Effect of reaction kinetics of polymer electrolyte on the ion‐conductive behavior for poly(oligo oxyethylene methacrylate)–LiTFSI mixtures

The effect of the reaction kinetics on the ionic conductivity for a comblike‐type polyether (MEO) electrolyte with lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) was characterized by DSC, complex impedance measurements, and ¹H pulse NMR spectroscopy. The ionic conductivity of these electrolytes was affected by the reaction condition of the methacrylate monomer and revealed by the glass transition temperature (T_g), spin–spin relaxation time (T₂), steric effects of the terminal groups, and the number of charge carriers indicated by the VTF kinetic parameter. In this system, the electrolytes prepared by the reaction heating rate of 10°C/min of MEO–H and 15°C/min of MEO–CH₃ showed maximum ionic conductivity, σ_i, two to three times higher in magnitude than that of the σ_i of the others at room temperature. As experimental results, the reaction kinetic rate affected the degree of conversion, the ionic conductivity, and the relaxation behaviors of polyether electrolytes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2149–2156, 2003     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

A study of aromatic polyester/chlorinated polymer blends

A large number of studies have been devoted in recent years to the miscibility behavior of linear polyesters with chlorinated polymers, including poly(vinyl chloride) (PVC), chlorinated PVC, chlorinated poly(ethylenes), and copolymers of vinylidene chloride (Saran). However, similar studies with aromatic polyesters are lacking. It is the purpose of this paper to compare the properties of blends made of poly(ethylene terephthalate), poly(butylene terephthalate) or poly(hexamethylene terephthalate) and of various chlorinated polymers. It is shown that a high concentration of chlorine atoms is required to achieve miscibility. Moreover, there is a “miscibility window” in terms of the carbonyl concentration of polyesters, immiscibility being found for carbonyl concentrations outside this window, A similar behavior was observed before for linear polyester/chlorinated polymer blends and for polyester/polycarbonate blends. Solid state small-angle light scattering experiments were also conducted to follow the morphology of the blends as a function of composition. Spherulites were found but their size vary with composition.     

Practical Design Model for Calculating Bubble Diffuser Contactor Ozone Transfer Efficiency

Ozone transfer to water or wastewater is necessary before desirable, effective ozone reactions occur. Several factors affect ozone transfer efficiency, including water quality characteristics, contactor configuration, and applied ozone characteristics. The design model presented in this paper addresses all factors affecting ozone transfer. The model was used to compare measured transfer efficiency with predicted transfer efficiency at four full-scale wastewater ozone disinfection facilities. A relatively good prediction was obtained at each plant.

The paper presents an example calculation of ozone transfer efficiency. Also, the effect of changes to some of the factors affecting transfer efficiency is presented, such as changes in diffuser depth, plant elevation, ozone concentration, water quality (i.e., ozone demand), pH, detention time, temperature, and acombination of factors. The design model may be used to evaluate the effect of changes in plant design on transfer efficiency, but cannot provide an absolute value for transfer efficiency until difficult-to-measure parameters, such as bubble diameter, are known.     

Thermal degradation studies of several pyrrone films

The thermal degradation of several polyimidazopyrrolone (pyrrone) films was studied in air and in vacuum over the range of 100–1000°C. by thermogravimetric analysis (TGA), with the use of both isothermal heating and programmed heating rates of 2, 3, 5, and 7.5°C./min. At pressures of 10^?6 torr or less, maximum weight losses average 30% at 800°C. Rates of volatilization and activation energies were derived to provide comparison between these ladder-type polymers. Mass spectrometric analysis of the pyrolysis gases evolved under vacuum conditions showed that CO, CO₂, and H₂O were the primary volatile products and that they were formed throughout the period of weight loss. Approximate correlation between changes in weight and changes in the total pressure for the vacuum tests indicates that mass spectrometric results could provide quantitative as well as qualitative data. The importance of sample history prior to heating and of sample geometry in developing meaningful and reproducible TGA results is aptly demonstrated. The ability of these materials to absorb readily 5–7 wt.-% of water under ambient conditions and the effect of this property upon weight loss measurements are shown.     

Characteristics of the lipase from the mold,Geotrichum candidum: A review

The moldGeotrichum candidum produces an extracellular lipase, readily concentrated by removal of the culture medium in which the microorganism is grown. The lipase is characterized by a unique, but not absolute, specificity for fatty acids containingcis-9 orcis,cis-9, 12 unsaturation, hydrolyzing both regardless of position within the triglyceride molecule. The enzyme also hydrolyzescis-9-16∶1,cis,trans-9,12-18∶2,trans,cis-9,12-18∶2, palmitoyl oleate and cholesteryl oleate. Digested at comparatively slow rates are:trans,trans-9,12-18∶2, double bond positional isomers of 18∶1 (other thancis-9), stearolic acid, oleoylpalmitate, dilinoleoyl phosphatidyl choline, and saturated acids. The enzyme has an optimum pH of 8.2, and the lyophilized powder is extremely stable, retaining activity for at least eight years when stored at-20 C. A purification of 81-fold has been achieved. One of five papers presented in the Symposium “Microbial Lipolytic Enzymes,” AOCS Spring Meeting, New Orleans, April 1973. Scientific contribution 556, Agricultural Experiment Station, University of Connecticut, Storrs, Conn. 06268.     

High temperature swelling of coal/tetralin mixtures in a high pressure microdilatometer

High pressure microdilatometer experiments were performed on a subbituminous (Wyodak) and a bituminous (Illinois no. 6) coal in helium and hydrogen atmospheres with and without added tetralin. Wyodak coal samples showed no swelling but contractions ranging between 24 and 40 vol% upon heating at 20 and 100 °C min^{− 1} under helium or hydrogen pressures between 150 and 1000 psig (˜1.0–6.9 MPa). Under the same conditions, Illinois no. 6 coals displayed contractions (25–60 vol%) prior to swelling up to 117 vol%. Upon tetralin addition (at 35–190 wt% of the coal), Wyodak coal samples did not swell but showed an increasing contraction with increasing helium or hydrogen pressure due to a slight softening and fusion of the coal particles. In contrast, addition of tetralin at much lower concentrations (5–35 wt%) had a marked effect on the contraction and swelling behaviour of Illinois no. 6. A maximum swelling of 200 vol% was obtained at a tetralin addition of 30 wt%. The increased swelling results from more extensive softening and fusion of coal particles in the presence of tetralin. Both coals showed a decreasing char yield with increasing tetralin concentration. The substantially lower extent of interaction observed between Wyodak coal samples and tetralin compared to Illinois no. 6 coal can be attributed to the differences in pore structure and/or chemical constitution of the two coal samples. Examination of the resultant solids by optical microscopy revealed the microstructural changes produced by thermal treatment in dilatometer experiments.     

Organolithium route to poly(arylsilane)s

Various poly(arylsilane)s The poly(carbosilane)s prepared in this way are of higher molecular weight than when prepared by the Wurtz-type condensation route previously reported. TG shows 40–50% overll weight loss attained at 500–600°C.     

Chemical analysis of volatiles emitted by Pinus svlvestris after induction by insect oviposition

Gas chromatography – mass spectrometry analyses of the headspace volatiles of Scots pine (Pinus sylvestris) induced by egg deposition of the sawfly Diprion pini were conducted. The odor blend of systemically oviposition-induced pine twigs, attractive for the eulophid egg parasitoid Chrysonotomyia ruforum, was compared to volatiles released by damaged pine twigs (control) that are not attractive for the parasitoid. The mechanical damage inflicted to the control twigs mimicked the damage by a sawfly female prior to egg deposition. The odor blend released by oviposition-induced pine twigs consisted of numerous mono- and sesquiterpenes, which all were also present in the headspace of the artificially damaged control twigs. A quantitative comparison of the volatiles from oviposition-induced twigs and controls revealed that only the amounts of (E)--farnesene were significantly higher in the volatile blend of the oviposition-induced twigs. Volatiles from pine twigs treated with jasmonic acid (JA) also attract the egg parasitoid. No qualitative differences were detected when comparing the composition of the headspace of JA-treated pine twigs with the volatile blend of untreated control twigs. JA-treated pine twigs released significantly higher amounts of (E)--farnesene. However, the JA treatment induced a significant increase of the amount of further terpenoid components. The release of terpenoids by pine after wounding, egg deposition, and JA treatment is discussed with special respect to (E)--farnesene.     

Moisture absorption behavior of rubber‐modified epoxy resins

The moisture absorption behavior of diglycidyl ether of bisphenol A/ethylene diamine resins incorporating a carboxy‐terminated butadiene–acrylonitrile rubber was investigated and associated with their morphology of phase separation. Although the diffusion coefficient of moisture was increased with the rubber content, its activation energy and free volume for moisture diffusion were barely changed until phase inversion occurred. After phase inversion, the free volume was significantly increased, and the activation energy decreased. In addition, the moisture absorption also reduced the β‐transition temperature of the resins and slightly increased the glass‐transition temperature before phase inversion. However, the reverse was found after phase inversion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3718–3724, 2002