热处理对La0.63Gd0.2Mg0.17Ni3.1Co0.3Al0.1储氢合金微观组织和电化学性能的影响

在氩气气氛和1173 K保温条件下对La0.63 Gd0.2 Mg0.17Ni3.1 Co0.3 Al0.1储氢合金进行不同时间(t=8 ～168 h)的热处理,采用电感耦合等离子发射光谱(ICP)、X射线衍射(XRD)、电子探针显微分析方法(EPMA)和电化学测试分析方法对比研究了退火时间对合金显微组织演化和电化学性能的影响.研究结果表明,铸态合金组织由Ce2 Ni7型、Gd2Co7型、Pr5 Co19型、PuNi3型和CaCu5型相组成,其Ce2 Ni7型相的丰度为78.9％,随退火时间的延长,退火合金中Ce2 Ni7型相的丰度逐渐增加,当退火时间t=168 h时其相丰度达到94.5％,Ce2 Ni7型相结构的晶胞参数和晶胞体积随退火时间增加而减小.电化学测试分析表明,退火合金电极的电化学性能与Ce2 Ni7型相的丰度有密切关系,退火时间对合金电极的活化性能影响不大,但合金电极放电容量随退火时间的延长逐渐提高,当t=168 h时,合金电极放电容量达到最大值386.8mAh·g-1;退火时间对合金电极循环稳定性的提高和改善有不同程度的影响,当退火时间t=16～168 h时,经100次充放电循环后,其电极容量保持率S100=90.3％～91.5％.热处理能有效改善合金电极电化学反应的动力学性能,但不同退火时间对合金电极的高倍率放电性能影响不明显.     

La0.7-xNdxMg0.3Ni3.4Al0.1(x=0～0.4)储氢合金的相结构及电化学性能

采用真空烧结方式制备了AB3.5型La0.7-xNdxMg0.3Ni3.4Al0.1(x=0,0.1,0.2,0.3和0.4)储氢合金.XRD分析表明,所有合金均由LaNi5,La2Ni7和LaNi3三相组成.当Nd含量增加时,合金中的LaNi5和La2Ni7相含量有不同程度的增加,而LaNi3相相应减少.电化学性能测试表明,添加适量的Nd能改善合金电极的循环稳定性,其中La0.6Nd0.1Mg0.3Ni3.4Al0.1合金具有相对较好的综合性能,其最大放电容量达到322.4 mAh·g-1,循环50周的容量保持率(S50)达到89.98%.     

CoO添加剂对La0.7Mg0.3(Ni0.85Co0.15)3.5贮氢合金电化学性能的影响

为了改善La-Mg-Ni-Co型贮氢合金电极材料的电化学循环稳定性，采用真空中频感应电炉熔炼的方法制备了La0.7Mg0.3（Ni0.85Co0.15）3．5合金，研究了CoO添加剂（添加量分别为0％，2．5％，5％和15％）对其电化学性能的影响。结果表明，当以机械混合的方式在铸态La0.7Mg0．3（Ni0.85Co0.15）3．5合金粉中添加5％CoO时，可使合金电极在高温、低温和室温时的放电容量及室温充放电循环寿命大幅度提高。电化学测试及X射线衍射（XRD）分析结果表明，CoO可能是通过促进La0.7Mg0.3（Ni0．85Co0.15）35合金中某个（些）相的电化学反应，及其本身在充放电过程中发生可逆电化学反应，改善La0．7Mg0．3（Ni0．85Co0．15）3．5合金电化学性能。     

La15Fe77B8型储氢合金的结构和电化学性能

研究了快淬和退火态La15Fe77B8型储氢合金的组织结构和电化学性能。应用中频感应熔炼-快淬方法制备了La15Fe77B8型储氢合金,其组成为La15Fe2Ni72Mn7B2Al2。结构分析表明:快淬La15Fe2Ni72Mn7B2Al2合金为多相结构,包括LaNi5相、La3Ni13B2相和(Fe,Ni)相,快淬合金经1223 K保温3 h,然后在873 K保温3 h退火处理后,LaNi5相增加,La3Ni13B2相几乎消失,(Fe,Ni)相增加且形态变大。电化学测试表明,退火合金的最大容量(307 mAh.g-1)略小于快淬合金(309 mAh.g-1),而循环稳定性有所改善。退火合金电极的倍率放电能力(HRD)低于快淬合金,原因在于交换电流密度(I0)及氢在合金中的扩散系数(D)降低。快淬和退火合金电极在低温233 K时均能放出55%的容量。     

La-Mg-Ni系A2B7型贮氢合金的结构与电化学性能

合金结构研究表明,La2-xMgxNi7(x=0.3～0.8)主要由Ce2Ni7,Gd2Co7,PuNi3型物相组成.合金中Mg含量对合金相结构有着重要影响,主相的晶胞参数随Mg含量(x)的增加呈线性减小,合金的吸放氢平台也随之升高.电化学测试表明,随合金中Mg含量的增加,合金电极的放电容量先增大后减小,合金电极的循环稳定性呈恶化趋势,La1.4Mg0.6Ni7合金电极具有最高的电化学放电容量(378 mAh·g-1),La1.6Mg0.4Ni7合金电极具有最佳的循环稳定性(S270=81%).合金电极的高倍率放电性能(HRD)随Mg含量的增加而增大.当合金中Mg含量较低时(x≤0.5),合金电极反应速度控制步骤为氢在合金体相中的扩散;当Mg含量较高时(x≥0.5),合金电极反应速度控制步骤转变为电极表面的电荷转移.     

储氢合金La0.7-xCexMg0.3Ni2.4Co0.6(x=0～0.4)电化学性能研究

研究了以Ce部分取代La对AB3型储氢合金La0.7-xCexMg0.3Ni2.4Co0.6(x=0~0.4)结构和电化学性能的影响.实验表明,该系列合金主要包含LaNi3相和LaNi5相.随着Ce含量的增加,合金电极的最大放电容量逐渐降低,但循环稳定性得到了明显改善.     

La_(0.63)Gd_(0.2)Mg_(0.17)Ni_(3.2-x)Co_(0.3)Al_x(x=0～0.4)储氢合金的微观组织和电化学性能

采用真空感应熔炼方法制备了La0.83Mg0.17Ni3.1Co0.3Al0.1和La0.63Gd0.2Mg0.17Ni3.2-xCo0.3Alx(x=0~0.4)贮氢合金,并在氩气气氛900℃进行退火处理。通过X射线衍射(XRD)、显微电子探针(EPMA)分析方法和电化学测试分析研究了Gd和Al元素对合金微观组织和电化学性能的影响。研究结果表明,该系列合金退火组织主要由Ce2Ni7/Gd2Co7型、Pr5Co19型、PuNi3型和CaCu5型相组成;Gd元素的加入使合金中CaCu5型相明显减少,Ce2Ni7型/Gd2Co7型相显著增加,x=0.1时其相丰度达到81.2%;随Al含量x不断增加,合金中CaCu5型相丰度逐渐增多,当x=0.1~0.2时,CaCu5型相丰度为4%~5%,x=0.4时,其相丰度达到66.65%。电化学测试分析表明,Gd和Al元素对合金电极活化性能影响不大,当x=0.1时,含Gd合金电极放电容量达到最大值391 mAh.g-1,随Al含量x进一步增加,合金电极放电容量降低。含Gd和加入适量的Al元素可使合金电极循环稳定性得到明显提高,当Al含量x=0.1,0.2时,经100次充放电循环后其电极容量保持率S100分别为93.7%和90.1%,其中La0.63Gd0.2Mg0.17Ni3.1Co0.3Al0.1合金具有最好的综合电化学性能。     

硼对La17Fe76B7型储氢合金结构和电化学性能的影响

采用中频感应熔炼-快淬方法制备了La17Fe3Mn5Al2Ni73-xBx(x=0,1,3,5)储氢合金。结构分析表明,不含B的合金为双相结构,主相为LaNi5相,第二相为La2Ni7相,含B合金均由LaNi5相、La2Ni7相和La3Ni13B2相组成,且随着B含量的增加,LaNi5相和La2Ni7相减少,La3Ni13B2相逐渐增加。电化学测试表明,随着B含量的增加,合金的活化性能、最大放电容量不同程度下降,而循环稳定性有所改善。合金电极的倍率放电能力(HRD)随着B含量的增加呈先增大后减小的趋势,表明适量的B有利于提高合金的高倍率放电性能。合金电极的交换电流密度(I0)随着B含量的增加先增大后减小,而氢在合金中的扩散系数(D)则逐渐增大,表明合金的高倍率放电性能主要取决于合金表面的电荷转移能力。     

La0.5Mg0.5(Ni1-xCox)2.28(x=0.0～0.2)储氢合金的相结构和电化学性能

用冷坩埚磁悬浮熔炼方法制备La0.5Mg0.5(Ni1-xCox)2.28(x=0.0～0.2)贮氢电极合金,采用SEM,EDS,XRD,P-C-T测试及三电极电化学性能测试研究合金的相成分、相结构、P-C-T曲线和电化学性能.EDS结合XRD分析表明,La0.5Mg0.5Ni2.28及La0.5Mg0.5(Ni0.85Co0.15)2.28合金主相均为MgSnCu4型的LaMgNi4相,还包括LaNi5和(La,Mg)Ni3相.P-C-T曲线显示,合金均有双放氢平台,合金的贮氢量由Co替代量x=0.0时的1.24%增大至极大值x=0.15时的1.27%.电化学性能测试表明,随Co含量增加,最大放电容量从329.0mAh·g-1(x=0.0)增大到337.5 mAh·g-1(x=0.15),合金活化性能及高倍率放电性能明显改善;循环稳定性无明显变化.     

镁含量对RE-Mg-Ni系A2B7型储氢合金结构与性能的影响

采用感应熔炼方法制备了La0.8-xGd0.2MgxNi3.1Co0.3Al0.1(x=0, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4)储氢合金, 并在氩气气氛和1173 K下进行退火处理. 合金相结构分析结果表明, 镁含量(x)较低时合金以Ce2Ni7型为主相结构, A2B7型相丰度(Ce2Ni7+Gd2Co7)达到98.8%; 镁含量较高时合金相由A2B7型、 CaCu5型和PuNi3型物相构成, 随着镁含量的增加, PuNi3型和CaCu5型相组成逐渐增多, 其晶胞参数随Mg含量的增加而减小, 同时合金的吸氢平台也随之升高. 电化学测试结果表明, 随着合金中Mg含量增加, 合金电极的最大放电容量和循环稳定性均呈先增大后减小的规律, 其中x=0.15时合金电极具有最高的电化学放电容量(393 mA·h/g)和最佳的循环寿命(S100=92.82%). 合金电极的高倍率放电性能(HRD)随Mg含量的增加先减小再增大然后又减小, 适量的Mg元素改善了合金电极的动力学性能.     

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.     

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。     

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^-。     

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。