Moisture absorption behavior of rubber‐modified epoxy resins

The moisture absorption behavior of diglycidyl ether of bisphenol A/ethylene diamine resins incorporating a carboxy‐terminated butadiene–acrylonitrile rubber was investigated and associated with their morphology of phase separation. Although the diffusion coefficient of moisture was increased with the rubber content, its activation energy and free volume for moisture diffusion were barely changed until phase inversion occurred. After phase inversion, the free volume was significantly increased, and the activation energy decreased. In addition, the moisture absorption also reduced the β‐transition temperature of the resins and slightly increased the glass‐transition temperature before phase inversion. However, the reverse was found after phase inversion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3718–3724, 2002     

Effects of dietary oils and methyl ethyl ketone peroxide onin vivo lipid peroxidation and antioxidants in rat heart and liver

Weanling male Sprague-Dawley rats were fed diets for four weeks which differed in their content of n−6 (corn oil; CO) and n−3 fatty acids (fish oil; FO), but were similar in their content of saturated and monounsaturated fatty acids and vitamin E. At the end of the four-week feeding period, each dietary group was subdivided into two groups. One group received a single placebo injection of α-tocopherol-stripped corn oil (TSCO); the other group received a single injection of the free radical generator, methyl ethyl ketone peroxide (MEKP), in TSCO. Twenty-four hours after injection, the effect of dietary oil and MEKP treatment on endogenous lipid peroxide (LPO) production (measured as methylene blue formed by the “Determiner LPO” assay), glutathione (GSH) and vitamin E content, and fatty acid composition of phosphatidylcholine and phosphatidylethanolamine in heart and liver from unfasted animals were measured. FO-fed rats had significantly heavier hearts and livers, increased levels of n−3 fatty acids in membrane phospholipids, and higher liver LPO levels than CO-fed rats. MEKP treatment resulted in significantly lower body weights and liver GSH levels. The data indicate that dietary n−3 fatty acids increase lipid peroxidation in liver somewhat more than in heart. The study also demonstrates that the effect of induced oxidative stress due to a single dose of MEKP on lipid peroxide formation and antioxidant status in tissues from unfasted animals was independent of the dietary oils.     

Nanoscratch testing to assess the fiber adhesion of short‐carbon‐fiber composites

In a composite material, the degree of adhesion between the fiber and the matrix plays an important role in the overall performance of the material. Because the load between the fiber and the matrix is realized throughout the interphase region material, a lot of effort has gone into characterizing the strength of the interphase. In this study, nanoscratch tests on the composite samples were used to provide a relative measure of adhesion in different composite materials. Carbon‐filled nylon 6,6 and polycarbonate resins were evaluated with this method. The carbon fillers we used were polyacrylonitrile‐based carbon fibers sized and surface‐treated for the respective matrix and pitch‐based carbon fibers without any sizing or surface treatment. Tensile and X‐ray photoelectron spectroscopy data for the composites we considered are also presented to compare to the nanoscratch results. It is shown that nanoscratch testing on the composites, with the proposed data analysis, can be an effective tool for determining the relative degree of adhesion between different composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 328–335, 2007     

Maceral and rank influences on the morphology of coal char

Concentrates of vitrinite and inertinite macerals have been pyrolysed in a flame under conditions representative of the initial stages of pulverized coal combustion. Char was distinguished from soot by size analysis and the char yield correlated with the proximate analysis. The char morphology was studied by optical microscopy and quantitative measurements of porosity and pore size were made using image analysis. Vitrinite and inertinite produce chars of characteristic morphology. The softening behaviour of inertinite varies with coal rank and can be related to the optical reflectance. The porosity of vitrinite chars approaches that of inertinite chars at high rank.     

Spectroscopic and electrical properties of 3-alkyl pyrrole-pyrrole copolymers

Three types of copolymers composed of pyrrole and 3-alkyl pyrroles (with alkyl being pentyl, nonyl and undecyl) have been synthesized. A strong linear dependency of the alkyl chain length on the as-prepared copolymer physical properties is demonstrated via (a) DSC (for phase transition temperatures and enthalpy changes) and (b) UV-vis (for wavelengths of the polaronic and bipolaronic electronic transitions, and ratio of the corresponding absorbances). A trend in the copolymers' doping level vs alkyl chain length is also estimated, via IR, by taking the ratio of band intensities of the stretching modes of the polaronic and bipolaronic species. The copolymers are found to be soluble in organic solvents and their solutions can be cast onto glass substrates or metals resulting in thin films, which can be used as the electroactive component of Schottky diodes. The electrical properties of these diodes are also found to be dependent on increasing 3-alkyl chain length.     

Synergistic Sex Pheromone Components of White-Spotted Tussock Moth, Orgyia thyellina

In 1996, the exotic white-spotted tussock moth (WSTM), Orgyia thyellina (Lepidoptera: Lymantriidae), was discovered in Auckland, New Zealand. Because establishment of WSTM would threaten New Zealand's orchard industry and international trade, eradication of WSTM with microbial insecticide was initiated. To monitor and complement eradication of WSTM by capture of male moths in pheromone-baited traps, pheromone components of female WSTM needed to be identified. Coupled gas chromatographic–electroantennographic detection analysis of pheromone gland extract revealed several compounds that elicited responses from male moth antennae. Mass spectra of the two most EAD-active compounds suggested, and comparative GC-MS of authentic standards confirmed, that they were (Z)-6-heneicosen-11-one (Z6–11-one) and (Z)-6-heneicosen-9-one, the latter termed here thyellinone. In field experiments in Japan, Z6–11-one plus thyellinone at a 100:5 ratio attracted WSTM males, whereas either ketone alone failed to attract a single male moth. Addition of further candidate pheromone components did not enhance attractiveness of the binary blend. Through the 1997–1998 summer, 45,000 commercial trap lures baited with 2000 g of Z6–11-one and 100 g of thyellinone were deployed in Auckland towards eradication of the residual WSTM population.Dedicated to my dear mother in honor of her 75th birthday     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

Decadienoates: Sex Pheromone Components of Nettle Caterpillars Darna trima and D. bradleyi

This study was undertaken to identify sex pheromone components of nettle caterpillars Darna trima and Darna bradleyi (Lepidoptera: Limacodidae) whose larvae defoliate oil palm, Elaeis guineensis, in southeast Asia. Coupled gas chromatographic–electroantennographic detection (GCEAD) analyses of pheromone gland extracts revealed two antennally active compounds produced by female D. trima and two by female D. bradleyi. Molecular structures of these candidate pheromone components were identified by electron-impact and chemical-ionization mass spectrometry; retention-index calculations on DB-5, DB-23, and DB-210 columns; microanalytical treatments, as well as syntheses of "auxilliary" compounds that facilitated identification of the compounds. The compounds from D. trima were 2-methylbutyl (E)-7,9-decadienoate (A) and (E)-2-hexenyl (E)-7,9decadienoate (B); from D. bradleyi we identified methyl (E)-7,9-decadienoate (C), and isobutyl (E)-7,9-decadienoate (D). In field experiments in Malaysia, (S)-2-methylbutyl (E)-7,9-decadienoate (SA) in combination with B proved to be essential and synergistic pheromone components for attraction of male D. trima. (R)-2-Methylbutyl (E)-7,9-decadienoate (RA) had no behavioral activity. Compound D singly attracted male D. bradleyi, but addition of C to D at a 1 : 10 ratio significantly enhanced attractiveness of the bait. Synthetic pheromone blends were more effective trap baits than unmated female moths and could be developed for monitoring populations of D. trima and D. bradleyi in Asian oil palm plantations.     

Polymer translational diffusion: 2. Non-theta solutions,polystyrene in butan-2-one

The diffusion of linear polystyrene under non-theta conditions in butan-2-one has been studied by Rayleigh light scattered linewidth measurements for the molecular weight range of 2.08 × 10⁶ to 8.7 × 10⁶ and as a function of concentration. By extrapolation of diffusion coefficient values to zero concentration we find that $\text{D}{}_0\text{= 5.5 × 10}{}^{\mathrm{?4}}\text{M}\text{?}{}^{\mathrm{?0.561}}{}_{\mathrm{w}}\text{cm}{}^2\text{s}{}^{\mathrm{?1}}$. The first order concentration dependence $\text{k}{}_{\mathrm{<mtext>d</mtext>}}\text{c}$ changes sign as the molecular weight increases, $\text{k}{}_{\mathrm{<mtext>d</mtext>}}$ being fairly small and negative at low molecular weights and increasingly positive above $\text{M}\text{?}{}_{\mathrm{w}}\text{?230 000}$.     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase, photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.