反相微乳液介质中纳米Sm2O3的制备

用十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/钐盐水溶液(氨水)所形成的反相微乳液体系,控制合成Sm2O3球形纳米粒子.绘制出25℃下CTAB/正丁醇/正辛烷/钐盐水溶液(氨水)体系的拟三元相图,得到了反相微乳液区.在此反相微乳区内合成了Sm2O3的前驱体,对前驱体进行热分析(TG-DSC),确定了得到纳米Sm2O3产物的适宜焙烧温度为900℃,并考察了微乳液中反应物浓度、反应时间等因素对合成产物的影响.采用X射线衍射(XRD)、透射电镜(TEM)、激光粒度仪(NSA)、荧光光谱(FS)仪等分析方法对Sm2O3产物的形貌、晶形、粒径及荧光性质进行了表征.结果表明,25℃下利用反相微乳液法,成功地制备了粒径分布较窄、分散性良好的球形纳米Sm2O3粒子,粒径约20 nm左右,且表现出较强的荧光性质.     

反相微乳液介质中纳米Sm2O3的制备

用十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/钐盐水溶液(氨水)所形成的反相微乳液体系, 控制合成Sm2O3球形纳米粒子. 绘制出25 ℃下CTAB/正丁醇/正辛烷/钐盐水溶液(氨水)体系的拟三元相图, 得到了反相微乳液区.在此反相微乳区内合成了Sm2O3的前驱体, 对前驱体进行热分析(TG-DSC), 确定了得到纳米Sm2O3产物的适宜焙烧温度为900 ℃, 并考察了微乳液中反应物浓度、反应时间等因素对合成产物的影响. 采用X射线衍射(XRD)、透射电镜(TEM)、激光粒度仪(NSA)、荧光光谱(FS)仪等分析方法对Sm2O3产物的形貌、晶形、粒径及荧光性质进行了表征. 结果表明, 25 益下利用反相微乳液法, 成功地制备了粒径分布较窄、分散性良好的球形纳米Sm2O3粒子, 粒径约20 nm左右, 且表现出较强的荧光性质.     

CTAB/正丁醇-正辛烷-水和盐水的拟三元体系相图及微乳液微观结构的电导研究

绘制了CTAB/正丁醇-正辛烷-水和Al(NO₃)3(或Na2WO4)盐水拟三元体系的35℃相图.用电导法并结合电解质理论讨论了微乳液的微观结构,将整个微乳液单相区分为W/O微乳区、O/W微乳区和B.C.双连续区,并且用渗滤理论确定了一个分散相质点为W/O球状结构的反胶团微乳液区.     

微乳液法制备YF3:Er纳米材料

微乳液[1～2]通常是由表面活性剂、助表面活性剂(通常为醇类)、油(通常为碳氢化合物)和水(或电解质水溶液)组成的透明的、各向同性的热力学稳定体系.微乳液中,微小的水池被表面活性剂所组成的单分子层界面所包围而形成微乳颗粒,其大小可控制在几至几十纳米之间.微小的"水池"尺度小且彼此分离,因而构不成水相,通常称为"微反应器".本文采用了CTAB、正丁醇、正辛烷和水等组成的微乳液体系[3].     

粒径可控纳米CeO_2的微乳液法合成

以十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/硝酸铈(Ce(NO3)3)水溶液(氨水)所形成的反相微乳液体系合成CeO2前驱体,利用热重(TG)和X射线衍射(XRD)分析方法确定了得到纳米CeO2的适宜焙烧温度为550℃,CeO2前驱体经550℃焙烧后得到纳米CeO2.采用XRD、透射电镜(TEM)、紫外-可见(UV-Vis)分光光度计等表征手段分别对纳米CeO2的晶形、形貌、粒径及紫外吸收性质进行了表征,该纳米CeO2粒子具有立方晶型结构,分散性较好、粒径范围为5-18nm.考察了微乳液中正辛烷与正丁醇质量比、Ce(NO3)3浓度对纳米CeO2粒径的影响,结果表明:利用微乳液法,通过改变微乳液中正辛烷与正丁醇质量比、Ce(NO3)3浓度能够对纳米CeO2粒径进行有效控制;纳米CeO2的粒径均随着正辛烷与正丁醇质量比和Ce(NO3)3浓度的增大而减小.同时,对不同条件下制得的纳米CeO2的紫外吸收性质进行了考察.     

CTAB反相微乳液中水辛烷分子的自扩散研究

利用电导测量确定了CTAB/正丁醇/正辛烷/水四组分体系的相态,在反相微乳液区有明显的渗滤现象,通过脉冲梯度场核磁共振方法研究了反相微乳液中水和辛烷分子的自扩散行为,采用双指数拟合得出辛烷的自扩散系数。对于体系中出现的渗滤现象以及水和辛烷分子自扩散系数反常的原因,从分子水平上进行了解释。水和自扩散系数(2～7×10^-10m·s^-1)比一般文献值高,其原因：一是水在油相中有较大的溶解度;二是渗滤现象的存在,由于液滴间相互作用的增强和：粘性“碰撞而导致液滴的融合,以及由此而形成的瞬时水相连续通道,使水的自扩散系数增大。而辛烷自扩散系数比一般文献值小,则是由于在微乳液液滴的栅栏中表面活性剂分子烃链与辛烷分子间范德华引力所造成。     

微乳液体系相图的研究及其在纳米氟化物制备中的应用

绘制了十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C₄H₉OH)/正辛烷(n-C₈H₁₈)/水[或NH₄F溶液、或Ba(NO₃)₂溶液、或KNO₃-Mg(NO₃)₂混合溶液]四组分微乳体系的拟三元相图.观察了电导率随水(或盐溶液)含量变化的规律,很好地印证了微乳液体系的相行为.选取相图中微乳区点作为最佳条件,制备了KMgF₃纳米粒子.     

CTAB反相微乳液中水辛烷分子的自扩散研究

利用电导测量确定了CTAB/正丁醇/正辛烷/水四组分体系的相态,在反相微乳液区有明显的渗滤现象,通过脉冲梯度场核磁共振方法研究了反相微乳液中水和辛烷分子的自扩散行为,采用双指数拟合得出辛烷的自扩散系数。对于体系中出现的渗滤现象以及水和辛烷分子自扩散系数反常的原因,从分子水平上进行了解释。水和自扩散系数(2～7×10^-10m·s^-1)比一般文献值高,其原因：一是水在油相中有较大的溶解度;二是渗滤现象的存在,由于液滴间相互作用的增强和：粘性“碰撞而导致液滴的融合,以及由此而形成的瞬时水相连续通道,使水的自扩散系数增大。而辛烷自扩散系数比一般文献值小,则是由于在微乳液液滴的栅栏中表面活性剂分子烃链与辛烷分子间范德华引力所造成。     

聚乙二醇在Triton X-114/正辛烷/正丁醇/水反相微乳液中的增 溶研究

研究了加入聚合物对TritonX-114/正辛烷/正丁醇/水组分体系相态的影响。利用次甲基蓝(MB)作为吸附探针,而以恶唑烷氮氧自由基(5-doxylstearicacid,5-DNS)作为自旋探针,研究了加入聚合物对TX-114/正辛烷/正丁醇/水反相微乳液的微结构影响。结果表明:聚合添加使W/O微乳液区缩小,而液晶区则更靠近水一端(增溶更多水)。该反相微乳液中存在三种状态水:结合水、束缚水、体相水。加入聚合物可以替代先前存在于TX-114聚氧乙烯链上的一些水分子,使其微极性减小,而且使表面活性剂分子在界面上的排列更为松散,本研究结果对探讨聚合物对W/O微乳液微结构的影响及此类体系在其它方面应用有重要意义。     

油酸单乙醇酰胺聚氧乙烯醚微乳液体系的研究

以油酸单乙醇酰胺聚氧乙烯醚作为乳化剂制备水包油型微乳液.通过拟三元相图、粒径大小及粒径分布确定较优配方:复配表面活性剂(由油酸单乙醇酰胺聚氧乙烯醚和吐温20组成)的亲水亲油平衡值(HLB值)为15,助表面活性剂为正丁醇,复配表面活性剂与助表面活性剂的质量比(Km值)为1,混合表面活性剂与正辛烷的质量比(S/O值)=1∶...     

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.     

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。