Platinum-group metal cyclodextrin complexes and their use as command-cure catalysts in silicones

The Command-Cure concept is defined for a curable formulation as one with long work-like at ambient temperature and rapid cure time at elevated temperature. This concept is explored for a curable silicone system, cured via hydrosilylation. CODMCl₂ complexes (COD=1.5-cyclo-octadiene:M=Pt. Pd) are reacted with beta-cyclodextrin (-CD) to make 11 inclusion compounds,M=Pd.2;M=Pt.4. Compounds2 and4 were analyzed by¹H NMR and X-ray powder diffraction. Their catalytic ability was evaluated in a model system as well as a polymeric system that gels upon cure. Surprisingly, the Pd analog2 was a good command-cure catalyst whereas the guest compound CODPdCl₂,1, was not active in the hydrosilylation reaction. The Pt analog,4, was an effective command-cure catalyst while the corresponding guest. CODPtCl₂,3, was too active at low temperature in the hydrosilylation reaction. Additional Pt compounds and one Rh inclusion compound were evaluated as command cure catalysts. These inclusion compounds were: 11 -CD:[CODRhCl]₂,5: 11 -CD:CpPtMe₃,6 (Cp=cyclopentadienyl): 12 -CD:MeCpPtMe₃,7; 12 -CO:CODPtMe₂,8. The effectiveness of4 8 was evaluated in a number of silicone systems.     

Effect of growth temperature on the positional distribution of eicosapentaenoic acid andrans hexadecenoic acid in the phospholipids of aVibrio species of bacterium

Phosphatidylethanolamine (PE) and phosphatidylglycerol (PG) were isolated from aVibrio species of bacterium, known to produce eicosapentaenoic acid (20∶5n−3) andtrans-hexadecenoic acid (16∶1n−7), and subjected to phospholipase A₂ degradation to determine the positional distribution of component fatty acids. At the two growth temperatures studied (20 and 5°C), both 20∶5n−3 andtrans 16∶1 n−7 were located mainly at positionsn−2 in PE. Increases in the proportions of 20∶5n−3 andtrans 16∶1n−7 in positionsn−2 with decreasing growth temperature were balanced mainly by decreases in the level ofiso-15∶0. In PG,trans 16∶1n−7 was located predominantly in positionsn-1, although the difference between the two positions was not as great as in PE. Eicosapentaenoic acid was preferentially located in positionsn-2 of PG, particularly at 5°C when it comprised 29.9% of the total fatty acids in this position. It is concluded thattrans 16∶1n−7/20∶5n−3 is not a major molecular species of phospholipid in this species ofVibrio and that changes in the levels of molecular species of PE containingiso-15∶0 may feature in thermal acclimation.     

Differences in fatty acid composition of immature and mature articular cartilage in humans and sheep

Chondrocytes are imbedded in an avascular, highly charged extracellular matrix which could form a barrier to the transfer of dietary essential fatty acids (EFA) to chondrocytes. A study was designed to assess the composition of immature and mature joint cartilage with respect to essential and nonessential fatty acids relevant to EFA deficiency. Cartilage and muscle samples were obtained from human fetus, infant and adult cadavers, and from fetal and mature sheep. Lipid extracts were prepared and the fatty acid composition determined. In human and sheep joint cartilage, linoleic acid (LA; 18∶2n−6) content was lower, and n−9 eicosatrienoic acid (ETrA; 20∶3n−9) and arachidonic acid (AA; 20∶4n−6) were higher in fetuses compared to mature subjects. An intermediate pattern was seen in infant cartilage. n−3 Fatty acids tended to be higher in fetal than in mature cartilage in humans and in sheep. In human muscle (and in other noncartilaginous comparison tissues), similar differences between fetuses and adults were seen in LA and AA, but not in ETrA. In fetal sheep muscle, very low LA, reduced AA and raised ETrA levels compared to mature sheep muscle were seen. However, although the pattern is characteristic of EFA deficiency, the abundance of n−6 EFA in liver and spleen of human fetuses and of n−3 EFA in liver and spleen of fetal sheep suggests that placental transfer of EFA is not likely to be limiting. During fetal development, the metabolism of fatty acids is distinctive and differs between the species. ETrA appears to be a readily measurable component of some tissues at certain stages of development when its presence in tissues does not indicate EFA deficiency.     

Coefficients of dynamic friction and the mechanical melting mechanism for vinylidene chloride copolymers

Previous research and this research indicate that the mechanical melting for poly(vinylidene chloride) copolymers (PVDC) is complex. Mechanical melting is defined as the melting (or devitrification) of a polymer when a significant portion of the thermal energy originates from a mechanical energy dissipative process. PVDC mechanically melted on a moving metal surface at temperatures of the test instrument that were considerably lower than the differential scanning calorimetry (DSC) onset melting temperature. PVDC formulated with low levels of high density polyethylene (HDPE), however, melted at metal temperatures near the DSC onset melting temperature. Two different mechanical melting mechanisms are proposed to explan the data, and the frictional data are discussed with respect to solids conveying in a single-screw, plasticating extruder.     

An electrostatic powder spray process for manufacturing thermoplastic composites

Manufacture of thermoplastic composites is expensive because of the difficulty of impregnating the resin into the fibers. Powder processing shows great promise as an impregnation technique for cost-effective manufacturing. This paper discusses an electrostatic powder spray impregnation technique that uses glass fibers. A geodesic fiber spreader is used to spread the fibers locally in the region of maximum powder deposition. A negative corona electrostatic spray gun is employed to charge and direct the powder for coating both sides of the spread fiber tow. The process has been used to impregnate glass fibers with poly(aryl ether ketone ketone) powder. The effect of the powder mass flow, corona voltage, and fiber tow velocity on powder deposition has been investigated. Particle image velocimetry is utilized to determine particle velocities. Compression molded panels have been produced and tested in three point bending.     

Microstructures and Mechanical Properties Prediction for Ti-Based Alloys

Titanium alloys have been used in demanding applications such as the chemical industry and aerospace, thanks to their excellent corrosion resistance, low density, and high-mechanical strength. There have been many research activities recently on titanium alloys, mainly focusing on experiments. The kinetics of phase transformations and the relationship between the microstructure and the final mechanical properties has not been widely studied by computer modeling. In this work, a comprehensive finite-element model coupled with thermodynamic calculations has been developed to simulate the microstructure evolution and predict the final mechanical properties resulting from solidification and to solid phase transformation. This model can be applied to casting and heat treatment processes. The predictions are validated by comparison with experimental measurements. The results show that this model can accurately predict the microstructure, volume fraction of different phases, and the final yield strength of titanium alloys.     

A quick method for evaluating the thresholds of workpiece surface damage in machining

This paper proposes a Pendulum-Based Cutting Test (PBCT) methodology which allows quick cutting tests for surface integrity evaluation along with providing cutting energies associated with particular level of workpiece surface damage, this is backed by an unified cutting energy model that links damage level of machined surface with energy partition in the cutting area. PBCT method could rapidly define the energy transferred to the workpiece that incurs particular magnitude of surface damage without using conventional machine tools and monitor the cutting process while only limited amount of materials is required. A demonstration of the proposed method is presented for Inconel718.     

Microstructural changes in homopolymers and polymer blends induced by elastic strain pulverization

A novel polymer processing technique known as elastic strain pulverization (ESP) involves the simultaneous effects of high pressure and shear deformation to pulverize polymers. Homopolymers and blends of commercially important postconsumer plastics, including high-density and low-density polyethylene (HDPE, LDPE), polypropylene (PP), and poly styrene (PS) are studied by several characterization techniques to determine the effects of ESP on the microstructure. Electron spin resonance spectroscopy confirms that free radicals are generated by the mechanical rupture of main chain carbon bonds during pulverization by ESP. The possibility of these free radicals terminating by heterogeneous combination to form compatibilizing block or graft copolymers in coprocessed polymer blends establishes the potential of ESP in commingled plastics recycling. Differential scanning calorimetry (DSC) and polarized light microscopy of homopolymers and blends indicate that crystalline structure is drastically altered by ESP processing. Spherulite size reduction is also observed in both crystalline/crystalline and crystalline/amorphous blends after ESP. These results are consistent with homogenization that may be due to the formation of compatibilizing copolymers by heterogeneous macroradical combination. © 1995 John Wiley & Sons, Inc.     

Synthesis,structure, and properties of poly(dimethylsiloxane) networks reinforced by in situ-precipitated silica–titania,silica–zirconia,and silica–alumina mixed oxides

Several novel fillers, specifically silica–titania, silica–zirconia, and silica–alumina mixed oxides, have been successfully precipitated into poly(dimethylsiloxane) (PDMS) networks using a sol-gel approach. The resulting filled networks were found to have very good mechanical properties. In comparison with networks filled only with silica, these materials had good extensibilities as well as high strengths. Filler particle diameters were generally several hundred angstroms, but were found to decrease with increase in crosslink density of the networks. The distributions of particle size were relatively narrow, and there was very little particle aggregation. The presence of in situ silica–titania and silica–zirconia mixed oxides can also increase the onset temperature for degradation of the PDMS. © 1995 John Wiley & Sons, Inc.     

Simultaneous removal of phosphorus and foulants in a hybrid coagulation/membrane filtration system

At many wastewater treatment plants, chemical addition is required to meet the requirements for discharge of phosphorus. Membrane filtration is an attractive option for removing the chemically precipitated phosphorus, but that process can be impeded by fouling of the membrane by effluent organic matter (EfOM). In the current study, membrane fouling and ortho-P removal were explored in hybrid adsorbent/membrane systems dosed with alum and/or a new aluminum-based adsorbent (heated aluminum oxide particles, HAOPs). HAOPs prevented fouling more effectively than alum did, even though the two adsorbents removed similar amounts of EfOM. The HAOPs were particularly effective when they were pre-deposited on the membrane (as opposed to being mixed into the feed upstream). On the other hand, alum removed ortho-P more efficiently than HAOPs did. Combining both adsorbents in a single membrane system takes advantage of the most attractive features of each, accomplishing good ortho-P removal while simultaneously minimizing fouling. In addition to being potentially applicable directly, the results demonstrate the potential benefits of using multiple coagulants and/or adsorbents in a single hybrid membrane system.