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排序方式: 共有101条查询结果,搜索用时 62 毫秒
1.
Tim R. Dargaville Julie M. Elliott Mathew Celina 《Journal of Polymer Science.Polymer Physics》2006,44(22):3253-3264
Films of piezoelectric PVDF and P(VDF‐TrFE) were exposed to vacuum UV (115–300 nm VUV) and γ‐radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after γ‐irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV‐irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV‐irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d33 piezoelectric coefficients and D‐E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D‐E loops after exposure to either γ‐ or VUV‐radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV‐irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV‐radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3253–3264, 2006 相似文献
2.
A novel dual stage chemiluminescence detection system incorporating individually controlled hot stages has been developed and applied to probe for material interaction effects during polymer degradation. Utilization of this system has resulted in experimental confirmation for the first time that in an oxidizing environment a degrading polymer A (in this case polypropylene, PP) is capable of infecting a different polymer B (in this case polybutadiene, HTPB) over a relatively large distance. In the presence of the infectious degrading polymer A, the thermal degradation of polymer B is observed over a significantly shorter time period. Consistent with infectious volatiles from material A initiating the degradation process in material B it was demonstrated that traces (micrograms) of a thermally sensitive peroxide in the vicinity of PP could induce degradation remotely. This observation documents cross-infectious phenomena between different polymers and has major consequences for polymer interactions, understanding fundamental degradation processes and long-term aging effects under combined material exposures. 相似文献
3.
Correlation of antioxidant depletion and mechanical performance during thermal degradation of an HTPB elastomer 总被引:1,自引:0,他引:1
M. Celina J.M. Skutnik Elliott S.T. Winters R.A. Assink L.M. Minier 《Polymer Degradation and Stability》2006,91(8):1870-1879
Thermal degradation studies of a stabilized HTPB based elastomer were conducted at temperatures from 50 °C to 110 °C. The concentration of extractable antioxidant (AO2246) in the polymer was quantified via AO extraction and a gas chromatography-based method using internal standards. The decrease in extractable AO levels as a function of time and temperature was evaluated and correlated with mechanical property changes. Most importantly, AO depletion features were found to be temperature dependent. At elevated temperatures (>80 °C) extractable AO levels decreased rapidly and faster than the concurrent loss in mechanical properties. While extractable AO concentrations decrease quickly, the material is able to maintain some useful mechanical properties, perhaps via non-extractable or grafted AO species formed during degradation providing additional protection. At lower aging temperatures extractable or free AO levels decreased more slowly than the mechanical properties. Therefore, for condition monitoring purposes a universal correlation between AO levels and aging state or material condition could not be established. Most importantly, however, loss of mechanical properties and oxidative degradation is observed at lower temperatures despite significant levels of free antioxidant in the material. The antioxidant appears to be limited in its effectiveness to completely prevent degradation reactions, or only fractions of the total AO available are actually involved in the inhibition process. 相似文献
4.
We describe our full report of the catalytic asymmetric addition of simple and functionalized dialkylzinc reagents to a broad range of saturated ketones and enones. The functionalized organozinc reagents contain esters, silyl ethers, alkyl chlorides, and alkyl bromides. In general, the resulting tertiary alcohol products are isolated with high ee's. With some substrates, yields are low as a result of the formation of aldol byproducts. Most substrates undergo additions with good yields reaching as high as 91%. 相似文献
5.
Previous investigations of the first ionization of aqueous sulfur dioxide or ‘sulfurous acid’ have led to ΔH 1 0 values ranging from ?15 to ?24.5 kJ-mol?1. To help with selection of a ‘best’ value for this enthalpy of ionization we have made calorimetric measurements of enthalpies associated with adding dilute perchloric acid to dilute aqueous sulfur dioxide and sodium bisulfite. Results have led to ΔH 1 0 =?17.40 kJ-mol?1, which we have combined with K1=0.0139 and the related ΔG 1 0 =10.60 kJ-mol?1 to obtain ΔS 1 0 =?93.9 J-K?1-mol?1 for the first ionization, all referring to 25°C. 相似文献
6.
Modelling, simulation and optimal control for a lithium-ion battery cell is discussed. The model involves ionic concentrations, currents and potentials in the electrodes and the separator together with the battery temperature as state variables. The resulting system is a nonlinear PDAE system with 10 partial, 1 ordinary differential and 4 algebraic equations involving the Butler-Volmer kinetics for describing the interaction of ionic currents and potentials. Time-optimal charging of the battery subject to age-preventing leads to a state-constrained optimal control problem which is solved in two ways. A first-discretize-then-optimize approach leads to a high-dimensional nonlinear optimization problem which is solved by an efficient solver. As an alternative, a feedback control law along an active arc of the state constraint of order 1 is derived to formulate and solve the corresponding so-called induced optimization problem. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
7.
8.
Celina Love Jan Steinkühler David T. Gonzales Naresh Yandrapalli Tom Robinson Rumiana Dimova Dr. T.-Y. Dora Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6006-6013
In situ, reversible coacervate formation within lipid vesicles represents a key step in the development of responsive synthetic cellular models. Herein, we exploit the pH responsiveness of a polycation above and below its pKa, to drive liquid–liquid phase separation, to form single coacervate droplets within lipid vesicles. The process is completely reversible as coacervate droplets can be disassembled by increasing the pH above the pKa. We further show that pH-triggered coacervation in the presence of low concentrations of enzymes activates dormant enzyme reactions by increasing the local concentration within the coacervate droplets and changing the local environment around the enzyme. In conclusion, this work establishes a tunable, pH responsive, enzymatically active multi-compartment synthetic cell. The system is readily transferred into microfluidics, making it a robust model for addressing general questions in biology, such as the role of phase separation and its effect on enzymatic reactions using a bottom-up synthetic biology approach. 相似文献
9.
Caldeira J Figueirinhas JL Santos C Godinho MH 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,170(2):213-219
Correlation of the g-tensor of a paramagnetic active center of a protein with its structure provides a unique experimental information on the electronic structure of the metal site. To address this problem, we made solid films containing metalloprotein (Desulfovibrio gigas cytochrome c(3)) microcrystals. The microcrystals in a liquid crystalline polymer medium (water/hydroxypropylcellulose) were partially aligned by a shear flow. A strong orientation effect of the metalloprotein was observed by EPR spectroscopy and polarizing optical microscopy. The EPR spectra of partially oriented samples were simulated, allowing for molecular orientation distribution function determination. The observed effect results in enhanced sensitivity and resolution of the EPR spectra and provides a new approach towards the correlation of spectroscopic data, obtained by EPR or some other technique, with the three-dimensional structure of a protein or a model compound. 相似文献
10.
[reaction: see text] The catalytic asymmetric addition of phenyl groups from diphenylzinc to ketones is reported. The catalyst, generated from a dihydroxy bis(sulfonamide) ligand and titanium tetraisopropoxide, gives good to excellent enantioselectivities with a range of substrates. 相似文献