Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Sprouting side chain conformations in X-PLOR simulations of peptides

A scheme for sprouting peptide side chains using X-PLOR is introduced using an example from the collagen system to show how reasonable starting structures for minimization studies may be created. © 1993 John Wiley & Sons, Inc.     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Zeros of functions with finite Dirichlet integral

In this paper, we refine a result of Nagel, Rudin, and Shapiro (1982) concerning the zeros of holomorphic functions on the unit disk with finite Dirichlet integral.

     

PT Symmetry in Quantum Field Theory

The Hamiltonian H specifies the energy levels and the time evolution of a quantum theory. It is an axiom of quantum mechanics that H be Hermitian. The Hermiticity of H guarantees that the energy spectrum is real and that the time evolution is unitary (probability preserving). In this talk we investigate an alternative formulation of quantum mechanics in which the mathematical requirement of Hermiticity is replaced by the more physically transparent condition of space-time reflection (PT) symmetry. We show that if the PT symmetry of a Hamiltonian H is not broken, then the spectrum of H is real. Examples of PT-symmetric non-Hermitian Hamiltonians are H=p ²+ix ³ and H=p ²-x ⁴. The crucial question is whether PT-symmetric Hamiltonians specify physically acceptable quantum theories in which the norms of states are positive and the time evolution is unitary. The answer is that a Hamiltonian that has an unbroken PT symmetry also possesses a physical symmetry that we call C. Using C, we show how to construct an inner product whose associated norm is positive definite. The result is a new class of fully consistent complex quantum theories. Observables exhibit CPT symmetry, probabilities are positive, and the dynamics is governed by unitary time evolution.     

On the Causes and Effects of Contaminations during rf Diode Deposition of Cr-Si Alloys

Investigations to the causes and effects of contaminants at the rf diode deposition of CrSi films in a non-heated high vacuum apparatus were carried out comparing an oxygen-free fusion target with an oxygen-containing cermet target. The films of the fusion target contained considerable amounts of oxygen; analogously the oxygen concentration in the films was increased in the case of the cermet target. Moreover, hydrogen was found. The concentration of the contaminants decreased with the sputtering power, however the rate of incorporation increased. For high sputtering rates the contamination process was reproducible and independent of the plant conditioning; the deposited films were depth-homogeneous. The reasons for this behaviour lie in water sources which are activated first of all by the discharge itself. The electrical properties found are explained by the contaminants and the deposition conditions.     

A numerical study of a rotationally degenerate hyperbolic system. Part I. The Riemann problem

We study numerically the Riemann problem for a 2 x 2 system of conservation laws with a cubic flux function, a particular case of the class of models introduced by Keyfitz and Kranzer. The system is not strictly hyperbolic, and the classical Lax theory for hyperbolic systems is not directly applicable. Correspondingly, some numerical schemes which are accurate for strictly hyperbolic systems are not well behaved for this example. When they do work, different schemes yield markedly different results for certain data. We explain this effect by observing that, near these data, viscous regularization is non-uniform as the viscosity tends to zero. This fact does not contradict the well-posedness of the hyperbolic model; it does imply that precise control of the viscosity introduced into a computational method is crucial for generating the correct numerical solutions. We examine all of these issues and comment on their implications for similar systems which arise in continuum mechanics.