Thermo-Mechanical Properties of Semi-Degradable Poly(β-amino ester)-co-Methyl Methacrylate Networks under Simulated Physiological Conditions

Poly(β-amino ester) networks are being explored for biomedical applications, but they may lack the mechanical properties necessary for long term implantation. The objective of this study is to evaluate the effect of adding methyl methacrylate on networks’ mechanical properties under simulated physiological conditions. The networks were synthesized in two parts: (1) a biodegradable crosslinker was formed from a diacrylate and amine, (2) and then varying concentrations of methyl methacrylate were added prior to photopolymerizing the network. Degradation rate, mechanical properties, and glass transition temperature were studied as a function of methyl methacrylate composition. The crosslinking density played a limited role on mechanical properties for these networks, but increasing methyl methacrylate concentration improved the toughness by several orders of magnitude. Under simulated physiological conditions, networks showed increasing toughness or sustained toughness as degradation occurred. This work establishes a method of creating degradable networks with tailorable toughness while undergoing partial degradation.     

Micro-channel development and hydrogen adsorption properties in templated microporous carbons containing platinum nanoparticles

Ordered microporous carbons containing dispersed platinum nanoparticles were fabricated and chosen as suitable models to investigate micro-structure development and hydrogen transport properties of zeolite-templated carbons. X-ray photoelectron spectroscopy analysis revealed that the enhanced heat of adsorption is related to the narrow micro-channels templated from the zeolite and the presence of certain CO groups on the carbon. The lack of a well-defined and intense rotational transition line and the persistent broad H₂ recoil spectrum in neutron scattering results suggests a distribution of binding sites. Most interestingly, hydrogen diffusion occurs on two time scales, consisting of a fast liquid-like jump diffusion on the timescale of picoseconds along with an even faster bulk-like diffusion. The liquid-like motion is characterized by a diffusion constant of (2.1 ± 0.3) × 10⁻⁸ m²/s with an activation energy of ca. 77 K; both values indicate somewhat lower mobility than similar dynamics of H₂ on nanotubes, activated carbon XC-72, or Grafoil, yet greater mobility than that of bulk liquid. These unusual characteristics for hydrogen in carbons are believed to arise from the network of narrow pores in this zeolite-templated image of the zeolite. In fact, the diffusion constants of the templated carbons are extremely similar to those measured for zeolite 13X.     

Enhanced high-temperature polymer electrolyte membrane for fuel cells based on polybenzimidazole and ionic liquids

Polybenzimidazole (PBI)/ionic liquid (IL) composite membranes were prepared from an organosoluble, fluorine-containing PBI with ionic liquid, 1-hexyl-3-methylimidazolium tri?uoromethanesulfonate (HMI-Tf). PBI/HMI-Tf composite membranes with different HMI-Tf concentrations have been prepared. The ionic conductivity of the PBI/HMI-Tf composite membranes increased with both the temperature and the HMI-Tf content. The composite membranes achieve high ionic conductivity (1.6 × 10⁻² S/cm) at 250 °C under anhydrous conditions. Although the addition of HMI-Tf resulted in a slight decrease in the methanol barrier ability and mechanical properties of the PBI membranes, the PBI/HMI-Tf composite membranes have demonstrated high thermal stability up to 300 °C, which is attractive for high-temperature (>200 °C) polymer electrolyte membrane fuel cells.     

High styrene–rubber ionomers,an alternative to thermoplastic elastomers

High styrene rubber ionomers were prepared by sulfonating styrene–butadiene rubber of high styrene content (high styrene rubber) in 1,2‐dichloroethane using acetyl sulfate reagent, followed by neutralization of the precursor acids using methanolic zinc acetate. The ionomers were characterized using X‐ray fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), dynamic mechanical analysis (DMA), and also by the evaluation of mechanical properties. The FTIR studies of the ionomer reveal that the sulfonate groups are attached to the benzene ring. The NMR spectra give credence to this observation. Results of DMA show an ionic transition (T_i) in addition to glass–rubber transition (T_g). Incorporation of ionic groups results in improved mechanical properties as well as retention of properties after three cycles of processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2294–2300, 2002     

Micromechanisms of Tack of Soft Adhesives Based on Styrenic Block Copolymers

The tackiness of model soft adhesive layers based on styrene‐isoprene‐styrene block copolymers and a tackifying resin were investigated with a flat‐ended cylindrical steel probe. The contact between the probe and the adhesive was maintained for 1 s at a nominal pressure of 1 MPa before being detached at a constant velocity. The effect of resin content, probe velocity during debonding and temperature were systematically investigated. Failure was initiated by two main mechanisms: an interfacial cavitation at low debonding rates, giving relatively low adhesion energies, and a bulk cavitation process at higher debonding rates, which gave much higher adhesion energies. In both cases failure occurred at the end by interfacial detachment of fibrils. The characteristic probe velocity where the transition between these two mechanisms took place was controlled primarily by the linear viscoelastic properties of the adhesives. However, the important quantitative parameters obtained from a tack test, i.e., the maximum debonding stress and the adhesion energy, could not be predicted by the linear viscoelastic properties of these adhesives alone.     

Phylloquinone (vitamin K1) and dihydrophylloquinone content of fats and oils

Assessment of vitamin K (VK) dietary intakes has been limited by the incompleteness of VK food composition data for the U.S. food supply, particularly for VK-rich oils. The phylloquinone (VK-1) and 2′,3′-dihydrophylloquinone (dK) concentrations of margarines and spreads (n=43), butter (n=4), shortening (n=4), vegetable oils (n=6), and salad dressings (n=24) were determined by RP-HPLC with fluorescence detection. Each sample represented a composite of units or packages obtained from 12 or 24 outlets, which were geographically representative of the U.S. food supply. Butter, which is derived from animal fat sources, had less VK-1 compared to vegetable oil sources. The VK-1 and dK of the margarines and spreads increased with fat content and the degree of hydrogenation, respectively. In some margarines or spreads and in all shortenings, the dK concentrations were higher than the corresponding VK-1 concentrations. As the fat content of salad dressings increased, the VK-1 concentrations also increased. Fat-free foods had <1 μg/100 g of either form of the vitamin. No dK was detected in the salad dressings or oils tested. Some margarines, spreads, and salad dressings may be significant sources of vitamin K in the U.S. food supply.     

Synthesis of N,N-diethyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}amine via in situ diazotisation and coupling in supercritical carbon dioxide

The synthesis of azo dyes via a conventional aqueous-based diazotisation and coupling reaction requires the use of relatively high concentrations of mineral acids, which leads to high electrolyte concentrations in wastewater. Reported in this paper is an environmentally benign one-pot method for the synthesis of a nonionic azo dye, N,N -diethyl- N -{4-[( E )-(4-nitrophenyl)diazenyl]phenyl}amine, in supercritical carbon dioxide without using a mineral acid. The product yield increased significantly with temperature, with 91% theoretical yield afforded at 80 °C. The pressure of the system had little influence on product yield.     

An improved accelerated weathering protocol to anticipate Florida exposure behavior of coatings

A new accelerated weathering protocol has been developed which closely replicates the performance of automotive and aerospace coating systems exposed in South Florida. IR spectroscopy was used to verify that the chemical composition changes that occurred during accelerated weathering in devices with a glass filter that produced a high fidelity reproduction of sunlight’s UV spectrum matched those that occurred during natural weathering. Gravimetric water absorption measurements were used to tune the volume of water absorption during accelerated weathering to match that which occurred during natural weathering in South Florida. The frequency of water exposure was then scaled to the appropriate UV dose. A variety of coating systems were used to verify the correlation between the physical failures observed in the accelerated weathering protocol and natural weathering in South Florida. The new accelerated weathering protocol correctly reproduced gloss loss, delamination, cracking, blistering, and good performance in a variety of diverse coating systems. For automotive basecoat/clearcoat paint systems, the new weathering protocol shows significant acceleration over both Florida and previous accelerated weathering tests. For monocoat aerospace systems, the new weathering protocol showed less acceleration than for automotive coatings, but was still an improvement over previous accelerated tests and was faster than Florida exposure.     

Structural Studies and Valence Band Splitting Parameters in Ordered Vacancy Compound AgGa7Se12

The threefold absorption in the fundamental absorption region of the ternary chalcopyrite AgGa₇Se₁₂, an ordered defect compound of AgGaSe₂, is analyzed to elucidate the three closely spaced band gaps in its valence band due to the lifting of degeneracy of the Γ₁₅ level. Hopfield’s quasi cubic model is employed to extract the crystal-field and spin–orbit splitting parameters and the linear hybridisation of orbitals model for evaluating the percentage contribution of Ag d-orbital and Ga and Se p-orbitals to the p–d hybridization of orbitals. The observed optical properties are correlated with the structural parameters like deformation parameter, anion displacement and anion–cation bond lengths that are deduced from X-ray diffraction data. The compound films for the studies are prepared by a modified form of Gunther’s three temperature technique and the compositional analysis was done by energy dispersive analysis of X-rays. X-ray photoelectron spectroscopy confirms the compound formation while atomic force microscopic technique was used for surface morphological analysis. The electrical resistivity of these n-type semi-conducting films is assessed to be ~5 Ωm and the films are found to be photosensitive.     

Microwave dielectric properties of flexible butyl rubber–strontium cerium titanate composites

Butyl rubber–strontium cerium titanate (BS) composites have been prepared by hot pressing. The tensile tests show that the BS composites are flexible. The dielectric properties of the composites have been investigated at 1 MHz and 5 GHz as a function of ceramic contents. The composite with volume fraction 0.43 of ceramic filler has a dielectric constant (ε_r) of 11.9 and dielectric loss (tan δ) 1.8 × 10^?3 at 5 GHz. The measured values of ε_r are compared with the effective values calculated using different theoretical models. The thermal conductivity of the composites is found to increase with ceramic contents and reaches a value of 4.5 Wm^?1 K^?1 for maximum filler loading 0.43 volume fraction. The coefficient of thermal expansion of the composites decreases gradually with filler loading and reaches a minimum value of 30.2 ppm °C^?1 at a volume fraction 0.43. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012