Rheological analysis of vapor‐grown carbon nanofiber‐reinforced polyethylene composites

The melt rheological analysis of high‐density polyethylene reinforced with vapor‐grown carbon nanofibers (VGCNFs) was performed on an oscillatory rheometer. The influence of frequency, temperature, and nanofiber concentration (up to 30 wt %) on the rheological properties of composites was investigated. Specifically, the viscosity increase is accompanied by an increase in the elastic melt properties, represented by the storage modulus G′, which is much higher than the increase in the loss modulus G″. The composites and pure PE exhibit a typical shear thinning behavior as complex viscosity decreases rapidly with the increase of shearing frequency. The shear thinning behavior is much more pronounced for the composites with high fiber concentration. The rheological threshold value for this system was found to be around 10 wt % of VGCNF. The damping factor was reduced significantly by the inclusion of nanofibers into the matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 155–162, 2004     

3-D molecular assembly of function in titania-based composite material systems

Various examples of composite titania-based nanostructured materials exhibiting cooperative functionalities between different active components are presented. The fabrication of these integrated composite materials is based on one-pot supramolecular templating techniques combined with acidic sol-gel chemistry. The defined 3-D nanoscale organization and integration of various functional components results in advanced optoelectronic and photonic applications such as visible light sensitization of mesoporous titania photocatalysts with cadmium sulfide nanocrystals acting as sensitizing integral part of the mesopore wall structure, narrow bandwidth emission from rare earth ion activated nanocrystalline mesoporous titania films, and mirrorless lasing in dye-doped hybrid organic/inorganic mesostructured titania waveguides.     

Iridoid glycoside metabolism and sequestration byPoladryas minuta (Lepidoptera: Nymphalidae) feeding onPenstemon virgatus (Scrophulariaceae)

A bivoltine checkerspot butterfly,Poladryas minuta, is aPenstemon specialist, not known to utilize any other plant genus for oviposition and larval feeding. At several intermontane plains sites of central Colorado, the butterfly utilizesPenstemon virgatus as its sole host plant. Analysis of the host plant showed it to contain three cinnamyl-type catalpol esters (scutellarioside-II, globularin, globularicisin) and catalpol. The host plant contained an average of 10% dry weight iridoids, but some variation among individual plants and leaves within plants was noted. Field-collected butterflies contained 2.1–8.7% dry weight catalpol, but no other iridoids. Adults from larvae fedP. virgatus in the lab contained 4.2–9.0% dry weight catalpol and excreted large amounts of catalpol in the meconium. No catalpol was found in the larval frass. Larvae did not consume three alternate iridoid-containing host-plant species, and most eventually died rather than feed on the alternate plants. Larvae did consume small amounts of artificial diets containing the alternate species andP. virgatus, but most went into diapause and some died. Survival was good on artificial diet containing 10% dry weight of the iridoid esters fromP. virgatus. Only catalpol was found in pupae and adults, but it was absent from the larval frass. The cinnamic-type acids expected from larval hydrolysis of the esters were not found in larval frass, pupae, or adults. These results are contrasted with those found for another checkerspot,Euphydryas anicia, which consumes a different host-plant species but was present at one of the same sites withPoladryas minuta.Paper 15 in the series Chemistry of the Scrophulariaceae. Paper 14 Boros, C.M., Stermitz, F.R., and Harris, G.H. 1990.J. Nat. Prod. 5372–80.     

Lipase-catalyzed esterification of lactic acid with straight-chain alcohols

Enzymatic synthesis of esters of lactic acid and straight-chain alcohols with different chain lengths (C₆–C₁₈) were investigated in batch reactions with hexadecanol (C₁₆) as the model alcohol. Cyclohexane was the best solvent for higher ester yields, and the best biocatalyst was the immobilized Candida antarctica lipase B (Novozym 435) as well as the textile-immobilized Candida sp. lipase. A method was established to obtain ester yields in the range of 71 to 82% for the different alcohols, and the most favorable conditions for the esterification reaction using Novozym 435 were an equimolar ratio of lactic acid to alcohol, each at a concentration of 120 mM each; a 50°C reaction temperature; 190 rpm shaking speed; and the addition of 100 mg molecular sieves (4 Å) for drying. The ester yield increased with increasing lipase load, and a yield of 79.2% could be obtained after 24 h of reaction at 20 wt% of Novozym 435. The immobilized Candida sp. lipase prepared in the laboratory also could be used to produce esters of lactic acid and straight-chain alcohols, but it had a much lower activity than Novozym 435 with a temperature optimum of 40°C.     

Novel biocatalysts: Recent developments

The limited number of suitably well characterized biocatalysts continues to limit progress in the application of biological routes in the synthesis of compounds for novel pharmaceuticals, materials, or performance chemicals. In this situation, the discovery of novel biocatalysts or novel functionalities or substrates on existing ones is an important task. This work describes a range of novel biocatalysts obtained recently through one of three techniques: environmental sampling or screening, protein engineering on existing enzymes, or extension of the catalytic profile of existing catalysts.     

Reactions of glycerol with poly(ethylene ether carbonate) polyols

Poly(ethylene ether carbonate) polyols can be modified by chemical reactions with polyglycol modifiers under conditions of elevated temperatures and reduced pressures. The modifier becomes chemically incorporated into the modified polyol and is used to control properties such as moisture sensitivity, CO₂ content, T_g, density, etc. in the resultant polyol. However, glycerol cannot be used as a modifier for poly(ethylene ether carbonate) polyols under the same conditions since it reacts with poly(ethylene ether carbonate) polyols by a transesterification reaction sequence to form glyceryl carbonate. As the temperature is increased, the glyceryl carbonate decomposes to yield glycidol and carbon dioxide. These reactions are conveniently followed by ¹³C-NMR. The preparation of glyceryl carbonate by this process has not been previously reported.     

Application of image analysis based on SEM and chemical mapping on PC mortars under sulfate attack

The degradation mechanisms of cementitious materials exposed to sulfate solutions have been controversial, despite considerable research. In this paper, two methodologies of image analysis based on scanning electron microscope and chemical mapping are used to analyse Portland cement mortars exposed to sodium sulfate solution. The effects of sulfate concentration in solution and water to cement ratio of mortar, which are considered as the most sensitive factors to sulfate attack, are investigated respectively by comparing the macro expansion with microstructure analysis. It is found that the sulfate concentration in pore solution, expressed as sulfate content in C-S-H, plays a critical role on the supersaturation with respect to ettringite and so on the expansion force generated.     

Combination of the Elevated Stearic Acid Trait with Other Fatty Acid Traits in Soybean

Stearic acid is one of five major fatty acids found in soybean oil. It is a fully saturated lipid and is known for neutral or positive effects on LDL cholesterol when consumed by humans. Unfortunately, stearic acid only accounts for about 4% of the total seed oil produced in commodity soybean. Previous work has shown that stearic acid can reach levels as high as 28% of the total oil fraction when the SACPD-C gene, encoding the delta-9-stearoyl-acyl carrier protein desaturase responsible for most of the stearic acid variation in soybean seed, is ablated in combination with other loci. In order to increase stearic acid content and create soybeans with improved utility based on fatty acid composition, we combined mutations in SACPD-C with other mutations in the fatty acid biosynthetic pathway. Soybean plants carrying mutant alleles of both SACPD-C and FAD2-1A produce seed with stearic acid levels from 14% to 21%, and with elevated levels of oleic acid. Soybeans carrying mutations in both SACPD-C and FAD3A or FAD3C have both statistically significantly elevated levels of stearic acid (from 15–21%) and statistically reduced linolenic acid levels. Neither mutant combination appears to affect other agronomic properties such as plant morphology or seed protein levels making this a potentially viable trait.     

Chemical and morphological effects of blended sulfonated poly(styrene-isobutylene-styrene) and isopentylamine for direct methanol fuel cell applications

In this study, blend membranes based on a combination of sulfonated poly (styrene-isobutylene-styrene) (SIBS) with isopentylamine (IPA) were synthetized as potential candidates for direct methanol fuel cell (DMFC) applications. The impact of sulfonation level (57–93 mol%) and percentage of IPA incorporation (1, 3, and 5 wt%) were analyzed via different properties of the resulting membrane. FTIR analysis showed that IPA was successfully incorporated into the sulfonated polymer matrix and also confirmed the interaction between the sulfonic and amine groups. This interaction generates significant morphological changes in the nanostructure of the membranes that are evident through results of small angle x-ray scattering and atomic force microscopy analysis. Proton conductivity and methanol permeability of the membranes were also analyzed. Proton conductivity was significantly enhanced with the incorporation of IPA at an optimum loading, creating additional paths for the conduction of protons through the membrane. It was also sensitive to the morphological changes produced after the IPA incorporation and the interconnection between the ionic domains. Methanol permeability increased slightly due to the additional water domains and the inability of the isopentyl groups of IPA to block the free-volume in the membrane. Despite this, the selectivity (proton conductivity over methanol permeability) of the membranes was comparable to the state-of-the-art Nafion®, especially at an optimum IPA incorporation of 3 wt%.     

Effect of substrate surface roughness on the adherence of NiCrAlY thermal spray coatings

The adherence of plasma sprayed NiCrAlY bond coats can be improved by an appropriate substrate surface finish. The interface fracture energy for crack propagation along the coating/substrate interface has been measured for different surface roughness by means of a specially designed four-point bending test. An increase of the interface fracture energy of about 15% was observed for a three times higher surface roughness. In addition, four-point bending tests with the coating on the side face of bending specimens were performed to analyze the fracture and spalling behavior of the coatings both under large tensile and compressive substrate deformations.