Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow

Zero shear viscosities, ₀, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in ₀ (T) and in M _c , the critical molecular weight determined in plots of log ₀ vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M _c declines considerably. The former observation is explained by analogy to the transition from fragile to hard glasses resulting from increased crosslinking. The latter effect can also be rationalized in terms of a physical network reducing the molecular weight that is required for the formation of entanglements.     

聚合物熔体三维挤出胀大的数值模拟

采用有限元方法分析K-BKZ本构方程描述的聚合物熔体的三维挤出胀大.对于本构方程中偏应力张量的计算,首先给出质点的运动轨迹,分段求出局部的变形梯度张量,再求出整体的变形梯度、Cauchy-Green应变张量和 Finger应变张量,沿轨迹采用分段高斯积分计算应力.把应力作为方程的右端项,给出迭代方法,求解非线性方程组.并根据自由面处的边界条件,迭代得出出口处自由面的最终位置.对轴对称流道和矩形流道进行分析计算,并把结果与二维分析和实验结果进行了比较,显示方法是可行的.     

The double phosphates MIMIIPO4 (MI – Na,K; MII – Mg,Mn, Co,Ni, Zn) – synthesis from chloride melts and characterization

The particularities of the chemical interaction in systems M^IPO₃‐M^IIO(or Mn₂O₃)‐M^ICl (M^I – Na, K; M^II – Mg, Co, Ni, Zn) have been investigated at the temperature 1073 K and molar ratios P/M^x = 1 or 2 and M^ICl/(M^IPO₃ + M^IIO(or Mn₂O₃)) = 30. The conditions of formation of complex phosphates M^ІM^IIPO₄ and Na₄Ni₃(PO₄)₂P₂O₇ have been found. Influences of the nature of alkali and bivalent metals on the products composition were discussed. The advantages of chloride melts using (synthesis time reduction and temperature reducing) for preparing of complex phosphates were shown. The synthesized compounds have been characterized using the powder X‐ray diffraction, Fourier transform infrared and diffuse reflectance spectroscopies.     

Molecular weight distributions from linear viscoelastic measurements

A method is presented whereby the molecular weight distribution of a molten polymer can be determined from measured values of the storage and loss moduli (the response of the system to small amplitude oscillatory shear flow). The Curtiss-Bird theory for the constitutive behavior of polymer melts is used. This results in an integral equation relating the moduli to the molecular weight distribution. The method that we describe here uses a regularization scheme with quadratic programming to extract the MWD from the components of the moduli (or, equivalently, from the components of the complex viscosity). We verify the applicability of the scheme by considering concocted data for given molecular weight distributions. The scheme is also used to predict the molecular weight distributions of polystyrene from complex viscosity data that have been presented in the literature. Variations between the predicted and measured molecular weight distributions can be attributed to the inadequacy of the underlying molecular theory at large frequencies. The predicted average molecular weights obtained using the truncated dynamic data are in reasonable agreement with the experimental values.     

Phase equilibria in random multiblock copolymers

A mean-field theory for domain structures in random multiblock copolymer melts is developed. We focus on the finite molecular weight effects resulting in a competition between macroscopic phase separation and microdomain formation in the system. We identify an essential parameter N ε controlling the phase behavior of the system, where N is the number of blocks per chain and ε is the composition asymmetry parameter (= the difference between the mean copolymer composition and its critical value). The phase diagram involving N ε and the reduced temperature as variables is obtained. The regions of coexistence of two or more phases are identified. We show that a superstructure formation on cooling is always pre-empted by a macroscopic phase separation of the macroscopically homogeneous (disordered) system yielding two homogeneous phases: H ₀↦H ₁ + H ₂. The third (lamellar) phase separates on further cooling. Then hexagonal and body-centred-cubic phases take over if N ε 1. As the Flory interaction parameter χ increases further, the standard transitions BCC↦HEX↦LAM take place. Received 13 July 2001     

高温下煤中矿物质对气化反应的影响

利用XRD对1100℃~1500℃高温下矿物质在弱还原气氛中的变化进行考察,并利用RIR对矿物质进行半定量分析,发现随着温度的升高莫来石含量增大,而SiO₂含量下降,符合SiO₂-Al₂O₃二元相图的变化。高温下部分无定形矿物质发生熔融,主要为硅铝酸盐。在煤焦二氧化碳气化过程中,熔融的硅铝酸盐与煤焦表面接触阻碍气化反应进行。利用FT-IR测定了硅铝酸盐结构的变化,说明高温下矿物质对气化反应的影响与硅铝酸盐的聚合程度存在一定的关系。     

Local mobility in grafted polydimethylsiloxane melts

Spin–lattice relaxation time constants, T₁, were studied for low-molecular-weight linear and grafted polydimethylsiloxane over a wide temperature and frequency range. Quantitative evaluations of proton T₁ measurements indicated two relaxation processes: anisotropic rotation of methyl groups around the Si–C bond (low temperature process) and motions of the PDMS side-chains connected with the glass transition (high temperature process). Additional analyses of the T₁ relaxation dispersion profiles revealed specific local segment fluctuation times, which are characteristic of the coherent motions in the grafted polymer chains.     

Globules of annealed amphiphilic copolymers: Surface structure and interactions

A mean-field theory of globules of random amphiphilic copolymers in selective solvents is developed for the case of an annealed copolymer sequence: each unit can be in one of two states, H (insoluble) or P (soluble or less insoluble). The study is focussed on the regime when H and P units tend to form long blocks, and when P units dominate in the dilute phase, but are rare in the globule core. A first-order coil-to-globule transition is predicted at some T = T _cg. The globule core density at the transition point increases as the affinity of P units to the solvent, ˜, is increased. Two collapse transitions, coil → “loose” globule and “loose” globule → “dense” globule, are predicted if ˜ is high enough and P units are marginally soluble or weakly insoluble. H and P concentration profiles near the globule surface are obtained and analyzed in detail. It is shown that the surface excess of P units rises as ˜ is increased. The surface tension decreases in parallel. Considering the interaction between close enough surfaces of two globules, we show that they always attract each other at a complete equilibrium. It is pointed out, however, that such equilibrium may be difficult to reach, so that partially equilibrium structures (defined by the condition that a chain forming one globule does not penetrate into the core of the other globule) are relevant. It is shown that at such partial equilibrium the interaction is repulsive, so the globules may be stabilized from aggregation. The strongest repulsion is predicted at the coil-to-globule transition point T _cg: the repulsion force decreases with the distance between the surfaces according to a power law. In the general case (apart from T _cg) the force vs. distance decay becomes exponential; the decay length ξ diverges as T → T _cg. The developed theory explains certain anomalous properties observed for globules of amphiphilic homopolymers.     

Curved polymer and polyelectrolyte brushes beyond the Daoud-Cotton model

We revise the classical Daoud-Cotton (DC) model to describe conformations of polymer and polyelectrolyte chains end-grafted to convex spherical and cylindrical surfaces. In the framework of the DC model, local stretching of chains in the brush does not depend on the degree of polymerization of grafted chains, and the polymer density profile follows a single-exponent power law. This model, however, does not correspond to a minimum in free energy of the curved brush. The nonlocal (NL) approximation exploited in the present paper implies the minimization of the overall free energy of the brush and predicts that the polymer density profile does not follow a single-exponent power law. In the limit of large surface curvature the NL approximation provides the same scaling laws for brush thickness and free energy as the local DC model. Numerical prefactors are however different. Extra extension of chains in the brush interior region leads to larger equilibrium brush thickness and lower free energy per chain. A significant difference between outcomes of the two models is found for brushes formed by ionic polymers, particularly for weakly dissociating (p H-sensitive) polyelectrolytes at low solution salinity.     

Channel, tube, and Taylor–Couette flow of complex viscoelastic fluid models

We show how to formulate two-point boundary value problems to compute laminar channel, tube, and Taylor–Couette flow profiles for some complex viscoelastic fluid models of differential type. The models examined herein are the Pom-Pom Model [McLeish and Larson 42:81–110, (1998)] the Pompon Model [Öttinger 40:317–321, (2001)] and the Two Coupled Maxwell Modes Model (Beris and Edwards 1994). For the two-mode Upper-Convected Maxwell Model, we calculate analytical solutions for the three flow geometries and use the solutions to validate the numerical methodology. We illustrate how to calculate the velocity, pressure, conformation tensor, backbone orientation tensor, backbone stretch, and extra stress profiles for various models. For the Pom-Pom Model, we find that the two-point boundary value problem is numerically unstable, which is due to the aphysical non-monotonic shear stress vs shear rate prediction of the model. For the other two models, we compute laminar flow profiles over a wide range of pressure drops and inner cylinder velocities. The volumetric flow rate and the nonlinear viscoelastic material properties on the boundaries of the flow geometries are determined as functions of the applied pressure drop, allowing easy analysis of experimentally measurable quantities.