Mg0.9-xTi0.1PdxNi(x=O.04～0.1)贮氢合金电极腐蚀行为研究

研究了Pd部分替代Mg对Mg0.9-xTi0.1PdxNi(x=0.04～0.1)贮氢合金腐蚀性能的影响.利用机械合金化方法制备了Mg0.9-xTi0.1PdxNi(x=0.04～0.1)贮氢合金.XRD和TEM分析表明经120 h球磨后该合金完全非晶化.循环充放电测试结果表明,Pd的替代有效地延长了Mg0.9-xTi0.1PdxNi(x=0.04～0.1)合金的循环寿命.采用开路电位测量,阳极极化,电化学阻抗和X射线光电子能谱研究了该合金的腐蚀行为.结果表明,随着Pd含量增加,合金腐蚀电位正移,初始腐蚀电流下降,腐蚀电流增加的速度变缓.采用本文提出的等效电路模型较好地拟合了合金的电化学阻抗谱.分析表明,随着Pd含量的增加,合金表面钝化膜厚度和电阻逐渐增大.X射线光电子能谱分析表明,Pd的加入减弱了合金在充放电过程中的氧化程度.当Pd含量达到0.1时,Mg0.9-xTi0.1PdxNi(x=0.04～0.1)合金的耐腐蚀性能最好,其放电容量保持率最高.     

钇对AZ91镁合金微观组织及腐蚀性能影响的研究

通过金相分析、扫描电镜析及化学成分分析等测试手段,对添加不同含量Y的AZ91镁合金的微观组织和腐蚀性能进行了研究。结果表明,加入Y后,合金中有稀土相Al4MgY生成,并显著细化了合金的微观组织,合金微观组织由典型的枝晶组织转变为细小的等轴晶组织,当Y含量达到1.52%时,合金组织的细化程度最大;Y的加入,减少了合金中的-βMg17Al12相,并使β相断续、弥散,同时合金的耐腐蚀性能提高,在3.5%NaCl水溶液腐蚀实验中,稀土含量为1.52%Y的合金耐腐蚀性能最好。     

Mg0.9－xTi0.1PdxNi(x=0.04～0.1)贮氢合金电极腐蚀行为研究

研究了Pd部分替代Mg对Mg0.9－xTi0.1PdxNi(x=0.04～0.1)贮氢合金腐蚀性能的影响. 利用机械合金化方法制备了Mg0.9－xTi0.1PdxNi(x=0.04～0.1)贮氢合金. XRD和TEM分析表明经120 h球磨后该合金完全非晶化. 循环充放电测试结果表明, Pd的替代有效地延长了Mg0.9－xTi0.1PdxNi(x=0.04～0.1)合金的循环寿命. 采用开路电位测量, 阳极极化, 电化学阻抗和X射线光电子能谱研究了该合金的腐蚀行为. 结果表明, 随着Pd含量增加, 合金腐蚀电位正移, 初始腐蚀电流下降, 腐蚀电流增加的速度变缓. 采用本文提出的等效电路模型较好地拟合了合金的电化学阻抗谱. 分析表明, 随着Pd含量的增加, 合金表面钝化膜厚度和电阻逐渐增大. X射线光电子能谱分析表明, Pd的加入减弱了合金在充放电过程中的氧化程度. 当Pd含量达到0.1时, Mg0.9－xTi0.1PdxNi(x=0.04～0.1)合金的耐腐蚀性能最好, 其放电容量保持率最高.     

Mg_(0.9-x)Ti_(0.1)Pd_xNi(x=0.04～0.1)贮氢合金电极腐蚀行为研究

研究了Pd部分替代Mg对Mg0.9-xTi0.1PdxNi(x=0.04～0.1)贮氢合金腐蚀性能的影响.利用机械合金化方法制备了Mg0.9-xTi0.1PdxNi(x=0.04～0.1)贮氢合金.XRD和TEM分析表明经120h球磨后该合金完全非晶化.循环充放电测试结果表明,Pd的替代有效地延长了Mg0.9-xTi0.1PdxNi(x=0.04～0.1)合金的循环寿命.采用开路电位测量,阳极极化,电化学阻抗和X射线光电子能谱研究了该合金的腐蚀行为.结果表明,随着Pd含量增加,合金腐蚀电位正移,初始腐蚀电流下降,腐蚀电流增加的速度变缓.采用本文提出的等效电路模型较好地拟合了合金的电化学阻抗谱.分析表明,随着Pd含量的增加,合金表面钝化膜厚度和电阻逐渐增大.X射线光电子能谱分析表明,Pd的加入减弱了合金在充放电过程中的氧化程度.当Pd含量达到0.1时,Mg0.9-xTi0.1PdxNi(x=0.04～0.1)合金的耐腐蚀性能最好,其放电容量保持率最高.     

钇对MB25镁合金组织及强度的影响

通过金相观察、电子探针分析和强度测试,发现钇(Y)对MB25镁合金具有明显细化晶粒作用。在该合金中,当Y低于0.9wt％时,随着Y含量增加,其分布均匀,晶界变窄;当Y等于0.9wt％时,合金的组织和强度均最佳。     

钇对AB_5型La_(0.7-x)Y_xCe_(0.3)Ni_(3.9)Co_(0.45)Mn_(0.35)Al_(0.3)储氢合金的组织和电化学性能的影响

用真空电弧熔炼和热处理(1000℃×10 h)制备了AB_5型La_(0.7-x)Y_xCe_(0.3)Ni_(3.9)Co_(0.45)Mn_(0.35)Al_(0.3)(x=0, 0.1, 0.2, 0.3, 0.4)退火合金,研究了A端Y元素对退火合金微观组织、相结构及电化学性能的影响。XRD和SEM电镜分析结果表明,退火合金微观组织均有CaCu_5型主相和少量第二相组成,随Y含量的增大,主相的晶胞参数a,c及晶胞体积V依次减小。电化学测试结果表明:经100次充放电循环后的容量保持率S_(100)=77.6%～88.1%,合金电极的高倍率放电性能HRD_(900)=86.9%～92.9%。Y元素的添加对提高合金的循环寿命效果显著。其中Y含量x=0.2时的合金具有较好的综合电化学性能, 100次充放电后的循环寿命S_(100)=88.1%,高倍率放电性能HRD_(900)=92.9%。合金电极反应动力学由合金表面电荷转移速率和氢在合金体相中的扩散共同控制。     

无镁超点阵结构A_2B_7型La_(1-x)Y_xNi_(3.25)Mn_(0.15)Al_(0.1)合金的储氢和电化学性能

采用真空电弧熔炼和热处理(950℃×10 h)方法制备了新型无镁超点阵结构A_2B_7型La_(1-x)Y_xNi_(3.25)Mn_(0.15)Al_(0.1)(x=0,0.25,0.50,0.67,0.75,0.85,1.00)退火合金,研究了A端稀土Y元素对退火合金微观组织结构、储氢行为及电化学性能的影响.结果表明,退火合金微观组织的主相均由Ce_2Ni_7型结构组成,随稀土Y含量x增大,Ce_2Ni_7型主相丰度呈先增加后减小的规律,同时Ce_2Ni_7型主相的晶胞体积V逐渐减小.气体储氢时,x=0~0.25合金无压力-组成-温度(PCT)曲线平台且易形成氢致非晶化;当x≥0.50时,合金能有效抑制储氢时的氢致非晶化倾向且具有明显的吸/放氢平台特征,吸氢平台压范围为0.026~0.097 MPa,最大储氢量为1.418%~1.48%(质量分数),储氢性能得到极大改善.电化学测试结果表明,x=0.50~0.85的合金具有较高的电化学放电容量(350.4~381 mA·h/g),经100次充放电循环后容量保持率S100=52%~85%,其中稀土Y含量x=0.67~0.75时的合金具有良好的储氢性能及较好的综合电化学性能.合金电极的高倍率放电性能HRD900=64.5%~85.7%,氢原子在合金体相中的扩散是电极反应动力学过程的控制步骤.     

V2.1TiNi0.4Zr0.06Cux(x=0-0.12)储氢合金的微结构及电化学性能

采用磁悬浮感应熔炼方法制备了V2.1TiNi0.4Zr0.06Cux (x=0-0.12)储氢合金, 经XRD、SEM、EDS和电化学测试等系统研究了Cu添加量对合金微结构及电化学性能的影响. 结果表明, 所有合金均由V基固溶体主相和C14型Laves第二相组成, 且第二相沿主相晶界形成三维网状分布; 合金主相和第二相的晶胞体积均随着Cu含量x的增加而增大. 电化学性能测试表明, 添加适量(x=0.03-0.06)的Cu可以提高合金的最大放电容量, 并对活化性能基本没有影响; 而过高的Cu添加量(x≥0.09)会降低合金的放电容量. 此外, 添加Cu可使合金的高倍率放电性能得到明显改善, 充放电循环稳定性有所提高. 在所研究的合金样品中, V2.1TiNi0.4Zr0.06Cu0.03合金具有最佳的综合性能.     

热处理温度对La-Y-Ni合金相结构和电化学性能的影响

采用磁悬浮感应熔炼法制备了组分为LaY_2Ni_(9.7)Mn_(0.5)Al_(0.3)的合金,在不同温度(1 073～1 373 K)下对合金进行热处理,利用X射线衍射法(XRD)、电子探针(EPMA)和电化学性能测试等方法,系统地研究了热处理温度对合金相结构和电化学性能的影响。结果表明,热处理可以显著提高合金的相均匀度,随着热处理温度的升高合金中的主相Ce_2Ni_7相先增加后减少。电化学研究表明,合金电极的最大放电容量、倍率性能和循环稳定性随着热处理温度的升高均呈现先升高后降低的趋势,与Ce_2Ni_7相含量的变化一致。电化学压力-组成-温度(P-C-T)测试表明,合金具有2个放氢平台,且随着热处理温度的升高合金的放氢坪台压增加。当热处理温度为1 273 K时,合金的Ce_2Ni_7相含量最高为86.53%(w/w),电化学性能最佳,最大放电容量为386.80 mAh·g~(-1)(60mA·g~(-1)),在电流密度为900 mA·g~(-1)时的高倍率性能HRD_(900)=89.45%,循环300周后的容量保持率S_(300)=72.18%(300 mA·g~(-1))。     

V2.1TiNi0.4Zr0.06Cux（x=0-0.12）储氢合金的微结构及电化学性能

采用磁悬浮感应熔炼方法制备了V2.1TiNi0.4Zr0.06Cux(x=0-0.12)储氢合金,经XRD、SEM、EDS和电化学测试等系统研究了Cu添加量对合金微结构及电化学性能的影响.结果表明,所有合金均由V基固溶体主相和C14型Laves第二相组成,且第二相沿主相晶界形成三维网状分布;合金主相和第二相的晶胞体积均随着Cu含量x的增加而增大.电化学性能测试表明,添加适量(x=0.03-0.06)的Cu可以提高合金的最大放电容量,并对活化性能基本没有影响:而过高的Cu添加量(x≥0.09)会降低合金的放电容量.此外,添加Cu可使合金的高倍率放电性能得到明显改善,充放电循环稳定性有所提高.在所研究的合金样品中,V2.1TiNi0.4Zr0.06Cu0.03合金具有最佳的综合性能.     

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。     

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.     

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。     

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.     

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。     

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.     

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.