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.     

Dynamics of ion beam modification of polymer films

Thin polymer films were irradiated in a high vacuum environment with energetic (～2 MeV) ions. The emitted molecular species were studied with a quadrupole mass spectrometer during bombardment. The emitted species are predominantly small molecules. The efficiency of emission depends strongly upon the electronic energy loss of the incident ions in the film and, hence, upon the velocity and atomic number of the incident ion. The emission efficiency of all species decreases with increasing damage in the film. By pulsing the ion beam, the time dependence of irradiation induced emission of molecular species from the films has been studied. Emission delays of hundreds of milliseconds are observed in some cases. These delays are found to depend upon the emitted species as well as the host film and seem to be associated with diffusion of the species in the films.     

How high growth economies impact global information technology departments

By the very nature of information technology (IT), change and dynamism have always been significant drivers on its path to further development—and it has traditionally been the Western countries leading these. Now the picture is changing. The new high growth economies of the world (also known as BRIC countries) are increasingly pressing forward as active IT development drivers. Internal IT organizations of international companies are experiencing these global shifts firsthand and are facing changes in their traditional roles. This exploratory research is aimed at clarifying the context of the impact of high growth economies on such IT departments of Western-rooted enterprises. Forty-six interviews were conducted with IT managers, HR managers and expatriates emphasizing the importance of intercultural interaction, maturing IT economies, change in IT landscape and entrepreneurship.     

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.     

Insect sex pheromones

The half-lives (t _1/2) for evaporative loss ofn-alkyl andn-alkenyl acetates from rubber septa were determined at temperatures varying from 15 to 35 °C. The changes int _1/2 with temperature gave high correlations with the equation, Int _1/2 = H/RT+y _o where H is the heat of vaporization,R is the gas constant,T is the absolute temperature, andy _o is a constant. Half-lives changed dramatically with temperature and the degree of change with temperature increased with increasing molecular weight. For mixtures, component ratios changed with temperature, but the degree was modest. At 20 °C there was a 7.5-fold ratio oft _1/2 between members of the homologousn-alkyl orn-alkenyl acetates differing by two carbon atoms. The large change int _1/2 with temperature and with number of carbon atoms is a consequence of the thermodynamic relationships and the temperature range of pheromone usage. Therefore, a similar degree of change inf _1/2 with temperature and number of carbon atoms will apply to other formulations of the same type (those in which the rate of evaporation is first order). The values oft _1/2 at 20 °C mainly agreed very well with those reported previously at room temperature. However, our previously reported values for pentadecyl and hexadecyl acetate were revised. Half-lives were shown to depend on the vapor pressure of a compound in the formulation substrate, but not on the vapor pressure of the pure compound.Mention of a commercial or proprietary product does not constitute an endorsement by the USDA.     

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.     

Inhibition of lipid peroxidation in UVA‐treated skin fibroblasts by luteolin and its glucosides

Ultraviolet A (UVA) radiation causes oxidative damage to human skin cells. This damage may be reduced or prevented using plant compounds as photoprotectants. To investigate the relationship between chemical structure and UVA‐protective activity, three structurally related flavonoids, namely luteolin, luteolin‐7‐O‐glucoside (both present in artichoke) and luteolin‐4'‐O‐glucoside (present in wild carrot), were studied. Human skin fibroblasts exposed to UVA (250 and 500 kJ/m²) were treated with each flavonoid (30 µM) for 18 h prior to irradiation. The extent of lipid peroxidation in the cellular extracts was assessed as lipid peroxides and malondialdehyde (MDA). Luteolin and luteolin‐7‐O‐glucoside both prevented a significant increase in lipid peroxides at 250 kJ/m², but at 500 kJ/m² their effectiveness was clearly attenuated. Contrastingly, luteolin‐4'‐O‐glucoside was pro‐oxidant at both radiation doses. Measurements of MDA levels highlighted that luteolin was clearly more effective than the two glucosides at both 250 and 500 kJ/m². Overall, these results show clear differences between the three flavonoids and suggest that the B ring 3',4'‐dihydroxy group, lacking in luteolin‐4'‐O‐glucoside, may be particularly important. Flavonoid: transition metal ion chelation studies confirmed the influence of the 3',4'‐dihydroxy group, which is also relevant to the quenching of singlet oxygen. These features as well as the greater lipophilic nature of luteolin together explain the superior activity of this flavonoid which may be potentially useful as a supplement in photoprotective skin preparations.     

Preparation of glycol derivatives of partially hydrogenated soybean oil fatty acids and their potential as lubricants

Glycol diesters and mixtures of mono- and diesters have been prepared from methyl esters of partially hydrogenated soybean oil fatty acids and diethylene, dipropylene, neopentyl and triethylene glycols. The catalyst used in these reactions was a mixture of calcium acetate/barium acetate (3∶1, w/w). The reactions were carried out under nitrogen with 0.5% catalyst at temperatures in the range of 190–275°C. Borated esters of mixed mono- and diesters were prepared with 0.33 equivalent of boric acid per 1.0 equivalent hydroxyl group on the ester. Refractive indices, viscosities, and flash and fire points were determined for diesters, mixed mono- and diesters, and mixed diesters and borated esters. The viscosities, flash points and fire points indicate that these esters can be used as a component of lubricating oils. Wear-prevention characteristics of mixed diesters and borated esters indicated that they can be used as antifriction additives in lubricating oils. Lecture presented at the joint meeting of the International Society for Fat Research and the American Oil Chemists' Society in Toronto, May 10, 1992.