氖气在聚乙烯醇多层塑料球壳内的渗透性能

采用乳液法结合等离子体涂层制备聚苯乙烯(PS)-聚乙烯醇(PVA)-辉光放电聚合物(GDP)多层塑料空心微球。通过测量不同充气平衡时间和平衡温度下球内气体的总量研究了氖气对塑料球的气体渗透系数。研究表明,当充氖温度为60、70、80、90℃时,微球充气平衡的时间分别为70~100 h、50~90 h、30~60 h,20~40 h。室温(25℃)时氖气对塑料球的渗透系数为0.5×10~19~2.0×10~19mol/(m·s·Pa),对于直径300μm,PVA壁厚2μm的微球,充Ne后的保气半寿命约3~12 d。当外压为4 MPa,平衡温度为80℃时,球内可充氖2.6~3.2 MPa。     

温度和样品保存方式对酚试剂法测甲醛的影响1

对比不同显色温度及保存方式下的甲醛样品吸光度及含量,结果表明,样品显色完全所需时间随显色温度的升高而缩短,当温度低于22℃时,显色反应应在恒温水浴锅34℃保温10 min。另外,冰箱内冷藏保存的样品稳定性要优于常温保存,常温下甲醛样品应在采样后12 h内检测,而冷藏时甲醛样品可至少稳定48 h。     

WS-Ⅰ型微量水份测定仪的研制

测定气体中痕量水份有露点仪、电解水份仪、压电水份仪和氧化铝水份仪等,各有优缺点;就灵敏度、连续性和操作繁简来说,以氧化铝水份仪为佳。1941年Kaller首先发表了氧化铝作介质的电容电阻湿度计。Cutting和Jason为现代氧化铝湿度计奠定了理论和实践方面的基础。美国Pana公司和爱尔兰Shaw公司已生产多种型号的商品仪器。而国内,未见有报导。WS—I型微量水份仪即根据氧化铝电容、电阻原理而设计並研制的仪器。可连续测定氢、氮、氩、空气等洁净气体中的水份,测量范围为-90℃～-20℃露点(相当于0.1～1000ppmv);测量准确度为±3℃露点;测量重复性为±1℃露点。     

含钦苯乙烯单体及其聚合物的合成与表征

合成并表征了含2,6吡啶二羧酸根二茂钛基团的苯乙烯单体.通过含钛单体与苯乙烯的溶液共聚反应得到了稳定性高且可溶的共聚物.所得到的共聚物能溶于THF,CHZCh和甲苯中,其玻璃化转变温度为106℃.该含钛聚苯乙烯有望应用于惯性约束聚变(ICF)实验靶用聚合物微球的制备.     

SrCe0.9Yb0.1O3-α陶瓷的导电性

以高温固相反应法合成了质子导电性氧化物陶瓷SrCe0.9Yb0.1O3-α.粉末XRD结果表明,该陶瓷样品为单一斜方相钙钛矿型结构.以陶瓷样品为固体电解质、多孔性铂为电极,采用交流阻抗谱技术和气体浓差电池方法分别测定了样品在600～1000 ℃下、干燥空气及湿润氢气中的电导率及离子迁移数,研究了样品的离子导电特性.结果表明,在600～1000 ℃下干燥空气中,陶瓷样品的最大电导率为0.026 S·cm-1,氧离子迁移数为0.03～0.2,是一个氧离子与空穴的混合导体;在湿润氢气中,陶瓷样品的最大电导率为0.015 S·cm-1. 600～800 ℃时,陶瓷样品的质子迁移数为1,是一个纯的质子导体,而在900～1000 ℃时,陶瓷样品的质子迁移数为0.91～0.97,是一个质子与电子的混合导体,质子电导占主导.     

X射线荧光光谱法测定萤石中氟化钙

采用X射线荧光光谱仪可以快速准确测定萤石中总钙的含量.但测定其中氟化钙含量时,一方面,由于样品中碳酸钙计入钙量,从而造成氟化钙测定结果准确性较差.另一方面,铜、锌等金属元素在熔融制样时对铂金坩埚腐蚀较大,因此需要进行酸处理除去碳酸钙及铜、锌等金属元素.然而,样品经过酸处理后,质量会发生变化,造成熔剂与样品的比例不一致,从而影响测定结果.对样品前处理条件、XRF分析中熔片和仪器工作条件等进行了优化,建立了熔融制样、X射线荧光光谱法（XRF）准确测定萤石中氟化钙含量的方法.方法干扰少,具有良好的准确度和精密度,操作简单,提高了分析效率.     

用于PM2.5样品测定的全反射X荧光仪的研制

研制适用于PM2.5样品分析的Mo靶和W靶全反射X荧光仪(TXRF)。该仪器主要部分为光路和软件系统,经过光路系统的设计、加工、调试,使入射光达到全反射;软件开发实现了控制和数据获取处理功能。Mo靶TXRF测量各元素检出限(ng)分别为K 9.4,Ca 4.1,Sc 8.5,Ti 3.0,V 3.5,Cr 3.2,Mn 1.5,Fe 0.99,Ni 0.24,Cu 0.63,Zn 0.5,Pb1.6,Ba 11.9;W靶TXRF测量各元素检出限(ng)分别为Na 1 935,Mg 1 087,Al 1 310,K 19.4,Ca 8.8,Sc 7.0,Ti 13.5,V 7.8,Cr 2.3,Mn 4.0,Fe 4.5,Ni 4.5,Ba 6.2。重复测量100 ng的Ba和200 ng的Ti各6次,测定结果的相对标准偏差分别为5.3%,1.4%;51.2μg/cm2 Zn和9.0μg/cm2 Ca测量结果与标准值的相对偏差分别为0.2%,5.8%。用Mo靶、W靶TXRF分别连续测量标准薄膜Cu样和Fe样4 h,测定结果的相对极差分别为5.1%,6.0%。该仪器检测限低,测量重复性、准确度、长期稳定性均满足ng量级微量元素的测量需求,可用于大气微尘样品的直接测量。     

小型高分辨电子轰击离子源反射式飞行时间质谱仪的研制

常用的气体分析质谱仪使用四极杆质谱作为分析器,分辨率一般低于300,无法解决同质量数离子带来的干扰问题.本实验自行研制了一种小型高分辨气体分析质谱仪,它采用电子轰击离子源反射式飞行时间质量分析器.仪器腔体总长45 cm,在m/z 28的位置,质量分辨率达到3000(Full width at half maximum,FWHM),实现了CO和N2的半峰谷分离;在m/z 69的位置,仪器分辨率达到5000(FWHM).在直接大气压进样条件下,可以检测到空气中136Xe(含量7.8 μ g/m3)和80Kr(含量2.8 μg/m3).使用ADC采集时,仪器的动态范围为1 06.该仪器将作为高端气体质谱仪,应用于过程监测在线分析、环境有机挥发物研究、热分析质谱及催化反应监测等领域.     

骨铅体内测量系统最佳测量位置的选择

^109Cd K XRF骨铅体内测量系统对体重指数大的对象测量所得的结果误差较大。测量时胫骨在探测器前的位置对测量结果误差的影响很大。采用模拟重指数大的被测对象的大体模,与原来的标准体模在探测器前不同距离时进行测量的对比分析表明,体重指数大的被测对象因其胫骨周围组织层较厚,造成康普顿计数大量增加。若胫骨与探测器的距离太近,仪器不能正常工作,致使X能谱图谱形畸变,得到不正确的结果。因此,在测量时,应保持胫骨在探测器前的距离为25mm,同时,应注意相干散射峰的峰位变化,保持仪器即时显示的死时间30%左右,以保证最后测量结果的精密度和准确度。     

镧、锰掺杂改性CeO2-ZrO2-Al2O3固溶体的性能

采用共沉淀法制备了一系列La, Mn共掺杂的CeO2-ZrO2-A12O3(CZA)复合氧化物, 采用BET, XRD, H2-TPR, XPS和XRF等方法对样品进行表征. 结果表明, 全部样品均形成了稳定的CZA固溶体, 经600 ℃焙烧后表现出良好的织构性能, 1000 ℃老化后, La, Mn共掺杂样品具有最佳的高温稳定性; H2-TPR测试表明, La, Mn之间存在正协同效应, 共掺杂的样品具有最佳的低温还原性能和高温稳定性; XPS结果表明, 掺杂La可有效抑制在焙烧过程中Mn向表面的迁移, 从而保持较高的表面吸附氧浓度.     

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。     

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.     

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.     

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.

     

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。     

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.     

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。