不同条件对硫酸钙结晶影响的实验研究

近年来由于微波化学的快速发展使人们认识到微波作为一种手段对化学反应的过程有着深刻的影响，在材料领域更是得到了日益广泛的应用，因此把微波应用于结晶过程也成为人们关注的热点。早在1966年磁场就被应用于晶体的生长。近年来，已有很多文献报道电场、磁场对晶体生长的影响。     

固相配位化学反应研究 L ⅩⅩⅢ.等温电导法研究醋酸锰和草酸的室温固相化学反应

本文利用等温电导法考察了醋酸锰和草酸的室温固相配位化学反应的制样方法对实验结果的影响，并获得了该反应的动力学参量。     

Relaxational behavior of birefringence of aqueous carboxymethylcellulose under an alternating electric field at frequencies ranging from 0.1 Hz to 100 kHz

The d. c. component of birefringence of aqueous carboxymethylcellulose (CMC) under an a. c. electric field was measured at frequencies ranging from 0.1 Hz to 100 kHz. Three samples of different molecular weights were studied with varying degree of neutralization, polymer concentration and added salt concentration. The dispersion curve of birefringence consists of three relaxation bands,A, B andC in order of decreasing frequency. RelaxationB with a negative relaxation strength is ascribed to end-over-end rotation of almost rodlike CMC molecules. RelaxationA with a positive strength is attributed to the relaxation of electrical polarizability along the minor axis of molecule. RelaxationC possesses also a positive strength and is induced by clusters of CMC molecules.Dedicated to Prof. Dr. F. H. Müller.     

Forces at the nuclei of a molecule in the presence of non-uniform electric field

The interaction Hamiltonian within the Bloch gauge for the potentials of the electric field has been used to define electric multipole moment operators. Perturbation theory has been applied to evaluate the induced electronic moments and electric field at the nuclei in the presence of spatially non-uniform electric fields of high intensity. Multipole nuclear electric shielding tensors have been defined to describe the contributions arising from a non-homogeneous electric field. These quantities are useful to rationalize linear and non-linear responses of a molecule in the presence of intense external electric perturbations.     

Morphology and electric conductivity of cross-linked polyethylene–carbon black blends prepared by gelation/ crystallization from solutions

 Ultra-high-molecular-weight polyethylene (UHMWPE) – carbon black (CB) blends were prepared by gelation/ crystallization from PE dilute solutions containing CB particles. The UHMWPE/CB composition chosen were 1/0.15, 1/0.25, 1/0.5, 1/0.75, 1/1, 1/3, 1/5, and 1/9, etc. The cross-linking of PE chains was performed by chemical reaction of dicumyl-peroxide at 160 ^°C. X-ray diffraction patterns indicate that the crystallinity of PE within the blends decreased drastically through the chemical reaction at high temperature. The sample preparation method by gelation/crystallization provided the UHMWPE–CB system with various CB contents up to 90% and the conductivities for the resultant specimens were in the range from 10^-9 to 1 Ω^-1 cm^-1 corresponding to the electric conductivity range of semiconductors. The blends assured thermal stability of electric conductivity by cross-linking of PE chains, although the mechanical property such as the storage and loss moduli were very sensitive to temperature. The conductivity of the blends with CB content ≥20% were almost independent of temperature up to 220 ^°C and the values in the heating and cooling processes were almost the same. On the other hand, for the UHMWPE–CB blends with 13% CB content corresponding to the critical one, temperature dependence of electric resistivity showed positive temperature coefficient (PTC) effect. The PTC intensities for non-cross-linked and cross-linked materials were lower than that of the corresponding low-molecular-weight-polyethylene (LMWPE)–CB blend but the maximum peak appeared at 160 ^°C which is higher than the peak temperature of LMWPE–CB blend. Received: 10 December 1997 Accepted: 9 April 1998     

Electric conductivity in a fibrous porous medium with thin but polarized double layers

The electric conduction in the fibrous medium constructed by a homogeneous array of parallel, identical, charged, circular cylinders having an arbitrary zeta potential filled with the solution of a symmetrically charged electrolyte is analytically examined. The thickness of the electric double layers surrounding the dielectric cylinders is assumed to be small relative to the radius of each cylinder and to the gap width between two neighboring cylinders, but the polarization of the mobile ions in the diffuse layers is allowed. The effect of interactions among individual cylinders is taken into explicit account by employing a unit cell model. The appropriate equations of conservation of electrochemical potential energies of ionic species are solved for each cell, in which a cylinder is envisaged to be surrounded by a coaxial cylindrical shell of the fluid solution. Analytical expressions for the effective electric conductivity are obtained in closed forms as functions of the porosity of the fiber matrix and other characteristics of the porous system. Comparisons of the results of the cell model with different conditions at the outer boundary of the cell are made. Under an otherwise identical condition, the electric conductivity in a porous medium composed of an array of parallel cylinders in the transverse direction is smaller than that of a suspension of spheres. The effect of interactions among the cylinders or spheres on the effective conductivity can be quite significant under appropriate conditions.     

Molecular simulation of electrolytes in nanopores

Behaviour of electrolytes confined in cylindrical and slit pores are studied by computer simulations at the molecular level. Previous equilibrium and structural properties obtained by Monte Carlo techniques using the restrictive primitive model are discussed. Transport properties are calculated by the canonical molecular dynamics technique for ions with Lennard–Jones cores. Assuming an external electric potential, the chemical potential of individual ions can be balanced without the need for a grand canonical procedure. The mobility of the counterion is affected by the surface charge density. At a high surface charge, the mean square axial displacement of the counterion calculated is lower than the bulk value due to its high concentration near the charged wall.     

Intrinsic Surface Reaction Constant in 1-pK Model of Mg-Fe Hydrotalcite-like Compounds

The relationship among intrinsic surface reaction constant (K) in 1-pK model, point of zero net charge (PZNC) and structural charge density (σst) for amphoteric solid with structural charges was established in order to investigate the effect of σst on pK. The theoretical analysis based on 1-pK model indicates that the independent PZNC of electrolyte concentration (c) exists for amphoteric solid with structural charges. A common intersection point (CIP) should appear on the acid-base titration curves at different c, and the pH at the CIP is pHPZNC. The pK can be expressed as pK=-pHPZNC log[(1 2αPZNC)/(1-2αPZNC)], where αPZNC≡σst/eNANs, in which e is the elementary charge, NA the Avogadro‘s constant and Ns the total density of surface sites. For solids without structural charges, pK=-pHPZNC. The pK values of hydrotalcite-like compounds (HTlc) with general formula of [Mg1-xFex(OH)2](Cl,OH)x were evaluated. With increasing x, the pK increases, which can be explained based on the affinity of metal cations for H^- or OH^- and the electrostatic interaction between charging surface and H^- or OH^-.     

Evaluation of Multicenter Electronic Attraction, Electric Field and Electric Field Gradient Integrals with Screened and Nonscreened Coulomb Potentials over Integer and Noninteger n Slater Orbitals

By the use of complete orthonormal sets of -exponential-type orbitals, where ( = 1, 0, –1, –2,...) the multicenter electronic attraction (EA), electric field (EF) and electric field gradient (EFG) integrals of nonscreened and Yukawa-like screened Coulomb potentials are expressed through the two-center overlap integrals with the same screening constants and the auxiliary functions introduced in our previous paper (I.I. Guseinov, J. Phys. B, 3 (1970) 1399). The recurrence relations for auxiliary functions are useful for the calculation of multicenter EA, EF and EFG integrals for arbitrary integer and noninteger values of principal quantum numbers, screening constants, and location of slater-type orbitals. The convergence of the series is tested by calculating concrete cases.     

Raman spectra of aqueous lithium sulfate and potassium thiocyanate in strong electric fields

The effects of high-voltage pulsed discharge (HVPD) activation on the Raman spectra of saturated aqueous solutions of lithium sulfate (Li₂SO₄/H₂O) in the range of the ν₁(A) totally symmetric vibrations of the SO ₄ ^2? anion and on the spectra of potassium thiocyanate KSCN/H₂O in the region of the ν₁(C≡N) vibrations of the SCN^? anion have been studied. The temperature dependences of the width and frequency of the corresponding spectral lines have been investigated.