钇对Fe-Cr-Al合金氧化膜粘附性的影响

利用热重分析,扫描电镜及能谱分析等手段研究了合金中弥散分布的Ｙ,Ｙ２Ｏ３及离子注入Ｙ＾＋对Ｆｅ－２３Ｃｒ－５Ａｌ合金１１００℃恒温氧化行为的影响。不含Ｙ的Ｆｅ２３Ｃｒ５Ａｌ合金氧化膜起皱,长时间氧化后冷却过程中膜发生开裂剥落。合金离子注入１＊１０＾１７Ｙ＾＋／ｃｍ＾２后氧化膜粘附性得到了改善。合金中加入弥散的Ｙ或Ｙ２Ｏ３改变了氧化膜形貌,膜平坦致密,不开裂剥落,不含Ｙ的Ｆｅ２３Ｃｒ５Ａｌ合金氧化膜皱褶形貌的形成及膜发生剥落的原因与氧化膜生长机制及合金中Ｓ的界面偏聚有关,Ｙ提高Ｆｅ－Ｃｒ－Ａｌ合金氧化膜粘附性的原因主要在Ｙ易与Ｓ形成稳定的硫化物,从而阻止了Ｓ在膜／合金界面偏聚。Ｙ提高Ａｌ２Ｏ３膜粘附性的原因还在于改变了Ａｌ２Ｏ３膜的生长机制。     

稳定金属卟啉催化环己烷羟基化反应

在稳定金属卟啉一次氯酸钠模拟体系中，环己烷常温常压下氧化成环己醇和微量环己酮。金属卟啉的活性依次下降，ＦｅＴＤＣＭＮＰＰβ－Ｂｒ８．Ｃｌ〉ＦｅＴＤＣＰＰβ－Ｂｒ．Ｃｌ〉ＦｅＴＤＣＭＮＰＰ．Ｃｌ》ＦｅＴＰＰ．Ｃｌ其稳定性依同样的顺序递减，锰卟啉的活性低于相应的铁卟啉，其活性下降顺序与铁卟啉相同。在金属卟啉基间引入强吸电子ＮＯ２取代基能提高它的活性与稳定性，但卟啉环上β－Ｂｒ取代基的作用更强。     

Ce^3＋在钼钛矿型KMF3（M=Mg,Ca,Sr,Ba）基质中的发光特性

采用高温固相反应法，在Ａｒ气氛中合成了ＫＭＦ３（Ｍ＝Ｍｇ，Ｃａ，Ｓｒ，Ｂａ）基质化合物和掺杂Ｃｅ＾３＋的磷光体。经Ｘ射线衍射分析确定，ＫＭｇＦ３和ＫＣａＦ３属于立方晶系、钙钛矿型结构，ＫＳｒＦ３和ＫＢａＦ３具有类似的结构。测定了ＫＭＦ３：Ｃｅ＾３＋的发光光谱，观察到与其结构对应的分为二种不同的光谱结构，讨论了Ｃｅ＾３＋的取代格信。     

簇合物SFeCO2（CO）9的合成方法研究

簇合物ＳＦｅＣｏ＿２（ＣＯ）＿９的合成方法研究赵转云，武和平，殷元骐（中国科学院兰州化学物理研究所兰州７３００００）ＳＦｅＣｏ＿２（ＣＯ）＿９是一四面体构型的潜手性簇合物，由此为前体，合成簇合物ＳＦｅＣｏＭ（ＣＯ）＿ｘ（Ｍ＝Ｃｒ，Ｍｏ，Ｗ，Ｒｈ，Ｒｕ...     

碳氧定向反应Fe／C系催化剂中助剂的作用

本文采用微反－色谱，穆斯堡尔谱及ＸＰＳ等分析手段，研究了碳氧定向反应生成ＣＯ的Ｆｅ／Ｃ系催化剂中助剂Ｋ，Ｃｒ的作用。结果表明，助剂能大大提高定向氧化反应活性，并能稳定主活性组分的价态和提高其分散度。复合催化剂Ｆｅ－Ｋ－Ｃｒ／Ｃ无论在催化活性，稳定性及抗烧结性能方面都优于单组分催化剂。     

Ce~（3＋）在钙钛矿型KMF_3（M＝Mg、Ca、Sr、Ba）基质中的发光特性

采用高温固相反应法，在Ａｒ气氛中合成了ＫＭＦ３（Ｍ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）基质化合物和掺杂Ｃｅ３＋的磷光体。经Ｘ射线衍射分析确定，ＫＭｇＦ３和ＫＣａＦ３属于立方晶系、钙钛矿型结构，ＫＳｒＦ３和ＫＢａＦ３具有类似的结构。测定了ＫＭＦ３∶Ｃｅ３＋的发光光谱，观察到与其结构对应的分为二种不同的光谱结构，讨论了Ｃｅ３＋的取代格位     

FeO4^2—与ClO^—共存体系的氧化还原滴定分析法

在重铬酸钾容量法测Ｆｅ＾２＋和硫酸亚铁铵容量法测Ｃｒ（Ⅳ）的基础上,提出ＦｅＯ４＾２－与ＣｌＯ＾－共存体系的氧化还原滴定分析法。该方法实用、可靠、对样品分析,结果令人满意。     

SrFeCo0.5O3.25+δ粉体的合成和透氧膜的制备及其性能研究

采用甘氨酸－硝酸盐法合成Ｓｒ－Ｃｏ－Ｆｅ复合氧化物超细粉体,用以制备组成为ＳｒＦｅＣｏ０．５Ｏ３。２５＋δ（ＳＦＣ）致密透氧陶瓷膜,结果表明粉体分散性和烧结性能好,残碳量可忽略,组成符合给定的化学计量比。对ＳｒＦｅＣ０．５Ｏ３．２５＋δ陶瓷膜材料进行了相结构、微结构、电导和氧渗透性能的研究,所获得的ＳＦＣ透氧膜材料有较高的氧渗透率,并与传统的固相反应法制得的样品进行了比较。     

表面电沉积Ni—La2O3复合镀层的Fe26Cr1Mo不锈钢的氧化行为研究

Ｆｅ２６Ｃｒ１Ｍｏ不锈钢在９００℃氧化时，生成的氧化层在冷却过程中大量剥落，经表面共电沉积ＮｉＬａ２Ｏ３复合镀层后，抗热循环能力明显提高。     

杂多化合物催化性能的研究—第四周期过渡金属取代的钼磷三元杂多化合物在环己烯氧化反应中的催化作用

过渡金属单取代的杂多化合物［（ｎ－Ｃ４Ｈ９）４Ｎ］８－ｎ［ＰＺｎ＋ＢｒＭｏ１１Ｏ３９］（Ｚ＝Ｍ２＋ｎ、Ｆｅ３＋、Ｃｏ２＋、Ｎｉ２＋、Ｃｕ２＋）对以过氧化氢为氧化剂的环己烯氧化反应具有良好的催化性能．基于动力学、红外光谱及电化学方法的研究，对反应机理作了讨论．认为这类取代的杂多化合物与Ｈ２Ｏ２作用形成了活性中间体，活性中心为参与取代的过渡金属离子．     

还原型和氧化型谷胱甘肽在磁性Fe3O4纳米粒子上的吸附组装

研究了Fe3O4磁性纳米粒子在水溶液中对还原型谷胱甘肽(GSH)和氧化型谷胱甘肽(GSSG)的吸附。分别测定了两种物质在不同温度下的吸附等温线,比较了研究结果,并用Freundlich吸附等温式对数据进行拟合,根据公式计算出相关的吸附热力学函数值,研究了碳化二亚胺含量和pH对吸附结果的影响,并从吸附量和脱附实验结果探讨了其可能的吸附机理。结果表明,还原型谷胱甘肽和氧化型谷胱甘肽在Fe3O4表面的吸附是不可逆的,加入强电解质基本不能够脱附,两者间形成了部分共价键。     

Measurements of interface stress of silicon dioxide in contact with water-phenol mixtures by bending of microcantilevers

We use the bending of silicon microcantilevers to measure changes in mechanical stress at interfaces between phenol-water mixtures and SiO(2). The curvature of the microcantilever is measured by an optical system that combines a rapidly scanning laser beam, a position-sensitive detector, and lock-in detection to achieve a long-time stability on the order of 6 mN m(-1) over 4 h and a short-time sensitivity of better than 1 mN m(-1). Thermally oxidized Si shows the smallest changes in interface stress as a function of phenol concentration in water. For hydrophilic SiO(2) prepared by chemical treatment, the change in interface stress at 5 wt % phenol in water is larger than that of thermally oxidized Si by -60 mN m(-1); for SiO(2) formed by exposure of the silicon microcantilever to ozone, the change in surface stress is larger than that of thermally oxidized Si by -330 mN m(-1).     

Interfacial chemistry in internally oxidized (Cu,Mg)-alloys

(Cu,Mg) alloys are internally oxidized at different oxygen chemical potential at 900°C. Oxidation scale microstructure is studied by SEM and TEM. MgO forms as large magnesia agglomerates without any special orientation relationship and isolated cubo-octahedral topotaxial MgO precipitates, the shape of which varies with decreasing oxygen activity from octahedral to cubic. The interfaces of the cubo-octahedral precipitates are studied in detail by CTEM, HREM and EELS. At the highest oxygen activity, important rigid-body contraction/expansion across the interface is found together with a strong modification in the interfacial electronic structure (compared to the adjacent bulk phases) indicating important hybridization of O 2p and Cu 3d states. Both suggest oxide bonding. At lower oxygen activity, interfaces show increasing structural disorder in the copper phase and microfaceting or terracing of the interfacial plane; the intensity of interfacial ELNES features associated to the O 2p and Cu 3d hybridization diminishes and finally disappears with decreasing oxygen activity. Changes with oxygen chemical potential in precipitate morphology, interface atomic and electronic structure are explained by Gibbs’ adsorption/desorption of excess oxygen to the interface. Adsorption isotherms are modeled for various configurations and compared to the experimental results.     

Electrochemical,Chemical and Enzymatic Oxidations of Phenothiazines

The oxidation of several phenothiazine drugs (phenothiazine, promethazine hydrochloride, promazine hydrochloride, trimeprazine hydrochloride and ethopropazine hydrochloride) has been carried out in aqueous acidic media by electrochemical, chemical and enzymatic methods. The chemical oxidation was performed in acetic acid with hydrogen peroxide or in formate buffers using persulfate. The enzymatic oxidation was performed in acetate or ammonium formate buffer by the enzyme horseradish peroxidase in the presence of H₂O₂. Molecules with, in the lateral chain, two carbon atoms (2C) separating the ring nitrogen and the terminal nitrogen, showed two parallel oxidation pathways, that is (i) formation of the corresponding sulfoxide and (ii) cleavage of the lateral chain with liberation of phenothiazine (PHZ) oxidized products (PHZ sulfoxide and PHZ quinone imine). Molecules with three carbon atoms (3C) separating the two nitrogens were oxidized to the corresponding sulfoxide. The chemical oxidation of all the studied molecules by hydrogen peroxide resulted in the corresponding sulfoxide with no break of the lateral chain. Oxidation by persulfate yielded, for the 3C derivatives, only the corresponding sulfoxide, but it produced cleavage of the lateral chain for the 2C derivatives. The origin of the distinct oxidation pattern between 2C and 3C molecules might be related to steric effects due to the lateral chain. The data are of interest in drug metabolism studies, especially for the early search. In the case of 2C phenothiazines, the results predict the possibility of an in vivo cleavage of the lateral chain with liberation of phenothiazine oxidized products which are known to produce several adverse side effects.     

Synthesis and Characterization of New Adhesion Promoter for Grafting Conducting Polymer on Oxide Substrate

For grafting polypyrrole layers on oxidic substrates, the synthesis and characterization of a new adhesion promoter 11‐(pyrrol‐3‐yl) undecyl trimethoxysilane (PyTMS) were described in this article. The oxidation potential of PyTMS was determined by cyclic voltammetry. The grafting behavior of such an adhesion promoter on oxidized surface and chemical deposition of polypyrrole over the modified oxidized surface were studied. The adsorbed layer on the oxidized substrates thus formed was determined by both contact angle measurements and X‐ray photoelectron spectroscopy. Chemical polymerization of terminal pyrrole moieties on such substrates yielded adhesive polypyrrole films, and SEM image showed that the morphology of the polypyrrole films was influenced by the experimental conditions.     

Effects of the reaction medium on the chemical nature of the surface of carbon catalysts during esterification, ester hydrolysis, and hydrogen peroxide decomposition

The state of the surfaces of hydrogenated and some cation-substituted forms of oxidized carbons before and after liquid and gas phase catalysis of esterification, ester hydrolysis, and decomposition of aqueous hydrogen peroxide have been studied by IR spectroscopy and chemical analysis. It was found that surface reactions between functional groups and the absorbed reagents (esterification) or products (hydrolysis) or the formation of new functional groups by redox decomposition of H₂O₂ can occur alongside normal processes on the carbons. It has been shown that the biggest change in the chemical nature of the surface (along with the initial reduction of catalytic activity up to the establishment of the stationary state) occurs with the hydrogenated form of the oxidized carbons in comparisons with the cation-substituted carbons. It was observed that when ionic forms of oxidized carbons were used there was practically no change in the chemical nature of the surface, and that the catalytic activity was greater which makes them promising catalysts for the processes studied. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 34, No. 1, pp. 47–52, January–February, 1998.     

Effect of carbon fiber surface functionality on the moisture absorption behavior of carbon fiber/epoxy resin composites

Polyacrylonitrile (PAN)‐based carbon fibers were electrochemically oxidized in aqueous ammonium bicarbonate with increasing current density. The electrochemical treatment led to significant changes of surface physical properties and chemical structures. The oxidized fibers showed much cleaner surfaces and increased levels of oxygen functionalities. However, it was found that there was no correlation between surface roughness and the fiber/resin bond strength, i.e. mechanical interlocking did not play a major role in fiber/resin adhesion. Increases in surface chemical functionality resulted in improved fiber/resin bonding and increased interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composites. The relationship between fiber surface functionality and the hydrothermal aging behavior of carbon fiber/epoxy composites was investigated. The existence of free volume resulted from poor wetting of carbon fibers by the epoxy matrix and the interfacial chemical structure were the governing factors in the moisture absorption process of carbon fiber/epoxy composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Oxidation, deformation, and destruction of carbon nanotubes in aqueous ceric sulfate

A simple wet chemical method involving only ultrasonic processing in dilute ceric sulfate (CS) was used to functionalize carbon nanotubes (CNTs). Unexpectedly, single-walled and multiwalled carbon nanotubes (SWCNTs and MWCNTs) were cut, oxidized, and disintegrated by sonication in 0.1 N CS for 2-5 h. Transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectroscopy (XRD), Raman scattering, and photoacoustic Fourier transform infrared spectroscopy (FTIR) were used to probe wall damage during the chemical processing. Cyclic voltammetry and impedance spectroscopy were used to evaluate the conductivity of the CS-treated CNTs. This one-step process resulted in the destruction of SWCNTs to produce nonconducting amorphous carbon. MWCNTs were oxidized and converted to graphitic materials and amorphous carbon with retained conductivity.     

Characterization of oxidized tannins: comparison of depolymerization methods,asymmetric flow field-flow fractionation and small-angle X-ray scattering

Condensed tannins are a major class of plant polyphenols. They play an important part in the colour and taste of foods and beverages. Due to their chemical reactivity, tannins are not stable once extracted from plants. A number of chemical reactions can take place, leading to structural changes of the native structures to give so-called derived tannins and pigments. This paper compares results obtained on native and oxidized tannins with different techniques: depolymerization followed by high-performance liquid chromatography analysis, small-angle X-ray scattering (SAXS) and asymmetric flow field-flow fractionation (AF4). Upon oxidation, new macromolecules were formed. Thioglycolysis experiments showed no evidence of molecular weight increase, but thioglycolysis yields drastically decreased. When oxidation was performed at high concentration (e.g., 10 g L⁻¹), the weight average degree of polymerization determined from SAXS increased, whereas it remained stable when oxidation was done at low concentration (0.1 g L⁻¹), indicating that the reaction was intramolecular, yet the conformations were different. Differences in terms of solubility were observed; ethanol being a better solvent than water. We also separated soluble and non-water-soluble species of a much oxidized fraction. Thioglycolysis showed no big differences between the two fractions, whereas SAXS and AF4 showed that insoluble macromolecules have a weight average molecular weight ten times higher than the soluble ones.     

Electrode interfaces switchable by physical and chemical signals for biosensing, biofuel, and biocomputing applications

This review outlines advances in designing modified electrodes with switchable properties controlled by various physical and chemical signals. Irradiation of the modified electrode surfaces with various light signals, changing the temperature of the electrolyte solution, application of a magnetic field or electrical potentials, changing the pH of the solutions, and addition of chemical/biochemical substrates were used to change reversibly the electrode activity. The increasing complexity in the signal processing was achieved by integration of the switchable electrode interfaces with biomolecular information processing systems mimicking Boolean logic operations, thus allowing activation and inhibition of electrochemical processes on demand by complex combinations of biochemical signals. The systems reviewed range from simple chemical compositions to complex mixtures modeling biological fluids, where the signal substrates were added at normal physiological and elevated pathological concentrations. The switchable electrode interfaces are considered for future biomedical applications where the electrode properties will be modulated by the biomarker concentrations reflecting physiological conditions.