A solution thermodynamic study of soybean oil/solvent systems by inverse gas chromatography

Inverse gas chromatography (IGC) has seen wide application in the characterization of molten polymers, fibrous materials, and natural products, such as proteins and carbohydrates, over the past fifteen years. This study describes a relatively simple IGC technique for evaluating solute-solvent interactions using a refined soybean oil as a solvent. Utilizing soybean columns that are 5–20% by weight of the inert support has allowed the determination of a number of thermodynamic solution parameters for 22 solute-solvent pairs in the temperature range of 55–125°C. Weight and mole fraction activity coefficients, along with Henry's Law constants at infinite dilution, are presented for six solute classes. In general, activity coefficients increase with carbon number for n-alkanes, alkyl-substituted benzenes, and n-alkanoic acids at all temperatures investigated, while the reverse is found for the n-alkanols. The activity coefficient data indicate that aromatic solutes, chlorinated hydrocarbons, ketones, and cyclohexane can readily dissolve soybean oil. Calculated heats of mixing for n-alkanols were found to be positive (to 2.84 kcal/mole) while recorded enthalpic interactions were weak for aromatic solutes, lower alkanes, and chlorinated hydrocarbons. The relevance of the above data to such problems as oil dissolution and solvent devolatilization are discussed. Presented at the American Oil Chemists' Society Annual Meeting in Phoenix, Arizona, in May 1988.     

Enlargement of the micropores of a caking bituminous coal by controlled oxidation

In a study of the enlargement of pores of coals it has been found that treatment of a bituminous coal (PSOC No. 371, from the Pennsylvania State University Coal Section) with a 5:95 O₂:N₂ stream 4 h at 400 °C increases the surface area as measured by nitrogen adsorption at 77K by a factor of at least 50 to a value 52 m² g^?1. The increase in pore size was accompanied by a 9.7% weight loss. Simultaneously, the area as measured by carbon dioxide at 195K increased from 61 to 136 m² g^?1 and that measured by carbon dioxide at room temperature increased from 125 to 237 m² g^?1. Attempts to enlarge the pores by oxidation with hydrogen peroxide or ozone were unsuccessful. A Pittsburgh coal subject to a small percentage of oxygen in nitrogen or steam at 300 to 400 °C showed a surface area as measured by nitrogen adsorption of less than 1 m² g^?1 both before and after such pretreatment. This same coal with a 5:95 O₂:N₂ stream for 4 h at 450 °C showed a surface area of 110 m² g^?1 measured by nitrogen adsorption at 77K.     

Design of a commercial solar-powered greenhouse

A completely solar-powered greenhouse complex has been designed for climate controlled food production in hot, humid environments. The concept uses passive design features to provide irrigation water from saline water sources. This paper discusses the overall system concept and the solar still subsystem which has been designed to provide a continuous fresh water supply. While incorporating many innovative features, the use of proven technologies and passive design results in a system that should compete economically with current, more traditional designs.     

Analysis of subcellular phosphatidyl choline in developing rabbit lung

Phosphatidyl choline is a major lung surfactant. Insufficient development of the surfactant in neonates is often associated with the Respiratory Distress Syndrome. The concentration and fatty acid composition of phosphatidyl choline have not been studied in the subcellular organelles of the developing lung. This study has investigated the development of the concentration and fatty acid composition of phosphatidyl choline in subcellular fractions of 28-day and 30-day fetal and maternal New Zealand rabbit lungs. The concentration of total phospholipids in lamellar bodies increased four to five fold from 28-day fetus to 30-day fetus which, in turn, was similar to the maternal level. Total phospholipid content increased only about 50% in mitochondria and microsomes. The percentage of phosphatidyl choline among total phospholipids in lamellar bodies increased successively from 60% at 28 days gestation to 84% at 30 days gestation and leveled at 84% in maternal lamellar bodies. Microsomal PC increased steadily from 52% in the 28-day fetus to 65% in the adult. Analysis of the fatty acid composition of phosphatidyl choline in lamellar bodies confirmed 16∶0 as the major fatty acid, and its content remained constant from 28 days gestation to adult. In contrast, the content of 16∶0 of the microsomal phosphatidyl choline decreased with increasing gestation. Changes of several unsaturated fatty acid components were observed in both lamellar bodies and microsomes in the developing lungs. Maturational development of phosphatidyl choline is reflected in an increase in the concentration of this surfactant, particularly in lamellar bodies, and possibly in remodeling of fatty acid composition in both lamellar bodies and microsomes.     

Kinetic Analysis of Solution-Precipitation During Liquid-Phase Sintering of Alumina

Densification controlled by solution-precipitation during liquid-phase sintering was analyzed for the aluminamagnesium aluminosilicate glass system. As a model system for liquid-phase sintering, narrowly sized alumina powders and up to 20 vol% magnesium aluminosilicate glass samples were isothermally sintered at 1550° to 1650°C. Densification rate increases with increasing liquid content and sintering temperature but decreases with increasing density. For samples with >15% grain growth, the densification rate during the solution-precipitation stage of sintering was proportional to (particle size)⁻² and thus interface reaction-controlled. Activation energies ranged from 270 to 500 kJ/mol over the relative density range of 66% to 96%, respectively. The low activation energy is attributed to densification by particle rearrangement, whereas the higher activation energy is due to densification controlled by interface-reaction-controlled solution-precipitation. Intermediate activation energies are attributed to simultaneous densification by the two mechanisms.     

Preparation of Silicon Carbide/Aluminum Nitride Ceramics Using Organometallic Precursors

Solid solutions of 2H -SiC/AlN can be prepared at temperatures less than 1600°C by rapid pyrolysis ("hot drop") of mixtures of [(Me₃Si)_0.80((CH₂=CH)MeSi)_1.0(MeHSi)_0.35] _n (VPS) or [MeHSiCH₂] _n (MPCS) with [R₂AlNH₂]₃, where R=Et, i -Bu or simply by slow pyrolysis of the precursor mixture in the case of [Et₂AlNH₂]₃. In contrast, slow pyrolysis of mixtures of VPS or MPCS with [ i -Bu₂AlNH₂]₃ yields a composite of 2 H -AlN and 3 C -SiC at 1600°C, which transforms into a single 2 H -SiC/AlN solid solution on heating to 2000°C. The influences of the nature of the precursor and processing conditions on the structure, composition, and purity of the SiC/AlN materials are discussed.     

Silicon Nitride Derived from an Organometallic Polymeric Precursor: Preparation and Characterization

Partially crystalline Si₃N₄, with nanosized crystals and a specific surface area greater than 200 m²/g, is obtained by pyrolysis of a commercially available vinylic polysilane in a stream of anhydrous NH₃ to 1000°C. This polymer does not contain N initially. Crystallization to high-purity α-Si₃N₄ proceeds with additional heating above 1400°C under N₂. The changes in crystallinity, powder morphology, infrared spectra, and elemental compositions, for samples annealed from 1000° to 1600°C under N₂, are consistent with an amorphous-to-crystalline transformation. Although macroscopic consolidation and local densification occur at 1400°C, volatilization and accompanying weight loss limit bulk densification. The effect of temperature on specific surface area is examined and related to the sintering process. These results are applicable to pyrolysis, decomposition, and crystallization studies of ceramics synthesized by polymeric precursor routes.     

Herbivore Oral Secreted Bacteria Trigger Distinct Defense Responses in Preferred and Non-Preferred Host Plants

Insect symbiotic bacteria affect host physiology and mediate plant-insect interactions, yet there are few clear examples of symbiotic bacteria regulating defense responses in different host plants. We hypothesized that plants would induce distinct defense responses to herbivore- associated bacteria. We evaluated whether preferred hosts (horsenettle) or non-preferred hosts (tomato) respond similarly to oral secretions (OS) from the false potato beetle (FPB, Leptinotarsa juncta), and whether the induced defense triggered by OS was due to the presence of symbiotic bacteria in OS. Both horsenettle and tomato damaged by antibiotic (AB) treated larvae showed higher polyphenol oxidase (PPO) activity than those damaged by non-AB treated larvae. In addition, application of OS from AB treated larvae induced higher PPO activity compared with OS from non-AB treated larvae or water treatment. False potato beetles harbor bacteria that may provide abundant cues that can be recognized by plants and thus mediate corresponding defense responses. Among all tested bacterial isolates, the genera Pantoea, Acinetobacter, Enterobacter, and Serratia were found to suppress PPO activity in tomato, while only Pantoea sp. among these four isolates was observed to suppress PPO activity in horsenettle. The distinct PPO suppression caused by symbiotic bacteria in different plants was similar to the pattern of induced defense-related gene expression. Pantoea inoculated FPB suppressed JA-responsive genes and triggered a SA-responsive gene in both tomato and horsenettle. However, Enterobacter inoculated FPB eliminated JA-regulated gene expression and elevated SA-regulated gene expression in tomato, but did not show evident effects on the expression levels of horsenettle defense-related genes. These results indicate that suppression of plant defenses by the bacteria found in the oral secretions of herbivores may be a more widespread phenomenon than previously indicated.     

Studies of water-soluble oligomers formed in emulsion copolymerization

A polymer chain transfer agent was synthesized by the reaction between poly(vinylbenzyl chloride) latex particles and 2-aminoethanethiol in a basic environment. In subsequent emulsion polymerization reactions, low molecular weight species were formed when waterborn oligomeric radicals diffused to the surface of these seed particles. These low molecular weight oligomers were separated by membrane filtration and their composition and molecular weight weight were analyzed by FTIR and mass spectroscopy. The measured composition results were compared with those that were calculated from the copolymerization equation. The molecular weights were compared with earlier experimental results that were obtained by isolation of oligomers formed when a water-soluble inhibitor was added to a reacting emulsion. Three seeded emulsion copolymerization systems, that is, styrene–acrylic acid, styrenemethacrylic acid, and styrene–methyl methacrylate, were investigated. The distribution of monomer in the water phase and in the copolymer particles was analyzed. The results show that the oligomer compositions for different copolymerization systems can be approximated reasonable well by the copolymerization equation, using the reactivity ratios obtained from bulk copolymerization. The length of the oligomer radicals formed depends on their composition and the properties of the polymer particles, such as surface charge, composition, size, and concentration. © 1994 John Wiley & Sons, Inc.     

HOW LIQUIDS SPREAD ON SOLIDS

A theory of the wetting of solids by liquids is put forward. The theory accounts for capillary pressure gradient, gravitational potential gradient, surface tension gradient, disjoining pressure gradient driving forces of flow in thick thin-films and of surface diffusion in thin thin-films. Disjoining pressure stems from the way intermolecular forces aggregate in submicroscopically thin films. For thick thin-films of slowly varying thickness the lubrication approximation to velocity distributions is appropriate. With this approximation the spontaneous, unsteady, two-dimensional spreading of liquid is shown to be governed by a nonlinear convective-diffusion equation for the evolution of the film thickness profile. The predictions of the theory agree with Marmur and Lelah's (1980, 1981) observations of water drops spreading on glass and with Bascom, Cottington and Singleterry's (1964) and Ludviksson and Lightfoot's (1971) observations of oils spreading on high energy surfaces. The theory is used to analyze Derjaguin and co-workers' (1944, 1957, 1970) blowing-off experiments designed to measure thin-film rheology. The theory is also used to buttress the proposition that much contact angle hysteresis is due simply to slow attainment of equilibrium.