Atomistic packing models for experimentally investigated swelling states induced by CO2 in glassy polysulfone and poly(ether sulfone)

Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO₂ gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006     

一类非经典扩散方程整体解的存在唯一性及长时间行为

本文讨论非经典扩散方程第一初边值问题整体解的存在唯一性及长时间行为，建立了一系列新的结果，较好地改进许多已有的结论．     

Very high coercivities of top-layer diffusion Au/FePt thin films

The Au/FePt samples were prepared by depositing a gold cap layer at room temperature onto a fully ordered FePt layer, followed by an annealing at 800 °C for the purpose of interlayer diffusion. After the deposition of the gold layer and the high-temperature annealing, the gold atoms do not dissolve into the FePt Ll₀ lattice. Compared with the continuous FePt film, the TEM photos of the bilayer Au(60 nm)/FePt(60 nm) show a granular structure with FePt particles embedded in Au matrix. The coercivity of Au(60 nm)/FePt(60 nm) sample is 23.5 kOe, which is 85% larger than that of the FePt film without Au top layer. The enhancement in coercivity can be attributed to the formation of isolated structure of FePt ordered phase.     

Wait-and-switch stochastic model of the non-Debye relaxation. Derivation of the Burr survival probability

Stochastic mechanism of relaxation, in which a dipole waits until a favourable condition for reorientation exists, is discussed. Assuming that an imposed direction of a dipole moment may be changed when a migrating defect reaches the dipole, we present a mathematically rigorous scheme relating the local random characteristics of a macroscopic system to its effective relaxation behaviour. We derive a relaxation function (the Burr survival probability) that is characterized by the stretched exponential or the power-law behaviour.     

Application of the finite Hankel transform to a diffusion problem without azimuthal symmetry

The problem treated in this paper concerns calculating the evolution of the pressure in a single-phase, slightly compressible fluid in a porous medium consisting of communicating layers. The fluid is produced through a point sink located on the side of an otherwise sealed cylindrical wellbore. This location of the sink causes the flow around the wellbore to be azimuthally asymmetric.The problem is solved through successive application of Laplace, finite Fourier and finite Hankel transforms. Although apparently straightforward, this approach leads to serious numerical difficulties. The published form of the inversion formula for the finite Hankel transform leads to inaccurate computation for the higher azimuthal modes even with 128 bit arithmetic. An alternative form is developed which enables accurate evaluation of the solution with the more practical 64 bit arithmetic. The technique for two-layer solution presented here can be directly extended to a problem with a larger number of communicating layers. This is the first instance of successful application of the finite Hankel transform to an azimuthally asymmetric diffusion problem.     

Na2CO3调质钙基脱硫剂硫化机理实验研究

对经Na2CO3溶液调质石灰石煅烧产物CaO的物理结构及硫化特性进行了研究,发现同等条件下调质后石灰石煅烧产物CaO(M-CaO)比未经调质的CaO(N-CaO)具有更高的钙转化率.利用XRD技术对CaO晶体结构进行了测定,通过比较二者的晶胞参数和晶格畸变度等并结合其孔特性,证实M-CaO之所以比N-CaO具有更高的钙转化率,是由于M-CaO比N-CaO具有更高的晶体缺陷浓度,使得在硫化反应过程中通过产物层的扩散具有更高的离子扩散率.     

Ce偶-偶同位素低激发态性质的IBM2描述

通过考虑同类核子相干对间的四极相互作用，在IBM2中对Ce偶－偶同位素^128Ce-^138Ce的低激发态能谱和E2跃迁几率及分支比进行了理论分析，计算结果有效地改善了IBM中这些核的γ带能谱的Staggering现象描述，与实验观察到的低激发态结果基本一致。     

Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004     

Properties of polystyrene-poly(methylmethacrylate) random and diblock copolymers in dilute and semidilute solutions

Solution properties for random and diblock copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA) have been measured by dynamic and total intensity light scattering in solvents of differing quality. The results are compared with the corresponding properties for PS and PMMA homopolymers of similar molecular weight, in order to determine if interactions between unlike monomers are significant. The hydrodynamic radius (R_h) and diffusion second virial coefficient (k_d) for the random copolymer are found to be larger than the corresponding values for the homopolymers in a solvent which is near-theta for the two homopolymers, whereas no such effect is observed for the block copolymer. This suggests that most intrachain interactions occur a relatively short distance along the chain backbone. In a mutual good solvent R_h and k_d of the random copolymer are comparable to the average of the values for the homopolymers, indicating that in a good solvent monomer/solvent interactions dominate over monomer/monomer interactions. For an isolated diblock copolymer in a mutual good solvent, there is no evidence that interactions between unlike monomers lead to additional expansion of the entire molecule, as measured by R_h, nor expansion of the individual blocks as probed by light scattering with one block optically masked. However, at low but finite concentration there is evidence (the coefficients of the binary interaction terms in the viscosity and the mutual diffusion coefficient, and the second and third virial coefficients) that a weak ordering effect may exist in block copolymer solutions, far from the conditions where microphase separation occurs. Finally, measurements of ternary polymer-polymer-solvent solutions show no dependence on monomer composition or monomer distribution for the tracer diffusion of probe PS-PMMA copolymers in a PMMA/toluene matrix. This indicate that the frictional interaction is largely unaffected by interactions between unlike monomers. However, there is evidence that the thermodynamic interaction is more unfavorable between a random copolymer and the homopolymer matrix than between a diblock and the matrix. © 1994 John Wiley & Sons, Inc.     

Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.