Thermal degradation of poly(vinyl chloride)

This paper presents an initial attempt at describing poly(vinyl chloride) (PVC) thermal degradation through a semi-detailed and lumped kinetic model. A mechanism of 40 species and pseudocomponents (molecules and radicals) involved in about 250 reactions permits quite a good reproduction of the main characteristics of PVC degradation and volatilization. The presence of the two step mechanism—the first step of which corresponds to dehydrochlorination and the second to the tar release and residue char formation—are correctly predicted both in quantitative terms and in the temperature ranges. The model was validated by comparison with several thermo gravimetric analyses, both dynamic at different heating rates, and isothermal. When compared with the typical one step global apparent degradation models, the approach proposed here spans quite large operative ranges, especially when it comes to predicting product distributions. The initial results of these product predictions, even though quite preliminary, are encouraging and confirm the validity of the model.     

Survey of ligand field parameters of strong field d complexes obtained from the g matrix

Using a newly proposed approach involving an internally consistent set of equations, the ligand field parameters Δ/ξ, V/ξ and k are obtained from literature values of the g matrix for strong field d⁵ systems of various conformations in which |Δ/ξ|≤10. Qualitative analysis of the observed results is done using the Angular Overlap Model, AOM.     

The relaxation field for the general case of electrolyte mixtures

The relaxation field for solutions of mixed electrolytes of any type is calculated. the calculation is based on the well-known treatment due to Fuoss-Onsager with the same distance parameter for all the ions in solution. A general conductance-continuity equation has been established and an improved iterative method of calculation, using Laplace transforms, is proposed. The relaxation-field results are derived to the second iteration in the perturbation method of integration.     

The electronic spectrum of VCr

The electronic spectrum of VCr has been studied using the complete-active-space self-consistent field complete-active-space second-order perturbation theory approach. Potential-energy curves for 12 electronic states have been computed. Transition energies, with respect to the X² ground state, for some of the calculated electronic states are (with possible experimental values within parentheses) 0.53 eV (0.56) for A²⁺, 1.03 eV (1.14) for A⁴, 1.20 eV (1.14) for B², 1.45 eV (1.51) for B⁴, 1.60 eV (1.51, 1.78) for C², and 1.61 eV (1.63) for A^4–. AcknowledgementsThe research reported in this communication was supported by a grant from the Swedish Natural Science Research Council (NFR). S. Alex and D.G. Leopold are acknowledged for providing results from their negative ion photoelectron spectroscopy on VCr.Contribution to Björn Roos Honorary Issue     

Magnetic field effects on the crystal orientation and surface morphology of electrodeposited iron films

The effects of a magnetic field (5 T) on crystal orientation and surface morphology were investigated for iron films electrodeposited in ferrous aqueous solution. XRD measurements for the iron films showed that the preferred orientation parallel to the substrate was determined by the current density and not influenced by the magnetic field. By X-ray pole figure measurements, however, the crystal texture of the iron films electrodeposited at 10 mA cm^–2 and 30 mA cm^–2 was found to be controlled by the magnetic field. That is, the (110) planes were orientated in same direction of the magnetic field vector at angles of 30° and 35° to the direction normal to the substrate plane at 10 mA cm^–2 and 30 mA cm^–2, respectively. When the morphology was observed by SEM, iron grains at 30 mA cm^–2 changed from a triangular pyramid shape at 0 T to a complex star-like shape at 5 T.Presented at the 3rd International Symposium on Electrochemical Processing of Tailored Materials held at the 53rd Annual Meeting of the International Society of Electrochemistry, 15–20 September 2002, Düsseldorf, Germany     

高频聚焦超声声场和温度场的仿真研究*

为探究临床常用的7 MHz高频聚焦超声在多层生物组织中的声传播以及毫秒级时间内的生物传热规律问题,基于Westervelt方程和Pennes传热方程,使用有限元方法建立高频聚焦超声辐照多层组织的非线性热黏性声传播及传热模型。首先分析了线性模型和非线性模型之间的差异,然后在非线性模型下探究换能器的参数对声场和温度场的影响。仿真结果显示：在7 MHz频率下,当换能器输出声功率超过5 W时,声波传播的非线性效应不可忽视(p <0.05);当声功率从5 W增大到15 W时,非线性模型与线性模型预测的温度偏差从20%增加到34.703%;高频聚焦超声波的非线性行为比低频更加显著,基频能量向高次谐波转移的程度增大,声功率为10 W和15 W时4次谐波与基波之比分别达到7.33%和12.12%;高频换能器参数的改变对组织中声场和温度场分布的影响较大,换能器焦距从12 mm减小到11.2 mm,焦点处最高温度增加了77%。结果表明,7 MHz聚焦超声的非线性声传播需要考虑到4次谐波的影响。该文提出的多层组织非线性仿真模型可为高频聚焦超声换能器参数优化及制定安全、有效的术前治疗方案提供理论参考。     

声纹信号-图形差分场增强和多头自注意力机制的变压器工作状态辨识方法*

为提升电力变压器工作状态的智能监测水平,提出声纹信号-图形差分场增强和多头自注意力机制的变压器工作状态辨识方法。基于图形差分场技术将声纹信号映射为二维图像,再借助多头注意力机制的视觉转换器实现图像信息的深层挖掘与状态辨识,采用梯度加权类激活映射实现分类结果的可解释性分析。搭建了包含变压器4种典型工作状态下的实验模拟测试系统平台,实验结果表明：所提方法不仅能够有效表征变压器声纹信号的状态特征,且分类辨识精度相较于“时频图+引入多头注意力机制的变换网络”与“图形差分场+引入残差模块的卷积神经网络”的常规方法有显著提升,提升约6%,同时也具备较好的鲁棒性,可为电气设备的故障检测研究提供一定参考。     

On Physically Unacceptable Numerical Solutions Yielding Strong Chaotic Signals

Physically unacceptable chaotic numerical solutions of nonlinear circuits and systems are discussed in this paper. First, as an introduction, a simple example of a wrong choice of a numerical solver to deal with a second-order linear ordinary differential equation is presented. Then, the main result follows with the analysis of an ill-designed numerical approach to solve and analyze a particular nonlinear memristive circuit. The obtained trajectory of the numerical solution is unphysical (not acceptable), as it violates the presence of an invariant plane in the continuous systems. Such a poor outcome is then turned around, as we look at the unphysical numerical solution as a source of strong chaotic sequences. The 0–1 test for chaos and bifurcation diagrams are applied to prove that the unacceptable (from the continuous system point of view) numerical solutions are, in fact, useful chaotic sequences with possible applications in cryptography and the secure transmission of data.     

Microscale Thermophoresis and Molecular Modelling to Explore the Chelating Drug Transportation in the Milk to Infant

The microscale thermophoresis (MST) technique was utilized to investigate lactoferrin–drug interaction with the iron chelator, deferiprone, using label-free system. MST depends on the intrinsic fluorescence of one interacting partner. The results indicated a significant interaction between lactoferrin and deferiprone. The estimated binding constant for the lactoferrin–deferiprone interaction was 8.9 × 10⁻⁶ ± 1.6, SD, which is to be reported for the first time. Such significant binding between lactoferrin and deferiprone may indicate the potentiation of the drug secretion into a lactating mother’s milk. The technique showed a fast and simple approach to study protein–drug interaction while avoiding complicated labeling procedures. Moreover, the binding behavior of deferiprone within the binding sites of lactoferrin was investigated through molecular docking which reflected that deferiprone mediates strong hydrogen bonding with ARG121 and ASP297 in pocket 1 and forms H-bond and ionic interaction with ASN640 and ASP395, respectively, in pocket 2 of lactoferrin. Meanwhile, iron ions provide ionic interaction with deferiprone in both of the pockets. The molecular dynamic simulation further confirmed that the binding of deferiprone with lactoferrin brings conformational changes in lactoferrin that is more energetically stable. It also confirmed that deferiprone causes positive correlation motion in the interacting residues of both pockets, with strong negative correlation motion in the loop regions, and thus changes the dynamics of lactoferrin. The MM-GBSA based binding free energy calculation revealed that deferiprone exhibits ∆G TOTAL of −63,163 kcal/mol in pocket 1 and −63,073 kcal/mol in pocket 2 with complex receptor–ligand difference in pocket 1 and pocket 2 of −117.38 kcal/mol and −111.54 kcal/mol, respectively, which in turn suggests that deferiprone binds more strongly in the pocket 1. The free energy landscape of the lactoferrin–deferiprone complex also showed that this complex remains in a high energy state that confirms the strong binding of deferiprone with the lactoferrin. The current research concluded that iron-chelating drugs (deferiprone) can be transported from the mother to the infant in the milk because of the strong attachment with the lactoferrin active pockets.     

聚合物气体辅助注射成型制品的形态结构

作为一种由常规注射成型发展起来的聚合物加工技术,气体辅助注射成型具有节约原材料、缩短成型周期以及提高制品性能等优点,已得到广泛的应用.由于气辅成型过程是一个在刚、柔双重约束界面条件下进行的多相复杂体系的多次流动过程,因而其形态结构的形成、发展和演化要远比常规注塑成型复杂.然而在气辅成型的形态结构方面,国内外的研究一直以来开展得较少.近年来,作者在聚合物及其共混物、复合材料气辅成型制品的形态结构方面已开展了广泛的研究工作,本文对这些工作和一些重要结果作了总结,并简要分析了成型过程中剪切场对形态演化的影响,最后对该研究方向的发展趋势作了展望.