Effect of Sr^2＋ on Properties of Li0.2375＋xLa0.5875-xSrxTiO3-LaPO4 System

Ionicconductingsolidmaterialshavereceivedconsiderableattentioninthelastfewyearsduetotheirpotentialutilityinhighenergybatteriesandotherelec trochemicaldevices .SeveralsystemsoflithiumfastionconductorsareknowntoshowhighlithiumionconductivitysuchasγLi3PO4 typesolidsolution[1] ,LiTi2 (PO4 ) 3anditsderivations[2～4 ] andLi14 Zn(GeO4 ) 3solidsolution[5] .However ,exceptforlowpowerapplications ,onemajorproblemwiththepracticalapplicationsisitslowconductivityatroomtemperature .Recentyears ,morean…     

Formation and Characterization of Li0.24 ＋ 2x La0.59-x Mx TiO3-LaPO4 （M = K, Na） System

Ionic conductingsolid materials has received con-siderable attention in the last few years due to theirpotential utilityin high energy batteries and other elec-trochemical devices . Several systems of lithium fastion conductors ,such as γ-Li3PO4-type sol…     

生物医用Ti-6Al-7Nb合金高温变形行为研究

为了研究用于外科植入生物材料Ti-6Al-7Nb合金的热变形行为,利用Gleeble 2000热模拟实验机对Ti-6Al-7Nb合金在750～900℃温度范围和0.001～10.000 s-1应变速率范围内进行等温热压缩实验,试验在氩气保护下进行,采用金相显微镜和透射电镜观察热变形后的组织;通过计算变形激活能分析Ti-6Al-7Nb合金在热压缩过程中的变形机制。结果表明:流变应力在经历加工硬化阶段后均表现出流变软化现象,在较低应变速率ε=0.001～0.100 s-1时,材料的软化主要受α相动态再结晶影响;而在较高应变速率ε=1～10 s-1时,材料基本不发生再结晶,其软化是由于钛合金在变形过程中的绝热效应造成的。通过Arrhenius方程计算出合金在750,800,850和900℃下的变形激活能分别为209.25,196.01,194.01和130.40 kJ.mol-1;在750～850℃下的激活能接近于α-Ti的自扩散激活能(200 kJ.mol-1),表明在750～850℃的变形由α-Ti自扩散参与的动态再结晶控制;在900℃下激活能略低于β-Ti的自扩散激活能(160 kJ.mol-1),说明在900℃下的变形机制由β相的动态回复控制。综合考虑变形行为与组织细化因素,温度在750～850℃,变形速率在0.01～0.10 s-1范围为良性热加工区域。     

Kinetic determination of the fast exchanging substrate water molecule in the S3 state of photosystem II

In a previous communication we showed from rapid isotopic exchange measurements that the exchangeability of the substrate water at the water oxidation catalytic site in the S3 state undergoes biphasic kinetics although the fast phase could not be fully resolved at that time [Messinger, J., Badger, M., and Wydrzynski, T. (1995) Proc. Natl. Acad. Sci. U.S.A. 92, 3209-3213]. We have since improved the time resolution for these measurements by a further factor of 3 and report here the first detailed kinetics for the fast phase of exchange. First-order exchange kinetics were determined from mass spectrometric measurements of photogenerated O2 as a function of time after injection of H218O into spinach thylakoid samples preset in the S3 state at 10 degreesC. For measurements made at m/e = 34 (i. e., for the mixed labeled 16,18O2 product), the two kinetic components are observed: a slow component with k1 = 2.2 +/- 0.1 s-1 (t1/2 approximately 315 ms) and a fast component with k2 = 38 +/- 4 s-1 (t1/2 approximately 18 ms). When the isotopic exchange is measured at m/e = 36 (i.e., for the double labeled 18,18O2 product), only the slow component (k1) is observed, clearly indicating that the substrate water undergoing slow isotopic exchange provides the rate-limiting step in the formation of the double labeled 18,18O2 product. When the isotopic exchange is measured as a function of temperature, the two kinetic components reveal different temperature dependencies in which k1 increases by a factor of 10 over the range 0-20 degreesC while k2 increases by only a factor of 3. Assuming simple Arrhenius behavior, the activation energies are estimated to be 78 +/- 10 kJ mol-1 for the slow component and 39 +/- 5 kJ mol-1 for the fast component. The different kinetic components in the 18O isotopic exchange provide firm evidence that the two substrate water molecules undergo separate exchange processes at two different chemical sites in the S3 state, prior to the O2 release step (t1/2 approximately 1 ms at 20 degreesC). The results are discussed in terms of how the substrate water may be bound at two separate metal sites.     

Hydrogen bonding effects on amine rotation rates in crystalline amino acids

Rates of rotation for amines in a variety of crystalline environments are reported, and the trends are explained in terms of the strengths of local hydrogen bonding interactions. Proton spin-lattice relaxation times (T1) and deuterium broad-line NMR spectra have been measured for D-, DL- and L- aspartic acid, two polymorphs of glycine, alanine, and leucine in the temperature range from -40 to 110 degrees C. The energy barriers for amine rotation are 27 +/- 2 kJ mol-1 for D- or L-aspartic acid and 22 +/- 2 kJ mol-1 for DL-aspartic acid; these energies are slightly lower than the previously reported value for the L from based on direct proton T1 measurements at 60 MHz. The values for the alpha and gamma forms of glycine were 24 +/- 2 and 30 +/- 2 kJ mol-1 respectively, that for L-alanine was 40 +/- 2 and that for L-leucine was 49 +/- 3 kJ mol-1. These are all in rough agreement with previously reported values (although the differences for the polymorphs of glycine and for L- vs. DL-aspartic acid were not reported). Crystal structures of these amino acids indicate differences in hydrogen bonding environments around the R-NH3+ groups that are probably responsible for the different activation barriers. A molecular mechanics calculation of the rotation energy barriers for L- and DL-aspartic acid based on the crystal structures gave satisfactory agreement with experimental results if a uniform (and arbitrarily chosen) dielectric constant of 2.5 was assumed. Differences between L- and DL-aspartic acids and between two polymorphs of glycine were well represented qualitatively. Including additional neighboring molecules not involved in the hydrogen bonding or including periodic boundary conditions to describe the crystal packing did not significantly affect these results. If vacuum dielectric constants are used, the barriers are uniformly overestimated, and if the experimental macroscopic dielectric constant values are used, the barriers are generally underestimated. Dielectric constants differ substantially from one amino acid to another and significantly affect the estimated barriers; in fact, the bulk dielectric constants appear to be the major difference between the highest and the lowest values. The difficulty of accurately including dielectric relaxation into molecular mechanics calculations resulted in the disagreement between experimental measurements and theoretical calculations.     

High-temperature deformation processing of Ti-24Al-20Nb

Power dissipation maps have been generated in the temperature range of 900 ‡C to 1150 ‡C and strain rate range of 10^-3 to 10 s^-1 for a cast aluminide alloy Ti-24Al-20Nb using dynamic material model. The results define two distinct regimes of temperature and strain rate in which efficiency of power dissipation is maximum. The first region, centered around 975 ‡C/0.1 s^-1, is shown to correspond to dynamic recrystallization of the α₂ phase and the second, centered around 1150 ‡C/0.001 s^-1, corresponds to dynamic recovery and superplastic deformation of the β phase. Thermal activation analysis using the power law creep equation yielded apparent activation energies of 854 and 627 kJ/mol for the first and second regimes, respectively. Reanalyzing the data by alternate methods yielded activation energies in the range of 170 to 220 kJ/mol and 220 to 270 kJ/mol for the first and second regimes, respectively. Cross slip was shown to constitute the activation barrier in both cases. Two distinct regimes of processing instability—one at high strain rates and the other at the low strain rates in the lower temperature regions—have been identified, within which shear bands are formed. Formerly with the Defence Metallurgical Research Laboratory     

Study on Kinetics of Natural Rubber Vulcanization by S/La（DiPDP）3

Kinetics of natural rubber （NR） vulcanization by lanthanum O, O＇-diisopropyldithiophosphate [ La（DiPDP）3 ] was studied. La（DiPDP）3 had remarkable accelerating effect on the vulcanization of NR. The rate constant k6 of the reaction that turned polysulphidic cross-links into the modified main chain was higher than that of desulfuration reaction of polysulfidic cross-links （k3 ）. The activation energies （Ea2, Ea3, and Ea6） of the formation, desulfuration, and decomposition of polysulfidic cross-links were 87.57,102.34, and 95.01 kJ · mol^-1, respectively. Activation energy （Eas） of the reaction that turned the cross-link precursors into the modified main chain was 82.67 kJ · mol^-1. It could be concluded that the proportion of polysulphidic cross-links was higher than mono- and di- sulphidic cross-links during induction and curing periods, mono- and di- sulphidic cross-links increased as curing temperature rose. In the temperature range of 140 - 160 ℃, the amounts of polysulphidic cross-links were similar. However, over 160℃, mono- and di- sulphidic cross-links increased rapidly. Moreover, cross-link density of the vulcanizates was determined from the equilibrium-swelling data. A chemical probe detected the concentration of polysulphidic cross-links of vulcanizates. The change trend of the results predicated from equation corresponded to that of the experimental results.     

十水草酸镧的热分解及其动力学分析

用热重-差热(TG-DTA)技术,在不同升温速率条件下,研究了十水草酸镧在空气气氛下的热分解过程.分别采用Ozawa-Flynm-Wall法、Kissinger法、Crane法和同步热分析法确定其热分解动力学参数.TG-DTA曲线表明:十水草酸镧分解为四个阶段,前两个阶段为脱水过程,后两个阶段为La_2(C_2O_4)_3的分解过程.实验计算得出四步反应表观活化能E分别为83.92、76.04、136.26、162.61 k J·mol-1左右;指前因子A分别为4.92×10~(10)、6.1×10~7、2.1×10~9、8.46×10~6s-1左右;反应级数n均为1左右,并用Coats-Redfem积分法得出第三步分解机理受F1控制.     

Synthesis and Electrical Properties of La0.8Sr0.2-xCaxCo0.9Fe0.1O3-δ

Ａｎｉｍｐｏｒｔａｎｔｇｏａｌｉｎｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆｓｏｌｉｄｏｘ ｉｄｅｆｕｅｌｃｅｌｌｓ (ＳＯＦＣｓ)ｉｓｔｏｒｅｄｕｃｅｔｈｅｏｐｅｒａｔｉｎｇｔｅｍ ｐｅｒａｔｕｒｅｏｆｔｈｅｆｕｅｌｃｅｌｌｓｔａｃｋｆｒｏｍ 10 0 0℃ｔｏｂｅｌｏｗ85 0℃ｓｏａｓｔｏｇｅｔａｎｏｐｔｉｍｕｍｔｒａｄｅ ｏｆｆｂｅｔｗｅｅｎｐｅｒ ｆｏｒｍａｎｃｅａｎｄｌｉｆｅｔｉｍｅｏｆｔｈｅｓｔａｃｋａｎｄｔｏｒｅｄｕｃｅｔｈｅｏｖｅｒａｌｌｓｙｓｔｅｍｃｏｓｔ[1] .Ｔｏａｃｈｉｅｖｅｔｈｉｓｄｅｓｔｉｎａｔ…     

Preparation of Sm_2Fe_(17)Alloys in Ca-Sm_2O_3-Fe System

Sm2Fe17alloyisanimportantprecursorforthe preparationofSm2Fe17Nxmagnet.Sincethenitrogen containedSm2Fe17(Sm2Fe17Nx)alloy,asapermanent magnetmaterial,possessesahigherCurietempera ture,largeranisotropyfield,betterresistancetooxi dationandthermalstability,and…     

Thermochemical Study on Coordination Complex of Neodymium Trichloroacetic Acid with 8-Hydroxyquinoline

Ｂｏｔｈｒａｒｅｅａｒｔｈｉｏｎｓ[1 ] ａｎｄ 8 ｈｙｄｒｏｘ ｙｑｕｉｎｏｌｉｎｅｐｏｓｓｅｓｓａｎｔｉｂａｃｔｅｒｉａｌｆｕｎｃｔｉｏｎ[2 ] ,ａｎｄｔｈｅｉｒｃｏｍｐｌｅｘｅｓｈａｖｅｍｏｒｅｐｏｗｅｒｆｕｌｄｉｓｉｎ ｆｅｃｔｉｏｎ .Ｔｈｅｂｉｎａｒｙｃｏｍｐｌｅｘｅｓｏｆｔｈｅｍｗｅｒｅｒｅ ｐｏｒｔｅｄａｓｅａｒｌｙａｓ 1 96 3.Ｍｅａｎｗｈｉｌｅ ,ｔｈｅｒｅ ｓｅａｒｃｈｏｎｔｈｅｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｏｆｔｈｅｍｈａｓｂｅｃｏｍｅｖｅｒｙａｃｔｉｖｅｉｎｒｅｃｅｎｔｙｅａｒｓａｎ…     

稀土对T91耐热钢动态再结晶行为影响

采用Gleeble-1500热/力模拟试验机进行压缩试验,研究了不同变形条件下微量稀土对T91耐热钢动态再结晶行为的影响.分析绘制了稀土加入前后实验钢的真应力-真应变曲线、再结晶-温度-时间图、再结晶图及功率耗散图,并计算了高温下实验钢的再结晶激活能.在变形温度为850~1100℃,变形速率为0.004~10 s^-1变形条件下,变形温度越高和变形速率越低,动态再结晶越容易发生.稀土加入会产生固溶强化,稀土元素与碳原子发生交互作用,且在晶界处或晶界附近偏聚,使变形抗力与峰值应变均增大,再结晶激活能由354.6 kJ·mol^-1提高到397.2 kJ·mol^-1.另外,稀土会显著推迟再结晶发生时间,扩大再结晶的时间间隔,推迟再结晶动力学过程.     

间羧基苦胺酸偶氮变色酸与铜的显色反应及铝合金中铜的光度法测定

在磷酸介质中 ,Cu 与间羧基苦胺酸偶氮变色酸反应生成络合比为 1∶2的稳定蓝色络合物 ,络合物在 663nm处有最大吸收 ,其摩尔吸光系数为 2.88× 10 4,铜含量在 0～ 2 5 μg/2 5mL遵守比尔定律 ,方法用于铝合金中铜含量的测定 ,铜的标准加入回收率在 95 %～ 10 2 %之间 ,结果满意。     

DIBK-TBP萃取分离锆铪的热力学研究

对二异丁基甲酮(DIBK)和TBP从HSCN介质中协同萃取锆铪的性能及热力学进行研究,采用对数函数外推法求得DIBK-TBP体系萃取反应的热力学平衡常数分别为log(K12,Zr)=4.73和log(K12,Hf)=-5.09,锆铪与SCN-形成配合物Zr(SCN)3+和Hf(SCN)3+的稳定性常数分别为1×109.86和1×10-0.80,而铪的分配比在硫氰酸盐存在时要大于锆的分配比,说明过渡金属离子锆和铪在硫氰酸盐存在时与一般金属离子与配位体形成的配合物的稳定性常数愈大,金属离子的分配比愈大的规律相矛盾,并计算出萃取反应的焓变分别为ΔHZr=-11.43 kJ.mol-1和ΔHHf=-7.80 kJ.mol-1,说明对锆铪的萃取反应为放热反应,升高温度不利于萃取反应的进行,常温下自由能变分别为ΔGZr=-26.54 kJ.mol-1和ΔGHf=28.57 kJ.mol-1,熵变分别为ΔSZr=51.54 J.(K.mol)-1和ΔSHf=-124.07 J.(K.mol)-1,说明铪离子比锆离子更易与SCN-形成配位键,从而生成中性分子Hf(SCN)4与有机相发生溶剂化作用而进入有机相中。     

Ti和Si对铁液黏度和凝固性质的影响

通过振荡杯高温熔体黏度仪对含Ti铁液的黏度进行测定,研究在冷却过程中Ti、Si对铁液黏度、黏流活化能、凝固温度以及凝固速度的影响.发现含Ti铁液在发生凝固以前,其黏度差别不大,黏流活化能为37.07~44.03 kJ·mol^-1.Ti含量对铁液的凝固温度和凝固速度影响较大,Ti含量高的铁液开始凝固温度较高,而且凝固速度更快.硅含量低是钒钛铁液凝固温度低的主要原因.     

Kinetics of the thermal dissociation of Co4S3 under reduced pressure

Kinetics of the thermal dissociation of Co₄S₃ were investigated under reduced pressures of 5 × 10^-2 and 1.5 × 10^-4 mm Hg in the temperature range 1120° to 1405°C. The initial 10 pct dissociation was found to take place in accordance with a linear rate law, with activation energies of 20 and 17 kcal per mole under low and high vacuums, respectively. Subsequent dissociation up to about 35 pct was observed to be parabolic in nature, with activation energies of 38 and 40 kcal per mole under the respective vacuums. Further dissociation up to about 90 pct was found to fit into another linear rate law, with activation energies of 47 and 49 kcal per mole under the reduced pressures of 5 × 10^-2 and 1.5 × 10^-4 mm Hg, respectively. Beyond 90 pct, the dissociation was found to be very sluggish. These results have been interpreted with the help of the Co-S phase diagram. It has also been possible to achieve more than 99 pct dissociation of Co₄S₃ in 2 hr at 1405°C under low vacuum or 1355°C under high vacuum.     

Analysis of the reaction coordinate of photosynthetic water oxidation by kinetic measurements of 355 nm absorption changes at different temperatures in photosystem II preparations suspended in either H2O or D2O

Flash-induced absorption changes at 355 nm were measured at different temperatures within the range of 2 degrees C S2) = 14 kJ/mol, EA(S2-->S3) = 35 kJ/mol, and EA(S3-->-->S0 + O2) = 21 kJ/mol for theta > 11 degrees C, 67 kJ/mol for theta < 11 degrees C in PS II core complexes dissolved in H2O; (b) replacement of exchangeable protons by deuterons causes only minor changes ( S2, S2 --> S3, and S3 -->--> S0 + O2, respectively. The corresponding values of PS II membrane fragments are 1.3, 1.3, and 1. 4. Based on these results and corresponding EA data reported in the literature for PS II membrane fragments from spinach [Renger, G., & Hanssum, B. (1992) FEBS Lett. 299, 28-32] and PS II particles from the thermophilic cyanobacterium Synechococcus vulcanus Copeland [Koike, H., Hanssum, B., Inoue, Y., & Renger, G. (1987) Biochim. Biophys. Acta 893, 524-533], the reaction coordinate of the redox sequence in the WOC is inferred to be almost invariant to the evolutionary development from cyanobacteria to higher plants. Furthermore, the rather high activation energy of the S2 --> S3 transition provides evidence for a significant structural change coupled with this reaction. Implications for the mechanism of photosynthetic water oxidation are discussed.     

CaCO3抑制三氧化钼挥发热力学及动力学分析

三氧化钼（MoO₃）的挥发特性是导致Mo收得率较低的主要原因,采用CaCO₃对MoO₃进行稳定化处理是抑制MoO₃挥发的行之有效的方法。从热力学及动力学角度研究了CaCO₃和MoO₃低温固相反应。结果表明,二者在450℃就可反应生成稳定CaMO₄,600～700℃反应速率较快且MoO₃未开始挥发,在此温度区间对MoO₃预处理效果较好。采用Coats-Redfern法计算了不同升温速率下CaC0₃和MoO₃固相反应动力学参数,活化能（E）和指前因子（A）分别为167.45 kJ/mol、1.22×10⁷s^-1,速率常数k=1.22×10⁷×exp（-20 140/T）。     

Synthesis, Structure and Ionic Conductivity of La2／3-x Li3x MoO4

AlargenumberofM0 .5A0 .5M′O4 (M :rareearthion ,Bi3+,Fe3+,Cr3+,etc .A :alkaliion ,Cu+,Ag+,etc .M′ :Mo ,W )withtetragonalscheelite typestructurehavegoodcatalyticproperties .Aslumines centsubstrates ,theyhaveexcellentsensitizationtolu minescenceofrareearthion .Manyresearchesontheirstructure ,catalytic ,magneticandluminescentproper tieshavebeenmadesince 196 0s[1～ 10 ] .Thegeneralformulaforcompoundswiththetetragonalscheelite typestructureisAM′O4 wherethecationM′istetrahe drallycoordinat…     

铸轧AZ31镁合金的高温拉伸性能

研究了铸轧AZ31镁合金的高温拉伸性能和变形机制.在300~450℃条件下,分别以恒定拉伸速率10^-3 s^-1和10^-2 s^-1进行拉伸至失效试验,在真实应变率为2×10^-4~2×10^-2 s^-1的范围内进行变应变率拉伸试验.当拉伸速率为10^-2s^-1时,试样在400℃和450℃的延伸率均超过100%;当拉伸速率为10^-3 s^-1时,试样在400℃和450℃的延伸率均超过200%,该条件下的应力指数ⁿ≈3,蠕变激活能^Q=148.77 kJ·mol^-1,变形机制为溶质牵制位错蠕变和晶界滑移的协调机制.通过光学金相显微镜和扫描电子显微镜观察显示试样断口处存在由于发生动态再结晶和晶粒长大而形成的粗大晶粒,断裂形式为空洞长大并连接导致的韧性断裂.