticle coupling.

Microgels at the Water/Oil Interface: In Situ Observation of Structural Aging and Two-Dimensional Magnetic Bead Microrheology.

PubMed

Huang, Shilin; Gawlitza, Kornelia; von Klitzing, Regine; Gilson, Laurent; Nowak, Johannes; Odenbach, Stefan; Steffen, Werner; Auernhammer, Günter K

2016-01-26

Stimuli-responsive microgels can be used as stabilizers for emulsions. However, the details of structure and the viscoelastic property of the microgel-laden interface are still not well-known. We synthesized fluorescently labeled microgels and used confocal microscopy to observe their arrangement at the water/oil interface. The microgels aggregated spontaneously at the interface, and the aggregated structure reorganized due to thermal motion. The structure of the interfacial layer formed by microgels depended on the microgel concentration at the interface. We suggest that the structure was controlled by the aggregation and adsorption of microgels at the interface. The interparticle separation between microgels at the interface decreased over time, implying a slow aging process of the microgels at the interface. Magnetic beads were introduced at the interface and used to trigger deformation of the microgel layer. Under compression and shear the microgels in the aggregated structure rearranged, leading to plastic deformation, and some elastic responses were also observed.

In situ grain fracture mechanics during uniaxial compaction of granular solids

NASA Astrophysics Data System (ADS)

Hurley, R. C.; Lind, J.; Pagan, D. C.; Akin, M. C.; Herbold, E. B.

2018-03-01

Grain fracture and crushing are known to influence the macroscopic mechanical behavior of granular materials and be influenced by factors such as grain composition, morphology, and microstructure. In this paper, we investigate grain fracture and crushing by combining synchrotron x-ray computed tomography and three-dimensional x-ray diffraction to study two granular samples undergoing uniaxial compaction. Our measurements provide details of grain kinematics, contacts, average intra-granular stresses, inter-particle forces, and intra-grain crystal and fracture plane orientations. Our analyses elucidate the complex nature of fracture and crushing, showing that: (1) the average stress states of grains prior to fracture vary widely in their relation to global and local trends; (2) fractured grains experience inter-particle forces and stored energies that are statistically higher than intact grains prior to fracture; (3) fracture plane orientations are primarily controlled by average intra-granular stress and contact fabric rather than the orientation of the crystal lattice; (4) the creation of new surfaces during fracture accounts for a very small portion of the energy dissipated during compaction; (5) mixing brittle and ductile grain materials alters the grain-scale fracture response. The results highlight an application of combined x-ray measurements for non-destructive in situ analysis of granular solids and provide details about grain fracture that have important implications for theory and modeling.

The mechanisms for nanoparticle surface diffusion and chain self-assembly determined from real-time nanoscale kinetics in liquid

DOE PAGES

Woehl, Taylor J.; Prozorov, Tanya

2015-08-20

The mechanisms for nanoparticle self-assembly are often inferred from the morphology of the final nanostructures in terms of attractive and repulsive interparticle interactions. Understanding how nanoparticle building blocks are pieced together during self-assembly is a key missing component needed to unlock new strategies and mechanistic understanding of this process. Here we use real-time nanoscale kinetics derived from liquid cell transmission electron microscopy investigation of nanoparticle self-assembly to show that nanoparticle mobility dictates the pathway for self-assembly and final nanostructure morphology. We describe a new method for modulating nanoparticle diffusion in a liquid cell, which we employ to systematically investigate themore » effect of mobility on self-assembly of nanoparticles. We interpret the observed diffusion in terms of electrostatically induced surface diffusion resulting from nanoparticle hopping on the liquid cell window surface. Slow-moving nanoparticles self-assemble predominantly into linear 1D chains by sequential attachment of nanoparticles to existing chains, while highly mobile nanoparticles self-assemble into chains and branched structures by chain–chain attachments. Self-assembly kinetics are consistent with a diffusion-driven mechanism; we attribute the change in self-assembly pathway to the increased self-assembly rate of highly mobile nanoparticles. Furthermore, these results indicate that nanoparticle mobility can dictate the self-assembly mechanism and final nanostructure morphology in a manner similar to interparticle interactions.« less

Plasmonic Library Based on Substrate-Supported Gradiential Plasmonic Arrays

PubMed Central

2014-01-01

We present a versatile approach to produce macroscopic, substrate-supported arrays of plasmonic nanoparticles with well-defined interparticle spacing and a continuous particle size gradient. The arrays thus present a “plasmonic library” of locally noncoupling plasmonic particles of different sizes, which can serve as a platform for future combinatorial screening of size effects. The structures were prepared by substrate assembly of gold-core/poly(N-isopropylacrylamide)-shell particles and subsequent post-modification. Coupling of the localized surface plasmon resonance (LSPR) could be avoided since the polymer shell separates the encapsulated gold cores. To produce a particle array with a broad range of well-defined but laterally distinguishable particle sizes, the substrate was dip-coated in a growth solution, which resulted in an overgrowth of the gold cores controlled by the local exposure time. The kinetics was quantitatively analyzed and found to be diffusion rate controlled, allowing for precise tuning of particle size by adjusting the withdrawal speed. We determined the kinetics of the overgrowth process, investigated the LSPRs along the gradient by UV–vis extinction spectroscopy, and compared the spectroscopic results to the predictions from Mie theory, indicating the absence of local interparticle coupling. We finally discuss potential applications of these substrate-supported plasmonic particle libraries and perspectives toward extending the concept from size to composition variation and screening of plasmonic coupling effects. PMID:25137554

An experimental study of phase transitions in a complex plasma

NASA Astrophysics Data System (ADS)

Smith, Bernard Albert Thomas, II

In semiconductor manufacturing, contamination due to particulates significantly decreases the yield and quality of device fabrication, therefore increasing the cost of production. Dust particle clouds can be found in almost all plasma processing environments including both plasma etching devices and in plasma deposition processes. Dust particles suspended within such plasmas will acquire an electric charge from collisions with free electrons in the plasma. If the ratio of inter-particle potential energy to the average kinetic energy is sufficient, the particles will form either a "liquid" structure with short range ordering or a crystalline structure with long range ordering. Otherwise, the dust particle system will remain in a gaseous state. Many experiments have been conducted over the past decade on such complex plasmas to discover the character of the systems formed, but more work is needed to fully understand these structures. This paper describes the processes involved in setting up the CASPER GEC RF Reference Cell and the modifications necessary to examine complex plasmas. Research conducted to characterize the system is outlined to demonstrate that the CASPER Cell behaves as other GEC Cells. In addition, further research performed shows the behavior of the complex plasma system in the CASPER Cell is similar to complex plasmas studied by other groups in this field. Along the way analysis routines developed specifically for this system are described. New research involving polydisperse dust distributions is carried out in the system once the initial characterization is finished. Next, a system to externally vary the DC bias in the CASPER Cell is developed and characterized. Finally, new research conducted to specifically examine how the complex plasma system reacts to a variable DC bias is reported. Specifically, the response of the interparticle spacing to various system parameters (including the external DC bias) is examined. Also, a previously unreported phenomenon, namely layer splitting, is examined.

Magnetic and structural properties of nanoparticles of nickel oxide

NASA Astrophysics Data System (ADS)

Shim, Hyunja (Jenny)

In this dissertation, magnetic properties of NiO nanoparticles (NP) prepared by the sol-gel method in the size range D = 5 nm to 20 nm, with and without oleic acid (OA) coating, are reported. Transmission electron microscopy (TEM) studies show the morphology of the smaller particles to be primarily rod-like, changing over to nearly spherical shapes for D >10 nm. Average sizes D of NP determined by x-ray diffraction (XRD) are compared with the results from TEM. From the analysis of the XRD line intensities, the particle size dependence of the Debye-Waller factors for Ni and O atoms are derived. It is found that the Debye-Waller factors of nickel and oxygen atoms in smaller particles are larger than those in bulk NiO. For the coated and uncoated NiO nanorods of 5 nm diameter, variations of the magnetization M with temperature T (5 K to 370 K) and temperature variations of the EMR (electron magnetic resonance) spectra were measured to determine the respective blocking temperatures TB(m) and TB(EMR). The following differences are noted: (1) TB(m) is reduced from 230 K (uncoated) to 85 K(coated) for H = 25 Oe; (2) Decrease of TB(m) with H is weaker and the ratio TB(EMR)/T B(m) is smaller for the uncoated particles. These differences are due to stronger interparticle interaction present in the uncoated particles. Temperature variation (5 K-300 K) of the AC magnetic susceptibilities (chi' and chi") at various frequencies f (0.1-10,000 Hz) are reported for the coated and uncoated 5 nm diameter nanorods of NiO. Using the peak in chi' as the blocking temperature TB, it is observed that TB increases with increasing f. The data for the two samples fit the Vogel-Fulcher law: f = f0exp[-Ea/k(TB-T0)] with f 0 = 9.2 x 1011 Hz, Ea/k = 1085 K and T0 = 162 K (0 K) for the uncoated (coated) particles. This shows that T0 provides a good measure of the effects of interparticle interactions on magnetic relaxation and that these interactions are essentially eliminated with the OA coating. For all the particles, measurements of M versus T (5 K-370 K) in the zero-field cooled (ZFC) and field-cooled (FC) modes are used to determine the average blocking temperature TP. For the OA coated particles, TP increases with increase in size D as expected for superparamagnetic particles. However for the uncoated NP, TP decreases initially with increase in size for D < 10 nm; but for D > 10 nm, TP follows the same trend as for the coated NP. These differences are interpreted in terms of significant interparticle interaction. The data of M vs. the applied field H for T > TP are fit to the modified Langevin function: M = M0 L (muPH/kBT) + chiaH, to determine the magnetic moment muP per particle as a function of size D. The variation of muP with size D is interpreted in terms of the fraction of spins on the surface layer of the particles which contribute to mu P. It is observed that this fraction varies as 1/D reaching nearly 100 % for the 5 nm particles. From the temperature dependence of M0 and extrapolating to M0 → 0, the Neel temperatures TN for various sizes are determined. TN for NiO nanoparticles is found to decreases rapidly with decrease in size for D < 10 nm.

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

Filippov, A. V., E-mail: fav@triniti.ru

The interaction of two charged point macroparticles located in Wigner–Seitz cells of simple cubic (SC), body-centered cubic (BCC), or face-centered cubic (FCC) lattices in an equilibrium plasma has been studied within the Debye approximation or, more specifically, based on the linearized Poisson–Boltzmann model. The shape of the outer boundary is shown to exert a strong influence on the pattern of electrostatic interaction between the two macroparticles, which transforms from repulsion at small interparticle distances to attraction as the interparticle distance approaches half the length of the computational cell. The macroparticle pair interaction potential in an equilibrium plasma is shown tomore » be nevertheless the Debye one and purely repulsive for likely charged macroparticles.« less

Theory of interparticle correlations in dense, high-temperature plasmas. V - Electric and thermal conductivities

NASA Technical Reports Server (NTRS)

Ichimaru, S.; Tanaka, S.

1985-01-01

Ichimaru et al. (1985) have developed a general theory in which the interparticle correlations in dense, high-temperature multicomponent plasmas were formulated systematically over a wide range of plasma parameters. The present paper is concerned with an extension of this theory, taking into account the problems of the electronic transport in such high-density plasmas. It is shown that the resulting theory is capable of describing the transport coefficients accurately over a wide range of the density and temperature parameters. Attention is given to electric and thermal conductivities, generalized Coulomb logarithms, a comparison of the considered theory with other theories, and a comparison of the theory with experimental results.

Anomalous temperature-dependent heat transport in one-dimensional momentum-conserving systems with soft-type interparticle interaction

NASA Astrophysics Data System (ADS)

Xiong, Daxing

2017-04-01

We numerically investigate the heat transport problem in a one-dimensional momentum-conserving lattice with a soft-type (ST) anharmonic interparticle interaction. It is found that with the increase of the system's temperature, while the introduction of ST anharmonicity softens phonons and decreases their velocities, this type of nonlinearity like its hard type (HT) counterpart, can still not be able to fully damp the longest wavelength phonons. Therefore, a usual anomalous temperature dependence of heat transport with certain scaling properties similarly to those shown in the Fermi-Pasta-Ulam-β -like systems with HT interactions can be seen. Our detailed examination from simulations verifies this temperature-dependent behavior well.

Combined electron energy-loss and cathodoluminescence spectroscopy on individual and composite plasmonic nanostructures

NASA Astrophysics Data System (ADS)

Coenen, Toon; Schoen, David T.; Brenny, Benjamin J. M.; Polman, Albert; Brongersma, Mark L.

2016-05-01

We systematically investigate the plasmonic "dolmen" geometry and its constituent elements using electron energy-loss spectroscopy and cathodoluminescence spectroscopy. In particular, we study the effects of the particle size and spacing on the resonant behavior and interparticle coupling. Because we apply both techniques on the same structures we can directly compare the results and investigate the radiative versus nonradiative character of the different modes. We find that the cathodoluminescence response is significantly lower than the electron energy-loss response for higher-energy modes because strong absorption reduces the scattering efficiency in this regime. Furthermore, we show that the overall resonant response roughly scales with size as expected for plasmonic structures but that the transverse resonant modes do become more dominant in larger structures due to a relative reduction in Ohmic dissipation. Using EELS and CL we can rigorously study coupling between the elements and show that the coupling diminishes for larger spacings.

Polycatenar Ligand Control of the Synthesis and Self-Assembly of Colloidal Nanocrystals.

PubMed

Diroll, Benjamin T; Jishkariani, Davit; Cargnello, Matteo; Murray, Christopher B; Donnio, Bertrand

2016-08-24

Hydrophobic colloidal nanocrystals are typically synthesized and manipulated with commercially available ligands, and surface functionalization is therefore typically limited to a small number of molecules. Here, we report the use of polycatenar ligands derived from polyalkylbenzoates for the direct synthesis of metallic, chalcogenide, pnictide, and oxide nanocrystals. Polycatenar molecules, branched structures bearing diverging chains in which the terminal substitution pattern, functionality, and binding group can be independently modified, offer a modular platform for the development of ligands with targeted properties. Not only are these ligands used for the direct synthesis of monodisperse nanocrystals, but nanocrystals coated with polycatenar ligands self-assemble into softer bcc superlattices that deviate from conventional harder close-packed structures (fcc or hcp) formed by the same nanocrystals coated with commercial ligands. Self-assembly experiments demonstrate that the molecular structure of polycatenar ligands encodes interparticle spacings and attractions, engineering self-assembly, which is tunable from hard sphere to soft sphere behavior.

Optical analysis of the fine crystalline structure of artificial opal films.

PubMed

Lozano, G; Dorado, L A; Schinca, D; Depine, R A; Míguez, H

2009-11-17

Herein, we present a detailed analysis of the structure of artificial opal films. We demonstrate that, rather than the generally assumed face centered cubic lattice of spheres, opal films are better approximated by rhombohedral assemblies of distorted colloids. Detailed analysis of the optical response in a very wide spectral range (0.4 < or = a/lambda < or = 2, where a is the conventional lattice constant), as well as at perpendicular and off-normal directions, unambiguously shows that the interparticle distance coincides very approximately with the expected diameter only along directions contained in the same close-packed plane but differs significantly in directions oblique to the [111] one. A full description of the real and reciprocal lattices of actual opal films is provided, as well as of the photonic band structure of the proposed arrangement. The implications of this distortion in the optical response of the lattice are discussed.

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

PubMed Central

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

2015-01-01

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

Relating structure and flow of soft colloids

NASA Astrophysics Data System (ADS)

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

2013-11-01

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

Powder fed sheared dispersal particle generator

NASA Technical Reports Server (NTRS)

Morrisette, E. L.; Bushnell, D. M. (Inventor)

1984-01-01

A particle generating system is described which is capable of breaking up agglomerations of particles and producing a cloud of uniform, submicron-sized particles at high pressure and high flow rates. This is achieved by utilizing a tubular structure which has injection microslits on is periphery to accept and disperse the desired particle feed. By suppling a carrying fluid at a pressure, of approximately twice the ambient pressure of the velocimeter's settling chamber, the microslits operate at choked flow conditions. The shearing action of this choked flow is sufficient to overcome interparticle bonding forces, thereby breaking up the agglomerates of the particles feed into individual particles.

Strengthening of ferrous binder jet 3D printed components through bronze infiltration

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

Cordero, Zachary C.; Siddel, Derek H.; Peter, William H.

Fully-dense, net shape objects have been fabricated from a rapidly-solidified ferrous powder using binder-jet 3D printing and molten bronze infiltration. X-ray diffraction, scanning electron microscopy, and differential thermal analysis were used to characterize the structural evolution of the powder feedstock during an infiltration heating cycle. Microindentation and bend tests were performed on the infiltrated material to evaluate its mechanical properties. The infiltrated material had an 11 GPa hardness and moderate damage tolerance. It was found that infiltration improved both the ductility and strength of the sintered preforms by eliminating the stress concentration at the interparticle necks.

Strengthening of ferrous binder jet 3D printed components through bronze infiltration

DOE PAGES

Cordero, Zachary C.; Siddel, Derek H.; Peter, William H.; ...

2017-04-08

Fully-dense, net shape objects have been fabricated from a rapidly-solidified ferrous powder using binder-jet 3D printing and molten bronze infiltration. X-ray diffraction, scanning electron microscopy, and differential thermal analysis were used to characterize the structural evolution of the powder feedstock during an infiltration heating cycle. Microindentation and bend tests were performed on the infiltrated material to evaluate its mechanical properties. The infiltrated material had an 11 GPa hardness and moderate damage tolerance. It was found that infiltration improved both the ductility and strength of the sintered preforms by eliminating the stress concentration at the interparticle necks.

Self-assembly of silica nanoparticles by tuning substrate-adsorbate interaction

NASA Astrophysics Data System (ADS)

Utsav, Khanna, Sakshum; Mukhopadhayay, Indrajit; Banerjee, Rupak

2018-05-01

We report on self-assembled nanodisc formations of silica nanoparticles on a surface modified silicon substrate using modified Langmuir-Schafer deposition technique (stamping). The size, inter-particle separation as well as the packing of the silica nanoparticles within the nanodiscs formed spontaneously can be tuned by the surface pressure applied on the water surface. We obtain self-assembled nanodiscs of silica nanoparticle arranged in a hexagonal symmetry. We also observe that by varying the surface pressure of deposition at the water-molecule-air interface we obtain such 2D disc-shaped structure with varying sizes and a packing ratio of the silica nanoparticle.

Evolution of Plasmonic Metamolecule Modes in the Quantum Tunneling Regime.

PubMed

Scholl, Jonathan A; Garcia-Etxarri, Aitzol; Aguirregabiria, Garikoitz; Esteban, Ruben; Narayan, Tarun C; Koh, Ai Leen; Aizpurua, Javier; Dionne, Jennifer A

2016-01-26

Plasmonic multinanoparticle systems exhibit collective electric and magnetic resonances that are fundamental for the development of state-of-the-art optical nanoantennas, metamaterials, and surface-enhanced spectroscopy substrates. While electric dipolar modes have been investigated in both the classical and quantum realm, little attention has been given to magnetic and other "dark" modes at the smallest dimensions. Here, we study the collective electric, magnetic, and dark modes of colloidally synthesized silver nanosphere trimers with varying interparticle separation using scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). This technique enables direct visualization and spatially selective excitation of individual trimers, as well as manipulation of the interparticle distance into the subnanometer regime with the electron beam. Our experiments reveal that bonding electric and magnetic modes are significantly impacted by quantum effects, exhibiting a relative blueshift and reduced EELS amplitude compared to classical predictions. In contrast, the trimer's electric dark mode is not affected by quantum tunneling for even Ångström-scale interparticle separations. We employ a quantum-corrected model to simulate the effect of electron tunneling in the trimer which shows excellent agreement with experimental results. This understanding of classical and quantum-influenced hybridized modes may impact the development of future quantum plasmonic materials and devices, including Fano-like molecular sensors and quantum metamaterials.

Mechanics of Granular Materials (MGM)

NASA Technical Reports Server (NTRS)

Alshibli, Khalid A.; Costes, Nicholas C.; Porter, Ronald F.

1996-01-01

The constitutive behavior of uncemented granular materials such as strength, stiffness, and localization of deformations are to a large extend derived from interparticle friction transmitted between solid particles and particle groups. Interparticle forces are highly dependent on gravitational body forces. At very low effective confining pressures, the true nature of the Mohr envelope, which defines the Mohr-Coulomb failure criterion for soils, as well as the relative contribution of each of non-frictional components to soil's shear strength cannot be evaluated in terrestrial laboratories. Because of the impossibility of eliminating gravitational body forces on earth, the weight of soil grains develops interparticle compressive stresses which mask true soil constitutive behavior even in the smallest samples of models. Therefore the microgravity environment induced by near-earth orbits of spacecraft provides unique experimental opportunities for testing theories related to the mechanical behavior of terrestrial granular materials. Such materials may include cohesionless soils, industrial powders, crushed coal, etc. This paper will describe the microgravity experiment, 'Mechanics of Granular Materials (MGM)', scheduled to be flown on Space Shuttle-MIR missions. The paper will describe the experiment's hardware, instrumentation, specimen preparation procedures, testing procedures in flight, as well as a brief summary of the post-mission analysis. It is expected that the experimental results will significantly improve the understanding of the behavior of granular materials under very low effective stress levels.

A Radiation Chemistry Code Based on the Greens Functions of the Diffusion Equation

NASA Technical Reports Server (NTRS)

Plante, Ianik; Wu, Honglu

2014-01-01

Ionizing radiation produces several radiolytic species such as.OH, e-aq, and H. when interacting with biological matter. Following their creation, radiolytic species diffuse and chemically react with biological molecules such as DNA. Despite years of research, many questions on the DNA damage by ionizing radiation remains, notably on the indirect effect, i.e. the damage resulting from the reactions of the radiolytic species with DNA. To simulate DNA damage by ionizing radiation, we are developing a step-by-step radiation chemistry code that is based on the Green's functions of the diffusion equation (GFDE), which is able to follow the trajectories of all particles and their reactions with time. In the recent years, simulations based on the GFDE have been used extensively in biochemistry, notably to simulate biochemical networks in time and space and are often used as the "gold standard" to validate diffusion-reaction theories. The exact GFDE for partially diffusion-controlled reactions is difficult to use because of its complex form. Therefore, the radial Green's function, which is much simpler, is often used. Hence, much effort has been devoted to the sampling of the radial Green's functions, for which we have developed a sampling algorithm This algorithm only yields the inter-particle distance vector length after a time step; the sampling of the deviation angle of the inter-particle vector is not taken into consideration. In this work, we show that the radial distribution is predicted by the exact radial Green's function. We also use a technique developed by Clifford et al. to generate the inter-particle vector deviation angles, knowing the inter-particle vector length before and after a time step. The results are compared with those predicted by the exact GFDE and by the analytical angular functions for free diffusion. This first step in the creation of the radiation chemistry code should help the understanding of the contribution of the indirect effect in the formation of DNA damage and double-strand breaks.

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

Raghuwanshi, Vikram Singh; Garusinghe, Uthpala Manavi; Ilavsky, Jan

Controlling nanoparticles (NPs) aggregation in cellulose/NPs composites allows to optimise NPs driven properties and their applications. Polyelectrolytes are used to control NPs aggregation and their retention within the fibrous matrix. Here in this study, we aim at evaluating how a polyelectrolyte (Cationic Polyacrylamide; CPAM, molecular weight: 13 MDa, charge: 50%, Radius of gyration: 30–36 nm) adsorbs and re-conforms onto the surface of silica(SiO 2) NPs differing in diameter (8, 22 and 74 nm) and to investigate the respective NPs aggregation in cellulose matrices. SEM shows the local area distribution of NPs in composites. Ultra-SAXS (USAXS) allows to evaluate the averagemore » NPs size distribution and the inter-particle interactions at length scale ranging from 1 to 1000 nm. USAXS data analysis reveals that CPAM covers multiple NPs of the smaller diameter (8 nm), presumably with a single chain to form large size NPs aggregates. As the NPs diameter is increased to 22 nm, CPAM re-conforms over NP surface forming a large shell of thickness 5.5 nm. For the composites with NPs of diameter 74 nm, the CPAM chain re-conforms further onto NP surface and the surrounding shell thickness decreases to 2.2 nm. Lastly, structure factor analysis reveals higher structural ordering for NPs as increases their diameter, which is caused by different conformations adopted by CPAM onto NPs surface.« less

Effect of nanoparticles size and polyelectrolyte on nanoparticles aggregation in a cellulose fibrous matrix

DOE PAGES

Raghuwanshi, Vikram Singh; Garusinghe, Uthpala Manavi; Ilavsky, Jan; ...

2017-09-18

Controlling nanoparticles (NPs) aggregation in cellulose/NPs composites allows to optimise NPs driven properties and their applications. Polyelectrolytes are used to control NPs aggregation and their retention within the fibrous matrix. Here in this study, we aim at evaluating how a polyelectrolyte (Cationic Polyacrylamide; CPAM, molecular weight: 13 MDa, charge: 50%, Radius of gyration: 30–36 nm) adsorbs and re-conforms onto the surface of silica(SiO 2) NPs differing in diameter (8, 22 and 74 nm) and to investigate the respective NPs aggregation in cellulose matrices. SEM shows the local area distribution of NPs in composites. Ultra-SAXS (USAXS) allows to evaluate the averagemore » NPs size distribution and the inter-particle interactions at length scale ranging from 1 to 1000 nm. USAXS data analysis reveals that CPAM covers multiple NPs of the smaller diameter (8 nm), presumably with a single chain to form large size NPs aggregates. As the NPs diameter is increased to 22 nm, CPAM re-conforms over NP surface forming a large shell of thickness 5.5 nm. For the composites with NPs of diameter 74 nm, the CPAM chain re-conforms further onto NP surface and the surrounding shell thickness decreases to 2.2 nm. Lastly, structure factor analysis reveals higher structural ordering for NPs as increases their diameter, which is caused by different conformations adopted by CPAM onto NPs surface.« less

Analysis and Modeling of Structure Formation in Granular and Fluid-Solid Flows

NASA Astrophysics Data System (ADS)

Murphy, Eric

Granular and multiphase flows are encountered in a number of industrial processes with particular emphasis in this manuscript given to the particular applications in cement pumping, pneumatic conveying, fluid catalytic cracking, CO2 capture, and fast pyrolysis of bio-materials. These processes are often modeled using averaged equations that may be simulated using computational fluid dynamics. Closure models are then required that describe the average forces that arise from both interparticle interactions, e.g. shear stress, and interphase interactions, such as mean drag. One of the biggest hurdles to this approach is the emergence of non-trivial spatio-temporal structures in the particulate phase, which can significantly modify the qualitative behavior of these forces and the resultant flow phenomenology. For example, the formation of large clusters in cohesive granular flows is responsible for a transition from solid-like to fluid-like rheology. Another example is found in gas-solid systems, where clustering at small scales is observed to significantly lower in the observed drag. Moreover, there remains the possibility that structure formation may occur at all scales, leading to a lack of scale separation required for traditional averaging approaches. In this context, several modeling problems are treated 1) first-principles based modeling of the rheology of cement slurries, 2) modeling the mean solid-solid drag experienced by polydisperse particles undergoing segregation, and 3) modeling clustering in homogeneous gas-solid flows. The first and third components are described in greater detail. In the study on the rheology of cements, several sub-problems are introduced, which systematically increase in the number and complexity of interparticle interactions. These interparticle interactions include inelasticity, friction, cohesion, and fluid interactions. In the first study, the interactions between cohesive inelastic particles was fully characterized for the first time. Next, kinetic theory was used to predict the cooling of a gas of such particles. DEM was then used to validate this approach. A study on the rheology of dry cohesive granules with and without friction was then carried out, where the physics of different flow phenomenology was exhaustively explored. Lastly, homogeneous cement slurry simulations were carried out, and compared with vane-rheometer experiments. Qualitative agreement between simulation and experiment were observed. Lastly, the physics of clustering in homogeneous gas-solid flows is explored in the hopes of gaining a mechanistic explanation of how particle-fluid interactions lead to clustering. Exact equations are derived, detailing the evolution of the two particle density, which may be closed using high-fidelity particle-resolved direct numerical simulation. Two canonical gas-solid flows are then addressed, the homogeneously cooling gas-solid flow (HCGSF) and sedimenting gas-solid flow (SGSF). A mechanism responsible for clustering in the HCGSF is identified. Clustering of plane-wave like structures is observed in the SGSF, and the exact terms are quantified. A method for modeling the dynamics of clustering in these systems is proposed, which may aid in the prediction of clustering and other correlation length-scales useful for less expensive computations.

Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

NASA Astrophysics Data System (ADS)

Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail; O'Keeffe, Michael

2014-12-01

We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

Real-space mapping of the strongly coupled plasmons of nanoparticle dimers.

PubMed

Kim, Deok-Soo; Heo, Jinhwa; Ahn, Sung-Hyun; Han, Sang Woo; Yun, Wan Soo; Kim, Zee Hwan

2009-10-01

We carried out the near-field optical imaging of isolated and dimerized gold nanocubes to directly investigate the strong coupling between two adjacent nanoparticles. The high-resolution (approximately 10 nm) local field maps (intensities and phases) of self-assembled nanocube dimers reveal antisymmetric plasmon modes that are starkly different from a simple superposition of two monomeric dipole plasmons, which is fully reproduced by the electrodynamics simulations. The result decisively proves that, for the closely spaced pair of nanoparticles (interparticle distance/particle size approximately 0.04), the strong Coulombic attraction between the charges at the interparticle gap dominates over the intraparticle charge oscillations, resulting in a hybridized dimer plasmon mode that is qualitatively different from those expected from a simple dipole-dipole coupling model.

Determining the interparticle force laws in amorphous solids from a visual image.

PubMed

Gendelman, Oleg; Pollack, Yoav G; Procaccia, Itamar

2016-06-01

We consider the problem of how to determine the force laws in an amorphous system of interacting particles. Given the positions of the centers of mass of the constituent particles we propose an algorithm to determine the interparticle force laws. Having n different types of constituents we determine the coefficients in the Laurent polynomials for the n(n+1)/2 possibly different force laws. A visual providing the particle positions in addition to a measurement of the pressure is all that is required. The algorithm proposed includes a part that can correct for experimental errors in the positions of the particles. Such a correction of unavoidable measurement errors is expected to benefit many experiments in the field.

Investigation of colloidal PbS quantum dot-based solar cells with near infrared emission.

PubMed

Lim, Sungoh; Kim, Yohan; Lee, Jeongno; Han, Chul Jong; Kang, Jungwon; Kim, Jiwan

2014-12-01

Colloidal quantum dots (QD)-based solar cells with near infrared (NIR) emission have been investigated. Lead sulfide (PbS) QDs, which have narrow band-gap and maximize the absorption of NIR spectrum, were chosen as active materials for efficient solar cells. The inverted structure of indium tin oxide/titanium dioxide/PbS QDs/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)/silver (ITO/TiO2/PbS QDs/ PSS/Ag) was applied for favorable electron and hole seperation from the PbS QD. Through the ligand exchange by 1,2-Ethanedithiol (EDT), the interparticle distance of the PbS QDs in thin film became closer and the performance of the PbS QD-based solar cells was improved. Our PbS QD-based inverted solar cells showed open circuit voltages (V(oc)) of 0.33 V, short circuit current density (J(sc)) of 10.89 mA/cm2, fill factor (FF) of 30%, and power conversion efficiency (PCE) of 1.11%. In our PbS QD-based multifunctional solar cell, the NIR light emission intensity was simply detected with photodiode system, which implies the potential of multi-functional diode device for various applications.

In-situ USAXS/SAXS Investigation of Tunable Structural Color in Amorphous Photonic Crystals During Electrophoretic Deposition

NASA Astrophysics Data System (ADS)

Bukosky, Scott; Hammons, Joshua; Han, Jinkyu; Freyman, Megan; Lee, Elaine; Cook, Caitlyn; Kuntz, Joshua; Worsley, Marcus; Han, Thomas Yong; Ristenpart, William; Pascall, Andrew

2017-11-01

Amorphous photonic crystals (APCs) formed via electrophoretic deposition (EPD) exhibit non-iridescent, angle-independent, structural colors believed to arise from changes in the particle-particle interactions and inter-particle spacing, representing a potential new paradigm for display technologies. However, particle dynamics on nanometer length scales that govern the displayed color, crystallinity, and other characteristics of the photonic structures, are not well understood. In this work, in-situ USAXS/SAXS studies of three-dimensional colloidal particle arrays were performed in order to identify their structural response to applied external electric fields. These results were compared to simultaneously acquired UV-Vis spectra to tie the overall electrically induced structure of the APCs directly to the observed changes in visible color. The structural evolution of the APCs provides new information regarding the correlation between nano-scale particle-particle interactions and the corresponding optical response. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-ABS-736068.

Models for the Immediate Environment of Ions in Aqueous Solutions of Neodymium Chloride

NASA Astrophysics Data System (ADS)

Smirnov, P. R.; Grechin, O. V.

2018-01-01

Radial distribution functions of neodymium chloride aqueous solutions in a wide range of concentrations under ambient conditions are calculated from experimental data obtained earlier via X-ray diffraction analysis. Different models of the structural organization of the system are developed. The optimum versions are determined by calculating theoretical functions for each model and comparing their fit to the experimental functions. Such quantitative characteristics of the immediate environment of Nd3+ and Cl- ions as coordination numbers, interparticle distances, and varieties of ion pairs are determined. It is shown that the average number of water molecules in the first coordination sphere of the cation falls from 9 to 6.2 as the concentration rises. The structure of the systems over the whole range of concentrations is determined by ion associates of the noncontact type.

Devolatilization Studies of Oil Palm Biomass for Torrefaction Process through Scanning Electron Microscopy

NASA Astrophysics Data System (ADS)

Daud, D.; Abd. Rahman, A.; Shamsuddin, A. H.

2016-03-01

In this work, palm oil biomass consisting of empty fruit bunch (EFB), mesocarp fibre and palm kernel shell (PKS) were chosen as raw material for torrefaction process. Torrefaction process was conducted at various temperatures of 240 °C, 270 °C and 300 °C with a residence time of 60 minutes. The morphology of the raw and torrefied biomass was then observed through Scanning Electron Microscopy (SEM) images. Also, through this experiment the correlation between the torrefaction temperatures with the volatile gases released were studied. From the observation, the morphology structure of the biomass exhibited inter-particle gaps due to the release of volatile gases and it is obviously seen more at higher temperatures. Moreover, the change of the biomass structure is influenced by the alteration of the lignocellulose biomass.

Flow Function of Pharmaceutical Powders Is Predominantly Governed by Cohesion, Not by Friction Coefficients.

PubMed

Leung, Lap Yin; Mao, Chen; Srivastava, Ishan; Du, Ping; Yang, Chia-Yi

2017-07-01

The purpose of this study was to demonstrate that the flow function (FFc) of pharmaceutical powders, as measured by rotational shear cell, is predominantly governed by cohesion but not friction coefficients. Driven by an earlier report showing an inverse correlation between FFc and the cohesion divided by the corresponding pre-consolidation stress (Wang et al. 2016. Powder Tech. 294:105-112), we performed analysis on a large data set containing 1130 measurements from a ring shear tester and identified a near-perfect inverse correlation between the FFc and cohesion. Conversely, no correlation was found between FFc and friction angles. We also conducted theoretical analysis and estimated such correlations based on Mohr-Coulomb failure model. We discovered that the correlation between FFc and cohesion can sustain as long as the angle of internal friction at incipient flow is not significantly larger than the angle of internal friction at steady-state flow, a condition covering almost all pharmaceutical powders. The outcome of this study bears significance in pharmaceutical development. Because the cohesion value is strongly influenced by the interparticle cohesive forces, this study effectively shows that it is more efficient to improve the pharmaceutical powder flow by lowering the interparticle cohesive forces than by lowering the interparticle frictions. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Colorimetric monitoring of nanometer distance changes in DNA-templated plasmon rulers (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lermusiaux, Laurent; Bidault, Sebastien

2016-03-01

The nanometer-scale sensitivity of plasmon coupling allows the translation of minute morphological changes in nanostructures into macroscopic optical signals. In particular, single nanostructure scattering spectroscopy provides a direct estimation of interparticle distances in gold nanoparticle (AuNP) dimers linked by a short DNA double-strand [M. P. Busson et al, Nano Lett. 11, 5060 (2011)]. We demonstrate here that this spectroscopic information can be inferred from simple widefield measurements on a calibrated color camera [L. Lermusiaux et al, ACS Nano 9, 978 (2015)]. This allows us to analyze the influence of electrostatic and steric interparticle interactions on the morphology of DNA-templated AuNP groupings. Furthermore, polarization-resolved measurements on a color CCD provide a parallel imaging of AuNP dimer orientations. We apply this spectroscopic characterization to identify dimers featuring two different conformations of the same DNA template. In practice, the biomolecular scaffold contains a hairpin-loop that opens after hybridization to a specific DNA sequence and increases the interparticle distance [L. Lermusiaux et al, ACS Nano 6, 10992 (2012)]. These results open exciting perspectives for the parallel sensing of single specific DNA strands using plasmon rulers. We discuss the limits of this approach in terms of the physicochemical stability and reactivity of these nanostructures and demonstrate the importance of engineering the AuNP surface chemistry, in particular using amphiphilic ligands [L. Lermusiaux and S. Bidault, Small (2015), in press].

Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes

PubMed Central

Paulo Coelho, Joao; Osío Barcina, José; Aicart, Emilio; Tardajos, Gloria; Cruz-Gil, Pablo; Salgado, Cástor; Díaz-Núñez, Pablo

2018-01-01

Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays. PMID:29547539

Pressure and compressibility factor of bidisperse magnetic fluids

NASA Astrophysics Data System (ADS)

Minina, Elena S.; Blaak, Ronald; Kantorovich, Sofia S.

2018-04-01

In this work, we investigate the pressure and compressibility factors of bidisperse magnetic fluids with relatively weak dipolar interactions and different granulometric compositions. In order to study these properties, we employ the method of diagram expansion, taking into account two possible scenarios: (1) dipolar particles repel each other as hard spheres; (2) the polymer shell on the surface of the particles is modelled through a soft-sphere approximation. The theoretical predictions of the pressure and compressibility factors of bidisperse ferrofluids at different granulometric compositions are supported by data obtained by means of molecular dynamics computer simulations, which we also carried out for these systems. Both theory and simulations reveal that the pressure and compressibility factors decrease with growing dipolar correlations in the system, namely with an increasing fraction of large particles. We also demonstrate that even if dipolar interactions are too weak for any self-assembly to take place, the interparticle correlations lead to a qualitative change in the behaviour of the compressibility factors when compared to that of non-dipolar spheres, making the dependence monotonic.

Computer simulation of liquid metals

NASA Astrophysics Data System (ADS)

Belashchenko, D. K.

2013-12-01

Methods for and the results of the computer simulation of liquid metals are reviewed. Two basic methods, classical molecular dynamics with known interparticle potentials and the ab initio method, are considered. Most attention is given to the simulated results obtained using the embedded atom model (EAM). The thermodynamic, structural, and diffusion properties of liquid metal models under normal and extreme (shock) pressure conditions are considered. Liquid-metal simulated results for the Groups I - IV elements, a number of transition metals, and some binary systems (Fe - C, Fe - S) are examined. Possibilities for the simulation to account for the thermal contribution of delocalized electrons to energy and pressure are considered. Solidification features of supercooled metals are also discussed.

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

Rabin, S.A.; Lotts, A.L.; Hammond, J.P.

Uranium --molybdenum alloy rods containing from 10 to 15 wt% Mo and 1/16- in. in diameter were successfully fabricated by hot rotary swaging, followed by machining to remove the protective sheathing (Inconel with molybdenum barrier). Structurally strong rods with densities greater than 95% of theoretical were produced from both calciumreduced uranium mixed with hydrogen-reduced molybdenum and acid-cleaned, prealloyed shot when reduced in area about 55% at 1050 or 1100 deg C. Alloy homogeneity was good with prealloyed powders; however, traces of molybdenum -rich, gamma phase persisted in the elemental uranium -molybdenum material after swaging at 1100 deg C. Swagings embodyingmore » hydride uranium or oxide- contaminated prealloyed shot were unsatisfactory because of insufficient consolidation or poor interparticle bonding. (auth)« less

Universal linear and nonlinear electrodynamics of a Dirac fluid

NASA Astrophysics Data System (ADS)

Sun, Zhiyuan; Basov, Dmitry N.; Fogler, Michael M.

2018-03-01

A general relation is derived between the linear and second-order nonlinear ac conductivities of an electron system in the hydrodynamic regime of frequencies below the interparticle scattering rate. The magnitude and tensorial structure of the hydrodynamic nonlinear conductivity are shown to differ from their counterparts in the more familiar kinetic regime of higher frequencies. Due to universality of the hydrodynamic equations, the obtained formulas are valid for systems with an arbitrary Dirac-like dispersion, ranging from solid-state electron gases to free-space plasmas, either massive or massless, at any temperature, chemical potential, or space dimension. Predictions for photon drag and second-harmonic generation in graphene are presented as one application of this theory.

Electrostatic interaction between dissimilar colloids at fluid interfaces

NASA Astrophysics Data System (ADS)

Majee, Arghya; Schmetzer, Timo; Bier, Markus

2018-04-01

The electrostatic interaction between two nonidentical, moderately charged colloids situated in close proximity of each other at a fluid interface is studied. By resorting to a well-justified model system, this problem is analytically solved within the framework of linearized Poisson-Boltzmann density functional theory. The resulting interaction comprises a surface and a line part, both of which, as functions of the interparticle separation, show a rich behavior including monotonic as well as nonmonotonic variations. In almost all cases, these variations cannot be captured correctly by using the superposition approximation. Moreover, expressions for the surface tensions, the line tensions and the fluid-fluid interfacial tension, which are all independent of the interparticle separation, are obtained. Our results are expected to be particularly useful for emulsions stabilized by oppositely charged particles.

[Roles of additives and surface control in slurry atomization

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

Tsai, S.C.

1992-06-01

As reported in the quarterly report of March of 1992, the relative viscosity of a Newtonian Coal Water Slurry (CWS) in the presence of an anionic polymeric dispersant is an order of magnitude higher than the prediction of the well established Krieger-Dougherty Equation which describes the relative viscosity of a non-aggregated Newtonian suspension as a function of particle volume fraction. Note that the anionic dispersant is used in such a quantity that the resulting interparticle electrostatic repulsion counter-balances the interparticle van der Waals attraction. Investigation continues to determine the mechanisms of such excess energy dissipation under shear. New experimental resultsmore » are presented in this report to verify the role of the anionic polymeric dispersant in such excess energy dissipation of CWS.« less

[Roles of additives and surface control in slurry atomization]. Quarterly report

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

Tsai, S.C.

1992-06-01

As reported in the quarterly report of March of 1992, the relative viscosity of a Newtonian Coal Water Slurry (CWS) in the presence of an anionic polymeric dispersant is an order of magnitude higher than the prediction of the well established Krieger-Dougherty Equation which describes the relative viscosity of a non-aggregated Newtonian suspension as a function of particle volume fraction. Note that the anionic dispersant is used in such a quantity that the resulting interparticle electrostatic repulsion counter-balances the interparticle van der Waals attraction. Investigation continues to determine the mechanisms of such excess energy dissipation under shear. New experimental resultsmore » are presented in this report to verify the role of the anionic polymeric dispersant in such excess energy dissipation of CWS.« less

Selective Laser Sintering of Nano Al2O3 Infused Polyamide

PubMed Central

Warnakula, Anthony; Singamneni, Sarat

2017-01-01

Nano Al2O3 polyamide composites are evaluated for processing by selective laser sintering. A thermal characterization of the polymer composite powders allowed us to establish the possible initial settings. Initial experiments are conducted to identify the most suitable combinations of process parameters. Based on the results of the initial trials, more promising ranges of different process parameters could be identified. The post sintering characterization showed evidence of sufficient inter-particle sintering and intra-layer coalescence. While the inter-particle coalescence gradually improved, the porosity levels slightly decreased with increasing laser power. The nano-filler particles tend to agglomerate around the beads along the solid tracks, possibly due to Van der Walls forces. The tensile stress results showed an almost linear increase with increasing nano-filler content. PMID:28773220

Theory of the classical electron gas

NASA Technical Reports Server (NTRS)

Guernsey, R. L.

1978-01-01

In a previous paper Cohen and Murphy (1969) used the Meeron resummation (1958) of the Mayer diagrams (1950) to calculate the pair correlation for the classical electron gas in thermal equilibrium. They found that successive terms in the expression for the pair correlation were more and more singular for small interparticle spacing, actually dominating the Debye-Hueckel result for sufficiently small distances. This led to apparent divergence in the higher order contributions to the internal energy. The present paper shows that the apparent anomalies in the Cohen-Murphy results can be removed without further resummation by a more careful treatment of the region of small interparticle spacing. It is shown that there is really no anomalous behavior at short range in any order and all integrals in the expression for the internal energy converge.

Influence of the flip-flop interaction on a single plasmon transport in 1D waveguide

NASA Astrophysics Data System (ADS)

Ko, Myong-Chol; Kim, Nam-Chol; Ho, Nam-Chol; Ryom, Ju-Song; Hao, Zhong-Hua; Li, Jian-Bo; Wang, Qu-Quan

2017-12-01

Transport of a single plasmon in the 1D waveguide coupled to two emitters with the flip-flop interaction is discussed theoretically via the real-space approach. We showed that the transmission and reflection of a single plasmon could be changeable by adjusting the flip-flop coupling strength of the QDs, the interaction of QDs with the metallic nanowaveguide, interparticle distance of the QDs and detuning. Setting the interparticle distances properly results in the switching between the complete transmission and the complete reflection. Especially, our results show that the QDs with the flip-flop interaction play important role in the transport of the propagating single plasmon, which is relevant to the Förster resonance energy transfer from donor QD to acceptor QD.

Resistance to densification, tensile strength and capsule-filling performance of some pharmaceutical diluents.

PubMed

Nikolakakis, I; Aragon, O B; Malamataris, S

1998-07-01

The purpose of this study was to compare some indicators of capsule-filling performance, as measured by tapped density under different conditions, and elucidate possible quantitative relationships between variation of capsule fill-weight (%CV) and gravitational and inter-particle forces (attractive or frictional) derived from measurements of particle size, true density, low compression and tensile strength. Five common pharmaceutical diluents (lactose, maize starch, talc, Emcocel and Avicel) were investigated and two capsule-filling methods (pouring powder and dosator nozzle) were employed. It was found that for the pouring-type method the appropriateness of Hausner's ratio (HR), Carr's compressibility index (CC%) and Kawakita's constant (alpha) as indicators of capsule fill-weight variation decreases in the order alpha > CC% > HR; the appropriateness of these indicators also decreases with increasing cylinder size and with impact velocity during tapping. For the dosator-type method the appropriateness of the indicators decreases in the order HR > CC% > alpha, the opposite of that for the pouring-type method; the appropriateness of the indicators increases with decreasing cylinder size and impact velocity. The relationship between %CV and the ratio of inter-particle attractive to gravitational forces calculated from measurements of particle size and true density (Fvdw/Wp) was more significant for the pouring-type capsule-filling method. For the dosator-type method a significant relationship (1% level) was found between %CV and the product of Fvdw/Wp and a function expressing the increase, with packing density (p(f)), in the ratio of frictional to attractive inter-particle forces derived from compression (P) and tensile-strength (T) testing, d(log(P/T))/d(p(f)). The value of tapped density in predictions of capsule-filling performance is affected by the testing conditions in a manner depending on the filling method applied. For the pouring-type method predictions can be based on the ratio of attractive (inter-particle) to gravitational forces, whereas for the dosator-type method the contribution of frictional and attractive forces should, because of packing density change, also be taken into account.

Structure-property relationships in oxide-dispersed iron-beryllia alloys

NASA Technical Reports Server (NTRS)

Wolf, S.; Grant, N. J.

1977-01-01

Two BeO dispersed iron alloys containing about 2.5 and 5.5 v/o dispersoid were produced by attritting, internally oxidizing, and extruding dilute, prealloyed Fe-Be powders. As-extruded alloys were given various thermomechanical treatments involving room temperature swaging and annealing above and below the allotropic transformation temperature. The elevated temperature rupture strengths were measured and correlated with changes in structure; strengthening trends were examined in the light of proposed models for such strengthening. The results obtained showed that the elevated temperature strength was determined by the oxide interparticle spacing (IPS) in recrystallized material and IPS as well as prior deformation in swaged specimens. In fact, a parametric correlation was found between rupture strength values in the longitudinal direction with prestrain during swaging. The overall pattern in strength and microstructural observations were more consistent with a strength-stored energy (substructure) dependence than a strength-grain shape (grain aspect ratio) relation.

Assembly of LiMnPO4 Nanoplates into Microclusters as a High-Performance Cathode in Lithium-Ion Batteries.

PubMed

Wang, Chao; Li, Shiheng; Han, Yuyao; Lu, Zhenda

2017-08-23

A novel structure of a carbon-coated LiMnPO 4 microcluster through emulsion-based self-assembly has been fabricated to yield a high-performance battery cathode. In this rational design, nanosized LiMnPO 4 plates are assembled into microclusters to achieve a dense packing and robust interparticle contact. In addition, the conductive carbon framework wrapping around these clusters functions as a fast electron highway, ensuring the high utilization of the active materials. The designed structure demonstrates enhanced specific capacity and cycling stability in lithium-ion batteries, delivering a discharge capacity of 120 mAh g -1 after 200 cycles at 0.2 C. It also shows a superior rate capability with discharge capacities of 139.7 mAh g -1 at 0.05 C, 131.7 mAh g -1 at 0.1 C, and 99.2 mAh g -1 at 1 C at room temperature.

Preparation of resveratrol-loaded nanoporous silica materials with different structures

NASA Astrophysics Data System (ADS)

Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

2014-11-01

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound.

Resolved simulations of a granular-fluid flow through a check dam with a SPH-DCDEM model

NASA Astrophysics Data System (ADS)

Birjukovs Canelas, Ricardo; Domínguez, Jose; Crespo, Alejandro; Gómez-Gesteira, Moncho; Ferreira, Rui M. L.

2017-04-01

Debris flows represent some of the most relevant phenomena in geomorphological events. Due to the potential destructiveness of such flows, they are the target of a vast amount of research. Experimental research in laboratory facilities or in the field is fundamental to characterize the fundamental rheological properties of these flows and to provide insights on its structure. However, characterizing interparticle contacts and the structure of the motion of the granular phase is difficult, even in controlled laboratory conditions, and possible only for simple geometries. This work addresses the need for a numerical simulation tool applicable to granular-fluid mixtures featuring high spatial and temporal resolution, thus capable of resolving the motion of individual particles, including all interparticle contacts and susceptible to complement laboratory research. The DualSPHysics meshless numerical implementation based on Smoothed Particle Hydrodynamics (SPH) is expanded with a Distributed Contact Discrete Element Method (DCDEM) in order to explicitly solve the fluid and the solid phase. The specific objective is to test the SPH-DCDEM approach by comparing its results with experimental data. An experimental set-up for stony debris flows in a slit check dam is reproduced numerically, where solid material is introduced through a hopper assuring a constant solid discharge for the considered time interval. With each sediment particle possibly undergoing several simultaneous contacts, thousands of time-evolving interactions are efficiently treated due to the model's algorithmic structure and the HPC implementation of DualSPHysics. The results, comprising mainly of retention curves, are in good agreement with the measurements, correctly reproducing the changes in efficiency with slit spacing and density. The encouraging results, coupled with the prospect of so far unique insights into the internal dynamics of a debris flow show the potential of high-performance resolved approaches to the description of the flow and the study of its mitigation strategies. This research as partially supported by Portuguese and European funds, within programs COMPETE2020 and PORL-FEDER, through project PTDC/ECM-HID/6387/2014 granted by the National Foundation for Science and Technology (FCT).

Controlling dynamic SERS hot spots on a monolayer film of Fe3O4@Au nanoparticles by a magnetic field.

PubMed

Guo, Qing-Hua; Zhang, Chen-Jie; Wei, Chao; Xu, Min-Min; Yuan, Ya-Xian; Gu, Ren-Ao; Yao, Jian-Lin

2016-01-05

A large surface-enhanced Raman scattering (SERS) effect is critically dependent on the gap distance of adjacent nanostructures, i.e., "hot spots". However, the fabrication of dynamically controllable hot spots still remains a remarkable challenge. In the present study, we employed an external magnetic field to dynamically control the interparticle spacing of a two-dimensional monolayer film of Fe3O4@Au nanoparticles at a hexane/water interface. SERS measurements were performed to monitor the expansion and shrinkage of the nanoparticles gaps, which produced an obvious effect on SERS activities. The balance between the electrostatic repulsive force, surface tension, and magnetic attractive force allowed observation of the magnetic-field-responsive SERS effect. Upon introduction of an external magnetic field, a very weak SERS signal appeared initially, indicating weak enhancement due to a monolayer film with large interparticle spacing. The SERS intensity reached maximum after 5s and thereafter remained almost unchanged. The results indicated that the observed variations in SERS intensities were fully reversible after removal of the external magnetic field. The reduction of interparticle spacing in response to a magnetic field resulted in about one order of magnitude of SERS enhancement. The combined use of the monolayer film and external magnetic field could be developed as a strategy to construct hot spots both for practical application of SERS and theoretical simulation of enhancement mechanisms. Copyright © 2015 Elsevier B.V. All rights reserved.

Plasmon-mediated binding forces on gold or silver homodimer and heterodimer

NASA Astrophysics Data System (ADS)

Liaw, Jiunn-Woei; Kuo, Ting-Yu; Kuo, Mao-Kuen

2016-02-01

This study theoretically investigates plasmon-mediated optical binding forces, which are exerted on metal homo or heterodimers, induced by the normal illumination of a linearly polarized plane wave or Gaussian beam. Using the multiple multipole method, we analyzed the optical force in terms of Maxwell's stress tensor for various interparticle distance at some specific wavelengths. Numerical results show that for a given wavelength there are several stable equilibrium distances between two nanoparticles (NPs) of a homodimer, which are slightly shorter than some integer multiples of the wavelength in medium, such that metal dimer acts as bonded together. At these specific interparticle distances, the optical force between dimer is null and serves a restoring force, which is repulsive and attractive, respectively, as the two NPs are moving closer to and away from each other. The spring constant of the restoring force at the first stable equilibrium is always the largest, indicating that the first stable equilibrium distance is the most stable one. Moreover, the central line (orientation) of a dimer tends to be perpendicular to the polarization of light. For the cases of heterodimers, the phenomenon of stable equilibrium interparticle distance still exists, except there is an extra net photophoretic force drifting the heterodimer as one. Moreover, gradient force provided by a Gaussian beam may reduce the stability of these equilibriums, so larger NPs are preferred to stabilize a dimer under illumination of Gaussian beam. The finding may pave the way for using optical manipulation on the gold or silver colloidal self-assembly.

Plasmon response evaluation based on image-derived arbitrary nanostructures.

PubMed

Trautmann, S; Richard-Lacroix, M; Dathe, A; Schneidewind, H; Dellith, J; Fritzsche, W; Deckert, V

2018-05-31

The optical response of realistic 3D plasmonic substrates composed of randomly shaped particles of different size and interparticle distance distributions in addition to nanometer scale surface roughness is intrinsically challenging to simulate due to computational limitations. Here, we present a Finite Element Method (FEM)-based methodology that bridges in-depth theoretical investigations and experimental optical response of plasmonic substrates composed of such silver nanoparticles. Parametrized scanning electron microscopy (SEM) images of surface enhanced Raman spectroscopy (SERS) active substrate and tip-enhanced Raman spectroscopy (TERS) probes are used to simulate the far-and near-field optical response. Far-field calculations are consistent with experimental dark field spectra and charge distribution images reveal for the first time in arbitrary structures the contributions of interparticle hybridized modes such as sub-radiant and super-radiant modes that also locally organize as basic units for Fano resonances. Near-field simulations expose the spatial position-dependent impact of hybridization on field enhancement. Simulations of representative sections of TERS tips are shown to exhibit the same unexpected coupling modes. Near-field simulations suggest that these modes can contribute up to 50% of the amplitude of the plasmon resonance at the tip apex but, interestingly, have a small effect on its frequency in the visible range. The band position is shown to be extremely sensitive to particle nanoscale roughness, highlighting the necessity to preserve detailed information at both the largest and the smallest scales. To the best of our knowledge, no currently available method enables reaching such a detailed description of large scale realistic 3D plasmonic systems.

Thickness Dependence of Magnetic Blocking in Granular Metallic Thin Films

NASA Astrophysics Data System (ADS)

Wang, J.-Q.; Zhao, Z.-D.; Whittenburg, S. L.

2002-03-01

Inter-particle interaction among single domain nano-size magnetic particles embedded in nonmagnetic matrix was studied. Attention was paid to concentrated Cu-Co granular thin films with a fixed magnetic volume fraction. By analyzing theoretical models and comparing with experimental results, we studied a dimensional constraint on the magnetic properties and found that as the film thickness reduces toward thin limit the inter-particle interaction plays important roles in modifying magnetic behavior. Experimental evidence showed that the peak temperature of the susceptibility for Cu80Co20 granular thin films strongly depends on the film thickness in the range of 0 120 nm (1). It was also observed that the spontaneous magnetization of the Co phase varies with the thickness though particle size remains constant. We calculated the dipolar interaction energy among magnetic particles including far-neighbor interaction for films with different thickness values. The calculation revealed that the interaction energy varies across the film from edge to edge and the average interaction energy is strongly dependent on film thickness. Good quantitative agreement of the calculated energy curve with the experimental blocking curve was achieved after taking the magnetization variation into account. In the calculation it is assumed the existence of 100 nm sized domain structures in granular film as demonstrate (2) by previous studies. *supported by DoD/DARPA grant No. MDA972-97-1-003. (1) L. M. Malkinski, J.-Q. Wang, et al, Appl. Phys. Lett. 75, 844 (1999). (2) A. Gavrin, et al, Appl. Phys. Lett. 66, 1683 (1995); Y. J. Chen, et al, Appl. Phys. Lett. 72, 2472 (1998).

Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

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

Metere, Alfredo, E-mail: alfredo.metere@mmk.su.se; Oleynikov, Peter; Dzugutov, Mikhail

2014-12-21

We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process,more » can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.« less

Tuning the structure of thermosensitive gold nanoparticle monolayers.

PubMed

Rezende, Camila A; Shan, Jun; Lee, Lay-Theng; Zalczer, Gilbert; Tenhu, Heikki

2009-07-23

Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

Theory of inhomogeneous quantum systems. III. Variational wave functions for Fermi fluids

NASA Astrophysics Data System (ADS)

Krotscheck, E.

1985-04-01

We develop a general variational theory for inhomogeneous Fermi systems such as the electron gas in a metal surface, the surface of liquid 3He, or simple models of heavy nuclei. The ground-state wave function is expressed in terms of two-body correlations, a one-body attenuation factor, and a model-system Slater determinant. Massive partial summations of cluster expansions are performed by means of Born-Green-Yvon and hypernetted-chain techniques. An optimal single-particle basis is generated by a generalized Hartree-Fock equation in which the two-body correlations screen the bare interparticle interaction. The optimization of the pair correlations leads to a state-averaged random-phase-approximation equation and a strictly microscopic determination of the particle-hole interaction.

A description of rotations for DEM models of particle systems

NASA Astrophysics Data System (ADS)

Campello, Eduardo M. B.

2015-06-01

In this work, we show how a vector parameterization of rotations can be adopted to describe the rotational motion of particles within the framework of the discrete element method (DEM). It is based on the use of a special rotation vector, called Rodrigues rotation vector, and accounts for finite rotations in a fully exact manner. The use of fictitious entities such as quaternions or complicated structures such as Euler angles is thereby circumvented. As an additional advantage, stick-slip friction models with inter-particle rolling motion are made possible in a consistent and elegant way. A few examples are provided to illustrate the applicability of the scheme. We believe that simple vector descriptions of rotations are very useful for DEM models of particle systems.

Simulations of electrically induced particle structuring on spherical drop surface

NASA Astrophysics Data System (ADS)

Hu, Yi; Vlahovska, Petia; Miksis, Michael

2016-11-01

Recent experiments (Ouriemi and Vlahovska, 2014) show intriguing surface patterns when a uniform electric field is applied to a droplet covered with colloidal particles. Depending on the particle properties and the electrical field intensity, particles organize into an equatorial belt, pole-to-pole chains, or dynamic vortices. Here we present a model to simulate the collective particle dynamics, which accounts for the electrohydrodynamic flow and particle dielectrophoresis due to the non-uniformity of local electrical field. In stronger electric fields, particles are expected to undergo Quincke rotation, inducing rotating clusters through inter-particle hydrodynamical interaction. We discuss how the field intensity influences the width, orientation and periodicity of the particle clusters. Our results provide insight into the various particle assembles discovered in the experiments.

Self-assembled thin films of Fe3O4-Ag composite nanoparticles for spintronic applications

NASA Astrophysics Data System (ADS)

Jiang, Chengpeng; Leung, Chi Wah; Pong, Philip W. T.

2017-10-01

Controlled self-assembly of multi-component magnetic nanoparticles could lead to nanomaterial-based magnetic devices with novel structures and intriguing properties. Herein, self-assembled thin films of Fe3O4-Ag composite nanoparticles (CNPs) with hetero-dimeric shapes were fabricated using interfacial assembly method. The CNP-assembled thin films were further transferred to patterned silicon substrates followed by vacuum annealing, producing CNP-based magnetoresistive (MR) devices. Due to the presence of intra-particle interfaces and inter-particle barriers, an enhanced MR ratio and a non-linear current-voltage relation were observed in the device. The results of this work can potentially pave the way to the future exploration and development of spintronic devices built from composite nanomaterials.

MEASUREMENT OF NANOPARTICLES IN WATER

EPA Science Inventory

Measuring nanoparticles in water differs from traditional dissolved solute measurement in several ways. The most salient difference is that nanoparticles are colloids rather than solutes and therefore are subject to the interparticle interactions (mainly electrostatic and Van de...

Integrated Analysis Seismic Inversion and Rockphysics for Determining Secondary Porosity Distribution of Carbonate Reservoir at “FR” Field

NASA Astrophysics Data System (ADS)

Rosid, M. S.; Augusta, F. F.; Haidar, M. W.

2018-05-01

In general, carbonate secondary pore structure is very complex due to the significant diagenesis process. Therefore, the determination of carbonate secondary pore types is an important factor which is related to study of production. This paper mainly deals not only to figure out the secondary pores types, but also to predict the distribution of the secondary pore types of carbonate reservoir. We apply Differential Effective Medium (DEM) for analyzing pore types of carbonate rocks. The input parameter of DEM inclusion model is fraction of porosity and the output parameters are bulk moduli and shear moduli as a function of porosity, which is used as input parameter for creating Vp and Vs modelling. We also apply seismic post-stack inversion technique that is used to map the pore type distribution from 3D seismic data. Afterward, we create porosity cube which is better to use geostatistical method due to the complexity of carbonate reservoir. Thus, the results of this study might show the secondary porosity distribution of carbonate reservoir at “FR” field. In this case, North – Northwest of study area are dominated by interparticle pores and crack pores. Hence, that area has highest permeability that hydrocarbon can be more accumulated.

Pure dipolar-interacted CoFe{sub 2}O{sub 4} nanoparticles and their magnetic properties

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

Xu, Shi-tao; School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000; Ma, Yong-qing, E-mail: yqma@ahu.edu.cn

2015-02-15

Graphical abstract: The mono-dispersed CoFe{sub 2}O{sub 4} nanoparticles with the uniform size of 10.5 ± 2 nm were first synthesized and then they were embedded in amorphous SiO{sub 2} matrix with different CoFe{sub 2}O{sub 4} nanoparticles’ concentrations. The large coercivity (3056 Oe) and the remanence ratio (0.63) were obtained by suitably diluting CoFe{sub 2}O{sub 4} nanoparticles into the SiO{sub 2} matrix. The reciprocal of the absolute maximum of δm and the M{sub r}/M{sub s} ratio behave in the same trend (as shown in (e)), indicating that the M{sub r}/M{sub s} ratio was dominated by the interparticle dipolar interaction. The presentmore » work is meaningful for revealing the underlying mechanism in nano-scaled magnetic system and improving the magnetic performance. - Highlights: • The mono-dispersed CoFe{sub 2}O{sub 4} nanoparticles with the uniform size of 10.5 ± 2 nm were synthesized by the thermal decomposition of metals acetylacetonates in solvents with high boiling point. • The large coercivity (3056 Oe) and the remanence ratio (0.63) were obtained by diluting CoFe{sub 2}O{sub 4} nanoparticles into the SiO{sub 2} matrix with a suitable concentration. • The surface anisotropy and interparticle dipolar interaction affect the magnetic performance and magnetic ordering state. • It was observed that the M{sub r}/M{sub s} ratio was dominated by the interparticle dipolar interaction. - Abstract: The mono-dispersed and uniform CoFe{sub 2}O{sub 4} nanoparticles were synthesized by the thermal decomposition of Fe(acac){sub 3} and Co(acac){sub 2}. Then the CoFe{sub 2}O{sub 4} nanoparticles were diluted in amorphous SiO{sub 2} matrix with different CoFe{sub 2}O{sub 4} nanoparticles’ concentrations. All samples show the positive or negative exchange bias behavior, indicating the presence of canted spin layer at the CoFe{sub 2}O{sub 4} nanoparticles’ surface. The large effective anisotropy constant (3.38 × 10{sup 6} erg/cm{sup 3}) was observed, which can be attributed to the induced surface anisotropy by the canted surface spins. The reduced magnetization (M{sub r}/M{sub s}) was dominated by the interparticle dipolar interaction while the coercivity (H{sub c}) was determined by the synergistic effects of the surface anisotropy, interparticle dipolar interaction and interface effect. By suitably diluting CoFe{sub 2}O{sub 4} in the SiO{sub 2} matrix, the high H{sub c} (3056 Oe) and the M{sub r}/M{sub s} (0.63) can be obtained, which is larger than most of those reported before. The present work is meaningful for revealing the underlying mechanism in nano-scaled magnetic system and improving the magnetic performance.« less

Is the Pauli exclusion principle the origin of electron localisation?

NASA Astrophysics Data System (ADS)

Rincón, Luis; Torres, F. Javier; Almeida, Rafael

2018-03-01

In this work, we inquire into the origins of the electron localisation as obtained from the information content of the same-spin pair density, γσ, σ(r2∣r1). To this end, we consider systems of non-interacting and interacting identical Fermions contained in two simple 1D potential models: (1) an infinite potential well and (2) the Kronig-Penney periodic potential. The interparticle interaction is considered through the Hartree-Fock approximation as well as the configuration interaction expansion. Morover, the electron localisation is described through the Kullback-Leibler divergence between γσ, σ(r2∣r1) and its associated marginal probability. The results show that, as long as the adopted method properly includes the Pauli principle, the electronic localisation depends only modestly on the interparticle interaction. In view of the latter, one may conclude that the Pauli principle is the main responsible for the electron localisation.

Avoidance of stress corrosion susceptibility in high strength aluminum alloys by control of grain boundary and matrix microstructure

NASA Technical Reports Server (NTRS)

Adler, P.; Deiasi, R.

1974-01-01

The relation of microstructure to the mechanical strength and stress corrosion resistance of highest strength and overaged tempers of BAR and 7050 aluminum alloys was investigated. Comparison is made with previously studied 7075 aluminum alloy. Optical microscopy, transmission electron microscopy, and differential scanning calorimetry were used to characterize the grain morphology, matrix microstructure, and grain boundary microstructure of these tempers. Grain boundary interparticle spacing was significant to stress corrosion crack propagation for all three alloys; increasing interparticle spacing led to increased resistance to crack propagation. In addition, the fire grain size in Bar and 7050 appears to enhance crack propagation. The highest strength temper of 7050 has a comparatively high resistance to crack initiation. Overall stress corrosion behavior is dependent on environment pH, and evaluation over a range of pH is recommended.

Multi-scale mechanics of granular solids from grain-resolved X-ray measurements

NASA Astrophysics Data System (ADS)

Hurley, R. C.; Hall, S. A.; Wright, J. P.

2017-11-01

This work discusses an experimental technique for studying the mechanics of three-dimensional (3D) granular solids. The approach combines 3D X-ray diffraction and X-ray computed tomography to measure grain-resolved strains, kinematics and contact fabric in the bulk of a granular solid, from which continuum strains, grain stresses, interparticle forces and coarse-grained elasto-plastic moduli can be determined. We demonstrate the experimental approach and analysis of selected results on a sample of 1099 stiff, frictional grains undergoing multiple uniaxial compression cycles. We investigate the inter-particle force network, elasto-plastic moduli and associated length scales, reversibility of mechanical responses during cyclic loading, the statistics of microscopic responses and microstructure-property relationships. This work serves to highlight both the fundamental insight into granular mechanics that is furnished by combined X-ray measurements and describes future directions in the field of granular materials that can be pursued with such approaches.

Ostwald ripening and interparticle-diffraction effects for illite crystals

USGS Publications Warehouse

Eberl, D.D.; Srodon, J.

1988-01-01

The Warren-Averbach method, an X-ray diffraction (XRD) method used to measure mean particle thickness and particle-thickness distribution, is used to restudy sericite from the Silverton caldera. Apparent particle-thickness distributions indicate that the clays may have undergone Ostwald ripening and that this process has modified the K-Ar ages of the samples. The mechanism of Ostwald ripening can account for many of the features found for the hydrothermal alteration of illite. Expandabilities measured by the XRD peak-position method for illite/smectites (I/S) from various locations are smaller than expandabilities measured by transmission electron microscopy (TEM) and by the Warren-Averbach (W-A) method. This disparity is interpreted as being related to the presence of nonswelling basal surfaces that form the ends of stacks of illite particles (short-stack effect), stacks that, according to the theory of interparticle diffraction, diffract as coherent X-ray scattering domains. -from Authors

Design principles for wave plate metasurfaces using plasmonic L-shaped nanoantennas

NASA Astrophysics Data System (ADS)

Tahir, Asad A.; Schulz, Sebastian A.; De Leon, Israel; Boyd, Robert W.

2017-03-01

Plasmonic L-shaped antennas are an important building block of metasurfaces and have been used to fabricate ultra-thin wave plates. In this work we present principles that can be used to design wave plates at a wavelength of choice and for diverse application requirements using arrays of L-shaped plasmonic antennas. We derive these design principles by studying the behavior of the vast parameter space of these antenna arrays. We show that there are two distinct regimes: a weak inter-particle coupling and a strong inter-particle coupling regime. We describe the behavior of the antenna array in each regime with regards to wave plate functionality, without resorting to approximate theoretical models. Our work is the first to explain these design principles and serves as a guide for designing wave plates for specific application requirements using plasmonic L-shaped antenna arrays.

DNA-controlled assembly of a NaTl lattice structure from gold nanoparticles and protein nanoparticles

NASA Astrophysics Data System (ADS)

Cigler, Petr; Lytton-Jean, Abigail K. R.; Anderson, Daniel G.; Finn, M. G.; Park, Sung Yong

2010-11-01

The formation of diamond structures from tailorable building blocks is an important goal in colloidal crystallization because the non-compact diamond lattice is an essential component of photonic crystals for the visible-light range. However, designing nanoparticle systems that self-assemble into non-compact structures has proved difficult. Although several methods have been proposed, single-component nanoparticle assembly of a diamond structure has not been reported. Binary systems, in which at least one component is arranged in a diamond lattice, provide alternatives, but control of interparticle interactions is critical to this approach. DNA has been used for this purpose in a number of systems. Here we show the creation of a non-compact lattice by DNA-programmed crystallization using surface-modified Qβ phage capsid particles and gold nanoparticles, engineered to have similar effective radii. When combined with the proper connecting oligonucleotides, these components form NaTl-type colloidal crystalline structures containing interpenetrating organic and inorganic diamond lattices, as determined by small-angle X-ray scattering. DNA control of assembly is therefore shown to be compatible with particles possessing very different properties, as long as they are amenable to surface modification.

Significance of Nanoparticles and the Role of Amino Acids in Structuring Them-A Review.

PubMed

Kulandaisamy, Arockia Jayalatha; Rayappan, John Bosco Balaguru

2018-08-01

Nanoparticles has occupied an eminent place in our tech-facilitated society. The processes involved in synthesizing nanoparticles are important not only to find their applications, but also to make them eco-friendly. Attempts are being made to replace the use of harmful surfactants/reagents by amino acids, in the due course of nanoparticle synthesis. Especially in synthesizing the multifunctional metal and metal oxide nanoparticles the use of amino acids as surfactant/as catalyst, helps to obtain required size and shape. Amino acids have the inherent property in directing and assembling the superstructures. They have the tendency to act as a capping agent and their presence during the synthesis processes alters the synthesized particles' morphology. Review has been made to study the role of amino acids like histidine, lysine, arginine in structuring ZnO, FeO, Au and Ag nanoparticles. The change in their morphology that resulted due to the addition of amino acids has been compared. It is important to understand the role of amino acids in synthesizing the nanoparticles, and so it is more important to understand the internal energy variation of the same. To achieve this, the interaction between the bio (amino acids) and non-bio (metal and metal oxide) nanoparticles are to be discussed both experimentally and theoretically. At times the theoretical characterization, especially at low dimensions, help us to understand inter-particle interaction and intra-particle interaction by determining their chemical potential and Lennard-Jones potential. This review has been concluded with a model to characterize the precursor solution (amino acids and inorganic materials) by considering the Equation of State for liquids, which could also be extended to determine the structure factor of nanoparticles.

Layer-by-layer charging in non-volatile memory devices using embedded sub-2 nm platinum nanoparticles

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

Ramalingam, Balavinayagam; Zheng, Haisheng; Gangopadhyay, Shubhra, E-mail: gangopadhyays@missouri.edu

In this work, we demonstrate multi-level operation of a non-volatile memory metal oxide semiconductor capacitor by controlled layer-by-layer charging of platinum nanoparticle (PtNP) floating gate devices with defined gate voltage bias ranges. The device consists of two layers of ultra-fine, sub-2 nm PtNPs integrated between Al{sub 2}O{sub 3} tunneling and separation layers. PtNP size and interparticle distance were varied to control the particle self-capacitance and associated Coulomb charging energy. Likewise, the tunneling layer thicknesses were also varied to control electron tunneling to the first and second PtNP layers. The final device configuration with optimal charging behavior and multi-level programming was attainedmore » with a 3 nm Al{sub 2}O{sub 3} initial tunneling layer, initial PtNP layer with particle size 0.54 ± 0.12 nm and interparticle distance 4.65 ± 2.09 nm, 3 nm Al{sub 2}O{sub 3} layer to separate the PtNP layers, and second particle layer with 1.11 ± 0.28 nm PtNP size and interparticle distance 2.75 ± 1.05 nm. In this device, the memory window of the first PtNP layer saturated over a programming bias range of 7 V to 14 V, after which the second PtNP layer starts charging, exhibiting a multi-step memory window with layer-by-layer charging.« less

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

Radiom, Milad, E-mail: milad.radiom@unige.ch; Ducker, William, E-mail: wducker@vt.edu; Robbins, Brian

The hydrodynamic interaction of two closely spaced micron-scale spheres undergoing Brownian motion was measured as a function of their separation. Each sphere was attached to the distal end of a different atomic force microscopy cantilever, placing each sphere in a stiff one-dimensional potential (0.08 Nm{sup −1}) with a high frequency of thermal oscillations (resonance at 4 kHz). As a result, the sphere’s inertial and restoring forces were significant when compared to the force due to viscous drag. We explored interparticle gap regions where there was overlap between the two Stokes layers surrounding each sphere. Our experimental measurements are the firstmore » of their kind in this parameter regime. The high frequency of oscillation of the spheres means that an analysis of the fluid dynamics would include the effects of fluid inertia, as described by the unsteady Stokes equation. However, we find that, for interparticle separations less than twice the thickness of the wake of the unsteady viscous boundary layer (the Stokes layer), the hydrodynamic interaction between the Brownian particles is well-approximated by analytical expressions that neglect the inertia of the fluid. This is because elevated frictional forces at narrow gaps dominate fluid inertial effects. The significance is that interparticle collisions and concentrated suspensions at this condition can be modeled without the need to incorporate fluid inertia. We suggest a way to predict when fluid inertial effects can be ignored by including the gap-width dependence into the frequency number. We also show that low frequency number analysis can be used to determine the microrheology of mixtures at interfaces.« less

Controlling Non-Equilibrium Structure Formation on the Nanoscale.

PubMed

Buchmann, Benedikt; Hecht, Fabian Manfred; Pernpeintner, Carla; Lohmueller, Theobald; Bausch, Andreas R

2017-12-06

Controlling the structure formation of gold nanoparticle aggregates is a promising approach towards novel applications in many fields, ranging from (bio)sensing to (bio)imaging to medical diagnostics and therapeutics. To steer structure formation, the DNA-DNA interactions of DNA strands that are coated on the surface of the particles have become a valuable tool to achieve precise control over the interparticle potentials. In equilibrium approaches, this technique is commonly used to study particle crystallization and ligand binding. However, regulating the structural growth processes from the nano- to the micro- and mesoscale remains elusive. Here, we show that the non-equilibrium structure formation of gold nanoparticles can be stirred in a binary heterocoagulation process to generate nanoparticle clusters of different sizes. The gold nanoparticles are coated with sticky single stranded DNA and mixed at different stoichiometries and sizes. This not only allows for structural control but also yields access to the optical properties of the nanoparticle suspensions. As a result, we were able to reliably control the kinetic structure formation process to produce cluster sizes between tens of nanometers up to micrometers. Consequently, the intricate optical properties of the gold nanoparticles could be utilized to control the maximum of the nanoparticle suspension extinction spectra between 525 nm and 600 nm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Recent Advances in Multi-component Particles Assembly.

PubMed

Guo, Dan; Song, Yanlin

2018-03-09

Particles assembly and co-assembly have been research frontiers in chemistry and material science in the past few decades. To achieve a large variety of intricate structures and functional materials, remarkable progress has been made in the particle assembly principles and strategies. It can be summarized that the particle assembly is driven by intrinsic interparticle interaction or the external control. In this article, we focus on binary or ternary particles co-assembly and review the principles and feasible strategies. These advances have led to new disciplines of microfabrication technology and material engineering. Although remarked achievement on particle-based structures has been made, it is still challenging to fully develop general and facile strategies to precisely control the one-dimensional (1D) co-assembly. This article reviews the recent development on multi-component particles co-assembly, which significantly increases structural complexity and functional diversity. In particular, we highlight the advances in the particles co-assembly of well-ordered 1D binary superstructures by liquid soft confinement. Finally, prospective outlook for future trends in this field is proposed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Parking simulation of three-dimensional multi-sized star-shaped particles

NASA Astrophysics Data System (ADS)

Zhu, Zhigang; Chen, Huisu; Xu, Wenxiang; Liu, Lin

2014-04-01

The shape and size of particles may have a great impact on the microstructure as well as the physico-properties of particulate composites. However, it is challenging to configure a parking system of particles to a geometrical shape that is close to realistic grains in particulate composites. In this work, with the assistance of x-ray tomography and a spherical harmonic series, we present a star-shaped particle that is close to realistic arbitrary-shaped grains. To realize such a hard particle parking structure, an inter-particle overlapping detection algorithm is introduced. A serial sectioning approach is employed to visualize the particle parking structure for the purpose of justifying the reliability of the overlapping detection algorithm. Furthermore, the validity of the area and perimeter of solids in any arbitrary section of a plane calculated using a numerical method is verified by comparison with those obtained using an image analysis approach. This contribution is helpful to further understand the dependence of the micro-structure and physico-properties of star-shaped particles on the realistic geometrical shape.

Dynamical arrest, percolation, gelation, and glass formation in model nanoparticle dispersions with thermoreversible adhesive interactions.

PubMed

Eberle, Aaron P R; Castañeda-Priego, Ramón; Kim, Jung M; Wagner, Norman J

2012-01-24

We report an experimental study of the dynamical arrest transition for a model system consisting of octadecyl coated silica suspended in n-tetradecane from dilute to concentrated conditions spanning the state diagram. The dispersion's interparticle potential is tuned by temperature affecting the brush conformation leading to a thermoreversible model system. The critical temperature for dynamical arrest, T*, is determined as a function of dispersion volume fraction by small-amplitude dynamic oscillatory shear rheology. We corroborate this transition temperature by measuring a power-law decay of the autocorrelation function and a loss of ergodicity via fiber-optic quasi-elastic light scattering. The structure at T* is measured using small-angle neutron scattering. The scattering intensity is fit to extract the interparticle pair-potential using the Ornstein-Zernike equation with the Percus-Yevick closure approximation, assuming a square-well interaction potential with a short-range interaction (1% of particle diameter). (1) The strength of attraction is characterized using the Baxter temperature (2) and mapped onto the adhesive hard sphere state diagram. The experiments show a continuous dynamical arrest transition line that follows the predicted dynamical percolation line until ϕ ≈ 0.41 where it subtends the predictions toward the mode coupling theory attractive-driven glass line. An alternative analysis of the phase transition through the reduced second virial coefficient B(2)* shows a change in the functional dependence of B(2)* on particle concentration around ϕ ≈ 0.36. We propose this signifies the location of a gel-to-glass transition. The results presented herein differ from those observed for depletion flocculated dispersion of micrometer-sized particles in polymer solutions, where dynamical arrest is a consequence of multicomponent phase separation, suggesting dynamical arrest is sensitive to the physical mechanism of attraction.

Effect of spatial confinement on magnetic hyperthermia via dipolar interactions in Fe3O4 nanoparticles for biomedical applications

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

Sadat, M E; Patel, Ronak; Sookoor, Jason

2014-09-01

In this work, the effect of nanoparticle confinement on the magnetic relaxation of iron oxide (Fe3O4) nanoparticles (NP) was investigated by measuring the hyperthermia heating behavior in high frequency alternating magnetic field. Three different Fe3O4 nanoparticle systems having distinct nanoparticle configurations were studied in terms of magnetic hyperthermia heating rate and DC magnetization. All magnetic nanoparticle (MNP) systems were constructed using equivalent ~10nm diameter NP that were structured differently in terms of configuration, physical confinement, and interparticle spacing. The spatial confinement was achieved by embedding the Fe3O4 nanoparticles in the matrices of the polystyrene spheres of 100 nm, while themore » unconfined was the free Fe3O4 nanoparticles well-dispersed in the liquid via PAA surface coating. Assuming the identical core MNPs in each system, the heating behavior was analyzed in terms of particle freedom (or confinement), interparticle spacing, and magnetic coupling (or dipole-dipole interaction). DC magnetization data were correlated to the heating behavior with different material properties. Analysis of DC magnetization measurements showed deviation from classical Langevin behavior near saturation due to dipole interaction modification of the MNPs resulting in a high magnetic anisotropy. It was found that the Specific Absorption Rate (SAR) of the unconfined nanoparticle systems were significantly higher than those of confined (the MNPs embedded in the polystyrene matrix). This increase of SAR was found to be attributable to high Néel relaxation rate and hysteresis loss of the unconfined MNPs. It was also found that the dipole-dipole interactions can significantly reduce the global magnetic response of the MNPs and thereby decrease the SAR of the nanoparticle systems.« less

Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

PubMed

Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

2016-04-25

Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Late Diagenetic Cements in the Murray Formation, Gale Crater, Mars: Implications for Postdepositional Fluid Flow

NASA Astrophysics Data System (ADS)

Kah, L. C.; Kronyak, R. E.; Van Beek, J.; Nachon, M.; Mangold, N.; Thompson, L. M.; Wiens, R. C.; Grotzinger, J. P.; Schieber, J.

2015-12-01

The Murray formation in its type section at Pahrump Hills, consists of approximately 14 meters of recessive-weathering mudstone interbedded with decimeter-scale cross-bedded sandstone in the upper portions of the exposed section. Mudstone textures vary from massive, to poorly laminated, to well laminated. Unusual 3-dimensional crystal clusters and dendrites occur in the lowermost part of the section and are erosionally resistant with respect to the host rock. Crystal clusters consist of elongate lathes that occur within individual blocks of the fractured substrate. Individual lathes show tabular morphologies with a pseudo-rectangular cross-section and the three dimensional morphology of the crystal clusters cross-cut host rock lamination with little or no deformation. Dendritic structures are typically larger and show predominantly planar growth aligned with bedding planes. Individual lathes within the dendrites are elongate and pseudo-rectangular in cross-section. Unlike crystal clusters, dendritic morphologies appear to nucleate at bedrock fractures and near mineralized veins. Here we show evidence that crystal clusters and dendrites are post-depositional, potentially burial diagenetic features. Association of features with through-going fractures suggests that fractures may have been a primary transport pathway for ions responsible for dendrite growth. Even where dendrites do not occur, enhanced cementation suggests that fluids permeated the rock matrix. We suggest that growth of clusters proceeded as inter-particle crystal growth, wherein mineral growth within inter-particle spaces resulted in cementation and porosity loss, with little further effect on the rock matrix. Crystal clusters and dendrites are most likely to form when mineral saturation states are highest, for instance with initial intrusion of fracture-borne fluids and mixing with ambient pore fluids, and thus emphasize the importance of fractures in ion transport during late diagenesis.

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.

Stability diagram for dense suspensions of model colloidal Al2O3 particles in shear flow.

PubMed

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.

Cascade of Solitonic Excitations in a Superfluid Fermi Gas: From Solitons and Vortex Rings to Solitonic Vortices

NASA Astrophysics Data System (ADS)

Ku, Mark; Mukherjee, Biswaroop; Yefsah, Tarik; Zwierlein, Martin

2015-05-01

We follow the evolution of a superfluid Fermi gas of 6Li atoms following a one-sided π phase imprint. Via tomographic imaging, we observe the formation of a planar dark soliton, and its subsequent snaking and decay into a vortex ring. The latter eventually breaks at the boundary of the superfluid, finally leaving behind a single, remnant solitonic vortex. The nodal surface is directly imaged and reveals its decay into a vortex ring via a puncture of the initial soliton plane. At intermediate stages we find evidence for more exotic structures resembling Φ-solitons. The observed evolution of the nodal surface represents dynamics that occurs at the length scale of the interparticle spacing, thus providing new experimental input for microscopic theories of strongly correlated fermions.

The effect of multiplicity of stellar encounters and the diffusion coefficients in a locally homogeneous three-dimensional stellar medium: Removing the classical divergence

NASA Astrophysics Data System (ADS)

Rastorguev, A. S.; Utkin, N. D.; Chumak, O. V.

2017-08-01

Agekyan's λ-factor that allows for the effect of multiplicity of stellar encounters with large impact parameters has been used for the first time to directly calculate the diffusion coefficients in the phase space of a stellar system. Simple estimates show that the cumulative effect, i.e., the total contribution of distant encounters to the change in the velocity of a test star, given the multiplicity of stellar encounters, is finite, and the logarithmic divergence inherent in the classical description of diffusion is removed, as was shown previously byKandrup using a different, more complex approach. In this case, the expressions for the diffusion coefficients, as in the classical description, contain the logarithm of the ratio of two independent quantities: the mean interparticle distance and the impact parameter of a close encounter. However, the physical meaning of this logarithmic factor changes radically: it reflects not the divergence but the presence of two characteristic length scales inherent in the stellar medium.

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

Wei Chen; Kan, A.T.; Tomson, M.B.

Both the adsorption and the desorption processes play important roles in the transport and fate of organic contaminants in water-sediments and groundwater systems. The adsorption-desorption processes are shown to be influenced by a number of factors, including sediments organic carbon content, contaminant aqueous solubility, aqueous-phase concentration as well as some natural environmental factors such as pH, pE, ionic strength and temperature. External mechanical forces, such as sediment perturbation, and repeated dredging will also have finite effect on the microscopic interparticle forces that control bonds between large and small grain particles. The objective of this research is to study the influencesmore » of various environmental effects on the equilibrium or non-equilibrium desorption behavior of nonpolar organic pollutants in historically contaminated natural sediments of Lake Charles, LA. Differences of desorption behavior between freshly and historically contaminated sediments will be compared in order to evaluated the desorption mechanism. The influences of particle size, mineral composition, organic matter concentration, and aqueous phase matrix composition on desorption behaviour will also be evaluated.« less

Monodisperse self-assembly in a model with protein-like interactions

NASA Astrophysics Data System (ADS)

Wilber, Alex W.; Doye, Jonathan P. K.; Louis, Ard A.; Lewis, Anna C. F.

2009-11-01

We study the self-assembly behavior of patchy particles with "proteinlike" interactions that can be considered as a minimal model for the assembly of viral capsids and other shell-like protein complexes. We thoroughly explore the thermodynamics and dynamics of self-assembly as a function of the parameters of the model and find robust assembly of all target structures considered. Optimal assembly occurs in the region of parameter space where a free energy barrier regulates the rate of nucleation, thus preventing the premature exhaustion of the supply of monomers that can lead to the formation of incomplete shells. The interactions also need to be specific enough to prevent the assembly of malformed shells, but while maintaining kinetic accessibility. Free energy landscapes computed for our model have a funnel-like topography guiding the system to form the target structure and show that the torsional component of the interparticle interactions prevents the formation of disordered aggregates that would otherwise act as kinetic traps.

Tunable magnetic properties by interfacial manipulation of L1(0)-FePt perpendicular ultrathin film with island-like structures.

PubMed

Feng, C; Wang, S G; Yang, M Y; Zhang, E; Zhan, Q; Jiang, Y; Li, B H; Yu, G H

2012-02-01

Based on interfacial manipulation of the MgO single crystal substrate and non-magnetic AIN compound, a L1(0)-FePt perpendicular ultrathin film with the structure of MgO/FePt-AIN/Ta was designed, prepared, and investigated. The film is comprised of L1(0)-FePt "magnetic islands," which exhibits a perpendicular magnetic anisotropy (PMA), tunable coercivity (Hc), and interparticle exchange coupling (IEC). The MgO substrate promotes PMA of the film because of interfacial control of the FePt lattice orientation. The AIN compound is doped to increase the difference of surface energy between FePt layer and MgO substrate and to suppress the growth of FePt grains, which takes control of island growth mode of FePt atoms. The AIN compound also acts as isolator of L1(0)-FePt islands to pin the sites of FePt domains, resulting in the tunability of Hc and IEC of the films.

Self-assembly of triangular particles via capillary interactions

NASA Astrophysics Data System (ADS)

Bedi, Deshpreet; Zhou, Shangnan; Ferrar, Joseph; Solomon, Michael; Mao, Xiaoming

Colloidal particles adsorbed to a fluid interface deform the interface around them, resulting in either attractive or repulsive forces mediated by the interface. In particular, particle shape and surface roughness can produce an undulating contact line, such that the particles will assume energetically-favorable relative orientations and inter-particle distances to minimize the excess interfacial surface area. By expediently selecting specific particle shapes and associated design parameters, capillary interactions can be utilized to promote self-assembly of these particles into extended regular open structures, such as the kagome lattice, which have novel mechanical properties. We present the results of numerical simulations of equilateral triangle microprisms at an interface, including individually and in pairs. We show how particle bowing can yield two distinct binding events and connect it to theory in terms of a capillary multipole expansion and also to experiment, as presented in an accompanying talk. We also discuss and suggest design principles that can be used to create desirable open structures.

Preparation and characterization of supported magnetic nanoparticles prepared by reverse micelles

PubMed Central

Han, Luyang; Biskupek, Johannes; Kaiser, Ute; Ziemann, Paul

2010-01-01

Summary Monatomic (Fe, Co) and bimetallic (FePt and CoPt) nanoparticles were prepared by exploiting the self-organization of precursor loaded reverse micelles. Achievements and limitations of the preparation approach are critically discussed. We show that self-assembled metallic nanoparticles can be prepared with diameters d = 2–12 nm and interparticle distances D = 20–140 nm on various substrates. Structural, electronic and magnetic properties of the particle arrays were characterized by several techniques to give a comprehensive view of the high quality of the method. For Co nanoparticles, it is demonstrated that magnetostatic interactions can be neglected for distances which are at least 6 times larger than the particle diameter. Focus is placed on FePt alloy nanoparticles which show a huge magnetic anisotropy in the L10 phase, however, this is still less by a factor of 3–4 when compared to the anisotropy of the bulk counterpart. A similar observation was also found for CoPt nanoparticles (NPs). These results are related to imperfect crystal structures as revealed by HRTEM as well as to compositional distributions of the prepared particles. Interestingly, the results demonstrate that the averaged effective magnetic anisotropy of FePt nanoparticles does not strongly depend on size. Consequently, magnetization stability should scale linearly with the volume of the NPs and give rise to a critical value for stability at ambient temperature. Indeed, for diameters above 6 nm such stability is observed for the current FePt and CoPt NPs. Finally, the long-term conservation of nanoparticles by Au photoseeding is presented. PMID:21977392

Modeling of hot-mix asphalt compaction : a thermodynamics-based compressible viscoelastic model

DOT National Transportation Integrated Search

2010-12-01

Compaction is the process of reducing the volume of hot-mix asphalt (HMA) by the application of external forces. As a result of compaction, the volume of air voids decreases, aggregate interlock increases, and interparticle friction increases. The qu...

Sputtering-growth of seeded Au nanoparticles for nanogap-assisted surface-enhanced Raman scattering (SERS) biosensing

NASA Astrophysics Data System (ADS)

Fu, Chit Yaw; U. S., Dinish; Rautela, Shashi; Goh, Douglas Wenda; Olivo, Malini

2011-12-01

Gold-coated array patterned with tightly-packed nanospheres was developed as a substrate base for constructing SERSenriched nanogaps with Au-nanoparticles (GNPs). Using 1,2-ethanedithiol as a linker, Au-NPs (=17-40nm) were anchored covalently on the sphere-array. Thin Au layer was sputtered on the substrate to mask the citrate coating of GNPs that could demote the sensing mechanism. The negatively-charged GNP surface warrants the colloidal stability, but the resulting repulsive force keeps the immobilized NPs apart by about 40nm. The attained gap size is inadequately narrow to sustain any intense enhancement owing to the near-field nature of SERS. Minimal amount of NaCl was then added to slightly perturb the colloidal stability by reducing their surface charge. Notably, the interparticle-gap reduces at increasing amount of salt, giving rise to increased packing density of GNPs. The SERS enhancement is also found to exponentially increase at decreasing gap size. Nevertheless, the minimum gap achieved is limited to merely 7nm. Excessive addition of salt would eventually induce complete aggregation of particles, forming clustered NPs on the array. A simple sputtering-growth approach is therefore proposed to further minimize the interparticle gap by enlarging the seeded NPs based on mild sputtering. The SEM images confirm that the gap below 7nm is achievable. With advent of the colloidal chemistry, the combined salt-induced aggregation and sputtering-growth techniques can be applied to engineer interparticle gap that is crucial to realize an ultrasensitive SERS biosensor. The proposed two-step preparation can be potentially adopted to fabricate the SERS-enriched nanogaps on the microfluidics platform.

Enhanced phenol-photodegradation by particulate semiconductor mixtures: interparticle electron-jump.

PubMed

Karunakaran, C; Dhanalakshmi, R; Gomathisankar, P; Manikandan, G

2010-04-15

Degradation of phenol on suspended TiO(2), ZnO, CdO, Fe(2)O(3), CuO, ZnS and Nb(2)O(5) particles under UV-A light exhibit identical photokinetic behavior; follow first-order kinetics, display linear dependence on the photon flux and slowdown with increase of pH. All the semiconductors show sustainable photocatalytic activity. Dissolved O(2) is essential for the photodegradation and oxidizing agents like H(2)O(2), Na(2)BO(3), K(2)S(2)O(8), KBrO(3), KIO(3) and KIO(4), reducing agents such as NaNO(2) and Na(2)SO(3) and sacrificial electron donors like hydroquinone, diphenyl amine and trimethyl amine enhance the degradation. However, the photocatalysis is insensitive to pre-sonication. Two particulate semiconductors present together, under suspension and at continuous motion, enhance the photocatalytic degradation up to about four-fold revealing interparticle electron-jump. 2009 Elsevier B.V. All rights reserved.

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.

Electrical Resistivity Measurement of Petroleum Coke Powder by Means of Four-Probe Method

NASA Astrophysics Data System (ADS)

Rouget, G.; Majidi, B.; Picard, D.; Gauvin, G.; Ziegler, D.; Mashreghi, J.; Alamdari, H.

2017-10-01

Carbon anodes used in Hall-Héroult electrolysis cells are involved in both electrical and chemical processes of the cell. Electrical resistivity of anodes depends on electrical properties of its constituents, of which carbon coke aggregates are the most prevalent. Electrical resistivity of coke aggregates is usually characterized according to the ISO 10143 standardized test method, which consists of measuring the voltage drop in the bed of particles between two electrically conducing plungers through which the current is also applied. Estimation of the electrical resistivity of coke particles from the resistivity of particle bed is a challenging task and needs consideration of the contribution of the interparticle void fraction and the particle/particle contact resistances. In this work, the bed resistivity was normalized by subtracting the interparticle void fraction. Then, the contact size was obtained from discrete element method simulation and the contact resistance was calculated using Holm's theory. Finally, the resistivity of the coke particles was obtained from the bed resistivity.

Microscopic origin and macroscopic implications of lane formation in mixtures of oppositely-driven particles

NASA Astrophysics Data System (ADS)

Whitelam, Stephen

Colloidal particles of two types, driven in opposite directions, can segregate into lanes. I will describe some results on this phenomenon obtained by simple physical arguments and computer simulations. Laning results from rectification of diffusion on the scale of a particle diameter: oppositely-driven particles must, in the time taken to encounter each other in the direction of the drive, diffuse in the perpendicular direction by about one particle diameter. This geometric constraint implies that the diffusion constant of a particle, in the presence of those of the opposite type, grows approximately linearly with Peclet number, a prediction confirmed by our numerics. Such environment-dependent diffusion is statistically similar to an effective interparticle attraction; consistent with this observation, we find that oppositely-driven colloids display features characteristic of the simplest model system possessing both interparticle attractions and persistent motion, the driven Ising lattice gas. Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

About improving efficiency of the P3 M algorithms when computing the inter-particle forces in beam dynamics

NASA Astrophysics Data System (ADS)

Kozynchenko, Alexander I.; Kozynchenko, Sergey A.

2017-03-01

In the paper, a problem of improving efficiency of the particle-particle- particle-mesh (P3M) algorithm in computing the inter-particle electrostatic forces is considered. The particle-mesh (PM) part of the algorithm is modified in such a way that the space field equation is solved by the direct method of summation of potentials over the ensemble of particles lying not too close to a reference particle. For this purpose, a specific matrix "pattern" is introduced to describe the spatial field distribution of a single point charge, so the "pattern" contains pre-calculated potential values. This approach allows to reduce a set of arithmetic operations performed at the innermost of nested loops down to an addition and assignment operators and, therefore, to decrease the running time substantially. The simulation model developed in C++ substantiates this view, showing the descent accuracy acceptable in particle beam calculations together with the improved speed performance.

Experimental detection of long-distance interactions between biomolecules through their diffusion behavior: numerical study.

PubMed

Nardecchia, Ilaria; Spinelli, Lionel; Preto, Jordane; Gori, Matteo; Floriani, Elena; Jaeger, Sebastien; Ferrier, Pierre; Pettini, Marco

2014-08-01

The dynamical properties and diffusive behavior of a collection of mutually interacting particles are numerically investigated for two types of long-range interparticle interactions: Coulomb-electrostatic and dipole-electrodynamic. It is shown that when the particles are uniformly distributed throughout the accessible space, the self-diffusion coefficient is always lowered by the considered interparticle interactions, irrespective of their attractive or repulsive character. This fact is also confirmed by a simple model to compute the correction to the Brownian diffusion coefficient due to the interactions among the particles. These interactions are also responsible for the onset of dynamical chaos and an associated chaotic diffusion which still follows an Einstein-Fick-like law for the mean-square displacement as a function of time. Transitional phenomena are observed for Coulomb-electrostatic (repulsive) and dipole-electrodynamic (attractive) interactions considered both separately and in competition. The outcomes reported in this paper clearly indicate a feasible experimental method to probe the activation of resonant electrodynamic interactions among biomolecules.

Jamming criticality revealed by removing localized buckling excitations.

PubMed

Charbonneau, Patrick; Corwin, Eric I; Parisi, Giorgio; Zamponi, Francesco

2015-03-27

Recent theoretical advances offer an exact, first-principles theory of jamming criticality in infinite dimension as well as universal scaling relations between critical exponents in all dimensions. For packings of frictionless spheres near the jamming transition, these advances predict that nontrivial power-law exponents characterize the critical distribution of (i) small interparticle gaps and (ii) weak contact forces, both of which are crucial for mechanical stability. The scaling of the interparticle gaps is known to be constant in all spatial dimensions d-including the physically relevant d=2 and 3, but the value of the weak force exponent remains the object of debate and confusion. Here, we resolve this ambiguity by numerical simulations. We construct isostatic jammed packings with extremely high accuracy, and introduce a simple criterion to separate the contribution of particles that give rise to localized buckling excitations, i.e., bucklers, from the others. This analysis reveals the remarkable dimensional robustness of mean-field marginality and its associated criticality.

Formation and dissociation of dust molecules in dusty plasma

NASA Astrophysics Data System (ADS)

Yan, Jia; Feng, Fan; Liu, Fucheng; Dong, Lifang; He, Yafeng

2016-09-01

Dust molecules are observed in a dusty plasma experiment. By using measurements with high spatial resolution, the formation and dissociation of the dust molecules are studied. The ion cloud in the wake of an upper dust grain attracts the lower dust grain nearby. When the interparticle distance between the upper dust grain and the lower one is less than a critical value, the two dust grains would form a dust molecule. The upper dust grain always leads the lower one as they travel. When the interparticle distance between them is larger than the critical value, the dust molecule would dissociate. Project supported by the National Natural Science Foundation of China (Grant Nos. 11205044 and 11405042), the Natural Science Foundation of Hebei Province, China (Grant Nos. A2011201006 and A2012201015), the Research Foundation of Education Bureau of Hebei Province, China (Grant No. Y2012009), the Program for Young Principal Investigators of Hebei Province, China, and the Midwest Universities Comprehensive Strength Promotion Project, China.

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations.

PubMed

Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath; Narayanan, Suresh; Faraone, Antonio

2017-11-08

The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasi-elastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. In addition, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that the level of chain-chain entanglements is not significantly affected. The shear-induced changes in the interparticle bridging reflect the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations

DOE PAGES

Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath; ...

2017-09-28

The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasielastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. Additionally, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that themore » level of chain-chain entanglements is not significantly affected. The shearinduced changes in the interparticle bridging reflects on the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.« less

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations

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

Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath

The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasielastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. Additionally, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that themore » level of chain-chain entanglements is not significantly affected. The shearinduced changes in the interparticle bridging reflects on the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.« less

A smoothed particle hydrodynamics framework for modelling multiphase interactions at meso-scale

NASA Astrophysics Data System (ADS)

Li, Ling; Shen, Luming; Nguyen, Giang D.; El-Zein, Abbas; Maggi, Federico

2018-01-01

A smoothed particle hydrodynamics (SPH) framework is developed for modelling multiphase interactions at meso-scale, including the liquid-solid interaction induced deformation of the solid phase. With an inter-particle force formulation that mimics the inter-atomic force in molecular dynamics, the proposed framework includes the long-range attractions between particles, and more importantly, the short-range repulsive forces to avoid particle clustering and instability problems. Three-dimensional numerical studies have been conducted to demonstrate the capabilities of the proposed framework to quantitatively replicate the surface tension of water, to model the interactions between immiscible liquids and solid, and more importantly, to simultaneously model the deformation of solid and liquid induced by the multiphase interaction. By varying inter-particle potential magnitude, the proposed SPH framework has successfully simulated various wetting properties ranging from hydrophobic to hydrophilic surfaces. The simulation results demonstrate the potential of the proposed framework to genuinely study complex multiphase interactions in wet granular media.

Force measurements in stiff, 3D, opaque granular materials

NASA Astrophysics Data System (ADS)

Hurley, Ryan C.; Hall, Stephen A.; Andrade, José E.; Wright, Jonathan

2017-06-01

We present results from two experiments that provide the first quantification of inter-particle force networks in stiff, 3D, opaque granular materials. Force vectors between all grains were determined using a mathematical optimization technique that seeks to satisfy grain equilibrium and strain measurements. Quantities needed in the optimization - the spatial location of the inter-particle contact network and tensor grain strains - were found using 3D X-ray diffraction and X-ray computed tomography. The statistics of the force networks are consistent with those found in past simulations and 2D experiments. In particular, we observe an exponential decay of normal forces above the mean and a partition of forces into strong and weak networks. In the first experiment, involving 77 single-crystal quartz grains, we also report on the temporal correlation of the force network across two sequential load cycles. In the second experiment, involving 1099 single-crystal ruby grains, we characterize force network statistics at low levels of compression.

Monolithic photonic crystals created by partial coalescence of core-shell particles.

PubMed

Lee, Joon-Seok; Lim, Che Ho; Yang, Seung-Man; Kim, Shin-Hyun

2014-03-11

Colloidal crystals and their derivatives have been intensively studied and developed during the past two decades due to their unique photonic band gap properties. However, complex fabrication procedures and low mechanical stability severely limit their practical uses. Here, we report stable photonic structures created by using colloidal building blocks composed of an inorganic core and an organic shell. The core-shell particles are convectively assembled into an opal structure, which is then subjected to thermal annealing. During the heat treatment, the inorganic cores, which are insensitive to heat, retain their regular arrangement in a face-centered cubic lattice, while the organic shells are partially fused with their neighbors; this forms a monolithic structure with high mechanical stability. The interparticle distance and therefore stop band position are precisely controlled by the annealing time; the distance decreases and the stop band blue shifts during the annealing. The composite films can be further treated to give a high contrast in the refractive index. The inorganic cores are selectively removed from the composite by wet etching, thereby providing an organic film containing regular arrays of air cavities. The high refractive index contrast of the porous structure gives rise to pronounced structural colors and high reflectivity at the stop band position.

Simple analysis of scattering data with the Ornstein-Zernike equation

NASA Astrophysics Data System (ADS)

Kats, E. I.; Muratov, A. R.

2018-01-01

In this paper we propose and explore a method of analysis of the scattering experimental data for uniform liquidlike systems. In our pragmatic approach we are not trying to introduce by hands an artificial small parameter to work out a perturbation theory with respect to the known results, e.g., for hard spheres or sticky hard spheres (all the more that in the agreement with the notorious Landau statement, there is no physical small parameter for liquids). Instead of it being guided by the experimental data we are solving the Ornstein-Zernike equation with a trial (variational) form of the interparticle interaction potential. To find all needed correlation functions this variational input is iterated numerically to satisfy the Ornstein-Zernike equation supplemented by a closure relation. Our method is developed for spherically symmetric scattering objects, and our numeric code is written for such a case. However, it can be extended (at the expense of more involved computations and a larger amount of required experimental input information) for nonspherical particles. What is important for our approach is that it is sufficient to know experimental data in a relatively narrow range of the scattering wave vectors (q ) to compute the static structure factor in a much broader range of q . We illustrate by a few model and real experimental examples of the x-ray and neutron scattering data how the approach works.

Effects of poly (ε-caprolactone) coating on the properties of three-dimensional printed porous structures.

PubMed

Zhou, Zuoxin; Cunningham, Eoin; Lennon, Alex; McCarthy, Helen O; Buchanan, Fraser; Clarke, Susan A; Dunne, Nicholas

2017-06-01

Powder-based inkjet three-dimensional printing (3DP) to fabricate pre-designed 3D structures has drawn increasing attention. However there are intrinsic limitations associated with 3DP technology due to the weak bonding within the printed structure, which significantly compromises its mechanical integrity. In this study, calcium sulphate ceramic structures demonstrating a porous architecture were manufactured using 3DP technology and subsequently post-processed with a poly (ε-caprolactone) (PCL) coating. PCL concentration, immersion time, and number of coating layers were the principal parameters investigated and improvement in compressive properties was the measure of success. Interparticle spacing within the 3DP structures were successfully filled with PCL material. Consequently the compressive properties, wettability, morphology, and in vitro resorption behaviour of 3DP components were significantly augmented. The average compressive strength, Young׳s modulus, and toughness increased 217%, 250%, and 315%, following PCL coating. Addition of a PCL surface coating provided long-term structural support to the host ceramic material, extending the resorption period from less than 7 days to a minimum of 56 days. This study has demonstrated that application of a PCL coating onto a ceramic 3DP structure was a highly effective approach to addressing some of the limitations of 3DP manufacturing and allows this advanced technology to be potentially used in a wider range of applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

Discovery of a Frank-Kasper [sigma] Phase in Sphere-Forming Block Copolymer Melts

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

Lee, Sangwoo; Bluemle, Michael J.; Bates, Frank S.

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma ({sigma}) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the {sigma} phase in undiluted linear block copolymers (and certain branchedmore » dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.« less

Bent dark soliton dynamics in two spatial dimensions beyond the mean field approximation

NASA Astrophysics Data System (ADS)

Mistakidis, Simeon; Katsimiga, Garyfallia; Koutentakis, Georgios; Kevrekidis, Panagiotis; Schmelcher, Peter; Theory Group of Fundamental Processes in Quantum Physics Team

2017-04-01

The dynamics of a bented dark soliton embedded in two spatial dimensions beyond the mean-field approximation is explored. We examine the case of a single bented dark soliton comparing the mean-field approximation to a correlated approach that involves multiple orbitals. Fragmentation is generally present and significantly affects the dynamics, especially in the case of stronger interparticle interactions and in that of lower atom numbers. It is shown that the presence of fragmentation allows for the appearance of solitonic and vortex structures in the higher-orbital dynamics. In particular, a variety of excitations including dark solitons in multiple orbitals and vortex-antidark complexes is observed to arise spontaneously within the beyond mean-field dynamics. Deutsche Forschungsgemeinschaft (DFG) in the framework of the SFB 925 ``Light induced dynamics and control of correlated quantum systems''.

Electromagnetic energy transport in nanoparticle chains via dark plasmon modes.

PubMed

Solis, David; Willingham, Britain; Nauert, Scott L; Slaughter, Liane S; Olson, Jana; Swanglap, Pattanawit; Paul, Aniruddha; Chang, Wei-Shun; Link, Stephan

2012-03-14

Using light to exchange information offers large bandwidths and high speeds, but the miniaturization of optical components is limited by diffraction. Converting light into electron waves in metals allows one to overcome this problem. However, metals are lossy at optical frequencies and large-area fabrication of nanometer-sized structures by conventional top-down methods can be cost-prohibitive. We show electromagnetic energy transport with gold nanoparticles that were assembled into close-packed linear chains. The small interparticle distances enabled strong electromagnetic coupling causing the formation of low-loss subradiant plasmons, which facilitated energy propagation over many micrometers. Electrodynamic calculations confirmed the dark nature of the propagating mode and showed that disorder in the nanoparticle arrangement enhances energy transport, demonstrating the viability of using bottom-up nanoparticle assemblies for ultracompact opto-electronic devices. © 2012 American Chemical Society

Following in Real Time the Two-Step Assembly of Nanoparticles into Mesocrystals in Levitating Drops.

PubMed

Agthe, Michael; Plivelic, Tomás S; Labrador, Ana; Bergström, Lennart; Salazar-Alvarez, German

2016-11-09

Mesocrystals composed of crystallographically aligned nanocrystals are present in biominerals and assembled materials which show strongly directional properties of importance for mechanical protection and functional devices. Mesocrystals are commonly formed by complex biomineralization processes and can also be generated by assembly of anisotropic nanocrystals. Here, we follow the evaporation-induced assembly of maghemite nanocubes into mesocrystals in real time in levitating drops. Analysis of time-resolved small-angle X-ray scattering data and ex situ scanning electron microscopy together with interparticle potential calculations show that the substrate-free, particle-mediated crystallization process proceeds in two stages involving the formation and rapid transformation of a dense, structurally disordered phase into ordered mesocrystals. Controlling and tailoring the particle-mediated formation of mesocrystals could be utilized to assemble designed nanoparticles into new materials with unique functions.

Communication: Programmable self-assembly of thin-shell mesostructures

DOE PAGES

Halverson, Jonathan D.; Tkachenko, Alexei V.

2017-10-13

For this article, we study numerically the possibility of programmable self-assembly of various thin-shell architectures. They include clusters isomorphic to fullerenes C 20 and C 60, finite and infinite sheets, tube-shaped and toroidal mesostructures. Our approach is based on the recently introduced directionally functionalized nanoparticle platform, for which we employ a hybrid technique of Brownian dynamics with stochastic bond formation. By combining a number of strategies, we were able to achieve a near-perfect yield of the desired structures with a reduced “alphabet” of building blocks. Among those strategies are the following: the use of bending rigidity of the interparticle bondmore » as a control parameter, programming the morphology with a seed architecture, use of chirality-preserving symmetries for reduction of the particle alphabet, and the hierarchic approach.« less

Communication: Programmable self-assembly of thin-shell mesostructures

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

Halverson, Jonathan D.; Tkachenko, Alexei V.

For this article, we study numerically the possibility of programmable self-assembly of various thin-shell architectures. They include clusters isomorphic to fullerenes C 20 and C 60, finite and infinite sheets, tube-shaped and toroidal mesostructures. Our approach is based on the recently introduced directionally functionalized nanoparticle platform, for which we employ a hybrid technique of Brownian dynamics with stochastic bond formation. By combining a number of strategies, we were able to achieve a near-perfect yield of the desired structures with a reduced “alphabet” of building blocks. Among those strategies are the following: the use of bending rigidity of the interparticle bondmore » as a control parameter, programming the morphology with a seed architecture, use of chirality-preserving symmetries for reduction of the particle alphabet, and the hierarchic approach.« less

Trace contaminant adsorption and sorbent regeneration in closed ecological systems

NASA Technical Reports Server (NTRS)

Arnold, C. R.; Kersels, G. J.; Merrill, R. P.; Robell, A. J.; Wheeler, A.

1972-01-01

Correlation was obtained for determining sorptive capacity of carbon for pure and mixed contaminants under dry and humid conditions at various temperatures. Vacuum desorption rates were investigated for single particles and for sorbent beds. For sorbent beds, rate-determining step is Knudsen diffusion through interparticle voids.

A Facile Method to In-Situ Synthesize Porous Ni₂GeO₄ Nano-Sheets on Nickel Foam as Advanced Anode Electrodes for Li-Ion Batteries.

PubMed

Ma, Delong; Shi, Xiaomin; Hu, Anming

2016-11-19

A strategy for growth of porous Ni₂GeO₄ nanosheets on conductive nickel (Ni) foam with robust adhesion as a high-performance electrode for Li-ion batteries is proposed and realized, through a facile two-step method. It involves the low temperature hydro-thermal synthesis of bimetallic (Ni, Ge) hydroxide nanosheets precursor on Ni foam substrates and subsequent thermal transformation to porous Ni₂GeO₄ nanosheets. The as-prepared Ni₂GeO₄ nanosheets possess many interparticle mesopores with a size range from 5 to 15 nm. The hierarchical structure of porous Ni₂GeO₄ nanosheets supported by Ni foam promises fast electron and ion transport, large electroactive surface area, and excellent structural stability. The efficacy of the specially designed structure is demonstrated by the superior electrochemical performance of the generated Ni₂GeO₄ nanosheets including a high capacity of 1.8 mA·h·cm -2 at a current density of 50 μA·cm -2 , good cycle stability, and high power capability at room temperature. Because of simple conditions, this fabrication strategy may be easily extended to other mixed metal oxides (M x GeO y ).

Spontaneous formation of nanostructures inside inkjet-printed colloidal drops

NASA Astrophysics Data System (ADS)

Yang, Xin; Thorne, Nathaniel; Sun, Ying

2013-11-01

Nanostructures formed in inkjet-printed colloidal drops are systematically examined with different substrates and ink formulations. Various deposition patterns from multi-ring, radial spoke, firework to spider web, foam and island structures are observed. With a high particle loading, deposition transitions from multi-ring near the drop edge to spider web and finally to foam and islands in the center of the drop with 20 nm sulfate-modified polystyrene particles. At the same particle loading, 200 nm particles self-assemble into radial spokes at the drop edge and islands in the center, due to reduced contact line pinning resulted from less particles. In drops with a low particle concentration, due to fingering instability of the contact line, 20 nm particles form radial spokes enclosed by a ring, while 200 nm particles assemble into firework-like structures without a ring. Moreover, at a high particle loading, ruptures are observed on the multi-ring structure formed by 20 nm carboxylic-modified particles, due to stronger capillary forces from the contact line. Furthermore, for a drop printed on a less hydrophilic substrate, the interparticle interactions enable a more uniform deposition rather than complex nanostructures.

Modeling shear-induced particle ordering and deformation in a dense soft particle suspension

NASA Astrophysics Data System (ADS)

Liao, Chih-Tang; Wu, Yi-Fan; Chien, Wei; Huang, Jung-Ren; Chen, Yeng-Long

2017-11-01

We apply the lattice Boltzmann method and the bead-spring network model of deformable particles (DPs) to study shear-induced particle ordering and deformation and the corresponding rheological behavior for dense DP suspensions confined in a narrow gap under steady external shear. The particle configuration is characterized with small-angle scattering intensity, the real-space 2D local order parameter, and the particle shape factors including deformation, stretching and tilt angles. We investigate how particle ordering and deformation vary with the particle volume fraction ϕ (=0.45-0.65) and the external shear rate characterized with the capillary number Ca (=0.003-0.191). The degree of particle deformation increases mildly with ϕ but significantly with Ca. Under moderate shear rate (Ca  =  0.105), the inter-particle structure evolves from string-like ordering to layered hexagonal close packing (HCP) as ϕ increases. A long wavelength particle slithering motion emerges for sufficiently large ϕ. For ϕ  =  0.61, the structure maintains layered HCP for Ca  =  0.031-0.143 but gradually becomes disordered for larger and smaller Ca. The correlation in particle zigzag movements depends sensitively on ϕ and particle ordering. Layer-by-layer analysis reveals how the non-slippery hard walls affect particle ordering and deformation. The shear-induced reconfiguration of DPs observed in the simulation agrees qualitatively with experimental results of sheared uniform emulsions. The apparent suspension viscosity increases with ϕ but exhibits much weaker dependence compared to hard-sphere suspensions, indicating that particle deformation and unjamming under shear can significantly reduce the viscous stress. Furthermore, the suspension shear-thins, corresponding to increased inter-DP ordering and particle deformation with Ca. This work provides useful insights into the microstructure-rheology relationship of concentrated deformable particle suspensions.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Modeling shear-induced particle ordering and deformation in a dense soft particle suspension.

PubMed

Liao, Chih-Tang; Wu, Yi-Fan; Chien, Wei; Huang, Jung-Ren; Chen, Yeng-Long

2017-11-01

We apply the lattice Boltzmann method and the bead-spring network model of deformable particles (DPs) to study shear-induced particle ordering and deformation and the corresponding rheological behavior for dense DP suspensions confined in a narrow gap under steady external shear. The particle configuration is characterized with small-angle scattering intensity, the real-space 2D local order parameter, and the particle shape factors including deformation, stretching and tilt angles. We investigate how particle ordering and deformation vary with the particle volume fraction ϕ (=0.45-0.65) and the external shear rate characterized with the capillary number Ca (=0.003-0.191). The degree of particle deformation increases mildly with ϕ but significantly with Ca. Under moderate shear rate (Ca  =  0.105), the inter-particle structure evolves from string-like ordering to layered hexagonal close packing (HCP) as ϕ increases. A long wavelength particle slithering motion emerges for sufficiently large ϕ. For ϕ  =  0.61, the structure maintains layered HCP for Ca  =  0.031-0.143 but gradually becomes disordered for larger and smaller Ca. The correlation in particle zigzag movements depends sensitively on ϕ and particle ordering. Layer-by-layer analysis reveals how the non-slippery hard walls affect particle ordering and deformation. The shear-induced reconfiguration of DPs observed in the simulation agrees qualitatively with experimental results of sheared uniform emulsions. The apparent suspension viscosity increases with ϕ but exhibits much weaker dependence compared to hard-sphere suspensions, indicating that particle deformation and unjamming under shear can significantly reduce the viscous stress. Furthermore, the suspension shear-thins, corresponding to increased inter-DP ordering and particle deformation with Ca. This work provides useful insights into the microstructure-rheology relationship of concentrated deformable particle suspensions.

An NMR Study of Biomimetic Fluorapatite – Gelatine Mesocrystals

PubMed Central

Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

2015-01-01

The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals. PMID:26515127

Convoluted Quasi Sturmian basis for the two-electron continuum

NASA Astrophysics Data System (ADS)

Ancarani, Lorenzo Ugo; Zaytsev, A. S.; Zaytsev, S. A.

2016-09-01

In the construction of solutions for the Coulomb three-body scattering problem one encounters a series of mathematical and numerical difficulties, one of which are the cumbersome boundary conditions the wave function should obey. We propose to describe a Coulomb three-body system continuum with a set of two-particle functions, named Convoluted Quasi Sturmian (CQS) in. They are built using recently introduced Quasi Sturmian (QS) functions which have the merit of possessing a closed form. Unlike a simple product of two one-particle functions, by construction, the CQS functions look asymptotically like a six-dimensional outgoing spherical wave. The proposed CQS basis is tested through the study of the double ionization of helium by high-energy electron impact in the framework of the Temkin-Poet model. An adequate logarithmic-like phase factor is further included in order to take into account the Coulomb interelectronic interaction and formally build the correct asymptotic behavior when all interparticle distances are large. With such a phase-factor (that can be easily extended to take into account higher partial waves) rapid convergence of the expansion can be obtained.

Mesoscale simulations of shock compaction of a granular ceramic: effects of mesostructure and mixed-cell strength treatment

NASA Astrophysics Data System (ADS)

Derrick, J. G.; LaJeunesse, J. W.; Davison, T. M.; Borg, J. P.; Collins, G. S.

2018-04-01

The shock response of granular materials is important in a variety of contexts but the precise dynamics of grains during compaction is poorly understood. Here we use 2D mesoscale numerical simulations of the shock compaction of granular tungsten carbide to investigate the effect of internal structure within the particle bed and ‘stiction’ between grains on the shock response. An increase in the average number of contacts with other particles, per particle, tends to shift the Hugoniot to higher shock velocities, lower particle velocities and lower densities. This shift is sensitive to inter-particle shear resistance. Eulerian shock physics codes approximate friction between, and interlocking of, grains with their treatment of mixed cell strength (stiction) and here we show that this has a significant effect on the shock response. When studying the compaction of particle beds it is not common to quantify the pre-compaction internal structure, yet our results suggest that such differences should be taken into account, either by using identical beds or by averaging results over multiple experiments.

Coagulation mechanism of salt solution-extracted active component in Moringa oleifera seeds.

PubMed

Okuda, T; Baes, A U; Nishijima, W; Okada, M

2001-03-01

This study focuses on the coagulation mechanism by the purified coagulant solution (MOC-SC-PC) with the coagulation active component extracted from M. oleifera seeds using salt solution. The addition of MOC-SC-PC tap water formed insoluble matters. This formation was responsible for kaolin coagulation. On the other hand, insoluble matters were not formed when the MOC-SC-PC was added into distilled water. The formation was affected by Ca2+ or other bivalent cations which may connect each molecule of the active coagulation component in MOC-SC-PC and form a net-like structure. The coagulation mechanism of MOC-SC-PC seemed to be an enmeshment of Kaolin by the insoluble matters with the net-like structure. In case of Ca2+ ion (bivalent cations), at least 0.2 mM was necessary for coagulation at 0.3 mgC l-1 dose of MOC-SC-PC. Other coagulation mechanisms like compression of double layer, interparticle bridging or charge neutralization were not responsible for the coagulation by MOC-SC-PC.

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

PubMed

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

2017-02-22

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

Effect of surfactant types and their concentration on the structural characteristics of nanoclay

NASA Astrophysics Data System (ADS)

Zawrah, M. F.; Khattab, R. M.; Saad, E. M.; Gado, R. A.

2014-03-01

A series of organo-modified nanoclays was synthesized using three different surfactants having different alkyl chain lengths and concentrations [0.5-5.0 cation exchange capacity (CEC)]. These surfactants were Ethanolamine (EA), Cetyltrimethylammoniumbromide (CTAB) and Tetraoctadecylammoniumbromide (TO). The obtained modified nanoclays were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) and compared with unmodified nanoclay. The results of XRD analysis indicated that the basal d-spacing has increased with increasing alkyl chain length and surfactant concentration. From the obtained microstructures of these organo-modified nanoclays, the mechanism of surfactant adsorption was proposed. At relatively low loading of surfactant, most of surfactant entered the spacing by an ion-exchange mechanism and is adsorbed onto the interlayer cation sites. When the concentration of the surfactant exceeds the CEC of clay, the surfactant molecules then adhere to the surface adsorbed surfactant. Some surfactants entered the interlayers, whereas the others were attached to the clay surface. When the concentration of surfactant increased further beyond 2.0 CEC, the surfactants might occupy the inter-particle space within the house-of-cards aggregate structure.

Pentaethylenehexamine-Loaded Hierarchically Porous Silica for CO2 Adsorption

PubMed Central

Ji, Changchun; Huang, Xin; Li, Lei; Xiao, Fukui; Zhao, Ning; Wei, Wei

2016-01-01

Recently, amine-functionalized materials as a prospective chemical sorbent for post combustion CO2 capture have gained great interest. However, the amine grafting for the traditional MCM-41, SBA-15, pore-expanded MCM-41 or SBA-15 supports can cause the pore volume and specific surface area of sorbents to decrease, significantly affecting the CO2 adsorption-desorption dynamics. To overcome this issue, hierarchical porous silica with interparticle macropores and long-range ordering mesopores was prepared and impregnated with pentaethylenehexamine. The pore structure and amino functional group content of the modified silicas were analyzed by scanning electron microscope, transmission electron microscope, N2 adsorption, X-ray powder diffraction, and Fourier transform infrared spectra. Moreover, the effects of the pore structure as well as the amount of PEHA loading of the samples on the CO2 adsorption capacity were investigated in a fixed-bed adsorption system. The CO2 adsorption capacity reached 4.5 mmol CO2/(g of adsorbent) for HPS−PEHA-70 at 75 °C. Further, the adsorption capacity for HPS-PEHA-70 was steady after a total of 15 adsorption-desorption cycles. PMID:28773956

Self-assembly of colloids with magnetic caps

NASA Astrophysics Data System (ADS)

Novak, E. V.; Kantorovich, S. S.

2017-06-01

In our earlier work (Steinbach et al., 2016 [1]) we investigated a homogeneous system of magnetically capped colloidal particles that self-assembled via two structural patterns of different symmetry. The particles could form a compact, equilateral triangle with a three-fold rotational symmetry and zero dipole moment and a staggered chain with mirror symmetry with a net magnetisation perpendicular to the chain. The system exhibited a bistability already in clusters of three particles. Based on observations of a real magnetic particles system, analytical calculations and molecular dynamics simulations, it has been shown that the bistability is a result of an anisotropic magnetisation distribution with rotational symmetry inside the particles. The present study is a logical extension of the above research and forms a preparatory stage for the study of a self-assembly of such magnetic particles under the influence of an external magnetic field. Since the magnetic field is only an additive contribution to the total ground state energy, we can study the interparticle interaction energies of candidate ground state structures based on the field-free terms.

Using Space for a Better Foundation on Earth: Mechanics of Granular Materials. Educational Brief. Grades 5-8.

ERIC Educational Resources Information Center

Alshibli, Khalid

This publication presents a science activity and instructional information on mechanics of granular materials, interparticle friction and geometric interlocking between particles which is a fundamental concept in many fields like earthquakes. The activity described in this document focuses on the principal strength of granular materials,…

Numerical and experimental analysis of the sedimentation of spherical colloidal suspensions under centrifugal force

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.

Modeling and simulation of dielectrophoretic collective dynamics in a suspension of polarizable particles under the action of a gradient AC electric field.

PubMed

Tada, Shigeru; Shen, Yan; Qiu, Zhiyong

2017-06-01

When a suspension of polarizable particles is subjected to a gradient AC electric field, the particles exhibit collective motion due to an interaction between the dipole induced in the particles and the spatial gradient of the electric field; this is known as dielectrophoresis. In the present study, the collective dynamics of suspended particles in a parallel-plate electric chamber was investigated by simulating numerically the trajectories of individual particles under the action of combined dielectrophoretic and dipole-dipole interparticle forces. The particles were transported by the dielectrophoretic forces toward the grounded electrodes. Before long, when the particles approached the site of the minimum field strength, attractive/repulsive interparticle forces became dominant and acted among the particles attempting to form a column-like cluster, having the particles distribution in concentric circles in its cross-section, in line with the centerline of the grounded electrodes. Our results also well reproduced the transient particle aggregation that was observed experimentally. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonlinear waves in repulsive media supported by spatially localized parity-time-symmetric potentials

NASA Astrophysics Data System (ADS)

Devassy, Lini; Jisha, Chandroth P.; Alberucci, Alessandro; Kuriakose, V. C.

2017-06-01

We study the existence, stability and dynamics of solitons in a PT-symmetric potential in the presence of a local defocusing nonlinearity. For the sake of concreteness, we refer to Bose-Einstein condensates, where defocusing nonlinearity stems from a repulsive inter-particle interaction. Two kinds of transverse profiles for the gain-loss mechanism, i.e., the imaginary part of the potential, are considered. Differently from the attractive inter-particle interaction, solitons exist only inside a narrow band of chemical potential and particle number. The existence region shrinks as the magnitude of the gain-loss is increased, with the soliton ceasing to exist above the linear exceptional point, that is, the point at which PT symmetry is broken. Using linear stability analysis together with full numerical simulations of the Gross-Pitaevskii equation, we show that solitons survive on temporal scales much longer than the diffusion time. For magnitude of gain-loss close to the exceptional point, stability depends on the transverse profile of the gain-loss mechanism and the magnitude of the nonlinear excitation.

Generating a stationary infinite range tractor force via a multimode optical fibre

NASA Astrophysics Data System (ADS)

Ebongue, C. A.; Holzmann, D.; Ostermann, S.; Ritsch, H.

2017-06-01

Optical fibres confine and guide light almost unattenuated and thus convey light forces to polarizable nano-particles over very long distances. Radiation pressure forces arise from scattering of guided photons into free space while gradient forces are based on coherent scattering between different fibre modes or propagation directions. Interestingly, even scattering between co-propagating modes induces longitudinal forces as the transverse confinement of the light modes creates mode dependent longitudinal wave-vectors and photon momenta. We generalize a proven scattering matrix based approach to calculate single as well as inter-particle forces to include several forward and backward propagating modes. We show that an injection of the higher order mode only in a two mode fibre will induce a stationary tractor force against the injection direction, when the mode coupling to the lower order mode dominates against backscattering and free space losses. Generically this arises for non-absorbing particles at the centre of a waveguide. The model also gives improved predictions for inter-particle forces in evanescent nanofibre fields as experimentally observed recently. Surprisingly strong tractor forces can also act on whole optically bound arrays.

Microscopic information processing and communication in crowd dynamics

NASA Astrophysics Data System (ADS)

Henein, Colin Marc; White, Tony

2010-11-01

Due, perhaps, to the historical division of crowd dynamics research into psychological and engineering approaches, microscopic crowd models have tended toward modelling simple interchangeable particles with an emphasis on the simulation of physical factors. Despite the fact that people have complex (non-panic) behaviours in crowd disasters, important human factors in crowd dynamics such as information discovery and processing, changing goals and communication have not yet been well integrated at the microscopic level. We use our Microscopic Human Factors methodology to fuse a microscopic simulation of these human factors with a popular microscopic crowd model. By tightly integrating human factors with the existing model we can study the effects on the physical domain (movement, force and crowd safety) when human behaviour (information processing and communication) is introduced. In a large-room egress scenario with ample exits, information discovery and processing yields a crowd of non-interchangeable individuals who, despite close proximity, have different goals due to their different beliefs. This crowd heterogeneity leads to complex inter-particle interactions such as jamming transitions in open space; at high crowd energies, we found a freezing by heating effect (reminiscent of the disaster at Central Lenin Stadium in 1982) in which a barrier formation of naïve individuals trying to reach blocked exits prevented knowledgeable ones from exiting. Communication, when introduced, reduced this barrier formation, increasing both exit rates and crowd safety.

Gravity-driven, dry granular flows over a loose bed in stationary and homogeneous conditions

NASA Astrophysics Data System (ADS)

Meninno, Sabrina; Armanini, Aronne; Larcher, Michele

2018-02-01

Flows involving solid particulates have been widely studied in recent years, but their dynamics are still a complex issue to model because they strongly depend on the interaction with the boundary conditions. We report on laboratory investigations regarding homogeneous and steady flows of identical particles over a loose bed in a rectangular channel. Accurate measurements were carried out through imaging techniques to estimate profiles of the mean velocity, solid concentration, and granular temperature for a large set of flow rates and widths. Vertical and transversal structures observed in the flow change as interparticle interactions become more collisional, and they depend on the bottom over which the flow develops. The lateral confinement has a remarkable effect on the flow, especially for narrow channels compared with the grain size, and a hydraulic analogy is able to show how the walls influence the mechanisms of friction and energy dissipation.

Structural evolution and mechanical behaviour of Pt nanoparticle superlattices at high pressure

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

Zhu, Jinlong; Quan, Zewei; Wang, Chenyu

High pressure is an effective means for tuning the interparticle distances of nanoparticle (NP) superlattice and thus for modifying their physical properties and functionalities. In this work, we determined the evolutio of inter-NP distances of a Pt NP superlattice with increasing pressure using an in situ synchrotro small-angle X-ray scattering (SAXS) technique in a diamond-anvil cell (DAC). Transmission electro microscopy (TEM) was used to characterize the microstructures of pre- and post-compression samples Our results demonstrate that the evolution of Pt NP assemblies with increasing pressure consists of fou stages: (1) ligand elastic response, (2) uniform compression, (3) ligand detachment frommore » NP surfaces, an (4) deviatoric compression of ligands between neighboring NPs. Lastly, by controlling the magnitudes of applie pressure and deviatoric stress, one can sinter NPs into novel architectures such as nanowires an nanoceramics.« less

Photonic Architectures for Equilibrium High-Temperature Bose-Einstein Condensation in Dichalcogenide Monolayers

PubMed Central

Jiang, Jian-Hua; John, Sajeev

2014-01-01

Semiconductor-microcavity polaritons are composite quasiparticles of excitons and photons, emerging in the strong coupling regime. As quantum superpositions of matter and light, polaritons have much stronger interparticle interactions compared with photons, enabling rapid equilibration and Bose-Einstein condensation (BEC). Current realizations based on 1D photonic structures, such as Fabry-Pérot microcavities, have limited light-trapping ability resulting in picosecond polariton lifetime. We demonstrate, theoretically, above-room-temperature (up to 590 K) BEC of long-lived polaritons in MoSe2 monolayers sandwiched by simple TiO2 based 3D photonic band gap (PBG) materials. The 3D PBG induces very strong coupling of 40 meV (Rabi splitting of 62 meV) for as few as three dichalcogenide monolayers. Strong light-trapping in the 3D PBG enables the long-lived polariton superfluid to be robust against fabrication-induced disorder and exciton line-broadening. PMID:25503586

Steady state rheology from homogeneous and locally averaged simple shear simulations

NASA Astrophysics Data System (ADS)

Shi, Hao; Luding, Stefan; Magnanimo, Vanessa

2017-06-01

Granular materials and particulate matter are ubiquitous in our daily life and they display interesting bulk behaviors from static to dynamic, solid to fluid or gas like states, or even all these states together. To understand how the micro structure and inter-particle forces influence the macroscopic bulk behavior is still a great challenge today. This short paper presents stress controlled homogeneous simple shear results in a 3D cuboidal box using MercuryDPM software. An improved rheological model is proposed for macroscopic friction, volume fraction and coordination number as a function of inertial number and pressure. In addition, the results are compared with the locally averaged data from steady state shear bands in a split bottom ring shear cell and very good agreement is observed in low to intermediate inertia regime at various confining pressure but not for high inertia collisional granular flow.

Molecular dynamics study of the structure and interparticle interactions of polyethylene glycol-conjugated PAMAM dendrimers.

PubMed

Lee, Hwankyu; Larson, Ronald G

2009-10-08

We performed molecular dynamics (MD) simulations of one or two copies of polyethylene glycol of molecular weight 550 (PEG550) and 5000 (PEG5000) daltons, conjugated to generation 3 (G3) to 5 (G5) polyamidoamine (PAMAM) dendrimers with explicit water using a coarse-grained model. We found the radii of gyration of these dendrimer-PEG molecules to be close to those measured in experiments by Hedden and Bauer (Hedden , R. C. ; Bauer , B. J. Macromolecules 2003 , 36 , 1829.). Densely grafted PEG ligands (>50% of the dendrimer surface) extend like brushes, with layer thickness in agreement with theory for starlike polymers. Two dendrimer-PEG complexes in the box drift away from each other, indicating that no aggregation is induced by either short or long PEG chains, conflicting with a recent view that the cytotoxicity of some PEGylated particles might be due to particle aggregation for long PEG lengths.

Effect of granular activated carbon on the aerobic granulation of sludge and its mechanism.

PubMed

Tao, Jia; Qin, Lian; Liu, Xiaoying; Li, Bolin; Chen, Junnan; You, Juan; Shen, Yitian; Chen, Xiaoguo

2017-07-01

The granulation of activated sludge and effect of granular activated carbon (GAC) was investigated under the alternative anaerobic and aerobic conditions. The results showed that GAC accelerated the granulation, but had no obvious effect on the bacterial community structure of granules. The whole granulation process could be categorized into three phases, i.e. lag, granulation and granule maturation phase. During lag period GAC provided nuclei for sludge to attach, and thus enhanced the morphological regularization of sludge. During granulation period the granule size increased significantly due to the growth of bacteria in granules. GAC reduced the compression caused by the inter-particle collisions and thus accelerate the granulation. GAC has no negative effect on the performance of SBR, and thus efficient simultaneous removal of COD, nitrogen and phosphorus were obtained during most of the operating time. Copyright © 2017. Published by Elsevier Ltd.

Simulation of Orientation in Injection Molding of High Aspect Ratio Particle Thermoplastic Composites

NASA Astrophysics Data System (ADS)

Vélez-García, Gregorio M.; Ortman, Kevin C.; Eberle, Aaron P. R.; Wapperom, Peter; Baird, Donald G.

2008-07-01

A 2D coupled Hele-Shaw flow approximation for predicting the flow-induced orientation of high aspect ratio particles in injection molded composite parts is presented. For a highly concentrated short glass fiber PBT suspension, the impact of inter-particle interactions and the orientation at the gate is investigated for a center-gated disk using material parameters determined from rheometry. Experimental orientation is determined from confocal laser micrographs using the methods of ellipses. The constitutive equations are discretized using discontinuous Galerkin Finite Elements. Model predictions are significantly improved by using a localized orientation measured experimentally at the gate region instead of random or averaged gapwise measured orientation assumed in previous studies. The predicted profile in different radial positions can be related to the layered structure along the gapwise direction. Model modifications including interactions have lower impact than the initial conditions.

Recent Advances in the Theory and Simulation of Model Colloidal Microphase Formers.

PubMed

Zhuang, Yuan; Charbonneau, Patrick

2016-08-18

This mini-review synthesizes our understanding of the equilibrium behavior of particle-based models with short-range attractive and long-range repulsive (SALR) interactions. These models, which can form stable periodic microphases, aim to reproduce the essence of colloidal suspensions with competing interparticle interactions. Ordered structures, however, have yet to be obtained in experiments. In order to better understand the hurdles to periodic microphase assembly, marked theoretical and simulation advances have been made over the past few years. Here, we present recent progress in the study of microphases in models with SALR interactions using liquid-state theory and density-functional theory as well as numerical simulations. Combining these various approaches provides a description of periodic microphases, and gives insights into the rich phenomenology of the surrounding disordered regime. Ongoing research directions in the thermodynamics of models with SALR interactions are also presented.

Selective transformations between nanoparticle superlattices via the reprogramming of DNA-mediated interactions

DOE PAGES

Zhang, Yugang; Pal, Suchetan; Srinivasan, Babji; ...

2015-05-25

The rapid development of self-assembly approaches has enabled the creation of materials with desired organization of nanoscale components. However, achieving dynamic control, wherein the system can be transformed on demand into multiple entirely different states, is typically absent in atomic and molecular systems and has remained elusive in designed nanoparticle systems. Here, we demonstrate with in situ small-angle x-ray scattering that, by using DNA strands as inputs, the structure of a three-dimensional lattice of DNA-coated nanoparticles can be switched from an initial 'mother' phase into one of multiple 'daughter' phases. The introduction of different types of re-programming DNA strands modifiesmore » the DNA shells of the nanoparticles within the superlattice, thereby shifting interparticle interactions to drive the transformation into a particular daughter phase. We mapped quantitatively with free-energy calculations the selective re-programming of interactions onto the observed daughter phases.« less

Structural evolution and mechanical behaviour of Pt nanoparticle superlattices at high pressure

DOE PAGES

Zhu, Jinlong; Quan, Zewei; Wang, Chenyu; ...

2016-02-05

High pressure is an effective means for tuning the interparticle distances of nanoparticle (NP) superlattice and thus for modifying their physical properties and functionalities. In this work, we determined the evolutio of inter-NP distances of a Pt NP superlattice with increasing pressure using an in situ synchrotro small-angle X-ray scattering (SAXS) technique in a diamond-anvil cell (DAC). Transmission electro microscopy (TEM) was used to characterize the microstructures of pre- and post-compression samples Our results demonstrate that the evolution of Pt NP assemblies with increasing pressure consists of fou stages: (1) ligand elastic response, (2) uniform compression, (3) ligand detachment frommore » NP surfaces, an (4) deviatoric compression of ligands between neighboring NPs. Lastly, by controlling the magnitudes of applie pressure and deviatoric stress, one can sinter NPs into novel architectures such as nanowires an nanoceramics.« less

Constitutive and Stability Behavior of Soils in Microgravity Environment

NASA Technical Reports Server (NTRS)

Alshibli, Khalid A.; Sture, Stein; Costes, Nicholas

2000-01-01

All aspects of soil stability, bearing capacity, slope stability, the supporting capacity of deep foundations, and penetration resistance depend on soil strength. The stress-deformation and stress-deformation-time behavior of soils are of importance in any problem where ground movements are of interest. In most engineering materials, the strength is derived from internal chemical and physico-chemical forces of interaction, which bond the atoms, molecules, and particles together. In soils, the constitutive relations are mainly derived from interparticle friction between particles and particle groups and dilatancy, and to a lesser extent from particle bonding by weak electrostatic, physico-chemical, and coulomb forces. For engineering purposes, soils are classified as cohesive (clays and silts; typical particle sizes range from 10 nm to 10 micrometers) and cohesionless (sand and gravel; typical particle sizes range from 10 micrometers to 75 mm). The mechanical or constitutive properties of cohesionless soils or granular materials are highly fabric-dependent, highly non-linear, and non-conservative with engineering properties primarily depending on the effects of gravity through self-weight and on the tractions or forces applied to the soil mass. Under moderate-to-high stress levels, the influence of gravity on the behavior of laboratory test specimens may not be pronounced and, therefore, the test results in terrestrial (1-g) environment may be sufficiently conclusive. However at low interparticle stresses, which can result either from low applied (confining) stresses or from excess pore fluid pressures developed within the soil mass without corresponding changes in the applied stresses, the presence of gravitational body forces acting on solid particles and interstitial fluids exerts a pronounced influence on movement of individual particles or particle groups. Such motions, in turn, cause changes in soil fabric which results in significant changes in the interparticle friction forces contributing to the soil's strength and deformation characteristics.

Acoustic attraction, repulsion and radiation force cancellation on a pair of rigid particles with arbitrary cross-sections in 2D: Circular cylinders example

NASA Astrophysics Data System (ADS)

Mitri, F. G.

2017-11-01

The acoustic radiation forces arising on a pair of sound impenetrable cylindrical particles of arbitrary cross-sections are derived. Plane progressive, standing or quasi-standing waves with an arbitrary incidence angle are considered. Multiple scattering effects are described using the multipole expansion formalism and the addition theorem of cylindrical wave functions. An effective incident acoustic field on a particular object is determined, and used with the scattered field to derive closed-form analytical expressions for the radiation force vector components. The mathematical expressions for the radiation force components are exact, and have been formulated in partial-wave series expansions in cylindrical coordinates involving the angle of incidence, the reflection coefficient forming the progressive or the (quasi)standing wave field, the addition theorem, and the expansion coefficients. Numerical examples illustrate the analysis for two rigid circular cross-sections immersed in a non-viscous fluid. Computations for the dimensionless radiation force functions are performed with emphasis on varying the angle of incidence, the interparticle distance, the sizes of the particles as well as the characteristics of the incident field. Depending on the interparticle distance and angle of incidence, one of the particles yields neutrality; it experiences no force and becomes unresponsive (i.e., ;invisible;) to the linear momentum transfer of the effective incident field due to multiple scattering cancellation effects. Moreover, attractive or repulsive forces between the two particles may arise depending on the interparticle distance, the angle of incidence and size parameters of the particles. This study provides a complete analytical method and computations for the axial and transverse radiation force components in multiple acoustic scattering encompassing the cases of plane progressive, standing or quasi-standing waves of arbitrary incidence by a pair of scatterers. Potential applications concern the prediction of the forces used in acoustically-engineered metamaterials with reconfigurable periodicities, cloaking devices, and liquid crystals to name a few examples.

Confocal Imaging of Confined Quiescent and Flowing Colloid-polymer Mixtures

PubMed Central

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

The effect of adsorbed liquid and material density on saltation threshold: Insight from laboratory and wind tunnel experiments

NASA Astrophysics Data System (ADS)

Yu, Xinting; Hörst, Sarah M.; He, Chao; Bridges, Nathan T.; Burr, Devon M.; Sebree, Joshua A.; Smith, James K.

2017-11-01

Saltation threshold, the minimum wind speed for sediment transport, is a fundamental parameter in aeolian processes. Measuring this threshold using boundary layer wind tunnels, in which particles are mobilized by flowing air, for a subset of different planetary conditions can inform our understanding of physical processes of sediment transport. The presence of liquid, such as water on Earth or methane on Titan, may affect the threshold values to a great extent. Sediment density is also crucial for determining threshold values. Here we provide quantitative data on density and water content of common wind tunnel materials (including chromite, basalt, quartz sand, beach sand, glass beads, gas chromatograph packing materials, walnut shells, iced tea powder, activated charcoal, instant coffee, and glass bubbles) that have been used to study conditions on Earth, Titan, Mars, and Venus. The measured density values for low density materials are higher compared to literature values (e.g., ∼30% for walnut shells), whereas for the high density materials, there is no such discrepancy. We also find that low density materials have much higher water content and longer atmospheric equilibration timescales compared to high density sediments. We used thermogravimetric analysis (TGA) to quantify surface and internal water and found that over 80% of the total water content is surface water for low density materials. In the Titan Wind Tunnel (TWT), where Reynolds number conditions similar to those on Titan can be achieved, we performed threshold experiments with the standard walnut shells (125-150 μm, 7.2% water by mass) and dried walnut shells, in which the water content was reduced to 1.7%. The threshold results for the two scenarios are almost the same, which indicates that humidity had a negligible effect on threshold for walnut shells in this experimental regime. When the water content is lower than 11.0%, the interparticle forces are dominated by adsorption forces, whereas at higher values the interparticle forces are dominated by much larger capillary forces. For materials with low equilibrium water content, like quartz sand, capillary forces dominate. When the interparticle forces are dominated by adsorption forces, the threshold does not increase with increasing relative humidity (RH) or water content. Only when the interparticle forces are dominated by capillary forces does the threshold start to increase with increasing RH/water content. Since tholins have a low methane content (0.3% at saturation, [Curtis, D. B., Hatch, C. D., Hasenkopf, C. A., et al., 2008. Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds. Icarus, 195, 792. http://dx.doi.org/10.1016/j.icarus.2008.02.003]), we believe tholins would behave similarly to quartz sand when subjected to methane moisture.

Facile Fabrication of a Silver Nanoparticle Immersed, Surface-Enhanced Raman Scattering Imposed Paper Platform through Successive Ionic Layer Absorption and Reaction for On-Site Bioassays.

PubMed

Kim, Wansun; Kim, Yeon-Hee; Park, Hun-Kuk; Choi, Samjin

2015-12-23

We introduce a novel, facile, rapid, low-cost, highly reproducible, and power-free synthesizable fabrication method of paper-based silver nanoparticle (AgNP) immersed surface-enhanced Raman scattering (SERS) platform, known as the successive ionic layer absorption and reaction (SILAR) method. The rough and porous properties of the paper led to direct synthesis of AgNPs on the surface as well as in the paper due to capillary effects, resulting in improved plasmon coupling with interparticles and interlayers. The proposed SERS platform showed an enhancement factor of 1.1 × 10(9), high reproducibility (relative standard deviation of 4.2%), and 10(-12) M rhodamine B highly sensitive detection limit by optimizing the SILAR conditions including the concentration of the reactive solution (20/20 mM/mM AgNO3/NaBH4) and the number of SILAR cycles (six). The applicability of the SERS platform was evaluated using two samples including human cervical fluid for clinical diagnosis of human papillomavirus (HPV) infection, associated with cervical cancer, and a malachite green (MG) solution for fungicide and parasiticide in aquaculture, associated with human carcinogenesis. The AgNP-immersed SERS-functionalized platform using the SILAR technique allowed for high chemical structure sensitivity without additional tagging or chemical modification, making it a good alternative for early clinical diagnosis of HPV infection and detection of MG-activated human carcinogenesis.

Electron spin resonance in Cu1-xFexCr2Se4 nanoparticles synthesized with the thermal decomposition method

NASA Astrophysics Data System (ADS)

Edelman, I. S.; Zharkov, S. M.; Pankrats, A. I.; Vorotynov, A. M.; Tugarinov, V. I.; Ivantsov, R. D.; Petrov, D. A.; Velikanov, D. A.; Lin, Chun-Rong; Chen, Chin-Chang; Tseng, Yaw-Teng; Hsu, Hua-Shu

2017-08-01

In this paper, we present a study of the electron spin resonance (ESR) of nanoparticles (NPs) of Cu1-xFexCr2Se4 chalcogenides with x = 0, 0.2, and 0.4. NPs were synthesized via the thermal decomposition of metal chloride salts and selenium powder in a high-temperature organic solvent. According to the XRD and HRTEM data, the NPs were single crystalline nearly hexagonal plates with the structure close to CuCr2Se4 (Fd-3m, a = 10.337 Å). For x = 0 and 0.2, the NPs tend to form long stacks consisting of the plates ;face to face; attached to each other due to the magnetostatic interparticle interaction. Only separate NPs were observed in the case of x = 0.4. Peculiarities were revealed in the ESR temperature behavior for the NPs with x = 0 and 0.2 consistent with the features in the temperature dependences of the NPs magnetization. The non-monotonous dependence of the resonance field Hres on the temperature with a kink near 130 K and the energy gap in the resonance spectrum depending on the type of nanoparticle compacting are the distinct peculiarities. One of the main factors is discussed in order to explain the peculiarities: the coexistence of two types of anisotropy in the Cu1-xFexCr2Se4 NPs, in-plain shape anisotropy and magnetocrystalline anisotropy with four easy axes, which increases strongly with the temperature decrease.

Using Space for a Better Foundation on Earth: Mechanics of Granular Materials. Educational Brief. Grades 9-12.

ERIC Educational Resources Information Center

Alshibli, Khalid

This publication presents a science activity and instructional information on the mechanics of granular materials, interparticle friction and geometric interlocking between particles which is a fundamental concept in many fields like in the study of earthquakes. This document describes the Mechanics of Granular Materials (MGM) experiments which…

Ground-state energy of HeH+

NASA Astrophysics Data System (ADS)

Zhou, Bing-Lu; Zhu, Jiong-Ming; Yan, Zong-Chao

2006-06-01

The nonrelativistic ground-state energy of He4H+ is calculated using a variational method in Hylleraas coordinates. Convergence to a few parts in 1010 is achieved, which improves the best previous result of Pavanello [J. Chem. Phys. 123, 104306 (2005)]. Expectation values of the interparticle distances are evaluated. Similar results for He3H+ are also presented.

The Glass Bead Game: experimental sintering of rhyolitic ash reveals complex behaviour of irregular multiphase particles

NASA Astrophysics Data System (ADS)

Pope, Robyn; Tuffen, Hugh; Owen, Jacqueline; James, Mike; Wadsworth, Fabian

2016-04-01

Sintering of magmatic particles profoundly influences the permeability, strength and compaction of fragmented magma in conduits and pyroclastic deposits. It involves initial rounding and agglutination of particles, with formation of inter-particle necks, followed by progressive viscous collapse of pores. The sintering behaviour of ash particles within tuffisite veins, which may mediate shallow outgassing in silicic eruptions, is of particular interest. Experimental studies on homogeneous synthetic glasses[1] have shown sintering rates to be time, temperature and grainsize-dependent, reflecting the influence of melt viscosity and pore-melt interfacial tension. A key objective is to reconstruct the temperature-time path of naturally sintered samples, so here we investigate the sintering of natural, angular ash fragments, to explore whether similar simple relationships emerge for more complex particle morphologies and internal textures. A glass-rich ballistic rhyolite bomb from the Cordón Caulle 2011-2012 eruption was ground and sieved to create various grainsizes of angular ash particles. The bomb contains 70 wt.% SiO2, 0.25 wt.% H2O, and ~30 vol.% crystal phases, as phenocrysts and microlites of plagioclase and pyroxenes. Particles were spread thinly over a sapphire surface in an N2-purged heated stage, and heated to 900, 1000 and 1100 °C, corresponding to melt viscosities of 105.4-107.7 Pa.s. Images were collected every 10-600 s during isothermal sintering over tens of minutes to hours. Quantitative image analysis using ImageJ allowed quantification of evolving particle size and shape (diameter and roundness) and inter-particle neck width. The rate of particle rounding was expected to be highest for smallest particles, and to decrease through time, but unlike synthetic glass bead experiments, no simple trends emerged. When the temporal evolution of particle roundness was tracked, some particles showed an unexpected, systematic increase in rounding rate with time (type A), whereas others showed the expected decrease (type B), or an increase followed by a decrease (type C). The relationship between evolving particle roundness and diameter showed similarly diverse trends, and no distinction could be made between type A, B and C based on initial roundness, size or other characteristic. The development of inter-particle necks was quantified via measurements of the rate of neck width evolution. These rates proved broadly similar for different grain sizes at a given temperature, suggesting that the initial grain size was not the primary controlling factor on neck width growth. Our results highlight both the complexity of sintering in multiphase magmas with irregular particle shapes, and the difficulty of adequately using two-dimensional imagery to characterise evolving three-dimensional morphologies. Future work should employ tomographic techniques to characterise four-dimensional sintering, and analyse large particle populations to overcome the stochastic effects of variable particle texture and morphology. [1] Vasseur J et al. 2013, GRL 40, 5658-5664.

Directional Carrier Transfer in Strongly Coupled Binary Nanocrystal Superlattice Films Formed by Assembly and in Situ Ligand Exchange at a Liquid–Air Interface

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

Wu, Yaoting; Li, Siming; Gogotsi, Natalie

Two species of monodisperse nanocrystals (NCs) can self-assemble into a variety of complex 2D and 3D periodic structures, or binary NC superlattice (BNSL) films, based on the relative number and size of the NCs. BNSL films offer great promise for both fundamental scientific studies and optoelectronic applications; however, the utility of as-assembled structures has been limited by the insulating ligands that originate from the synthesis of NCs. Here we report the application of an in situ ligand exchange strategy at a liquid–air interface to replace the long synthesis ligands with short ligands while preserving the long-range order of BNSL films.more » This approach is demonstrated for BNSL structures consisting of PbSe NCs of different size combinations and ligands of interest for photovoltaic devices, infrared detectors, and light-emitting diodes. To confirm enhanced coupling introduced by ligand exchange, we show ultrafast (~1 ps) directional carrier transfer across the type-I heterojunction formed by NCs of different sizes within ligand-exchanged BNSL films. In conclusion, this approach shows the potential promise of functional BNSL films, where the local and long-range energy landscape and electronic coupling can be adjusted by tuning NC composition, size, and interparticle spacing.« less

Fast-pulverization enabled simultaneous enhancement on cycling stability and rate capability of C@NiFe2O4 hierarchical fibrous bundle

NASA Astrophysics Data System (ADS)

Chen, Zerui; Zhang, Yu; Wang, Xiaoling; Sun, Wenping; Dou, Shixue; Huang, Xin; Shi, Bi

2017-09-01

Electrochemical-grinding induced pulverization is the origin of capacity fading in NiFe2O4. Increasing current density normally accelerates the pulverization that deteriorates lithium storage properties of NiFe2O4. Here we show that the high current induced fast-pulverization can serve as an efficient activation strategy for quick and simultaneous enhancement on cycling stability and rate capability of NiFe2O4 nanoparticles (NPs) that are densely packed on the hierarchically structured carbon nanofiber strand. At a high current density, the pulverization of NiFe2O4 NPs can be accomplished in a few cycles exposing more active surface. During the fast-pulverization, the hierarchically structured carbon nanofiber strand maintains conductive contact for the densely packed NiFe2O4 NPs regardless of charge or discharge, which also effectively suppresses the repetitive breaks and growths of solid-electrolyte-interphase (SEI) via multiple-level structural adaption that favourites the quick formation of a thin and dense SEI, thus providing strong interparticle connectivity with enhancement on cycling stability and rate capability (e.g. doubled capacity). Our findings demonstrate the potential importance of high current induced fast-pulverization as an efficient activation strategy for achieving durable electrode materials suffering from electrochemical-grinding effects.

Stability and Structure of Star-Shape Granules

NASA Astrophysics Data System (ADS)

Zhao, Yuchen; Bares, Jonathan; Liu, Kevin; Zheng, Matthew; Dierichs, Karola; Menges, Achim; Behringer, Robert

Columns made of convex noncohesive grains like sand collapse after being released from a confining container. While various architectures built by concave grains are stable. We explore why these structures are stable, and how stable they can be. We performed experiments by randomly pouring identical star-shape particles into hollow cylinders resting on glass or a roughened base, and then observed how stable these granular columns were after carefully lifting the cylinders. We used particles that are made of acrylics and have six 9 mm arms, which extend symmetrically in xyz directions. We investigated the probability of creating a stable column and other mechanical stability aspects. We define r as the weight fraction of particles that fall out of the column after the confining cylinder is removed. r gradually increases as the column height increases, or the column diameter decreases. We found high column stability when the inter-particle friction was greater. We also explored experiment conditions such as initial vibration of columns when they were confined and loading on the top. In order to understand the inner structure leading to stability, we obtained 3D CT reconstruction data of stable columns. We will discuss coordination number and orientation, etc. We acknowledge supports from W.M.Keck Foundation and Research Triangle MRSEC.

Discrete elastic model for two-dimensional melting.

PubMed

Lansac, Yves; Glaser, Matthew A; Clark, Noel A

2006-04-01

We present a network model for the study of melting and liquid structure in two dimensions, the first in which the presence and energy of topological defects (dislocations and disclinations) and of geometrical defects (elemental voids) can be independently controlled. Interparticle interaction is via harmonic springs and control is achieved by Monte Carlo moves which springs can either be orientationally "flipped" between particles to generate topological defects, or can be "popped" in force-free shape, to generate geometrical defects. With the geometrical defects suppressed the transition to the liquid phase occurs via disclination unbinding, as described by the Kosterlitz-Thouless-Halperin-Nelson-Young model and found in soft potential two-dimensional (2D) systems, such as the dipole-dipole potential [H. H. von Grünberg, Phys. Rev. Lett. 93, 255703 (2004)]. By contrast, with topological defects suppressed, a disordering transition, the Glaser-Clark condensation of geometrical defects [M. A. Glaser and N. A. Clark, Adv. Chem. Phys. 83, 543 (1993); M. A. Glaser, (Springer-Verlag, Berlin, 1990), Vol. 52, p. 141], produces a state that accurately characterizes the local liquid structure and first-order melting observed in hard-potential 2D systems, such as hard disk and the Weeks-Chandler-Andersen (WCA) potentials (M. A. Glaser and co-workers, see above). Thus both the geometrical and topological defect systems play a role in melting. The present work introduces a system in which the relative roles of topological and geometrical defects and their interactions can be explored. We perform Monte Carlo simulations of this model in the isobaric-isothermal ensemble, and present the phase diagram as well as various thermodynamic, statistical, and structural quantities as a function of the relative populations of geometrical and topological defects. The model exhibits a rich phase behavior including hexagonal and square crystals, expanded crystal, dodecagonal quasicrystal, and isotropic liquid phases. In this system the geometrical defects effectively control the melting, reducing the solid-liquid transition temperature by a factor of relative to the topological-only case. The local structure of the dense liquid has been investigated and the results are compared to that from simulations of WCA systems.

Magnetic Core-Shell Morphology of Structurally Uniform Magnetite Nanoparticles

NASA Astrophysics Data System (ADS)

Krycka, Kathryn

2011-03-01

Magnetic nanoscale structures are intriguing, in part, because of the exotic properties that emerge compared with bulk. The reduction of magnetic moment per atom in magnetite with decreasing nanoparticle size, for example, has been hypothesized to originate from surface disordering to anisotropy-induced radial canting, which are difficult to distinguish using conventional magnetometry. Small-angle neutron scattering (SANS) is ideal for probing structure, both chemical and magnetic, from nm to microns across an ensemble of particles. Adding polarization analysis (PASANS) of the neutron spin orientation before and after interaction with the scattering particles allows the magnetic structure to be separated into its vector components. Application of this novel technique to 9 nm magnetite nanoparticles closed-packed into face-centered crystallites with order of a micron revealed that at nominal saturation the missing magnetic moments unexpectedly interacted to form well-ordered shells 1.0 to 1.5 nm thick canted perpendicular to their ferrimagnetic cores between 160 to 320 K. These shells additionally displayed intra-particle ``cross-talk'', selecting a common orientation over clusters of tens of nanoparticles. However, the shells disappeared when the external field was removed and interparticle magnetic interactions were negligible (300 K), confirming their magnetic origin. This work has been carried out in collaboration with Ryan Booth, Julie Borchers, Wangchun Chen, Liv Dedon, Thomas Gentile, Charles Hogg, Yumi Ijiri, Mark Laver, Sara Majetich, James Rhyne, and Shannon Watson.

Colloidal Metamaterials at Optical Frequencies

DTIC Science & Technology

2014-07-18

NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES...8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR...optical constants from Johnson and Christy) with a 2 nm interparticle spacing. All calculations were performed assuming an aqueous embedding medium (n

Flocculation and Settling Velocity Estimates for Reservoir Sedimentation Analysis

DTIC Science & Technology

2016-02-01

viscosity ). Stokes’ law is commonly used to describe settling velocity of a single particle and is applicable when the particle Reynolds number (Rep...fluid viscosity , and ν is kinematic viscosity . Several researchers recognize that large, fast-settling particles disobey the laminar boundary...interparticle attraction caused by electrostatic and physiochemical forces. These properties give clays their stickiness and control essential

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

PubMed Central

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; Lupton, John M.; Boehme, Christoph

2015-01-01

Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm. PMID:25868686

Intra- and interparticle magnetism of cobalt-doped iron-oxide nanoparticles encapsulated in a synthetic ferritin cage

NASA Astrophysics Data System (ADS)

Skoropata, E.; Desautels, R. D.; Falvo, E.; Ceci, P.; Kasyutich, O.; Freeland, J. W.; van Lierop, J.

2014-11-01

We present an in-depth examination of the composition and magnetism of cobalt (Co2 +)-doped iron-oxide nanoparticles encapsulated in Pyrococcus furiosus ferritin shells. We show that the Co2 + dopant ions were incorporated into the γ -Fe2O3/Fe3O4 core, with small paramagnetic-like clusters likely residing on the surface of the nanoparticle that were observed for all cobalt-doped samples. In addition, element-specific characterization using Mössbauer spectroscopy and polarized x-ray absorption indicated that Co2 + was incorporated exclusively into the octahedral B sites of the spinel-oxide nanoparticle. Comparable superparamagnetic blocking temperatures, coercivities, and effective anisotropies were obtained for 7%, 10%, and 12% cobalt-doped nanoparticles, and were only slightly reduced for 3% cobalt, indicating a strong effect of cobalt incorporation, with a lesser effect of cobalt content. Due to the regular particle size and separation that result from the use of the ferritin cage, a comparison of the effects of interparticle interactions on the disordered assembly of nanoparticles was also obtained that indicated significantly different behaviors between undoped and cobalt-doped nanoparticles.

Ion mediated targeting of cells with nanoparticles

NASA Astrophysics Data System (ADS)

Maheshwari, Vivek; Fu, Jinlong

2010-03-01

In eukaryotic cells, Ca^2+ ions are necessary for intracellular signaling, in activity of mitochondria and a variety of other cellular process that have been linked to cell apoptosis, proteins synthesis and cell-cycle regulation. Here we show that Ca^2+ ions, serving as the bio-compatible interface can be used to target Saccharomyces cerevisiae (SaC, baker's yeast), a model eukaryotic cell, with Au nanoparticles (10 nm). The Ca^2+ ions bind to the carboxylic acid groups in the citrate functionalized Au nanoparticles. This transforms the nanoparticles into micron long 1-D branched chain assemblies due to inter-particle dipole-dipole interaction and inter-particle bonding due to the divalent nature of the Ca^2+ ion. A similar transformation is observed with the use of divalent ions Mg^2+, Cd^2+ and Fe^2+. The 1-D assembly aids the interfacing of ion-nanoparticles on the cell by providing multiple contact points. Further monovalent ions such as Na^+ are also effective for the targeting of the cell with nanoparticles. However Na-Au nanoparticles are limited in their deposition as they exist in solution as single particles. The cells remain alive after the deposition process and their vitality is unaffected by the interfacing with ion-nanoparticles.

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

DOE PAGES

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; ...

2015-04-14

Here, weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices,more » which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair’s zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.« less

Hydrogen bonding and interparticle forces in platelet alpha-Al2O3 dispersions: yield stress and zeta potential.

PubMed

Khoo, Kay-Sen; Teh, E-Jen; Leong, Yee-Kwong; Ong, Ban Choon

2009-04-09

Adsorbed phosphate on smooth platelet alpha-Al2O3 particles at saturation surface coverage gives rise to strong interparticle attractive forces in dispersion. The maximum yield stress at the point of zero charge was increased by 2-fold. This was attributed to a high density of intermolecular hydrogen bonding between the adsorbed phosphate layers of the interacting particles. Adsorbed citrate at saturation surface coverage, however, reduced the maximum yield stress by 50%. It adsorbed to form a very effective steric barrier as intramolecular hydrogen bonding between -OH and the free terminal carboxylic group prevented strong interactions with other adsorbed citrate molecules residing on the second interacting particle. This steric barrier kept the interacting platelet particles further apart, thereby weakening the van der Waals attraction. The platelet alpha-Al2O3 dispersions were flocculated at all pH level. These dispersions displayed a maximum yield stress at the point of zero zeta potential at the pH approximately 8.0. They also obeyed the yield stress-DLVO force model as characterized by a linear decrease in the yield stress with the square of the zeta potential.

Particle force model effects in a shock-driven multiphase instability

NASA Astrophysics Data System (ADS)

Black, W. J.; Denissen, N.; McFarland, J. A.

2018-05-01

This work presents simulations on a shock-driven multiphase instability (SDMI) at an initial particle volume fraction of 1% with the addition of a suite of particle force models applicable in dense flows. These models include pressure-gradient, added-mass, and interparticle force terms in an effort to capture the effects neighboring particles have in non-dilute flow regimes. Two studies are presented here: the first seeks to investigate the individual contributions of the force models, while the second study focuses on examining the effect of these force models on the hydrodynamic evolution of a SDMI with various particle relaxation times (particle sizes). In the force study, it was found that the pressure gradient and interparticle forces have little effect on the instability under the conditions examined, while the added-mass force decreases the vorticity deposition and alters the morphology of the instability. The relaxation-time study likewise showed a decrease in metrics associated with the evolution of the SDMI for all sizes when the particle force models were included. The inclusion of these models showed significant morphological differences in both the particle and carrier species fields, which increased as particle relaxation times increased.

The role of interparticle heterogeneities in the selenization pathway of Cu-Zn-Sn-S nanoparticle thin films: A real-time study

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

Carter, Nathaniel J.; Mainz, Roland; Walker, Bryce C.

2015-06-10

Real-time energy dispersive x-ray diffraction (EDXRD) analysis has been utilized to observe the selenization of Cu-Zn-Sn-S nanoparticle films coated from three nanoparticle populations: Cu- and Sn-rich particles roughly 5 nm in size, Zn-rich nanoparticles ranging from 10 to 20 nm in diameter, and a mixture of both types of nanoparticles (roughly 1:1 by mass), which corresponds to a synthesis recipe yielding CZTSSe solar cells with reported total-area efficiencies as high as 7.9%. The EDXRD studies presented herein show that the formation of copper selenide intermediates during the selenization of mixed-particle films can be primarily attributed to the small, Cu- andmore » Sn-rich particles. Moreover, the formation of these copper selenide phases represents the first stage of the CZTSSe grain growth mechanism. The large, Zn-rich particles subsequently contribute their composition to form micrometer-sized CZTSSe grains. In conclusion, these findings enable further development of a previously proposed selenization pathway to account for the roles of interparticle heterogeneities, which in turn provides a valuable guide for future optimization of processes to synthesize high quality CZTSSe absorber layers.« less

Ultrafast dynamics of photogenerated electrons in CdS nanocluster multilayers assembled on solid substrates: effects of assembly and electrode potential.

PubMed

Yagi, Ichizo; Mikami, Kensuke; Okamura, Masayuki; Uosaki, Kohei

2013-07-22

The ultrafast dynamics of photogenerated electrons in multilayer assemblies of CdS nanoparticles prepared on quartz and indium-tin oxide (ITO) substrates were followed by femtosecond (fs) visible-pump/mid-IR probe spectroscopy. Based on the observation of the photoinduced transient absorption spectra in the broad mid-IR range at the multilayer assembly of CdS nanoparticles, the occupation and fast relaxation of higher electronic states (1P(e)) were clarified. As compared with the electron dynamics of isolated (dispersed in solution) nanoparticles, the decay of photoexcited electrons in the multilayer assembly was clearly accelerated probably due to both electron hopping and scattering during interparticle electron tunneling. By using an ITO electrode as a substrate, the effect of the electric field on the photoelectron dynamics in the multilayer assembly was also investigated in situ. Both the amplitude and lifetime of photoexcited electrons gradually reduced as the potential became more positive. This result was explained by considering the reduction of the interparticle tunneling probability and the increase in the electron-transfer rate from the CdS nanoparticle assembly to the ITO electrode. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold nanoparticle flow sensors designed for dynamic X-ray imaging in biofluids.

PubMed

Ahn, Sungsook; Jung, Sung Yong; Lee, Jin Pyung; Kim, Hae Koo; Lee, Sang Joon

2010-07-27

X-ray-based imaging is one of the most powerful and convenient methods in terms of versatility in applicable energy and high performance in use. Different from conventional nuclear medicine imaging, contrast agents are required in X-ray imaging especially for effectively targeted and molecularly specific functions. Here, in contrast to much reported static accumulation of the contrast agents in targeted organs, dynamic visualization in a living organism is successfully accomplished by the particle-traced X-ray imaging for the first time. Flow phenomena across perforated end walls of xylem vessels in rice are monitored by a gold nanoparticle (AuNP) (approximately 20 nm in diameter) as a flow tracing sensor working in nontransparent biofluids. AuNPs are surface-modified to control the hydrodynamic properties such as hydrodynamic size (DH), zeta-potential, and surface plasmonic properties in aqueous conditions. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray nanoscopy (XN), and X-ray microscopy (XM) are used to correlate the interparticle interactions with X-ray absorption ability. Cluster formation and X-ray contrast ability of the AuNPs are successfully modulated by controlling the interparticle interactions evaluated as flow-tracing sensors.

A discrete element model for the influence of surfactants on sedimentation characteristics of magnetorheological fluids

NASA Astrophysics Data System (ADS)

Son, Kwon Joong

2018-02-01

Hindering particle agglomeration and re-dispersion processes, gravitational sedimentation of suspended particles in magnetorheological (MR) fluids causes inferior performance and controllability of MR fluids in response to a user-specified magnetic field. Thus, suspension stability is one of the principal factors to be considered in synthesizing MR fluids. However, only a few computational studies have been reported so far on the sedimentation characteristics of suspended particles under gravity. In this paper, the settling dynamics of paramagnetic particles suspended in MR fluids was investigated via discrete element method (DEM) simulations. This work focuses particularly on developing accurate fluid-particle and particle-particle interaction models which can account for the influence of stabilizing surfactants on the MR fluid sedimentation. Effect of the stabilizing surfactants on interparticle interactions was incorporated into the derivation of a reliable contact-impact model for DEM computation. Also, the influence of the stabilizing additives on fluid-particle interactions was considered by incorporating Stokes drag with shape and wall correction factors into DEM formulation. The results of simulations performed for model validation purposes showed a good agreement with the published sedimentation measurement data in terms of an initial sedimentation velocity and a final sedimentation ratio.

Physical and environmental factors affecting the persistence of explosives particles (Conference Presentation)

NASA Astrophysics Data System (ADS)

Papantonakis, Michael R.; Nguyen, Viet K.; Furstenberg, Robert; White, Caitlyn; Shuey, Melissa; Kendziora, Christopher A.; McGill, R. Andrew

2017-05-01

Knowledge of the persistence of trace explosives materials is critical to aid the security community in designing detection methods and equipment. The physical and environmental factors affecting the lifetimes of particles include temperature, airflow, interparticle distance, adlayers, humidity, particle field size and vapor pressure. We are working towards a complete particle persistence model that captures the relative importance of these effects to allow the user, with known environmental conditions, to predict particle lifetimes for explosives or other chemicals. In this work, particles of explosives are sieved onto smooth glass substrates using particle sizes and loadings relevant to those deposited by fingerprint deposition. The coupon is introduced into a custom flow cell and monitored under controlled airflow, humidity and temperature. Photomicroscopy images of the sample taken at fixed time intervals are analyzed to monitor particle sublimation and characterized as a size-independent radial sublimation velocity for each particle in the ensemble. In this paper we build on previous work by comparing the relationship between sublimation of different materials and their vapor pressures. We also describe the influence of a sebum adlayer on particle sublimation, allowing us to better model `real world' samples.

Characterization of poly methyl methaacrylate and reduced graphene oxide composite for application as electrolyte in dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Shrivatsav, Roshan; Mahalingam, Vignesh; Lakshmi Narayanan, E. R.; Naveen Balaji, N.; Balu, Murali; Krishna Prasad, R.; Kumaresan, Duraisamy

2018-04-01

Quasi-solid state iodide/triiodide redox electrolyte containing reduced graphene oxide and poly (methyl methaacrylate) (RGO-PMMA) composites for the fabrication of more durable, high performance dye sensitized solar cells are prepared. The morphological analysis of prepared RGO-PMMA composites showed formation of spherical like morphologies of RGO dispersed PMMA particles with their macroscopic inter-particle networks having voids. The x ray diffraction and electrical conductivity studies showed the addition of 1 wt% of filler RGO into amorphous PMMA matrix increased the electrical conductivity of the polymer composite about three orders of magnitude from 10‑7 and 10‑4 S cm‑1. Further, the photovoltaic current-voltage analysis of DSSCs with different RGO-PMMA composite based iodide/triiodide redox electrolytes showed the highest power conversion efficiency of 5.38% and the fill factor 0.63 for 2% RGO-PMMA electrolyte. The EIS analysis showed an increased recombination resistance (Rct2) at TiO2 electrode/dye/electrolyte interface due to the better electrical conductivity of RGO with good ionic conductivity in 2% RGO-PMMA composite based redox electrolyte boosted the generation of a high current density and fill factor in their DSSCs.

Sampling and Visualizing Creases with Scale-Space Particles

PubMed Central

Kindlmann, Gordon L.; Estépar, Raúl San José; Smith, Stephen M.; Westin, Carl-Fredrik

2010-01-01

Particle systems have gained importance as a methodology for sampling implicit surfaces and segmented objects to improve mesh generation and shape analysis. We propose that particle systems have a significantly more general role in sampling structure from unsegmented data. We describe a particle system that computes samplings of crease features (i.e. ridges and valleys, as lines or surfaces) that effectively represent many anatomical structures in scanned medical data. Because structure naturally exists at a range of sizes relative to the image resolution, computer vision has developed the theory of scale-space, which considers an n-D image as an (n + 1)-D stack of images at different blurring levels. Our scale-space particles move through continuous four-dimensional scale-space according to spatial constraints imposed by the crease features, a particle-image energy that draws particles towards scales of maximal feature strength, and an inter-particle energy that controls sampling density in space and scale. To make scale-space practical for large three-dimensional data, we present a spline-based interpolation across scale from a small number of pre-computed blurrings at optimally selected scales. The configuration of the particle system is visualized with tensor glyphs that display information about the local Hessian of the image, and the scale of the particle. We use scale-space particles to sample the complex three-dimensional branching structure of airways in lung CT, and the major white matter structures in brain DTI. PMID:19834216

Simulation study on the structural properties of colloidal particles with offset dipoles.

PubMed

Rutkowski, David M; Velev, Orlin D; Klapp, Sabine H L; Hall, Carol K

2017-05-03

A major research theme in materials science is determining how the self-assembly of new generations of colloidal particles of complex shape and surface charge is guided by their interparticle interactions. In this paper, we describe results from quasi-2D Monte Carlo simulations of systems of colloidal particles with offset transversely-oriented extended dipole-like charge distributions interacting via an intermediate-ranged Yukawa potential. The systems are cooled slowly through an annealing procedure during which the temperature is lowered in discrete steps, allowing the system to equilibrate. We perform ground state calculations for two, three and four particles at several shifts of the dipole vector from the particle center. We create state diagrams in the plane spanned by the temperature and the area fraction outlining the boundaries between fluid, string-fluid and percolated states at various values of the shift. Remarkably we find that the effective cooling rate in our simulations has an impact on the structures formed, with chains being more prevalent if the system is cooled quickly and cyclic structures more prevalent if the system is cooled slowly. As the dipole is further shifted from the center, there is an increased tendency to assemble into small cyclic structures at intermediate temperatures. These systems further self-assemble into open lattice-like arrangements at very low temperatures. The novel structures identified might be useful for photonic applications, new types of porous media for filtration and catalysis, and gel matrices with unusual properties.

Memory versus irreversibility in the thermal densification of amorphous glasses

NASA Astrophysics Data System (ADS)

Ovadyahu, Z.

2017-06-01

We report on dynamic effects associated with thermally annealing amorphous indium-oxide films. In this process, the resistance of a given sample may decrease by several orders of magnitude at room temperatures, while its amorphous structure is preserved. The main effect of the process is densification, i.e., increased system density. The study includes the evolution of the system resistivity during and after the thermal treatment, the changes in the conductance noise, and the accompanying changes in the optical properties. The sample resistance is used to monitor the system dynamics during the annealing period as well as the relaxation that ensues after its termination. These reveal slow processes that fit well with a stretched-exponential law, a behavior that is commonly observed in structural glasses. There is an intriguing similarity between these effects and those obtained in high-pressure densification experiments. Both protocols exhibit the "slow spring-back" effect, a familiar response of memory foams. A heuristic picture based on a modified Lennard-Jones potential for the effective interparticle interaction is argued to qualitatively account for these densification-rarefaction phenomena in amorphous materials, whether affected by thermal treatment or by application of high pressure.

Structure and Symmetry of Ground States of Colloidal Clusters

NASA Astrophysics Data System (ADS)

Klein, Ellen D.; Rogers, W. Benjamin; Manoharan, Vinothan N.

We experimentally study colloidal clusters consisting of 6 to 100 spherical particles bound together with short range, DNA-mediated attractions. These clusters are a model system for understanding colloidal self-assembly and dynamics, since the positions and motion of all particles can be observed in real space. For 10 particles and fewer, the ground states are degenerate, and, as shown in previous work, the probabilities of observing specific clusters depend primarily on their rotational entropy, which is determined by symmetry. Thus less symmetric structures are more frequently observed. However, for larger numbers of particles the ground states appear to be subsets of close-packed lattices, which tend to have higher symmetry. To understand how this transition occurs as a function of the number of particles, we coat colloidal particles with complementary DNA strands that induce a short-range, temperature-dependent interparticle attraction. We then assemble and anneal an ensemble of clusters with 10 or more particles. We characterize the number of apparent ground states, their symmetries, and their probabilities as a function of the size of the cluster using confocal microscopy. This work is supported by NSF DMR-1306410. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program.

The magnetic structure and palaeomagnetic recording fidelity of sub-micron greigite (Fe3S4)

NASA Astrophysics Data System (ADS)

Valdez-Grijalva, Miguel A.; Nagy, Lesleis; Muxworthy, Adrian R.; Williams, Wyn; Fabian, Karl

2018-02-01

We present the results of a finite-element micromagnetic model of 30nm to 300nm greigite (Fe3S4) grains with a variety of equant morphologies. This grain size range covers the magnetic single-domain (SD) to pseudo single-domain (PSD) transition, and possibly also the PSD to multi-domain (MD) transition. The SD-PSD threshold d0 is determined to be 50nm ≤d0 ≤ 56nm depending on grain shape. The nudged elastic-band method was used to determine the room temperature energy barriers between stable states and thus the blocking volumes. It is found that, in the absence of interparticle magnetostatic interactions, the magnetisation of equant SD greigite is not stable on a geological scale and only PSD grains ≥ 70nm can be expected to carry a stable magnetisation over billion-year timescales, i.e., all non-interacting SD particles are essentially superparamagnetic. We further identify a mechanism for the PSD to multi-domain (MD) transition, which is of a continuous nature from PSD nucleation up to 300nm, when structures typical of MD behaviour like closure domains begin to form.

Application of relativistic distorted-wave method to electron-impact excitation of highly charged Fe XXIV ion embedded in weakly coupled plasmas

NASA Astrophysics Data System (ADS)

Chen, Zhanbin

2018-05-01

The process of excitation of highly charged Fe XXIV ion embedded in weakly coupled plasmas by electron impact is studied, together with the subsequent radiative decay. For the target structure, the calculation is performed using the multiconfiguration Dirac-Hartree-Fock method incorporating the Debye-Hückel potential for the electron-nucleus interaction. Fine-structure levels of the 1s22p and 1s2s2p configurations and the transition properties among these levels are presented over a wide range of screening parameters. For the collision dynamics, the distorted-wave method in the relativistic frame is adopted to include the effect of plasma background, in which the interparticle interactions in the system are described by screened interactions of the Debye-Hückel type. The continuum wave function of the projectile electron is obtained by solving the modified Dirac equations. The influence of plasma strength on the cross section, the linear polarization, and the angular distribution of x-ray photon emission are investigated in detail. Comparison of the present results with experimental data and other theoretical predictions, when available, is made.

Particle packing from an earth science viewpoint

NASA Astrophysics Data System (ADS)

Rogers, C. D. F.; Dijkstra, T. A.; Smalley, I. J.

1994-04-01

Particle packings are relevant to many aspects of the Earth sciences, and there is a long history of the study of packings from an Earth science viewpoint. Packings have also been studied in connection with other subjects and disciplines. Allen (1982) produced a major review which provides a solid base for Earth science related studies. This review complements Allen's work and in particular focuses on advances in the study of random packings over the last ten years. Transitions from packing to packing may be as important as the packings themselves, and possibly easier to model. This paper places emphasis on certain neglected works, in particular Morrow and Graves (1969) and the packing transition envelope, Kahn (1956) and the measurement of packing parameters, Griffiths (1962) on packings in one-dimension, and Getis and Boots (1978) on packings in two dimensions. Certain packing problems are relevant to current areas of study including structure collapse in loess (hydroconsolidation), flowslides in very sensitive soils, wind erosion, jewel quality in opals and the structure and functions of sand dunes. The region where interparticle forces become active (particles < 200 μm) is considered and the implications for packing are examined.

An adaptive extended finite element method for the analysis of agglomeration of colloidal particles in a flowing fluid

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

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.

Block Copolymer Micelles for Photonic Fluids and Crystals.

PubMed

Poutanen, Mikko; Guidetti, Giulia; Gröschel, Tina I; Borisov, Oleg V; Vignolini, Silvia; Ikkala, Olli; Gröschel, Andre H

2018-04-24

Block copolymer micelles (BCMs) are self-assembled nanoparticles in solution with a collapsed core and a brush-like stabilizing corona typically in the size range of tens of nanometers. Despite being widely studied in various fields of science and technology, their ability to form structural colors at visible wavelength has not received attention, mainly due to the stringent length requirements of photonic lattices. Here, we describe the precision assembly of BCMs with superstretched corona, yet with narrow size distribution to qualify as building blocks for tunable and reversible micellar photonic fluids (MPFs) and micellar photonic crystals (MPCs). The BCMs form free-flowing MPFs with an average interparticle distance of 150-300 nm as defined by electrosteric repulsion arising from the highly charged and stretched corona. Under quiescent conditions, millimeter-sized MPCs with classical FCC lattice grow within the photonic fluid-medium upon refinement of the positional order of the BCMs. We discuss the generic properties of MPCs with special emphasis on surprisingly narrow reflected wavelengths with full width at half-maximum (fwhm) as small as 1 nm. We expect this concept to open a generic and facile way for self-assembled tunable micellar photonic structures.

X-ray scattering data and structural genomics

NASA Astrophysics Data System (ADS)

Doniach, Sebastian

2003-03-01

High throughput structural genomics has the ambitious goal of determining the structure of all, or a very large number of protein folds using the high-resolution techniques of protein crystallography and NMR. However, the program is facing significant bottlenecks in reaching this goal, which include problems of protein expression and crystallization. In this talk, some preliminary results on how the low-resolution technique of small-angle X-ray solution scattering (SAXS) can help ameliorate some of these bottlenecks will be presented. One of the most significant bottlenecks arises from the difficulty of crystallizing integral membrane proteins, where only a handful of structures are available compared to thousands of structures for soluble proteins. By 3-dimensional reconstruction from SAXS data, the size and shape of detergent-solubilized integral membrane proteins can be characterized. This information can then be used to classify membrane proteins which constitute some 25% of all genomes. SAXS may also be used to study the dependence of interparticle interference scattering on solvent conditions so that regions of the protein solution phase diagram which favor crystallization can be elucidated. As a further application, SAXS may be used to provide physical constraints on computational methods for protein structure prediction based on primary sequence information. This in turn can help in identifying structural homologs of a given protein, which can then give clues to its function. D. Walther, F. Cohen and S. Doniach. "Reconstruction of low resolution three-dimensional density maps from one-dimensional small angle x-ray scattering data for biomolecules." J. Appl. Cryst. 33(2):350-363 (2000). Protein structure prediction constrained by solution X-ray scattering data and structural homology identification Zheng WJ, Doniach S JOURNAL OF MOLECULAR BIOLOGY , v. 316(#1) pp. 173-187 FEB 8, 2002

Ground-state energy of HeH{sup +}

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

Zhou Binglu; Zhu Jiongming; Yan Zongchao

2006-06-15

The nonrelativistic ground-state energy of {sup 4}HeH{sup +} is calculated using a variational method in Hylleraas coordinates. Convergence to a few parts in 10{sup 10} is achieved, which improves the best previous result of Pavanello et al. [J. Chem. Phys. 123, 104306 (2005)]. Expectation values of the interparticle distances are evaluated. Similar results for {sup 3}HeH{sup +} are also presented.

Sign Reversal of Coulom Interaction Between Two Quasiparticles in Momentum Space

NASA Astrophysics Data System (ADS)

Fan, J. D.; Malozovsky, Yuriy M.

2013-06-01

The main misconception regarding the interaction between quasiparticles stems from the assertion that the interaction energy between two quasiparticles is exactly identical to that of the renormalized interaction between two particles due to interparticle interaction in the Fermi system. If the main concept regarding the definition of quasiparticle as a weakly excited state of the Fermi system with conservation of charge and spin is paramount (except for the charge and spin separation models), the concept of the interaction between quasiparticles is very different from the assumption in the common sense. In this paper, we will prove a general theorem that the interaction between two quasiparticles is very much different from the renormalized interaction between two particles. The major difference lies in two places: the interaction between two quasiparticles is just negative to the renormalized interaction between two particles, and the interaction energy between the two particles is proportional to the product of two Fermi liquid renormalization factors. The result shed light on the reinterpretation of Cooper's pairing without invoking electron-photon interaction.

In situ microscopy of the self-assembly of branched nanocrystals in solution

DOE PAGES

Sutter, Eli; Tkachenko, Alexei V.; Sutter, Peter; ...

2016-04-04

Here, solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifiesmore » the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.« less

Self Diffusion in Nano Filled Polymer Melts: a Molecular Dynamics Simulation Study

NASA Astrophysics Data System (ADS)

Desai, Tapan; Keblinski, Pawel

2003-03-01

SELF DIFFUSION IN NANO FILLED POLYMER MELTS: A MOLECULAR DYNAMICS SIMULATION STUDY* T. G. Desai,P. Keblinski, Material Science and Engineering Department, Rensselaer Polytechnic Institute, Troy, NY. Using molecular dynamics simulations, we studied the dynamics of the polymeric systems containing immobile and analytically smooth spherical nanoparticles. Each chain consisted of N monomers connected by an anharmonic springs described by the finite extendible nonlinear elastic, FENE potential. The system comprises of 3nanoparticles and the rest by freely rotating but not overlapping chains. The longest chain studied has a Radius of gyration equal to particle size radius and comparable to inter-particle distance. There is no effect on the structural characteristics such as Radius of gyration or end to end distance due to the nanoparticles. Diffusion of polymeric chains is not affected by the presence of either attractive or repulsive nanoparticles. In all cases Rouse dynamics is observed for short chains with a crossover to reptation dynamics for longer chains.

In situ microscopy of the self-assembly of branched nanocrystals in solution

NASA Astrophysics Data System (ADS)

Sutter, Eli; Sutter, Peter; Tkachenko, Alexei V.; Krahne, Roman; de Graaf, Joost; Arciniegas, Milena; Manna, Liberato

2016-04-01

Solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifies the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.

Role of ligand-ligand vs. core-core interactions in gold nanoclusters.

PubMed

Milowska, Karolina Z; Stolarczyk, Jacek K

2016-05-14

The controlled assembly of ligand-coated gold nanoclusters (NCs) into larger structures paves the way for new applications ranging from electronics to nanomedicine. Here, we demonstrate through rigorous density functional theory (DFT) calculations employing novel functionals accounting for van der Waals forces that the ligand-ligand interactions determine whether stable assemblies can be formed. The study of NCs with different core sizes, symmetry forms, ligand lengths, mutual crystal orientations, and in the presence of a solvent suggests that core-to-core van der Waals interactions play a lesser role in the assembly. The dominant interactions originate from combination of steric effects, augmented by ligand bundling on NC facets, and related to them changes in electronic properties induced by neighbouring NCs. We also show that, in contrast to standard colloidal theory approach, DFT correctly reproduces the surprising experimental trends in the strength of the inter-particle interaction observed when varying the length of the ligands. The results underpin the importance of understanding NC interactions in designing gold NCs for a specific function.

Prescribed nanoparticle cluster architectures and low-dimensional arrays built using octahedral DNA origami frames

DOE PAGES

Tian, Ye; Wang, Tong; Liu, Wenyan; ...

2015-05-25

Three-dimensional mesoscale clusters that are formed from nanoparticles spatially arranged in pre-determined positions can be thought of as mesoscale analogues of molecules. These nanoparticle architectures could offer tailored properties due to collective effects, but developing a general platform for fabricating such clusters is a significant challenge. Here, we report a strategy for assembling 3D nanoparticle clusters that uses a molecular frame designed with encoded vertices for particle placement. The frame is a DNA origami octahedron and can be used to fabricate clusters with various symmetries and particle compositions. Cryo-electron microscopy is used to uncover the structure of the DNA framemore » and to reveal that the nanoparticles are spatially coordinated in the prescribed manner. We show that the DNA frame and one set of nanoparticles can be used to create nanoclusters with different chiroptical activities. We also show that the octahedra can serve as programmable interparticle linkers, allowing one- and two-dimensional arrays to be assembled that have designed particle arrangements.« less

3D simulation of friction stir welding based on movable cellular automaton method

NASA Astrophysics Data System (ADS)

Eremina, Galina M.

2017-12-01

The paper is devoted to a 3D computer simulation of the peculiarities of material flow taking place in friction stir welding (FSW). The simulation was performed by the movable cellular automaton (MCA) method, which is a representative of particle methods in mechanics. Commonly, the flow of material in FSW is simulated based on computational fluid mechanics, assuming the material as continuum and ignoring its structure. The MCA method considers a material as an ensemble of bonded particles. The rupture of interparticle bonds and the formation of new bonds enable simulations of crack nucleation and healing as well as mas mixing and microwelding. The simulation results showed that using pins of simple shape (cylinder, cone, and pyramid) without a shoulder results in small displacements of plasticized material in workpiece thickness directions. Nevertheless, the optimal ratio of longitudinal velocity to rotational speed makes it possible to transport the welded material around the pin several times and to produce a joint of good quality.

Localized transversal-rotational modes in linear chains of equal masses.

PubMed

Pichard, H; Duclos, A; Groby, J-P; Tournat, V; Gusev, V E

2014-01-01

The propagation and localization of transversal-rotational waves in a two-dimensional granular chain of equal masses are analyzed in this study. The masses are infinitely long cylinders possessing one translational and one rotational degree of freedom. Two dispersive propagating modes are predicted in this granular crystal. By considering the semi-infinite chain with a boundary condition applied at its beginning, the analytical study demonstrates the existence of localized modes, each mode composed of two evanescent modes. Their existence, position (either in the gap between the propagating modes or in the gap above the upper propagating mode), and structure of spatial localization are analyzed as a function of the relative strength of the shear and bending interparticle interactions and for different boundary conditions. This demonstrates the existence of a localized mode in a semi-infinite monatomic chain when transversal-rotational waves are considered, while it is well known that these types of modes do not exist when longitudinal waves are considered.

Thermodynamic scaling of glassy dynamics and dynamic heterogeneities in metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Hu, Yuan-Chao; Shang, Bao-Shuang; Guan, Peng-Fei; Yang, Yong; Bai, Hai-Yang; Wang, Wei-Hua

2016-09-01

A ternary metallic glass-forming liquid is found to be not strongly correlating thermodynamically, but its average dynamics, dynamic heterogeneities including the high order dynamic correlation length, and static structure are still well described by thermodynamic scaling with the same scaling exponent γ. This may indicate that the metallic liquid could be treated as a single-parameter liquid. As an intrinsic material constant stemming from the fundamental interatomic interactions, γ is theoretically predicted from the thermodynamic fluctuations of the potential energy and the virial. Although γ is conventionally understood merely from the repulsive part of the inter-particle potentials, the strong correlation between γ and the Grüneisen parameter up to the accuracy of the Dulong-Petit approximation demonstrates the important roles of anharmonicity and attractive force of the interatomic potential in governing glass transition of metallic glassformers. These findings may shed light on how to understand metallic glass formation from the fundamental interatomic interactions.

Prescribed nanoparticle cluster architectures and low-dimensional arrays built using octahedral DNA origami frames

NASA Astrophysics Data System (ADS)

Tian, Ye; Wang, Tong; Liu, Wenyan; Xin, Huolin L.; Li, Huilin; Ke, Yonggang; Shih, William M.; Gang, Oleg

2015-07-01

Three-dimensional mesoscale clusters that are formed from nanoparticles spatially arranged in pre-determined positions can be thought of as mesoscale analogues of molecules. These nanoparticle architectures could offer tailored properties due to collective effects, but developing a general platform for fabricating such clusters is a significant challenge. Here, we report a strategy for assembling three-dimensional nanoparticle clusters that uses a molecular frame designed with encoded vertices for particle placement. The frame is a DNA origami octahedron and can be used to fabricate clusters with various symmetries and particle compositions. Cryo-electron microscopy is used to uncover the structure of the DNA frame and to reveal that the nanoparticles are spatially coordinated in the prescribed manner. We show that the DNA frame and one set of nanoparticles can be used to create nanoclusters with different chiroptical activities. We also show that the octahedra can serve as programmable interparticle linkers, allowing one- and two-dimensional arrays to be assembled with designed particle arrangements.

Surface-Enhanced Raman Spectroscopy: Substrates and Analyzers You Can Use

NASA Astrophysics Data System (ADS)

Inscore, Frank; Shende, Chetan; Sengupta, Atanu; Huang, Hermes; Farquharson, Stuart

2010-08-01

Following the recognition of the surface-enhanced Raman scattering effect in 1977, there was an explosion of research aimed at understanding this phenomenon of molecular interactions with nano-scale particles, and more than 1000 papers were published by 1982. Since the mid-1990's there has been a resurgence in SERS-based research with the detection of single-molecules and the acknowledgement of "hot-spots". These measurements provoked new examination of SERS theory with a focus on the structure of these hot spots: fractal clusters, edges, or inter-particle gaps. Meanwhile, Real-Time Analyzers has been developing SERS-active sample systems and analyzers to exploit this phenomenon for trace chemical analysis. This presentation reviews the analytical capabilities and limitations for many of the SERS-active substrates, as well as RTA's metal-doped sol-gels. The latter includes the use of the sol-gels in sample systems and analyzers, and their application to poisons in water supplies, food contamination, drug and explosives detection and proteomics.

Layer Splitting in a Complex Plasma

NASA Astrophysics Data System (ADS)

Smith, Bernard; Hyde, Truell; Matthews, Lorin; Johnson, Megan; Cook, Mike; Schmoke, Jimmy

2009-11-01

Dust particle clouds are found in most plasma processing environments and many astrophysical environments. Dust particles suspended within such plasmas often acquire an electric charge from collisions with free electrons in the plasma. Depending upon the ratio of interparticle potential energy to average kinetic energy, charged dust particles can form a gaseous, liquid or crystalline structure with short to longer range ordering. An interesting facet of complex plasma behavior is that particle layers appear to split as the DC bias is increased. This splitting of layers points to a phase transition differing from the normal phase transitions found in two-dimensional solids. In 1993, Dubin noted that as the charged particle density of an initially two-dimensional Coulomb crystal increases the system's layers split at specific charge densities. This work modeled ions in a Paul or Penning trap, but may be applicable to dusty plasma systems as well. This work will discuss this possibility along with splitting observed in the CASPER GEC rf Reference Cell at specific pressures and powers.

Shock Interaction of Metal Particles in Condensed Explosive Detonation

NASA Astrophysics Data System (ADS)

Ripley, Robert; Zhang, Fan; Lien, Fue-Sang

2005-07-01

For detonation propagation in a condensed explosive with metal particles, a macro-scale physical model describing the momentum transfer between the explosive and particles has yet to be completely established. Previous 1D and 2D meso-scale modeling studies indicated that significant momentum transfer from the explosive to the particles occurs as the leading shock front crosses the particles, thus influencing the initiation and detonation structure. In this work, 3D meso-scale modeling is conducted to further study the two-phase momentum transfer during the shock diffraction and subsequent detonation in liquid nitromethane containing packed metal particles. Detonation of the condensed explosive is computed using an Arrhenius reaction model and a hybrid EOS model that combines the Mie-Gruneisen equation for reactants and the JWL equation for products. The compressible particles are modeled using the Tait EOS, where the material strength is negligible. The effect of particle packing configuration and inter-particle spacing is shown by parametric studies. Finally, a physical description of the momentum transfer is discussed.

Melting of 2D colloidal crystals

NASA Astrophysics Data System (ADS)

Maret, G.; Eisenmann, C.; Gasser, U.; Vongruenberg, H. H.; Keim, P.; Zahn, K.

2004-11-01

We study melting of 2D crystals of super-paramagnetic colloidal particles confined by gravity to a flat air-water interface. The effective system temperature is given by the strength of the dipolar inter-particle interaction controlled by an external magnetic field B. Particle positions are obtained by video-microscopy. In vertical B-field crystals are hexagonal and we find all features of the 2-step melting scenario predicted by KTHNY-theory. In particular, quantitative agreement is found for the translational and orientational order parameters related to bound and isolated dislocations and disclinations. From particle position fluctuations wave-vector (q) dependent normal-mode spring constants are obtained in agreement with phonon band structure calculations. The elastic constants (q=0 limit) soften near melting in quantitative agreement with KTHNY. By tilting B away from vertical anisotropic 2D crystals are generated; at small tilting angles they melt through a quasi-hexatic phase, while at higher tilts a centered rectangular phase is found which melts into a 2D smectic-like phase through orientation-dependent dislocations.

Self-replication with magnetic dipolar colloids

NASA Astrophysics Data System (ADS)

Dempster, Joshua M.; Zhang, Rui; Olvera de la Cruz, Monica

2015-10-01

Colloidal self-replication represents an exciting research frontier in soft matter physics. Currently, all reported self-replication schemes involve coating colloidal particles with stimuli-responsive molecules to allow switchable interactions. In this paper, we introduce a scheme using ferromagnetic dipolar colloids and preprogrammed external magnetic fields to create an autonomous self-replication system. Interparticle dipole-dipole forces and periodically varying weak-strong magnetic fields cooperate to drive colloid monomers from the solute onto templates, bind them into replicas, and dissolve template complexes. We present three general design principles for autonomous linear replicators, derived from a focused study of a minimalist sphere-dimer magnetic system in which single binding sites allow formation of dimeric templates. We show via statistical models and computer simulations that our system exhibits nonlinear growth of templates and produces nearly exponential growth (low error rate) upon adding an optimized competing electrostatic potential. We devise experimental strategies for constructing the required magnetic colloids based on documented laboratory techniques. We also present qualitative ideas about building more complex self-replicating structures utilizing magnetic colloids.

Rotating states of self-propelling particles in two dimensions.

PubMed

Chen, Hsuan-Yi; Leung, Kwan-Tai

2006-05-01

We present particle-based simulations and a continuum theory for steady rotating flocks formed by self-propelling particles (SPPs) in two-dimensional space. Our models include realistic but simple rules for the self-propelling, drag, and interparticle interactions. Among other coherent structures, in particle-based simulations we find steady rotating flocks when the velocity of the particles lacks long-range alignment. Physical characteristics of the rotating flock are measured and discussed. We construct a phenomenological continuum model and seek steady-state solutions for a rotating flock. We show that the velocity and density profiles become simple in two limits. In the limit of weak alignment, we find that all particles move with the same speed and the density of particles vanishes near the center of the flock due to the divergence of centripetal force. In the limit of strong body force, the density of particles within the flock is uniform and the velocity of the particles close to the center of the flock becomes small.

Chalcogenide nanocrystal assembly: Controlling heterogeneity and modulating heterointerfaces

NASA Astrophysics Data System (ADS)

Davis, Jessica

This dissertation work is focused on developing methods to facilitate charge transport in heterostructured materials that comprise a nanoscale component. Multicomponent semiconductor materials were prepared by (1) spin coating of discrete nanomaterials onto porous silicon (pSi) or (2) self-assembly. Spin-coating of colloidal quantum dot (QD) PbS solutions was employed to create prototype PbS QD based radiation detection devices using porous silicon (pSi) as an n-type support and charge transport material. These devices were initially tested as a photodetector to ascertain the possibility of their use in high energy radiation detection. Short chain thiolate ligands (4-fluorothiophenolate) and anion passivation at the particle interface were evaluated to augment interparticle transport. However, the samples showed minimum interaction with the light source possibly due to poor infiltration into the pSi. The second project was also driven by the potential synergistic properties that can be achieved in multicomponent metal chalcogenide nanostructures, potentially useful in optoelectronic devices. Working with well-established methods for single component metal chalcogenide (MQ) particle gels this dissertation research sought to develop practical methods for co-gelation of different component particles with complimentary functionalities. By monitoring the kinetics of aggregation using time resolved dynamic light scattering and NMR spectroscopy the kinetics of aggregation of the two most common crystal structures for CdQ nanocrystals was studied and it was determined that the hexagonal (wurtzite) crystal structure aggregated faster than the cubic (zinc blende) crystal structure. For gel coupling of nanoparticles with differing Q (Q=S, Se and Te), once we accounted for the crystal structure effects, it was determined that the relative redox characteristics of Q govern the reaction rate. The oxidative sol-gel assembly routes were also employed to fabricate metal chalcogenide NC gels with different NC components with control over the degree of mixing. In order to control the degree of mixing, the factors that underscore sol-gel oxidative assembly were elucidated and the aggregation and gelation kinetics of metal chalcogenide QDs were monitored through time-resolved dynamic light scattering (TR-DLS), and nuclear magnetic resonance spectroscopy (NMR). Through these kinetic studies of the surface speciation of metal chalcogenides, control over heterogeneity in dual component CdSe-ZnS system, was achieved through adjustment of the capping ligand, the native crystal structure and the chalcogenide, thereby changing the relative rates of assembly for each component independently.

Magnesium Nanocomposites: Current Status and Prospects for Army Applications

DTIC Science & Technology

2011-09-01

and reinforcement that cannot be produced through melt-based processing . In mechanical alloying , the powder and milling media are placed into...mixing vessels that are agitated in a high-energy milling machine. During the mixing process , the powder particles undergo repeated cycles of cold ...welding and fracturing of interparticle bonds. At the end of the process , the powder has been alloyed to the desired composition. Although typically used

Rapid solidification and dynamic compaction of Ni-base superalloy powders

NASA Technical Reports Server (NTRS)

Field, R. D.; Hales, S. J.; Powers, W. O.; Fraser, H. L.

1984-01-01

A Ni-base superalloy containing 13Al-9Mo-2Ta (in at. percent) has been characterized in both the rapidly solidified condition and after dynamic compaction. Dynamically compacted specimens were examined in the as-compacted condition and observations related to current theories of interparticle bonding. In addition, the recrystallization behavior of the compacted material at relatively low temperature (about 0.5-0.75 Tm) was investigated.

Oligonucleotide flexibility dictates crystal quality in DNA-programmable nanoparticle superlattices.

PubMed

Senesi, Andrew J; Eichelsdoerfer, Daniel J; Brown, Keith A; Lee, Byeongdu; Auyeung, Evelyn; Choi, Chung Hang J; Macfarlane, Robert J; Young, Kaylie L; Mirkin, Chad A

2014-11-12

The evolution of crystallite size and microstrain in DNA-mediated nanoparticle superlattices is dictated by annealing temperature and the flexibility of the interparticle bonds. This work addresses a major challenge in synthesizing optical metamaterials based upon noble metal nanoparticles by enabling the crystallization of large nanoparticles (100 nm diameter) at high volume fractions (34% metal). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green-Kubo relation for viscosity tested using experimental data for a two-dimensional dusty plasma

NASA Astrophysics Data System (ADS)

Feng, Yan; Goree, J.; Liu, Bin; Cohen, E. G. D.

2011-10-01

The theoretical Green-Kubo relation for viscosity is tested using experimentally obtained data. In a dusty plasma experiment, micron-sized dust particles are introduced into a partially ionized argon plasma, where they become negatively charged. They are electrically levitated to form a single-layer Wigner crystal, which is subsequently melted using laser heating. In the liquid phase, these dust particles experience interparticle electric repulsion, laser heating, and friction from the ambient neutral argon gas, and they can be considered to be in a nonequilibrium steady state. Direct measurements of the positions and velocities of individual dust particles are then used to obtain a time series for an off-diagonal element of the stress tensor and its time autocorrelation function. This calculation also requires the interparticle potential, which was not measured experimentally but was obtained using a Debye-Hückel-type model with experimentally determined parameters. Integrating the autocorrelation function over time yields the viscosity for shearing motion among dust particles. The viscosity so obtained is found to agree with results from a previous experiment using a hydrodynamical Navier-Stokes equation. This comparison serves as a test of the Green-Kubo relation for viscosity. Our result is also compared to the predictions of several simulations.

Plasticizing aqueous suspensions of concentrated alumina with maltodextrin sugar

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

Schilling, C.H.; Bellman, R.A.; Smith, R.M.

1999-01-01

Aqueous suspensions of submicrometer, 20 vol% Al{sub 2}O{sub 3} powder exhibited a transition from strongly flocculated, thixotropic behavior to a low-viscosity, Newtonian-like state upon adding small amounts of maltodextrin (0.03 g of maltodextrin/(g of Al{sub 2}O{sub 3})). These suspensions could be filter pressed to highly dense (57%) and extrudable pastes only when prepared with maltodextrin. The authors analyzed the interaction of maltodextrin with Al{sub 2}O{sub 3} powder surfaces and quantitatively measured the resulting claylike consolidation, rheological, and extrusion behaviors. Benbow extrusion parameters were comparable to, but higher than, those of kaolin at approximately the same packing density of 57 vol%.more » In contrast, Al{sub 2}O{sub 3} filter cakes without maltodextrin at 57 vol% density were too stiff to be extruded. Measurements of rheological properties, acoustophoresis, electrophoresis, sorption isotherms, and diffuse reflectance Fourier infrared spectroscopy supported the hypothesis that sorbate-mediated steric hindrance, rather than electrostatic, interparticle repulsion, is important to enhancing the consolidation and fluidity of maltodextrin-Al{sub 2}O{sub 3} suspensions. Viscosity measurements on aqueous maltodextrin solutions indicated that free maltodextrin in solution does not improve suspension fluidity by decreasing the viscosity of the interparticle solution.« less

Reentrant equilibrium disordering in nanoparticle–polymer mixtures

DOE PAGES

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

2017-01-31

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

Optical binding of two microparticles levitated in vacuum

NASA Astrophysics Data System (ADS)

Arita, Yoshihiko; Wright, Ewan M.; Dholakia, Kishan

2017-04-01

Optical binding refers to an optically mediated inter-particle interaction that creates new equilibrium positions for closely spaced particles [1-5]. Optical binding of mesoscopic particles levitated in vacuum can pave the way towards the realisation of a large scale quantum bound array in cavity-optomechanics [6-9]. Recently we have demonstrated trapping and rotation of two mesoscopic particles in vacuum using a spatial-light-modulator-based approach to trap more than one particle, induce controlled rotation of individual particles, and mediate interparticle separation [10]. By trapping and rotating two vaterite particles, we observe intensity modulation of the scattered light at the sum and difference frequencies with respect to the individual rotation rates. This first demonstration of optical interference between two microparticles in vacuum has lead to a platform to explore optical binding. Here we demonstrate for the first time optically bound two microparticles mediated by light scattering in vacuum. We investigate autocorrelations between the two normal modes of oscillation, which are determined by the centre-of-mass and the relative positions of the two-particle system. In situ determination of the optical restoring force acting on the bound particles are based on measurement of the oscillation frequencies of the autocorrelation functions of the two normal modes, thereby providing a powerful and original platform to explore multiparticle entanglement in cavity-optomechanics.

RMS roughness-independent tuning of surface wettability by tailoring silver nanoparticles with a fluorocarbon plasma polymer.

PubMed

Choukourov, A; Kylián, O; Petr, M; Vaidulych, M; Nikitin, D; Hanuš, J; Artemenko, A; Shelemin, A; Gordeev, I; Kolská, Z; Solař, P; Khalakhan, I; Ryabov, A; Májek, J; Slavínská, D; Biederman, H

2017-02-16

A layer of 14 nm-sized Ag nanoparticles undergoes complex transformation when overcoated by thin films of a fluorocarbon plasma polymer. Two regimes of surface evolution are identified, both with invariable RMS roughness. In the early regime, the plasma polymer penetrates between and beneath the nanoparticles, raising them above the substrate and maintaining the multivalued character of the surface roughness. The growth (β) and the dynamic (1/z) exponents are close to zero and the interface bears the features of self-affinity. The presence of inter-particle voids leads to heterogeneous wetting with an apparent water contact angle θ a = 135°. The multivalued nanotopography results in two possible positions for the water droplet meniscus, yet strong water adhesion indicates that the meniscus is located at the lower part of the spherical nanofeatures. In the late regime, the inter-particle voids become filled and the interface acquires a single valued character. The plasma polymer proceeds to grow on the thus-roughened surface whereas the nanoparticles keep emerging away from the substrate. The RMS roughness remains invariable and lateral correlations propagate with 1/z = 0.27. The surface features multiaffinity which is given by different evolution of length scales associated with the nanoparticles and with the plasma polymer. The wettability turns to the homogeneous wetting state.

Constructing a Multiple Covalent Interface and Isolating a Dispersed Structure in Silica/Rubber Nanocomposites with Excellent Dynamic Performance.

PubMed

Zheng, Junchi; Han, Dongli; Zhao, Suhe; Ye, Xin; Wang, Yiqing; Wu, Youping; Dong, Dong; Liu, Jun; Wu, Xiaohui; Zhang, Liqun

2018-06-13

Realizing and manipulating a fine dispersion of silica nanoparticles (NPs) in the polymer matrix is always a great challenge. In this work, we first successfully synthesized N, N'-bis[3-(triethoxysilyl)propyl-isopropanol]-propane-1,3-diamine (TSPD), which was a new interface modifier, aiming to promote the dispersion of silica NPs. Through Fourier transform infrared spectroscopy, nuclear magnetic resonance analysis, and mass spectroscopy, we verified that TSPD contains together six ethoxy groups at its two ends. Then, we used this TSPD to modify the pure silica NPs, and this modified silica was abbreviated as D-MS, which is realized by the thermal gravimetric analysis examination, scanning electron microscopy analysis, and dynamic light scattering results. It was clearly observed that D-MS NPs are connected to one another but are not conglutinated tightly, exhibiting a novel predispersed structure with around 1-2 nm certain extent of interparticle distance. Next, we fabricated the following four elastomer nanocomposites such as pure silica/natural rubber (NR) composite (PS-NR), D-MS/NR composite (DMS-NR), bis-(γ-triethoxysilylpropyl)-tetrasulfide (TESPT)-modified silica/NR composite (TS-NR), and TESPT-modified D-MS/NR composite (T&DMS-NR) and found that the Payne effect is the smallest for T&DMS-NR via the combination use of the D-MS and the traditional coupling agent TESPT, which is attributed to its best dispersion state evidenced by the transmission electron microscopy results. Moreover, by measuring a series of other important mechanical performances such as the stress-strain curve, the dynamic strain dependence of the loss factor, and the heat build-up, we concluded that the T&DMS-NR system greatly exceeds those of the three other rubber composites. In general, this new approach provides a good opportunity to prepare a silica/rubber composite with excellent properties in mechanical strength and dynamic behavior by tailoring the fine dispersion of NPs.

Three-dimensional and time-ordered surface-enhanced Raman scattering hotspot matrix.

PubMed

Liu, Honglin; Yang, Zhilin; Meng, Lingyan; Sun, Yudie; Wang, Jie; Yang, Liangbao; Liu, Jinhuai; Tian, Zhongqun

2014-04-09

The "fixed" or "flexible" design of plasmonic hotspots is a frontier area of research in the field of surface-enhanced Raman scattering (SERS). Most reported SERS hotspots have been shown to exist in zero-dimensional point-like, one-dimensional linear, or two-dimensional planar geometries. Here, we demonstrate a novel three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, simply achieved by evaporating a droplet of citrate-Ag sols on a fluorosilylated silicon wafer. In situ synchrotron-radiation small-angle X-ray scattering (SR-SAXS), combined with dark-field microscopy and in situ micro-UV, was employed to explore the evolution of the 3D geometry and plasmonic properties of Ag nanoparticles in a single droplet. In such a droplet, there is a distinct 3D geometry with minimal polydispersity of particle size and maximal uniformity of interparticle distance, significantly different from the dry state. According to theoretical simulations, the liquid adhesive force promotes a closely packed assembly of particles, and the interparticle distance is not fixed but can be balanced in a small range by the interplay of the van der Waals attraction and electrostatic repulsion experienced by a particle. The "trapping well" for immobilizing particles in 3D space can result in a large number of hotspots in a 3D geometry. Both theoretical and experimental results demonstrate that the 3D hotspots are predictable and time-ordered in the absence of any sample manipulation. Use of the matrix not only produces giant Raman enhancement at least 2 orders of magnitude larger than that of dried substrates, but also provides the structural basis for trapping molecules. Even a single molecule of resonant dye can generate a large SERS signal. With a portable Raman spectrometer, the detection capability is also greatly improved for various analytes with different natures, including pesticides and drugs. This 3D hotspot matrix overcomes the long-standing limitations of SERS for the ultrasensitive characterization of various substrates and analytes and promises to transform SERS into a practical analytical technique.

Porosity and mechanical properties of zirconium ceramics

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

Buyakova, S., E-mail: sbuyakova@ispms.tsc.ru; Kulkov, S.; Tomsk Polytechnic University

2015-11-17

Has been studied a porous ceramics obtained from ultra-fine powders. Porous ceramic ZrO{sub 2}(MgO), ZrO{sub 2}(Y{sub 2}O{sub 3}) powder was prepared by pressing and subsequent sintering of compacts homologous temperatures ranging from 0.63 to 0.56 during the isothermal holding duration of 1 to 5 hours. The porosity of ceramic samples was from 15 to 80%. The structure of the ceramic materials produced from plasma-sprayed ZrO{sub 2} powder was represented as a system of cell and rod structure elements. Cellular structure formed by stacking hollow powder particles can be easily seen at the images of fracture surfaces of obtained ceramics. Theremore » were three types of pores in ceramics: large cellular hollow spaces, small interparticle pores which are not filled with powder particles and the smallest pores in the shells of cells. The cells generally did not have regular shapes. The size of the interior of the cells many times exceeded the thickness of the walls which was a single-layer packing of ZrO{sub 2} grains. A distinctive feature of all deformation diagrams obtained in the experiment was their nonlinearity at low deformations which was described by the parabolic law. It was shown that the observed nonlinear elasticity for low deformation on deformation diagrams is due to mechanical instability of the cellular elements in the ceramic carcass.« less

Fabrication of water-dispersible and highly conductive PSS-doped PANI/graphene nanocomposites using a high-molecular weight PSS dopant and their application in H2S detection

NASA Astrophysics Data System (ADS)

Cho, Sunghun; Lee, Jun Seop; Jun, Jaemoon; Kim, Sung Gun; Jang, Jyongsik

2014-11-01

This work describes the fabrication of poly(4-styrenesulfonic acid)-doped polyaniline/graphene (PSS-doped PANI/graphene) nanocomposites and their use as sensing elements for hydrogen sulfide (H2S) detection. PSS with a weight-average molecular weight (Mw) of 1.96 × 106 was synthesized using low-temperature free-radical polymerization. The PSS was used as both a doping agent and a binding agent for the polymerization of aniline monomers in a biphasic system (water-chloroform) at -50 °C. The high Mw of PSS resulted in relatively large particle sizes and smooth surfaces of the PSS-doped PANI. These physical characteristics, in turn, resulted in low interparticle resistance and high conductivity. In addition, the PSS allowed homogeneous dispersion of reduced graphene sheets through electrostatic repulsion. The prepared PSS-doped PANI/graphene solutions showed good compatibility with flexible poly(ethylene terephthalate) (PET) substrates, making them suitable for flexible sensor electrodes. Changes in the charge-transport properties, such as protonation level, conjugation length, crystalline structure, and charge-transfer resistance, of the electrode materials were the main factors influencing the electrical and sensor performance of the PSS-doped PANI-based electrodes. PSS-doped PANI/graphene composites containing 30 wt% graphene showed the highest conductivity (168.4 S cm-1) and the lowest minimum detection level (MDL) for H2S gas (1 ppm). This result is consistent with the observed improvements in charge transport in the electrode materials via strong π-π stacking interactions between the PANI and the graphene sheets.This work describes the fabrication of poly(4-styrenesulfonic acid)-doped polyaniline/graphene (PSS-doped PANI/graphene) nanocomposites and their use as sensing elements for hydrogen sulfide (H2S) detection. PSS with a weight-average molecular weight (Mw) of 1.96 × 106 was synthesized using low-temperature free-radical polymerization. The PSS was used as both a doping agent and a binding agent for the polymerization of aniline monomers in a biphasic system (water-chloroform) at -50 °C. The high Mw of PSS resulted in relatively large particle sizes and smooth surfaces of the PSS-doped PANI. These physical characteristics, in turn, resulted in low interparticle resistance and high conductivity. In addition, the PSS allowed homogeneous dispersion of reduced graphene sheets through electrostatic repulsion. The prepared PSS-doped PANI/graphene solutions showed good compatibility with flexible poly(ethylene terephthalate) (PET) substrates, making them suitable for flexible sensor electrodes. Changes in the charge-transport properties, such as protonation level, conjugation length, crystalline structure, and charge-transfer resistance, of the electrode materials were the main factors influencing the electrical and sensor performance of the PSS-doped PANI-based electrodes. PSS-doped PANI/graphene composites containing 30 wt% graphene showed the highest conductivity (168.4 S cm-1) and the lowest minimum detection level (MDL) for H2S gas (1 ppm). This result is consistent with the observed improvements in charge transport in the electrode materials via strong π-π stacking interactions between the PANI and the graphene sheets. Electronic supplementary information (ESI) available: FE-SEM images of PSS-doped PANI/graphene nanocomposites and graphene sheets, FT-IR spectra of PSS with different Mw, XRD patterns of PSS-doped PANI polymerized with different Mw of PSS, FT-IR spectra of GO, RGO, PSS-coated GO, and PSS-coated RGO, fully XPS scanned spectra of PSS-doped PANI/graphene nanocomposites, cyclic voltammogram of PSS-doped PANI/graphene nanocomposites at different scan rates (10 to 50 mV-1), and I-V characteristics of PSS-doped PANI/graphene nanocomposites with a thickness of 5 μm. See DOI: 10.1039/c4nr04413d

Modification of Structure and Tribological Properties of the Surface Layer of Metal-Ceramic Composite under Electron Irradiation in the Plasmas of Inert Gases

NASA Astrophysics Data System (ADS)

Ovcharenko, V. E.; Ivanov, K. V.; Mohovikov, A. A.; Yu, B.; Xu, Yu; Zhong, L.

2018-01-01

Metal-ceramic composites are the main materials for high-load parts in tribomechanical systems. Modern approaches to extend the operation life of tribomechanical systems are based on increasing the strength and tribological properties of the surface layer having 100 to 200 microns in depth. The essential improvement of the properties occurs when high dispersed structure is formed in the surface layer using high-energy processing. As a result of the dispersed structure formation the more uniform distribution of elastic stresses takes place under mechanical or thermal action, the energy of stress concentrators emergence significantly increases and the probability of internal defects formation reduces. The promising method to form the dispersed structure in the surface layer is pulse electron irradiation in the plasmas of inert gases combining electron irradiation and ion bombardment in one process. The present work reports upon the effect of pulse electron irradiation in plasmas of different inert gases with different atomic mass and ionization energy on the structure and tribological properties of the surface layer of TiC/(Ni-Cr) metal-ceramic composite with the volume ratio of the component being 50:50. It is experimentally shown that high-dispersed heterophase structure with a fraction of nanosized particles is formed during the irradiation. Electron microscopy study reveals that refining of the initial coarse TiC particles occurs via their dissolution in the molten metal binder followed by the precipitation of secondary fine particles in the interparticle layers of the binder. The depth of modified layer and the fraction of nanosized particles increase when the atomic number of the plasma gas increases and ionization energy decreases. The wear resistance of metal-ceramic composite improves in accordance to the formation of nanocrystalline structure in the surface layer.

Coastal Benthic Boundary Layer (CBBL) Research Program

DTIC Science & Technology

1998-09-01

of gas volume and bubble size distribution on the basis of field seismo-acoustic signature remains . Indirect seismic evidence (large scale) of gas...regime was dominated by reversing tidal currents with typical speeds of 10-cm s -1 or less. Maximum bed shear stresses remained too low to resuspend or...Waals attractive force are assumed to remain unchanged for separations less than the cut-off distance, and (2) the mechanical interparticle normal force

Rheological behavior of clay-nanoparticle hybrid-added bentonite suspensions: specific role of hybrid additives on the gelation of clay-based fluids.

PubMed

Jung, Youngsoo; Son, You-Hwan; Lee, Jung-Kun; Phuoc, Tran X; Soong, Yee; Chyu, Minking K

2011-09-01

Two different types of clay nanoparticle hybrid, iron oxide nanoparticle clay hybrid (ICH) and Al(2)O(3)-SiO(2) nanoparticle clay hybrid (ASCH), were synthesized and their effects on the rheological properties of aqueous bentonite fluids in steady state and dynamic state were explored. When ICH particles were added, bentonite particles in the fluid cross-link to form relatively well-oriented porous structure. This is attributed to the development of positively charged edge surfaces in ICH that leads to strengthening of the gel structure of the bentonite susensions. The role of ASCH particles on the interparticle association of the bentonite fluids is different from that of ICH and sensitive to pH. As pH of ASCH-added bentonite suspensions increased, the viscosity, yield stress, storage modulus, and flow stress decreased. In contrast, at low pH, the clay suspensions containing ASCH additives were coagulated and their rheological properties become close to those of ICH added bentonite fluids. A correlation between the net surface charge of the hybrid additives and the rheological properties of the fluids indicates that the embedded nanoparticles within the interlayer space control the variable charge of the edge surfaces of the platelets and determine the particles association behavior of the clay fluids.

Morphology of clusters of attractive dry and wet self-propelled spherical particle suspensions.

PubMed

Alarcón, Francisco; Valeriani, Chantal; Pagonabarraga, Ignacio

2017-01-25

In order to assess the effect of hydrodynamics in the assembly of active attractive spheres, we simulate a semi-dilute suspension of attractive self-propelled spherical particles in a quasi-two dimensional geometry comparing the case with and without hydrodynamics interactions. To start with, independent of the presence of hydrodynamics, we observe that depending on the ratio between attraction and propulsion, particles either coarsen or aggregate forming finite-size clusters. Focusing on the clustering regime, we characterize two different cluster parameters, i.e. their morphology and orientational order, and compare the case when active particles behave either as pushers or pullers (always in the regime where inter-particle attractions compete with self-propulsion). Studying cluster phases for squirmers with respect to those obtained for active Brownian disks (indicated as ABPs), we have shown that hydrodynamics alone can sustain a cluster phase of active swimmers (pullers), while ABPs form cluster phases due to the competition between attraction and self-propulsion. The structural properties of the cluster phases of squirmers and ABPs are similar, although squirmers show sensitivity to active stresses. Active Brownian disks resemble weakly pusher squirmer suspensions in terms of cluster size distribution, structure of the radius of gyration on the cluster size and degree of cluster polarity.

Characterization of the crystal structure, kinematics, stresses and rotations in angular granular quartz during compaction

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

Hurley, Ryan C.; Herbold, Eric B.; Pagan, Darren C.

Three-dimensional X-ray diffraction (3DXRD), a method for quantifying the position, orientation and elastic strain of large ensembles of single crystals, has recently emerged as an important tool for studying the mechanical response of granular materials during compaction. Applications have demonstrated the utility of 3DXRD and X-ray computed tomography (XRCT) for assessing strains, particle stresses and orientations, inter-particle contacts and forces, particle fracture mechanics, and porosity evolution in situ . Although past studies employing 3DXRD and XRCT have elucidated the mechanics of spherical particle packings and angular particle packings with a small number of particles, there has been limited effort tomore » date in studying angular particle packings with a large number of particles and in comparing the mechanics of these packings with those composed of a large number of spherical particles. Therefore, the focus of the present paper is on the mechanics of several hundred angular particles during compaction using in situ 3DXRD to study the crystal structure, kinematics, stresses and rotations of angular quartz grains. Comparisons are also made between the compaction response of angular grains and that of spherical grains, and stress-induced twinning within individual grains is discussed.« less

Tuning the structure and habit of iron oxide mesocrystals

DOE PAGES

Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; ...

2016-07-11

A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and themore » quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.« less

Characterization of the crystal structure, kinematics, stresses and rotations in angular granular quartz during compaction

DOE PAGES

Hurley, Ryan C.; Herbold, Eric B.; Pagan, Darren C.

2018-06-28

Three-dimensional X-ray diffraction (3DXRD), a method for quantifying the position, orientation and elastic strain of large ensembles of single crystals, has recently emerged as an important tool for studying the mechanical response of granular materials during compaction. Applications have demonstrated the utility of 3DXRD and X-ray computed tomography (XRCT) for assessing strains, particle stresses and orientations, inter-particle contacts and forces, particle fracture mechanics, and porosity evolution in situ . Although past studies employing 3DXRD and XRCT have elucidated the mechanics of spherical particle packings and angular particle packings with a small number of particles, there has been limited effort tomore » date in studying angular particle packings with a large number of particles and in comparing the mechanics of these packings with those composed of a large number of spherical particles. Therefore, the focus of the present paper is on the mechanics of several hundred angular particles during compaction using in situ 3DXRD to study the crystal structure, kinematics, stresses and rotations of angular quartz grains. Comparisons are also made between the compaction response of angular grains and that of spherical grains, and stress-induced twinning within individual grains is discussed.« less

A study of inter-particle bonds in dry bauxite waste resulting in atmospheric aerosols

NASA Astrophysics Data System (ADS)

Wagh, Arun S.; Thompson, Bentley

1988-02-01

Bauxite and Alumina production are one of the main activities of several third world countries such as Jamaica, Brazil, India, Guinea, eastern European countries such as Hungary and Rumania and advanced countries such as Australia, West Germany, Japan and the United States. The mining operations lead to dust pollution, but the refining of bauxite to alumina yield large amounts of highly caustic sludge waste, called "Red Mud". Millions of tons of the waste produced in every country are stored in containment dams or natural valleys. This leads to ground water pollution, destruction of plant and bird life and is hazardous to human settlement in earthquake prone regions like Jamaica. As a result several companies have been looking into dry mud stacking which involves thickening the mud in the refining plants and sprying it on the slopes to sun dry it. Typically it involves a drying field of about two hundred acres, which could act as a potential source of caustic dust. In Jamaica one company has started disposing of the mud in this way. The aerosol formation from such areas depends mainly on the integrity of the top dry layers. Presently this is done by studying the approximate parameters such as the friability of the mud. However, following the recent advances in powder technology it has been possible for us to develop an instrument to study the average interparticle forces between the red mud particles. The instrument is based on the principle of a tensometer and a split cell is used to load specimens. A load cell is used to measure the force and a chart recorder is used for plotting separation and the force. The present study reports elemental composition of the dust and its health hazards. It also reports the physical measurement of the average interparticle force as a function of their separation in the Jamaican mud. The effect of ultraviolet radiation on the strength of the material is studied to see the effect of sun-drying of the waste. The five-fold increase in tensile strength indicates that laterisation process is responsible for this phenomenon in Jamaican red mud. The study is crucial to the development of dust free mud stacking by the proper modifications in the process technology. Finally, such a case study is general enough in the characterisation of other sources of aerosols.

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

PubMed

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

2012-01-07

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

Low Temperature Regolith Bricks for In-Situ Structural Material

NASA Technical Reports Server (NTRS)

Grossman, Kevin; Sakthivel, Tamil S.; Mantovani, James; Seal, Sudipta

2016-01-01

Current technology for producing in-situ structural materials on future missions to Mars or the moon relies heavily on energy-intensive sintering processes to produce solid bricks from regolith. This process requires heating the material up to temperatures in excess of 1000 C and results in solid regolith pieces with compressive strengths in the range of 14000 to 28000 psi, but are heavily dependent on the porosity of the final material and are brittle. This method is currently preferred over a low temperature cementation process to prevent consumption of precious water and other non-renewable materials. A high strength structural material with low energy requirements is still needed for future colonization of other planets. To fulfill these requirements, a nano-functionalization process has been developed to produce structural bricks from regolith simulant and shows promising mechanical strength results. Functionalization of granular silicate particles into alkoxides using a simple low temperature chemical process produces a high surface area zeolite particles that are held together via inter-particle oxygen bonding. Addition of water in the resulting zeolite particles produces a sol-gel reaction called "inorganic polymerization" which gives a strong solid material after a curing process at 60 C. The aqueous solution by-product of the reaction is currently being investigated for its reusability; an essential component of any ISRU technology. For this study, two batches of regolith bricks are synthesized from JSC-1A; the first batch from fresh solvents and chemicals, the second batch made from the water solution by-product of the first batch. This is done to determine the feasibility of recycling necessary components of the synthesis process, mainly water. Characterization including BET surface area, SEM, and EDS has been done on the regolith bricks as well as the constituent particles,. The specific surface area of 17.53 sq m/g (average) of the granular regolith material was obtained from nitrogen adsorption isotherm measurement. The size, shape and textures of regolith from SEM shows that the particles are 25-50 micrometers in size and mostly irregular in shape (Figure 1a). The elemental composition of regolith was identified from EDS analysis showed the presence of Si, Al, Fe, Na, Mg, Ca, Ti, O and C (see figure 1b). Each set of cylindrical brick samples were prepared by low energy process, and cured for 21 and 28 days, respectively to compare their compressive strength. Figure 1c, and d shows the JSC-1A brick and the compressive strength measurements. The results from the 21 day cured bricks (2 bricks) have been done and yielded an aver-age strength of 3050 psi, considerably higher than Portland cement mortars (Type IV and V). This promising technology provides the benefits of construction material similar to concrete, with a low complexity, low energy synthesis process and the likelihood of complete reusability of precious resources. Compressive strength using this method can be improved by increasing the surface area of the particles, using bi-modal particle size distribution, and adding certain additives to increase inter-particle forces.

Erosion of cohesive soil layers above underground conduits

NASA Astrophysics Data System (ADS)

Luu, Li-Hua; Philippe, Pierre; Noury, Gildas; Perrin, Jérôme; Brivois, Olivier

2017-06-01

Using a recently developed 2D numerical modelling that combines Discrete Element (DEM) and Lattice Boltzmann methods (LBM), we simulate the destabilisation by an hydraulic gradient of a cohesive granular soil clogging the top of an underground conduit. We aim to perform a multi-scale study that relates the grain scale behavior to the macroscopic erosion process. In particular, we study the influence of the flow conditions and the inter-particle contact forces intensity on the erosion kinetic.

Tuning and synthesis of metallic nanostructures by mechanical compression

DOEpatents

Fan, Hongyou; Li, Binsong

2015-11-17

The present invention provides a pressure-induced phase transformation process to engineer metal nanoparticle architectures and to fabricate new nanostructured materials. The reversible changes of the nanoparticle unit cell dimension under pressure allow precise control over interparticle separation in 2D or 3D nanoparticle assemblies, offering unique robustness for interrogation of both quantum and classic coupling interactions. Irreversible changes above a threshold pressure of about 8 GPa enables new nanostructures, such as nanorods, nanowires, or nanosheets.

Effect of Nanoscale Fillers on the Local Mechanical Behavior of Polymer Nanocomposites

DTIC Science & Technology

2009-12-01

the interparticle spacing can be related to the particle volume fraction, vp, and the particle diameter, d, by [2] r = d 6v„ d) I I (b) Figure...VGCNFs), namely as- fabricated (PR-24-XT PS), high temperature hear treated (PR-24-XT-HHT-LD), and high temperature hear treated and oxidatively...Therefore, hear treatment had a severe effect on the fracture toughness of composites with embedded VGCNFs. This agrees with composite level

Overcoming the Coupling Dilemma in DNA-Programmable Nanoparticle Assemblies by "Ag+ Soldering".

PubMed

Wang, Huiqiao; Li, Yulin; Liu, Miao; Gong, Ming; Deng, Zhaoxiang

2015-05-20

Strong coupling between nanoparticles is critical for facilitating charge and energy transfers. Despite the great success of DNA-programmable nanoparticle assemblies, the very weak interparticle coupling represents a key barrier to various applications. Here, an extremely simple, fast, and highly efficient process combining DNA-programming and molecular/ionic bonding is developed to address this challenge, which exhibits a seamless fusion with DNA nanotechnology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Different singularities in the functions of extended kinetic theory at the origin of the yield stress in granular flows

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

Berzi, Diego; Vescovi, Dalila

2015-01-15

We use previous results from discrete element simulations of simple shear flows of rigid, identical spheres in the collisional regime to show that the volume fraction-dependence of the stresses is singular at the shear rigidity. Here, we identify the shear rigidity, which is a decreasing function of the interparticle friction, as the maximum volume fraction beyond which a random collisional assembly of grains cannot be sheared without developing force chains that span the entire domain. In the framework of extended kinetic theory, i.e., kinetic theory that accounts for the decreasing in the collisional dissipation due to the breaking of molecularmore » chaos at volume fractions larger than 0.49, we also show that the volume fraction-dependence of the correlation length (measure of the velocity correlation) is singular at random close packing, independent of the interparticle friction. The difference in the singularities ensures that the ratio of the shear stress to the pressure at shear rigidity is different from zero even in the case of frictionless spheres: we identify that with the yield stress ratio of granular materials, and we show that the theoretical predictions, once the different singularities are inserted into the functions of extended kinetic theory, are in excellent agreement with the results of numerical simulations.« less

Self-Consistency of the Theory of Elementary Stage Rates of Reversible Processes and the Equilibrium Distribution of Reaction Mixture Components

NASA Astrophysics Data System (ADS)

Tovbin, Yu. K.

2018-06-01

An analysis is presented of one of the key concepts of physical chemistry of condensed phases: the theory self-consistency in describing the rates of elementary stages of reversible processes and the equilibrium distribution of components in a reaction mixture. It posits that by equating the rates of forward and backward reactions, we must obtain the same equation for the equilibrium distribution of reaction mixture components, which follows directly from deducing the equation in equilibrium theory. Ideal reaction systems always have this property, since the theory is of a one-particle character. Problems arise in considering interparticle interactions responsible for the nonideal behavior of real systems. The Eyring and Temkin approaches to describing nonideal reaction systems are compared. Conditions for the self-consistency of the theory for mono- and bimolecular processes in different types of interparticle potentials, the degree of deviation from the equilibrium state, allowing for the internal motions of molecules in condensed phases, and the electronic polarization of the reagent environment are considered within the lattice gas model. The inapplicability of the concept of an activated complex coefficient for reaching self-consistency is demonstrated. It is also shown that one-particle approximations for considering intermolecular interactions do not provide a theory of self-consistency for condensed phases. We must at a minimum consider short-range order correlations.

Role of collisions in erosion of regolith during a lunar landing.

PubMed

Berger, Kyle J; Anand, Anshu; Metzger, Philip T; Hrenya, Christine M

2013-02-01

The supersonic gas plume of a landing rocket entrains lunar regolith, which is the layer of loose solids covering the lunar surface. This ejection is problematic due to scouring and dust impregnation of surrounding hardware, reduction in visibility for the crew, and spoofing of the landing sensors. To date, model predictions of erosion and ejection dynamics have been based largely on single-trajectory models in which the role of interparticle collisions is ignored. In the present work, the parameters affecting the erosion rate of monodisperse solids are investigated using the discrete element method (DEM). The drag and lift forces exerted by the rocket exhaust are incorporated via one-way coupling. The results demonstrate that interparticle collisions are frequent in the region immediately above the regolith surface; as many as 20% of particles are engaged in a collision at a given time. These collisions play an important role both in the erosion dynamics and in the final trajectories of particles. In addition, a direct assessment of the influence of collisions on the erosion rate is accomplished via a comparison between a "collisionless" DEM model and the original DEM model. This comparison shows that the erosion dynamics change drastically when collisions are considered and that the erosion rate is dependent on the collision parameters (coefficient of restitution and coefficient of friction). Physical explanations for these trends are provided.

Modeling of particle agglomeration in nanofluids

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

Krishna, K. Hari; Neti, S.; Oztekin, A.

2015-03-07

Agglomeration strongly influences the stability or shelf life of nanofluid. The present computational and experimental study investigates the rate of agglomeration quantitatively. Agglomeration in nanofluids is attributed to the net effect of various inter-particle interaction forces. For the nanofluid considered here, a net inter-particle force depends on the particle size, volume fraction, pH, and electrolyte concentration. A solution of the discretized and coupled population balance equations can yield particle sizes as a function of time. Nanofluid prepared here consists of alumina nanoparticles with the average particle size of 150 nm dispersed in de-ionized water. As the pH of the colloid wasmore » moved towards the isoelectric point of alumina nanofluids, the rate of increase of average particle size increased with time due to lower net positive charge on particles. The rate at which the average particle size is increased is predicted and measured for different electrolyte concentration and volume fraction. The higher rate of agglomeration is attributed to the decrease in the electrostatic double layer repulsion forces. The rate of agglomeration decreases due to increase in the size of nano-particle clusters thus approaching zero rate of agglomeration when all the clusters are nearly uniform in size. Predicted rates of agglomeration agree adequate enough with the measured values; validating the mathematical model and numerical approach is employed.« less

Rearrangements and Yielding in Concentrated Suspensions of Hard and Soft Colloids

NASA Astrophysics Data System (ADS)

Petekidis, Georgios; Carrier, Vincent; Vlassoppoulos, Dimitris; Pusey, Peter; Ballauff, Matthias

2004-03-01

The rheology and microscopic particle rearrangements of concentrated colloidal suspensions were studied by a combination of conventional rheology and Light Scattering under shear (LS Echo). In particular we studied the rheological response and the microscopic particle dynamics under shear near and above the glass transitions concentration. Measurements were done in model hard and soft sphere particles (sterically stabilized PMMA and PS-PNIPA microgels respectively) to assess the effect of inter-particle interactions. Creep and recovery measurements and dynamic strain sweeps showed that glasses of hard particles can tolerate surprisingly large strains, up to at least 15probes the extent of irreversible particle rearrangement under oscillatory shear, verified that within their cage particles move reversibly at least up to such a strain. Such a behavior was attributed to 'cage elasticity', the ability of a particle and its neighbors to retain their relative positions within the cage under quite large distortion [1]. The onset of irreversible rearrangements measured by LS echo decreased with decreasing frequency revealing an interplay between shear and Brownian forces. The effects of interparticle interactions were studied using soft thermoreversible migrogel particles where a glass state may be reached either increasing the particle concentration or decreasing the temperature. Here, although particle rearrangements appear to be reversible up to strains as high as 100sweep is observed at much lower strains. [1] G. Petekidis, D. Vlassopoulos and P.N. Pusey, Faraday Discuss., 123, 287 (2003)

Recrystallization and grain growth phenomena in a particle-reinforced aluminum composite

NASA Astrophysics Data System (ADS)

van Aken, D. C.; Krajewski, P. E.; Vyletel, G. M.; Allison, J. E.; Jones, J. W.

1995-06-01

Recrystallization and grain growth in a 2219/TiC/15p composite were investigated as functions of the amount of deformation and deformation temperature. Both cold and hot deformed samples were annealed at the normal solution treatment temperature of 535 °C. It was shown that large recrystallized grain diameters, relative to the interparticle spacing, could be produced in a narrow range of deformation for samples cold-worked and those hot-worked below 450 °C. For cold-worked samples, between 4 to 6 pct deformation, the recrystallized grain diameters varied from 530 to 66 μm as the amount of deformation increased. Subsequent grain growth was not observed in these recrystallized materials and noncompact grain shapes were observed. For deformations greater than 15 pct, recrystallized grain diameters less than the interparticle spacing were observed and subsequent grain growth produced a pinned grain diameter of 27 μm. The pinned grain diameter agreed well with an empirical model based on three dimensional (3-D) Monte Carlo simulations of grain growth and particle pinning in a two-phase material. Tensile properties were determined as a function of grain size, and it was shown that grain size had a weak influence on yield strength. A maximum in the yield strength was observed at a grain size larger than the normal grain growth and particle-pinned diameter.

Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

NASA Astrophysics Data System (ADS)

Corradini, Patricia Gon; Pires, Felipe I.; Paganin, Valdecir A.; Perez, Joelma; Antolini, Ermete

2012-09-01

The effect of the relationship between particle size ( d), inter-particle distance ( x i ), and metal loading ( y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x i / d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x i / d can be always obtained. For y ≥ 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x i / d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x i / d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x i / d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

Genetically Programmable Thermoresponsive Plasmonic Gold/Silk-Elastin Protein Core/Shell Nanoparticles

PubMed Central

2015-01-01

The design and development of future molecular photonic/electronic systems pose the challenge of integrating functional molecular building blocks in a controlled, tunable, and reproducible manner. The modular nature and fidelity of the biosynthesis method provides a unique chemistry approach to one-pot synthesis of environmental factor-responsive chimeric proteins capable of energy conversion between the desired forms. In this work, facile tuning of dynamic thermal response in plasmonic nanoparticles was facilitated by genetic engineering of the structure, size, and self-assembly of the shell silk-elastin-like protein polymers (SELPs). Recombinant DNA techniques were implemented to synthesize a new family of SELPs, S4E8Gs, with amino acid repeats of [(GVGVP)4(GGGVP)(GVGVP)3(GAGAGS)4] and tunable molecular weight. The temperature-reversible conformational switching between the hydrophilic random coils and the hydrophobic β-turns in the elastin blocks were programmed to between 50 and 60 °C by site-specific glycine mutation, as confirmed by variable-temperature proton NMR and circular dichroism (CD) spectroscopy, to trigger the nanoparticle aggregation. The dynamic self-aggregation/disaggregation of the Au-SELPs nanoparticles was regulated in size and pattern by the β-sheet-forming, thermally stable silk blocks, as revealed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The thermally reversible, shell dimension dependent, interparticle plasmon coupling was investigated by both variable-temperature UV–vis spectroscopy and finite-difference time-domain (FDTD)-based simulations. Good agreement between the calculated and measured spectra sheds light on design and synthesis of responsive plasmonic nanostructures by independently tuning the refractive index and size of the SELPs through genetic engineering. PMID:24712906

Directed-assembly of ordered nanoparticle arrays exploiting multiple adsorption mechanisms on a self-assembling biological template

NASA Astrophysics Data System (ADS)

Shindel, Matthew M.

Developing processes to fabricate inorganic architectures with designer functionalities at increasingly minute length-scales is of chief concern in the fields of nanotechnology and nanoscience. This enterprise requires assembly mechanisms with the capacity to tailor both the spatial arrangement and material composition of a system's constituent building blocks. To this end, significant advances can be made by turning to biology, as the natural world has evolved the ability to generate intricate nanostructures, which can potentially be employed as templates for inorganic nanosystems. We explore this biotemplating methodology using two-dimensional streptavidin crystals, investigating the ability of the protein lattice to direct the assembly of ordered metallic nanoparticle arrays. We demonstrate that the adsorption of nanoparticles on the protein monolayer can be induced through both electrostatic and molecular recognition (ligand-receptor) interactions. Furthermore, the dynamics of adsorption can be modulated through both environmental factors (e.g. pH), and by tailoring particle surface chemistry. When the characteristic nanoparticle size is on the order of the biotemplate's unit-cell dimension, electrostatically-mediated adsorption occurs in a site-specific manner. The nanoparticles exhibit a pronounced preference for adhering to the areas between protein molecules. The two-dimensional structure of the resultant nanoparticle ensemble consequently conforms to that of the underlying protein crystal. Through theoretical calculations, simulation and experiment, we show that interparticle spacing in the templated array is influenced by the screened-coulombic repulsion between particles, and can thus be tuned by controlling ionic strength during deposition. Templating ordered nanoparticle arrays via ligand-receptor mediated adsorption, and the constrained growth of metallic nanoparticles directly on the protein lattice from ionic precursors are also examined. Overall, this work demonstrates that the streptavidin crystal system possesses unique utility for nanoscale, directed-assembly applications.

Extrusion and rheology of fine particulate ceramic pastes

NASA Astrophysics Data System (ADS)

Mazzeo, Fred Anthony

A rheological study was conducted on an extruded blend of two alumina powders, Alcoa A-3500-SG and Reynolds ERC. These extruded blends were mixed in four compositions, varying in distribution modulus. This work focuses on the interaction of the composition components, mainly particle size distribution and amount of water at a constant binder amount. The rheological parameters of extruded pastes, Sigma, Tau, alpha and beta, were determined by using capillary rheometry modeling by the methodology set forth by Benbow and Bridgwater. This methodology makes use of capillary rheometer to determine extrusion parameters, which describe the flow behavior of a paste. The parameter values are indirectly determined by extrapolating high shear rate information obtained by the extrusion process. A goal of this research was to determine fundamental rheological properties directly from fundamental rheological equations of state. This was accomplished by assessing the material properties by using a dynamic stress rheometer. The rheological parameters used in this study to characterize the paste are elastic modulus, viscosity, tan delta, and relaxation time. This technique approaches a step closer in understanding the microstructural influence on flow behavior of a paste. This method directly determines rheological properties by using linear viscoelastic theory, giving a quantitative analysis of material properties. A strong correlation between the elastic modulus and sigma, and viscosity and alpha is shown to exist, indicating a relationship between these two techniques. Predictive process control methodology, based on particle packing modeling, quantitatively determined structural parameters useful in evaluating a composition. The determined parameters are: distribution modulus, interparticle separation distance, porosity, and particle crowding index, which are important to understand the extrudates packed state. A connection between the physical structure of the extrudate and its rheological behavior, can lead to a better understanding of what conditions and parameters are necessary to characterize the extrusion process. This study shows how particle packing and particle size influences the rheological behavior of the paste. Results showed that an optimally packed system was found to occur at a distribution modulus of 0.51. This system was determined both experimentally and quantitatively to exhibit the lowest porosity at any water content. The 0.51 system required a lower amount of water to extrude and the parameters of both rheological techniques agreed well, in which all parameters are influenced by the packing state of the paste, and a consistent trend was generally found. The capillary rheometry results can be explained by the strong interaction of particles that occurs at high shear rates. The dynamic stress rheometer results can be explained by the particle packing characteristics, interparticle separation distance and particle-crowding index, and the capillary forces between particles. The excess amount of liquid that is present in the structure decreases the role of the capillary attraction between particles and an increase in the particle size role on the rheological behavior of the pastes occurs.

Fabrication and characterization of silica aerogel as synthetic tissues for medical imaging phantoms

NASA Astrophysics Data System (ADS)

In, Eunji; Naguib, Hani

2015-05-01

Medical imaging plays an important role in the field of healthcare industry both in clinical settings and in research and development. It is used in prevention, early detection of disease, in choosing the optimal treatment, during surgical interventions and monitoring of the treatment effects. Despite much advancement in the last few decades, rapid change on its technology development and variety of imaging parameters that differ with the manufacturer restrict its further development. Imaging phantom is a calibrating medium that is scanned or imaged in the field of medical imaging to evaluate, analyze and tune the performance of various imaging devices. A phantom used to evaluate an imaging device should respond in a similar manner to how human tissue and organs would act in that specific imaging modality. There has been many research on the phantom materials; however, there has been no attempt to study on the material that mimics the structure of lung or fibrous tissue. So with the need for development of gel with such structure, we tried to mimic this structure with aerogel. Silica aerogels have unique properties that include low density (0.003g/cm) and mesoporosity (pore size 2-50nm), with a high thermal insulation value (0.005W/mK) and high surface area (500-1200m-2/g).] In this study, we cross-linked with di-isocyanate, which is a group in polyurethane to covalently bond the polymer to the surface of silica aerogel to enhance the mechanical properties. By formation of covalent bonds, the structure can be reinforced by widening the interparticle necks while minimally reducing porosity.

Arrangement at the nanoscale: Effect on magnetic particle hyperthermia

NASA Astrophysics Data System (ADS)

Myrovali, E.; Maniotis, N.; Makridis, A.; Terzopoulou, A.; Ntomprougkidis, V.; Simeonidis, K.; Sakellari, D.; Kalogirou, O.; Samaras, T.; Salikhov, R.; Spasova, M.; Farle, M.; Wiedwald, U.; Angelakeris, M.

2016-11-01

In this work, we present the arrangement of Fe3O4 magnetic nanoparticles into 3D linear chains and its effect on magnetic particle hyperthermia efficiency. The alignment has been performed under a 40 mT magnetic field in an agarose gel matrix. Two different sizes of magnetite nanoparticles, 10 and 40 nm, have been examined, exhibiting room temperature superparamagnetic and ferromagnetic behavior, in terms of DC magnetic field, respectively. The chain formation is experimentally visualized by scanning electron microscopy images. A molecular Dynamics anisotropic diffusion model that outlines the role of intrinsic particle properties and inter-particle distances on dipolar interactions has been used to simulate the chain formation process. The anisotropic character of the aligned samples is also reflected to ferromagnetic resonance and static magnetometry measurements. Compared to the non-aligned samples, magnetically aligned ones present enhanced heating efficiency increasing specific loss power value by a factor of two. Dipolar interactions are responsible for the chain formation of controllable density and thickness inducing shape anisotropy, which in turn enhances magnetic particle hyperthermia efficiency.

Synthesis of Ferrofluids Made of Iron Oxide Nanoflowers: Interplay between Carrier Fluid and Magnetic Properties

PubMed Central

Dughiero, Fabrizio; Forzan, Michele; Bertani, Roberta

2017-01-01

Ferrofluids are nanomaterials consisting of magnetic nanoparticles that are dispersed in a carrier fluid. Their physical properties, and hence their field of application are determined by intertwined compositional, structural, and magnetic characteristics, including interparticle magnetic interactions. Magnetic nanoparticles were prepared by thermal decomposition of iron(III) chloride hexahydrate (FeCl3·6H2O) in 2-pyrrolidone, and were then dispersed in two different fluids, water and polyethylene glycol 400 (PEG). A number of experimental techniques (especially, transmission electron microscopy, Mössbauer spectroscopy and superconducting quantum interference device (SQUID) magnetometry) were employed to study both the as-prepared nanoparticles and the ferrofluids. We show that, with the adopted synthesis parameters of temperature and FeCl3 relative concentration, nanoparticles are obtained that mainly consist of maghemite and present a high degree of structural disorder and strong spin canting, resulting in a low saturation magnetization (~45 emu/g). A remarkable feature is that the nanoparticles, ultimately due to the presence of 2-pyrrolidone at their surface, are arranged in nanoflower-shape structures, which are substantially stable in water and tend to disaggregate in PEG. The different arrangement of the nanoparticles in the two fluids implies a different strength of dipolar magnetic interactions, as revealed by the analysis of their magnetothermal behavior. The comparison between the magnetic heating capacities of the two ferrofluids demonstrates the possibility of tailoring the performances of the produced nanoparticles by exploiting the interplay with the carrier fluid. PMID:29113079

Synthesis of Ferrofluids Made of Iron Oxide Nanoflowers: Interplay between Carrier Fluid and Magnetic Properties.

PubMed

Spizzo, Federico; Sgarbossa, Paolo; Sieni, Elisabetta; Semenzato, Alessandra; Dughiero, Fabrizio; Forzan, Michele; Bertani, Roberta; Del Bianco, Lucia

2017-11-05

Ferrofluids are nanomaterials consisting of magnetic nanoparticles that are dispersed in a carrier fluid. Their physical properties, and hence their field of application are determined by intertwined compositional, structural, and magnetic characteristics, including interparticle magnetic interactions. Magnetic nanoparticles were prepared by thermal decomposition of iron(III) chloride hexahydrate (FeCl₃·6H₂O) in 2-pyrrolidone, and were then dispersed in two different fluids, water and polyethylene glycol 400 (PEG). A number of experimental techniques (especially, transmission electron microscopy, Mössbauer spectroscopy and superconducting quantum interference device (SQUID) magnetometry) were employed to study both the as-prepared nanoparticles and the ferrofluids. We show that, with the adopted synthesis parameters of temperature and FeCl₃ relative concentration, nanoparticles are obtained that mainly consist of maghemite and present a high degree of structural disorder and strong spin canting, resulting in a low saturation magnetization (~45 emu/g). A remarkable feature is that the nanoparticles, ultimately due to the presence of 2-pyrrolidone at their surface, are arranged in nanoflower-shape structures, which are substantially stable in water and tend to disaggregate in PEG. The different arrangement of the nanoparticles in the two fluids implies a different strength of dipolar magnetic interactions, as revealed by the analysis of their magnetothermal behavior. The comparison between the magnetic heating capacities of the two ferrofluids demonstrates the possibility of tailoring the performances of the produced nanoparticles by exploiting the interplay with the carrier fluid.

The Role of Repulsion in Colloidal Crystal Engineering with DNA

DOE PAGES

Seo, Soyoung E.; Li, Tao; Senesi, Andrew J.; ...

2017-10-24

Hybridization interactions between DNA-functionalized nanoparticles (DNA-NPs) can be used to program the crystallization behavior of superlattices, yielding access to complex three-dimensional structures with more than 30 different lattice symmetries. The first superlattice structures using DNA-NPs as building blocks were identified almost a decade ago, yet the role of repulsive interactions in guiding structure formation is still largely unexplored. In this paper, a comprehensive approach is taken to study the role of repulsion in the assembly behavior of DNA-NPs, enabling the calculation of interparticle interaction potentials based on experimental results. In this work, we used two different means to assemble DNA-NPs—Watson–Crickmore » base-pairing interactions and depletion interactions—and systematically varied the salt concentration to study the effective interactions in DNA-NP superlattices. A comparison between the two systems allows us to decouple the repulsive forces from the attractive hybridization interactions that are sensitive to the ionic environment. We find that the gap distance between adjacent DNA-NPs follows a simple power law dependence on solution ionic strength regardless of the type of attractive forces present. This result suggests that the observed trend is driven by repulsive interactions. To better understand such behavior, we propose a mean-field model that provides a mathematical description for the observed trend. Finally, this model shows that the trend is due to the variation in the effective cross-sectional diameter of DNA duplex and the thickness of DNA shell.« less

The Role of Repulsion in Colloidal Crystal Engineering with DNA

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

Seo, Soyoung E.; Li, Tao; Senesi, Andrew J.

Hybridization interactions between DNA-functionalized nanoparticles (DNA-NPs) can be used to program the crystallization behavior of superlattices, yielding access to complex three-dimensional structures with more than 30 different lattice symmetries. The first superlattice structures using DNA-NPs as building blocks were identified almost a decade ago, yet the role of repulsive interactions in guiding structure formation is still largely unexplored. In this paper, a comprehensive approach is taken to study the role of repulsion in the assembly behavior of DNA-NPs, enabling the calculation of interparticle interaction potentials based on experimental results. In this work, we used two different means to assemble DNA-NPs—Watson–Crickmore » base-pairing interactions and depletion interactions—and systematically varied the salt concentration to study the effective interactions in DNA-NP superlattices. A comparison between the two systems allows us to decouple the repulsive forces from the attractive hybridization interactions that are sensitive to the ionic environment. We find that the gap distance between adjacent DNA-NPs follows a simple power law dependence on solution ionic strength regardless of the type of attractive forces present. This result suggests that the observed trend is driven by repulsive interactions. To better understand such behavior, we propose a mean-field model that provides a mathematical description for the observed trend. Finally, this model shows that the trend is due to the variation in the effective cross-sectional diameter of DNA duplex and the thickness of DNA shell.« less

The Role of Repulsion in Colloidal Crystal Engineering with DNA

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

Seo, Soyoung E.; Li, Tao; Senesi, Andrew J.

Hybridization interactions between DNA-functionalized nanoparticles (DNA-NPs) can be used to program the crystallization behavior of superlattices, yielding access to complex three-dimensional structures with more than 30 different lattice symmetries. The first superlattice structures using DNA-NPs as building blocks were identified almost two decades ago, yet the role of repulsive interactions in guiding structure formation is still largely unexplored. Here, a com-prehensive approach is taken to study the role of repulsion in the assembly behavior of DNA-NPs, enabling the calculation of interparticle interaction potentials based on experimental results. In this work, we used two different means to assemble DNA-NPs—Watson-Crick base pairingmore » interactions and depletion interactions—and systematically varied the salt concen-tration to study the effective interactions in DNA-NP superlattices. A comparison between the two systems allows us to decouple the repulsive forces from the attractive hybridization interactions that are sensitive to the ionic environment. We find that the gap distance between adjacent DNA-NPs follows a simple power law dependence on solution ionic strength regardless of the type of attractive forces present. This result suggests that the observed trend is driven by repulsive inter-actions. To better understand such behavior, we propose a mean-field model that provides a mathematical description for the observed trend. This model shows that the trend is due to the variation in the effective cross-sectional diameter of DNA duplex and the thickness of DNA shell.« less

The accurate assessment of small-angle X-ray scattering data

DOE PAGES

Grant, Thomas D.; Luft, Joseph R.; Carter, Lester G.; ...

2015-01-23

Small-angle X-ray scattering (SAXS) has grown in popularity in recent times with the advent of bright synchrotron X-ray sources, powerful computational resources and algorithms enabling the calculation of increasingly complex models. However, the lack of standardized data-quality metrics presents difficulties for the growing user community in accurately assessing the quality of experimental SAXS data. Here, a series of metrics to quantitatively describe SAXS data in an objective manner using statistical evaluations are defined. These metrics are applied to identify the effects of radiation damage, concentration dependence and interparticle interactions on SAXS data from a set of 27 previously described targetsmore » for which high-resolution structures have been determined via X-ray crystallography or nuclear magnetic resonance (NMR) spectroscopy. Studies show that these metrics are sufficient to characterize SAXS data quality on a small sample set with statistical rigor and sensitivity similar to or better than manual analysis. The development of data-quality analysis strategies such as these initial efforts is needed to enable the accurate and unbiased assessment of SAXS data quality.« less

Dynamic Electrorheological Effects of Rotating Particles:

NASA Astrophysics Data System (ADS)

Yu, K. W.; Gu, G. Q.; Huang, J. P.; Xiao, J. J.

Particle rotation leads to a steady-state which is different from the equilibrium state in the absence of rotational motion. The change of the polarization of the particle due to the rotational motion is called the dynamic electrorheological effect (DER). There are three cases to be considered: rotating particles in a dc field, particle rotation due to a rotating field and spontaneous rotation of particle in dc field (Quincke rotation). In the DER of rotating particles, the particle rotational motion generally reduces the interparticle force between the particles. The effect becomes pronounced when the frequency is on the order of the relaxation rate of the surface charges. In the electrorotation of particles, the mutual interaction between approaching particles will change the electrorotation spectrum significantly. The electrorotation spectrum depends strongly on the medium conductivity as well as the conductivity contrast between the particle and the medium. 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. This has an implication of a new class of material.

Bi-continuous Multi-component Nanocrystal Superlattices for Solar Energy Conversion

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

Kagan, Cherie; Murray, Christopher; Kikkawa, James

2017-06-14

Our SISGR program studied an emerging class of nanomaterials wherein different combinations of semiconductor or semiconductor and plasmonic nanocrystals (NCs) are self-assembled into three-dimensional multi-component superlattices. The NC assemblies were designed to form bicontinuous semiconductor NC sublattices with type-II energy offsets to drive charge separation onto electron and hole transporting sublattices for collection and introduce plasmonic NCs to increase solar absorption and charge separation. Our group is expert in synthesizing and assembling an extraordinary variety of artificial systems by tailoring the NC building blocks and the superlattice unit cell geometry. Under this DOE BES Materials Chemistry program, we introduced chemicalmore » methods to control inter-particle distance and to dope NC assemblies, which enabled our demonstration of strong electronic communication between NCs and the use of NC thin films as electronic materials. We synthesized, assembled and structurally, spectroscopically, and electrically probed NC superlattices to understand and manipulate the flow of energy and charge toward discovering the design rules and optimizing these complex architectures to create materials that efficiently convert solar radiation into electricity.« less

Density Scaling of Glassy Dynamics and Dynamic Heterogeneities in Glass-forming Liquids.

NASA Astrophysics Data System (ADS)

Hu, Yuan-Chao; Yang, Yong; Wang, Wei-Hua

The discovery of density scaling in strongly correlating systems is an important progress for understanding the dynamic behaviors of supercooled liquids. Here we found for a ternary metallic glass-forming liquid, it is not strongly correlating thermodynamically, but its average dynamics, dynamic heterogeneities and static structure are still well described by density scaling with the same scaling exponent γ. As an intrinsic material constant stemming from the fundamental interatomic interactions, γ is theoretically predicted from the thermodynamic fluctuations of potential energy and the virial. Although γ is conventionally understood merely from the repulsive part of the inter-particle potentials, the strong correlation between γ and the Grüneisen parameter up to the accuracy of the Dulong-Petit approximation demonstrates the important roles of anharmonicity and attractive force of the interatomic potential in governing glass transition of metallic glass-formers. The supercooled dynamics and density scaling behaviors will also be discussed in model glass-forming liquids with tunable attractive potentials to further quantify the nonperturbative roles of attractive interactions. We acknowledge the support from ''Peter Ho Conference Scholarships'' of City University of Hong Kong.

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

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

Srivastava, Sunita; Kishore, Suhasini; Narayanan, Suresh

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

A Printing-Centric Approach to the Electrostatic Modification of Polymer/Clay Composites for use in 3D Direct-Ink Writing

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

Rauzan, Brittany; Lehman, Sean; McCracken, Josell

Polymer/clay composite inks are exceptionally useful materials for fabrication processes based on 3D direct-ink writing, however, there remains an insufficient understanding of how their physiochemical dynamics impact printability. Using a model system, N-isopropylacrylamide/Laponite, the electrostatic interactions between Laponite platelets are modified to tune critical rheological properties in order to improve printability. Rheological measurements and X-ray scattering experiments are carried out to monitor the nano/micro-structural dynamics and complex physicochemical interactions of Laponite as it impacts complex modulus in the linear region, flow behavior, thixotropy, and yield stress of the composite ink. Modification of the electrostatic interactions between platelets reduces the yieldmore » stress of the material, while maintaining a complex microstructure that allows for sufficient recovery times upon removal of stress to form stable, and thus printable, filaments. A printing-centric approach is established based on a fundamental understanding of electrostatic inter-particle interactions, harnessing the innate microstructure of Laponite in 3D direct-ink writing of composites.« less

Understanding Radionuclide Interactions with Layered Materials

NASA Astrophysics Data System (ADS)

Wang, Y.

2015-12-01

Layered materials play an important role in nuclear waste management and environmental cleanup. Better understanding of radionuclide interactions with those materials is critical for engineering high-performance materials for various applications. This presentation will provide an overview on radionuclide interactions with two general categories of layered materials - cationic clays and anionic clays - from a perspective of nanopore confinement. Nanopores are widely present in layered materials, either as the interlayers or as inter-particle space. Nanopore confinement can significantly modify chemical reactions in those materials. This effect may cause the preferential enrichment of radionuclides in nanopores and therefore directly impact the mobility of the radionuclides. This effect also implies that conventional sorption measurements using disaggregated samples may not represent chemical conditions in actual systems. The control of material structures on ion exchange, surface complexation, and diffusion in layered materials will be systematically examined, and the related modeling approaches will be discussed. This work was performed at Sandia National Laboratories, which is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the DOE under contract DE-AC04-94AL8500.

A high performance quasi-solid-state supercapacitor based on CuMnO2 nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Lu; Arif, Muhammad; Duan, Guorong; Chen, Shenming; Liu, Xiaoheng

2017-07-01

Mixed metal or transition metal oxides hold an unveiled potential as one of the most promising energy storage material because of their excellent stability, reliable conductivity, and convenient use. In this work, CuMnO2 nanoparticles are successfully prepared by a facile hydrothermal process with the help of dispersing agent cetyltrimethylammonium bromide (CTAB). CuMnO2 nanoparticles possess a uniform quadrilateral shape, small size (approximately 25 × 25 nm-35 × 35 nm), excellent dispersity, and large specific surface specific (56.9 m2 g-1) with an interparticle mesoporous structure. All these characteristics can bring benefit for their application in supercapacitor. A quasi-solid-state symmetric supercapacitor device is assembled by using CuMnO2 nanoparticles as both positive electrode and negative electrode. The device exhibits good supercapacitive performance with a high specific capacitance (272 F g-1), a maximum power density of 7.56 kW kg-1 and a superior cycling stability of 18,000 continuous cycles, indicating an excellent potential to be used in energy storage device.

Symmetry-enriched Bose-Einstein condensates in a spin-orbit-coupled bilayer system

NASA Astrophysics Data System (ADS)

Cheng, Jia-Ming; Zhou, Xiang-Fa; Zhou, Zheng-Wei; Guo, Guang-Can; Gong, Ming

2018-01-01

We consider the fate of Bose-Einstein condensation with time-reversal symmetry and inversion symmetry in a spin-orbit-coupled bilayer system. When these two symmetry operators commute, all the single-particle bands are exactly twofold degenerate in the momentum space. The scattering in the twofold-degenerate rings can relax the spin-momentum locking effect from spin-orbit-coupling interaction and thus can realize the spin-polarized plane-wave phase even when the interparticle interaction dominates. When these two operators anticommute, the lowest two bands may have the same minimal energy, but with totally different spin structures. As a result, the competition between different condensates in these two energetically degenerate rings can give rise to different stripe phases with atoms condensed at two or four collinear momenta. We find that the crossover between these two cases is accompanied by the excited band condensation when the interference energy can overcome the increased single-particle energy in the excited band. This effect is not based on strong interaction and thus can be realized even with moderate interaction strength.

Rapid and selective lead (II) colorimetric sensor based on azacrown ether-functionalized gold nanoparticles

NASA Astrophysics Data System (ADS)

Alizadeh, A.; Khodaei, M. M.; Karami, Ch; Workentin, M. S.; Shamsipur, M.; Sadeghi, M.

2010-08-01

A gold nanoparticle (AuNPs)-based simple and fast colorimetric sensor for selective detecting of Pb(II) in aqueous solution has been developed. Monodisperse AuNPs (approx. 2.0 nm diameter) has been prepared facilely and further modified with an alkanethiol-bearing monoazacrown ether terminus. These AuNPs are shown to selectively sense Pb2 + through color change, which is visually discernible by an appearance of the surface plasmon band (SPB) at 520 nm. The recognition mechanism is attributed to the unique structure of the monoazacrown ether attached to AuNPs and metal sandwich coordination between two azacrown ether moieties that are attached to separate nanoparticles. This inter-particle cross-linking results in an aggregation and apparent color change from brown to purple. Additionally, TEM experiments support the optical absorption data proving the aggregation between azacrown ether-capped gold nanoparticles. This AuNP-based colorimetric assay is a facile and robust method and allows fast detection of Pb2 + at ambient temperatures. More importantly, the developed technique does not utilize enzymatic reactions, light-sensitive dye molecules, lengthy protocols or sophisticated instrumentation.

Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting coatings and sunscreens

NASA Astrophysics Data System (ADS)

Faure, Bertrand; Salazar-Alvarez, German; Ahniyaz, Anwar; Villaluenga, Irune; Berriozabal, Gemma; De Miguel, Yolanda R.; Bergström, Lennart

2013-04-01

This review describes recent efforts on the synthesis, dispersion and surface functionalization of the three dominating oxide nanoparticles used for photocatalytic, UV-blocking and sunscreen applications: titania, zinc oxide, and ceria. The gas phase and liquid phase synthesis is described briefly and examples are given of how weakly aggregated photocatalytic or UV-absorbing oxide nanoparticles with different composition, morphology and size can be generated. The principles of deagglomeration are reviewed and the specific challenges for nanoparticles highlighted. The stabilization of oxide nanoparticles in both aqueous and non-aqueous media requires a good understanding of the magnitude of the interparticle forces and the surface chemistry of the materials. Quantitative estimates of the Hamaker constants in various media and measurements of the isoelectric points for the different oxide nanoparticles are presented together with an overview of different additives used to prepare stable dispersions. The structural and chemical requirements and the various routes to produce transparent photocatalytic and nanoparticle-based UV-protecting coatings, and UV-blocking sunscreens are described and discussed.

Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting coatings and sunscreens

PubMed Central

Faure, Bertrand; Salazar-Alvarez, German; Ahniyaz, Anwar; Villaluenga, Irune; Berriozabal, Gemma; De Miguel, Yolanda R; Bergström, Lennart

2013-01-01

This review describes recent efforts on the synthesis, dispersion and surface functionalization of the three dominating oxide nanoparticles used for photocatalytic, UV-blocking and sunscreen applications: titania, zinc oxide, and ceria. The gas phase and liquid phase synthesis is described briefly and examples are given of how weakly aggregated photocatalytic or UV-absorbing oxide nanoparticles with different composition, morphology and size can be generated. The principles of deagglomeration are reviewed and the specific challenges for nanoparticles highlighted. The stabilization of oxide nanoparticles in both aqueous and non-aqueous media requires a good understanding of the magnitude of the interparticle forces and the surface chemistry of the materials. Quantitative estimates of the Hamaker constants in various media and measurements of the isoelectric points for the different oxide nanoparticles are presented together with an overview of different additives used to prepare stable dispersions. The structural and chemical requirements and the various routes to produce transparent photocatalytic and nanoparticle-based UV-protecting coatings, and UV-blocking sunscreens are described and discussed. PMID:27877568

Solitonic Excitations in Fermionic Superfluids and Progress towards Fermi Gas in Uniform Potential

NASA Astrophysics Data System (ADS)

Ku, Mark; Mukherjee, Biswaroop; Guardado-Sanchez, Elmer; Yan, Zhenjie; Patel, Parth; Yefsah, Tarik; Struck, Julian; Zwierlein, Martin

2015-05-01

We follow the evolution of a superfluid Fermi gas of 6Li atoms following a one-sided π phase imprint. Via tomographic imaging, we observe the formation of a planar dark soliton, and its subsequent snaking and decay into a vortex ring. The latter eventually breaks at the boundary of the superfluid, finally leaving behind a single, remnant solitonic vortex. The nodal surface is directly imaged and reveals its decay into a vortex ring via a puncture of the initial soliton plane. At intermediate stages we find evidence for more exotic structures resembling Φ-solitons. The observed evolution of the nodal surface represents dynamics that occurs at the length scale of the interparticle spacing, thus providing new experimental input for microscopic theories of strongly correlated fermions. We also report on the trapping of fermionic atoms of 6Li in a quasi-homogenous all-optical potential, and discuss progress towards directly observing the momentum distribution of the fermions in a box. This new tool offers the possibility to quantitatively study Fermi gases at finite temperature and in the presence of spin-imbalance, with unprecedented accuracy.

Spiral waves in driven strongly coupled Yukawa systems

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Das, Amita

2018-06-01

Spiral wave formations are ubiquitous in nature. In the present paper, the excitation of spiral waves in the context of driven two-dimensional dusty plasma (Yukawa system) has been demonstrated at particle level using molecular-dynamics simulations. The interaction amidst dust particles is modeled by the Yukawa potential to take account of the shielding of dust charges by the lighter electron and ion species. The spatiotemporal evolution of these spiral waves has been characterized as a function of the frequency and amplitude of the driving force and dust neutral collisions. The effect of strong coupling has been studied, which shows that the excited spiral wave structures get clearer as the medium gets more strongly coupled. The radial propagation speed of the spiral wave is observed to remain unaltered with the coupling parameter. However, it is found to depend on the screening parameter of the dust medium and decreases when it is increased. In the crystalline phase (with screening parameter κ >0.58 ), the spiral wavefronts are shown to be hexagonal in shape. This shows that the radial propagation speed depends on the interparticle spacing.

Spatial Statistics of Deep-Water Ambient Noise; Dispersion Relations for Sound Waves and Shear Waves

DTIC Science & Technology

2014-09-30

marine sediments. New focus is on very fine- grained sediments (silt and clay ). OBJECTIVES 1) The scientific objective of the deep-water ambient...density, grain size and overburden pressure. A new focus is on the inter-particle cohesive forces in silts and clays and their role in controlling wave...algebraic expressions. The GS theory is the basis for new research on very fine-grained sediments (silts and clays ), in which inter-granular cohesion is

Influence of PVP in magnetic properties of NiSn nanoparticles prepared by polyol method

NASA Astrophysics Data System (ADS)

Bobadilla, L. F.; García, C.; Delgado, J. J.; Sanz, O.; Romero-Sarria, F.; Centeno, M. A.; Odriozola, J. A.

2012-11-01

The influence of PVP on the magnetic properties of NiSn nanoparticles prepared by polyol method has been studied. NiSn nanoparticles exhibit superparamagnetic behavior although there is a ferromagnetic contribution due to particles agglomerated below the blocking temperature. The particle size is controlled by the addiction of PVP in varying amounts. The addition of PVP also favours the particles isolation, narrow the particle size distribution and decrease the interparticle interaction strength increasing the superparamagnetic contribution.

Pycnonuclear reaction rates for binary ionic mixtures

NASA Technical Reports Server (NTRS)

Ichimaru, S.; Ogata, S.; Van Horn, H. M.

1992-01-01

Through a combination of compositional scaling arguments and examinations of Monte Carlo simulation results for the interparticle separations in binary-ionic mixture (BIM) solids, we have derived parameterized expressions for the BIM pycnonuclear rates as generalizations of those in one-component solids obtained previously by Salpeter and Van Horn and by Ogata et al. We have thereby discovered a catalyzing effect of the heavier elements, which enhances the rates of reactions among the lighter elements when the charge ratio exceeds a critical value of approximately 2.3.

Studying the compactibility of the VT22 high-strength alloy powder obtained by the PREP method

NASA Astrophysics Data System (ADS)

Kryuchkov, D. I.; Berezin, I. M.; Nesterenko, A. V.; Zalazinsky, A. G.; Vichuzhanin, D. I.

2017-12-01

Compression curves are plotted for VT22 high-strength alloy powder under conditions of uniaxial compression at room temperature. The density of the compacted briquette at the loading and unloading stages is determined. It is demonstrated that strong interparticle bonds are formed in the area of the action of shear deformation. The results are supposed to be used to identify the flow model of the material studied and to perform the subsequent numerical modeling of the compaction process.

Dynamical density functional theory analysis of the laning instability in sheared soft matter.

PubMed

Scacchi, A; Archer, A J; Brader, J M

2017-12-01

Using dynamical density functional theory (DDFT) methods we investigate the laning instability of a sheared colloidal suspension. The nonequilibrium ordering at the laning transition is driven by nonaffine particle motion arising from interparticle interactions. Starting from a DDFT which incorporates the nonaffine motion, we perform a linear stability analysis that enables identification of the regions of parameter space where lanes form. We illustrate our general approach by applying it to a simple one-component fluid of soft penetrable particles.

Correlated wave functions for three-particle systems with Coulomb interaction - The muonic helium atom

NASA Technical Reports Server (NTRS)

Huang, K.-N.

1977-01-01

A computational procedure for calculating correlated wave functions is proposed for three-particle systems interacting through Coulomb forces. Calculations are carried out for the muonic helium atom. Variational wave functions which explicitly contain interparticle coordinates are presented for the ground and excited states. General Hylleraas-type trial functions are used as the basis for the correlated wave functions. Excited-state energies of the muonic helium atom computed from 1- and 35-term wave functions are listed for four states.

Nanoparticle-nanoparticle vs. nanoparticle-substrate hot spot contributions to the SERS signal: studying Raman labelled monomers, dimers and trimers.

PubMed

Sergiienko, Sergii; Moor, Kamila; Gudun, Kristina; Yelemessova, Zarina; Bukasov, Rostislav

2017-02-08

We used a combination of Raman microscopy, AFM and TEM to quantify the influence of dimerization on the surface enhanced Raman spectroscopy (SERS) signal for gold and silver nanoparticles (NPs) modified with Raman reporters and situated on gold, silver, and aluminum films and a silicon wafer. The overall increases in the mean SERS enhancement factor (EF) upon dimerization (up by 43% on average) and trimerisation (up by 96% on average) of AuNPs and AgNPs on the studied metal films are within a factor of two, which is moderate when compared to most theoretical models. However, the maximum ratio of EFs for some dimers to the mean EF of monomers can be as high as 5.5 for AgNPs on a gold substrate. In contrast, for dimerization and trimerization of gold and silver NPs on silicon, the mean EF increases by 1-2 orders of magnitude relative to the mean EF of single NPs. Therefore, hot spots in the interparticle gap between gold nanoparticles rather than hot spots between Au nanoparticles and the substrate dominate SERS enhancement for dimers and trimers on a silicon substrate. However, Raman labeled noble metal nanoparticles on plasmonic metal films generate on average SERS enhancement of the same order of magnitude for both types of hot spot zones (e.g. NP/NP and NP/metal film).

Preparation of resveratrol-loaded nanoporous silica materials with different structures

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

Popova, Margarita, E-mail: mpopova@orgchem.bas.bg; Szegedi, Agnes; Mavrodinova, Vesselina

2014-11-15

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated.more » Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol.« less

Novel forms of colloidal self-organization in temporally and spatially varying external fields: from low-density network-forming fluids to spincoated crystals

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).

Thin silica shell coated Ag assembled nanostructures for expanding generality of SERS analytes

PubMed Central

Kang, Yoo-Lee; Lee, Minwoo; Kang, Homan; Kim, Jaehi; Pham, Xuan-Hung; Kim, Tae Han; Hahm, Eunil; Lee, Yoon-Sik; Jeong, Dae Hong

2017-01-01

Surface-enhanced Raman scattering (SERS) provides a unique non-destructive spectroscopic fingerprint for chemical detection. However, intrinsic differences in affinity of analyte molecules to metal surface hinder SERS as a universal quantitative detection tool for various analyte molecules simultaneously. This must be overcome while keeping close proximity of analyte molecules to the metal surface. Moreover, assembled metal nanoparticles (NPs) structures might be beneficial for sensitive and reliable detection of chemicals than single NP structures. For this purpose, here we introduce thin silica-coated and assembled Ag NPs (SiO2@Ag@SiO2 NPs) for simultaneous and quantitative detection of chemicals that have different intrinsic affinities to silver metal. These SiO2@Ag@SiO2 NPs could detect each SERS peak of aniline or 4-aminothiophenol (4-ATP) from the mixture with limits of detection (LOD) of 93 ppm and 54 ppb, respectively. E-field distribution based on interparticle distance was simulated using discrete dipole approximation (DDA) calculation to gain insight into enhanced scattering of these thin silica coated Ag NP assemblies. These NPs were successfully applied to detect aniline in river water and tap water. Results suggest that SiO2@Ag@SiO2 NP-based SERS detection systems can be used as a simple and universal detection tool for environment pollutants and food safety. PMID:28570633

Insights into DNA-mediated interparticle interactions from a coarse-grained model

NASA Astrophysics Data System (ADS)

Ding, Yajun; Mittal, Jeetain

2014-11-01

DNA-functionalized particles have great potential for the design of complex self-assembled materials. The major hurdle in realizing crystal structures from DNA-functionalized particles is expected to be kinetic barriers that trap the system in metastable amorphous states. Therefore, it is vital to explore the molecular details of particle assembly processes in order to understand the underlying mechanisms. Molecular simulations based on coarse-grained models can provide a convenient route to explore these details. Most of the currently available coarse-grained models of DNA-functionalized particles ignore key chemical and structural details of DNA behavior. These models therefore are limited in scope for studying experimental phenomena. In this paper, we present a new coarse-grained model of DNA-functionalized particles which incorporates some of the desired features of DNA behavior. The coarse-grained DNA model used here provides explicit DNA representation (at the nucleotide level) and complementary interactions between Watson-Crick base pairs, which lead to the formation of single-stranded hairpin and double-stranded DNA. Aggregation between multiple complementary strands is also prevented in our model. We study interactions between two DNA-functionalized particles as a function of DNA grafting density, lengths of the hybridizing and non-hybridizing parts of DNA, and temperature. The calculated free energies as a function of pair distance between particles qualitatively resemble experimental measurements of DNA-mediated pair interactions.

Self-assembly of noble metal nanoparticles into sub-100 nm colloidosomes with collective optical and catalytic properties† †Electronic supplementary information (ESI) available: Additional experimental details, TEM images, FTIR spectra, size distributions, FDTD simulations, SERS analysis, electrochemical measurements, extension of the self-assembly approach to other metals and comparison of the FAOR results with those from the literature. See DOI: 10.1039/c7sc01841j

PubMed Central

Zhang, Lei; Fan, Qikui; Sha, Xiao; Zhong, Ping; Zhang, Jie; Yin, Yadong

2017-01-01

Self-assembly at the nanoscale represents a powerful tool for creating materials with new structures and intriguing collective properties. Here, we report a novel strategy to synthesize nanoscale colloidosomes of noble metals by assembling primary metal nanoparticles at the interface of emulsion droplets formed by their capping agent. This strategy produces noble metal colloidosomes of unprecedentedly small sizes (<100 nm) in high yield and uniformity, which is highly desirable for practical applications. In addition, it enables the high tunability of the composition, producing a diversity of monometallic and bimetallic alloy colloidosomes. The colloidosomes exhibit interesting collective properties that are different from those of individual colloidal nanoparticles. Specifically, we demonstrate Au colloidosomes with well-controlled interparticle plasmon coupling and Au–Pd alloy colloidosomes with superior electrocatalytic performance, both thanks to the special structural features that arise from the assembly. We believe this strategy provides a general platform for producing a rich class of miniature colloidosomes that may have fascinating collective properties for a broad range of applications. PMID:29619198

Structure-selective hot-spot Raman enhancement for direct identification and detection of trace penicilloic acid allergen in penicillin.

PubMed

Zhang, Liying; Jin, Yang; Mao, Hui; Zheng, Lei; Zhao, Jiawei; Peng, Yan; Du, Shuhu; Zhang, Zhongping

2014-08-15

Trace penicilloic acid allergen frequently leads to various fatal immune responses to many patients, but it is still a challenge to directly discriminate and detect its residue in penicillin by a chemosensing way. Here, we report that silver-coated gold nanoparticles (Au@Ag NPs) exhibit a structure-selective hot-spot Raman enhancement capability for direct identification and detection of trace penicilloic acid in penicillin. It has been demonstrated that penicilloic acid can very easily link Au@Ag NPs together by its two carboxyl groups, locating itself spontaneously at the interparticle of Au@Ag NPs to form strong Raman hot-spot. At the critical concentration inducing the nanoparticle aggregation, Raman-enhanced effect of penicilloic acid is ~60,000 folds higher than that of penicillin. In particular, the selective Raman enhancement to the two carboxyl groups makes the peak of carboxyl group at C6 of penicilloic acid appear as a new Raman signal due to the opening of β-lactam ring of penicillin. The surface-enhanced Raman scattering (SERS) nanoparticle sensor reaches a sensitive limit lower than the prescribed 1.0‰ penicilloic acid residue in penicillin. The novel strategy to examine allergen is more rapid, convenient and inexpensive than the conventional separation-based assay methods. Copyright © 2014 Elsevier B.V. All rights reserved.

Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte.

PubMed

Kang, Taewook; Oh, Seogil; Kim, Honggon; Yi, Jongheop

2005-06-21

A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH < 2), thus facilitating the approach of hydrolyzed silica sol to the surface of the membrane, poly(sodium 4-styrenesulfonate) (Na+PSS-, denoted as PSS-) was used as an ionic linker. The use of PSS- led to a significant reduction in positive charge on the ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.

Ray-theory approach to electrical-double-layer interactions.

PubMed

Schnitzer, Ory

2015-02-01

A novel approach is presented for analyzing the double-layer interaction force between charged particles in electrolyte solution, in the limit where the Debye length is small compared with both interparticle separation and particle size. The method, developed here for two planar convex particles of otherwise arbitrary geometry, yields a simple asymptotic approximation limited to neither small zeta potentials nor the "close-proximity" assumption underlying Derjaguin's approximation. Starting from the nonlinear Poisson-Boltzmann formulation, boundary-layer solutions describing the thin diffuse-charge layers are asymptotically matched to a WKBJ expansion valid in the bulk, where the potential is exponentially small. The latter expansion describes the bulk potential as superposed contributions conveyed by "rays" emanating normally from the boundary layers. On a special curve generated by the centers of all circles maximally inscribed between the two particles, the bulk stress-associated with the ray contributions interacting nonlinearly-decays exponentially with distance from the center of the smallest of these circles. The force is then obtained by integrating the traction along this curve using Laplace's method. We illustrate the usefulness of our theory by comparing it, alongside Derjaguin's approximation, with numerical simulations in the case of two parallel cylinders at low potentials. By combining our result and Derjaguin's approximation, the interaction force is provided at arbitrary interparticle separations. Our theory can be generalized to arbitrary three-dimensional geometries, nonideal electrolyte models, and other physical scenarios where exponentially decaying fields give rise to forces.

Dark-dark-soliton dynamics in two density-coupled Bose-Einstein condensates

NASA Astrophysics Data System (ADS)

Morera, I.; Mateo, A. Muñoz; Polls, A.; Juliá-Díaz, B.

2018-04-01

We study the one-dimensional dynamics of dark-dark solitons in the miscible regime of two density-coupled Bose-Einstein condensates having repulsive interparticle interactions within each condensate (g >0 ). By using an adiabatic perturbation theory in the parameter g12/g , we show that, contrary to the case of two solitons in scalar condensates, the interactions between solitons are attractive when the interparticle interactions between condensates are repulsive g12>0 . As a result, the relative motion of dark solitons with equal chemical potential μ is well approximated by harmonic oscillations of angular frequency wr=(μ /ℏ ) √{(8 /15 ) g12/g } . We also show that, in finite systems, the resonance of this anomalous excitation mode with the spin-density mode of lowest energy gives rise to alternating dynamical instability and stability fringes as a function of the perturbative parameter. In the presence of harmonic trapping (with angular frequency Ω ) the solitons are driven by the superposition of two harmonic motions at a frequency given by w2=(Ω/√{2 }) 2+wr2 . When g12<0 , these two oscillators compete to give rise to an overall effective potential that can be either single well or double well through a pitchfork bifurcation. All our theoretical results are compared with numerical solutions of the Gross-Pitaevskii equation for the dynamics and the Bogoliubov equations for the linear stability. A good agreement is found between them.

Investigating Compaction by Intergranular Pressure Solution Using the Discrete Element Method

NASA Astrophysics Data System (ADS)

van den Ende, M. P. A.; Marketos, G.; Niemeijer, A. R.; Spiers, C. J.

2018-01-01

Intergranular pressure solution creep is an important deformation mechanism in the Earth's crust. The phenomenon has been frequently studied and several analytical models have been proposed that describe its constitutive behavior. These models require assumptions regarding the geometry of the aggregate and the grain size distribution in order to solve for the contact stresses and often neglect shear tractions. Furthermore, analytical models tend to overestimate experimental compaction rates at low porosities, an observation for which the underlying mechanisms remain to be elucidated. Here we present a conceptually simple, 3-D discrete element method (DEM) approach for simulating intergranular pressure solution creep that explicitly models individual grains, relaxing many of the assumptions that are required by analytical models. The DEM model is validated against experiments by direct comparison of macroscopic sample compaction rates. Furthermore, the sensitivity of the overall DEM compaction rate to the grain size and applied stress is tested. The effects of the interparticle friction and of a distributed grain size on macroscopic strain rates are subsequently investigated. Overall, we find that the DEM model is capable of reproducing realistic compaction behavior, and that the strain rates produced by the model are in good agreement with uniaxial compaction experiments. Characteristic features, such as the dependence of the strain rate on grain size and applied stress, as predicted by analytical models, are also observed in the simulations. DEM results show that interparticle friction and a distributed grain size affect the compaction rates by less than half an order of magnitude.

Shape effects on time-scale divergence at athermal jamming transition of frictionless non-spherical particles

NASA Astrophysics Data System (ADS)

Yuan, Ye; Jin, Weiwei; Liu, Lufeng; Li, Shuixiang

2017-10-01

The critical behaviors of a granular system at the jamming transition have been extensively studied from both mechanical and thermodynamic perspectives. In this work, we numerically investigate the jamming behaviors of a variety of frictionless non-spherical particles, including spherocylinder, ellipsoid, spherotetrahedron and spherocube. In particular, for a given particle shape, a series of random configurations at different fixed densities are generated and relaxed to minimize interparticle overlaps using the relaxation algorithm. We find that as the jamming point (i.e., point J) is approached, the number of iteration steps (defined as the "time-scale" for our systems) required to completely relax the interparticle overlaps exhibits a clear power-law divergence. The dependence of the detailed mathematical form of the power-law divergence on particle shapes is systematically investigated and elucidated, which suggests that the shape effects can be generally categorized as elongation and roundness. Importantly, we show the jamming transition density can be accurately determined from the analysis of time-scale divergence for different non-spherical shapes, and the obtained values agree very well with corresponding ones reported in literature. Moreover, we study the plastic behaviors of over-jammed packings of different particles under a compression-expansion procedure and find that the jamming of ellipsoid is much more robust than other non-spherical particles. This work offers an alternative approximate procedure besides conventional packing algorithms for studying athermal jamming transition in granular system of frictionless non-spherical particles.

State-of-the-art Nanofabrication in Catalysis.

PubMed

Karim, Waiz; Tschupp, Simon A; Herranz, Juan; Schmidt, Thomas J; Ekinci, Yasin; van Bokhovenac, Jeroen A

2017-04-26

We present recent developments in top-down nanofabrication that have found application in catalysis research. To unravel the complexity of catalytic systems, the design and use of models with control of size, morphology, shape and inter-particle distances is a necessity. The study of well-defined and ordered nanoparticles on a support contributes to the understanding of complex phenomena that govern reactions in heterogeneous and electro-catalysis. We review the strengths and limitations of different nanolithography methods such as electron beam lithography (EBL), photolithography, extreme ultraviolet (EUV) lithography and colloidal lithography for the creation of such highly tunable catalytic model systems and their applications in catalysis. Innovative strategies have enabled particle sizes reaching dimensions below 10 nm. It is now possible to create pairs of particles with distance controlled with an extremely high precision in the order of one nanometer. We discuss our approach to study these model systems at the single-particle level using X-ray absorption spectroscopy and show new ways to fabricate arrays of single nanoparticles or nanoparticles in pairs over a large area using EBL and EUV-achromatic Talbot lithography. These advancements have provided new insights into the active sites in metal catalysts and enhanced the understanding of the role of inter-particle interactions and catalyst supports, such as in the phenomenon of hydrogen spillover. We present a perspective on future directions for employing top-down nanofabrication in heterogeneous and electrocatalysis. The rapid development in nanofabrication and characterization methods will continue to have an impact on understanding of complex catalytic processes.

Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry

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

Durham, Jessica L.; Huang, Jianping; Zhang, Bingjie

In this paper, silver hollandite (Ag 1.4Mn 8O 16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag 1.4Mn 8O 16 and L-Ag 1.4Mn 8O 16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag 1.4Mn 8O 16 nanorods compared to L-Ag 1.4Mn 8O 16 which facilitates more intimate connection of themore » S-Ag 1.4Mn 8O 16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag 1.4Mn 8O 16 delivered a capacity 15X higher than L-Ag 1.4Mn 8O 16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag 1.4Mn 8O 16 and formation of Ag 0 on insertion of 3.8 Li + intercalation. However, the samples of L-Ag 1.4Mn 8O 16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. Finally, the findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the α-MnO 2 type structure.« less

Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry

DOE PAGES

Durham, Jessica L.; Huang, Jianping; Zhang, Bingjie; ...

2017-12-16

In this paper, silver hollandite (Ag 1.4Mn 8O 16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag 1.4Mn 8O 16 and L-Ag 1.4Mn 8O 16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag 1.4Mn 8O 16 nanorods compared to L-Ag 1.4Mn 8O 16 which facilitates more intimate connection of themore » S-Ag 1.4Mn 8O 16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag 1.4Mn 8O 16 delivered a capacity 15X higher than L-Ag 1.4Mn 8O 16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag 1.4Mn 8O 16 and formation of Ag 0 on insertion of 3.8 Li + intercalation. However, the samples of L-Ag 1.4Mn 8O 16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. Finally, the findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the α-MnO 2 type structure.« less

Theranostic self-assembly structure of gold nanoparticles for NIR photothermal therapy and X-Ray computed tomography imaging.

PubMed

Deng, Heng; Zhong, Yanqi; Du, Meihong; Liu, Qinjun; Fan, Zhanming; Dai, Fengying; Zhang, Xin

2014-01-01

The controllable self-assembly of amphiphilic mixed polymers grafted gold nanoparitcles (AuNPs) leads to strong interparticle plasmonic coupling, which can be tuned to the near-infrared (NIR) region for enhanced photothermal therapy (PTT). In this study, an improved thiolation method was adopted for ATRP and ROP polymer to obtain amphiphilic brushes of PMEO2MA-SH and PCL-SH. By anchoring PCL-SH and PMEO2MA-SH onto the 14 nm AuNPs, a smart hybrid building block for self-assembly was obtained. Increasing the PCL/PMEO2MA chain ratio from 0.8:1, 2:1 and 3:1 to 7:1, the structure of gold assemblies (GAs) was observed to transfer from vesicle to large compound micelle (LCM). Contributed to the special dense packed structure of gold nanoparticles in LCM, the absorption spectrometry of gold nanoparticles drastically red-shifted from 520 nm to 830 nm, which endowed the GAs remarkable NIR photothermal conversion ability. In addition, gold has high X-ray absorption coefficient which qualifies gold nanomaterial a potential CT contrast agent Herein, we obtain a novel gold assembly structure which can be utilized as potential photothermal therapeutic and CT contrast agents. In vitro and In vivo studies testified the excellent treatment efficacy of optimum GAs as a PTT and CT contrast agent. In vitro degradation test, MTT assay and histology study indicated that GAs was a safe, low toxic reagent with good biodegradability. Therefore, the optimum GAs with strong NIR absorption and high X-ray absorption coefficient could be used as a theranostic agent and the formation of novel gold large compound micelle might offers a new theory foundation for engineering design and synthesis of polymer grafted AuNPs for biomedical applications.

Hyaluronic acid based hydrogel system for soft tissue regeneration and drug delivery

NASA Astrophysics Data System (ADS)

Jha, Amit Kumar

We have developed hyaluronic acid (HA)-based, biomimetic hydrogel matrices that are hierarchically structured, mechanically robust and biologically active. Specifically, HA-based hydrogel particles (HGPs) with controlled sizes, defined porosity, and improved stability were synthesized using different inverse emulsion systems and crosslinking chemistries. The resultant particles either contained residual functional groups or were rendered reactive by subsequent chemical modifications. HA-based doubly crosslinked networks (DXNs) were synthesized via covalent crosslinking of HA HGPs with soluble HA macromers carrying mutually reactive functional groups. These hybrid matrices are hierarchical in nature, consisting of densely crosslinked HGPs integrated in a loosely connected secondary matrix. Their mechanical properties and degradation kinetics can be readily tuned by varying the particle size, functional group density, intra- and interparticle crosslinking. To improve the biological functions of HA HGPs, perlecan domain I (PlnDI), a basement membrane proteoglycan that has strong affinity for various heparin binding growth factors (HBGFs), was successfully conjugated to the particles through the core protein via a flexible poly(ethylene glycol) (PEG) linker. The immobilized PlnDI maintains its ability to bind bone morphogenetic proteins (BMP-2) and modulates its in vitro release. A similar, sustained release of BMP-2 was achieved by encapsulating BMP-2-loaded HGPs within a photocrosslinked HA matrix. When encapsulated in HA DXNs, primary bovine chondrocytes were able to maintain their phenotype, proliferate readily and produce abundant glycosaminoglycan. Finally, cell-adhesive HA DXNs were fabricated by encapsulating gelatin-decorated HA HGPs in a secondary HA matrix. Human MSCs were shown to adhere to the composite matrix through the focal adhesion sites clustered on particle surface. The cell-adhesive composite matrices supported hMSC proliferation and migration into the gels. Human MSCs were undifferentiated during the early time points of culture, however differentiated into osteoblast phenotype after 28 days of culture. In summary, the HA-based hydrogel matrices are hierarchically structured, mechanically robust and enzymatically stable, capable of mediating cellular functions through the spatial and temporal presentation of defined biological cues. These hydrogel systems are promising candidates for soft tissue regeneration.

Simulations of curved assemblies in soft matter and biological systems

NASA Astrophysics Data System (ADS)

Qiao, Cong

Viruses are small infectious agents that replicate only inside living cells of other organisms. In the viral life cycle, the self-assembly of the outer protein shell (capsid) is an essential step. We study this process in the hope of shedding light on development of antiviral drugs, gene therapy and other virus-related technologies that can benefit the humankind. More fundamentally, learning about the process of viral capsid assembly can elucidate the assembly mechanisms of a wide range of complex structures. In this work, we use molecular dynamics simulations and coarse-grained computational models to study viral capsid assembly in several situations where geometric constraints play a role in dictating assembly outcomes. We first focus on icosahedral viruses with single-stranded RNA genomes, in which case the capsid usually assembles around the genomic RNA. It is consistently observed in experiments that such viral particles are ''overcharged'', meaning the net negative charge on the viral genome is greater than the net positive charge on the viral capsid. We computationally investigate the mechanisms that lead to ``overcharging'', and more broadly, how the encapsidated genome length is influenced by the capsid. We perform both dynamical simulations of the assembly process and equilibrium calculations to determine the optimal genome length (meaning that which maximizes the assembly yield and/or minimizes the free energy of the assembled virus). We find that the optimal genome length is determined by the interplay between capsid size, net capsid charge, distribution of capsid charge and nucleic acid structures. Our simulations demonstrate that overcharging results from a combination of electrostatic screening and the geometric constraints associated with encapsulating a nucleic acid inside of a spherical virus. We then study the assembly of the immature HIV. In contrast to icosahedral viruses, the immature HIV forms an asymmetric particle, consisting of continuous regularly packed regions with local hexagonal order and vacancies. A similar lattice structure has been observed in experiments in which mutually attractive colloidal particles pack on the surface of a spherical droplet (G. Meng, J. Paulose, D. R. Nelson, and V. N. Manoharan, ''Elastic instability of a crystal growing on a curved surface'', Science 343, 634-637 (2014).), suggesting that the two systems experience a similar form of geometric frustration. We therefore study the adsorption and packing of spherical particles on a spherical template, as a function of the strength and range of interparticle attractions, as well as the radius of the spherical template. We observe that the adsorbed particles form two different classes of packing arrangements, one with icosahedrally ordered topological defects, and the other with highly disordered defects and vacancies. The latter regime is consistent with experiments on colloidal packing on spherical droplets and the immature HIV lattice. Our results suggest that the transition between these regimes is controlled by the range of the interparticle attractions. In the last chapter, we study a model for the assembly and budding of a capsid on a membrane, such as occurs during the exit of the immature HIV virus from a cell. We use a coarse-grained subunit model to represent the capsid proteins, and a fluid membrane model to represent the cell membrane. We find that the size and structure of the assembled capsid depends sensitively on the timescale of budding.

Transport regimes spanning magnetization-coupling phase space

NASA Astrophysics Data System (ADS)

Baalrud, Scott D.; Daligault, Jérôme

2017-10-01

The manner in which transport properties vary over the entire parameter-space of coupling and magnetization strength is explored. Four regimes are identified based on the relative size of the gyroradius compared to other fundamental length scales: the collision mean free path, Debye length, distance of closest approach, and interparticle spacing. Molecular dynamics simulations of self-diffusion and temperature anisotropy relaxation spanning the parameter space are found to agree well with the predicted boundaries. Comparison with existing theories reveals regimes where they succeed, where they fail, and where no theory has yet been developed.

Fast Characterization of Magnetic Impurities in Single-Wall Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Chen, Feng; Xue, Y. Y.; Hadijiev, Viktor G.; Chu, C. W.; Nikolaev, Pasha; Arepalli, Sivaram

2003-01-01

We have demonstrated that the magnetic susceptibility measurement is a non-destructive, fast and accurate method to determine the residual metal catalysts in a few microgram single-wall carbon nanotube (SWCNT) sample. We have studied magnetic impurities in raw and purified SWCNT by magnetic susceptibility measurements, transmission electron microscopy, and thermogravimetry. The data suggest that the saturation magnetic moment and the effective field, which is caused by the interparticle interactions, decreases and increases respectively with the decrease of the particle size. Methods are suggested to overcome the uncertainty associated.

Equilibrium Phase Behavior of a Continuous-Space Microphase Former.

PubMed

Zhuang, Yuan; Zhang, Kai; Charbonneau, Patrick

2016-03-04

Periodic microphases universally emerge in systems for which short-range interparticle attraction is frustrated by long-range repulsion. The morphological richness of these phases makes them desirable material targets, but our relatively coarse understanding of even simple models hinders controlling their assembly. We report here the solution of the equilibrium phase behavior of a microscopic microphase former through specialized Monte Carlo simulations. The results for cluster crystal, cylindrical, double gyroid, and lamellar ordering qualitatively agree with a Landau-type free energy description and reveal the nontrivial interplay between cluster, gel, and microphase formation.

Polyelectrolyte properties of single stranded DNA measured using SAXS and single molecule FRET: beyond the wormlike chain model

PubMed Central

Meisburger, Steve P.; Sutton, Julie L.; Chen, Huimin; Pabit, Suzette A.; Kirmizialtin, Serdal; Elber, Ron; Pollack, Lois

2013-01-01

Nucleic acids are highly charged polyelectrolytes that interact strongly with salt ions. Rigid, base-paired regions are successfully described with worm like chain models, but non base-paired single stranded regions have fundamentally different polymer properties because of their greater flexibility. Recently, attention has turned to single stranded nucleic acids due to the growing recognition of their biological importance, as well as the availability of sophisticated experimental techniques sensitive to the conformation of individual molecules. We investigate polyelectrolyte properties of poly(dT), an important and widely studied model system for flexible single stranded nucleic acids, in physiologically important mixed mono- and di-valent salt. We report measurements of the form factor and interparticle interactions using SAXS, end to end distances using smFRET, and number of excess ions using ASAXS. We present a coarse-grained model that accounts for flexibility, excluded volume, and electrostatic interactions in these systems. Predictions of the model are validated against experiment. We also discuss the state of all-atom, explicit solvent Molecular Dynamics simulations of poly(dT), the next step in understanding the complexities of ion interactions with these highly charged and flexible polymers. PMID:23606337

Transport Regimes Spanning Magnetization-Coupling Phase Space

NASA Astrophysics Data System (ADS)

Baalrud, Scott D.; Tiwari, Sanat; Daligault, Jerome

2017-10-01

The manner in which transport properties vary over the entire parameter-space of coupling and magnetization strength is explored. Four regimes are identified based on the relative size of the gyroradius compared to other fundamental length scales: the collision mean free path, Debye length, distance of closest approach and interparticle spacing. Molecular dynamics simulations of self-diffusion and temperature anisotropy relaxation spanning the parameter space are found to agree well with the predicted boundaries. Comparison with existing theories reveals regimes where they succeed, where they fail, and where no theory has yet been developed. The results suggest that magnetic fields may be used to assist ultracold neutral plasma experiments to reach regimes of stronger electron coupling by reducing heating of electrons in the direction perpendicular to the magnetic field.. By constraining electron motion along the direction of the magnetic field, the overall electron temperature is reduced nearly by a factor of three. A large temperature anisotropy develops as a result, which can be maintained for a long time in the regime of high electron magnetization. Work supported by LDRD project 20150520ER at LANL, AFOSR FA9550-16-1-0221 and US DOE Award DE-SC00161.

Dispersion of Rod-like Particles of Nafion in Salt-Free Water/1-Propanol and Water/Ethanol Solutions.

PubMed

Yamaguchi, Makoto; Matsunaga, Takuro; Amemiya, Kazuki; Ohira, Akihiro; Hasegawa, Naoki; Shinohara, Kazuhiko; Ando, Masaki; Yoshida, Toshihiko

2014-12-26

The dispersion of perfluorinated sulfonic acid ionomers in catalyst inks is an important factor controlling the performance of catalyst layers in membrane electrode assemblies of proton exchange membrane fuel cells (PEMFCs). The effect of water/alcohol composition on the dispersion of H-Nafion in water/1-propanol and water/ethanol solutions was studied by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and (19)F nuclear magnetic resonance ((19)F NMR) spectroscopy. Hydrodynamic radii calculated from DLS decay profiles and the radii and interparticle distance of rod-like particles derived from SAXS profiles showed almost the same dependence on alcohol concentration. 1-Propanol was more effective than ethanol to induce changes in the characteristic lengths of the rod-like particles. The motional narrowing in the (19)F NMR spectra by addition of 1-propanol indicates selective solvation of the rod-like particles. We suppose this might have decreased their radii and induced their elongation, which eventually led to extension of the ordered regions as observed in the hydrodynamic radii. Our study helps to clarify the dispersion of Nafion in aqueous alcohol solutions, which has implications for the performance of PEMFCs.

Plasmonic Heterodimers with Binding Site-Dependent Hot Spot for Surface-Enhanced Raman Scattering.

PubMed

Tian, Yuanyuan; Shuai, Zhenhua; Shen, Jingjing; Zhang, Lei; Chen, Shufen; Song, Chunyuan; Zhao, Baomin; Fan, Quli; Wang, Lianhui

2018-06-01

A novel plasmonic heterodimer nanostructure with a controllable self-assembled hot spot is fabricated by the conjugation of individual Au@Ag core-shell nanocubes (Au@Ag NCs) and varisized gold nanospheres (GNSs) via the biotin-streptavidin interaction from the ensemble to the single-assembly level. Due to their featured configurations, three types of heterogeneous nanostructures referred to as Vertice, Vicinity, and Middle are proposed and a single hot spot forms between the nanocube and nanosphere, which exhibits distinct diversity in surface plasmon resonance effect. Herein, the calculated surface-enhanced Raman scattering enhancement factors of the three types of heterodimers show a narrow distribution and can be tuned in orders of magnitude by controlling the size of GNSs onto individual Au@Ag NCs. Particularly, the Vertice heterodimer with unique configuration can provide extraordinary enhancement of the electric field for the single hot spot region due to the collaborative interaction of lightning rod effect and interparticle plasmon coupling effect. This established relationship between the architecture and the corresponding optical properties of the heterodimers provides the basis for creating controllable platforms which can be exploited in the applications of plasmonic devices, electronics, and biodetection. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot-Volumes as Uniform and Reproducible SERS-Detection Enhancers in Weakly-Coupled Metallic Nanohelices

NASA Astrophysics Data System (ADS)

Caridad, José M.; Winters, Sinéad; McCloskey, David; Duesberg, Georg S.; Donegan, John F.; Krstić, Vojislav

2017-03-01

Reproducible and enhanced optical detection of molecules in low concentrations demands simultaneously intense and homogeneous electric fields acting as robust signal amplifiers. To generate such sophisticated optical near-fields, different plasmonic nanostructures were investigated in recent years. These, however, exhibit either high enhancement factor (EF) or spatial homogeneity but not both. Small interparticle gaps or sharp nanostructures show enormous EFs but no near-field homogeneity. Meanwhile, approaches using rounded and separated monomers create uniform near-fields with moderate EFs. Here, guided by numerical simulations, we show how arrays of weakly-coupled Ag nanohelices achieve both homogeneous and strong near-field enhancements, reaching even the limit forreproducible detection of individual molecules. The unique near-field distribution of a single nanohelix consists of broad hot-spots, merging with those from neighbouring nanohelices in specific array configurations and generating a wide and uniform detection zone (“hot-volume”). We experimentally assessed these nanostructures via surface-enhanced Raman spectroscopy, obtaining a corresponding EF of ~107 and a relative standard deviation <10%. These values demonstrate arrays of nanohelices as state-of-the-art substrates for reproducible optical detection as well as compelling nanostructures for related fields such as near-field imaging.

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

PubMed

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

2017-01-25

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

Highly stable CuO incorporated TiO(2) catalyst for photo-catalytic hydrogen production from H(2)O.

PubMed

Bandara, J; Udawatta, C P K; Rajapakse, C S K

2005-11-01

A CuO incorporated TiO(2) catalyst was found to be an active photo-catalyst for the reduction of H(2)O under sacrificial conditions. The catalytic activity originates from the photogeneration of excited electrons in the conduction bands of both TiO(2) and CuO resulting in a build-up of excess electrons in the conduction band of CuO. Consequently, the accumulation of excess electrons in CuO causes a negative shift in the Fermi level of CuO. The efficient inter-particle charge transfer leads to a higher catalytic activity and the formation of highly reduced states of TiO(2)/CuO, which are stable even under oxygen saturated condition. Negative shift in the Fermi level of CuO of the catalyst TiO(2)/CuO gains the required over-voltage necessary for efficient water reduction reaction. The function of CuO is to help the charge separation and to act as a water reduction site. The amount of CuO and crystalline structure were found to be crucial for the catalytic activity and the optimum CuO loading was ca. approximately 5-10%(w/w).

Erasing no-man’s land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles

NASA Astrophysics Data System (ADS)

Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

2014-09-01

One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point located in the `no-man’s land’. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, as spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon, carbon and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

Gravitational collapse of colloidal gels: Origins of the tipping point

NASA Astrophysics Data System (ADS)

Padmanabhan, Poornima; Zia, Roseanna

2016-11-01

Reversible colloidal gels are soft viscoelastic solids in which durable but reversible bonds permit on-demand transition from solidlike to liquidlike behavior; these O(kT) bonds also lead to ongoing coarsening and age stiffening, making their rheology inherently time dependent. To wit, such gels may remain stable for an extended time, but then suddenly collapse, sedimenting to the bottom of the container (or creaming to the top) and eliminating any intended functionality of the material. Although this phenomenon has been studied extensively in the experimental literature, the microscopic mechanism underlying the collapse is not well understood. Effects of gel age, interparticle attraction strength, and wall effects all have been shown to affect collapse behavior, but the microstructural transformations underlying the 'tipping point' remain murky. To study this behavior, we conduct large-scale dynamic simulation to model the structural and rheological evolution of colloidal gels subjected to various gravitational stresses, examining the detailed micromechanics in three temporal regimes: slow sedimentation prior to collapse; the tipping point leading to the onset of rapid collapse; and the subsequent compaction of the material as it approaches its final bed height. Acknowledgment for funding and support from the Office of Naval Research; the National Science Foundation; and NSF XSEDE.

Parametric instabilities in resonantly-driven Bose–Einstein condensates

NASA Astrophysics Data System (ADS)

Lellouch, S.; Goldman, N.

2018-04-01

Shaking optical lattices in a resonant manner offers an efficient and versatile method to devise artificial gauge fields and topological band structures for ultracold atomic gases. This was recently demonstrated through the experimental realization of the Harper–Hofstadter model, which combined optical superlattices and resonant time-modulations. Adding inter-particle interactions to these engineered band systems is expected to lead to strongly-correlated states with topological features, such as fractional Chern insulators. However, the interplay between interactions and external time-periodic drives typically triggers violent instabilities and uncontrollable heating, hence potentially ruling out the possibility of accessing such intriguing states of matter in experiments. In this work, we study the early-stage parametric instabilities that occur in systems of resonantly-driven Bose–Einstein condensates in optical lattices. We apply and extend an approach based on Bogoliubov theory (Lellouch et al 2017 Phys. Rev. X 7 021015) to a variety of resonantly-driven band models, from a simple shaken Wannier–Stark ladder to the more intriguing driven-induced Harper–Hofstadter model. In particular, we provide ab initio numerical and analytical predictions for the stability properties of these topical models. This work sheds light on general features that could guide current experiments to stable regimes of operation.

Yielding in a strongly aggregated colloidal gel: 2D simulations and theory

NASA Astrophysics Data System (ADS)

Roy, Saikat; Tirumkudulu, Mahesh

2015-11-01

We investigated the micro-structural details and the mechanical response under uniaxial compression of the strongly aggregating gel starting from low to high packing fraction.The numerical simulations account for short-range inter-particle attractions, normal and tangential deformation at particle contacts,sliding and rolling friction, and preparation history. It is observed that in the absence of rolling resistance(RR),the average coordination number varies only slightly with compaction whereas it is significant in the presence of RR. The particle contact distribution is isotropic throughout the consolidation process. In both cases, the yield strain is constant with the volume fraction. The modulus values are very similar at different attraction, and with and without RR implying that the elastic modulus does not scale with attraction.The modulus was found to be a weak function of the preparation history. The increase in yield stress with volume fraction is a consequence of the increased elastic modulus of the network. However, the yield stress scales similarly both with and without RR. The power law exponent of 5.4 is in good agreement with previous simulation results. A micromechanical theory is also proposed to describe the stress versus strain relation for the gelled network.

Size and Structure of Clusters Formed by Shear Induced Coagulation: Modeling by Discrete Element Method.

PubMed

Kroupa, Martin; Vonka, Michal; Soos, Miroslav; Kosek, Juraj

2015-07-21

The coagulation process has a dramatic impact on the properties of dispersions of colloidal particles including the change of optical, rheological, as well as texture properties. We model the behavior of a colloidal dispersion with moderate particle volume fraction, that is, 5 wt %, subjected to high shear rates employing the time-dependent Discrete Element Method (DEM) in three spatial dimensions. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to model noncontact interparticle interactions, while contact mechanics was described by the Johnson-Kendall-Roberts (JKR) theory of adhesion. The obtained results demonstrate that the steady-state size of the produced clusters is a strong function of the applied shear rate, primary particle size, and the surface energy of the particles. Furthermore, it was found that the cluster size is determined by the maximum adhesion force between the primary particles and not the adhesion energy. This observation is in agreement with several simulation studies and is valid for the case when the particle-particle contact is elastic and no plastic deformation occurs. These results are of major importance, especially for the emulsion polymerization process, during which the fouling of reactors and piping causes significant financial losses.

Self-assembling Gold Nanoparticle Monolayers in a Three-phase System - Overcoming Ligand Size Limitations

NASA Astrophysics Data System (ADS)

Yang, Guang; Nanda, Jagjit; Wang, Boya; Chen, Gang; Hallinan, Daniel T., Jr.

An effective self-assembly technique was developed to prepare centimeter-scale monolayer gold nanoparticle (Au NP) films of long-range order with hydrophobic ligands. Aqueous Au NPs were entrapped in the organic/aqueous interface where the Au NP surface was in situ modified with different types of amine ligands, including amine-terminated polystyrene. The Au NPs then spontaneously relocated to the air/water interface to form an NP monolayer. The spontaneous formation of an Au NP film at the organic/water interface was due to the minimization of the system Helmholtz free energy. Self-assembled Au NP films has a hexagonal close packed structure. The interparticle spacing was dictated by the amine ligand length. Thus-assembled Au NP monolayers exhibit tunable surface plasma resonance and excellent spacial homogeneity of surface-enhanced Raman-scattering. The ``air/water/oil'' self-assembly method developed in this study not only benefits the fundamental understanding of NP ligand conformations, but is also promising to scale up the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. This study was financially supported by start-up funding supplied by the Florida State University and the FAMU-FSU College of Engineering.

A hydrodynamic mechanism for spontaneous formation of ordered drop arrays in confined shear flow

NASA Astrophysics Data System (ADS)

Singha, Sagnik; Zurita-Gotor, Mauricio; Loewenberg, Michael; Migler, Kalman; Blawzdziewicz, Jerzy

2017-11-01

It has been experimentally demonstrated that a drop monolayer driven by a confined shear flow in a Couette device can spontaneously arrange into a flow-oriented parallel chain microstructure. However, the hydrodynamic mechanism of this puzzling self-assembly phenomenon has so far eluded explanation. In a recent publication we suggested that the observed spontaneous drop ordering may arise from hydrodynamic interparticle interactions via a far-field quadrupolar Hele-Shaw flow associated with drop deformation. To verify this conjecture we have developed a simple numerical-simulation model that includes the far-field Hele-Shaw flow quadrupoles and a near-field short-range repulsion. Our simulations show that an initially disordered particle configuration self-organizes into a system of particle chains, similar to the experimentally observed drop-chain structures. The initial stage of chain formation is fast; subsequently, microstructural defects in a partially ordered system are removed by slow annealing, leading to an array of equally spaced parallel chains with a small number of defects. The microstructure evolution is analyzed using angular and spatial order parameters and correlation functions. Supported by NSF Grants No. CBET 1603627 and CBET 1603806.

Shell Thickness Dependence of Interparticle Energy Transfer in Core-Shell ZnSe/ZnSe Quantum Dots Doping with Europium

NASA Astrophysics Data System (ADS)

Liu, Ni; Li, Shuxin; Wang, Caifeng; Li, Jie

2018-04-01

Low-toxic core-shell ZnSe:Eu/ZnS quantum dots (QDs) were prepared through two steps in water solution: nucleation doping and epitaxial shell grown. The structural and morphological characteristics of ZnSe/ZnS:Eu QDs with different shell thickness were explored by transmission electron microscopy (TEM) and X-ray diffraction (XRD) results. The characteristic photoluminescence (PL) intensity of Eu ions was enhanced whereas that of band-edge luminescence and defect-related luminescence of ZnSe QDs was decreased with increasing shell thickness. The transformation of PL intensity revealed an efficient energy transfer process between ZnSe and Eu. The PL intensity ratio of Eu ions ( I 613) to ZnSe QDs ( I B ) under different shell thickness was systemically analyzed by PL spectra and time-resolved PL spectra. The obtained results were in agreement with the theory analysis results by the kinetic theory of energy transfer, revealing that energy was transmitted in the form of dipole-electric dipole interaction. This particular method of adjusting luminous via changing the shell thickness can provide valuable insights towards the fundamental understanding and application of QDs in the field of optoelectronics.

Effect of radiation-induced amorphization on smectite dissolution.

PubMed

Fourdrin, C; Allard, T; Monnet, I; Menguy, N; Benedetti, M; Calas, G

2010-04-01

Effects of radiation-induced amorphization of smectite were investigated using artificial irradiation. Beams of 925 MeV Xenon ions with radiation dose reaching 73 MGy were used to simulate the effects generated by alpha recoil nuclei or fission products in the context of high level nuclear waste repository. Amorphization was controlled by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. An important coalescence of the smectite sheets was observed which lead to a loss of interparticle porosity. The amorphization is revealed by a loss of long-range structure and accompanied by dehydroxylation. The dissolution rate far-from-equilibrium shows that the amount of silica in solution is two times larger in the amorphous sample than in the reference clay, a value which may be enhanced by orders of magnitude when considering the relative surface area of the samples. Irradiation-induced amorphization thus facilitates dissolution of the clay-derived material. This has to be taken into account for the safety assessment of high level nuclear waste repository, particularly in a scenario of leakage of the waste package which would deliver alpha emitters able to amorphize smectite after a limited period of time.

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

NASA Astrophysics Data System (ADS)

Zheng, Yuebing

2017-02-01

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

Quantum hydrodynamics: capturing a reactive scattering resonance.

PubMed

Derrickson, Sean W; Bittner, Eric R; Kendrick, Brian K

2005-08-01

The hydrodynamic equations of motion associated with the de Broglie-Bohm formulation of quantum mechanics are solved using a meshless method based upon a moving least-squares approach. An arbitrary Lagrangian-Eulerian frame of reference and a regridding algorithm which adds and deletes computational points are used to maintain a uniform and nearly constant interparticle spacing. The methodology also uses averaged fields to maintain unitary time evolution. The numerical instabilities associated with the formation of nodes in the reflected portion of the wave packet are avoided by adding artificial viscosity to the equations of motion. A new and more robust artificial viscosity algorithm is presented which gives accurate scattering results and is capable of capturing quantum resonances. The methodology is applied to a one-dimensional model chemical reaction that is known to exhibit a quantum resonance. The correlation function approach is used to compute the reactive scattering matrix, reaction probability, and time delay as a function of energy. Excellent agreement is obtained between the scattering results based upon the quantum hydrodynamic approach and those based upon standard quantum mechanics. This is the first clear demonstration of the ability of moving grid approaches to accurately and robustly reproduce resonance structures in a scattering system.

Enhanced Luminescent Stability through Particle Interactions in Silicon Nanocrystal Aggregates

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

Miller, Joseph B.; Dandu, Naveen; Velizhanin, Kirill A.

2015-10-27

Close-packed assemblies of ligand-passivated colloidal nanocrystals can exhibit enhanced photoluminescent stability, but the origin of this effect is unclear. Here, we use experiment, simulation, and ab initio computation to examine the influence of interparticle interactions on the photoluminescent stability of silicon nanocrystal aggregates. The time-dependent photoluminescence emitted by structures ranging in size from a single quantum dot to agglomerates of more than a thousand is compared with Monte Carlo simulations of noninteracting ensembles using measured single-particle blinking data as input. In contrast to the behavior typically exhibited by the metal chalcogenides, the measured photoluminescent stability shows an enhancement with respectmore » to the noninteracting scenario with increasing aggregate size. We model this behavior using time-dependent density functional theory calculations of energy transfer between neighboring nanocrystals as a function of nanocrystal size, separation, and the presence of charge and/or surface-passivation defects. Our results suggest that rapid exciton transfer from “bright” nanocrystals to surface trap states in nearest-neighbors can efficiently fill such traps and enhance the stability of emission by promoting the radiative recombination of slowly diffusing excited electrons.« less

Influence of particle arrangement on the permittivity of an elastomeric composite

NASA Astrophysics Data System (ADS)

Tsai, Peiying J.; Nayak, Suchitra; Ghosh, Suvojit; Puri, Ishwar K.

2017-01-01

Elastomers are used as dielectric layers contained between the parallel conductive plates of capacitors. The introduction of filler particles into an elastomer changes its permittivity ɛ. When particle organization in a composite is intentionally varied, this alters its capacitance. Using numerical simulations, we examine how conductive particle chains introduced into polydimethylsiloxane (PDMS) alter ɛ. The effects of filler volume fraction ψ, interparticle d and interchain spacing a, zigzag angle θ between adjacent particles and overall chain orientation, particle size r, and clearance h between particles and the conductive plates are characterized. When filler particles are organized into chainlike structures rather than being just randomly distributed in the elastomer matrix, ɛ increases by as much as 85%. When particles are organized into chainlike forms, ɛ increases with increasing ψ and a, but decreases with increasing d and θ. A composite containing smaller particles has a higher ɛ when ψ <9 % while larger particles provide greater enhancement when ψ is larger than that value. To enhance ɛ, adjacent particles must be interconnected and the overall chain direction should be oriented perpendicular to the conductive plates. These results are useful for additive manufacturing on electrical applications of elastomeric composites.

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

Cross, S.L.; Lighty, R.G.

Coral-rudist reefs of the Lower Cretaceous Mural limestone, southeastern Arizona, show a pronounced relationship between specific reef facies, primary porosity, and early submarine diagenesis. These large open-shelf reefs differ from the well-studied low-relief rudist buildups, and provide an alternate analog for many Cretaceous reef reservoirs. Arizona buildups have diverse corals, high depositional relief, and a well-developed facies zonation from fore reef to back reef: skeletal grainstone talus, muddy fore reef with branching and lamellar corals, massive reef crest with abundant lamellar corals and sandy matrix, protected thickets of delicate branching corals and large rudist mounds, and a wide sediment apronmore » of well-washed coral, rudist, and benthic foraminiferal sands. These well-exposed outcrops permit a detailed facies comparison of primary interparticle porosity. Porosity as high as 40% in grainstones was occluded by later subsurface cements. Reef-framework interparticle porosity was negligible because fore-reef coral and back-reef rudist facies were infilled by muds, and high-energy reef-crest frameworks were filled by peloidal submarine cement crusts and muddy skeletal sands. These thick crusts coated lamellar corals in cryptic and open reef-crest areas, and are laminated with ripple and draped bed forms that suggest current influence. Similar peloidal crusts and laminated textures are common magnesium-calcite submarine cement features in modern reefs. By documenting specific facies control on early cementation and textural variability, patterns of late-stage subsurface diagenesis and secondary porosity may be more easily explained for Cretaceous reef reservoirs. Significant primary porosity might be retained between sands in back-reef facies and within coral skeletons.« less

Magnetic resonance studies of mixed chalcospinel CuCr2SxSe4-x (x = 0; 2) and CoxCu1-xCr2S4 (x = 0.1; 0.2) nanocrystals with strong interparticle interactions

NASA Astrophysics Data System (ADS)

Pankrats, A. I.; Vorotynov, A. M.; Tugarinov, V. I.; Zharkov, S. M.; Zeer, G. M.; Ramasamy, K.; Gupta, A.

2018-04-01

Magnetic resonance characteristics of mixed chalcospinel nanocrystals CuCr2SxSe4-x (x = 0 and 2) and CoxCu1-xCr2S4 (x = 0.1 and 0.2) have been investigated. It has been established based on TEM, SEM and resonance data that all the samples contain both blocks with sizes from 1 to 50 m of compacted nanosized crystallites and individual nanoparticles with sizes from 10 to 30 nm. The studies provide evidence of strong interparticle interaction in all the samples leading to high values of the blocking temperature. Magnetic dipolar field arise in the boundary regions of interacting adjacent nanocrystals below the blocking temperature. This results in inhomogeneous broadening of the magnetic resonance spectrum along with appearance of additional absorption lines. With increase in magnetic anisotropy at low temperatures, a shift of the resonance field along with line broadening are observed for all the studied compounds due to freezing of the moments in the nanoparticles, both in the individual and compacted ones. A gapped characteristic of the resonance spectrum is established below the freezing temperature Tfr, with the energy gap defined by the averaged magnetic anisotropy . Anionic substitution of sulfur by selenium results in a decrease in the magnetic anisotropy. In contrast, cationic substitution of copper by cobalt increases the magnetic anisotropy due to a strong contribution from the latter ion.

Length scale effects of friction in particle compaction using atomistic simulations and a friction scaling model

NASA Astrophysics Data System (ADS)

Stone, T. W.; Horstemeyer, M. F.

2012-09-01

The objective of this study is to illustrate and quantify the length scale effects related to interparticle friction under compaction. Previous studies have shown as the length scale of a specimen decreases, the strength of a single crystal metal or ceramic increases. The question underlying this research effort continues the thought—If there is a length scale parameter related to the strength of a material, is there a length scale parameter related to friction? To explore the length scale effects of friction, molecular dynamics (MD) simulations using an embedded atom method potential were performed to analyze the compression of two spherical FCC nickel nanoparticles at different contact angles. In the MD model study, we applied a macroscopic plastic contact formulation to determine the normal plastic contact force at the particle interfaces and used the average shear stress from the MD simulations to determine the tangential contact forces. Combining this information with the Coulomb friction law, we quantified the MD interparticle coefficient of friction and showed good agreement with experimental studies and a Discrete Element Method prediction as a function of contact angle. Lastly, we compared our MD simulation friction values to the tribological predictions of Bhushan and Nosonovsky (BN), who developed a friction scaling model based on strain gradient plasticity and dislocation-assisted sliding that included a length scale parameter. The comparison revealed that the BN elastic friction scaling model did a much better job than the BN plastic scaling model of predicting the coefficient of friction values obtained from the MD simulations.

Oleate-based hydrothermal preparation of CoFe2O4 nanoparticles, and their magnetic properties with respect to particle size and surface coating

NASA Astrophysics Data System (ADS)

Repko, Anton; Vejpravová, Jana; Vacková, Taťana; Zákutná, Dominika; Nižňanský, Daniel

2015-09-01

We present a facile and high-yield synthesis of cobalt ferrite nanoparticles by hydrothermal hydrolysis of Co-Fe oleate in the presence of pentanol/octanol/toluene and water at 180 or 220 °C. The particle size (6-10 nm) was controlled by the composition of the organic solvent and temperature. Magnetic properties were then investigated with respect to the particle size and surface modification with citric acid or titanium dioxide (leading to hydrophilic particles). The as-prepared hydrophobic nanoparticles (coated by oleic acid) had a minimum inter-particle distance of 2.5 nm. Their apparent blocking temperature (estimated as a maximum of the zero-field-cooled magnetization) was 180 K, 280 K and 330 K for the particles with size of 6, 9 and 10.5 nm, respectively. Replacement of oleic acid on the surface by citric acid decreased inter-particle distance to less than 1 nm, and increased blocking temperature by ca. 10 K. On the other hand, coating with titanium dioxide, supported by nitrilotri(methylphosphonic acid), caused increase of the particle spacing, and lowering of the blocking temperature by ca. 20 K. The CoFe2O4@TiO2 nanoparticles were sufficiently stable in water, methanol and ethanol. The particles were also investigated by Mössbauer spectroscopy and alternating-current (AC) susceptibility measurements, and their analysis with Vögel-Fulcher and power law. Effect of different particle coating and dipolar interactions on the magnetic properties is discussed.

Titania nanofibers as a photo-antenna for dye-sensitized solar hydrogen.

PubMed

Choi, Sung Kyu; Kim, Soonhyun; Ryu, Jungho; Lim, Sang Kyoo; Park, Hyunwoong

2012-09-01

Directionally grown TiO(2) nano-architectures can serve as effective platforms for photogenerated charges to flow vectorially through the architecture framework, promising an unexpectedly high efficiency. This study demonstrates that directionally aligned TiO(2) nanofibers (TNF) obtained via a simple rearrangement of randomly scattered TiO(2) nanoparticles (TNP) exhibit significantly enhanced activity in terms of hydrogen production from water under visible light (λ > 420 nm). It has been found that Eosin Y (EY)-sensitized hydrogen production with TNF is greater than those with TNP and commercial TiO(2) samples (Degussa P25 and Hombikat UV-100) by a factor of 7 and >140, respectively, in the presence of triethanolamine (TEOA) as an electron donor. The annealing of TNF at elevated temperatures reduces the amount of H(2) produced and changes various physicochemical properties. Attempts have been made to find correlation factors between hydrogen production and reaction parameters (e.g., pH-dependent EY adsorption, surface area, pore size, particle size, and anatase-to-rutile ratio), none of which have provided an apparent correlation. It was suggested that the interparticle electron transfer is facilitated when TiO(2) nanoparticles are physically interconnected, and TNF might work as a robust photo-antenna for efficiently collecting the photogenerated electrons. The photocurrent measurements in visible light-irradiated EY/TiO(2) suspensions indicate that the photocurrent of TNF is 50% higher than that of TNP, supporting the photo-antenna mechanism of TNF.

Effect of contact angle and contact angle hysteresis on the floatability of spheres at the air-water interface.

PubMed

Feng, Dong-Xia; Nguyen, Anh V

2017-10-01

The floatability of solid particles on the water surface governs many natural phenomena and industrial processes including film flotation and froth flotation separation of coal and valuable minerals. For many years, the contact angle (CA) has been postulated as the key factor in determining the particle floatability. Indeed, the maximum force (tenacity) supporting the flotation of fine spheres was conjectured to occur when the apical angle of the contact circle is equal to the contact angle. In this paper, the model predictions are reviewed and compared with experimental results. It is shown that CA can be affected by many physical and chemical factors such as surface roughness and chemical heterogeneity and can have a range of values known as the CA hysteresis. This multiple-valued CA invalidates the available theories on the floatability of spheres. Even the intuitive replacement of CA by the advancing (maximum) CA in the classical theories can be wrong. A few new examples are also reviewed and analyzed to demonstrate the significance of CA variation in controlling the particle floatability. They include the pinning of the contact line at the sharp edge, known as the Gibbs inequality condition, and the nearby interaction among floating particles, known as lateral inter-particle interaction. It is concluded that our quantitative understanding of the floatability of real particles being irregular and heterogeneous both morphologically and chemically is still far from being satisfactory. Copyright © 2017 Elsevier B.V. All rights reserved.

Isostructural solid-solid phase transition in monolayers of soft core-shell particles at fluid interfaces: structure and mechanics.

PubMed

Rey, Marcel; Fernández-Rodríguez, Miguel Ángel; Steinacher, Mathias; Scheidegger, Laura; Geisel, Karen; Richtering, Walter; Squires, Todd M; Isa, Lucio

2016-04-21

We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

DNA sensors and aptasensors based on the hemin/G-quadruplex-controlled aggregation of Au NPs in the presence of L-cysteine.

PubMed

Niazov-Elkan, Angelica; Golub, Eyal; Sharon, Etery; Balogh, Dora; Willner, Itamar

2014-07-23

L-cysteine induces the aggregation of Au nanoparticles (NPs), resulting in a color transition from red to blue due to interparticle plasmonic coupling in the aggregated structure. The hemin/G-quadruplex horseradish peroxidase-mimicking DNAzyme catalyzes the aerobic oxidation of L-cysteine to cystine, a process that inhibits the aggregation of the NPs. The degree of inhibition of the aggregation process is controlled by the concentration of the DNAzyme in the system. These functions are implemented to develop sensing platforms for the detection of a target DNA, for the analysis of aptamer-substrate complexes, and for the analysis of L-cysteine in human urine samples. A hairpin DNA structure that includes a recognition site for the DNA analyte and a caged G-quadruplex sequence, is opened in the presence of the target DNA. The resulting self-assembled hemin/G-quadruplex acts as catalyst that controls the aggregation of the Au NPs. Also, the thrombin-binding aptamer folds into a G-quadruplex nanostructure upon binding to thrombin. The association of hemin to the resulting G-quadruplex aptamer-thrombin complex leads to a catalytic label that controls the L-cysteine-mediated aggregation of the Au NPs. The hemin/G-qaudruplex-controlled aggregation of Au NPs process is further implemented for visual and spectroscopic detection of L-cysteine concentration in urine samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cavitation transition in the energy landscape: Distinct tensile yielding behavior in strongly and weakly attractive systems.

PubMed

Altabet, Y Elia; Fenley, Andreia L; Stillinger, Frank H; Debenedetti, Pablo G

2018-03-21

Particles with cohesive interactions display a tensile instability in the energy landscape at the Sastry density ρ S . The signature of this tensile limit is a minimum in the landscape equation of state, the pressure-density relationship of inherent structures sampled along a liquid isotherm. Our previous work [Y. E. Altabet, F. H. Stillinger, and P. G. Debenedetti, J. Chem. Phys. 145, 211905 (2016)] revisited the phenomenology of Sastry behavior and found that the evolution of the landscape equation of state with system size for particles with interactions typical of molecular liquids indicates the presence of an athermal first-order phase transition between homogeneous and fractured inherent structures, the latter containing several large voids. Here, we study how this tensile limit manifests itself for different interparticle cohesive strengths and identify two distinct regimes. Particles with sufficiently strong cohesion display an athermal first-order phase transition, consistent with our prior characterization. Weak cohesion also displays a tensile instability. However, the landscape equation of state for this regime is independent of system size, suggesting the absence of a first-order phase transition. An analysis of the voids suggests that yielding in the energy landscape of weakly cohesive systems is associated with the emergence of a highly interconnected network of small voids. While strongly cohesive systems transition from exclusively homogeneous to exclusively fractured configurations at ρ S in the thermodynamic limit, this interconnected network develops gradually, starting at ρ S , even at infinite system size.

Perpendicular magnetic anisotropy in granular multilayers of CoPd alloyed nanoparticles

NASA Astrophysics Data System (ADS)

Vivas, L. G.; Rubín, J.; Figueroa, A. I.; Bartolomé, F.; García, L. M.; Deranlot, C.; Petroff, F.; Ruiz, L.; González-Calbet, J. M.; Pascarelli, S.; Brookes, N. B.; Wilhelm, F.; Chorro, M.; Rogalev, A.; Bartolomé, J.

2016-05-01

Co-Pd multilayers obtained by Pd capping of pre-deposited Co nanoparticles on amorphous alumina are systematically studied by means of high-resolution transmission electron microscopy, x-ray diffraction, extended x-ray absorption fine structure, SQUID-based magnetometry, and x-ray magnetic circular dichroism. The films are formed by CoPd alloyed nanoparticles self-organized across the layers, with the interspace between the nanoparticles filled by the non-alloyed Pd metal. The nanoparticles show atomic arrangements compatible with short-range chemical order of L 10 strucure type. The collective magnetic behavior is that of ferromagnetically coupled particles with perpendicular magnetic anisotropy, irrespective of the amount of deposited Pd. For increasing temperature three magnetic phases are identified: hard ferromagnetic with strong coercive field, soft-ferromagnetic as in an amorphous asperomagnet, and superparamagnetic. Increasing the amount of Pd in the system leads to both magnetic hardness increment and higher transition temperatures. Magnetic total moments of 1.77(4) μB and 0.45(4) μB are found at Co and Pd sites, respectively, where the orbital moment of Co, 0.40(2) μB, is high, while that of Pd is negligible. The effective magnetic anisotropy is the largest in the capping metal series (Pd, Pt, W, Cu, Ag, Au), which is attributed to the interparticle interaction between de nanoparticles, in addition to the intraparticle anisotropy arising from hybridization between the 3 d -4 d bands associated to the Co and Pd chemical arrangement in a L 10 structure type.

Cavitation transition in the energy landscape: Distinct tensile yielding behavior in strongly and weakly attractive systems

NASA Astrophysics Data System (ADS)

Altabet, Y. Elia; Fenley, Andreia L.; Stillinger, Frank H.; Debenedetti, Pablo G.

2018-03-01

Particles with cohesive interactions display a tensile instability in the energy landscape at the Sastry density ρS. The signature of this tensile limit is a minimum in the landscape equation of state, the pressure-density relationship of inherent structures sampled along a liquid isotherm. Our previous work [Y. E. Altabet, F. H. Stillinger, and P. G. Debenedetti, J. Chem. Phys. 145, 211905 (2016)] revisited the phenomenology of Sastry behavior and found that the evolution of the landscape equation of state with system size for particles with interactions typical of molecular liquids indicates the presence of an athermal first-order phase transition between homogeneous and fractured inherent structures, the latter containing several large voids. Here, we study how this tensile limit manifests itself for different interparticle cohesive strengths and identify two distinct regimes. Particles with sufficiently strong cohesion display an athermal first-order phase transition, consistent with our prior characterization. Weak cohesion also displays a tensile instability. However, the landscape equation of state for this regime is independent of system size, suggesting the absence of a first-order phase transition. An analysis of the voids suggests that yielding in the energy landscape of weakly cohesive systems is associated with the emergence of a highly interconnected network of small voids. While strongly cohesive systems transition from exclusively homogeneous to exclusively fractured configurations at ρS in the thermodynamic limit, this interconnected network develops gradually, starting at ρS, even at infinite system size.

Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

PubMed

Joshi, Prachi; Gorski, Christopher A

2016-07-19

When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

Generalized Jastrow variational method for liquid3He-4He mixtures at T=0 K

NASA Astrophysics Data System (ADS)

Mirabbaszadeh, K.

1989-07-01

The ground state energy of a dilute solution of mass-3 fermions in liquid4He is analyzed by a variational procedure based on the Jastrow many body theory. The antisymmetry of the wave function for fermions is incorporated following the procedure given by Lado, Inguva, and Smith. A set of coupled integrodifferential equations is solved in the hypernetted chain approximation yielding expressions for the binding energy of3He-4He mixtures; the radial distribution function is given together with the total energy for various values of density and the interparticle separation r s.

Thermal properties of granulated materials.

NASA Technical Reports Server (NTRS)

Wechsler, A. E.; Glaser, P. E.; Fountain, J. A.

1972-01-01

Review of the thermophysical properties of granular materials or silicates believed to simulate the lunar surface layer. Emphasis is placed on thermal conductivity data and the effects of material and environmental variables on the thermal conductivity. There are three basic mechanisms of heat transfer in particulate materials: conduction by the gas contained in the void spaces between the particles; conduction within the solid particles and across the interparticle contacts; and thermal radiation within the particles, across the void spaces between particle surfaces, and between void spaces themselves. Gas and solid conduction, thermal radiation, and the interaction between conduction and radiation are considered.

Self-assembled inorganic clusters of semiconducting quantum dots for effective solar hydrogen evolution.

PubMed

Gao, Yu-Ji; Yang, Yichen; Li, Xu-Bing; Wu, Hao-Lin; Meng, Shu-Lin; Wang, Yang; Guo, Qing; Huang, Mao-Yong; Tung, Chen-Ho; Wu, Li-Zhu

2018-05-08

Owing to promoted electron-hole separation, the catalytic activity of semiconducting quantum dots (QDs) towards solar hydrogen (H2) production has been significantly enhanced by forming self-assembled clusters with ZnSe QDs made ex situ. Taking advantage of the favored interparticle hole transfer to ZnSe QDs, the rate of solar H2 evolution of CdSe QDs can be increased to ∼30 000 μmol h-1 g-1 with ascorbic acid as the sacrificial reagent, ∼150-fold higher than that of bare CdSe QDs clusters under the same conditions.

Efficient forward second-harmonic generation from planar archimedean nanospirals

DOE PAGES

Davidson, II, Roderick B.; Ziegler, Jed I.; Vargas, Guillermo; ...

2015-05-01

Here, the enhanced electric field at plasmonic resonances in nanoscale antennas can lead to efficient harmonic generation, especially when the plasmonic geometry is asymmetric on either inter-particle or intra-particle levels. The planar Archimedean nanospiral offers a unique geometrical asymmetry for second-harmonic generation (SHG) because the SHG results neither from arranging centrosymmetric nanoparticles in asymmetric groupings, nor from non-centrosymmetric nanoparticles that retain a local axis of symmetry. Here, we report forward SHG from planar arrays of Archimedean nanospirals using 15 fs pulses from a Ti:sapphire oscillator tuned to 800 nm wavelength.

Transport regimes spanning magnetization-coupling phase space

DOE PAGES

Baalrud, Scott D.; Daligault, Jérôme

2017-10-06

The manner in which transport properties vary over the entire parameter-space of coupling and magnetization strength is explored in this paper. Four regimes are identified based on the relative size of the gyroradius compared to other fundamental length scales: the collision mean free path, Debye length, distance of closest approach, and interparticle spacing. Molecular dynamics simulations of self-diffusion and temperature anisotropy relaxation spanning the parameter space are found to agree well with the predicted boundaries. Finally, comparison with existing theories reveals regimes where they succeed, where they fail, and where no theory has yet been developed.

Transport regimes spanning magnetization-coupling phase space

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

Baalrud, Scott D.; Daligault, Jérôme

The manner in which transport properties vary over the entire parameter-space of coupling and magnetization strength is explored in this paper. Four regimes are identified based on the relative size of the gyroradius compared to other fundamental length scales: the collision mean free path, Debye length, distance of closest approach, and interparticle spacing. Molecular dynamics simulations of self-diffusion and temperature anisotropy relaxation spanning the parameter space are found to agree well with the predicted boundaries. Finally, comparison with existing theories reveals regimes where they succeed, where they fail, and where no theory has yet been developed.

Controllability of the Coulomb charging energy in close-packed nanoparticle arrays.

PubMed

Duan, Chao; Wang, Ying; Sun, Jinling; Guan, Changrong; Grunder, Sergio; Mayor, Marcel; Peng, Lianmao; Liao, Jianhui

2013-11-07

We studied the electronic transport properties of metal nanoparticle arrays, particularly focused on the Coulomb charging energy. By comparison, we confirmed that it is more reasonable to estimate the Coulomb charging energy using the activation energy from the temperature-dependent zero-voltage conductance. Based on this, we systematically and comprehensively investigated the parameters that could be used to tune the Coulomb charging energy in nanoparticle arrays. We found that four parameters, including the particle core size, the inter-particle distance, the nearest neighboring number, and the dielectric constant of ligand molecules, could significantly tune the Coulomb charging energy.

The BCS-BEC crossover: From ultra-cold Fermi gases to nuclear systems

NASA Astrophysics Data System (ADS)

Strinati, Giancarlo Calvanese; Pieri, Pierbiagio; Röpke, Gerd; Schuck, Peter; Urban, Michael

2018-04-01

This report addresses topics and questions of common interest in the fields of ultra-cold gases and nuclear physics in the context of the BCS-BEC crossover. By this crossover, the phenomena of Bardeen-Cooper-Schrieffer (BCS) superfluidity and Bose-Einstein condensation (BEC), which share the same kind of spontaneous symmetry breaking, are smoothly connected through the progressive reduction of the size of the fermion pairs involved as the fundamental entities in both phenomena. This size ranges, from large values when Cooper pairs are strongly overlapping in the BCS limit of a weak inter-particle attraction, to small values when composite bosons are non-overlapping in the BEC limit of a strong inter-particle attraction, across the intermediate unitarity limit where the size of the pairs is comparable with the average inter-particle distance. The BCS-BEC crossover has recently been realized experimentally, and essentially in all of its aspects, with ultra-cold Fermi gases. This realization, in turn, has raised the interest of the nuclear physics community in the crossover problem, since it represents an unprecedented tool to test fundamental and unanswered questions of nuclear many-body theory. Here, we focus on the several aspects of the BCS-BEC crossover, which are of broad joint interest to both ultra-cold Fermi gases and nuclear matter, and which will likely help to solve in the future some open problems in nuclear physics (concerning, for instance, neutron stars). Similarities and differences occurring in ultra-cold Fermi gases and nuclear matter will then be emphasized, not only about the relative phenomenologies but also about the theoretical approaches to be used in the two contexts. Common to both contexts is the fact that at zero temperature the BCS-BEC crossover can be described at the mean-field level with reasonable accuracy. At finite temperature, on the other hand, inclusion of pairing fluctuations beyond mean field represents an essential ingredient of the theory, especially in the normal phase where they account for precursor pairing effects. After an introduction to present the key concepts of the BCS-BEC crossover, this report discusses the mean-field treatment of the superfluid phase, both for homogeneous and inhomogeneous systems, as well as for symmetric (spin- or isospin-balanced) and asymmetric (spin- or isospin-imbalanced) matter. Pairing fluctuations in the normal phase are then considered, with their manifestations in thermodynamic and dynamic quantities. The last two Sections provide a more specialized discussion of the BCS-BEC crossover in ultra-cold Fermi gases and nuclear matter, respectively. The separate discussion in the two contexts aims at cross communicating to both communities topics and aspects which, albeit arising in one of the two fields, share a strong common interest.

Understanding bulk behavior of particulate materials from particle scale simulations

NASA Astrophysics Data System (ADS)

Deng, Xiaoliang

Particulate materials play an increasingly significant role in various industries, such as pharmaceutical manufacturing, food, mining, and civil engineering. The objective of this research is to better understand bulk behaviors of particulate materials from particle scale simulations. Packing properties of assembly of particles are investigated first, focusing on the effects of particle size, surface energy, and aspect ratio on the coordination number, porosity, and packing structures. The simulation results show that particle sizes, surface energy, and aspect ratio all influence the porosity of packing to various degrees. The heterogeneous force networks within particle assembly under external compressive loading are investigated as well. The results show that coarse-coarse contacts dominate the strong network and coarse-fine contacts dominate the total network. Next, DEM models are developed to simulate the particle dynamics inside a conical screen mill (comil) and magnetically assisted impaction mixer (MAIM), both are important particle processing devices. For comil, the mean residence time (MRT), spatial distribution of particles, along with the collision dynamics between particles as well as particle and vessel geometries are examined as a function of the various operating parameters such as impeller speed, screen hole size, open area, and feed rate. The simulation results can help better understand dry coating experimental results using comil. For MAIM system, the magnetic force is incorporated into the contact model, allowing to describe the interactions between magnets. The simulation results reveal the connections between homogeneity of mixture and particle scale variables such as size of magnets and surface energy of non-magnets. In particular, at the fixed mass ratio of magnets to non-magnets and surface energy the smaller magnets lead to better homogeneity of mixing, which is in good agreement with previously published experimental results. Last but not least, numerical simulations, along with theoretical analysis, are performed to investigate the interparticle force of dry coated particles. A model is derived and can be used to predict the probabilities of hose-host (HH), host-guest (HG), and guest-guest (GG) contacts. The results indicate that there are three different regions dominated by HH, HG, and GG contacts, respectively. Moreover, the critical SAC for the transition of HG to GG contacts is lower than previously estimated value. In summary, particle packing, particle dynamics associated with various particle processing devices, and interparticle force of dry coated particles are investigated in this thesis. The results show that particle scale information such as coordination number, collision dynamics, and contact force between particles from simulation results can help better understand bulk properties of assembly of individual particles.

Programmed Nanomaterial Assemblies in Large Scales: Applications of Synthetic and Genetically- Engineered Peptides to Bridge Nano-Assemblies and Macro-Assemblies

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

Matsui, Hiroshi

Work is reported in these areas: Large-scale & reconfigurable 3D structures of precise nanoparticle assemblies in self-assembled collagen peptide grids; Binary QD-Au NP 3D superlattices assembled with collagen-like peptides and energy transfer between QD and Au NP in 3D peptide frameworks; Catalytic peptides discovered by new hydrogel-based combinatorial phage display approach and their enzyme-mimicking 2D assembly; New autonomous motors of metal-organic frameworks (MOFs) powered by reorganization of self-assembled peptides at interfaces; Biomimetic assembly of proteins into microcapsules on oil-in-water droplets with structural reinforcement via biomolecular recognition-based cross-linking of surface peptides; and Biomimetic fabrication of strong freestanding genetically-engineered collagen peptide filmsmore » reinforced by quantum dot joints. We gained the broad knowledge about biomimetic material assembly from nanoscale to microscale ranges by coassembling peptides and NPs via biomolecular recognition. We discovered: Genetically-engineered collagen-like peptides can be self-assembled with Au NPs to generate 3D superlattices in large volumes (> μm{sup 3}); The assembly of the 3D peptide-Au NP superstructures is dynamic and the interparticle distance changes with assembly time as the reconfiguration of structure is triggered by pH change; QDs/NPs can be assembled with the peptide frameworks to generate 3D superlattices and these QDs/NPs can be electronically coupled for the efficient energy transfer; The controlled assembly of catalytic peptides mimicking the catalytic pocket of enzymes can catalyze chemical reactions with high selectivity; and, For the bacteria-mimicking swimmer fabrication, peptide-MOF superlattices can power translational and propellant motions by the reconfiguration of peptide assembly at the MOF-liquid interface.« less

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2016-12-01

Aggregation kinetics and stability of colloidal particles have been extensively studied using bulk techniques such as dynamic light scattering; these techniques involve large ensembles of particles and interpretation of results is difficult when particles are non-spherical and poorly characterized, as is always the case with non-ideal natural hazardous materials such as asbestos fibers. These difficulties hinder greatly progress on fundamental understanding of whether the classic colloidal aggregation theories can be applied to natural materials and how the heterogeneity of particles (e.g., shape) affects the colloidal aggregation kinetics and structure. By using in-situ microscopy and particle tracking techniques, we were able to observe the particle-by-particle growth of aggregated formed by elongated particles (synthetic glass rods and natural asbestos fibers) and demonstrated the rod-shaped geometry induced novel structures and growth dynamics that challenge existing theory. In this study, we continue to use asbestos as model system of elongated colloidal contaminant, and investigate the effects of changing solution chemistry (e.g., ionic strength, pH, and natural organic matter (NOM)), on growth dynamics and aggregates structure. The results show that aggregate growth curves are self-similar with a characteristic timescale that increases with increasing pH. By varying ionic strength for fixed pH values, we determine that the ccc is sensitive to pH. Fractal dimension decreases slightly with increasing pH and decreasing ionic strength, indicating that stronger inter-particle repulsion create sparser aggregates; however, the magnitude of the solution chemistry effects is much smaller than that of colloid shape. In monovalent solutions, regardless of their concentration, HA drastically reduces the aggregation kinetics of asbestos fiber. This work may lead to enhanced prediction of the colloidal contaminants' mobility in the environment, bioavailability, and toxicity to organisms.

BILP-19-An Ultramicroporous Organic Network with Exceptional Carbon Dioxide Uptake.

PubMed

Klumpen, Christoph; Radakovitsch, Florian; Jess, Andreas; Senker, Jürgen

2017-08-12

Porous benzimidazole-based polymers (BILPs) have proven to be promising for carbon dioxide capture and storage. The polarity of their chemical structure in combination with an inherent porosity allows for adsorbing large amounts of carbon dioxide in combination with high selectivities over unpolar guest molecules such as methane and nitrogen. For this reason, among purely organic polymers, BILPs contain some of the most effective networks to date. Nevertheless, they are still outperformed by competitive materials such as metal-organic frameworks (MOFs) or metal doped porous polymers. Here, we report the synthesis of BILP-19 and its exceptional carbon dioxide uptake of up to 6 mmol•g-1 at 273 K, making the network comparable to state-of-the-art materials. BILP-19 precipitates in a particulate structure with a strongly anisotropic growth into platelets, indicating a sheet-like structure for the network. It exhibits only a small microporous but a remarkable ultra-microporous surface area of 144 m2•g-1 and 1325 m2•g-1, respectively. We attribute the exceptional uptake of small guest molecules such as carbon dioxide and water to the distinct ultra-microporosity. Additionally, a pronounced hysteresis for both guests is observed, which in combination with the platelet character is probably caused by an expansion of the interparticle space, creating additional accessible ultra-microporous pore volume. For nitrogen and methane, this effect does not occur which explains their low affinity. In consequence, Henry selectivities of 123 for CO2/N2 at 298 K and 12 for CO2/CH4 at 273 K were determined. The network was carefully characterized with solid-state nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, thermal gravimetry (TG) and elemental analyses as well as physisorption experiments with Ar, N2, CO2, CH4 and water.

Small angle x-ray scattering of chromatin. Radius and mass per unit length depend on linker length.

PubMed Central

Williams, S P; Langmore, J P

1991-01-01

Analyses of low angle x-ray scattering from chromatin, isolated by identical procedures but from different species, indicate that fiber diameter and number of nucleosomes per unit length increase with the amount of nucleosome linker DNA. Experiments were conducted at physiological ionic strength to obtain parameters reflecting the structure most likely present in living cells. Guinier analyses were performed on scattering from solutions of soluble chromatin from Necturus maculosus erythrocytes (linker length 48 bp), chicken erythrocytes (linker length 64 bp), and Thyone briareus sperm (linker length 87 bp). The results were extrapolated to infinite dilution to eliminate interparticle contributions to the scattering. Cross-sectional radii of gyration were found to be 10.9 +/- 0.5, 12.1 +/- 0.4, and 15.9 +/- 0.5 nm for Necturus, chicken, and Thyone chromatin, respectively, which are consistent with fiber diameters of 30.8, 34.2, and 45.0 nm. Mass per unit lengths were found to be 6.9 +/- 0.5, 8.3 +/- 0.6, and 11.8 +/- 1.4 nucleosomes per 10 nm for Necturus, chicken, and Thyone chromatin, respectively. The geometrical consequences of the experimental mass per unit lengths and radii of gyration are consistent with a conserved interaction among nucleosomes. Cross-linking agents were found to have little effect on fiber external geometry, but significant effect on internal structure. The absolute values of fiber diameter and mass per unit length, and their dependencies upon linker length agree with the predictions of the double-helical crossed-linker model. A compilation of all published x-ray scattering data from the last decade indicates that the relationship between chromatin structure and linker length is consistent with data obtained by other investigators. Images FIGURE 1 PMID:2049522

Self-Assembly of Heterogeneously Charged Particles under Confinement

PubMed Central

2013-01-01

Self-assembly—the spontaneous organization of microscopic units into well-defined mesoscopic structures—is a fundamental mechanism for a broad variety of nanotechnology applications in material science. The central role played by the anisotropy resulting from asymmetric shapes of the units and/or well-defined bonding sites on the particle surface has been widely investigated, highlighting the importance of properly designing the constituent entities in order to control the resulting mesoscopic structures. Anisotropy driven self-assembly can also result from the multipolar interactions characterizing many naturally occurring systems, such as proteins and viral capsids, as well as experimentally synthesized colloidal particles. Heterogeneously charged particles represent a class of multipolar units that are characterized by a competitive interplay between anisotropic attractive and repulsive interactions, due to the repulsion/attraction between charged-like/oppositely charged regions on the particle surface. In the present work, axially symmetric quadrupolar colloids are considered in a confined planar geometry; the role of both the overall particle charge and the patch extension as well as the effect of the substrate charge are studied in thermodynamic conditions such that the formation of extended structures is favored. A general tendency to form quasi-two-dimensional aggregates where particles align their symmetry axes within the plane is observed; among these planar self-assembled scenarios, a clear distinction between the formation of microcrystalline gels—branched networks consisting of purely crystalline domains—as opposed to disordered aggregates can be observed based on the specific features of the particle–particle interaction. Additionally, the possible competition of interparticle and particle–substrate interactions affects the size and the internal structure of the aggregates and can possibly inhibit the aggregation process. PMID:23627740

Assembly of Nanowire Arrays: Exploring Interparticle Interactions, Particle Orientation, and Mixed Particle Arrays

NASA Astrophysics Data System (ADS)

Kirby, David J.

This dissertation explores the fundamental interparticle and particle-substrate forces that contribute to nanowire assembly. Nanowires have a large aspect ratio which has made them favorable materials for applications in energy and sensing technologies. However, this anisotropy means that nanowires must be positioned and oriented during an assembly process. Within this work, the roles of gravity, van der Waals (VDW) attractions, and electrostatic repulsions are explored when different nanowire assemblies are created. Particles were synthesized by the template electrodeposition process so that stripes of different materials and therefore different VDW interactions could be patterned along the particle length. Electrostatic repulsions were provided by a small molecule coating or a porous silica shell to prevent aggregation during the assembly process. Chapters 2, 3, 5, 6, and 8 all used particles whose asymmetry was further adjusted by removal of a sacrificial segment to leave a partially etched nanowire (PEN), a rigid silica shell partially filled with a metal core. For these particles, the role of gravity was amplified due to the drastic density differences between the two segments. Topographic and high VDW surface interactions were patterned onto assembly substrates using photolithographic processing. These forces served as a passive template to direct nanowire assembly. The segment anisotropy of PENs allowed gravity to drive their sedimentation with the long axis perpendicular to the surface. The density difference between the two ends allowed them to convert between the horizontal and vertical orientation as they diffused on the substrate. Vertical arrays formed as particle concentrations increased while VDW attractions from neighboring PENs or the physical barrier of a microwell wall supported this structure. While vertical arrays were typically PENs, microwell walls were also able to enforce a vertical orientation on solid Au nanowires. These particles typically formed horizontal arrays on planar surfaces, but careful design of the microwell and nanowire dimensions enabled these particles to take on the vertical orientation. Solid nanowires and PENs with greater segment symmetry aligned parallel to the surface as gravity did not allow a conversion to the vertical orientation. When concentrated, these particles formed smectic row arrangements which were previously shown to originate from a balance of VDW attractions and electrostatic repulsions. Within rows of segmented particles, a preference was observed for like orientation of nearest neighbor particles (Chapter 6). With the aid of Monte Carlo simulations, it was determined that this observation was the result of small differences in VDW attractions between the two nanowire ends. Differences in VDW attraction were also applied to patterned surfaces (Chapter 7). Stripes of high VDW material (Au) were placed on a silica surface (a low VDW material). When relatively low surface concentrations were used, the high VDW regions collected Au nanowires and organized them into rows that were reminiscent of those observed on un-patterned surfaces at high particle concentrations. VDW and the gravitational force were explored as they combined to influence array orientation in binary PEN mixtures. Depending on the geometries of the particles combined, the contributions of gravity and interparticle interactions exhibited different balance in creating the final array. VDW and gravitational forces could also act as a force for reconfigurable nanowire assembly. In chapter 8, fluid flow was used to concentrate PENs and force them into horizontal arrangements. When fluid flow was stopped, van der Waals forces and gravity were responsible for a reorientation of the assembled particles into a standing array. These studies represent early steps into the future of nanowire assembly methods. I conclude this dissertation by discussing the implications of my work and providing perspective on their importance to the scientific community. I also offer suggestions for future work in nanowire assembly. These areas focus on the development of assembled nanowire devices, mixed nanowire assembly techniques, and potential stimuli responsive reconfigurable assemblies.

The Saturn Ring Observer: In situ studies of planetary rings

NASA Astrophysics Data System (ADS)

Nicholson, P. D.; Tiscareno, M. S.; Spilker, L. J.

2010-12-01

As part of the Planetary Science Decadal Survey recently undertaken by the NRC's Space Studies Board for the National Academy of Sciences, studies were commissioned for a number of potential missions to outer planet targets. One of these studies examined the technological feasibility of a mission to carry out in situ studies of Saturn's rings, from a spacecraft placed in a circular orbit above the ring plane: the Saturn Ring Observer. The technical findings and background are discussed in a companion poster by T. R. Spilker et al. Here we outline the science goals of such a mission. Most of the fundamental interactions in planetary rings occur on spatial scales that are unresolved by flyby or orbiter spacecraft. Typical particle sizes in the rings of Saturn are in the 1 cm - 10 m range, and average interparticle spacings are a few meters. Indirect evidence indicates that the vertical thickness of the rings is as little as 5 - 10 m, which implies a velocity dispersion of only a few mm/sec. Theories of ring structure and evolution depend on the unknown characteristics of interparticle collisions and on the size distribution of the ring particles. The SRO could provide direct measurements of both the coefficient of restitution -- by monitoring individual collisions -- and the particles’ velocity dispersion. High-resolution observations of individual ring particles should also permit estimates of their spin states. Numerical simulations of Saturn’s rings incorporating both collisions and self-gravity predict that the ring particles are not uniformly distributed, but are instead clustered into elongated structures referred to as “self-gravity wakes”, which are continually created and destroyed on an orbital timescale. Theory indicates that the average separation between wakes in the A ring is of order 30-100 m. Direct imaging of self-gravity wakes, including their formation and subsequent dissolution, would provide critical validation of these models. Other targets of observation by the SRO will include “propellers” (thought to be the signature of sub-km moonlets embedded in the rings), the “ropy” and “straw” structure seen in images of strong density waves and gap edges, and km-scale radial oscillations which may be signatures of “viscous overstabilities” in high-optical depth regions. Most of the science goals identified above could be accomplished by high-resolution nadir imaging of the rings from a platform that co-orbits with the ring particles, i.e., from a spacecraft in circular orbit a few km above the rings. The vertical displacement of the spacecraft is maintained by a continuous low-thrust ion engine, which can be tilted to provide a slow inward radial drift across the rings. Chemical thrusters permit the craft to `hop' over vertical obstacles in the rings (e.g., bending waves and inclined ringlets). In addition to an imaging system with a resolution of at least 10 cm (with 1 cm a desirable goal), other instrumentat ion might include a laser altimeter/range-finder to measure the effective thickness of the rings, as well as the vertical component of particle motions, aswell as in situ instruments to measure the density and composition of the neutral and ionized ring atmosphere, meteoritic and secondary dust fluxes, and local electric fields (especially in spoke regions).

Efficient light harvesting within a C153@Zr-based MOF embedded in a polymeric film: spectral and dynamical characterization.

PubMed

Gutiérrez, M; López-González, M; Sánchez, F; Douhal, A

2017-07-21

Light harvesting is a natural phenomenon that scientists try to mimic in artificial systems. Having this in mind, attention has been focused on using new smart-materials for photonics. Herein, we report on the photobehaviour of a Zr-NDC MOF (NDC = dimethyl 2,6-naphthalenedicarboxylate) and its composite material, Coumarin153@Zr-NDC, embedded within a polymeric membrane of poly[bisphenol A carbonate-co-4,4'-(3,3,5-trimethylcyclohexylidene)diphenol carbonate] (PC). For the mixed matrix membrane (MMM) Zr-NDC/PC, we observed interparticle excimer-like formation, taking place in times shorter than 15 ps and giving rise to a red-shifted broad emission band. The interparticle interactions are supported by the SEM images, as they reflect the contact between the MOF crystals. The C153@Zr-NDC/PC material presents an energy transfer (ET) process from the excited MOF to the trapped C153 molecules in 820 ps, with a 35 nm red-shifted emission band corresponding to C153 in PC. The fluorescence quantum yield, as a result of this ET from the MOF, is high enough (25%) to explore the possibility of using this new composite material in a LED device. To elucidate the observed photobehavior, we compared it with those of C153/PC and (2,6-NDC + C153)/PC films. These results shed light on the spectroscopic and dynamical properties of these new composite materials formed by a highly fluorescent molecule, and easily synthesized MOFs and polymeric matrices, opening the way for more research based on these mixed inorganic and organic compounds for possible applications in the fields of luminescence sensing and emitting devices.

Microscopic origin and macroscopic implications of lane formation in mixtures of oppositely driven particles

NASA Astrophysics Data System (ADS)

Klymko, Katherine; Geissler, Phillip L.; Whitelam, Stephen

2016-08-01

Colloidal particles of two types, driven in opposite directions, can segregate into lanes [Vissers et al., Soft Matter 7, 2352 (2011), 10.1039/c0sm01343a]. This phenomenon can be reproduced by two-dimensional Brownian dynamics simulations of model particles [Dzubiella et al., Phys. Rev. E 65, 021402 (2002), 10.1103/PhysRevE.65.021402]. Here we use computer simulation to assess the generality of lane formation with respect to variation of particle type and dynamical protocol. We find that laning results from rectification of diffusion on the scale of a particle diameter: oppositely driven particles must, in the time taken to encounter each other in the direction of the drive, diffuse in the perpendicular direction by about one particle diameter. This geometric constraint implies that the diffusion constant of a particle, in the presence of those of the opposite type, grows approximately linearly with the Péclet number, a prediction confirmed by our numerics over a range of model parameters. Such environment-dependent diffusion is statistically similar to an effective interparticle attraction; consistent with this observation, we find that oppositely driven nonattractive colloids display features characteristic of the simplest model system possessing both interparticle attractions and persistent motion, the driven Ising lattice gas [Katz, Leibowitz, and Spohn, J. Stat. Phys. 34, 497 (1984), 10.1007/BF01018556]. These features include long-ranged correlations in the disordered regime, a critical regime characterized by a change in slope of the particle current with the Péclet number, and fluctuations that grow with system size. By analogy, we suggest that lane formation in the driven colloid system is a phase transition in the macroscopic limit, but that macroscopic phase separation would not occur in finite time upon starting from disordered initial conditions.

Long-range forces affecting equilibrium inertial focusing behavior in straight high aspect ratio microfluidic channels

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

Reece, Amy E.; Oakey, John, E-mail: joakey@uwyo.edu

2016-04-15

The controlled and directed focusing of particles within flowing fluids is a problem of fundamental and technological significance. Microfluidic inertial focusing provides passive and precise lateral and longitudinal alignment of small particles without the need for external actuation or sheath fluid. The benefits of inertial focusing have quickly enabled the development of miniaturized flow cytometers, size-selective sorting devices, and other high-throughput particle screening tools. Straight channel inertial focusing device design requires knowledge of fluid properties and particle-channel size ratio. Equilibrium behavior of inertially focused particles has been extensively characterized and the constitutive phenomena described by scaling relationships for straight channelsmore » of square and rectangular cross section. In concentrated particle suspensions, however, long-range hydrodynamic repulsions give rise to complex particle ordering that, while interesting and potentially useful, can also dramatically diminish the technique’s effectiveness for high-throughput particle handling applications. We have empirically investigated particle focusing behavior within channels of increasing aspect ratio and have identified three scaling regimes that produce varying degrees of geometrical ordering between focused particles. To explore the limits of inertial particle focusing and identify the origins of these long-range interparticle forces, we have explored equilibrium focusing behavior as a function of channel geometry and particle concentration. Experimental results for highly concentrated particle solutions identify equilibrium thresholds for focusing that scale weakly with concentration and strongly with channel geometry. Balancing geometry mediated inertial forces with estimates for interparticle repulsive forces now provide a complete picture of pattern formation among concentrated inertially focused particles and enhance our understanding of the fundamental limits of inertial focusing for technological applications.« less

Computational analysis of electrical conduction in hybrid nanomaterials with embedded non-penetrating conductive particles

NASA Astrophysics Data System (ADS)

Cai, Jizhe; Naraghi, Mohammad

2016-08-01

In this work, a comprehensive multi-resolution two-dimensional (2D) resistor network model is proposed to analyze the electrical conductivity of hybrid nanomaterials made of insulating matrix with conductive particles such as CNT reinforced nanocomposites and thick film resistors. Unlike existing approaches, our model takes into account the impenetrability of the particles and their random placement within the matrix. Moreover, our model presents a detailed description of intra-particle conductivity via finite element analysis, which to the authors’ best knowledge has not been addressed before. The inter-particle conductivity is assumed to be primarily due to electron tunneling. The model is then used to predict the electrical conductivity of electrospun carbon nanofibers as a function of microstructural parameters such as turbostratic domain alignment and aspect ratio. To simulate the microstructure of single CNF, randomly positioned nucleation sites were seeded and grown as turbostratic particles with anisotropic growth rates. Particle growth was in steps and growth of each particle in each direction was stopped upon contact with other particles. The study points to the significant contribution of both intra-particle and inter-particle conductivity to the overall conductivity of hybrid composites. Influence of particle alignment and anisotropic growth rate ratio on electrical conductivity is also discussed. The results show that partial alignment in contrast to complete alignment can result in maximum electrical conductivity of whole CNF. High degrees of alignment can adversely affect conductivity by lowering the probability of the formation of a conductive path. The results demonstrate approaches to enhance electrical conductivity of hybrid materials through controlling their microstructure which is applicable not only to carbon nanofibers, but also many other types of hybrid composites such as thick film resistors.

Discrete element analysis of the mechanical properties of deep-sea methane hydrate-bearing soils considering interparticle bond thickness

NASA Astrophysics Data System (ADS)

Jiang, Mingjing; He, Jie; Wang, Jianfeng; Zhou, Yaping; Zhu, Fangyuan

2017-12-01

Due to increasing global energy demands, research is being conducted on the mechanical properties of methane hydrate-bearing soils (MHBSs), from which methane hydrate (MH) will be explored. This paper presents a numerical approach to study the mechanical properties of MHBSs. The relationship between the level of MH saturation and the interparticle bond thickness is first obtained by analyzing the scanning electron microscope images of MHBS samples, in which is the bridge connecting the micromechanical behavior captured by the DEM with the macroscopic properties of MHBSs. A simplified thermal-hydromechanical (THM) bond model that considers the different bond thicknesses is then proposed to describe the contact behavior between the soil particles and those incorporated into the discrete element method (DEM). Finally, a series of biaxial compression tests are carried out with different MH saturations under different effective confining pressures to analyze the mechanical properties of deep-sea MHBSs. The results of the DEM numerical simulation are also compared with the findings from triaxial compression tests. The results show that the macromechanical properties of deep-sea MHBSs can be qualitatively captured by the proposed DEM. The shear strength, cohesion, and volumetric contraction of deep-sea MHBSs increase with increasing MH saturation, although its influence on the internal friction angle is obscure. The shear strength and volumetric contraction increase with increasing effective confining pressure. The peak shear strength and the dilation of MHBSs increase as the critical bond thickness increases, while the residual deviator stress largely remains the same at a larger axial strain. With increasing the axial strain, the percentage of broken bonds increases, along with the expansion of the shear band.

Simulation of deterministic energy-balance particle agglomeration in turbulent liquid-solid flows

NASA Astrophysics Data System (ADS)

Njobuenwu, Derrick O.; Fairweather, Michael

2017-08-01

An efficient technique to simulate turbulent particle-laden flow at high mass loadings within the four-way coupled simulation regime is presented. The technique implements large-eddy simulation, discrete particle simulation, a deterministic treatment of inter-particle collisions, and an energy-balanced particle agglomeration model. The algorithm to detect inter-particle collisions is such that the computational costs scale linearly with the number of particles present in the computational domain. On detection of a collision, particle agglomeration is tested based on the pre-collision kinetic energy, restitution coefficient, and van der Waals' interactions. The performance of the technique developed is tested by performing parametric studies on the influence of the restitution coefficient (en = 0.2, 0.4, 0.6, and 0.8), particle size (dp = 60, 120, 200, and 316 μm), Reynolds number (Reτ = 150, 300, and 590), and particle concentration (αp = 5.0 × 10-4, 1.0 × 10-3, and 5.0 × 10-3) on particle-particle interaction events (collision and agglomeration). The results demonstrate that the collision frequency shows a linear dependency on the restitution coefficient, while the agglomeration rate shows an inverse dependence. Collisions among smaller particles are more frequent and efficient in forming agglomerates than those of coarser particles. The particle-particle interaction events show a strong dependency on the shear Reynolds number Reτ, while increasing the particle concentration effectively enhances particle collision and agglomeration whilst having only a minor influence on the agglomeration rate. Overall, the sensitivity of the particle-particle interaction events to the selected simulation parameters is found to influence the population and distribution of the primary particles and agglomerates formed.

The mechanisms of dispersion strengthening and fracture in Al-based XD(tm) alloys, part 1

NASA Technical Reports Server (NTRS)

Aikin, R. M., Jr.

1990-01-01

The influence of reinforcement size, volume fraction, and matrix deformation behavior on room and elevated temperature strength; the fracture toughness; and the fatigue crack growth rate of metal matrix composites of Al-4(pct)Cu-1.5(pct)Mg with TiB2 were examined. The influence of reinforcement volume fraction was also examined for pure aluminum with TiB2. Higher TiB2 volume fractions increased the tensile yield strength at both room and elevated temperatures, and reduced the elongation to fracture. Tensile tests also indicate that small particles provided a greater increase in strength for a given volume fraction than larger particles, whereas elongation to fracture appeared to be insensitive to reinforcement size. Interparticle spacing appears to be the factor that controls the strength of these alloys, with the exact nature of the dependence relying on the nature of dislocation slip in the matrix (planar vs. diffuse). The isothermal aging response of the precipitation strengthened Al-4(pct)Cu-1.5(pct)Mg alloys was not accelerated by the presence of TiB2. Cold work prior to artificial aging created additional geometrically necessary dislocations which serve as heterogeneous nucleation sites leading to accelerated aging, a finer precipitate size, and an increase in the strength of the alloy.

Theory of tailorable optical response of two-dimensional arrays of plasmonic nanoparticles at dielectric interfaces.

PubMed

Sikdar, Debabrata; Kornyshev, Alexei A

2016-09-22

Two-dimensional arrays of plasmonic nanoparticles at interfaces are promising candidates for novel optical metamaterials. Such systems materialise from 'top-down' patterning or 'bottom-up' self-assembly of nanoparticles at liquid/liquid or liquid/solid interfaces. Here, we present a comprehensive analysis of an extended effective quasi-static four-layer-stack model for the description of plasmon-resonance-enhanced optical responses of such systems. We investigate in detail the effects of the size of nanoparticles, average interparticle separation, dielectric constants of the media constituting the interface, and the nanoparticle position relative to the interface. Interesting interplays of these different factors are explored first for normally incident light. For off-normal incidence, the strong effects of the polarisation of light are found at large incident angles, which allows to dynamically tune the reflectance spectra. All the predictions of the theory are tested against full-wave simulations, proving this simplistic model to be adequate within the quasi-static limit. The model takes seconds to calculate the system's optical response and makes it easy to unravel the effect of each system parameter. This helps rapid rationalization of experimental data and understanding of the optical signals from these novel 'metamaterials', optimised for light reflection or harvesting.

Theory of tailorable optical response of two-dimensional arrays of plasmonic nanoparticles at dielectric interfaces

PubMed Central

Sikdar, Debabrata; Kornyshev, Alexei A.

2016-01-01

Two-dimensional arrays of plasmonic nanoparticles at interfaces are promising candidates for novel optical metamaterials. Such systems materialise from ‘top–down’ patterning or ‘bottom–up’ self-assembly of nanoparticles at liquid/liquid or liquid/solid interfaces. Here, we present a comprehensive analysis of an extended effective quasi-static four-layer-stack model for the description of plasmon-resonance-enhanced optical responses of such systems. We investigate in detail the effects of the size of nanoparticles, average interparticle separation, dielectric constants of the media constituting the interface, and the nanoparticle position relative to the interface. Interesting interplays of these different factors are explored first for normally incident light. For off-normal incidence, the strong effects of the polarisation of light are found at large incident angles, which allows to dynamically tune the reflectance spectra. All the predictions of the theory are tested against full-wave simulations, proving this simplistic model to be adequate within the quasi-static limit. The model takes seconds to calculate the system’s optical response and makes it easy to unravel the effect of each system parameter. This helps rapid rationalization of experimental data and understanding of the optical signals from these novel ‘metamaterials’, optimised for light reflection or harvesting. PMID:27652788

Parametric optimisation of heat treated recycling aluminium (AA6061) by response surface methodology

NASA Astrophysics Data System (ADS)

Ahmad, A.; Lajis, M. A.; Yusuf, N. K.; Shamsudin, S.; Zhong, Z. W.

2017-09-01

Alternating typical primary aluminium production with recycling route should benefit various parties, including the environment since the need of high cost and massive energy consumption will be ruled out. At present, hot extrusion is preferred as the effective solid-state recycling process compared to the typical method of melting the swarf at high temperature. However, the ideal properties of extruded product can only be achieved through a controlled process used to alter the microstructure to impart properties which benefit the working life of a component, which also known as heat treatment process. To that extent, this work ought to investigate the effect of extrusion temperature and ageing time on the hardness of the recycled aluminium chips. By employing Analysis of Variance (ANOVA) for full factorial design with centre point, a total of 11 runs were carried out randomly. Three dissimilar extrusion temperatures were used to obtain gear-shape billet. Extruded billets were cut and ground before entering the treatment phase at three different ageing times. Ageing time was found as the influential factor to affect the material hardness, rather than the extrusion temperature. Sufficient ageing time allows the impurity atoms to interfere the dislocation phenomena and yield great hardness. Yet, the extrusion temperatures still act to assist the bonding activities via interparticle diffusion transport matter.

Theoretical Studies of Strongly Interacting Fine Particle Systems

NASA Astrophysics Data System (ADS)

Fearon, Michael

Available from UMI in association with The British Library. A theoretical analysis of the time dependent behaviour of a system of fine magnetic particles as a function of applied field and temperature was carried out. The model used was based on a theory assuming Neel relaxation with a distribution of particle sizes. This theory predicted a linear variation of S_{max} with temperature and a finite intercept, which is not reflected by experimental observations. The remanence curves of strongly interacting fine-particle systems were also investigated theoretically. It was shown that the Henkel plot of the dc demagnetisation remanence vs the isothermal remanence is a useful representation of interactions. The form of the plot was found to be a reflection of the magnetic and physical microstructure of the material, which is consistent with experimental data. The relationship between the Henkel plot and the noise of a particulate recording medium, another property dependent on the microstructure, is also considered. The Interaction Field Factor (IFF), a single parameter characterising the non-linearity of the Henkel plot, is investigated. These results are consistent with a previous experimental study. Finally the results of the noise power spectral density for erased and saturated recording media are presented, so that characterisation of interparticle interactions may be carried out with greater accuracy.

Plasmonic refractive index sensing using strongly coupled metal nanoantennas: nonlocal limitations.

PubMed

Wang, Hancong

2018-06-25

Localized surface plasmon resonance based on coupled metallic nanoparticles has been extensively studied in the refractive index sensing and the detection of molecules. The amount of resonance peak-shift depends on the refractive index of surrounding medium and the geometry/symmetry of plasmonic oligomers. It has recently been found that as the feature size or the gap distance of plasmonic nanostructures approaches several nanometers, quantum effects can change the plasmon coupling in nanoparticles. However, most of the research on plasmonic sensing has been done based on classical local calculations even for the interparticle gap below ~3 nm, in which the nonlocal screening plays an important role. Here, we theoretically investigate the nonlocal effect on the evolution of various plasmon resonance modes in strongly coupled nanoparticle dimer and trimer antennas with the gap down to 1 nm. Then, the refractive index sensing in these nonlocal systems is evaluated and compared with the results in classical calculations. We find that in the nonlocal regime, both refractive index sensibility factor and figure of merit are actually smaller than their classical counterparts mainly due to the saturation of plasmon shifts. These results would be beneficial for the understanding of interaction between light and nonlocal plasmonic nanostructures and the development of plasmonic devices such as nanosensors and nanoantennas.

The effect of Y3+ substitution on the structural, optical band-gap, and magnetic properties of cobalt ferrite nanoparticles.

PubMed

Alves, T E P; Pessoni, H V S; Franco, A

2017-06-28

In this study we investigated the structural, optical band-gap, and magnetic properties of CoY x Fe 2-x O 4 (0 ≤ x ≤ 0.04) nanoparticles (NPs) synthesized using a combustion reaction method without the need for subsequent heat treatment or the calcing process. The particle size measured from X-ray diffraction (XRD) patterns and transmission electron microscope (TEM) images confirms the nanostructural character in the range of 16-36 nm. The optical band-gap (E g ) values increase with the Y 3+ ion (x) concentration being 3.30 and 3.58 eV for x = 0 and x = 0.04, respectively. The presence of yttrium in the cobalt ferrite (Y-doped cobalt ferrite) structure affects the magnetic properties. For instance, the saturation magnetization, M s and remanent magnetization, M r , decrease from 69 emu g -1 to 33 and 28 to 12 emu g -1 for x = 0 and x = 0.04, respectively. On the other hand the coercivity, H c , increases from 1100 to 1900 Oe for x = 0 and x = 0.04 at room temperature. Also we found that M s , M r , and H c decreased with increasing temperature up to 773 K. The cubic magnetocrystalline constant, K 1 , determined by using the "law of approach" (LA) to saturation decreases with Y 3+ ion concentration and temperature. K 1 values for x = 0 (x = 0.04) were 3.3 × 10 6 erg cm -3 (2.0 × 10 6 erg cm -3 ) and 0.4 × 10 6 erg cm -3 (0.3 × 10 6 erg cm -3 ) at 300 K and 773 K, respectively. The results were discussed in terms of inter-particle interactions induced by thermal fluctuations, and Co 2+ ion distribution over tetrahedral A-sites and octahedral B-sites of the spinel structure due to Y 3+ ion substitution.

Analysis of Gas-Particle Flows through Multi-Scale Simulations

NASA Astrophysics Data System (ADS)

Gu, Yile

Multi-scale structures are inherent in gas-solid flows, which render the modeling efforts challenging. On one hand, detailed simulations where the fine structures are resolved and particle properties can be directly specified can account for complex flow behaviors, but they are too computationally expensive to apply for larger systems. On the other hand, coarse-grained simulations demand much less computations but they necessitate constitutive models which are often not readily available for given particle properties. The present study focuses on addressing this issue, as it seeks to provide a general framework through which one can obtain the required constitutive models from detailed simulations. To demonstrate the viability of this general framework in which closures can be proposed for different particle properties, we focus on the van der Waals force of interaction between particles. We start with Computational Fluid Dynamics (CFD) - Discrete Element Method (DEM) simulations where the fine structures are resolved and van der Waals force between particles can be directly specified, and obtain closures for stress and drag that are required for coarse-grained simulations. Specifically, we develop a new cohesion model that appropriately accounts for van der Waals force between particles to be used for CFD-DEM simulations. We then validate this cohesion model and the CFD-DEM approach by showing that it can qualitatively capture experimental results where the addition of small particles to gas fluidization reduces bubble sizes. Based on the DEM and CFD-DEM simulation results, we propose stress models that account for the van der Waals force between particles. Finally, we apply machine learning, specifically neural networks, to obtain a drag model that captures the effects from fine structures and inter-particle cohesion. We show that this novel approach using neural networks, which can be readily applied for other closures other than drag here, can take advantage of the large amount of data generated from simulations, and therefore offer superior modeling performance over traditional approaches.

Clustering and heterogeneous dynamics in a kinetic Monte Carlo model of self-propelled hard disks

NASA Astrophysics Data System (ADS)

Levis, Demian; Berthier, Ludovic

2014-06-01

We introduce a kinetic Monte Carlo model for self-propelled hard disks to capture with minimal ingredients the interplay between thermal fluctuations, excluded volume, and self-propulsion in large assemblies of active particles. We analyze in detail the resulting (density, self-propulsion) nonequilibrium phase diagram over a broad range of parameters. We find that purely repulsive hard disks spontaneously aggregate into fractal clusters as self-propulsion is increased and rationalize the evolution of the average cluster size by developing a kinetic model of reversible aggregation. As density is increased, the nonequilibrium clusters percolate to form a ramified structure reminiscent of a physical gel. We show that the addition of a finite amount of noise is needed to trigger a nonequilibrium phase separation, showing that demixing in active Brownian particles results from a delicate balance between noise, interparticle interactions, and self-propulsion. We show that self-propulsion has a profound influence on the dynamics of the active fluid. We find that the diffusion constant has a nonmonotonic behavior as self-propulsion is increased at finite density and that activity produces strong deviations from Fickian diffusion that persist over large time scales and length scales, suggesting that systems of active particles generically behave as dynamically heterogeneous systems.

Complex Plasma Physics and Rising Above the Gathering Storm

NASA Astrophysics Data System (ADS)

Hyde, Truell

2008-11-01

Research in complex plasma is prevalent across a variety of regimes ranging from the majority of plasma processing environments to many astrophysical settings. Dust particles suspended within such plasmas acquire a charge from collisions with electrons and ions in the plasma. Depending upon the ratio of their interparticle potential energy to their average kinetic energy, once charged these particles can form a gaseous, liquid or crystalline structure with short to longer range ordering. The field of complex plasmas thus offers research opportunities across a wide range of academic disciplines including physics, chemistry, biology, mathematics, electrical engineering and nanoscience. The field of complex plasmas also offers unique educational research opportunities for combating many of the issues raised in Rising Above the Gathering Storm, recently published by the National Academies Press. CASPER's Educational Outreach programs, supported by the National Science Foundation, the Department of Education and the Department of Labor takes advantage of these opportunities through a variety of avenues including a REU / RET program, a High School Scholars Program, integrated curriculum development and the CASPER Physics Circus. Together, these programs impact thousands of students and parents while providing K-12 teachers with curriculum, supporting hands-on material and support for introducing plasma and basic physical science concepts into the classroom. Both research results and educational outreach concepts from the above will be discussed.

Engineered disorder and light propagation in a planar photonic glass

PubMed Central

Romanov, Sergei G.; Orlov, Sergej; Ploss, Daniel; Weiss, Clemens K.; Vogel, Nicolas; Peschel, Ulf

2016-01-01

The interaction of light with matter strongly depends on the structure of the latter at wavelength scale. Ordered systems interact with light via collective modes, giving rise to diffraction. In contrast, completely disordered systems are dominated by Mie resonances of individual particles and random scattering. However, less clear is the transition regime in between these two extremes, where diffraction, Mie resonances and near-field interaction between individual scatterers interplay. Here, we probe this transitional regime by creating colloidal crystals with controlled disorder from two-dimensional self-assembly of bidisperse spheres. Choosing the particle size in a way that the small particles are transparent in the spectral region of interest enables us to probe in detail the effect of increasing positional disorder on the optical properties of the large spheres. With increasing disorder a transition from a collective optical response characterized by diffractive resonances to single particles scattering represented by Mie resonances occurs. In between these extremes, we identify an intermediate, hopping-like light transport regime mediated by resonant interactions between individual spheres. These results suggest that different levels of disorder, characterized not only by absence of long range order but also by differences in short-range correlation and interparticle distance, exist in colloidal glasses. PMID:27277521

Dynamics of a suspension of interacting yolk-shell particles

DOE PAGES

Sánchez Díaz, L. E.; Cortes-Morales, E. C.; Li, X.; ...

2014-12-01

In this work we study the self-diusion properties of a liquid of hollow spherical particles (shells) bearing a smaller solid sphere in their interior (yolks). We model this system using purely repulsive hard-body interactions between all (shell and yolk) particles, but assume the presence of a background ideal solvent such that all the particles execute free Brownian motion between collisions, characterized by short-time self-diusion coecients D0 s for the shells and D0 y for the yolks. Using a softened version of these interparticle potentials we perform Brownian dynamics simulations to determine the mean squared displacement and intermediate scattering function ofmore » the yolk-shell complex. These results can be understood in terms of a set of eective Langevin equations for the N interacting shell particles, pre-averaged over the yolks' degrees of freedom, from which an approximate self-consistent description of the simulated self-diusion properties can be derived. Here we compare the theoretical and simulated results between them, and with the results for the same system in the absence of yolks. We nd that the yolks, which have no eect on the shell-shell static structure, in uence the dynamic properties in a predictable manner, fully captured by the theory.« less

Correlational approach to study interactions between dust Brownian particles in a plasma

NASA Astrophysics Data System (ADS)

Lisin, E. A.; Vaulina, O. S.; Petrov, O. F.

2018-01-01

A general approach to the correlational analysis of Brownian motion of strongly coupled particles in open dissipative systems is described. This approach can be applied to the theoretical description of various non-ideal statistically equilibrium systems (including non-Hamiltonian systems), as well as for the analysis of experimental data. In this paper, we consider an application of the correlational approach to the problem of experimental exploring the wake-mediated nonreciprocal interactions in complex plasmas. We derive simple analytic equations, which allows one to calculate the gradients of forces acting on a microparticle due to each of other particles as well as the gradients of external field, knowing only the information on time-averaged correlations of particles displacements and velocities. We show the importance of taking dissipative and random processes into account, without which consideration of a system with a nonreciprocal interparticle interaction as linearly coupled oscillators leads to significant errors in determining the characteristic frequencies in a system. In the examples of numerical simulations, we demonstrate that the proposed original approach could be an effective instrument in exploring the longitudinal wake structure of a microparticle in a plasma. Unlike the previous attempts to study the wake-mediated interactions in complex plasmas, our method does not require any external perturbations and is based on Brownian motion analysis only.

Erasing no-man's land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles.

PubMed

Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

2014-09-01

One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point [1] located in the "no-man's land" [2]. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, since spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water [3, 4]. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon [5], carbon [6] and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

General and Direct Method for Preparing Oligonucleotide-Functionalized Metal-Organic Framework Nanoparticles.

PubMed

Wang, Shunzhi; McGuirk, C Michael; Ross, Michael B; Wang, Shuya; Chen, Pengcheng; Xing, Hang; Liu, Yuan; Mirkin, Chad A

2017-07-26

Metal-organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactions of DNA, 11 distinct MOF particle-inorganic particle core-satellite clusters were synthesized. In these hybrid nanoclusters, the relative stoichiometry, size, shape, and composition of the building blocks can all be independently controlled. This work provides access to a new set of nucleic acid-nanoparticle conjugates, which may be useful as programmable material building blocks and as probes for measuring and manipulating intracellular processes.

The synthesis of high yield Au nanoplate and optimized optical properties

NASA Astrophysics Data System (ADS)

Ni, Yuan; Kan, Caixia; Xu, Juan; Liu, Yang

2018-02-01

The applications of Au nanoplates based on the tunable plasmon properties and enhanced electromagnetic field at the sharp tip and straight edges, have generated a great deal of interest in recent years, especially in the fields of the bio-chemical sensing and imaging. In this review, we focus on the synthesis of nanoscale platelike structures by multiple synthetic strategies (such as thermal solution method, seed-mediated method, seedless method, and some greener methods), and explore corresponding growth mechanism in different synthetic approaches. Other than to review the fabrication of Au nanoplates, the purification strategies are also discussed in order to support the applications in various fields. Modifying synthetic method to obtain well-defined nanoplates can tuned optical absorption from visible to near-infrared region. Moreover, the Au nanoplate dimers (vertex-to-vertex and edge-by-edge assemblies) can induce more specific plasmon properties and stronger localized field due to coupling of interparticles. Compared with 0D quasi-spherical nanoparticles and 1D nanorods, the 2D nanoplates can be applied as a good surface-enhanced Raman scattering (SERS) substrate because of the sharp corners and straight edges. This review will provide background information for the controllable synthesis of anisotropic nanoparticles and advance the application of coupled nanostructures.

Coupling of in-situ X-ray Microtomography Observations with Discrete Element Simulations-Application to Powder Sintering

NASA Astrophysics Data System (ADS)

Olmos, L.; Bouvard, D.; Martin, C. L.; Bellet, D.; Di Michiel, M.

2009-06-01

The sintering of both a powder with a wide particle size distribution (0-63 μm) and of a powder with artificially created pores is investigated by coupling in situ X-ray microtomography observations with Discrete Element simulations. The micro structure evolution of the copper particles is observed by microtomography all along a typical sintering cycle at 1050° C at the European Synchrotron Research Facilities (ESRF, Grenoble, France). A quantitative analysis of the 3D images provides original data on interparticle indentation, coordination and particle displacements throughout sintering. In parallel, the sintering of similar powder systems has been simulated with a discrete element code which incorporates appropriate sintering contact laws from the literature. The initial numerical packing is generated directly from the 3D microtomography images or alternatively from a random set of particles with the same size distribution. The comparison between the information drawn from the simulations and the one obtained by tomography leads to the conclusion that the first method is not satisfactory because real particles are not perfectly spherical as the numerical ones. On the opposite the packings built with the second method show sintering behaviors close to the behaviors of real materials, although particle rearrangement is underestimated by DEM simulations.

Nonlinear chiro-optical amplification by plasmonic nanolens arrays formed via directed assembly of gold nanoparticles.

PubMed

Biswas, Sushmita; Liu, Xiaoying; Jarrett, Jeremy W; Brown, Dean; Pustovit, Vitaliy; Urbas, Augustine; Knappenberger, Kenneth L; Nealey, Paul F; Vaia, Richard A

2015-03-11

Metal nanoparticle assemblies are promising materials for nanophotonic applications due to novel linear and nonlinear optical properties arising from their plasmon modes. However, scalable fabrication approaches that provide both precision nano- and macroarchitectures, and performance commensurate with design and model predictions, have been limiting. Herein, we demonstrate controlled and efficient nanofocusing of the fundamental and second harmonic frequencies of incident linearly and circularly polarized light using reduced symmetry gold nanoparticle dimers formed by surface-directed assembly of colloidal nanoparticles. Large ordered arrays (>100) of these C∞v heterodimers (ratio of radii R1/R2 = 150 nm/50 nm = 3; gap distance l = 1 ± 0.5 nm) exhibit second harmonic generation and structure-dependent chiro-optic activity with the circular dichroism ratio of individual heterodimers varying less than 20% across the array, demonstrating precision and uniformity at a large scale. These nonlinear optical properties were mediated by interparticle plasmon coupling. Additionally, the versatility of the fabrication is demonstrated on a variety of substrates including flexible polymers. Numerical simulations guide architecture design as well as validating the experimental results, thus confirming the ability to optimize second harmonic yield and induce chiro-optical responses for compact sensors, optical modulators, and tunable light sources by rational design and fabrication of the nanostructures.

Simulation of Electromigration Based on Resistor Networks

NASA Astrophysics Data System (ADS)

Patrinos, Anthony John

A two dimensional computer simulation of electromigration based on resistor networks was designed and implemented. The model utilizes a realistic grain structure generated by the Monte Carlo method and takes specific account of the local effects through which electromigration damage progresses. The dynamic evolution of the simulated thin film is governed by the local current and temperature distributions. The current distribution is calculated by superimposing a two dimensional electrical network on the lattice whose nodes correspond to the particles in the lattice and the branches to interparticle bonds. Current is assumed to flow from site to site via nearest neighbor bonds. The current distribution problem is solved by applying Kirchhoff's rules on the resulting electrical network. The calculation of the temperature distribution in the lattice proceeds by discretizing the partial differential equation for heat conduction, with appropriate material parameters chosen for the lattice and its defects. SEReNe (for Simulation of Electromigration using Resistor Networks) was tested by applying it to common situations arising in experiments with real films with satisfactory results. Specifically, the model successfully reproduces the expected grain size, line width and bamboo effects, the lognormal failure time distribution and the relationship between current density exponent and current density. It has also been modified to simulate temperature ramp experiments but with mixed, in this case, results.

Collision energy dependence of the reactions of metastable neon with small molecules

NASA Astrophysics Data System (ADS)

Noroski, Joseph H.

The reaction dynamics of Ne* (2p53 s 3P2, 3 P0) + X → [NeX]+ + e- (X = H2, CO, N2, NO, O2, CO 2, and C2H2) were studied with supersonic beams at various collision energies (E) via electron spectroscopy. Increasing E decreases the interparticle distance at which ionization occurs, allowing for exploration of the reaction potential energy surfaces via the kinetic energy epsilon of the ejected electron. Data were fit to give vibrational populations and line shifts (Deltaepsilons ), the difference between the excitation energy of Ne* and the vibronic energy of the target molecules, where vibronic excitation is due to Ne*. The resulting populations were compared to calculated or experimental Franck-Condon factors (FCfs), and vibrational progressions were identified. Deviation from Franck-Condon (FC) behavior was observed in all cases except for C2H 2, and all spectra at all E showed a blue shift except CO2. With increasing E, Deltaepsilons for H2 +, CO+, and N2 + increased with increasing E, while Deltaepsilon s decreased for NO+ and C2H2 +. The CO2+ spectra revealed a nearly constant red shift for the lowest three E and a blue shift for the highest E. O2+ showed a very small blue shift, but the O2+ populations were not determined due to an underlying continuum. Penning, excitation transfer, and ion-pair mechanisms are the most widely accepted for the reactions of metastable atoms. The closed-shell structure of H2, CO, and N2 and the large, increasing Deltaepsilon s suggest that their Ne* reactions proceed via the Penning mechanism. The open-shell structure of NO and its decreasing Deltaepsilons indicates changing dynamics and possibly also competition between all three mechanisms for Ne* + NO. The very small Deltaepsilons for O 2+ implies the excitation transfer mechanism for Ne* + O2. Ne* reactions with CO2 and C2H 2 both exhibited constant Deltaepsilons values for more than one E. This suggests that an excitation transfer mechanism is at work in these systems, but changes in Deltaepsilons at other E indicate that competing mechanisms may also be relevant. Lastly, a retrospective on authoring a solutions manual for a freshman chemistry textbook is offered.

Quantum confinement of a hydrogenic donor in a double quantum well: Through diamagnetic susceptibility

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

Vignesh, G.; Nithiananthi, P., E-mail: nithyauniq@gmail.com

2015-06-24

Diamagnetic susceptibility of a randomly distributed donor in a GaAs/Al{sub 0.3}Ga{sub 0.7}As Double Quantum Well has been calculated in its ground state as a function of barrier and well width. It is shown that the modification in the barrier and well dimension significantly influences the dimensional character of the donor through modulating the subband distribution and in turn the localization of the donor. The effect of barrier and well thickness on the interparticle distance has also been observed. Interestingly it opens up the possibility of tuning the susceptibility and monitoring the tunnel coupling among the wells.

Quantum confinement of a hydrogenic donor in a double quantum well: Through diamagnetic susceptibility

NASA Astrophysics Data System (ADS)

Vignesh, G.; Nithiananthi, P.

2015-06-01

Diamagnetic susceptibility of a randomly distributed donor in a GaAs/Al0.3Ga0.7As Double Quantum Well has been calculated in its ground state as a function of barrier and well width. It is shown that the modification in the barrier and well dimension significantly influences the dimensional character of the donor through modulating the subband distribution and in turn the localization of the donor. The effect of barrier and well thickness on the interparticle distance has also been observed. Interestingly it opens up the possibility of tuning the susceptibility and monitoring the tunnel coupling among the wells.