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81.
The melting of isothermally crystallized poly(vinylidene fluoride) (PVF2), produced in the intercrystalline spaces of poly(ethylene terephthalate) (PET) from its blends, showed a unique behavior: the melting temperature decreased with the increasing crystallinity of PVF2 (i.e., with increasing crystallization time) for PVF2 volume fractions of 0.64 and 0.51. The melting temperature of already crystallized PET also decreased as the PVF2 crystallization progressed and the isothermal crystallization temperature of PVF2 increased. Separate reasons were proposed to account for these behaviors. The equilibrium melting temperatures of PVF2 in the blends, measured by the Hoffman–Weeks extrapolation procedure, were used to calculate the polymer–polymer interaction parameter (χ21); only the noncrystallized portion of PET contributing to the mixed amorphous phase was considered. The χ21value (−1.75) was lower than χ12 (−0.14), calculated from the melting temperature depression of PET. However, when they were normalized to the unit volumes of the respective components, the two values were found to be the same. The crystallization rate of PVF2 decreased with an increasing volume fraction of PET in the blend. The Avrami exponent increased for the volume fraction of PVF2 (0.77) and then progressively decreased with an increasing volume fraction of PET. A gradual change in the nature of the regime transition from regime II/regime I to regime III/regime II with increasing PET concentration was observed. The value of the chain-extension factor of PVF2 significantly increased with an increase in the PET concentration in the blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2215–2227, 2004 相似文献
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Alexander J Artuso M Bebek C Berkelman K Browder T Cassel DG Cheu E Coffman DM Crawford G DeWire JW Drell PS Ehrlich R Galik RS Gittelman B Gray SW Halling AM Hartill DL Heltsley BK Kandaswamy J Katayama N Kreinick DL Lewis JD Ludwig GS Mistry NB Mueller J Nandi S Nordberg E O'Grady C Peterson D Pisharody M Riley D Sapper M Selen M Silverman A Stone S Worden H Worris M Sadoff AJ Avery P Besson D Garren L Yelton J Bowcock T Kinoshita K Pipkin FM Procario M Wilson R Wolinski J Xiao D Zhu Y 《Physical review letters》1990,65(13):1531-1534
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86.
Proteins are the main proton mediators in various biological proton circuits. Using proteins for the formation of long-range proton conductors is offering a bioinspired approach for proton conductive polymers. One of the main challenges in the field of proton conductors is to explore the local environment within the polymers, along with deciphering the conduction mechanism. Here, we show that the protonic conductivity across a protein-based biopolymer can be hindered using straightforward chemical modifications, targeting carboxylate- or amine-terminated residues of the protein, as well as exploring the effect of surface hydrophobicity on proton conduction. We further use the natural tryptophan residue as a local fluorescent probe for the inner local hydration state of the protein surface and its tendency to form hydrogen bonds with nearby water molecules, along with the dynamicity of the process. Our electrical and spectroscopic measurements of the different chemically-modified protein materials as well as the material at different water–aprotic solvent mixtures result in our fundamental understanding of the proton mediators within the material and gaining important insights on the proton conduction mechanism. Our biopolymer can be used as an attractive platform for the study of bio-related protonic circuits as well as a proton conducting biopolymer for various applications, such as protonic transistors, ionic transducers and fuel cells.Post formation modification of protein-based materials can attenuate the proton conduction efficiency resulting from change in conduction mechanism, charge carrier mobility, carrier concentrations and inner hydration layer. 相似文献
87.
The microwave spectrum of 1,2,4-trifluorobenzene has been observed in the range 12.5–18.0 GHz and 21.5–25.3 GHz at dry-ice temperature and assigned up to angular momentum state J = 39. The ground state rotational constants and the five quartic centrifugal distortion constants thus obtained are (in MHz): Ã = 3084.0037 ± 0.0108, B? = 1278.3614 ± 0.0062, C? = 903.6989 ± 0.0108, dj = ( ?4.599 ± 0.621) · 10?4, djk = (5.9757 ± 1.1586) · 10?3, dk = (11.4923 ± 2.0886) · 10?3, dwj = (4.0 ± 1.0) · 10?7, dwk=(?5.8± 1.1) · 10?6.The small value of Δ = 0.029 (amu Å2) shows that the molecule is planar and an r0 - structure using a regular hexagonal benzene ring with the bond lengths C-C = 1.397 Å, C-H = 1.084 Å and C-F = 1.312 Å, reproduces the rotational constants. 相似文献
88.
Alam MS Katayama N Kim IJ Li WC Lou XC Sun CR Bortoletto D Goldberg M Horwitz N Mestayer MD Moneti GC Sharma V Shipsey IP Skwarnicki T Csorna SE Letson T Brock IC Ferguson T Artuso M Bebek C Berkelman K Blucher E Byrd J Cassel DG Cheu E Coffman DM Crawford G DeSalvo R DeWire JW Drell PS Ehrlich R Galik RS Gittelman B Gray SW Halling AM Hartill DL Heltsley BK Kandaswamy J Kowalewski R Kreinick DL Kubota Y Lewis JD Mistry NB Mueller J Namjoshi R Nandi S Nordberg E O'Grady C Peterson D Pisharody M 《Physical review D: Particles and fields》1989,40(3):712-720
89.
B. M. Mandal U. S. Nandi S. R. Palit 《Journal of polymer science. Part A, Polymer chemistry》1969,7(6):1407-1414
Initiation of polymerization of methyl methacrylate, styrene, and acrylonitrile with the redox system Fe(III)—thiourea has been examined. For the heterophase polymerization any of the ferric salts, such as FeCl3, Fe2(SO4)3, and Fe(ClO4)3 can be used as oxidant, but there is no polymerization in the homogeneous phase when FeCl3 is used as oxidant. It was also observed that Fe(ClO4)3 retards the radical polymerization of styrene, though this salt has hardly any effect on the radical polymerization of methyl methacrylate. Further, the reaction between Fe(ClO4)3 and thiourea was found to be kinetically of second order. The rate is largely influenced by the nature of the solvent. It is concluded that apart from the dielectric constant of the solvents, specific effects like complex formation of Fe(III) with solvents should have a marked influence on the rate of this reaction. 相似文献
90.
Summary The kinetics of the aquation of four selenitoaquobisdiamine)cobalt(III) complexes to their respective diaquabis-(diamine)complexes (diamine=ethylenediamine en, propylenediamine pn, dimethylethylenediamine me2en and trimethylenediamine tmd) have been carried out conductimetrically in the 25–45 °C range. All reactions exhibit simple first order kinetics, and the rates increase with increasing temperature. In aqueous solution, the complex species exist in equilibrium with their respective hydroxo species, but only the hydroxo species are involved in the aquation process. This result is also reflected in the linear Arrhenius plot. The rates are higher in a 10% alcoholic solution than in water, but then decrease with increase in the alcohol content. A Grunwald-Winstein plot of rates in methanol yields slopes of 0.18 ± 0.04, 0.27±0.03, 0.43±0.03 and 0.34±0.02 for the four amines respectively. A dissociation mechanism is proposed for the aquation of all these complexes. 相似文献