取向、结晶、γ辐照聚对苯二甲酸乙二醇酯(PET)驻极体的陷阱性质

用拉伸、热处理和γ射线辐照的方法制备了一系列具有不同平面取向度、不同结晶度和不同分子链长度的PET试样.随平面取向度、结晶度和辐照剂量的增大,平均陷阱深度加深.由拉伸取向形成的结构陷阱俘获载流子能力随取向度增大而提高;由γ辐照形成的结构陷阱对俘获载流子的限制能力随辐照剂量增大而降低;由热结晶形成的结构陷阱俘获载流子能力在结晶度为20％时达到极值.提出了相应的三种陷阱模型.     

取向、结晶、γ辐照聚对苯二甲酸乙二醇酯(PET)驻极体的陷阱性质

 用拉伸、热处理和γ射线辐照的方法制备了一系列具有不同平面取向度、不同结晶度和不同分子链长度的PET试样.随平面取向度、结晶度和辐照剂量的增大,平均陷阱深度加深.由拉伸取向形成的结构陷阱俘获载流子能力随取向度增大而提高;由γ辐照形成的结构陷阱对俘获载流子的限制能力随辐照剂量增大而降低;由热结晶形成的结构陷阱俘获载流子能力在结晶度为20％时达到极值.提出了相应的三种陷阱模型.     

双向拉伸聚对苯二甲酸乙二醇酯驻极体的分立陷阱

用热释电极化温度扫描法在温度间隔为５℃的条件下研究了经过双向拉伸具有不同平面取向度的聚对苯二甲酸乙二醇酯ＰＥＴ驻极体试样，分离出对解俘获电流峰贡献的各分立陷阶电流峰．随平面取向度和脂肪链反式构象含量的提高，各分立陷阶深度增加．结构缺陷种类的增多使分立陷阱数由二个增至六个，并导致分立陷阱深度分布加宽．     

植入时间对超高分子量聚乙烯髋关节臼动态力学性能的影响

研究了γ辐照(2.5Mrad)消毒的超高分子量聚乙烯人造髋关节臼的动态力学性能随体内植入时间的关系。同时,比较了未经辐照的块状原料样品与未植入体内的髋关节臼样品二者之间的动态力学性能。结果表明,朱植入样品由于辐照形成交联网,其实数杨氏模量比原料样品高,γ峰向高温移动,而峰强下降。但随植入时间的增加,实数模量提高,并服从E_i≈E_0×exp(Dt~n)的关系式。并且,γ峰的内耗及虚数模量也都进一步增加。从体内的化学和力学作用,引起分子链的氧化断裂,密度或结晶度增加和网链分子破坏,在晶区与非晶区内部产生大量缺陷,解释了上述粘弹性变化的结果。     

γ-射线辐照对尼龙6纤维结构的影响

<正> 过去的大多数研究表明,高能射线辐照会引起聚乙烯及聚丙烯等稀烃类聚合物分子链交联及降解,而且会导致结晶度下降。张利华等人最近的研究表明,对于尼龙1010塑料,仅当辐照剂量高到一定程度后,辐照才会破坏结晶。此外,Stowe等人曾经研究过近紫外线对尼龙66纤维结构的影响,结果表明,在空气气氛中的近紫外辐照主要导致尼龙66纤维降解,并使纤维结晶度提高。有关高能射线辐照对高度取向的合成纤维结构及性能的影响的研究尚不多见。本工作将讨论γ-射线对于尼龙6纤维结构的影响。     

辐照聚甲醛聚合机理、结构与形态的研究——Ⅱ.三聚甲醛单晶辐照引发固相聚合产物的亚微观结构

三聚甲醛单晶经Co_(60)γ射线辐照可以得到一种结晶度很高的聚三聚甲醛。在辐照聚合制得的聚三聚甲醛的迴转图上,除出现普通聚甲醛的衍射点外,还存在着一些新的衍射斑点。 聚三聚甲醛沿着原来三聚甲醛的c轴可以劈成纤维,在迴转图中新的衍射斑点,当样品加温处理后会逐渐消失。 比较聚甲醛与三聚甲醛分子所占的空间,我们认为:聚甲醛确有四种不同取向的晶区,它们联结在一起形成许多曲棍状的微晶。     

四氟乙烯-全氟4-甲基-3,6-二氧杂△~7辛基磺酰氟共聚物的分子运动

本工作用振簧仪,在-150—80℃范围内,测试了四氟乙烯-全氟4-甲基-3,6-二氧杂△~7辛基磺酰氟共聚物的动态力学性能。样品是含有不同侧基数目的部分结晶共聚物。观察到四个松弛过程,按温度下降次序记为α、γ_1-、γ_2-、γ_3-。α峰(室温附近)系玻璃化转变。γ_1峰(-50℃,～215Hz)为主链有阻碍的短链段分子运动。γ_2-峰(-60℃,～230Hz)为侧基的分子运动。γ_3-峰(-77℃,～260Hz)为的链段运动,并且γ_3-峰的强度随结晶度增加而增强。     

不同纺速PET纤维的红外光谱

用红外光谱研究了纺速对PET纤维结晶度和取向度的影响。发现PET纤维的结晶度和取向度均随纱速的增加而增加,且结晶度和取向度与纺速关系曲线的斜率都在纺速3,300m/min处出现明显改变。表明纺速低于3,300m/min的纤维,随纺速增加以增加纤维取向度为主,而高于3,300m/min的纤维,则以增加结晶度为主.认为纺速为3,300m/min的PET纤维中中介态趋于饱和,因而易于诱发结晶。X射线衍射及DSC测试结果均与此相符。     

不同纺速PET纤维的红外光谱

用红外光谱研究了纺速对PET纤维结晶度和取向度的影响。发现PET纤维的结晶度和取向度随纺速的增加而增加,且结晶度和取向度与纺速的关系曲线的斜率都在纺速3300m/min处出现明显改变。表明纺速低于3300m/min的纤维随纺速增加以增加纤维的取向度为主,而高于3300m/min的纤维则以增加结晶度为主。认为纺速为3300m/min的PET纤维中中介态趋于饱和,因而易于诱发结晶。X-射线衍射与DSC测试结果均与此相符。     

KMgF_3及KMgF_3∶Eu~(2+)晶体的射线辐照效应

KMgF3∶Eu晶体中Eu3 →Eu2 的转换率在低浓度掺杂时接近100%,完全转换的饱和掺杂摩尔分数为0.29%.实验条件下,KMgF3晶体的X射线1 h辐照损伤可在约100 h后恢复;KMgF3∶Eu2 晶体经X射线辐照后,360 nm锐峰发射强度略有降低.不同剂量的γ射线辐照,KMgF3晶体热释光曲线的各个温度峰强度变化明显不同,即使小剂量辐照,造成的损伤也较难恢复,如γ射线辐照剂量为103Gy时,辐照损伤的恢复时间约需30 d.KMgF3∶Eu2 晶体360 nm锐峰发射强度随γ射线辐照剂量增大而呈线性降低.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

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.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.

     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

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。