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1.
Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts
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Debapriya Banerjee Kenneth S. Schweizer 《Journal of Polymer Science.Polymer Physics》2015,53(16):1098-1111
The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non‐microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials‐of‐mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption‐strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degree of dispersion also depends strongly on nanoparticle diameter relative to the block contour length. Small particles in copolymers with longer block lengths experience a more homopolymer‐like environment which renders them relatively insensitive to copolymer chemical heterogeneity and hinders dispersion. Larger particles (sufficiently larger than the monomer diameter) in copolymers of relatively short block lengths provide better dispersion than either a homopolymer or random copolymer. The theory also predicts a novel widening of the miscibility window for large particles upon increasing the overall molecular weight of copolymers composed of relatively long blocks. The influence of a positive chi‐parameter in the pure copolymer melt is briefly studied. Quantitative application to fullerenes in specific copolymers of experimental interest is performed, and miscibility predictions are made. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1098–1111 相似文献
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《Journal of separation science》2018,41(6):1319-1337
The present review discusses the theory and application of van't Hoff analysis in chiral chromatography, with main focus on liquid chromatography. The topics considered include the physical meaning of van't Hoff equation's parameters, interpretation of thermodynamic data in terms of retention and enantioseparation mechanisms, abnormal behavior of van't Hoff plots, and best practices to avoid biased results. 相似文献
4.
Monte Carlo simulation within the grand canonical ensemble, the histogram reweighting technique, and finite size scaling analysis are used to explore the phase behaviour of heteronuclear dimers, composed of A and B type atoms, on a square lattice. We have found that for the models with attractive BB and AB nearest-neighbour energy, uBB=uAB=−1, and for non-repulsive energy between AA nearest-neighbour sites, uAA<0, the system belongs to the universality class of the two-dimensional Ising model. However, when uAA>0, the system exhibits a non-universal critical behaviour. We have evaluated the dependences of the critical point characteristics on the value of uAA. 相似文献
5.
In basin modelling the thermodynamics of a multicomponent multiphase fluid flux are computationally too expensive when derived from an equation of state and the Gibbs equality constraints. In this article we present a novel implicit molar mass formulation technique using binary mixture thermodynamics. The two proposed solution methods, with and without cross derivative terms between components, are based on a preconditioned Newton‐GMRES scheme for each time‐step with analytical computation of the derivatives. These new algorithms reduce significantly the numerical effort for the computation of the molar masses, and we illustrate the behavior of these methods with numerical computations. Copyright © 2004 John Wiley & Sons Ltd. 相似文献
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L. A. Utracki 《Journal of Polymer Science.Polymer Physics》2004,42(15):2909-2915
The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004 相似文献
8.
In this paper, the possibility of using the gradients of the temperature and of the internal parameters as additional state variables in Continuum Thermodynamics is considered. The expressions of the two principles are discussed and Clausius–Duhem inequality is derived under an appropriate statement of the internal entropy production. Several formulations are proposed and compared to existing results in the literature. To cite this article: P. Ireman, Q.S. Nguyen, C. R. Mecanique 332 (2004). 相似文献
9.
The piston problem is investigated in the case where the length of the cylinder is infinite (on both sides) and the ratio m/M is a very small parameter, where m is the mass of one particle of the gaz and M is the mass of the piston. Introducing initial conditions such that the stochastic motion of the piston remains in the average at the origin (no drift), it is shown that the time evolution of the fluids, analytically derived from Liouville equation in a previous work, agrees with the Second Law of thermodynamics. We thus have a non equilibrium microscopical model whose evolution can be explicitly shown to obey the two laws of thermodynamics. 相似文献
10.
V. P. Maslov 《Theoretical and Mathematical Physics》2007,150(1):102-122
From the standpoint of thermodynamic averaging of fission microprocesses, we investigate the origin of radioactive release
in an NPP after an accident or after resource depletion. The genesis of the NPP release is interpreted as a new thermodynamic
phenomenon, a zeroth-order phase transition. This problem setting results in a problem in probabilistic number theory. We
prove the corresponding theorem leading to quantization of the Zipf law for the frequency of a zeroth-order phase transition
with different values of the jump of the Gibbs thermodynamic potential. We introduce the notion of hole dimension.
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Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 150, No. 1, pp. 118–142, January, 2007. 相似文献