Liquid crystalline acrylic copolymers for high-solids enamel coatings

Carboxyl functional liquid crystalline (LC) acrylic copolymers were synthesized and were compared with carboxyl functional control copolymers of M?_n about 5000–15,000. Both types were crosslinked with a hexakismethoxymethyl melamine (HMMM) resin at 150°C, a temperature below the clearing points of the LC copolymers. Birefringent phases were visible in the crosslinked films made from LC polymers. FT-IR indicated the presence of unreacted COOH in all crosslinked materials. Unreacted COOH groups in crosslinked LC copolymers appeared only slightly higher than those in crosslinked amorphous copolymers. The potential utility of these LC copolymers as binders for thermosetting coatings was assessed. Variables studied were HMMM content, the length of PHBA grafts, T_g and M?_n of the acrylic copolymer backbone, and functionality. Optimum LC copolymers have low backbone T_g (<O°C) and low functionality (< 7.5 mol %). Cured films of such copolymers have both high hardness (> 35 KHN), high impact resistance (> 80 in. ib), excellent adhesion, and good solvent resistance.     

Retarding effects of DNA on the autoxidation of liposomal suspensions

Deoxyribonucleic acid (DNA) is associated with the cell membrane of prokaryotes and the inner nuclear membrane of eukaryotes. The unsaturated fatty acids of phospholipids, which constitute the bilaminar structure of membranes, undergo autoxidation in the presence of O₂. Calf thymus DNA was incubated with methyl archidonate-enriched phosphatidyl choline liposomes in order to study the effect of DNA upon the oxidation of phospholipids while present in their natural in vivo bilayer configuration. DNA retarded the rate of lipid oxidation and the TBA test, but it did not alter the induction period. These results suggest that DNA is scavenging free radicals produced within the phospholipid bilayer.     

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.     

Moisture absorption by cyanate ester modified epoxy resin matrices. Part I. Effect of spiking parameters

The moisture absorption of cyanate ester modified epoxy resin matrices has been studied under thermal spiking conditions. Enhanced moisture absorption has been observed at spike-temperatures above 120 °C. The results of the desorption studies on both control specimens and the spiked specimens showed that some of the water molecules remained entrained in the polymer. It is postulated that this water could be associated with that which is hydrogen bonded or from the hydrolysis of isolated residual cyanate ester groups because the concentration of entrained water remains constant at spike-temperatures below 180 °C. Above 180 °C a thermally activated process, leading to chain scission as indicated by a reduced recoverability of the glass transition temperature (T_g) on drying.On isothermal resorption, the moisture concentration was found to be similar to that achieved through thermal spiking, showing that the entrained water at the lower spike-temperatures can also be achieved under mild conditions. The T_g is reversibly recovered to within 5 °C, which indicates a degree of relaxation rather than degradation. The moisture diffusion coefficient estimated from the resorption curves is lower than those estimated from the absorption and desorption curves. The isothermal resorption diffusion coefficient also decreased with increasing spike temperature. It is proposed that thermal spiking induced a relaxation of the network but as the spike-temperature approaches the transition region of the wet polymer, further hydrolytically induced relaxation events become feasible.     

Dietary linoleic, α-linolenic and oleic acids are oxidized at similar rates in rats fed a diet containing these acids in equal proportions

The objective of this study was to examine whether whole body oxidation rates of dietary linoleic, α-linolenic and oleic acids differ when the acids are provided in identical quantities. Male rats were fed for 10 wk a 15% fat (w/w) diet containing equal amounts of linoleic, α-linolenic and oleic acids (22.7, 23.0 and 23.2% of total fatty acids, respectively). At week 10, after overnight fasting, rats were intragastrically administered 20 μCi of either [1-¹⁴C]-labelled linoleic, α-linolenic or oleic acid in a 200-μL bolus of oil containing equal quantities of each fatty acid. The appearance of¹⁴CO₂ in expired air was then monitored hourly for 12h for each animal. A preliminary study had shown that growth and food consumption patterns in animals consuming the oil containing equal quantities of each of the fatty acids paralleled the patterns of animals that were self-selecting among separate diets, each of which contained one of the component oils. The appearance of¹⁴C, expressed as percent dose administered, peaked at 2–3 h post-dose for¹⁴C-labelled linoleic (5.28±0.37%/h), α-linolenic (6.92±0.51%/h) and oleic (5.98±0.44%/h) acids. Statistically these values were not significantly different. Cumulative¹⁴CO₂ excretion rates over 12 h were also similar for linoleic (27.2±0.9%), α-linolenic (26.8±1.2%) and oleic (25.9±1.2%) acids. The results suggest that the rat's capacity to oxidize 18-carbon unsaturated fatty acids is not affected by fatty acid unsaturation when these fatty acids are provided at equal dietary levels.     

Cyclic alkanes as geochemical markers in coal liquefaction products

Branched-chain/cyclic alkanes have been obtained, by solvent extraction and molecular-sieve adsorption, from a UK low-temperature (Rexco) coal tar, a USA fluidized-bed pyrolysis (FMC COED) coal tar, and a novel supercritical-gas-extract of a Turkish (Elbistan) lignite. Mass spectrometry (with gas chromatography and field-desorption) established the presence of mono-, di (including sesquiterpanes), tri-, tetra- (steranes only), and pentacyclic (triterpanes only) alkanes, including several steranes and triterpanes not previously reported as coal-tar constituents. The potential of cyclic alkanes as geochemical markers, even for commercial coal products subjected to appreciable heat treatment, is demonstrated by the identification of C₁₂, C₁₃, C₁₅ and C₁₆ dicyclics (including isoprenoid alkanes), C₁₇-C₂₆ tricyclics, and C₂₇ and C₂₉ hopane-type pentacyclics (triterpanes) in FMC, and of C₁₆-C₃₈ monocyclics, C₃₄-C₃₆ dicyclics, C₂₂-C₃₆ tricyclics, C₂₇-C₃₀ tetracyclics (steranes), and C₂₇, C₂₉, C₃₀, C₃₁, C₃₂, and C₃₃ hopane-type pentacyclics (triterpanes) in Rexco tar. Tetra- and pentacyclic alkanes were also preserved in the lignite extract.     

Assessment of response function in two PET scanners with and without interplane septa

The authors have assessed the response function both experimentally and theoretically for two commercial tomographs: CTI 931/08-12 and CTI 953B with and without interplane septa. Monte Carlo simulations were undertaken using the GEANT package from CERN. Spatial resolution (tomographic and axial) was calculated for line sources at various positions in the field of view. Sensitivity and scatter fraction (SF) were calculated for various source geometries as a function of energy discrimination. A very realistic response function in positron emission tomography (PET) is obtained by Monte Carlo methods, using global parameters to account for unsimulated phenomena such as scintillation light transport inside a detector block and its sharing among the various phototubes. Minor discrepancies remain for sensitivity and SF at high energy thresholds and may probably be explained by introducing the observed dispersion in the energy response for the various crystals within a detector block.     

Noise equivalent count measurements in a neuro-PET scanner with retractable septa

The noise-equivalent count-rate (NEC) performance of a neuro-positron emission tomography (PET) scanner has been determined with and without interplane septa on uniform cylindrical phantoms of differing radii and in human studies to assess the optimum count rate conditions that realize the maximum gain. In the brain, the effective gain in NEC performance for three-dimensions (3-D) ranges from >5 at low count rates to approximately 3.3 at 200 kcps (equivalent to 37 kcps in 2-D). The gains of the 3-D method assessed by this analysis are significant, and are shown to be highly dependent on count rate and object dimensions.     

Optimization of the in Situ Transesterification of Grain Sorghum (Milo) DDGS to Fatty Acid Methyl Esters and Fatty Acid Ethyl Esters

Distillers grains and solubles generated from the ethanol fermentation of grains contain acylglycerols (AG) that can be successfully converted to fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE), commonly known as biodiesel. However, when grain sorghum (milo) DDGS were used as a feedstock for in situ transesterification (IST) under the previously established optimal conditions for other AG-bearing substrates, the yield plateaued at only 32.2% (corrected in this study to 24.2%). Several IST studies have reported significantly higher conversions of AG-bearing substrates to FAME. Therefore, the goal of this IST study was to improve the conversion of the AG in milo DDGS to FAME and FAEE by varying the temperature of reaction, the concentrations of the base (sodium methylate, NaOMe), volume of methanol and ethanol, and the amount of moisture in DDGS. Methyl tert-butyl ester was also evaluated as a co-solvent intended to improve miscibility and reaction rate. Among these variables, the most effective change was an increase in temperature from 40 to 65 °C. The most successful reaction used a AG:NaOMe:MeOH molar ratio of 1.0:2.6:168.9. Those reaction conditions used 4.8 mmol NaOMe dissolved in 12.6 mL MeOH and resulted in a 79.8% conversion of AG to FAME.