Thermodynamic Study of the Molten Salt Binary System KHSO4−NaHSO4

The partial molar enthalpies of mixing of NaHSO₄ and KHSO₄ have been measured at 528 K by dropping samples of pure compounds into molten mixtures of NaHSO₄ and KHSO₄ in Calvet calorimeter. From these values the molar enthalpy of mixing has been deduced. The same method has been used for the determination of the heat capacity of the two pure compounds in the solid and liquid states. The phase diagram of this system has been confirmed by conductometric and thermal analysis methods. By an optimization method the excess entropy of the liquid mixtures was also calculated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nematic ordering in anisotropic elastomers: Effect of frozen anisotropy

Nematic ordering in anisotropic non-Gaussian elastomers is considered theoretically using mean field approximation. We focus on the effect of anisotropy during network cross-linking on the system elasticity and, in particular, on the so-called soft deformation mode. As the main result, we calculate the dependence of the elastomer free energy on the angle between the axis of “frozen” anisotropy and the nematic director. The dependence of the isotropic-nematic transition point on the orientational field acting on the monomers during the cross-linking process is also calculated. Received: 5 November 1997 / Revised and Accepted: 29 June 1998     

Dynamics of strongly entangled polymer systems: activated reptation

The effect of excluded-volume interactions on the reptation dynamics of long polymer chains is considered theoretically. It is shown that interactions give rise to an exponential increase of the reptation time, , if polymer chains are long enough: , where is the number of monomers per entanglement. We propose a novel dynamical mechanism of activated reptation implying that neighboring chains exchange conformations of their terminal fragments. It is shown that the exchange mechanism is compatible with the equilibrium polymer chain statistics and that it provides a bridge between the previous theories. Received: 25 July 1997 / Accepted: 8 October 1997     

Mean-field theory for polymer adsorption on curved surfaces

We discuss the influence of polymer adsorption on the curvature energy of an interface. Following an article by Clement and Joanny (J. Phys. II 7, 973 (1997)), a mean-field theory is used to calculate the surface tension, rigidity constants and spontaneous curvature associated with both reversible and irreversible polymer adsorption. In the case of irreversible polymer adsorption it is assumed that the amount of adsorbed polymer remains constant upon curving the interface. Unfortunately, constraining the amount of polymer by adding a Lagrange multiplier affects the thermodynamic state of the (free) polymer far away from the interface. Clement and Joanny solve this problem by removing the polymers in the bulk. We allow for the presence of free polymers, but to achieve this we have to apply a local external field to keep the adsorbed amount fixed. The results of the two approaches are compared and a physical interpretation is given. Received 25 July 2001 and Received in final form 5 December 2001     

Dynamical heterogeneity and diffusion in high-density Al2O3·2SiO2 melts

Dynamical heterogeneity (DH) in high-density Al₂O₃·2SiO₂ melts has been studied in a model containing 3025 atoms via molecular dynamics (MD) simulation and at the fixed density of 4.0 g/cm³. Non-Gaussian parameter of atomic species in the system has been found and discussed. We found a clear evidence of the existence of DH in high-density Al₂O₃·2SiO₂, which has specific features differed from those observed in the lower-density one. The most mobile and immobile atoms in the system have a tendency to form clusters and temperature dependence of their mean cluster size was found. On the other hand, diffusion constant of atomic species in the system has been calculated at temperatures ranged from 3150 to 7000 K. Calculations show that at relatively not high temperatures, temperature dependence of diffusion constant shows an Arrhenius law and at higher temperatures it shows a power law: D∝(T−T_C)^γ. Diffusion data of high-density melts have been compared with those for the low-density ones. Diffusion mechanism in the system has been discussed via the temperature dependence of diffusion constant ratio and activation energy. And we found the existence of cooperative diffusion mechanism in the system.     

Kinetics of microphase separation in interpenetrated polymer networks in solution

We present here a theoretical study of the early kinetics of the microphase separation in crosslinked polymer blends, made of two incompatible polymers A and B, dissolved in a common good solvent. Use is made of an extended blob model used previously for the investigation of the static properties of such a transition. We are interested in the variation of the relaxation rate, , versus the wave number q, in the vicinity of the spinodal temperature. We first show that kinetics is entirely dominated by local motions, which are of Rouse type. Slow motions are absent, because of the permanent presence of crosslinks. Second, we find that the characteristic frequency, (q ) = , increases with increasing wave number q according to a sixth power law, that is (q ) q^6{-9/4}, where is the overall monomer volume fraction. Therefore, the swelling of strands due to the excluded-volume forces leads to a renormalization of the characteristic frequency by a multiplicative factor scaling as ^{-9/4}. The main conclusion is that the presence of a good solvent necessitates relaxation rates less important than those relative to crosslinked mixtures in the molten state.     

Adsorption of a semiflexible wormlike chain

Adsorption of ideal polymers with stiff backbone onto a flat surface is considered theoretically. Both scaling approach and quantitative theory are developed. We predict a self-similar monomer concentration profile c(x) ∼ x ^-4/3 near the surface (when the distance to the surface x is much smaller than the chain persistence length l /2). The typical conformation of a weakly adsorbed chain can be viewed as a sequence of alternating flat (2-dimensional) trains of wormlike short loops (flat blobs) and coil-like (3-dimensional) loops forming a triple-layer structure: contact layer (x < Δ) of adsorbed fragments virtually laid on the surface, proximal layer (Δ < x < l) of flat blobs, and more dilute distal corona layer (x > l). Here Δ defines the range of monomer/surface attraction, Δ ≪ l. The adsorption transition is continuous. However, its relative width is small (T ^* is the adsorption temperature, ΔT is the relevant temperature interval): ∼ , i.e. a discontinuous transition in the limit Δ/l↦ 0. Received 10 October 2002 and Received in final form 22 November 2002 RID="a" ID="a"Permanent address: Physics Department, Moscow State University, Moscow 119992, Russia. e-mail: semenov@polly.phys.msu.ru     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Slow regions percolate near glass transition

A nanosecond scale in situ probe reveals that a bulk linear polymer undergoes a sharp phase transition as a function of the degree of conversion, as it nears the glass transition. The scaling behaviour is in the same universality class as percolation. The exponents γ and β are found to be 1.7±0.1 and 0.41±0.01 in agreement with the best percolation results in three dimensions. Received 29 August 2002 RID="a" ID="a"e-mail: erzan@gursey.gov.tr e-mail: erzan@itu.edu.tr     

Are changes in morphology clear indicators for the glass transition in thin polymer films? Tentative ideas

I present some tentative ideas on the possibility of plastic deformation which might be relevant in ultra-thin polymer films at temperatures close but below the glass transition temperature. Several possible sources for sufficiently strong forces are discussed. The relevance of such forces in experiments aiming at determining thin-film properties like the glass transition temperature, thermal expansion or surface morphology is discussed. Received 19 September 2001 and Received in final form 5 December 2001