钛合金微弧氧化陶瓷层及其复合膜层研究进展

本文介绍了近年电解液及添加剂在制备钛合金微弧氧化陶瓷层、将微弧氧化与其他表面处理技术相结合制备复合膜层方面的研究进展.对电解液在微弧氧化过程中的作用、对陶瓷层形貌、结构及性能的影响等方面进行了总结.根据电解液添加剂的组成和状态,将其分为有机物、可溶性盐、固体颗粒三类,阐述了各种添加剂在陶瓷层形成中作用机制.对基于微弧氧化技术的复合膜层研究情况进行了分析总结.展望了钛合金微弧氧化陶瓷层制备技术未来的研究趋势.     

电解液温度对二氧化钛纳米管阵列结构及光电性能的影响

以氟化铵(NH4F)、乙二醇溶液为电解液,在不同的电解液温度(0～50℃)条件下,采用电化学阳极氧化法制备二氧化钛(TiO2)纳米管阵列.采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、紫外-可见分光光度计(UV-Vis)对TiO2纳米管阵列的形貌、结构和光学性能进行表征.结果表明,电解液温度高于20℃均能制备出纳米管阵列.光照下电解液温度40℃时制备的TiO2纳米管阵列具有最高光电流密度(Iph)0.2408 mA/cm2.以活性艳红X-3B为目标降解物,在室温、紫外光照射条件下考察了电解液温度对光催化活性的影响,结果显示电解液温度40℃时制备的TiO2纳米管阵列具有最高的光催化活性.     

阳极氧化法制备TiO2有序多孔薄膜

采用二次阳极氧化工艺,以含有氟化铵和水的乙二醇体系作为电解液,在纯钛表面制备有序的TiO2多孔薄膜.通过改变预处理方式、电压、氧化时间和搅拌速度等实验参数来探究其对TiO2多孔薄膜形貌的影响.结果表明,抛光后Ti基片制得的TiO2多孔薄膜表面更加平整;TiO2纳米孔的孔径和孔间距随着阳极氧化电压升高在一定范围内线性增大;TiO2纳米孔的孔径随着阳极氧化时间延长增大,孔壁随时间延长减薄,通过控制氧化时间可以实现纳米孔薄膜向纳米管阵列的转变;搅拌速度在400 r/min时,能够获得有序的自组织TiO2多孔薄膜.     

TiO_2/氧化石墨烯纳米复合物的制备及结构变化

为了探讨TiO2/氧化石墨烯纳米复合物的制备技术及产物结构的变化规律,采用微波法将钛酸丁酯引入季铵盐/氧化石墨插层复合物的层间域内,钛酸丁酯经原位水解在氧化石墨层间生成Ti(OH)4,再经焙烧处理制备TiO2/氧化石墨烯纳米复合物。采用XRD、SEM、FTIR和XPS对原料和不同阶段生成的产物的结构及变化、微观形貌、氧化官能团特征和化学键特点进行表征。结果表明,钛酸丁酯在原位水解过程中将氧化石墨剥离为氧化石墨烯;TiO2/氧化石墨烯纳米复合物中锐钛矿型TiO2的形成温度比纯TiO2的提高了约100℃;TiO2/氧化石墨烯纳米复合物中的TiO2和纯TiO2的平均晶粒尺寸都随焙烧温度的升高而增大,但前者的平均晶粒尺寸均小于相同温度焙烧处理的纯TiO2的;在TiO2/氧化石墨烯纳米复合物中氧化石墨烯与TiO2之间形成Ti-O-C键,并抑制了锐钛矿型TiO2的形成,而氧化石墨烯作为阻隔层则阻碍了锐钛矿晶粒的长大。     

二次阳极氧化对TiO2纳米管阵列形貌及光电催化性能的影响

在含水量为2wt;的0.3wt; NH4F和乙二醇电解液中,通过二次阳极氧化法制备了高度有序的TiO2纳米管阵列(TNT).利用扫描电镜(SEM)、X射线衍射(XRD)表征方法对TiO2纳米管阵列的形貌、晶型进行表征.结果表明,二次阳极氧化法形成的TNT更加规整,纳米管孔径大小一致.XRD分析显示二次阳极氧化法形成的TNT锐钛矿相衍射峰更强.光催化降解实验表明,二次阳极氧化制备的TNT对X-3B的降解效率是一次阳极氧化TNT的1.45倍.     

阳极氧化工艺制备TiO2纳米管阵列及其碳包覆改性

首先采用阳极氧化工艺制备了TiO2纳米管阵列,然后利用水热工艺对其进行C包覆改性,探讨了热处理温度、F-浓度、阳极氧化电压、阳极氧化时间等参数对TiO2纳米管阵列形貌及性能的影响,并初步研究了其生长机理.通过实验得到TiO2纳米管阵列的最佳制备条件:F-浓度0.5wt;;阳极氧化电压30 V;阳极氧化时间1h;热处理温度450℃.C包覆改性后的TiO2纳米管阵列对可见光的吸收明显增强,尿素浓度为20wt;时制得的TiO2纳米管阵列对亚甲基蓝的光降解率高达92.7;,相较于未进行C包覆改性的TiO2纳米管阵列提高了7.9;,说明C包覆改性可以显著提高TiO2纳米管阵列的光催化性能.     

含氟电解液使用次数(n≤15)对TiO2纳米管阵列形貌及锂电性能的影响

为了降低含氟电解液对环境的不良影响和有用资源的浪费,本文以不同使用次数(n≤15)的含氟溶液作为电解液,采用阳极氧化法制备了一系列TiO2纳米管阵列(TiO2NT).然后借助SEM、恒流充/放电、循环稳定性及循环伏安(CV)技术研究了含氟电解液的使用次数(n≤15)对所制备纳米管阵列电极的形貌及脱/嵌锂离子性能的影响.结果表明:含氟电解液的使用次数(n≤15)对TiO2NT形貌的负面影响不明显;作为锂离子电池负极活性材料时,电化学脱/嵌锂性能也没有出现大幅降低.     

阳极氧化法在钛网上制备TiO2纳米管阵列的研究

以NH4F的乙二醇溶液为电解液,采用阳极氧化法在钛网表面制备了有序TiO2纳米管阵列.通过XRD、SEM等对TiO2纳米管阵列的结构、形貌进行表征,利用紫外-可见分光光度计对所制备样品的紫外可见吸收特性进行了表征.结果表明:在一定时间范围内,随着氧化时间的增加,纳米管管长和管径都会增大,但超过一定时间后,纳米管破损明显加剧且有脱落现象.另外,所制备样品的光学禁带(Eopt)比块状样品的大,但随着氧化时间的延长,纳米管的光学禁带并没有发生显著变化.不同时间下制备的纳米管对可见光的吸收率不一样.     

前驱体转化法制备TiSi2/YSZ陶瓷涂层

采用聚硅氮烷前驱体作为基体,添加惰性填料(YSZ)和活性填料(TiSi2)制备涂层浆料,在310s不锈钢表面利用前驱体转化法制备TiSi2/YSZ陶瓷涂层.通过TGA、XRD和SEM对涂层的物相组成和微观形貌进行了表征,并研究了TiSi2含量对涂层的隔热性能以及耐高温性能的影响.结果表明,所制备的涂层厚度在15～35μm之间,由于前驱体树脂裂解过程中的体积收缩,未添加TiSi2的涂层表面分布有大量裂纹且涂层部分脱落.裂解过程中,TiSi2氧化生成TiO2与SiO2后可使TiSi2体积膨胀,弥补了前驱体树脂的体积收缩.因此随着TiSi2含量的增加,涂层脱落面积减少,表面裂纹密度降低,当TiSi2的体积分数达41;时,涂层内部无裂纹产生,该涂层样品在1200℃氧化25 h后金属基底氧化增重降低88.8;,并表现出良好的隔热性能和抗热震性能.     

电解液浓度对BaxSr(1-x)TiO3微弧氧化膜微观结构及介电性能的影响

用Ba(OH)2·8H2O和Sr(OH)2·8H2O配制电解液,工艺参数分别设置为电流密度20 A/dm2、电流频率100Hz、反应时间20 min及占空比85;,采用微弧氧化法在工业纯Ti板(99.5;)表面原位生长BaxSr(1-x)TiO3薄膜.分析了相同Ba2+ /Sr+比条件下,电解液浓度对薄膜物相、表面形貌及薄膜厚度的影响.结果表明:所得薄膜均主要由四方相Ba0.5Sr0.5TiO3构成;Ba2+和Sr2+各为0.2 mol/L时所得薄膜的表面平整度及致密性最好,表面粗糙度值最小,并检测了该薄膜在不同频率下的介电常数和介电损耗,发现两者均随频率的增加而减小;薄膜厚度随电解液浓度的增加而增加.     

Modelling of mechanism of agglomeration of KCl crystallization

The article presents an analysis into agglomeration during KCl vacuum crystallization. The theoretical and experimental investigations into the mechanism of agglomeration during mass crystallization result in an extension of the growth phenomena within the known model equations. The basis for this is essentially constituted by the collision model concepts of the theory of floculation in disperse systems. The parameters derived from the microprocess analysis (energy dissipation, content of solids, growth rate of individual grains) lead to model equations which are confirmed by laboratory and test trials.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.