Unexpected drop of dynamical heterogeneities in colloidal suspensions approaching the jamming transition

As the glass (in molecular fluids\cite{Donth}) or the jamming (in colloids and grains\cite{LiuNature1998}) transitions are approached, the dynamics slow down dramatically with no marked structural changes. Dynamical heterogeneity (DH) plays a crucial role: structural relaxation occurs through correlated rearrangements of particle ``blobs'' of size $\xi$\cite{WeeksScience2000,DauchotPRL2005,Glotzer,Ediger}. On approaching these transitions, $\xi$ grows in glass-formers\cite{Glotzer,Ediger}, colloids\cite{WeeksScience2000,BerthierScience2005}, and driven granular materials\cite{KeysNaturePhys2007} alike, strengthening the analogies between the glass and the jamming transitions. However, little is known yet on the behavior of DH very close to dynamical arrest. Here, we measure in colloids the maximum of a ``dynamical susceptibility'', $\chi^*$, whose growth is usually associated to that of $\xi$\cite{LacevicPRE}. $\chi^*$ initially increases with volume fraction $\phi$, as in\cite{KeysNaturePhys2007}, but strikingly drops dramatically very close to jamming. We show that this unexpected behavior results from the competition between the growth of $\xi$ and the reduced particle displacements associated with rearrangements in very dense suspensions, unveiling a richer-than-expected scenario.Comment: 1st version originally submitted to Nature Physics. See the Nature Physics website fro the final, published versio

Local influence of boundary conditions on a confined supercooled colloidal liquid

We study confined colloidal suspensions as a model system which approximates the behavior of confined small molecule glass-formers. Dense colloidal suspensions become glassier when confined between parallel glass plates. We use confocal microscopy to study the motion of confined colloidal particles. In particular, we examine the influence particles stuck to the glass plates have on nearby free particles. Confinement appears to be the primary influence slowing free particle motion, and proximity to stuck particles causes a secondary reduction in the mobility of free particles. Overall, particle mobility is fairly constant across the width of the sample chamber, but a strong asymmetry in boundary conditions results in a slight gradient of particle mobility.Comment: For conference proceedings, "Dynamics in Confinement", Grenoble, March 201

Well dispersed fractal aggregates as filler in polymer-silica nanocomposites: long range effects in rheology

We are presenting a new method of processing polystyrene-silica nanocomposites, which results in a very well-defined dispersion of small primary aggregates (assembly of 15 nanoparticles of 10 nm diameter) in the matrix. The process is based on a high boiling point solvent, in which the nanoparticles are well dispersed, and controlled evaporation. The filler's fine network structure is determined over a wide range of sizes, using a combination of Small Angle Neutron Scattering (SANS) and Transmission Electronic Microscopy (TEM). The mechanical response of the nanocomposite material is investigated both for small (ARES oscillatory shear and Dynamical Mechanical Analysis) and large deformations (uniaxial traction), as a function of the concentration of the particles. We can investigate the structure-property correlations for the two main reinforcement effects: the filler network contribution, and a filler-polymer matrix effect. Above a silica volume fraction threshold, we see a divergence of the modulus correlated to the build up of a connected network. Below the threshold, we obtain a new additional elastic contribution of much longer terminal time than the matrix. Since aggregates are separated by at least 60 nm, this new filler-matrix contribution cannot be described solely with the concept of glassy layer (2nm)

The Effect of TiO2 on the Electrochemical Performance of Sb2O3 Anodes for Li-Ion Batteries

Antimony (Sb) and its composites have been recognized as potentially good anode materials for lithium-ion batteries (LIBs) due to their relatively high theoretical capacity of 660 mAh g−1 and to their low cost. However, Sb-based anodes suffer from a high-volume change during the lithiation/delithiation process that results in capacity fading and anode degradation after prolonged charge/discharge cycles. To address this issue, Sb2O3/TiO2 nanocomposite electrodes can be synthesized and used as anodes for LIBs with high capacity and good electrochemical stability. In the present work, TiO2@Sb2O3 composites with different (TiO2:Sb2O3) ratios of 0:1, 1:1, 1:4 and 3:1 were synthesized and directly used as anode materials for LIBs. The electrochemical performance of the TiO2/Sb2O3 composite anode with different ratios of TiO2 to Sb2O3 was evaluated by galvanostatic charge/discharge, rate performance and cyclic voltammetry. The 3:1 (TiO2:Sb2O3) composite anode delivered the highest capacity compared to those of the TiO2, SbO3, 1:1 (TiO2:Sb2O3) and 1:4 (TiO2:Sb2O3) electrodes. The TiO2@Sb2O3 composite anode with a 3:1 ratio exhibited a stabilized capacity of 536 mAh g−1 after 100 cycles at 100 mA g−1 and showed excellent rate performance, with current densities between 50 and 500 mA g−1. The improved electrochemical performance was attributed to the synergistic effect of TiO2 (i.e., the coating of Sb2O3 with TiO2) on reducing the volume change of the Sb anode material after prolonged charge/discharge cycles and on maintaining a stable interface between the electrolyte and the composite electrode material

The Physics of the Colloidal Glass Transition

As one increases the concentration of a colloidal suspension, the system exhibits a dramatic increase in viscosity. Structurally, the system resembles a liquid, yet motions within the suspension are slow enough that it can be considered essentially frozen. This kinetic arrest is the colloidal glass transition. For several decades, colloids have served as a valuable model system for understanding the glass transition in molecular systems. The spatial and temporal scales involved allow these systems to be studied by a wide variety of experimental techniques. The focus of this review is the current state of understanding of the colloidal glass transition. A brief introduction is given to important experimental techniques used to study the glass transition in colloids. We describe features of colloidal systems near and in glassy states, including tremendous increases in viscosity and relaxation times, dynamical heterogeneity, and ageing, among others. We also compare and contrast the glass transition in colloids to that in molecular liquids. Other glassy systems are briefly discussed, as well as recently developed synthesis techniques that will keep these systems rich with interesting physics for years to come.Comment: 56 pages, 18 figures, Revie

Spectroscopic investigations on PVDF-Fe2O3 nanocomposites

Polyvinylidene fluoride-iron oxide (PVDF-Fe2O3) nanocomposites have been obtained my melt mixing of PVDF with Fe2O3 nanoparticles. The interactions between the polymeric matrix and the nanofiller have been investigated by wide angle X-ray scattering (WAXS), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, using both red and green excitations (lasers). WAXS, FTIR, and Raman spectra confirm that all samples contain α PVDF as the major crystalline form of the polymeric matrix. Experimental data revealed small changes in the positions of X-ray lines as well as modifications of the width of X-ray lines upon loading by Fe2O3 nanoparticles. FTIR and Raman spectra are dominated by the lines of the polymeric matrix. Within the experimental errors, the positions of Raman lines are not affected by the wavelength of the incoming electromagnetic radiation, although they are sensitive to the strain of the polymeric matrix induced by addition of the nanofiller. The loading of the polymeric matrix with nanoparticles stretches the macromolecular chains, affecting their vibrational spectra (FTIR and Raman). A complex dependence of the positions of some Raman and FTIR lines on the loading with Fe2O3 is reported. The manuscript provides a detailed analysis of the effects of nanofiller on the position of WAXS, FTIR, and Raman lines

Centrifugal spinning and characterization of CO3O4 coated carbon fibers

Centrifugally spun polyacrylonitrile (PAN) microfibers surface-coated with Co3O4 nanoparticles (NPs) were prepared as precursors to produce coated Co3O4 carbon-composite fibers. The Co3O4/C composite fibers were obtained through a staged heating process during which the Co3O4PAN precursor fibers were stabilized over four hours at 200 °C, and subsequently the stabilized fibers were carbonized for six hours at 600 °C. The synthesis process presented in this work provides an effective strategy for the fabrication of surface coated-fiber materials, including composite fibers with good structure and morphology. The characterization of the Co3O4/C composite fibers was performed using SEM, EDS, XPS, XRD and BET. The SEM data indicated the fibers were micron-sized in diameter with a non-homogenous distribution of the Co3O4 NPs on both the Co3O4-PAN and the CO3O4-Carbon composite fibers. The EDS mapping of the cobalt showed it to be distributed throughout the samples on the surface, but areas of high concentrations of particles were observed. The powder XRD data showed a reduction of the Co(III)/Co(II) starting material into a combination of Co-metal and CoO. The XRD results were confirmed by the Co 2P XPS data, which showed a change from the pure Co3O4 NPs to a combination of Co(III), Co(II) and Co-metal. In addition, the binding of the Co3O4 nanoparticles to the PAN fibers before carbonization showed a change in the chemical environment, which included attachment through an N ligand on the fibers

The effect of the shear-thickening transition of model colloidal spheres on the sign of N1 and on the radial pressure profile in torsional shear flows

A novel rheometer plate was used to measure radial pressure profiles during cone-and-plate and parallel-plate shearing flows of a concentrated colloidal dispersion of polymethyl methacryalate spheres suspended in dioctyl phthalate. There is a long history of using suspensions of this type as a model rheological system. The measured pressure profile can be used to calculate N1 and N2, and also provides a check on the flow field in the rheometer. At shear rates just below onset of shear thickening, our measurements show that N1 is positive as predicted by Stokesian dynamics simulations of model Brownian hard spheres, but we are unable to determine the sign of N2. After the onset of thickening, we find that in both flow geometries the pressure increases sharply with radial position. This is in striking contrast to the pressure profiles ordinarily observed for viscoelastic liquids with the exception of certain liquid crystal polymers, for which the pressure decreases with radial position. Under these conditions, the apparent values of N1 and N2 are both negative with N2 N1, as predicted by the Stokesian dynamics simulations. However, the flow in the cone-and-plate rheometer may not be viscometric after the onset of shear thickening

On the thermogravimetric analysis of polymers: Polyethylene oxide powder and nanofibers

Thermogravimetric analysis of polyethylene oxide (powder and nanofibers obtained by force spinning water or chloroform solutions of polyethylene oxide) was studied using different theoretical models such as Friedman and Flynn-Wall-Ozawa. A semiempirical approach for estimating the “sigmoid activation energy” from the thermal degradation was suggested and confirmed by the experimental data on PEO powder and nanofibers\u27 mats. The equation allowed for calculating a “sigmoid activation energy” from a single thermogram using a single heating rate without requiring any model for the actual complex set of chemical reactions involved in the thermal degradation process. For PEO (powder and nanofibers obtained from water solutions), the “sigmoid activation energy” increased as the heating rate was increased. The sigmoid activation energy for PEO mats obtained from chloroform solutions exhibited a small decrease as the heating rate was increased. Thermograms\u27 derivatives were fitted to determine the coordinates of the inflection points. The “sigmoid activation energy” was compared to the activation energy determined from the Flynn-Wall-Ozawa model. Similarities between the thermal degradation of polyethylene oxide powder and of the nanofibers obtained from water solutions were discussed. Significant differences between the sigmoid activation energies of the mats obtained from water and chloroform solutions were reported

Synthesis and Characterization of Titanium Nitride–Carbon Composites and Their Use in Lithium-Ion Batteries

This work focuses on the synthesis of titanium nitride–carbon (TiN–carbon) composites by the thermal decomposition of a titanyl phthalocyanine (TiN(TD)) precursor into TiN. The synthesis of TiN was also performed using the sol-gel method (TiN(SG)) of an alkoxide/urea. The structure and morphology of the TiN–carbon and its precursors were characterized by XRD, FTIR, SEM, TEM, EDS, and XPS. The FTIR results confirmed the presence of the titanium phthalocyanine (TiOPC) complex, while the XRD data corroborated the decomposition of TiOPC into TiN. The resultant TiN exhibited a cubic structure with the FM3-M lattice, aligning with the crystal system of the synthesized TiN via the alkoxide route. The XPS results indicated that the particles synthesized from the thermal decomposition of TiOPC resulted in the formation of TiN–carbon composites. The TiN particles were present as clusters of small spherical particles within the carbon matrix, displaying a porous sponge-like morphology. The proposed thermal decomposition method resulted in the formation of metal nitride composites with high carbon content, which were used as anodes for Li-ion half cells. The TiN–carbon composite anode showed a good specific capacity after 100 cycles at a current density of 100 mAg−1