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91.
Fanqin Meng Steven F. Dec Don Williamson Phat Pham Michael A. Yandrasits Andrew M. Herring 《Electrochimica acta》2007,53(3):1372-1378
A perfluorosulfonic acid (PFSA) polymer with pendant side chain -O(CF2)4SO3H was doped with the heteropoly acids (HPAs), H3PW12O40 and H4SiW12O40. Infrared spectroscopy revealed a strong interaction between the HPA and the PFSA ionomer. Modes associated with the peripheral bonds of the HPA were shifted to lower wave numbers when doped into PFSA membranes. Small-angle X-ray scattering (SAXS) measurements showed the presence of large crystallites of HPA in the membrane with d spacings of ca. 10 Å, close to the lattice spacing observed in bulk HPA crystals. Under wet conditions the HPA was more dispersed and constrained the size of the sulfonic acid clusters to 20 Å at a 5 wt% HPA doping level, the same as in the vacuum treated ionomer samples. Under conditions of minimum hydration the HPA decreased the Ea for the self-diffusion of water from 27 to 15 kJ mol−1. The reverse trend was seen under 100% RH conditions. Proton conductivity measurements showed improved proton conductivity of the HPA doped PFSAs at a constant dew point of 80 °C for all temperatures up to 120 °C and at all relative hummidities up to 80%. The activation energy for proton conduction generally was lower than for the undoped materials at RH ≤80%. Significantly the Ea was 1/2 that of the undoped material at RHs of 40 and 60%. A practical proton conductivity of 113 mS cm−1 was observed at 100 °C and 80% RH. 相似文献
92.
Symon M. Mahungu Steven L. Hansen William E. Artz 《Journal of the American Oil Chemists' Society》1994,71(4):453-455
Static headspace and capillary gas chromatography/infrared spectroscopy-mass spectrometry were used to collect, separate,
identify and quantitate the oxidative and thermal decomposition products in heated triolein. Approximately 4 L of triolein
was heated in a deep-fat fryer at 190°C for 12 h each day for a total of 60 h, until it contained>-20% polymeric material.
The concentration of heptane and octane increased after 12 h heating, then decreased upon further heating, while the concentration
of volatile aldehydes decreased gradually during heating. After 12 h of heating, the concentrations of the major volatiles
changed as follows: heptane (16.36 to 30.17 ppm), octane (24.48 to 40.77 ppm), heptanal (21.68 ppm to 9.11 ppm), octanal (35.53
to 36.64 ppm), nonanal (68.95 to 43.16 ppm), (E)-2-decenal (135.00 to 89.00 ppm) and (E)-2-undecenal (88.50 to 61.00 ppm).
After 60 h of heating, when the oil contained over 20% polymeric material, the concentrations of heptane, octane, heptanal,
octanol, nonanal, (E)-2-decenal and (E)-2-undecenal were 5.16, 4.39, 5.45, 7.02, 18.07, 12.50 and 6.00 ppm, respectively. 相似文献
93.
Michael Kmetz Steven L. Suib Francis S. Galasso 《Journal of the American Ceramic Society》1989,72(8):1523-1524
The strength and toughness of fibrous composites depend on the interface properties which control the bonding between the fibers and matrices. One method of controlling the interface involves coating the fiber with an appropriate material. In a previous study, it was found that there is a definite advantage in using low coating temperatures to prevent fibers from degrading. We therefore were interested in a report that Mo2 C could be deposited from Mo(CO)6 at temperatures as low as 300° to 475°C. Our studies indicated that the material was not Mo2 C, but an oxycarbide, which, with an analogous tungsten oxycarbide coating, was applied to SiC yarns. Both oxycarbides could be converted to the metals by heat-treating in N2 . 相似文献
94.
This paper deals with the data-driven design of observer-based fault detection and control systems. We first introduce the definitions of the data-driven forms of kernel and image representations. It is followed by the study of their identification. In the context of a fault-tolerant architecture, the design of observer-based fault detection, feed-forward and feedback control systems are addressed based on the data-driven realization of the kernel and image representations. Finally, the main results are demonstrated on the laboratory continuous stirred tank heater (CSTH) system. 相似文献
95.
Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (Tg) rises above the cure temperature (Tcure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of Tcure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E1OH = 44 kJ mol?1) and secondary amine (E2OH = 48 kJ mol?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and Tcure. The relation between x, r, and Tg, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in Cp in the glassy region with x and Tcure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004 相似文献
96.
Linda J. McPheron Steven J. Seybold Andrew J. Storer David L. Wood Toshikazu Ohtsuka Isao Kubo 《Journal of chemical ecology》1997,23(12):2825-2839
The aggregation pheromone produced by maleIps paraconfusus (Coleoptera: Scolytidae) tunneling in Monterey pine,Pinus radiata, logs was trapped on Porapak Q. A concentration of an extract of trapped volatiles that attracted beetles was determined in the laboratory through a concentration–response analysis of walking behavior of males and females. The interruptant effects of four concentrations of verbenone on response to a constant concentration of this naturally produced aggregation pheromone were tested with males and females. Independent of its enantiomeric composition [99.5% (S)-(–), 93.1 % (S)-(–), and 98.3% (R)-(+)], verbenone significantly reduced the percentage of females (but not males) reaching the attractant source. However, when the time required for beetles of both sexes taken together to reach the attractant source was considered, verbenone of higher enantiomeric purity had a greater effect on beetle behavior. Solutions of 99.5% (S)-(–)- and 98.3% (R)-(+)-verbenone increased the time required for beetles to reach the attractive source when compared to 93.1% (S)-(–)-verbenone. When pooled across enantiomeric blends, increasing concentrations of verbenone resulted in slower responses in beetles that reached the attractant source within 2 min. Males and females did not respond to verbenone alone. 相似文献
97.
Volatile Emissions Triggered by Multiple Herbivore Damage: Beet Armyworm and Whitefly Feeding on Cotton Plants 总被引:5,自引:3,他引:5
Plants are commonly attacked by more than one species of herbivore, potentially causing the induction of multiple, and possibly competing, plant defense systems. In the present paper, we determined the interaction between feeding by the phloem feeder silverleaf whitefly (SWF), Bemisia tabaci Gennadius (B-biotype = B. argentifolii Bellows and Perring), and the leaf-chewing beet armyworm (BAW), Spodoptera exigua Hübner, with regard to the induction of volatile compounds from cotton plants. Compared to undamaged control plants, infestation with SWF did not induce volatile emissions or affect the number and density of pigment glands that store volatile and nonvolatile terpenoid compounds, whereas infestation by BAW strongly induced plant volatile emission. When challenged by the two insect herbivores simultaneously, volatile emission was significantly less than for plants infested with only BAW. Our results suggest that tritrophic level interactions between cotton, BAW, and natural enemies of BAW, that are known to be mediated by plant volatile emissions, may be perturbed by simultaneous infestation by SWF. Possible mechanisms by which the presence of whiteflies may attenuate volatile emissions from caterpillar-damaged cotton plants are discussed. 相似文献
98.
Rat hepatocytes in monolayer culture were utilized to determine if the decrease in glucose-6-phosphate dehydrogenase (G6PD)
activity resulting from the ingestion of fat can be mimicked by the addition of fatty acids to a chemically, hormonally defined
medium. G6PD activity in cultured hepatocytes was induced several-fold by insulin. Dexamethasone or T3 did not amplify the
insulin induction of G6PD. Glucose alone increased G6PD activity in cultured hepatocytes from fasted donors by nearly 500%.
Insulin in combination with glucose induced G6PD an additional two-fold. The increase in G6PD activity caused by glucose was
greater in hepatocytes isolated from 72 hr-fasted rats as compared to fed donor rats. Such a response was reminiscent of the
“overshoot” phenomenon in which G6PD activity is induced well above the normal level by fasting-refeeding rats a high glucose
diet. Addition of linoleate to the medium resulted in a significant suppression of insulin’s ability to induce G6PD, but linoleate
had no effect on the induction of G6PD activity by glucose alone. A shift to the right in the insulin-response curve for the
induction of G6PD also was detected for the induction of malic enzyme and acetyl-CoA carboxylase. Arachidonate (0.25 mM) was
a significantly more effective inhibitor of the insulin action than linoleate was. Apparently rat hepatocytes in monolayer
culture can be utilized as a model to investigate the molecular mechanism by which fatty acids inhibit the production of lipogenic
enzymes. In part, this mechanism of fatty acid inhibition involves desensitization of hepatocytes to the lipogenic action
of insulin. 相似文献
99.
Steven Swier Yong Sung Chun Jeffrey Gasa Montgomery T. Shaw R.A. Weiss 《Polymer Engineering and Science》2005,45(8):1081-1091
Sulfonated poly(ether ketone ketone) ionomers (SPEKK) with ion‐exchange capacities (IEC) between 0.2 and 3.4 meq/g were prepared by sulfonating PEKK with a mixture of concentrated and fuming sulfuric acids. Sulfonation occurs only on the phenyl rings attached to ether and ketone groups. The glass transition temperature of the dry SPEKK ionomers increased linearly with increasing IEC, and the ionomers were thermally stable to ~250°C, above which desulfonation occurred. Water‐swollen ionomers exhibited microphase separated morphologies, and the average correlation length determined by small angle X‐ray scattering increased with increasing IEC. The proton conductivity of hydrated SPEKK membranes measured by impedance spectroscopy ranged from ~10–3 to 10–1 S/cm as the IEC increased from ~1.0 to 2.4 meq/g. Single cell performance curves on membrane‐electrode assemblies (MEA) indicated that the SPEKK membranes approached the performance of Nafion? for an IEC of 2 meq/g. POLYM. ENG. SCI., 45:1081–1091, 2005. © 2005 Society of Plastics Engineers 相似文献
100.
Hyoun-Ee Kim Steven J. Zinkle William R. Allen 《Journal of the American Ceramic Society》1990,73(2):425-429
Alumina enriched in 17 O was successfully fabricated from aluminum isopropoxide and water containing the 17 O isotope. This material was necessary for an experiment to study the radiation damage expected in alumina exposed to a nuclear fusion reactor environment. The enrichment levels of specimens subjected to different preparation schedules were measured using a nuclear reaction analysis technique. Replacement of the 17 O isotope in the ceramic by atmospheric oxygen occurred readily. Therefore, successful fabrication of suitably enriched alumina specimens required that all processing steps be performed under vacuum or inertgas environments. The optimum fabrication procedure produced enriched alumina specimens of >99.5% of theoretical density, ∽10-μm grain size, and a flexural strength of 280 MPa. 相似文献