The Structure of the Irreversibly Bound Adhesion Promoter-Substrate Interfacial Layer of γ-Aminopropylsilanetriol on Crystalline Si, as Measured by XPS and FTIR

The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer.     

Initial stages of tin electrodeposition from sulfate baths in the presence of gluconate

Tin electrodeposition in its initial stages in acid sulfate/gluconate baths was studied with varying tin and gluconate concentrations using potential-controlled electrochemical techniques. The deposit morphology was observed by scanning electron microscopy (SEM). A comparison with tin electrodeposition from acid sulfate baths in the absence of gluconate was also carried out. Use of a highly acidic bath leads to nonuniform deposits, even in the presence of gluconate; at pH 4 deposits are uniform, brilliant and suitable for finishing applications. Tin crystallites have a well defined morphology which depends on bath agitation conditions. In the absence of agitation, the crystallites have the same tetragonal shape as in a sulfate bath without gluconate.     

Orientational crystallization and orientational drawing as strengthening methods for polyethylene

This paper reports on the theoretical and experimental studies of structure formation and strengthening (stiffening) of flexible-chain polymers. Two techniques of strengthening relying on the melt extrusion, i.e., orientational crystallization (crystallization initiated by melt extension) and drawing (uniaxial stretching of a crystallized polymer) are analysed by theory. The experiments involved preparation and study of melt extruded films and film fibers of linear polyethylene formed by the two techniques mentioned above. The effect of the degree of orientation and other parameters of the formation processes on the mechanical characteristics and the factors limiting the ultimate values of these characteristics are discussed. It is shown that multistage drawing succeeds in achieving a higher tensile strength and elastic modulus (1.2 and 35 GPa, respectively) than the orientational crystallization, which gives 0.8 and 15 GPa. The strengthening by drawing is accompanied by microcrack formation. In contrast, no discontinuities are observed in orientationally crystallized samples up to their ultimate extension.     

Determination of individual long-chain fatty acyl-CoA esters in heart and skeletal muscle

A method has been developed for determination of individual long-chain fatty acyl-CoA esters from heart and skeletal muscle using high performance liquid chromatography (HPLC). The esters were extracted from freezeclamped tissue of pig and rat hearts and rat skeletal muscle for analysis on a radially compressed C₁₈ 5μ reversephase column. Nine peaks in the extract with carbon chain lengths from C₁₂ to C₂₀ that subsequently disappeared on alkaline hydrolysis were identified. The major acyl-CoA peaks were 14∶1, 18∶2, 16∶0 and 18∶1 and additionally in rat heart 18∶0. Total long-chain acyl-CoA esters obtained by summation of the individual molecular species was 11.34±1.48 nmol/g wet wt. pig heart; 14.51±2.11 nmol/g wet wt. in rat heart, and 4.35±0.71 nmol/g wet wt. in rat skeletal muscle. These values were approximately 132% of those obtained using a separate procedure that measured total CoA by HPLC after alkaline hydrolysis of the esters. The described method demonstrates the quantitation of individual acyl-CoA species in muscle tissue. Therefore, it has a number of advantages in that it permits information to be obtained on the individual molecular species under various nutritional and metabolic conditions.     

DRY-RO membranes from cellulose acetate carbamates

Cellulose acetate carbamates (CACs) are the polymers which result when organic isocyanates are reacted with the free hydroxyl groups of cellulose acetate (CA). CACs are more hydrolytically stable and exhibit physical properties which are superior to those of their CA mixed ester analogs. Two synthetic approaches to CACs have been utilized in this study: (1) preformation, i.e., separate synthesis of such polymers prior to their inclusion in solutions for membrane casting; and (2) in situ formation, i.e., the inclusion of blocked isocyanates in standard dry process casting solutions of CA followed by thermal activation of the resultant dry membranes leading to regeneration of free isocyanate and subsequent CAC formation. Preformed CAC polymers have been prepared utilizing phenyl-, 3-chloropropyl-, 3-bromopropyl-, and 3-bromopropyl-(isothio)-, isocyanates. Polymers containing omega-halocarbamate moieties were quaternized with dimethylbenzylamine to produce ionogenic (QCAC) polymers containing quaternary ammonium groups. DRY-RO membranes from the QCACs exhibit flux/rejection values varying between 6–8 gfd at 98% rejection and 20 gfd at 90% rejection (0.5% NaCl feed at 400 psi and 25°C). In situ formation of CAC membranes has been effected with tolylene- and hexamethylene-diisocyantes, with quaternized isocyanate monomers employed for the preformed CAC polymers, and with specially tailored diisocyanates containing ionogenic groups. Crosslinking rendered all of the membranes acetone insoluble. Inasmuch as in situ formation substitutes the easy synthesis of blocked isocyanate monomers for the more difficult separate synthesis of preformed CAC polymers, it is anticipated that the former will replace the latter.     

Coupling of polystyrene to a silane-treated mica

This paper deals with the coupling of polystyrene to a closely packed and highly ordered cationic vinylbenzyl silane (CVBS) on mica. It is shown that a thermal treatment is required for maximum retention of polystyrene on treated mica. Moreover, a thermal treatment at 250°C is much more effective than one at 170°C. The effect of the number of silane monolayers on mica was investigated. In general, one monolayer of CVBS gave optimum retention of polystyrene. The addition of peroxides further improved this retention and at the same time allowed the use of lower treatment temperatures. Some data are presented which consider the importance of the silane solution concentration and silane functional groups.     

Nucleation and Growth of Magnesioferrite in MgO Containing 0.9% Fe3+

The initial stage of precipitation of magnesioferrite from a supersaturated solid solution of 0.9 cation % Fe³⁺ in MgO at 500 °C was studied by fitting the magnetization curves to 7000 Oe at low temperatures with the Brillouin function. The averase umber of Fe³⁺ ions in a precipitate particle, increased monotonically with aging time from 9 in the as-quenched condition to 88 after 16 h. The average spin quantum number per Fe³⁺ ion decreased to near its final value at an aging time corresponding to = 50. Thus the volume fraction of precipitate is near the final value when the average particle size is only about three unit cells of magnesioferrite.     

Selective hydrogenation of soybean oil in the presence of copper catalysts

Many investigators associate the poor keeping properties of soybean oil with its linolenic acid content. On the other hand the high linoleic acid content is a desired property from a nutritional point of view. We have therefore developed a process for the preferential reduction of the linolenic acid content by selective hydrogenation. Conventional catalysts for the hydrogenation of fats have a rather low selectivity in this respect. When linolenic acid in soybean oil is hardened (e.g., with a nickel catalyst), most of the linoleic acid is converted into less unsaturated acids. It was found that linolenic acid is hydrogenated much more preferentially in the presence of copper catalysts than in that of nickel and other hydrogenation catalysts. At a linolenic acid content of 2%, soybean oil hardened with nickel catalyst contained about 28% linoleic acid, whereas with copper catalyst the hardened soybean oil contained 49% linoleic acid. By means of our process it is possible to manufacture a good keepable oil of, e.g., I.V. 115 and containing 1% linolenic acid and 46% linoleic acid. The storage stability of this product is comparable with that of sunflower-seed oil. A liquid phase yield of 86% is obtained after winterization at 5C for 18 hr. The high selectivity for linolenate reduction of copper catalysts must be ascribed to the copper part of the catalyst. Investigations into the structure of the catalyst indicate that the active center consists of copper metal crystallites; whether these centers are promoted by the carrier or traces of other substances is under investigation.     

Fatty acid composition of oils from 21 species of marine fish,freshwater fish and shellfish

The fatty acid composition of body lipids was determined by GLC for 14 species of saltwater fish, three species of freshwater fish and four species of shellfish. In addition, liver lipids of two species and egg lipids of one species were analyzed for comparison with the fish body lipids. The various species ranged from lean to fatty and contained from 0.7~15.5% oil in the tissues. Certain major fatty acids were found to vary widely among the species, as follows: 1.6~8.0% myristic, 9.5~33.4% palmitic, 2.0~11.2% palmitoleic, 5.2~29.1% oleic, 0.7~10.5% eicosenoic, 5.0~21.5% eicosapentaenoic, 0.2~11.6% docosenoic and 5.9~26.2% docosahexaenoic acids. Analyses of two separate mullet-oil samples illustrated the wide differences that are possible for a single species caught during different seasons. Significant differences in the amt of particular fatty acids were found in comparing freshwater-fish analyses with analyses for marine fish. Oysters and scallops showed large amt of pentaenoic and hexaenoic acids in their oils. Presented in part at the AOCS Meeting, New York, 1960.