微乳液法制备MAl2O4：Eu^2＋，Dy^3＋（M=Ca，Sr，Ba）发光材料及其发光性能

采用微乳液法合成了MAl2O4：Eu^2＋，Dy^3＋（M=Ca，Sr，Ba）长余辉发光材料，并对其晶体结构和发光性能进行了比较与讨论。XRD分析表明，所合成的Ca2O4：Eu^2＋，Dy^3＋，SrAl2O4：Eu^2＋，Dy^3＋粉体为单斜晶系结构，BaAl2O4：Eu^2＋，Dy^3＋粉体为六方晶体结构。MAl2O4：Eu^2＋，Dy^3＋（M=Ca，Sr，Ba）发光材料的激发光谱都为一宽带连续谱，表明从紫外至可见光均可有效的激发该材料。发射光谱的发射波长峰值分别为440nm（M=Ca），520nm（M=Sr）和496nm（M=Ba）。对应的发光颜色分别为蓝色、黄绿色和蓝紫色。余辉衰减曲线分为快衰减、中间过渡衰减和随后极长的慢衰减过程，符合双曲线方程I=At^-n，余辉亮度与时间顺序为Sr〉Ca〉Ba。     

纳米棒状MAl2O4:Eu2+, Dy3+(M=Sr, Ba)长余辉发光材料的制备与性能

利用硝酸铝、硝酸锶/硝酸钡、尿素为原料,以一定比例H2O/正丁醇/CTAB的混合液作传递压力的介质进行反应,然后将得到的前驱体在还原气氛下高温煅烧,得到亮度高、余辉时间长的MAl2O4∶Eu^2＋,Dy^3＋纳米结构长余辉发光材料。TEM测试表明,高温煅烧后得到的MAl2O4∶Eu^2＋,Dy^3＋均为棒状结构,其激发光谱和发射光谱均为宽带,主发射峰分别为513和498 nm,是典型的Eu^2＋5d→4f跃迁。在对单掺Eu^2＋与双掺Eu^2＋,Dy^3＋比较的过程中,明显发现双掺Eu^2＋和Dy^3＋的强度增加,且余辉增强。材料的余辉强度随时间的变化由最初的快减过程和随后的慢减过程组成,符合I=t^-1.1双曲线规律。该方法操作简单,在不同的温度和时间下均合成出了棒状MAl2O4∶Eu^2＋,Dy^3＋,不需球磨,可直接应用。     

稀土氧化钕对铝酸盐长余辉发光材料性能的影响

制备了SrAl2O4:Eu2 ,Nd^3 和SrAl2O4:Eu^2 ,Dy^3 ,Nd^3 长余辉材料,研究了所合成的材料在不同波段紫外光激发条件下的发光光谱和激发光谱的差异和Eu^2 ,Dy^3 ,Nd^3 的摩尔掺杂浓度对材料的余辉性能的影响等。     

ZnO-P2O5:Tb3+玻璃的热释光研究

采用高温熔融法制备了ZnO-P2O5：Tb^3＋玻璃,并以热释光为手段,研究了基质组成、Tb^3＋掺杂浓度、熔制气氛、Tb^3＋与其他稀土离子共掺等因素对ZnO-P2O5：Tb^3＋玻璃的发光中心、陷阱浓度及陷阱能级分布的影响。结果表明：ZnO含量的增加,使得与Zn^2＋配位的氧空位的数量增多,导致50-150℃低温区对应的陷阱浓度增加;还原气氛下,Tb^3＋掺杂后,一方面形成发光中心使得热释光强度提高,另一方面,可能由于不等价取代基质中的Zn^2＋离子产生新的缺陷使得陷阱能级加深;空气气氛下,大部分Tb^3＋被氧化成Tb^4＋,发光中心浓度降低;Ce^3＋,Eu^3＋,Dy^3＋,Nd^3＋,Pr^3＋和Er^3＋与Tb^3＋共掺时,陷阱能级深度与陷阱中心的电荷密度发生了不同程度的变化。     

杂质的添加对SrAl2O：Eu^2＋,Dy^3＋余辉发光特性的改善

采用溶胶－凝胶法制备SrAl2O4:Eu^2 ,Dy^3 磷光体,并在合成过程中添加硼或硅以探讨光致发光及长余辉发光性质。发现硼、硅添加物不仅是助熔剂,且能改良SrAl2O4:Eu^2 ,Dy^3 之长余辉的持续时间及余辉发光强度。基于不同磷光体样品的实验结果比较,综合材料表面微结构观察、X射线衍射图谱、热释发光光谱与余辉衰减曲线的测量等实验结果分析,推断在SrAl2O4:Eu^2 ,Dy^3 中添加硼、硅可导致磷光体缺陷增加并稳定活化剂Eu^2 的价态。     

稀土发光材料在固体白光LED照明中的应用

固体白光发光二极管将成为21世纪新一代的节能光源. 要实现白光发射的重要途径之一是利用稀土发光材料的荧光转换技术, 把InGaN半导体管芯发射的460 nm蓝光或400 nm近紫外光转换成白光. 分别就这两种管芯报道了我们研制的发射蓝、绿、黄、红等不同颜色的稀土发光材料： YAG：Ce, Ca1-xSrxS：Eu^2＋, Ga2S3：Eu^2＋, MGa2S4：Eu^2＋（M=Ca, Sr, Ba）, SrGa^2＋xS4＋y：Eu^2＋, （Ca1-xSrx）Se：Eu^2＋, SrLaGa3S6O：Eu^2＋, （M1, M2）10（PO4）6X2, （M1=Ca, Sr, Ba; M2=Eu, Mn; X=F, Cl, Br）, NaEu0.92Sm0.08（MoO4）2, 并报道了由它们制成的白光发光二极管的色坐标、相关色温和显色指数等参数.     

H3BO3对微波等离子体法合成SrAl2O4:Eu2+,Dy3+的影响

采用微波等离子体法合成SrAl2O4：Eu^2＋ Dy^3＋长余辉发光材料,探讨了H3BO3的加入对材料的光谱性能、余辉性能、相组成结构、微观形貌的影响。结果表明,适量的添加助溶剂H3BO3,有利于增强材料的发光强度,延长余辉时间,但过量的添加反而会导致发光性能下降。本试验确定硼酸的最佳添加量为10％。综合检测分析结果推断,硼酸加入后在高温下大部分形成液相,并通过液相传质促进晶体生长,提高基质的结晶程度,同时促进稀土离子Eu^2＋,Dy^3＋进入晶格并使其分布更均匀;而少部分则会进入晶格发生B取代Al,引起晶体场畸变,从而提高了材料的发光强度和长余辉特性。     

锶铝比对稀土掺杂铝酸锶物相及发光性能的影响

用拟薄水铝石溶胶凝胶法成功制备了SrAl2O4：Eu^2 ，Dy^3 长余辉发光材料，样品无需球磨。XRD结果表明：当锶铝摩尔比Sr／Al＞0．3时，发光基质主相为SrAl2O4，杂质相为Sr4Al2O7，Sr／Al比值继续降低至0．25，发光相则以Sr4Al14O25为主，此时杂质相中含有Sr4Al2O7和Dy4Al2O9。Sr4Al2O7相对SrAl2O4：Eu^3 ，Dy^3 的发光性能影响很大，而对Sr4Al14O25：Eu^2 ，Dy^3 的发光性能影响不大。Dy4Al2O9对SrAl2O4和Sr4Al14O25发光主相的发光性能影响都不大。光谱检测结果表明SrAl2O4：Eu^2 ，Dy^3 发光光谱是中心位于520nm的带状谱。余辉检测结果表明发光主相为SrAl2O4和Sr4Al14O25时，光衰曲线符合I=ct^-n规律，n值分别为n=1．081和n=1．079。     

微波合成对SrAl2O4:Eu2+, Dy3+晶相和铕的价态的影响

为了在较低温度下合成性能优良的SrAl2O4：Eu^2＋,Dy^3＋（SAO—ED）发光材料,采用溶胶-凝胶-微波法在900℃烧结30min合成SAO—ED发光材料。产品的发光性能优于传统高温固相法1400℃烧结3h制备的产品。根据Henderson和Taylor提出的公式对SrAl2O4的XRD数据进行了量化,计算出单斜晶系（M）和六方晶系的比例;结果表明,溶胶-凝胶-微波法制备的产品中只有单斜晶系存在,而高温固相法制备的产品中有六方晶系存在,六方晶系不发光。另外,产品采用XANES表征了Eu离子存在的价态,发现溶胶一凝胶微波法制备的产品中残留的Eu^3＋的比例远低于传统高温固相法制备的产品。以上两种原因导致了产品的发光性能优于高温固相法制备的产品。     

碱土金属离子（Mg^2＋，Ca^2＋，Ba^2＋）掺杂对长余辉荧光粉SrAl2O4：Eu^2＋，Dy^2＋发光性能的影响

采用高温固相法制备了碱土金属离子（Mg^2＋,Ca^2＋,Ba^2＋）掺杂的SrAl2O4：Eu^2＋,Dy^3＋长余辉荧光粉。XRD谱分析表明,随着基质中掺入的碱土金属离子（Mg^2＋,Ca^2＋,Ba^2＋）浓度增加,基质晶格常数也随之发生变化。Mg^2＋,Ca^2＋和Ba^2＋ 3种碱土离子在SrAl2O4中的固溶范围分别为40％,15％和30％。光谱分析则表明在固溶范围内随着掺杂Mg^2＋,Ca^2＋和Ba^2＋浓度的增大,样品的发射峰值会在480～530nm范围出现规律性移动。适当浓度的Mg^2＋,Ba^2＋掺杂会不同程度地提高样品的发光强度,而Ca^2＋的掺杂则会降低发光强度。但是碱土金属离子（Mg^2＋,Ca^2＋,Ba^2＋）的掺杂并不能延长SrAl2O4：Eu^2＋,Dy^3＋荧光粉的余辉时间。     

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.

     

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。     

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.     

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。     

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.     

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。     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.