Rice husk silica as a sustainable filler in the tire industry

In this paper, we studied commercially available precipitated rice husk silica (RHS) with conventional precipitated silica, which has nearly the same surface area, and replaced part of the carbon black with RHS and conventional silica in a basic tread formulation. All formulations were mixed with the same amount of filler during the study. Silica was used at 15, 30 and 50 phr loading, and part of the carbon black was replaced by silica. Compound curing characteristics, physical properties, rebound resilience, heat generation, abrasion loss, dynamic properties and morphology were analyzed. The results indicated that RHS demonstrated compound properties comparable to those of conventional silica. As part of the carbon black was replaced with conventional silica, a slower cure rate, higher rebound resilience, lower heat generation, lower abrasion loss, and lower tan delta were observed with no significant change in physical properties, but some changes in physical properties were observed using one way ANOVA analysis. We found the same trend when replacing part of the carbon black with RHS, such as a slower cure rate, higher rebound resilience, lower heat generation, lower abrasion loss, and lower tan delta with no significant change in physical properties, but some changes in physical properties were observed using one way ANOVA. This sustainable material could be used to replace conventional silica in tire compounding, as well as to replace a portion of carbon black with RHS for improved heat build-up, rolling resistance, and abrasion loss.     

Viscoelastic properties of ultrathin polycarbonate films by liquid dewetting

A liquid dewetting method for the determination of the viscoelastic properties of ultrathin polymer films has been extended to study thickness effects on the properties of ultrathin polycarbonate (PC) films. PC films with film thicknesses ranging from 4 to 299 nm were placed on glycerol at temperatures from below the macroscopic glass transition temperature (T_g) to above it with the dewetting responses being monitored. It is found that the isothermal creep results for films of the same thickness, but dewetted at different temperatures can be superposed into one master curve, which is consistent with the fact of PC being a thermorheologically simple material. Furthermore, the results show that the T_g of PC thin films is thickness dependent, but the dependence is weaker than the results for freely standing films and similar to literature data for PC films supported on rigid substrates. It was also found that the rubbery plateau region for the PC films stiffens dramatically, but still less than what has been observed for freely standing polycarbonate films. The rubbery stiffening is discussed in terms of a recently reported model that relates macroscopic segmental dynamics with the stiffening. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1559–1566     

3D‐morphology reconstruction of nanoscale phase‐separation in polymer memory blends

In many organic electronic devices functionality is achieved by blending two or more materials, typically polymers or molecules, with distinctly different optical or electrical properties in a single film. The local scale morphology of such blends is vital for the device performance. Here, a simple approach to study the full 3D morphology of phase‐separated blends, taking advantage of the possibility to selectively dissolve the different components is introduced. This method is applied in combination with AFM to investigate a blend of a semiconducting and ferroelectric polymer typically used as active layer in organic ferroelectric resistive switches. It is found that the blend consists of a ferroelectric matrix with three types of embedded semiconductor domains and a thin wetting layer at the bottom electrode. Statistical analysis of the obtained images excludes the presence of a fourth type of domains. The criteria for the applicability of the presented technique are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1231–1237     

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

Highly dispersed palladium nanoclusters incorporated in amino‐functionalized silica spheres for the selective hydrogenation of succinic acid to γ‐butyrolactone

Highly dispersed palladium nanoclusters incorporated on amino‐functionalized silica sphere surfaces (Pd/SiO₂‐NH₂) were fabricated by a simple one‐pot synthesis utilizing 3‐(2‐aminoethylamino)propyltrimethoxysilane (AAPTS) as coordinating agent. Uniform palladium nanoclusters with an average size of 1.1 nm can be obtained during the co‐condensation of tetraethyl orthosilicate and AAPTS owing to the strong interaction between palladium species and amino groups in AAPTS. The palladium particle size can be controlled by addition of AAPTS and plays a significant role in the catalytic performance. The Pd/SiO₂‐NH₂ catalyst exhibits high catalytic activity for succinic acid hydrogenation with 100% conversion and 94% selectivity towards γ‐butyrolactone using 1,4‐dioxane as solvent at 240°C and 60 bar for 4 h. Moreover, the Pd/SiO₂‐NH₂ catalyst is robust and readily reusable without loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Small activation entropy bestows high-stability of nanoconfined D-mannitol

It has been a long-standing puzzling problem that some glasses exhibit higher glass transition temperatures(denoting high stability) but lower activation energy for relaxations(denoting low stability). In this paper, the relaxation kinetics of the nanoconfined D-mannitol(DM) glass was studied systematically using a high-precision and high-rate nanocalorimeter.The nanoconfined DM exhibits enhanced thermal stability compared to the free DM. For example, the critical cooling rate for glass formation decreases from 200 K/s to below 1 K/s; the Tg increases by about 20 K–50 K. The relaxation kinetics is analyzed based on the absolute reaction rate theory. It is found that, even though the activation energy E~*decreases,the activation entropy S~*decreases much more for the nanoconfined glass that yields a large activation free energy G~*and higher thermal stability. These results suggest that the activation entropy may provide new insights in understanding the abnormal kinetics of nanoconfined glassy systems.     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Scaling properties of fracture surfaces on glass strengthened by ionic exchange

In this work the results of the statistical topometric analysis of fracture surfaces of soda-lime-silica glass with and without ionic exchange treatment are reported. In this case, the mechanism of substitution is K⁺-Na⁺. atomic force microscopy (AFM) was employed to record the topometric data from the fracture surface. The roughness exponent (ζ) and the correlation length (ξ) were calculated by the variable bandwidth method. The analysis for both glasses (subjected and non-subjected to ionic exchange) for ζ shows a value ∼0.8, this value agrees well with that reported in the literature for rapid crack propagation in a variety of materials. The correlation length shows different values for each condition. These results, along with those of microhardness indentations suggest that the self-affine correlation length is influenced by the complex interactions of the stress field of microcracks with that resulting from the collective behavior of the point defects introduced by the strengthening mechanism of ionic exchange.     

Selectivity changes towards steroids in packed column supercritical fluid chromatography (SFC) induced by temperature and pressure variation

Summary Pressure/temperature variation in SFC was shown to influence selectivity towards steroids. Major changes were observed for polar column packings compared to non-polar packings and variation of the amount of modifier showed that this is valid over the whole investigated range. The effect is underlined by a fall in resolution in the low density range (low pressure/high temperature) for polar stationary phases and appears to be significantly larger than for non-polar phases. Major selectivity shifts induced by variation of the physical properties of the mobile phase are considered to be due to the greater effect of polar modifiers on the nature of polar stationary phases than on non-polar phases.     

Replica Symmetry Breaking in an Axial Model of Quadrupolar Glass

We investigate the replica symmetry breaking (RSB) in a neighborhood of the instability point of the replica-symmetric solution in the axial quadrupolar glass model. We show that the solution with the first-stage RSB is stable against the subsequent RSB. Although there is no reflection symmetry, the first-stage RSB solution continuously bifurcates from the replica-symmetric one. This implies that our model does not belong to either of the two classes into which spin glasses are usually divided.