pH值对AZ31镁合金表面植酸转化膜在模拟体液耐腐蚀性能的影响

采用沉积的方法在镁合金AZ31表面制备植酸转化膜并研究了pH值的影响. 利用极化曲线和电化学阻抗谱方法测定其耐腐蚀性能,用扫描电子显微镜观察转化膜的表面微观结构,用能谱测定转化膜的组成元素. 在理论上通过热力学的方法分析最佳pH值. 植酸转化膜可以提高镁合金AZ31的耐腐蚀性能. 当植酸溶液的pH=5时腐蚀效率达到了89.19%,此时腐蚀电位正移了156 mV,腐蚀电流密度与没有处理的试样相比减小了约一个数量级. 热力学分析表明植酸转化膜的耐腐蚀性能不仅受植酸根离子和镁离子浓度的影响,也与氢气释放的速率有关.     

AZ31镁合金表面聚吡咯的化学氧化合成及其耐蚀性能

以对甲苯磺酸钠为掺杂剂, 三氯化铁为氧化剂, 用化学氧化聚合法在AZ31 镁合金表面制备聚吡咯(PPy)膜. 采用傅里叶变换红外(FTIR)光谱分析了镁合金表面聚吡咯膜结构, 通过电化学极化曲线、电化学阻抗谱(EIS)研究了其耐蚀性能, 通过扫描电子显微镜(SEM)、X射线能量散射谱(EDS)分析了表面形貌和成分. 和镁合金裸样相比, 聚吡咯膜对镁合金腐蚀有一定的抑制作用. 硅烷预处理改善了镁合金/聚吡咯体系的耐腐蚀性能, 使腐蚀电位较镁合金裸样正移了110 mV, 电流密度减小了约2个数量级.     

硼砂-对苯二甲酸电解液中AZ91D镁合金的阳极氧化处理

研究了硼砂-对苯二甲酸环保型电解液中AZ91D镁合金的阳极氧化.考察了对苯二甲酸对镁合金阳极氧化过程及其氧化膜性能的影响,并利用扫描电镜(SEM)、X射线衍射(XRD)、能量散射谱(EDS)、动电化极化和电化学交流阻抗谱(EIS)等进行了分析表征.结果表明,对苯二甲酸的浓度对阳极氧化成膜过程、氧化膜的表面形貌、厚度、相结构和耐腐蚀性能都有重要影响.在硼酸盐电解液中加入适量的对苯二甲酸后,氧化电流密度降低,过度放电现象受到了明显的抑制,所制得的阳极氧化膜的质量也有了显著改善.氧化膜表面变得光滑、致密,膜厚度略有降低.氧化膜与镁合金基底的结合更紧密,而且其耐腐蚀性能也得到了明显增强.该研究对于镁合金阳极氧化处理工艺的环保化及阳极氧化膜质量的提高都具有积极意义.     

镁合金表面镧、钐稀土防护膜研究

利用化学转化处理在AZ31镁合金表面制备两种非铈稀土防护膜--镧膜和钐膜.采用电化学阻抗谱(EIS)方法评定膜层的防护效果,采用扫描电子显微镜(SEM)和能量色散谱(EDS)表征膜层的表面形貌及组成.结果表明:镁合金表面镧、钐转化膜均由相应的稀土氢氧化物/氧化物及基体金属氢氧化物/氧化物组成;镧转化膜均匀、致密,对基体金属防护效果好,而钐转化膜呈碎片状,部分覆盖基体表面,防护作用很弱.初步探讨了成膜机制.     

AZ31镁合金表面镧转化膜的形成机制

通过化学浸泡方法在AZ31镁合金表面制备了高防护性镧转化膜。X射线光电子能谱(XPS)对膜组成的测试结果表明:镧转化膜主要由氢氧化镧组成,另外还有少量氢氧化镁及碳酸镧、碳酸镁成分。电化学技术测量成膜过程中试样开路电位(OCP)的变化,分为剧增、降低、缓慢平稳增长3个阶段。原子力显微镜(AFM)对膜层形貌的表征结果表明:镧转化膜最初为均匀致密膜,后出现纤维结构,然后纤维结构不断稳定发展。在上述结果基础上讨论了镧转化膜的形成机制:成膜过程分为紧密层形成、纤维层萌生、纤维层稳定生长3个特征阶段,前两个阶段发生非常迅速,后一阶段持续时间较长,是成膜的主要过程。     

Galfan镀层镧盐转化膜的制备和耐蚀性能研究

将热浸镀Galfan钢板浸入含有20 g·L-1La(NO3)3·6H2O,10 m L·L-1H2O2,0.1 g·L-1Na F的处理液中,在70℃下处理10 s~30 min,从而在其表面获得镧盐转化膜。采用扫描电子显微镜(SEM)观察膜层的微观形貌,能谱仪(EDS)分析膜层的化学成分。采用中性盐雾试验和电化学极化曲线来研究膜层的耐蚀性能。结果表明,镧盐转化膜在晶界或相界等活性区域优先成膜并迅速生长,膜层形成不均匀。随着处理时间的延长,镧盐转化膜逐渐增厚,膜层的裂纹变多、扩大并脱落;膜层主要由Zn,Al,O和La元素组成。与未处理的热浸镀Galfan镀层相比,镧盐转化膜的腐蚀电流密度显著降低,极化电阻显著提高,基体耐腐蚀性能明显提高。     

镧和铈钝化镀锌钢板的研究

采用镧盐和铈盐钝化镀锌钢板,通过醋酸铅点滴,失重,中性盐雾和电化学交流阻抗实验检测试样耐腐蚀性能.实验结果显示镧盐和铈盐钝化试样的耐黑变时间分别为70和44 s;腐蚀速率为1.9979×10-3g·m-3·h-1和3.6523×10-3g·m-2·h-1;抗白锈时间为54和46 h;阻抗值大幅提高;实验结果表明镧盐和铈盐钝化处理能大幅度提高试样耐腐蚀性,镧盐转化膜相对于铈盐转化膜更耐腐蚀.清漆划格实验表明清漆在稀土钝化后的试样表面附着力良好;原子力扫描结果显示稀土转化膜由大量不定型的固体颗粒不均匀沉积而成;EDS检测结果表明镧盐转化膜由O,Fe,Zn和La组成,铈盐转化膜由O,Fe,Zn和Ce组成.     

不同添加剂对铝表面铈转化膜耐蚀性的影响

分别用聚二甲基硅氧烷(PDMS)和甲基丙烯酸甲酯(MMA)作为添加剂,将1060铝浸于稀土铈盐的溶液中,在其表面形成化学转化膜,通过扫描电镜、极化与阻抗测试等分析转化膜的形貌,并研究其耐腐蚀性能.结果表明,加入添加剂后转化膜形貌更加均匀、致密,耐腐蚀性能明显提高.PDMS有消泡作用,促进铈离子沉淀,提高膜层的平整性.MMA可发生聚合,参与转化膜的形成,改善膜层的致密性.分别在PDMS为1.48g·L-1和MMA为0.96g·L-1时得到最佳效果,浓度过低或过高都会抑制转化膜的转化.     

镁合金化学转化膜的制备及其性能研究

在磷酸钠-磷酸二氢铵-高锰酸钾体系中对镁合金进行化学转化处理.研究了磷酸钠、磷酸二氢铵、高锰酸钾、温度、时间和添加剂对转化膜性能的影响.通过对转化膜结构、成分及性能的测试评价,得到了性能较好的化学转化溶液配方:Na3PO4为5g·L-1,NH4H2PO4为15 g· L-1,KMnO4为1g· L-1,添加剂(NH4)6 Mo7O24为0.5g·L-1.由SEM可观察到转化膜的表面成“干枯河床”状.XRD和EDS检测表明,膜层的主要成分是Mg,Al12 Mg17和无定形相,膜层表面主要有Mn,Mg,K,O和Al等元素组成.腐蚀实验和电化学测试表明,添加剂能够降低转化膜的腐蚀率,转化膜较基体的腐蚀电位正移了0.73 V,提高了镁合金的耐蚀性.     

铅基稀土合金作为正极板栅的阳极膜性能

采用交流阻抗（EIS)、交流伏安（ACV）、循环伏安(CV)、腐蚀失重实验等方法研究了铅-钙-锡-铝-银合金中添加混合镧铈稀土在硫酸溶液中的阳极行为。 实验结果表明,混合镧铈稀土的添加能有效抑制阳极Pb(Ⅱ)膜的生长,降低Pb电极表面生成的Pb(Ⅱ)膜氧化膜电化学反应阻抗,改善阳极膜的导电性。 增强合金的耐腐蚀性能,并且增加析氧的过电位,抑制氧气的析出,降低电池的早期容量损失。 混合镧铈稀土的添加有利于提高电池的深循环寿命。 当镧铈混合稀土质量分数为0.5％时,各方面综合性能更优,效果更好。     

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。     

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。     

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.     

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.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

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.     

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.     

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。