Radiolytic unsaturation decay in polyethylene. Part III—the effect of certain chain transfer agents

Small amounts of certain halogenated compounds are found to have, at most, only a slight enhancing effect on the radiolytic decay rates of added poly-unsaturated compounds in polyethylene, but significantly increase the elastic modulus at 433 K (melt modulus) obtained thereby. Experiments with model chlorine-containing additives suggest that this increase is due to a more random distribution of polymer and monomer mediated crosslinks in the polymer, that it does not result from a significant increase in crosslinking and that it is mediated by chlorine atoms, in a similar manner to radiolytic hydrogen atoms, through facilitation of long range free radical migration. Although low molecular weight chloro-paraffins inhibit radiolytically induced growth of melt modulus in monomer containing polyethylenes, even very small additions of chlorinated polyethylenes, which form a separate phase, increase the melt modulus. This again indicates that the active species is the chlorine radical.     

Convergence rates for Markov chain order estimates using EDC criterion

The Efficient Determination Criterion (EDC) generalizes the AIC and BIC criteria and provides a class of consistent estimators for the order of a Markov chain with finite state space. In this note, we derive rates of convergence for the EDC estimates. *Partially supported by CNPq, CAPES/PROCAD, FAPDF/PRONEX, FINATEC and FUNPE/UnB. **Partially supported by CAPES.     

Influence of annealing and chain defects on the melting behaviour of poly(vinylidene fluoride)

The melting behaviour of poly(vinylidene fluoride) (PVDF) was investigated by differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering in order to study the influence of the chain defects content and of the temperature of annealing on the crystallization and melting behaviour.All the DSC scans show a double endotherm and the analysis of the data suggests that the low temperature endotherm is due to the melting of a population of thin lamellae, whose thickness increases during the annealing, but a high content of chain defects prevents the lamellar thickening and the main effect in this case is the crystallization of thin lamellae from a portion of polymer which did not crystallize during the quenching from the melt. Furthermore, the two melting endotherms, which are observed, can be partially ascribed to a melting-recrystallization process.Furthermore, stepwise isothermal cooling was performed in a differential scanning calorimeter followed by melting scans of fractionated PVDF samples to point out the possible presence of a series of endothermic peaks.     

教学质量的时齐马尔可夫链评估法

本文研究了教学质量评估中的一种定量分析方法──时齐马尔可夫链评估法．阐明了这种方法的理论依据及其实施程序、并指出它较之其他教学质量评估法更显合理．     

更新时间概率模型及其无偏估计定理的论证

本文提出应用小参数法 ,探讨 Markov链中相邻两次更新时刻内稀疏事件的概率估计问题 .建立了三种最重要的具有更新时间的概率模型 .通过小参数的引入和对概率式的幂展开 ,进而推证出幂渐近展开系数的模型估算法 .论证了无偏估计的重要定理 ,给出了概率估计式和无偏估计精度 .亦将许多算法扩展到Markov链的任意状态空间     

关于DHMM转化为齐次马尔可夫链的一个定理及其证明

本给出一个将DHMM转化为齐次马尔可夫链的定理，该定理提供了利用在理论上比较完善的齐次马尔可夫链来研究DHMM的一个方法．     

A rheological analysis of interactions in phenoxy/organoclay nanocomposites

Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.     

Study on antimony oxide self-assembled inside HZSM-5

Sb/ZSM-5 was obtained by solid-state reaction with the mixture of Sb₂O₃ and zeolite HZSM-5 under a dry nitrogen flow at 773 K. Characterization of the treated zeolite was undertaken with XRD, ²⁷Al MAS NMR, BET, TGA and FT-IR. The results revealed that part of the antimony oxides migrated into the channels of zeolite, and decreased the Brönsted acid sites in Sb/ZSM-5 remarkably. The other part of antimony oxides together with the amorphous alumino-silicate in the products distributed on the external surface of zeolite ZSM-5 and modified it, while the framework of ZSM-5 in crystal phase was retained. The structure of occluded antimony oxide inside the channels of ZSM-5 was studied by XRD Rietveld method. The result showed that their structure can be described as a chain of non-perfect [Sb₅O₅(H₂O)₂]_n⁵ⁿ⁺, which is parallel to the straight channel of ZSM-5. There is about 0.6 [Sb₅O₅(H₂O)₂]⁵⁺ unit in every cell of the ZSM-5 on an average.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4''-bipy)(H2O)5]n

A one-dimensional chain coordination polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4'-bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4'-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a - 1.1481(3), b =1.1230(2), c = 1.1759(3) nm, β = 97.054(4)°, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z= 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked together by one 4,4'-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(Ⅱ) ion is coordinated with two nitrogen atoms from two 4,4'-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

超高分子量PE凝胶膜的超拉伸性与旁式构象关系研究

通过ＩＲ方法，观测并讨论了在不同条件下制备的超高分子量ＰＥ（ＷＨＭＰＥ）凝胶膜中旁式（Ｇ构象）构象与超拉伸性的关系，提出了Ｇ构象浓度及分布对ＵＨＭＰＥ凝胶膜超拉伸性影响的新概念，同时也讨论了它与链缠结之间的联系，发现：反映Ｇ构象的相对浓度的比值σ＝Ｉ１３０３Ｉ１３５２随制膜浓度的增大而增加，在临界浓度Ｃ０（０．４～０．５ｇ＠１００ｍｌ）附近所形成的膜，具有超高拉伸性（λ＝２００），其Ｇ构象的变化与Ｍａｔｓｕｏ由比浓粘度提出的缠结链改变相对应；热处理温度比热处理时间对σ值的影响更显著，在一定温度下约４分钟后σ值基本不变；在σ值最低的温度范围拉伸，凝胶膜具有良好的超高拉伸性．