N.m.r. studies on the effect of water on the glass transition of polystyrene

These investigations are concerned with water-polymer interactions in polymer latices. It is known that water can act as a plasticizer for many solid polymers and cause a reduction in the glass transition temperature, T_g, of the amorphous regions. Experiments were carried out to determine whether pulsed n.m.r. techniques could be used to study the T_g of a polymer suspension and hence the influence of water and electrolyte on it. From T₁ and T₂ proton relaxation measurements as a function of temperature on polystyrene latex systems it was shown that the presence of water lowers the T_g of the polymer particles (by about 10°C), the effect being slightly greater in the presence of concentrated electrolyte. The extent of electrolyte penetration into the particles was deduced by studying relaxation as a function of particle diameter in latices containing paramagnetic Mn²⁺ ions. Using simple theories of relaxation and spin diffusion it was concluded that for all but the smallest particles electrolyte penetration is restricted to a very thin shell of the order of 1 nm. These conclusions were supported by the results of similar measurements on PTFE particles.     

Free-radical grafting of cellulose in N-methylmorpholine oxide: Water-soluble pam-g-cellulose copolymers

The homogeneous graft copolymerization of acrylamide (AM) onto cellulose initiated by t-butylperoxy-2-ethylhexanoate in a cellulose solvent, N-methylmorpholine oxide (NMMO), was investigated. The method afforded water-soluble PAM-g-cellulose copolymers in fair yields. The copolymers produced are of low molecular weight (50,000–100,000 M?_w). Little apparent homopolymerization was observed.     

Nutritional consequences of processing soybean oil

A major objective of commercial processing of soybean oil into edible products is to remove unwanted impurities from the oil with the least possible effect on nutritional quality of the oil. Soybean oil is an excellent dietary source of essential linoleic acid and also of tocopherols, which serve as sources of vitamin E and natural antioxidants. The data presented in this report indicate that the nutritional quality of soybean oil is largely retained after typical commercial processing conditions. Hydrogenation does reduce the level of essential fatty acids; however, typical commercial salad and cooking oils and shortenings made from partially hydrogenated soybean oil retain nutritionally significant levels of essential fatty acids. Tocopherols also are present at high levels in the finished oil. Among the unwanted components of crude soybean oil which are effectively removed by processing are pesticide residues, phosphatides, free fatty acids, color pigments, and compounds causing objectionable odors and flavors.     

Stereospecific synthesis ofcis andtrans fatty esters

Theerythro andthreo isomers of methyl 9,10-dihydroxyoctadecanoate and thethreo isomer of methyl 12,13-dihydroxy-cis-9-octadecenoate were converted into methylcis- andtrans-9-octadecenoate and methylcis-9,rans-12-octadecadienoate, respectively, by reaction of the dihydroxy ester with triethyl orthoformate to give the 2-ethoxy-1,3-dioxolane which was thermally decomposed to the unsaturated ester.     

Fat,cholesterol, and atherosclerosis

Summary Cholesterol is a universal constituent of all animal cells and therefore occurs in all foods of animal origin. Cholesterol is the mother substance of bile acid and of sex hormones and has other important physiological roles. Cholesterol is synthesized in the body from acetate obtainable from ingested carbohydrate, fat. or protein, of animal or vegetable origin. The fate of cholesterol in the body has not been definitely established. The cause of atherosclerosis is unknown. Atherosclerosis occurs in young as well as old individuals. Atherosclerosis is the number-one killer today. Diagnosis of atherosclerosis in the healthy individual is not possible. Treatment of atherosclerosis is empirical. Reduction of blood cholesterol levels by dietary means is difficult under conditions consonant with good nutrition. A well-balanced intake of all available foods on a modified total caloric basis appears to be the practical approach to the problem of fat, cholesterol, and atherosclerosis. Presented at the 47th Annual, Meeting, American Oil Chemists’ Society, Houston, Tex., April 23–25, 1956.     

A facile chemical synthesis of cholest-4-en-3-one. Carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and cholest-5-en-3-one

This paper presents a simplified method for the chemical synthesis of cholest-4-en-3-one, which is a naturally occurring steroid and a salient intermediate in steroid chemistry. Pyridinium chlorochromate (PCC) in refluxing benzene has been found to be an effective and convenient reagent for the oxidation and concomitant isomerization of cholest-5-en-3β-ol (cholesterol) to cholest-4-en-3-one in high yield. Also described are the carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and of the isolated reaction intermediate cholest-5-en-3-one. Based on a paper presented at the Symposium on Plant and Fungal Sterols: Biosynthesis Metabolism and function held at the AOCS Annual Meeting, Baltimore, MD, April 1990.     

Pressureless low temperature sintering of nanocrystalline zirconia ceramics via dry powder processing

Pressureless sintering approaches provide a simple avenue to manufacture dense ceramic parts with minimal processing equipment, but current pressureless sintering techniques have yet to demonstrate capabilities of producing dense ceramics while maintaining sub-50 nm grain sizes. Nanocrystalline yttria stablized zirconia ceramics were process from 4 mol% yttria stablized zirconia (4YSZ) nanopowders with a crystallite size of 7.5 nm using dry cold isostatic pressing (CIP) where powders are dried immediately prior to green compact formation and CIP vacuum bagging. It is shown that CIP pressures >75 000 psi (517 MPa) effectively remove pores larger than 100 nm and that pressureless sintering occurs at reduced temperatures for green densities ≥50%. Though the sintering kinetics are shown to be similar to other zirconia nanopowder sintering studies, the small initial crystallize size and reduced sintering temperature allowed densities as high as 97.2%, while retaining a ceramic grain size at or below 40 nm. Produced nanocrystalline 4YSZ ceramics with a grain size of 30.3 nm and a density of 96.3% had Vicker's hardnesses as high as 14.2 GPa and Vicker's indentation fracture resistance of 3.43 MPa·, demonstrating that simple processing approaches can be refined to fabricate nanocrystalline ceramics while maintaining high hardness and indentation fracture resistance.     

ABSORPTION AND DESORPTION TO AND FROM LIQUID FILMS ON INCLINED PLANES

Two published theoretical models are examined and applied to experimental results for absorption and desorption. The system used was CO₂/H₂O and studies were made for liquid film flow down inclined planes. Experimental results give “Reduced” values of mass ransfer rates.

Interferometric studies give interfacial concentration, penetration and film depths, and take-up of carbon dioxide. In the case of desorption the interferograms are distorted by “deflections.”

All the experimental values for absorption and desorption differ from those calculated from theoretical models.

Desorption is not a mirror image of absorption, and it is approximately 75% of the transfer rate of absorption over a wide operating range.

A comparison is made of the behaviour of static pools and flowing liquid films.