Polyether-metal salt complexes: 1. The elevation of the glass transition temperature of polyethers by metal salts

Various metal halides have been dispersed in high and low molecular weight, amorphous poly(propylene oxide), by solution blending techniques, to give single phase polymeric complexes which remained thermoplastic even at very high salt loadings. These complexes were amorphous and showed a single well-defined glass transition temperature (T_g) by differential thermal analysis with the T_g of the complex up to 140°C greater than the T_g of the parent polymer. The T_g elevation depended upon both the amount and the type of salt added and for a given salt the elevation followed a sigmoidal curve which levelled out at high salt concentrations. The T_g data have been interpreted in terms of a chelate ring model involving the co-ordination of two adjacent ether oxygen atoms in the polymer backbone to the salt. Using this model it was possible to consider the complex as a random copolymer consisting of complexed and uncomplexed monomer units. The contribution of crosslinking by metal salts to the elevation of T_g was assessed by studying poly(tetramethylene glycol)-zinc chloride complexes in which chelate formation is entropically unfavourable. Mechanical data are reported for ZnCl₂ complexes with high molecular weight poly(propylene oxide). The results indicate that ZnCl₂ increased the rubbery modulus and this has been interpreted in terms of ZnCl₂ forming a few, weak intermolecular crosslinks.     

Studies of space-averaged mass transport in the FM01-LC laboratory electrolyser

Measurements of the mass transport limited current for the reduction of ferricyanide in 1M m potassium hydroxide and of copper(II) in 1.5 m sulphuric acid as a function of electrolyte flow rate are used to characterize the space-averaged mass transport properties of the FM01 laboratory electrolyser, with and without six types of polymer mesh turbulence promoters. In the absence of a promoter, the results followed the equation For the cell with the preferred turbulence promoter, the corresponding equation is Pressure drop data are also reported and it is confirmed that the presence of a turbulence promoter need not lead to a significant increase in the pressure drop over the reactor.     

Electrooxidation of CO and CO/H2 mixtures on a Pt-Sn catalyst prepared by an implantation method

A new type of ion implantation technique is used to create a non-equilibrium Pt-Sn(IMP) near-surface alloy with ca. 8.6 at% Sn. The surface composition was determined by low-energy ion-scattering (LEIS). The kinetics of the electrooxidation of CO and 2% CO/H₂ mixtures on Pt-Sn(IMP) is essentially identical to that of Pt₃Sn(110). The fact that any non-equilibrium composition can be easily prepared by this implantation method opens an interesting practical opportunity to create a new Pt-Sn alloy fuel cell catalyst having an otherwise unobtainable surface composition of Sn. This method also appears to have general utility in alloy catalysis as a means of exploring compositions in thermodynamically unfavorable regions of the bulk phase diagram. This revised version was published online in July 2006 with corrections to the Cover Date.     

Elimination of the halphen response of cottonseed oils in conjunction with deodorization

Two simple but effective pilot-plant processes were developed to produce Halphen-negative cottonseed oil. Both involve treatment of the oil with cottonseed fatty acids in a conventional batch type of deodorizer in conjunction with deodorization. In one process, in which the acids were added to the oil, the cyclopropenoids were inactivated in as short a time as 5 min after the oil reached the maximum temperature of 450–455 F. In the other, in which the acids were generated in situ, the oil did not become Halphennegative until about an hour and 45 min after it reached maximum temperature. The excess acids produced by both methods were readily removed during conventional deodorization. In contrast, deodorization alone reduced the cyclopropenoid content of the oil to a low level (0.02%) but did not render it Halphen-negative even after 3 hr at maximum temperature. These new processes are directly applicable for use by refineries that have the batch type of deodorizers. For refineries that operate continuous or semicontinuous deodorizers, it should be relatively simple to design preheating vessels or heat exchangers to inactivate partially or completely the cyclopropenoids before deodorization. Presented at the AOCS Meeting, New Orleans, May 1967. So. Utiliz. Res. Dev. Div., ARS, USDA.     

Assessing the predictive capability of two‐phase models for the mechanical behavior of alumina/epoxy nanocomposites

A review of analytical modeling of particulate reinforcement is made as a prelude to the problem of microstructural inhomogeneity in nanocomposite materials. Noting the inevitability of dispersion nonuniformity, and variations in agglomerate morphology and filler‐matrix interaction, the need to question the application of such models to novel materials arises. Employing the mechanical properties of alumina/epoxy nanocomposites, with known dispersion characteristics, an evaluation of the predictive capability of various models for Young's modulus, strength, and failure strain is made. Comparison between models is accompanied by a discussion of the parameters used in the fitting of macroscopic behavior to microstructural features. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 869–879, 2005     

Quantitative estimation of sucrose esters of plamitic acid

Thin layer chromatography was adapted for direct quantitative estimation of sucrose esters of palmitic acid. Urea-phosphoric acid spray was used to detect the sucrose moiety of the various esters. The photometrically metermined density density of each spot on the thin layer plate was found to be proportional to its sucrose content. Ester content was then obtained by multiplying sucrose found by the factor, mol. wt. ester/mol. wt. sucrose. Ester mixtures were prepared by interesterifying sucrose with various proportions of methyl palmitate in dimethylformamide solution. Positional isomers were observed at each level of substitution but could not be adequately separated from each other for quantitative evaluation. Presented at the AOCS Meeting, Minneapolis, October 1969. So. Utiliz. Res. Dev. Div., ARS, USDA.     

Oxygen permeation of blends of copolymers of siloxanes and poly(methylmethacrylate)

A series of low molecular weight (≈40000) copolymers of methylmethacrylate (MMA) and 4-(methacryloyloxy)butylpentamethyldisiloxane (MBPD) have been synthesized by free radical polymerization in dimethylformamide solution. The microstructure, as derived from ¹³C NMR spectra, indicates that the copolymers are about 80% syndiotactic with an overall random distribution of mers. At room temperature, copolymers rich in MMA are clear, rigid glasses but become liquid at high MBPD content. Blends of these copolymers with PMMA are all heterogeneous with visible phase separation over most of the composition range. Differential scanning calorimetry studies show the presence of two T_g's when the relative concentration of PMMA to copolymer is high. Blends of two co-polymers of similar siloxane content produce clear films with no indication of phase separation. The permeability to oxygen at 25°C increases from 0.20 for pure PMMA to 3.0 (fmol/m·s·Pa.) for a copolymer of MMA/MBPD of the mole ratio of 3:1. Evaluation of the permeation behaviors of the blends suggests that blends rich in siloxane exist as a layered structure with the PMMA rich component dominating the observed permeability.     

冠带层新平台技术

子午线轮胎出现不久，就采用钢丝带束层代替了纤维带束层，这对于实现子午线轮胎提高使用寿命和改善操纵性能的潜能是必要的。     

Laboratory study of soil acidification and leaching of nutrients from a soil amended with various surface-incorporated acidifying agents

Granular S, finely-ground S, iron sulphate and aluminium sulphate were added at two rates to the surface (0–6 cm) of a soil and acidification and leaching of nutrients were measured over 12 months in a laboratory study. Iron and aluminium sulphate both rapidly lowered soil pH in the top 0–6 cm of the soil. There was little difference in soil pH after 3 and 12 months reaction of these two amendments. In contrast, for granular S and finely-ground S there were clear decreases in soil pH between 3 and 12 months reaction with the soil. Finely-ground S was oxidized in the soil faster than granular S and therefore had a more acidifying effect. The top 0–6 cm of the soil was acidified by all the agents used but the deeper soil was less affected. The only treatments which lowered the pH of the 12–18 cm layer below pH 6 were the high rates of iron and aluminium sulphate. Soil acidification resulted in a decrease in exchangeable Ca, Mg and K, an increase in exchangeable Al and a decrease in effective CEC in the acidified soil layers.At both levels of addition, total ionic strength of percolates from the soil followed the order: aluminium sulphate = iron sulphate > finely gound S > granular S > control and was higher at the higher rate of addition. The pH values of percolates followed the order: control > granular S > finely ground S > iron sulphate = aluminium sulphate and were lower at the higher rate of addition. For the amended soils there was a very close relationship between the pattern and total amounts of SO ₄ ^2- and Ca²⁺ leached.It was concluded that granular S is not an effective acidifying agent since it is oxidized very slowly in the soil and that acidfying agents should be incorporated to the depth that acidification is required.     

Control policies for an industrial acetylene hydrogenation reactor

This paper addresses the problem of finding optimal operational policies for an acetylene reactor for day to day operation. A lumped parameter model based on four main reactions is developed and used to examine the effects of the reactor manipulated variables on key reaction parameters. An optimal and a sub-optimal operational policy which minimize the ethylene loss over time are formulated and the solution techniques are presented. The results indicate that the reactor model is in good agreement with industrial plant data. The performance of the optimal control policy is very similar to the performance of the sub-optimal control policy. However, the sub-optimal formulation, while retaining the dominant features of the optimal response, reduces the computational requirements. Finally, some issues concerning the real-time implementation of an advanced acetylene reactor control scheme are presented. These include the estimation of the optimum regeneration cycle, a recursive model update algorithm, the process optimizer and their overall coordination. A preliminary analysis of the benefits associated with the advanced control scheme suggests a considerable reduction in the yearly ethylene loss.