链分子的构象弹性理论

研究基于旋转异构态模型、用末端距与构象能描述的链构象分布函数、以及链构象态在体系形变中的消失规则,发展了一个链分子的构象弹性理论.用该理论描述的理想形变行为,支持天然橡胶在大形变时应力陡然上翘归因于链构象变化的观点在物理上的合理性.该理论能够区别不同化学结构高分子所具有的不同形变行为,能够预报高分子形变中熵项与内能项各自的贡献.预报了天然橡胶形变中内能的贡献约为13%, 与实验相符.     

在“高聚物的结构与性能”课程中讲透高聚物的特点

通过对高分子链的柔性、聚合物独有的熵弹性、显著的粘弹性、特有的描述链段运动的WLF方程,可能实现的大尺寸取向和小尺寸解取向、银纹、单链凝聚态、折叠链片晶和伸直链晶体、分子量的多分散性、高分子溶液特性和高聚物熔体的弹性行为等的讨论,希望能突出“高聚物的结构与性能”课程中高聚物的特点。     

硬弹性聚丙烯纤维分子链的取向特征

硬弹性聚丙烯是在应变结晶和热结晶两个复合过程中形成的。利用双折射并结合广角X射线衍射（WAXD）等方法，研究了硬弹性聚丙烯在制备过程中晶相及非晶相分子链取向的变化，讨论了分了链的取向与硬弹性的关系。结果发现：降低熔体温度或提高熔体拉伸比可以提高晶相及非晶相分子链的取向，热处理时，晶相分子链的取向程度有所提高，而非晶相分子链的取向程度有所下降。在所研究的热处理温度的范围内，硬弹性聚丙烯的弹性回复率越高，晶相分子链的取向程度越高。     

界面层中模型高分子链构象的统计理论

高分子自由链在溶液、熔体或固体中的构象有完整的理论和实验工作 ,已是成熟的知识[1～ 4] .近年来 ,受限大分子构象的探索已成为新的热点[5] .界面是一种最简单的限制 ,将对其附近的高分子产生显著的影响 .除理论家的重视以外 ,界面附近高分子构象问题还与许多应用领域相关 .例如 ,液体高分子的表面张力 ,固体高分子的粘附 ,滑移 ,磨蚀等力学特性 ,甚至它们的光学和电学性质都与界面上的组成和分子构象相关[6] .ｄｅＧｅｎｎｅｓ[7] 最早强调界面附近的分子链构象问题的重要性 .他首先从理论上猜测长链的链端若与界面有强吸引作用 ,则它们…     

用耗散粒子动力学方法研究高分子链取向对形变液滴回缩法测定界面张力值的影响

在利用形变液滴回缩法(DDRM)测量了分子共混体系界面张力的过程中, 要求椭球液滴内高分子链应力松弛速度远快于椭球的回缩速度. 我们建立高分子链取向模型, 用耗散粒子动力学研究高分子链的取向及应力松弛对界面张力测量值的影响. 结果表明, 当高分子链沿着流场方向取向时, 应力是否完全松弛对界面张力测量值的影响较大, 当高分子链取向方向垂直于流场方向时, 应力是否松弛对测量值影响较小.     

聚肽分子链构象转变研究

聚肽分子链在一定的条件下可发生右旋分子链构象与左旋分子链构象间的构象转变 .文中提出了一个有关这一现象的统计理论解释 ,理论包含了两个重要的参数γ、ρ .γ与右旋和左旋分子链构象间能量差别有关 ;ρ与在左旋分子链段中启始一个右旋构象的结构单元所需能量有关 .进一步考虑了体系中酸分子存在对构象转变的影响 ,以解释新近发现的聚肽左、右旋多重分子链构象转变现象 .此外 ,运用核磁共振 (NMR)手段还对这一现象做了进一步的研究 .通过与实验结果和文献中报告的数据比较 ,证明这一理论可以很好地解释聚肽分子链中发生的左、右旋分子链构象转变     

聚苯基单醚喹噁啉薄膜的形变机理

非晶聚合物塑性变形机理主要包括银纹化和剪切屈服[1 ,2 ] .银纹化是链段局部排列疏松区域或缺陷在膨胀应力作用下成为银纹核 ,引发银纹 ,银纹 本体界面应变软化 ,银纹微纤拉伸的应变硬化过程 ,使得聚合物银纹微纤沿拉伸方向取向 ,伴随这一过程聚合物的体积增大[3] .剪切屈服是分子链沿拉伸方向的流动以及分子链间的滑移过程 ,这一过程使聚合物形状改变而体积不变 .聚合物的形变机理与聚合物的内在性质如临界缠结分子量 ,缠结密度或硬度等有关[4] .聚苯基单醚喹啉是一种高性能的芳杂环聚合物 ,它的玻璃化转变温度是 2 98℃ ,它具有耐高温…     

流变光学方法研究结晶高聚物的形变机理(摘要)

用光学方法研究结晶高聚物的形变和流动过程称为流变光学(Rheo-opties)。通常研究结构用的光学方法与动态力学试验装置相结合,还可观察其动态形变过程中相应的结构变化。 X射线衍射法可以测定高聚物形变过程中晶粒的取向。我们发现:聚乙烯随拉伸程度的增长昌区的取向程度也增加,但晶区的取向滞后于非晶区的取向且随晶区取向的增加其非晶区的取向逐渐松弛。因此,     

链段的讨论

无论是在聚合物的结构部分 ,还是在聚合物的性能部分 ,链段 (Ｓｅｇｍｅｎｔ)这一术语出现在《高分子物理》教科书的始终。初学者抓住这一点 ,将大有益处。1　一种特殊的运动单元　　高分子材料品种繁多 ,性能千变万化。有的柔软而富有弹性 ,可作为橡胶使用 ;有的质地坚硬 ,几何尺寸稳定 ,可作为塑料、结构材料使用 ;有的可纺丝、成膜 ,可作为纤维和薄膜使用。高分子材料之所以具有不同于低分子材料的这些独特的性能 ,是因为高分子运动的复杂性。　　高聚物多层次的微观结构影响了它的分子运动 ;而聚合物的性能 ,特别是力学性能又是高聚物分…     

在激光辐照下拉伸的聚对苯二甲酸乙二酯纤维的结构与性能

要提高聚对苯二甲酸乙二酯 (ＰＥＴ)纤维的力学性能 ,不仅要求分子链形成伸直链结晶 ,更主要的是增加晶区之间以及微原纤之间连接分子 (Ｔｉｅｍｏｌｅｃｕｌｅｓ)的数目及其取向程度[1,2 ] .研究表明 ,通过将拉伸工艺中的加热区域降低至 2ｍｍ ,可以使非晶态分子链更为伸展且规整排列[3 ] ,这样的非晶态结构可以更快地向结晶转化[3 ,4] ,容易形成伸直链结晶并增加连接分子的数目 .这种区域拉伸的实质是通过减小形变 (细颈 )区域而使形变速率显著提高 .采用ＣＯ2 激光辐照可以达到更高的形变速率 .这是由于ＣＯ2 激光的波长为 1 0 6μｍ ,…     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。