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141.
Jacquelyn A. Carioscia Lauren Schneidewind Casey O'Brien Robert Ely Caitlin Feeser Neil Cramer Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2007,45(23):5686-5696
The ability to prepare high Tg low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (Tg) for several thiol–norbornene materials. Results indicate that Tgs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high Tg materials. In particular, as much as a 70 °C increase in Tg was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007 相似文献
142.
Alexis C. Kaporis Lefteris M. Kirousis Yannis C. Stamatiou Malvina Vamvakari Michele Zito 《Discrete Applied Mathematics》2007,155(12):1525-1538
The problem of determining the unsatisfiability threshold for random 3-SAT formulas consists in determining the clause to variable ratio that marks the experimentally observed abrupt change from almost surely satisfiable formulas to almost surely unsatisfiable. Up to now, there have been rigorously established increasingly better lower and upper bounds to the actual threshold value. In this paper, we consider the problem of bounding the threshold value from above using methods that, we believe, are of interest on their own right. More specifically, we show how the method of local maximum satisfying truth assignments can be combined with results for the occupancy problem in schemes of random allocation of balls into bins in order to achieve an upper bound for the unsatisfiability threshold less than 4.571. In order to obtain this value, we establish a bound on the q-binomial coefficients (a generalization of the binomial coefficients). No such bound was previously known, despite the extensive literature on q-binomial coefficients. Finally, to prove our result we had to establish certain relations among the conditional probabilities of an event in various probabilistic models for random formulas. It turned out that these relations were considerably harder to prove than the corresponding ones for unconditional probabilities, which were previously known. 相似文献
143.
A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species. 相似文献
144.
用温度场论方法计算了F-L模型在有限温度和密度下的状态方程,分析了压强对净重子数密度的等温线.结果表明,在平均场近似下,F-L模型所给出的退禁闭相变为一级相变. 相似文献
145.
Recent X-ray diffraction studies on α-quartz (SiO2) by Kingmaet al [1], have shown the occurrence of a reversible, crystalline-to-crystalline, phase transition just prior to amorphization
at ≈ 21 GPa. This precursor transition has also been confirmed by our recent molecular dynamics simulation study [2]. In order
to investigate the possibility of a similar behaviour in other isostructural compounds, which also undergo pressure induced
amorphization, α-GeO2 and α-AlPO4 (berlinite form) were studied using energy dispersive X-ray diffraction. In either of these materials, no such phase transition
is detected prior to amorphization. The onset of amorphization and its reversal is found to be time dependent in GeO2. 相似文献
146.
Time differential perturbed angular correlation measurements of the 133–482 keVγ-γ cascade of181Ta in Hf-doped YBa2Cu3O7−x
are presented. The181Hf precurser nuclei are incorporated into the sample by thermal neutron irradiation. Two quadrupole interaction frequencies
are observed in the as-irradiated sample:v
Q1=161±10 MHz with intensityf
1=75%, asymmetry parameterη
1=0.32 and damping parameter Λ1=0.42, andv
Q2=1108±40 MHz withf
2=25%,η
2=0.62, and Λ2=0.60. On annealing the sample in air at various temperaturesT
a and quenching to room temperature,f
1 remained nearly constant forT
a<600°C andv
Q1 for all annealing temperatures indicating that these are insensitive to oxygen stoichiometry. This frequency is interpreted
to be due to181Hf substitutingY sites. BeyondT
a=600°C,f
1 increased and reached a constant value of 90% forT
a=800°C. The value ofv
Q2 showed a slight variation between 1086 and 1160 MHz, whilef
2 remained nearly constant at 25% forT
a<600°C. This component is identified to be due to181Hf substituting Cu 1 sites in the Cu-O chains of YBCO. Above 600°Cv
Q2 decreased and reached a value of 808 MHz beyond 750°C. 相似文献
147.
Ab initio energetic calculations based on the density functional theory (DFT) and projector augmented wave (PAW) pseudo-potentials method were performanced to determine the crystal structural parameters and phase transition data of the polymorphic rare-earth sesquioxides Ln2O3 (where Ln=La-Lu, Y, and Sc) with A-type (hexagonal) and B-type (monoclinic) configurations at ground state. The calculated results agree well with the limited experimental data and the critically assessed results. A set of systematic and self-consistent crystal structural parameters, energies and pressures of the phase transition were established for the whole series of the A- and B-type rare-earth sesquioxides Ln2O3. With the increase of the atomic number, the ionic radii of rare-earth elements Ln and the volumes of the sesquioxides Ln2O3 reflect the so-called “lanthanide contraction”. With the increase of the Ln3+-cation radius, the bulk modulus of Ln2O3 decreases and the polymorphic structures show a degenerative tendency. 相似文献
148.
Ummadisetty Subramanyam Swaminathan Sivaram 《Journal of polymer science. Part A, Polymer chemistry》2007,45(2):191-210
Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007 相似文献
149.
A. Hansen M.H. Jensen K. Sneppen G. Zocchi 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,6(1):157-161
We present a statistical mechanics treatment of the stability of globular proteins which takes explicitly into account the
coupling between the protein and water degrees of freedom. This allows us to describe both the cold and the warm unfolding,
thus qualitatively reproducing the known thermodynamics of proteins.
Received: 19 March 1998 / Revised and Accepted: 25 May 1998 相似文献
150.
Bryan B. Sauer Richard Beckerbauer Lixiao Wang 《Journal of Polymer Science.Polymer Physics》1993,31(12):1861-1872
The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main Tg, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that Tg is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc. 相似文献