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51.
Pawan K. Agarwal Richard T. Garner William W. Graessley 《Journal of Polymer Science.Polymer Physics》1987,25(10):2095-2111
We present an analysis of data on the intrinsic viscosity [η] of sulfo-polystyrene ionomers in several solvents for a variety of sulfonation levels and counterions. For solvents of low dielectric constant, 2 < ε < 18, [η] decreases from the base polymer value [η]0 with increasing substitution level. This behavior was attributed to intramolecular association of ionic dipoles. The ratio [η]/[η]0 was found to depend on a single reduced variable αAαSx, where x is the fractional substitution, αA depends only on the counterion, and αS ∝ ε?1 depends only on the solvent. For solvents of high dielectric constant, 36 < ε < 47, [η] increases approximately as x3, and counterion effects are small. This behavior was attributed to ionic dissociation, giving rise to a polyelectrolyte effect. Implications of the low ε results are discussed in relation to association-induced gelation behavior and possible generalizations of the reduced variables approach. 相似文献
52.
Marco Sangermano Roberta Bongiovanni Giulio Malucelli Aldo Priola Richard R. Thomas Charles M. Kausch Yongsin Kim 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):6943-6951
New fluorinated, polyfunctional propenyl ether functionalized resins were synthesized, and their behavior in cationic photopolymerization was investigated. The photopolymerization proceeded efficiently with a high double‐bond conversion (>90%), giving rise to UV‐cured coatings characterized by low glass‐transition temperatures (?33 °C ≤ glass‐transition temperature ≤ ?15 °C) and hydrophobic surface properties. A fluorinated additive was also employed as a reactive additive in the cationic photopolymerization of trimethylolpropane tripropenyl ether, increasing the double‐bond conversion, polymer network flexibility, thermal stability, and surface hydrophobicity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6943–6951, 2006 相似文献
53.
Olga Ordeig Craig E Banks Trevor J Davies F Javier del Campo Francesc Xavier Mu?oz Richard G Compton 《Analytical sciences》2006,22(5):679-683
Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array. 相似文献
54.
55.
Richard A. Cairncross Jeffrey G. Becker Shri Ramaswamy Ryan O'Connor 《Applied biochemistry and biotechnology》1996,131(1-3):774-785
Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing,
shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured
through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and
X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture
sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments,
crystalline and amorphous PLA films exhibit identical sorption isotherms. 相似文献
56.
Jon Samseth Richard J. Spontak Kell Mortensen 《Journal of Polymer Science.Polymer Physics》1993,31(4):467-474
Poly(siloxaneimide) (PSI) segmented copolymers exhibit organized microdomains if the blocks are sufficiently incompatible. As with neat diblock and triblock copolymers, the processing route employed to prepare films of PSI materials is expected to influence the dimensions and/or morphology of the resultant microstructure. In this work, small-angle neutron scattering (SANS) is utilized to characterize the disordered microstructure found in films of a series of PSI copolymers which are subjected to solvent casting and various thermal treatments. Microstructural dimensions such as the periodicity and correlation length are deduced from the Teubner-Strey (TS) model for disordered microemulsions. The scattering intensity of each copolymer up to q = 5.0 nm?1, where q is the scattering vector, is found to scale as q?2.8+?0.1. Results indicate that processing the materials as cast films or as melt-pressed films allowed to cool slowly has a small, but discernible, effect on microstructural characteristics. SANS profiles of films quenched from elevated temperatures reveal a clear transition in microdomain periodicity, which correlates well with the glass transition temperature of the imide microphase in these and other materials of similar chemical structure. © 1993 John Wiley & Sons, Inc. 相似文献
57.
The complete convergence theorem implies that starting from any initial distribution the one dimensional contact process converges to a limit ast. In this paper we give a necessary and sufficient condition on the initial distribution for the convergence to occur with exponential rapidity.This work was discussed while the authors were visiting the Nankai Mathematics Institute in Tianjin.Partially supported by the National Science Foundation, the Army Research Office through the Mathematical Sciences Institute at Cornell University, and a Guggenheim fellowship.Research supported by the National Science Foundation of China. 相似文献
58.
Richard Valenta 《Czechoslovak Journal of Physics》1990,40(10):1117-1122
In this article, homogeneous Parker's equation is solved. Relations for temperature, velocity and pressure are found. The possibility of low frequency approximation is shown and thermoacoustic effect in gas near plane motionless wall is treated.I would like to thank Prof. Zdenk kvor for his interest and encouragement. 相似文献
59.
We study the convergence properties of reduced Hessian successive quadratic programming for equality constrained optimization. The method uses a backtracking line search, and updates an approximation to the reduced Hessian of the Lagrangian by means of the BFGS formula. Two merit functions are considered for the line search: the
1 function and the Fletcher exact penalty function. We give conditions under which local and superlinear convergence is obtained, and also prove a global convergence result. The analysis allows the initial reduced Hessian approximation to be any positive definite matrix, and does not assume that the iterates converge, or that the matrices are bounded. The effects of a second order correction step, a watchdog procedure and of the choice of null space basis are considered. This work can be seen as an extension to reduced Hessian methods of the well known results of Powell (1976) for unconstrained optimization.This author was supported, in part, by National Science Foundation grant CCR-8702403, Air Force Office of Scientific Research grant AFOSR-85-0251, and Army Research Office contract DAAL03-88-K-0086.This author was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy, under contracts W-31-109-Eng-38 and DE FG02-87ER25047, and by National Science Foundation Grant No. DCR-86-02071. 相似文献
60.
Richard F. Serfozo 《Queueing Systems》1989,5(1-3):5-36
A Markovian network process describes the movement of discrete units among a set of nodes that process the units. There is considerable knowledge of such networks, often called queueing networks, in which the nodes operate independently and the routes of the units are independent. The focus of this study, in contrast, is on networks with dependent nodes and routings. Examples of dependencies are parallel processing across several nodes, blocking of transitions because of capacity constraints on nodes, alternate routing of units to avoid congestion, and accelerating or decelerating the processing rate at a node depending on downstream congestion. We introduce a general network process representing the numbers of units at the nodes and derive its equilibrium distribution. This distribution takes the form of a product of functions of vectors in which the arguments of the functions satisfy an interchangeability property. This new type of distribution may apply to other multi-variate processes as well. A basic idea in our approach is a linking of certain micro-level balance properties of the network routing to the processing rates at the nodes. The link is via routing-balance partitions of nodes that are inherent in any network. A byproduct of this approach is a general characterization of blocking of transitions without the restriction that the process is reversible, which had been a standard assumption. We also give necessary and sufficient conditions under which a unit moving in the network sees a time average for the unmoved units (called the MUSTA property). Finally, we discuss when certain flows between nodes in an open network are Poisson processes.This research was sponsored in part by Air Force Office of Scientific Research contract 84-0367. 相似文献