固体法稀土硼钒共渗的研究

研究了CeCl3对固体粉末法B－V共渗的动力学,民分,组织和性能的影响,在渗剂中添加CeCl3不仅具有明显的催渗作用,使渗大速度提高40％以上,并且Ce作为组元渗入工件表面后形成CeFe2新相,还使渗层硬度和耐磨性有较大提高,稀土是通过提高渗剂中的硼势和钒势,。活化渗件表面,降低硼和钒原子的扩散活能来提高B和V的渗入速度的。     

稀土催化低温熔融渗硫工艺及渗硫层组织形貌

利用稀土的催渗作用开发出一种低温熔融硫新工艺，采用XRD，SEM分析了硫化层的微观结构和表面形貌，并测定了其抗蚀性和显微硬度值。结果表明，采用该含复合稀土渗剂可较大幅度提高S在钢铁表面的渗速，以980℃低温淬火＋210℃低温回火态Cr12钢为基体，190℃下渗硫6h即可获得厚约10μm的渗硫层，且渗层厚度随渗硫时间增加而增加，其变化趋势呈抛物线型动力学曲线关系。稀土的催渗作用同其加入量有关，渗硫剂中复合添加5％（质量分数）左右的稀土化合物效果最佳。渗硫层组织疏松多孔，主要由FeS,FeS2相构成，其与基体结合良好，硬度较低（约Hmv300左右），并具有一定的耐蚀性。     

硅胶负载钒磷氧化物催化2,6-二氯甲苯氨氧化反应

对硅胶负载钒磷氧化物（ＶＰＯ）催化剂（ｎ（Ｖ）／ｎ（Ｐ）＝１）催化２,６－二氯甲苯（ＤＣＴ）氯氧化反应进行了研究。考察了反应温度、空气／ＤＣＴ比和氨／ＤＣＴ比等因素对反应的影响。反应温度对氨氧化反应影响较大,空气／ＤＣＴ比和氨／ＤＣＴ比对反应的影响很大。最佳反应条件为：Ｔ＝６７３Ｋ,ｎ（ａｉｒ）／ｎ（ＤＣＴ）＝３０,ｎ（ＮＨ３）／ｎ（ＤＣＴ）＝６．在此条件下,ＤＣＴ转化率为９０％,产率为５７％。与     

固定化生细胞生物催化的若干动态性质

通过啤酒发酵实验研究了以海藻酸盐为载体的固定化生长细胞生物催化作用的若干动态特性，在分批料的填充柱循环反应器中，产物抑制型的啤酒发酵，其Ｓ－ｔ，Ｐ－ｔ曲线与批式酵罐的Ｘｔ／Ｘｓｔ－Ｋｔ理论曲线相似，Ａ（λ＝５２０ｎｍ）的变化可作为简便的检测方法发酵周期的缩短呈现τｎ＝ψ＾ｎ－１（τ１－Ｃ）关系，式中ｎ＝２－４，这对生产上前期的成功应用是有力的支持，但在ｎ≥５时出现载体的崩和起泡现象，固相催化剂不能     

含质子柠檬酸氧钒（V）配合物中间体的合成和晶体结构

合成了含质子柠檬酸氧钒（Ｖ）配合物中间体ＮａＫ３［ＶＯ２（Ｈｃｉｔ）］２·７Ｈ２Ｏ，用红外光谱和Ｘ射线衍射进行了结构表征。结果表明：晶体属单斜晶系，Ｐ２１／ｎ空间群。晶胞参数ａ＝１．１２５８（２）ｎｍ，ｂ＝１．５７７４（３）ｎｍ，ｃ＝１６５５９（１）ｎｍ，β＝９８．５６８（９）°，Ｖ＝２．９０８（１）ｎｍ＾３，Ｚ＝４，Ｄｃ＝１．８５１ｇ·ｃｍ＾－３，Ｆ（０００）＝１６４０，μ（Ｃｕ Ｋα）＝１０４     

硅胶负载钒磷氧化物催化2 ,6-二氯甲苯氨氧化反应(英)

对硅胶负载钒磷氧化物（ＶＰＯ） 催化剂（ ｎ（Ｖ）／ ｎ（Ｐ） ＝ １） 催化２ ,６二氯甲苯（ＤＣＴ） 氨氧化反应进行了研究． 考察了反应温度、空气／ＤＣＴ 比和氨／ＤＣＴ 比等因素对反应的影响． 反应温度对氨氧化反应影响较大,空气／ＤＣＴ比和氨／ＤＣＴ 比对反应的影响不很大． 最佳反应条件为： Ｔ＝ ６７３ Ｋ, ｎ（ａｉｒ）／ｎ（ＤＣＴ） ＝ ３０ , ｎ（ＮＨ３）／ｎ（ＤＣＴ）＝ ６ ． 在此条件下,ＤＣＴ转化率为９０ ％ , 产率为５７ ％ ． 与使用（ＮＨ４）２［（ＶＯ）３（Ｐ２Ｏ７）２］ 催化剂的文献报道值相比,反应温度降低４０ Ｋ, 产率提高３４ ％ ．ＸＲＤ分析结果表明, ＶＰＯ／ＳｉＯ２ 催化剂中的活性组分以均匀分散的无定形状态存在,而未负载的ＶＰＯ催化剂中存在αＶＯＰＯ４ 和βＶＯＰＯ４ 晶相．     

稀土改性钛酸铅微粉的水热合成及其性能研究

用水热法合成了几种稀土（Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ）和锰掺杂改性的钛酸铅（ＰｂＴｉＯ３，简称ＰＴ）陶瓷微粉，研究了掺Ｌａ和Ｍｎ的ＰＴ固溶体的四方（铁电）相与立方（顺电）相之间的相变，掺杂Ｌａ（ｘ（Ｌａ）＝０．０４）和Ｍｎ（ｙ（Ｍｎ）＝０．０１）的ＰＴ固溶体的居里温度大约为４００℃，测定了稀土掺杂量（ｘ＝０．０４～０．０８）与其压电性能之间的关系，随Ｌａ掺杂量的增加，ＰＴ固溶体的ｄ３３增大，ｇ３３     

MINi5—xSnx合金贮氢性能研究

研究了富镧混合稀土贮氢合金ＭＩＮｉ５及加Ｓｎ后对合金的结构、活化性能、吸氢容量和平衡氢压等性能的影响。通过Ｘ射线衍射分析进行物相分析,测试了２９８,３１３,３３３Ｋ温度下合金的吸、放氢Ｐ－Ｃ－Ｔ曲线。结果表明,ＭＩＮｉ５－ｘＳｎｘ合金（ｘ＝０～０．４）为六言晶体结构的单相组织。以Ｓｎ部分取代Ｎｉ改善了ＭＩＮｉ５的活化特性,并使平台压力降低、吸、放氢滞后减小。随着Ｓｎ含量增加,晶胞体积增大,平衡氢压     

溶剂对螯合物稳定性的影响：镉（Ⅱ）—甘氨酸（苯丙氨酸）—乙醇／…

用ＰＨ－电位滴定法测定了３７℃、Ｉ＝０．１ｍｏｌ．ｄｍ＾－３（ＫＮＯ３）、乙醇／水混合溶剂中配合物Ｃｄ（Ａａ）ｎ（Ａａ－＝甘氨酸、苯丙氨酸，ｎ＝１，２的一、二级稳定常数ｌｇｋ１、ｌｇｋ２及配体Ａａ＾－的酸解离常数ｐｋ１、ｐｋ２。     

固相复合抗体放射免疫分析法测定人体SOD的含量

本文描述了固相复合抗体放射免疫分析法测定人血清和红血球中超氧化物歧化酶的含量，该法灵敏度为０．５ｎｇ，非特异为２．０±０．６％，批内误差在３．４％～４．２％（ｎ＝９）之间，批间误差在７．０％～７．５％（ｎ＝６）之间，经测定，人血清正常值为２９１±７９（ｘ±ｓ）ｎｇ／ｍＬ，红血球正常值为８６１±９５（ｘ±ｓ）×１０＾－６Ｈｂ。该法灵敏度高、特异性好，简便，快速，适于分析大量样品。     

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.     

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.     

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。     

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.     

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.

     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。