Methods for the determination of cyclopropenoid fatty acids. VII. The dilution-HBr-titration technique as a general method

The stepwise HBr titration method for the cyclopropenoid analysis of cottonseed oils is subject to serious inaccuracies when applied to samples containing higher cyclopropenoid concentrations, particularly if they contain appreciable amounts of alumina-adsorbable materials. A modification of the method is described which eliminates these sources of error. Its validity has been established by the analysis of a wide range of synthetic compositions including compositions containing massive amounts of interfering HBr-reactive substances and other alumina-adsorbable materials. The method with further modification can be used to analyze glycerides with the same high degree of accuracy. Presented at the AOCS Meeting in Houston, April 1965. So. Utiliz. Res. Dev. Div., ARS, USDA.     

Thermal Conductivity/Diffusivity of Silicon Carbide Whisker Reinforced Mullite

The thermal conductivity and diffusivity of silicon carbide whisker reinforced mullite was shown to increase with whisker content. This effect was much greater for vapor-liquid-solid (VLS) whiskers than for rice-hull (RH) whiskers. This suggests that the thermal conductivity for the VLS whiskers was significantly higher than for the RH whiskers. Due to preferred orientation of the whiskers, thermal conductivity and diffusivity of the composite samples exhibited significant anisotropy.     

Some mechanical properties of an epoxy resin system cured with multiple crosslinking agents

Arbitrary cure times and glass transition temperatures are reported for an epoxy resin cocrosslinked by various weight fractions of hexamethylenediamine (HMDA) and m-phenylenediamine (m-PLDA). The glass transition temperatures of the epoxy resin systems studied yielded an excellent fit to an empirical equation developed by Dyvik for copolymers. The cure time parameters were found to be a linear function of the weight fractions of each crosslinking agent present. The mechanical properties of the epoxy resins were measured by an in situ dynamic modulus technique which employed the use of a resin-coated metallic substrate.     

Hydrolytic degradation of ionically cross-linked polyphosphazene microspheres

The hydrolytic degradation of gel microspheres based on calcium cross-linked phosphazene polyelectrolytes, poly[di(carboxylatophenoxy)phosphazene] (PCPP) and poly[(carboxylatophenoxy) (glycinato)phosphazene] (PCGPP), was investigated. These microspheres are of importance as carriers in protein and cell encapsulation. Both PCPP and PCGPP ionotropic polyphosphazene hydrogels are degradable in an aqueous environment (pH 7.4, 37°C). The degradation rates can be increased by incorporation of hydrolysis sensitive glycinato groups as the pendant structures in the polymer (PCGPP). Hydrolysis of these polymer hydrogels led to low molecular weight (<1,000 Da) products. The erosion and molecular weight profiles varied also according to the molecular weight of the polyphosphazene constituting the gel beads. Another approach to affect the degradation rates consists of coating microspheres with poly-L -lysine. Ionotropic polyphosphazene hydrogels have potential as biodegradable devices for controlled drug delivery systems. © 1994 John Wiley & Sons, Inc.     

Mechanism of carbon nanotube growth from camphor and camphor analogs by chemical vapor deposition

Single walled nanotubes have been synthesized by chemical vapor deposition from camphor, camphor analogs (camphorquinone, norcamphor, norbornane, camphene, fenchone), and various other precursors (menthone, 2-decanone, benzene, methane). The high temperature conditions (865 °C) and Fe/Mo alumina catalyst used in the syntheses are archetypal conditions for the production of single walled carbon nanotubes. It has been shown that the mechanism of tube growth is unlikely to depend upon the production of reactive five- and six-member rings, as has been previously suggested. The results suggest that the presence of oxygen in the precursor does not significantly improve the quality of tubes by etching amorphous carbon: it is suggested that the control of the flux of the precursor to the catalyst is more important in the production of high quality tubes. There is, however, evidence for different distributions of tube diameter being produced from different precursors.     

N-phenylaminomethylation: A one-step route to N-substituted anilines from unsaturated fatty derivatives and olefins

Unsaturated fatty materials, such as ethyl oleate and oleonitrile, are found to react with carbon monoxide, hydrogen and aniline at 150 C to give N-monoalkylanilines. The alkyl group is derived from the unsaturated fatty material plus the group H-CH₂ added across the double bond. Similarly 1-decene, in a rapid reaction, gives N,N-di-n-undecylaniline and N-undecylaniline as major and minor products respectively. 1,2,3-Tris-(triphenylphosphine)trichlorohodium is an excellent catalyst for this reaction. Presented at the AOCS Meeting, San Francisco, April 1969.     

Chlorination of polystyrene

Chlorination of a low molecular weight polystyrene in the α position was studied by following changes in the infrared spectrum, glass transition temperature, and molecular weights of the polymer. The logarithm of the absorbance ratio at 2920 and 1500 cm^?1 as a function of mole per cent chlorination was linear. The glass transition temperatures, determined by use of a differential scanning calorimeter (DSC), were found to obey an equation developed by Dyvik for copolymers. The molecular weight of the chlorinated polystyrene decreased as a function of chlorination.     

The participation of soluble factors in the ω-oxidation of fatty acids in the liver of the sheep

The removal of soluble components from an ovine hepatic microsomal preparation decreased the ω-hydroxylation of dodecanoic and hexadecanoic acids. The results suggest that one or more soluble components play a role in the microsomal ω-hydroxylation of fatty acids. The possible roles in the reaction of catalase (known to stimulate the microsomal desaturations of fatty acids and alkylglycerols) and superoxide dismutase were investigated. The addition of these enzymes to the complete (but not the washed) microsomal preparation stimulated both the initial ω-hydroxylation reaction and the subsequent dehydrogenation reactions of the ω-oxidation pathway. The similarity of the effects of catalase and superoxide dismutase and stimulation of two different steps of the ω-oxidation pathway suggest that these agents are acting indirectly by removing active oxygen species rather than directly on the enzymes of microsomal fatty acid ω-hydroxylation.     

Cure rates of some epoxy systems

The property changes of Epon 828 crosslinked by either diethylenetriamine or m-phenylenediamine at several temperatures have been studied by two in situ techniques. The mechanical property changes were followed by continuously monitoring the changes in the fundamental frequency of vibration during cure of a resin-coated substrate acting as a cantilever reed. The disappearance of the reactive epoxy group was followed in situ by continuously monitoring the absorbance of the infrared epoxide band at 915 cm.^?1. Correlation of the two techniques was accomplished by normalizing both the mechanical property and infrared data. The apparent energy of activation was calculated to be 10.4 and 11.4 kcal. /mole, respectively, for the m-phenylenediamine and diethylenetriamine systems by the mechanical technique, and 11.0 kcal./mole for the m-phenylenediamine crosslinked system by the infrared technique.     

Effects of Particle Size on the Fusion of Soda–Lime–Silicate Glass Containing NaCl

The coupled effects of particle size and 1 wt% NaCl additions on the sequence of melting reactions in a multicomponent system (sand–soda ash–calcite–dolomite–feldspar) were studied using data from DTA, DTGA, and XRD interactively. Glass batches varied in average particle size from 250 μm to finer than 45 μm. Milestone events in the fusion process of the coarse particle base glass were elucidated. The termination temperature of the last significant reaction associated with CO₂ release was 35°C lower in the fine particle size batch than with the coarsest batch. Liquid-phase formation at ∼523°C in the batch with 1 wt% NaCl occurred to an increasingly sizable extent with decreasing particle size. This contrasts with a similar effect at ∼630°C for a comparable batch without NaCl via eutectic melting between soda ash and dolomite. Sodium chloride additions significantly enhanced dissolution of CaO relic.