离子注入钇对Co-30Cr-6Al合金氧化动力学及氧化膜粘附性的影响

利用热天平与声发射同步测试技术研究了Co-30Cr-6Al合金中离子注入2×10~(17)Y~+/cm~2对合金氧化速率及氧化膜粘附性的影响。结果表明,1000℃氧化时,钇能降低合金的氧化速率,1100℃氧化时,由于未注钇合金形成了Al_2O_3内层膜,其氧化速率反而降低。两种氧化条件下钇都显著地改善了氧化膜的抗剥落性。尽管如此,1100℃/10h氧化后注钇合金的氧化膜于冷却过程中较未注钇合金氧化膜易于发生破裂。1100℃更长时间氧化,注钇和未注钇两种合金的氧化膜于恒温过程中即发生破裂。     

电活性铁氰化镍膜电极对稀土钇的电控离子分离

通过电沉积方法分别在镀铂石英晶片和铂基底上制备了电活性铁氰化镍膜,并考察了膜电极在含钇离子溶液中的电控离子交换性能. 在0.1 mol·L^-1的硝酸钇溶液中,使用循环伏安法及石英晶体微天平技术测试考察了铁氰化镍膜对钇离子的置入释放性能及对应的质量变化,同时比较了铁氰化镍膜电极在Y(NO₃)₃和Sr(NO₃)₂溶液中的电化学性能. 在0.1 mol·L^-1 [Y(NO₃)₃ + Sr(NO₃)₂]混合溶液中,通过循环伏安法分析了薄膜对Y³⁺/Sr²⁺离子的选择性. 用扫描电子显微镜观察了铁氰化镍膜的表面形貌,并通过X射线光电子能谱仪测定了膜在氧化和还原状态下的元素组成. 结果表明,铁氰化镍膜在含Y³⁺溶液中具有良好的离子交换行为,其中氧化过程薄膜质量减少,对应着钇离子的释放;还原过程薄膜质量增加,对应钇离子的置入;在0.0 V或0.9 V调控膜电极的氧化还原状态实现对钇离子的有效分离.     

钇离子注入的H13钢的抗氧化研究

研究了强束流钇注入的H13钢高温氧化特性,同时分析了氧化层的结构和钢中注入钇后抗氧化的原因。结果表明,钇的注入改变了钢表面的氧化模式,同未注入区相比,注入区的氧化膜致密,与基体结合好,氧化速率下降。     

硫和钇在含钇Ni3Al基IC6合金高温氧化过程中的界面行为

利用电子探针的元素线扫描技术,研究了添加钇后的ＩＣ６合金中钇和硫在１１００℃氧化时的界面行为,发现加钇后,由于在金属熔体中能脱硫同时形成的富钇相也能在高温氧化过程中作为硫的陷阱,减少了硫在氧化物基体界面上的扩散偏聚,提高了氧化物／基体之间的结合力,使得所形成的氧化物不易剥落,从而提高合金的高温氧化能力。钇提高ＩＣ６合金高温抗氧化能力的另一个原因是,钇能扩散到所形成的氧化物的晶界,提高氧化物的晶 界     

钛表面二氧化钛膜中氧空位点缺陷传输性能的电化学研究

"钛/TiO2氧化膜/溶液"界面电极体系的电化学性能主要决定于钛表面的TiO2氧化物膜.本文利用多种电化学技术,结合半导体物理的Mott-Schottky分析和Einstein方程,研究了金属钛在1.0mol·L-1HClO4溶液中表面半导体TiO2氧化膜的生长及氧化膜中氧空位点缺陷在外加电场作用下的传输性能,并根据离子性电荷传输与电子性电荷传输对电场变化响应时间之不同特点,确定氧化膜中点缺陷扩散系数.结果表明,电极电位或阳极析氧反应对稳态电流(iss)、氧化膜的阳极化常数(α)、膜中电场强度()、以及膜中氧空位点缺陷的扩散系数(D0)等重要物理化学参数,均有显著影响,并依据氧化膜中的结构变化进行分析.     

注入Y离子对Ni3Al合金高温氧化行为的影响

以40 KeV的能量和3×1017 /cm2的剂量在Ni3Al合金中注入Y离子, 利用热重分析、 X射线衍射、扫描电镜、能谱分析和划痕分析等技术研究了离子注入对其900 ℃恒温氧化行为的影响. 结果表明 注入Y离子不仅改变了合金的氧化动力学, 而且改变了其氧化机理. 注入Y离子后合金氧化产物中的NiO含量大为增加, 从而降低了合金的抗氧化性能. 但Y离子的注入使NiO晶粒细化, 增强了氧化膜的塑性和粘附性.     

新型锂离子电池三维结构泡沫NiO电极的制备及电化学性能

通过固相氧化方法,以三维结构泡沫镍为基体和金属镍源,制备了三维结构泡沫氧化镍负极。XRD和SEM结果表明,经500℃氧化处理,泡沫镍基体上形成了NiO微米级的致密活性氧化层。通过充放电测试和循环伏安测试研究了电极的电化学性能,结果表明,三维结构泡沫氧化镍在放电电位区间0.05～3.2VvsLi/Li+,0.2C倍率下充放电,初始容量损失为20%,且经40次循环后,质量比容量为950mAh·g-1,三维泡沫氧化镍电极具有优异的循环容量保持性能。三维泡沫氧化镍具有的大的活性表面积,降低了界面反应的极化,从而提高了NiO电极的倍率放电性能。     

表面涂覆CeO_2对Co－40Cr合金氧化行为的影响

研究了表面涂覆ＣｅＯ２对Ｃｏ４０Ｃｒ合金在１０００℃、空气中恒温氧化和循环氧化的影响。并用扫描电镜／能谱（ＳＥＭ／ＥＤＸＳ）、电子探针（ＥＰＭＡ）、高分辨电子显微镜（ＨＲＥＭ）等测试手段对氧化膜的形貌和成分进行了观察分析。此外，还用声发射（ＡＥ）方法对氧化膜在热应力作用下发生的开裂和剥落进行了监测。结果表明，涂覆ＣｅＯ２后极大地提高了合金的抗恒温氧化和抗循环氧化性能。研究表明，涂覆的ＣｅＯ２主要以细小颗粒的形式高度弥散存在于氧化膜的外表面，并且主要分布于氧化物晶界上，其中部分ＣｅＯ２以更加细小（１０～２０ｎｍ）的形式存在于Ｃｒ２Ｏ３晶粒内部。这些弥散分布的ＣｅＯ２颗粒改变了Ｃｒ２Ｏ３氧化膜的生长机制，通过阻碍Ｃｒ３＋阳离子向外扩散，降低了氧化膜的生长速率，细化了氧化膜的晶粒并提高了膜的高温塑性，使氧化膜在基体上有较好的粘附性     

电活性质点Fe^2^+离子在六氰亚铁钒薄膜中的传输

电活性质点Fe^3^+可穿透六氰亚铁钒薄膜在玻璃碳基体电极表面于较负电位处直接氧化, 也可经VHF膜中氧化还原点位的媒介在较正电位处理膜-溶液界面及膜内部发生催化氧化. 两个过程分别在用VHF修饰过的旋转GC电极上的伏安曲线中产生, 可明确分辨的第一波和第二波. 第一波的极限电流受Fe^2^+离子在溶液中和膜中的扩散速率控制.VHF薄膜对Fe^2^+离子的透过能力, kDm/d, 为10^-^3-10^-^2cm.s^-^1数量级, 随膜厚度增大而减小, 不随溶液中Fe^2^+离子浓度改变.     

钇对激光熔覆钴基合金组织和高温腐蚀性能的影响

系统研究了在2Cr13和1Cr18Ni9Ti钢表面激光熔覆并含钇的钴基合金层的组织和表面涂盐的高温腐蚀行为,同时着重探讨了钇的作用。结果表明,添加钇的钴基合金覆层组织更细密,且与基体结合牢固;在表面涂有75％Na_2SO_4+25％NaCl盐膜条件下,其耐高温腐蚀性能获得极大提高;添加0.874％Y后,其表面能形成连续致密的保护性氧化膜,可阻碍氧、硫的扩散浸入,使其性能更佳。同时,添加钇后,内氧化层浅而细密,对内层合金元素向外表面扩散迁移起屏障作用。     

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。     

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.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

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^-。     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

微量钙的测定方法研究进展

介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。     

Stages of thermal decomposition of sodium oxo-salts of sulphur

Thermal behaviour of sodium oxo-salts of sulphur: Na₂SO₄, Na₂S₂O₇, Na₂S₂O₆, Na₂SO₃, Na₂S₂O₅, Na₂S₂O₄, Na₂S₂O₃, Na₂S₃O₆ and of sulphides Na₂S and Na₂S₂ was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase analysis.     

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.