Cure kinetics of neat and graphite-fiber-reinforced epoxy formulations

An investigation was carried out into the cure kinetics of neat and graphite fiber-reinforced epoxy formulation, composed of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) resin and diaminodiphenyl sulfone (DDS) curing agent. Two experimental techniques were employed: isothermal differential scanning calorimetry (IDSC) and dynamic differential scanning calorimetry (DDSC). An autocatalytic mechanism with the overall reaction rate order of 2 was found to describe adequately the cure kinetics, of the neat resin and the composite. All kinetic parameters, including reaction rate constants, activation energies and preexponential factors, were calculated and reported. The presence of graphite fibers in the composite had only a very small initial effect on the kinetics of cure.     

Mechanical properties of moist agglomerates in relation to granulation mechanisms part I. Deformability of moist,densified agglomerates

The mechanical properties of moist samples of fine, polydisperse powders are investigated by measuring the tensile strength by a diametrical compression test and the stress—strain relationship of samples exposed to uniaxial compression. The strengths determined by the two methods correlate well. The strength of moist samples compressed to porosities comparable to the level of intragranular porosities achieved by granulation in high-speed mixers is shown to be influenced significantly by particle interactions in addition to mobile liquid bondings. For a particular material the strength is controlled mainly by porosity and liquid saturation. It is shown that the effect of a growing liquid saturation is to reduce particle interactions and thus to facilitate densification during granulation. The deformability of moist samples, which is dependent on strength and deformation behaviour, is assessed for lactose and dicalcium phosphate.     

Secondary products from high pressure hydrogenation of crambe oil

Hydrogenation of crambe oil, mainly an α,α’-dierucoyl triglyceride, in the presence of cadmium promoted copper-chromite provides long chain waxes being sought as sperm whale oil replacements. Gas liquid chromatography and gas chromatography-mass spectrometry analyses of secondary products indicate, however, that reduction proceeds rather differently from Adkins-type hydrogenations of triglycerides over copper-chromium oxide catalysts. Monoand diunsaturated alkenes ranging from C₁₆-C₂₄, odd chain lengths included, constitute ca. 1% of the product. Esters of crambe acids with methyl, ethyl, n-propyl, and isopropyl alcohols account for less than 5%. These alcohols and traces of 1,2-propanediol from the hydrogenolysis of glycerol occur in either the head gas or the reaction mixture or both. In contrast to published results for Adkins-type hydrogenations of triglycerides, n-propyl alcohol is far more abundant than isopropyl alcohol or 1,2-propanediol. Isopropyl esters of C-18 acids are not present, and those of C-22 acids constitute no more than 2% of the total esters. Low proportion of isopropyl esters and enrichment of C-22 acids in the secondary products compared with C-18 acids suggest that the acyl substituent at the β-position of glycerol is eliminated during hydrogenation of crambe oil with a Cd−Cu−Cr catalyst. Presented at the AOCS Meeting, Mexico City, April 1974. ARS, USDA.     

Analysis and monitoring oftrans-isomerization by IR attenuated total reflectance spectrophotometry

Attenuated total reflectance for IR determination oftrans-isomers in fats appears to have distinct advantages over procedures currently used. The AOCS standard method CD 14-61 requires weighing and quantitative dilution of a sample with carbon disulfide before spectrophotometric analysis at 10.3 μm. In contrast, according to the attenuated total reflectance analytical procedure, one neither weighs nor dilutes but merely fills the cell with oil and reads at 10.3 μm. In addition to analyses fortrans-isomers in liquid oils, margarines and shortenings, attenuated total reflectance enables one to monitortrans-development continuously during hydrogenation. The presence of catalyst in unfiltered hydrogenated oils does not interfere with attenuated total reflectance measurements in contrast to classical transmission measurements. Unfiltered oil from the hydrogenator can be circulated through the attenuated total reflectance cell to recordtrans-isomerization during the reaction. ARS, USDA.     

Characterization of branched chain fatty acids from subcutaneous triacyglycerols of barley-fed lambs

The fatty acids of subcutaneous triacylglycerols (containing ca. 11% of branched chain components) from lambs fed on barley-rich diets were fractionated by treatment with mercuric acetate and by urea adduct formation to yield concentrates rich in the branched chain components, all of which were saturated. The concentrates were subjected to analysis by high resolution gas liquid chromatography in conjunction with mass spectrometry. The branched chain fatty acids consisted of a complex mixture of mono-, di-, and trimethyl substituted components. The greater part of the mixture comprised monomethyl substituted acids of chain length 10–17 carbon atoms. Within each of these molecular species, a number of positional isomers was identified, notably in respect of methyltetradecanoic acid (methyl substituent on carbon 2, 4, 6, 8, 10, and 12) and methylhexadecanoic acid (methyl substituent on carbon 2, 4, 6, 8, 12, and 14). Homologous series also could be recognized of one of which all eight members from 4-methyldecanoic acid to 4-methylheptadecanoic acid were identified; together they accounted for ca. 39% of the branched chain fatty acids which were sampled for mass spectrometry. The dibranched acids identified consisted of five members of a homologous series, ranging in chain length from 11–15 carbon atoms and with substituent methyl groups at positions 4 and 8. Though the identity of only one tribranched acid (2,6,10-trimethyltetradecanoic acid) was established, others also apparently were present in the mixture. The probable involvement of methylmalonate in the biosynthesis of these branched chain acids is discussed briefly, with particular reference to the availability of vitamin B₁₂ in relation to the activity of methylmalonyl coenzyme A mutase.     

High performance liquid chromatographic separation of sucrose fatty acid esters

The synthesis of sucrose fatty acid esters always results in complex mixtures. Two procedures for quantitative analysis of sucrose monoesters, respectively sucrose diesters, by means of high performance liquid chromatography on reversed-phase columns, are described. A mixture of methanol and water (85:15, v/v) was used for the separation of the monoesters, while methanol, ethyl acetate and water (65:25:10, v/v/v) was used for the separation of diesters. These methods gave information about the amount of monoesters and diesters in the product; the ratio between sucrose monopalmitate and sucrose monostearate, and the number of the most important structure isomers. A complete separation of all the possible diester products seemed to be impossible, due to the presence of more complex structure isomers. The described procedures can give important support during preparative work on sucrose fatty acid esters and also in the evaluation of these products for application purposes.     

Hyper-Spherical Search (HSS) algorithm: a novel meta-heuristic algorithm to optimize nonlinear functions

This paper proposes a novel optimization algorithm called Hyper-Spherical Search (HSS) algorithm. Like other evolutionary algorithms, the proposed algorithm starts with an initial population. Population individuals are of two types: particles and hyper-sphere centers that all together form particle sets. Searching the hyper-sphere inner space made by the hyper-sphere center and its particle is the basis of the proposed evolutionary algorithm. The HSS algorithm hopefully converges to a state at which there exists only one hyper-sphere center, and its particles are at the same position and have the same cost function value as the hyper-sphere center. Applying the proposed algorithm to some benchmark cost functions shows its ability in dealing with different types of optimization problems. The proposed method is compared with the genetic algorithm (GA), particle swarm optimization (PSO) and harmony search algorithm (HSA). The results show that the HSS algorithm has faster convergence and results in better solutions than GA, PSO and HSA.     

Massenspektrometrische Untersuchung von dimeren Fettsäuren aus einem thermisch und oxydativ belasteten Bratfett

Mass Spectrometric Investigation of Dimeric Fatty Acids from Frying Fats Subjected to Thermal and Oxidative Action Methyl esters of dimers from peanut oil subjected to thermal and oxidative action in an industrial frying plant were isolated by column chromatography and investigated by mass spectrometry. Di-unsaturated bicyclic and tetra-unsaturated acyclic structures were found to be the main components of the dimers. Dimers of very similar composition were synthesized. The mechanism of dimer formation is discussed.     

Cysteine adds to lipid hydroperoxide

Cysteine reacts with linoleic acid hydroperoxide to yield several products, some of which were identified as fatty acid-cysteine adducts. The addition was catalyzed by ferric chloride (10⁻⁵ M) by initiating free radical reactions. When isomerically pure 13-hydroperoxy-cis-9,trans-11-octadecadienoic acid and cysteine were reacted in 80% ethanol under N₂, the major adducts were 9-S-cysteine-13-hydroxy-10-ethoxy-trans-11-octadecenoic acid (I) and 9-S-cysteine-10,13-dihydroxy-trans-11-octadecenoic acid (II). When the reaction included both isomers of the hydroperoxide (13-and 9-hydroperoxide) and air, an adduct of 9-oxononanoic acid and cysteine also was isolated. Additional experiments gave information about possible mechanisms of I and II formation.