Enhancement of the light-scattering ability of coatings by using hollow pigments

The light-scattering properties of coatings based on monodisperse polymeric spheres of two different diameters (ca 0.5 and 1 m) were evaluated from reflectance measurements as a function of the wavelength from 400 to 700 nm. Some of these plastic pigments were hollow and it was noted that these particles gave coatings with a greater light-scattering ability than coatings based on solid particles of a similar size. It was possible to estimate the contribution of the internal pores to the scattering ability of the coating layers by saturating the layers with an oil of a refractive index similar to that of the polymeric pigment particles. A simple model accounting for the scattering provided by the internal pores of the hollow particles is suggested. The agreement between the experimental results and the prediction of the model is fair. It was noted that the light scattering coefficient of the coatings increased when the external diameter of their constituent hollow particles increased from ca 0.5 to 1 m.     

Monte Carlo simulation of polarizable systems: Early rejection scheme for improving the performance of adiabatic nuclear and electronic sampling Monte Carlo simulations

An early rejection scheme for trial moves in adiabatic nuclear and electronic sampling Monte Carlo simulation (ANES-MC) of polarizable intermolecular potential models is presented. The proposed algorithm is based on Swendsen–Wang filter functions for prediction of success or failure of trial moves in Monte Carlo simulations. The goal was to reduce the amount of calculations involved in ANES-MC electronic moves, by foreseeing the success of an attempt before making those moves. The new method was employed in Gibbs ensemble Monte Carlo (GEMC) simulations of the polarizable simple point charge-fluctuating charge (SPC-FQ) model of water. The overall improvement in GEMC depends on the number of swap attempts (transfer molecules between phases) in one Monte Carlo cycle. The proposed method allows this number to increase, enhancing the chemical potential equalization. For a system with 300 SPC-FQ water molecules, for example, the fractions of early rejected transfers were about 0.9998 and 0.9994 at 373 and 423 K, respectively. This means that the transfer moves consume only a very small part of the overall computing effort, making GEMC almost equivalent to a simulation in the canonical ensemble.     

Structure formation and dynamics of water in strong external electric fields

We have performed molecular dynamics computer simulations of water in homogeneous external electric fields which were varied in a wide range of field strengths. The dielectric response is found to be linear up to fields E₀≈0.01 V/Å from where dielectric saturation effects become important. At fields of E₀≈3 V/Å a phase transition into an ordered, ice-like structure is observed, which is stabilized through hydrogen-bonds. With an increasing external electric field, the frequency spectrum of the water dynamics shows a remarkable red shift of the intramolecular modes and a blue shift of the librational motions, where the frequency varies quadratically with the field strength. A simple analytical model is discussed which reproduces the observed behavior.     

超高效合相色谱法快速检测塑料食品接触材料中13种紫外吸收剂

建立了一种同时检测塑料食品接触材料中13种紫外吸收剂的超高效合相色谱法。以甲醇为溶剂对塑料食品接触材料样品进行超声提取，经C18固相萃取柱净化，过0.22 μm有机滤膜，采用超高效合相色谱仪分析。选择ACQUTY UPC² HSS C18 SB色谱柱（150 mm×3.0 mm，1.8 μm），以超临界二氧化碳为流动相，异丙醇为改性剂进行梯度洗脱，在最优色谱条件下，13种紫外吸收剂能够在4 min内实现有效分离。结果表明，在各自线性范围内，13种紫外吸收剂的线性关系良好，标准曲线相关系数不低于0.9985，检出限（S/N=3）为0.05~0.15 mg/kg，加标回收率为86.8%~115.7%，相对标准偏差为0.73%~5.61%。该方法快速简便，准确可靠，同时大大减少了有机溶剂的消耗，可用于塑料食品接触材料中13种紫外吸收剂的快速检测。     

Analyzing Anisotropic Exchange in a Pentanuclear Os2Ni3 Complex

Spin Hamiltonian parameters of a pentanuclear Os Ni cyanometallate complex are derived from ab initio wave function based calculations, namely valence-type configuration interaction calculations with a complete active space including spin-orbit interaction (CASOCI) in a single-step procedure. While fits of experimental data performed so far could reproduce the data but the resulting parameters were not satisfactory, the parameters derived in the present work reproduce experimental data and at the same time have a reasonable size. The one-centre parameters (local matrices and single-ion zero field splitting tensors) are within an expected range, the anisotropic exchange parameters obtained in this work for an Os−Ni pair are not exceedingly large but determine the low-T part of the experimental χT curve. Exchange interactions (both isotropic and anisotropic) obtained from CASOCI have to be scaled by a factor of 2.5 to obtain agreement with experiment, a known deficiency of such types of calculation. After scaling the parameters, the isotropic Os−Ni exchange coupling constant is cm⁻¹ and the D parameter of the (nearly axial) anisotropic Os−Ni exchange is ⁻¹, so anisotropic exchange is larger in absolute size than isotropic exchange. The negative value of the isotropic J (indicating antiferromagnetic coupling) seemingly contradicts the large-temperature behaviour of the temperature dependent susceptibility curve, but this is caused by the negative g value of the Os centres. This negative g value is a universal feature of a pseudo-octahedral coordination with configuration and strong spin-orbit interaction. Knowing the size of these exchange interactions is important because Os(CN) is a versatile building block for the synthesis of / magnetic materials.     

An $L^{\infty}$ Second Order Cartesian Method for 3D Anisotropic Interface Problems

A second order accurate method in the infinity norm is proposed for general three dimensional anisotropic elliptic interface problems in which the solution and its derivatives, the coefficients, and source terms all can have finite jumps across one or several arbitrary smooth interfaces. The method is based on the 2D finite element-finite difference (FE-FD) method but with substantial differences in method derivation, implementation, and convergence analysis. One of challenges is to derive 3D interface relations since there is no invariance anymore under coordinate system transforms for the partial differential equations and the jump conditions. A finite element discretization whose coefficient matrix is a symmetric semi-positive definite is used away from the interface; and the maximum preserving finite difference discretization whose coefficient matrix part is an M-matrix is constructed at irregular elements where the interface cuts through. We aim to get a sharp interface method that can have second order accuracy in the point-wise norm. We show the convergence analysis by splitting errors into several parts. Nontrivial numerical examples are presented to confirm the convergence analysis.     

Gaussian,non-Gaussian critical fluctuations in the Curie-Weiss model

It is known that at the critical temperature the Curie-Weiss mean-field model has non-Gaussian fluctuations and that internal fluctuations can be Gaussian. Here we compute the distribution of theq-mode magnetization fluctuations as a function of the temperature, the wave vectorq, and a fading out external field. We obtain new classes of probability distributions generated by this external field as well as new critical behavior in terms of its rate of fading out. We discuss also the susceptibility as the limitq tending to zero.     

On three conjectures by K. E. Shuler

Some fifteen years ago, Shuler formulated three conjectures relating to the large-time asymptotic properties of a nearest-neighbor random walk on ² that is allowed to make horizontal steps everywhere but vertical steps only on a random fraction of the columns. We give a proof of his conjectures for the situation where the column distribution is stationary and satisfies a certain mixing codition. We also prove a strong form of scaling to anisotropic Brownian motion as well as a local limit theorem. The main ingredient of the proofs is a large-deviation estimate for the number of visits to a random set made by a simple random walk on . We briefly discuss extensions to higher dimension and to other types of random walk.Dedicated to Prof. K. E. Shuler on the occasion of his 70th birthday, celebrated at a Symposium in his honor on July 13, 1992, at the University of California at San Diego, La Jolla, California.     

On quadratic forms of height two and a theorem of Wadsworth

Let and be anisotropic quadratic forms over a field of characteristic not . Their function fields and are said to be equivalent (over ) if and are isotropic. We consider the case where and is divisible by an -fold Pfister form. We determine those forms for which becomes isotropic over if , and provide partial results for . These results imply that if and are equivalent and , then is similar to over . This together with already known results yields that if is of height and degree or , and if , then and are equivalent iff and are isomorphic over .

     

Crosslinking of vinyl‐terminated biphenyl and naphthalene side‐chain liquid‐crystalline poly(epichlorohydrin) derivatives

We performed the crosslinking of vinyl‐terminated biphenyl and naphthalene side‐chain liquid‐crystalline polyethers using peroxide‐type initiators with and without the addition of tertiary amine promoters. The crosslinking temperatures were chosen in the range of mesophase stability to allow the mesophase order to be frozen. The biphenyl derivatives, with a high isotropization temperature, were crosslinked to a large extent. This led to anisotropic thermosets. To crosslink naphthalene derivatives, amine promoters were needed, but degrees of crosslinking were lower, and anisotropic elastomers were obtained. Crosslinking processes were studied by differential scanning calorimetry, polarized optical microscopy, and Fourier transform infrared spectroscopy. The nature of the frozen mesophase was confirmed by X‐ray diffraction studies on mechanically oriented samples. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2237–2244, 2002