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The mobility of polystyrene nanoparticles ranging in diameter from 300 nm to 2 μm was measured in dilute and semidilute solutions of partially hydrolyzed polyacrylamide. In this model system, the ratio of particle to polymer size controls the long-time diffusivity of nanoparticles. The particle dynamics transition from subdiffusive on short time scales to Fickian on long time scales, qualitatively similar to predictions for polymer dynamics using a Rouse model. The diffusivities extracted from the long-time Fickian regime, however, are larger than those predicted by the Stokes-Einstein equation and the bulk zero-shear viscosity and moreover do not collapse according to hydrodynamic models. The size-dependent deviations of the long-time particle diffusivities derive instead from the coupling between the dynamics of the particle and the polymer over the length scale of the particle. Although the long-time diffusivities collapse according to predictions, deviations of the short-time scaling exponents and the crossover time between subdiffusive and Fickian dynamics indicate that the particles are only partially coupled to the relaxation modes of the polymer.

Grafting of high molecular weight polymers to graphitic nanoplatelets is a critical step toward the development of high performance graphene nanocomposites. However, designing such a grafting route has remained a major impediment. Herein, we report a “grafting to” synthetic pathway by which high molecular weight polymer, poly(e-caprolactone) (PCL), is tethered, at high grafting density, to highly anisotropic graphitic nanoplatelets. The efficacy of this tethering route and the resultant structural arrangements within the composite are confirmed by neutron and X-ray scattering measurements in the melt and solution phase. In the semicrystalline state, X-ray analysis indicates that chain tethering onto the graphitic nanoplatelets results in conformational changes of the polymer chains, which enhance the nucleation process and aid formation of PCL crystallites. This is corroborated by the superior thermal properties of the composite, manifested in accelerated crystallization kinetics and a significant increas...

Particle-polymer attractions in nanocomposites can cause significant heterogeneities in the polymer dynamics and remarkably impact the material properties. Dynamical perturbations are generally expected to be limited to interfacial polymer segments. However, composites with highly anisotropic nanoparticles usually exhibit very low percolation thresholds. In such systems, the overlapping interfacial regions could result in a complex polymer relaxation behavior that is unanticipated from dilute nanoparticle dispersions in polymer matrices. To understand this behavior, we examine a system of percolated single-wall carbon nanotubes (SWNT) in a polymer matrix, PMMA, which is known to have strong interfacial binding. Neutron spectroscopy measurements on the composites reveal not only an interfacial polymer layer that is transiently pinned to the SWNT surface, but suggest that the percolated network forms a kinetic cage that dramatically restricts both local and cooperative relaxations of noninterfacial polymer segments. These findings should help guide theories and simulations of hierarchical polymer dynamics in nanocomposites.

Thermodynamic interactions in binary blends of a copolymer containing diene and olefin repeat units and a polyolefin were explored, through measurements of the effective binary Flory–Huggins intera...

Two matrix-free polystyrene-grafted silica nanocomposite samples with graft chain lengths of 35 and 112 kg/mol are characterized by calorimetry and rheometry, and results are compared to neat polys...

Blends of thermoset polymers offer an avenue to combine the mechanical properties of complementary high glass transition temperature systems. An epoxy resin with high tensile strength and modulus, composed of the diglycidyl ether of bisphenol A cured with an anhydride, was combined with polydicyclopentadiene, cured via ring-opening metathesis polymerization, to improve the toughness. An amphiphilic block copolymer, poly(1,4-butadiene-b-ethylene oxide), where 1,4-polybutadiene has a strong affinity for polydicyclopentadiene and poly(ethylene oxide) has a strong affinity for the epoxy resin, was added to control phase separation and manipulate the morphology of the thermoset blend, analogous to compatibilization in thermoplastic blends. A systematic study of the influence of block copolymer loading and blend composition on the structural morphology was performed, using a combination of ultrasmall-angle X-ray scattering (USAXS), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM)....

The morphology of a block copolymer of a near symmetric strongly-segregating poly(n-butyl acrylate) and poly(methyl methacrylate) tethered to a ∼15 nm silica nanoparticles is examined using a combination of microscopy techniques and small angle x-ray and neutron scattering. The copolymer components are strongly segregated and form a disordered structure that is possibly a combination of coexisting individual randomly placed core-shell structures and worm-like cylinders with 3–5 silica nanoparticles forming the core. With increasing temperature, the cylinders become shorter because of the improved thermodynamic compatibility between the two copolymer segments.

Thermodynamic interactions in polydiene/polyolefin blends composed of 1,2-polybutadiene (1,2-PBD) and fully saturated (with deuterium) 1,2-PBD were explored with small-angle neutron scattering (SANS). Two methods were employed to extract the temperature dependence of the Flory–Huggins interaction parameter, χ, from SANS data obtained in the single-phase region. First, Zimm analysis was conducted employing data obtained at low scattering angles, providing a model-independent method of characterizing χ. Next, the random phase approximation was fit to the full angle-dependent absolute scattering intensity. The χ parameter for 1,2-PBD/saturated 1,2-PBD was found to be large in magnitude at low temperatures and exhibited a strong temperature dependence. The experimentally measured χ, at high temperatures, was in agreement with predictions of solubility parameter theory based on PVT properties of the individual components. The large and strongly temperature-dependent χ parameter of the 1,2-PBD/saturated 1,2-PBD...

We measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale. Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Our results elucidate the physics underlying the slow relaxations of grafted polymer.

Non-isothermal ultra-fast cooling crystallization tests were conducted on three blown film grade bimodal high density polyethylene (HDPE) resins using a fast differential scanning calorimeter, the Flash DSC. Non-isothermal tests were performed at cooling rates between 50 and 4000°K/s, and the data were analyzed using the modified Avrami model by Jeziorny (Polymer, 1978, 19, 1142). Non-isothermal data were used to propose a new method named crystallization–time–temperature–superposition, and the two activation energies were obtained for each of the resins. This is very useful for obtaining theoretical crystallization kinetics data at different cooling rates, allowing its use in ultra-fast cooling polymer processes such as blown film. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017

A facile but efficient spray-coating method was recently developed to manufacture thin, flexible, and transparent epoxy films reinforced with well-exfoliated and highly-aligned α-zirconium phosphate (ZrP) nanoplatelets in smectic liquid crystalline order. Here, we investigate the scratch resistance of ZrP/epoxy nanocomposites prepared following the same spray-coating process. Comparison was made with neat epoxy coating to determine the impact of ZrP nanofillers. Tests were conducted with accordance to ASTM D7027 /ISO 19252 scratch standard and scratch mechanisms were studied using different experimental tools. Results show that scratch resistance is considerably improved after introducing ZrP nanofillers to the epoxy coating. This was reflected by the delay in microcracking and plowing damages and the decrease of scratch coefficient of friction. This result is attributed to the significant role of exfoliated and aligned ZrP nanofillers in enhancing the mechanical properties of the epoxy matrix. The usefulness of the current study in developing new coating systems for high-performance applications is discussed.

We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using X-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard-sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve solely as a function of normalized length scales. Instead, the diffusivities can be collapsed across two orders of magnitude in free polymer molecular weight and concentration and one order of magnitude in grafted molecular weight by incorporating the ratio of free to grafted polymer molecular weights. These results suggest that the soft interaction potential between polymer-grafted nanoparticles and free polymer allows polymer-grafted nanoparticles to diffuse faster than predicted based on bulk rheology and modifies the coupling between grafted particle dynamics and the relaxations of the surrounding free polymer.

The mechanical properties of two chemically distinct and complementary thermoset polymers were manipulated through development of thermoset blends. The thermoset blend system was composed of an anhydride-cured diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, contributing high tensile strength and modulus, and polydicyclopentadiene (PDCPD), which has a higher toughness and impact strength as compared to other thermoset polymers. Ultra-small-angle and small-angle X-ray scattering analysis explored the morphology of concurrently cured thermoset blends, revealing a macroscopically phase separated system with a surface fractal structure across blended systems of varying composition. The epoxy resin rich and PDCPD rich phases exhibited distinct glass transitions (Tg’s): the Tg observed at higher temperature was associated with the epoxy resin rich phase and was largely unaffected by the presence of PDCPD, whereas the PDCPD rich phase Tg systematically decreased with increasing epoxy resin content due ...

We investigate the structure and dynamics of silica nanoparticles and polymer chains in semidilute solutions of high molecular weight polystyrene in 2-butanone to determine the effect of long-range interparticle interactions on the coupling between particle and polymer dynamics. Particles at concentrations of 1–10 wt % are well dispersed in the semidilute polymer solutions and exhibit long-range electrostatic repulsions between particles. Because the particles are comparably sized to the radius of gyration of the polymer, the particle dynamics is predicted to couple to that of the polymer. We verify that the polymer structure and dynamics are not significantly affected by the particles, indicating that the particle–polymer coupling does not change with increasing particle loading. We find that the coupling between the dynamics of comparably sized particles and polymer results in subdiffusive particle dynamics, as expected. Over the interparticle distance, however, the particle dynamics is hindered and not...

The structural transitions occurring with change in pH for aqueous mixtures of a cationic surfactant (cetyltrimethylammonium bromide, CTAB) and a hydrotrope (sodium salicylate, NaSal) were investigated at various temperatures using dynamic light scattering and small-angle neutron scattering. Direct structural studies show a transition from rigid cylindrical micelles at neutral pH to spherical micelles at ∼ pH 2 upon protonation of salicylate molecules; however, an unanticipated reversion to flexible cylindrical micelles with further decrease in pH was observed. We also observed these microstructure transitions from cylinders at high pH to spherical micelles at intermediate pH to flexible cylindrical micelles at low pH were highly sensitive to temperature. Our results suggest that, in addition to the well-described electrostatic and hydrophobic interactions in cationic surfactant-hydrotrope mixtures, the pH-induced microstructural changes are potentially governed by complementary cation-π and hydrogen bonding interactions.

The structure of aqueous dispersions of poly(oligo(ethylene oxide) monomethyl methacrylate)-grafted silica nanoparticles was characterized using contrast variation small-angle neutron scattering studies. Modeling the low hybrid concentration dispersion scattering data using a fuzzy sphere and a polydisperse core–shell model, demonstrated that the polymer chains are highly swollen in the dispersions as compared to the dimensions of the free polymer chains in dilute solution. At higher hybrid concentrations, the dispersions were well described using a Percus–Yevick approximation to describe the structure factor. These structural characterization tools are excellent starting points for effective molecular level descriptors of dewetting and macroscopic phase transitions for polymer tethered hybrid nanoparticle systems.

We determine the conformational change of polystyrene chains grafted to silica nanoparticles dispersed in deuterated cyclohexane using small-angle neutron scattering. The cyclohexane/polystyrene system exhibits an upper-critical solution temperature below which the system phase separates. By grafting the polystyrene chains to a nano-sized spherical silica particle, we observe a significant suppression in the Θ-temperature, decreasing from ≈38 °C for free polystyrene chains in d12-cyclohexane to ≈34 °C for the polystyrene-grafted nanoparticles. Above this temperature, the grafted chains are swollen and extended from the particle surface, resulting in well-dispersed grafted nanoparticles. Below this temperature, the grafted chains fully expel the solvent and collapse on the particle surface, destabilizing the nanoparticle suspension and leading to aggregation. We attribute the suppression of the Θ-temperature to a competition between entropic and enthalpic energies arising from the structure of the polymer-grafted nanoparticle in which the enthalpic terms appear to dominate.

Simulations and experiments are conducted on mixtures containing polymer grafted nanoparticles in a chemically distinct polymer matrix, where the graft and matrix polymers exhibit attractive enthalpic interactions at low temperatures that become progressively repulsive as temperature is increased. Both coarse-grained molecular dynamics simulations, and X-ray scattering and neutron scattering experiments with deuterated polystyrene (dPS) grafted silica and poly(vinyl methyl ether) PVME matrix show that the sharp phase transition from (mixed) dispersed to (demixed) aggregated morphologies due to the increasingly repulsive effective interactions between the blend components is distinct from the continuous wetting-dewetting transition. Strikingly, this is unlike the extensively studied chemically identical graft-matrix composites, where the two transitions have been considered to be synonymous, and is also unlike the free (ungrafted) blends of the same graft and matrix homopolymers, where the wetting-dewetting is a sharp transition coinciding with the macrophase separation.

The development of interpenetrating polymer networks provides a route to create tough materials that maintain high strength and stiffness, suitable for meeting the demands of an off-shore wind turbine environment. This work has focused on a system composed of diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, contributing high tensile strength and modulus, and polydicyclopentadiene (polyDCPD), which has a higher toughness and impact strength as compared to other thermoset polymers. In situ Fourier transform infrared spectroscopy was used to explore the reaction kinetics in neat, diluted and sequentially cured mixtures of epoxy resin and polyDCPD. There were significant differences in the rate of network formation in the two neat systems, as the rate of anhydride curing of the epoxy was extremely slow at the temperatures required for reasonably measurable dicyclopentadiene (DCPD) ring-opening metathesis polymerization. The dissimilar kinetics of these two systems were leveraged in the design of a sequential curing protocol in which the DCPD was first cured in the presence of the epoxy resin components, followed by curing of the epoxy resin at an elevated temperature. The curing kinetics of the macroscopically phase separated domains of the epoxy resin components in the presence of the polyDCPD network behaved as expected for a diluted epoxy resin. These results provide the kinetic basis for future studies to prepare interpenetrating polymer networks which employ thermodynamic control of phase separation such as through the addition of compatibilizing molecules.

The interfacial behavior of water-soluble poly[oligo(ethylene oxide) monomethyl ether methacrylate], grafted from 15-nm-diameter silica nanoparticles using a living atom-transfer radical polymerization technique, was examined for hexane and water interfaces. The polymer-grafted nanoparticles reduced the hexane–water interfacial tension from ∼50 to ∼20 mN/m at concentrations of silica in the range of 1–10 ppm. The hydrodynamic size of the dispersed hybrid nanoparticle, a function of the molecular weight of the polymer and grafting density, was the dominant variable in determining the critical particle concentration and efficacy of the hybrid nanoparticles in reducing the hexane–water interfacial tension. A simple phenomenological model is used to explain the strong dependence of the critical particle concentration on the effective hydrodynamic size of the nanoparticles. Water–hexane and water–squalene emulsions formed using 1000 ppm of hybrid nanoparticles were stable for more than 60 days.

Heteroatom polymeric precursor with an aromatic substituent (polyurethane acrylate) was designed and found to generate nitrogen-doped graphene at 1000 °C. Upon thermal degradation, a nitrogenous fragment was liberated in situ. As a consequence, nitrogen-doped graphene was formed in a single step. Further, this methodology was extended for studying the effect of annealing nonheteroatom polymer with an aromatic substituent (styrene butadiene random copolymer) under similar conditions. The isolated product demonstrated undoped graphene-like structure. The mechanism of nitrogen-doped graphitization was studied by annealing different heteroatom polymer units with an aliphatic and aromatic framework in a chemical vapor deposition reactor. The effect of precursor heteroatom polymer structure and annealing temperature in the presence of copper catalyst on the efficacy of formation of nitrogen-doped graphene was examined. The nitrogen-doped graphene exhibited semiconducting behavior over semimetallic behavior of t...

We investigate the effects of geometric order and fluid rheology on the dispersion of micron-sized particles in two-dimensional microfluidic porous media. Particles suspended in a mixture of glycerol and water or in solutions of partially hydrolyzed polyacrylamide (HPAM) polymers were imaged as they flowed through arrays of microscale posts. From the trajectories of the particles, we calculated the velocity distributions and thereafter obtained the longitudinal and transverse dispersion coefficients. Particles flowed in the shear-thinning HPAM solution through periodic arrays of microposts were more likely to switch between streamlines, due to elastic instabilities. As a result, the distributions of particle velocity were broader in HPAM solutions than in glycerol-water mixtures for ordered geometries. In a disordered array of microposts, however, there was little difference between the velocity distributions obtained in glycerol-water and in HPAM solutions. Correspondingly, particles flowed through ordered post arrays in HPAM solutions exhibited enhanced transverse dispersion. This result suggests that periodic geometric order amplifies the effects of the elasticity-induced velocity fluctuations, whereas geometric disorder of barriers effectively averages out the fluctuations.

Gold nanorods grafted with short chain polymers are assembled into controlled open structures using polymer-induced depletion interactions and structurally characterized using small angle x-ray scattering. When the nanorod diameter is smaller than the radius of gyration of the depletant polymer, the depletion interaction depends solely on the correlation length of the polymer solution and not directly on the polymer molecular weight. As the polymer concentration increases, the stronger depletion interactions increasingly compress the grafted chains and push the gold nanorods closer together. By contrast, other structural characteristics such as the number of nearest neighbors and fractal dimension exhibit a non-monotonic dependence on polymer concentration. These parameters are maximal at intermediate concentrations, which are attributed to a crossover from reaction-limited to diffusion-limited aggregation. The control over structural properties of anisotropic nanoscale building blocks demonstrated here will be beneficial to designing and producing materials \emph{in situ} with specific direction-dependent nanoscale properties and provides a crucial route for advances in additive manufacturing.

A "grafting to" methodology for the attachment of a silane based polymer (SG) onto functionalized graphitic platelets is demonstrated. The siloxy end groups of the modifier were further cross-linked without addition of any external curative. These sterically stabilized nanoplatelets with a high grafting density ensured complete screening of the attractive interparticle interactions. As a result, a better dispersion of platelets was observed compared to the physically mixed platelets in the polymer matrix (SUG). The larger size of the polymer tethered graphitic particles and the greater extent of heat liberated due to grafting resulted in a higher enthalpic contribution in the case of SG compared to SUG. This makes the formation of SG thermodynamically more favorable compared to SUG. Presence of a hierarchical spatial arrangement with a good dispersion of graphitic platelets was observed within the siloxane matrix in the case of SG compared to SUG. The nanoparticle tethered composite generated exhibited an "instant" conducting adhesive behavior. The adhesive properties of the SG were found to be increased due to grafting of graphitic platelets when compared with the neat polymer. Further, SG exhibited a conductive character whereas the neat polymer and SUG demonstrated an insulating character.

We measure the mobility of nanoparticles at low concentrations in non-Newtonian semidilute aqueous solutions of high-molecular-weight polyelectrolyte polymers. Using optical microscopy and particle tracking algorithms, we image and track hydrophilic polystyrene nanoparticles of diameter 400 nm moving in aqueous solutions of partially hydrolyzed polyacrylamide of molecular weight 8 000 000 Da and concentration of 0.042—4.2 g/L. The effective diffusivity of the nanoparticles in the semidilute polymer solutions, extracted from the long-time limit of the mean-squared displacement using the Stokes–Einstein relation, is greater than that calculated from the zero-shear-rate viscosity measured using bulk rheology. For concentrations c > 0.42 g/L, the mean-square displacements (MSD) of particles measured as a function of lag time revealed that the particle dynamics are subdiffusive at short time scales and are Fickian on long time scales. The time scale for the crossover from subdiffusive to Fickian dynamics incre...

In purely viscous Newtonian fluids, mechanical mixing of the fluid stream as it moves through an unstructured porous medium controls the long-time dispersion of molecular tracers. In applications ranging from environmental remediation to materials processing, however, particles are transported through porous media in polymer solutions and melts, for which the fluid properties depend on the shear rate and extent of deformation. How the flow characteristics of polymer solutions affect the spreading of finite-sized particles remains poorly understood - both on the microscopic scale as local velocity profiles, and on the macroscale as dispersion. Here, we show across a range of flow rates and disordered porous media configurations that the long-time transport coefficients of particles flowed in water, in a viscous Newtonian fluid, and in a non-Newtonian shear-thinning polymer solution collapse onto scaling curves, independent of the fluid rheology. Thus the addition of polymer does not impact nanoparticle dispersion through disordered porous media.

The location and distribution of ibuprofen, a model nonsteroidal anti-inflammatory drug, in a phospholipid bilayer was examined in molecular detail by a combination of neutron diffraction and computer simulations. In addition to their use as antipyretic, analgesic, and anti-inflammatory drugs, such nonsteroidal anti-inflammatory drugs are used in the treatment of a number of diseases including cancer and Alzheimer's. As a side effect, they have been known to cause gastrointestinal toxicity, although the molecular mechanism of their action is poorly understood. In this study, we have used contrast variation-based neutron diffraction to determine the position of the drug in a 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine lipid bilayer and explore changes to the bilayer structure upon drug incorporation. In its charged state, the drug was found to locate in the polar headgroup region of the phospholipid bilayer, to induce bilayer thinning, and to increase the number of water molecules closely associated with the bilayer. These structural insights are consistent with molecular dynamics simulations and earlier macroscopic experiments of vesicle structure and dynamics. Using MD simulations, the neutral ibuprofen, typically observed at low pH and inaccessible to the diffraction studies, was found to locate deeper within the bilayer than the charged form.

The development of hierarchically ordered inorganic–polymer nanocomposites has traditionally focused on the nucleation of the crystalline, liquid crystalline, or ordered mesophase of the polymer by...

Water-dispersible polymer–silica nanocomposite particles, SiO2–ethylene oxide-based polymer nanoparticles hybrids, were synthesized using a “grafting-from” method, where polymer brushes were grown ...

The changes in morphology caused by the addition of organically modified layered silicate on equal volume fraction blends of polystyrene and poly(methyl methacrylate) are investigated. In thin films supported on silicon, without layered silicates, the PMMA forms a layer on the silicon, while the PS tend to minimize contact with both the hydrophilic silicon substrate and the PMMA phase, and tend to form discrete domains on top of the PMMA layer. With the introduction of layered silicates, the characteristic length scale of the structure decreases. On the other hand, in bulk samples, without the layered silicates, the equal volume fraction blend has the PS domains in a PMMA matrix. At 0.6 wt% of added silicate, in both thin film and bulk, the blend morphology converts from discrete to co-continuous. Electron micrographs reveal well dispersed silicate sheets locating at the interface between small PS domains in the PMMA phase. The change in morphology is conjectured to be the result of the interfacial location of the layered silicates rather than the change in viscosity ratio between the two phases.

Spherical nanoparticles of silica grafted with a dense brush of low-polydispersity polymers prepared by living radical polymerization are shown to form ordered crystalline structures. The minimum distance between nanoparticle surfaces, a good measure of the end-to-end distance of the tethered polymers, scales as the square root of the molecular weight of the polymer chains. The blending of the grafted nanoparticles with homopolymers of matched and mismatched molecular weights indicates that the crystalline order persists even with high amounts of homopolymer added and for such diluted systems with as little as 0.7 vol % silica.

The overall isothermal crystallization behavior of poly(ethylene oxide) (PEO) in single walled carbon nanotube (SWNT) based nanocomposites is studied with a focus on growth kinetics and morphological evolution of PEO using differential scanning calorimetry and in-situ small angle x-ray scattering measurements respectively. The characteristic time for crystallization of PEO increases due to the presence of lithium dodecyl sulfate (LDS) stabilized carbon nanotubes. Further, analysis of crystallization data using the Lauritzen–Hoffman regime theory of crystal growth shows the PEO chains stiffen in presence of LDS with an increased energy barrier associated with the nucleation and crystal growth, and the nanotubes further act as a barrier to chain transport or enhance the efficacy of the LDS action. The energy penalty and diffusional barrier to chain transport in the nanocomposites disrupt the crystalline PEO helical conformation. This destabilization leads to preferential growth of local nuclei resulting in formation of thinner crystal lamellae and suggests that the crystallization kinetics is strongly affected by the nucleation and crystal growth events. This study is particularly interesting considering the suppression of the PEO crystallinity in presence of small fraction of Lithium ion based surfactant and carbon nanotubes.

Silicon carbide nanofiber dispersion within a silicon oxycarbide glassy ceramic was achieved through a combination of a fast sol–gel procedure for in situ ceramic matrix synthesis and nanofiber conversion from sacrificial multiwalled carbon nanotube templates. Nanotubes were dispersed using both surfactant adsorption and a covalent sidewall modification scheme with gel-grafting capabilities. The combination of high temperature processing and silicon monoxide precursor concentrations allowed substantial carbothermal reduction of the nanotube templates, yielding silicon carbide nanofibers. The resulting nanocomposites were examined for density, Vickers microhardness, Young's modulus, and fracture toughness. The surfactant-assisted route inhibited ceramic densification, offering virtually no mechanical property enhancement. In contrast, the covalently functionalized nanotube templates at 0.8 wt% loading enhanced tensile modulus of 77% while simultaneously maintaining both Vickers microhardness and fracture toughness. These results indicate strong interfacial adhesion between the nanofiber surface and host matrix despite the abrupt chemical changes experienced during the high temperature processing.

Dispersions of multi-walled carbon nanotubes (MWNTs) assisted by surfactant adsorption were prepared for a number of ionic and non-ionic surfactants including sodium 4-dodecylbenzenesulfonate (NaDDBS), hexadecyl(trimethyl)azanium bromide (CTAB), sodium dodecane-1-sulfonate (SDS), Pluronic® F68, Pluronic® F127, and Triton® X-100 to examine the effects of nanotube diameter, surfactant concentration, and pH on nanotube dispersability. Nanotube diameter was found to be an important role in surfactant adsorption rendering single-walled carbon nanotube studies as unreliable in predicting MWNT dispersive behavior. Similar to other reports, increasing surfactant concentrations resulted in a solubility plateau. Quantification of nanotube solubility at these plateaus demonstrated that CTAB is the best surfactant for MWNTs at neutral pH conditions. Deviations from neutral pH demonstrated negligible influence on non-ionic surfactant adsorption. In contrast, both cationic and anionic surfactants were found to be poor dispersing aids for highly acidic solutions while, CTAB remained a good surfactant under strongly basic conditions. These pH dependent results were explained in the context of nanotube surface ionization and Debye length variation.

The melt state linear viscoelastic properties of spherical silica nanoparticles with grafted poly(n-butyl acrylate) chains of varying molecular weight were probed using linear small amplitude dynam...

Single wall carbon nanotubes (SWCNTs) were dispersed in polystyrene (PS) at 0.1, 0.2, 0.3 and 1.0 wt.% (weight percent) concentrations using a surfactant assisted method. The resulting nanocomposites were characterized for their electrical conductivity, mechanical strength and fracture toughness properties. Results show a significant improvement in electrical conductivity with electrical percolation occurring by 0.2 wt.% SWCNT loading and the SWCNT-PS nanocomposite fully conductive at 1.0 wt.%. Three-point bend tests showed a decline in flexural strength and break strain with the addition of 0.1 wt.% SWCNTs. Improvements in the flexural modulus, strength and break strain with increasing SWCNT wt.% content followed The fracture toughness of the SWCNT-PS nanocomposites, in terms of the critical stress-intensity factor KIC, was reduced relative to the neat material. From optical and high resolution scanning electron microscopy the presence of the carbon nanotubes is shown to have an adverse effect on the crazing mechanism in this PS material, resulting in a deterioration of the mechanical properties that depend on this mechanism.

Using the potential of mean constrained force method, molecular dynamics simulations with atomistic details were performed to examine the partitioning and nature of interactions of two nonsteroidal antiinflammatory drugs, namely aspirin and ibuprofen, in bilayers of dipalmitoylphosphatidylcholine. Two charge states (neutral and anionic) of the drugs were simulated to understand the effect of protonation or pH on drug partitioning. Both drugs, irrespective of their charge state, were found to have high partition coefficients in the lipid bilayer from water. However, the values and trends of the free energy change and the location of the minima in the bilayer are seen to be influenced by the drug structure and charge state. In the context of the transport of the drugs through the bilayer, the charged forms were found to permeate fully hydrated in contrast to the neutral forms that permeate unhydrated.

The dispersion of functionalized multiwalled carbon nanotubes (MWNTs) in various solvents is characterized. The nanotubes were functionalized using a Birch alkylation method that afforded a 50−100% increase in o-dichlorobenzene solubility while rendering measurable solubility in otherwise insoluble chloroform and decreasing solubility in N,N-dimethylformamide and N-methyl-2-pyrrolidinone. Dispersibility was contingent on fostering polar interactions between the functionalized nanotubes and solvent despite the purely dispersive nature of the aliphatic chains. Interpretation of these results was performed using the Hansen solubility parameters and the three component surface energy analysis pioneered by van Oss and co-workers. It was found that the simplest interpretation of the Hansen solubility parameter scheme was unable to explain the data. In contrast, the surface energy analysis provides a robust interpretation of the solubility and yields values of 45.6 ± 1.2, 0.78 ± 0.04, and 2.4 ± 0.9 mJ/m2 for the...

The melt rheological properties of layered silicate nanocomposites with maleic anhydride (MA) functionalized polypropylene are contrasted to those based on ammonium-terminated polypropylene. While the MA functionalized PP based nanocomposites exhibit solid-like linear viscoelastic behavior, consistent with the formation of a long-lived percolated nanoparticle network, the single-end ammonium functionalized PP based nanocomposites demonstrated liquid-like behavior at comparable montmorillonite concentrations. The differences in the linear viscoelasticity are attributed to the presence of bridging interactions in MA functionalized nanocomposites. Further, the transient shear stress of the MA functionalized nanocomposites in start-up of steady shear is a function of the shear strain alone, and the steady shear response is consistent with that of non-Brownian systems. The weak dependence of the steady first normal stress difference on the steady shear stress suggests that the polymer chain mediated silicate network contributes to such unique flow behavior.

The crystalline morphology in thin and ultrathin films of linear low-density polyethylene is reported here. Films with thickness ranging from 20 to 800 nm were isothermally crystallized at temperatures ranging from 90 to 119 °C, and the supermolecular and lamellar morphologies were observed by contact and tapping mode atomic force microscopies. Four distinct supermolecular morphologies were observed: banded spherulite, sheaflike, and two intermediate morphologies. The morphological transitions were significant in the films thinner than 200 nm. The sheaflike morphology occurred in the thinner films (

The response of fractal networks of dispersed single walled carbon nanotubes in poly(ethylene oxide) to continuous constant-rate shear flow is examined as functions of shear rate and nanotube concentration. The steady shear viscosity values are strong functions of shear rate and follow a power-law shear-thinning character, while the nanotube concentration dependence of the viscosity (at a fixed shear rate) is somewhat weaker than the scaling of the equilibrium modulus values. For dispersions with nanotube concentrations corresponding to the semidilute regime, the stress response to constant-rate continuous shear from rest demonstrates a stress maximum that decays to a steady value at long times. The stress maximum and steady shear behavior can be reconciled in terms of the changing structure at the mesoscale for the fractal networks. On the other hand, the transient development of the stress during the start-up experiments can be qualitatively reconciled in the context of a cluster dynamics model.

The hierarchical morphology of a nanocomposite with aligned single-walled carbon nanotubes results in templated growth of a semi-crystalline poly(-caprolactone) that is highly robust. The composite structure shows a significant mechanical reinforcement of the polymer.

Inthis report, we present a simple methodology facilitating theformation of A-B random copolymers with tunable sequencedistributions. We demonstrate that varying the degree ofblockiness in the sequence distribution of A and B monomershas a profound impact on the partition of random copolymersat interfaces.Random copolymers (RCPs) are long chain moleculesmade of covalently bound monomers comprising at least twodifferent chemical moieties (say, A and B). In addition to theoverall molecular weight, RCPs are characterized by theircomposition and monomer sequence distribution. The abilityof A-B RCPs to act as “homopolymers with tunable composi-tion”, ranging between A and B homopolymers, has recentlyattracted considerable attention in controlling polymer misci-bility

The dynamic mechanical properties of nanocomposites of functionalized single-walled carbon nanotubes dispersed in polystyrene are reported as a function of temperature. For nanocomposites containing less than 0.1 wt% nanotubes, the enhancement of the magnitude of the complex modulus | E ∗ | = E ′ 2 + E ″ 2 , where E′ and E″ are the elastic and loss moduli, respectively, exceeded the predictions of the Halpin–Tsai model (this model is often used to predict the properties of macroscopic composites). In this concentration range, however, the loss tangent, tan δ = E″/E′, of the nanocomposite remained comparable to that of pure PS, i.e., comparable elasticity. At larger concentrations the mechanical response became more elastic than PS, but the magnitude of the complex modulus fell appreciably below predictions based on the Halpin–Tsai model. An alternate hypothesis that relies on the role of attractive interactions between the nanotubes and polystyrene chains, and consistent with previous Raman scattering and glass transition temperature data, is proposed to describe the observed dynamic response.

Controlling the dispersion of nanoparticles in polymeric matrices is the most significant impediment in the development of high-perform ance polymer nanocomposite ma te rials and results primarily from the strong interpar ticle interactions between the nanopar ticles. This review examines the theoretical and experimental strategies employed in developing appropriate chemical and physical methods to achieve controlled dispersion of nanopar ticles. Methods to characterize the state of dispersion, including force and electron micros copy, and scattering, electrical, and mechanical spectroscopy, are considered with special emphasis on achieving quantitative meas ures of the dispersion. Some of the outstanding issues, such as long-term aging and the implication for the dispersion of nanopar ticles, development of high-throughput methods for rapid screening, and methods for in-line monitoring, are also discussed.

The dispersion of single-walled carbon nanotubes (SWNT) in poly(e-caprolactone) with the aid of a zwitterionic surfactant is reported. Melt rheology and electrical conductivity measurements indicate geometrical percolation and electrical percolation for nanocomposites with ∼0.08 wt % SWNT, implying an effective anisotropy for the nanotubes of at least 600. Spectroscopic measurements and comparison of dispersion using other surfactants established that the excellent dispersion is a result of the compatibilizing effect of the zwitterionic surfactant.

Linear viscoelastic and dielectric measurements were conducted for a blend of polyisoprene (PI, M = 19.9 × 103) and poly(4-tert-butyl styrene) (PtBS, M = 69.5 × 103) with a PI/PtBS composition of 8/2 (w/w). In general, PI and PtBS exhibit the lower-critical-solution-temperature (LCST) type phase behavior. At temperatures examined, T ≤ 70 °C, our PI/PtBS blend was in a statically homogeneous state. The PI chain has the so-called type-A dipoles parallel along the backbone, and its large-scale (global) motion activates prominent dielectric relaxation, while the PtBS chain has no type-A dipoles and its global motion is dielectrically inert. In fact, at angular frequencies ω between 101 s-1 and 105 s-1 and at T ≤ 70 °C, the dielectric signal of the blend was exclusively attributed to the PI chains therein. The time−temperature superposition failed for the dielectric loss e‘ ‘ of the PI chains, despite the fact that the blend was statically homogeneous. This result suggested that the frictional environment for ...

Differential dynamic microscopy (DDM) was used to investigate the diffusive dynamics of nanoparticles of diameter 200–400 nm that were strongly confined in a periodic square array of cylindrical nanoposts. The minimum distance between posts was 1.3–5 times the diameter of the nanoparticles. The image structure functions obtained from the DDM analysis were isotropic and could be fit by a stretched exponential function. The relaxation time scaled diffusively across the range of wave vectors studied, and the corresponding scalar diffusivities decreased monotonically with increased confinement. The decrease in diffusivity could be described by models for hindered diffusion that accounted for steric restrictions and hydrodynamic interactions. The stretching exponent decreased linearly as the nanoparticles were increasingly confined by the posts. Together, these results are consistent with a picture in which strongly confined nanoparticles experience a heterogeneous spatial environment arising from hydrodynamics and volume exclusion on time scales comparable to cage escape, leading to multiple relaxation processes and Fickian but non-Gaussian diffusive dynamics.

Carbon nanotubes (CNTs) with their remarkable set of intrinsic properties are outstanding materials to incorporate in and augment the properties of polymer matrices. Poly(ethylene oxide) (PEO) is a water-soluble, biocompatible polymer that has found various technological applications including as solid electrolytes in lithium-ion batteries and in various biomedical and tissue engineering applications. Homogeneous dispersion of anisotropic nanoparticles, especially carbon nanotubes, in a matrix polymer is hindered by strong inter-tube attraction and a weak entropic driving force for the disruption of nematic order of such rodlike nanoparticles. In this chapter, we discuss different pathways to disperse carbon nanotubes in PEO matrix and techniques to quantitatively characterize the state of dispersion. Beyond the geometrical percolation threshold, in their quiescent state, dispersed nanotubes show hierarchical fractal network consisting of aggregated flocs. Internal to the flocs, individual or small bundles of nanotubes overlap each other to form a dense mesh. The inter-floc interaction dominates the linear viscoelasticity. The nonlinear viscoelastic behavior is independent of network size and dominated by cluster dynamics. Interestingly, significant changes in the melting and crystallization behavior of PEO along with a decrease in fractional crystallinity in the presence of carbon nanotubes have been observed. The observed changes significantly exceed those observed for an equivalent Li+ ion concentration mixture. This finding is particularly interesting considering amorphous segment of PEO chains are responsible for ion transport in solid polymer electrolytes. Besides this other technological applications of the carbon nanotube-based PEO nanocomposites will also be discussed.

The effect of pressure on the phase behavior of a multicomponent polymer blend was studied by small-angle neutron scattering (SANS). The blend was composed of saturated polybutadiene with 89% 1,2-addition (component A), polyisobutylene (component B), and an A−C diblock copolymer, where block A was chemically identical to component A and block C was a saturated polybutadiene with 63% 1,2-addition (sPB63). At atmospheric pressure, the blend forms a lamellar phase at low temperature, forms a microemulsion phase at intermediate temperatures and is macrophase separated at high temperatures. No evidence of homogeneous phases was found at atmospheric pressure. Upon pressurization the A/B/A−C blend exhibited a homogeneous phase across a wide range of pressures and temperatures. The pressure dependencies of the Flory−Huggins interaction parameters in this system (χAB, χAC, χBC) were determined from SANS measurements on binary blends and used to model the thermodynamic properties of the multicomponent blend as a fu...