TiO2和O-Al2O3晶体的生长习性

通过水热法制备粉体的实验观察到金红石、锐钛矿和α-Al2O3晶体的生长习性．采用配位多面体生长习性法则合理地解释了Ti O2和α-Al2O3的生长习性．其主要结果为α-Al2O3晶体的生长习性为平板{0001}，其各晶面的生长速度为：V｛0001 }＜V｛1123}；锐钛矿的生长习性为四面体，其各晶面的生长速度为V<010>=V<001>>V<010>>V<111>．而PBC理论很难合理地解释α-Al2 O3晶体的生长习性．     

TiO2和α-Al2O3晶体的生长习性

通过水热法制备粉体的实验观察到金红石、锐钛矿和α－Ａｌ２Ｏ３晶体的生长习性,采用配位多面体生长习性法则合理地解释了ＴｉＯ２和α－Ａｌ２Ｏ３的生长习性,其主要结果为α－Ａｌ２Ｏ３晶体的生长飞快生为平板｛０００１｝,其各晶面的生长速度为：Ｖ｛０００１｝〈Ｖ｛１１２３｝〈Ｖ｛０１１２｝＝Ｖ｛１１２０｝〈Ｖ｛０１１０｝;金红石的生长习性为柱状,其各晶面的生长速度为;Ｖ〈１１０〉〈Ｖ〈１００〉〈Ｖ〈１０１〉     

金红石TiO2基质中[MoO4]2-基团的上转换发光

在978nm激光二极管的激发下,Mo掺杂的TiO₂材料表现出很强的宽带上转换发光,该发光来源于[MoO₄]^2-基团的激发态³T₁,³T₂能级到基态¹A₁能级的电子跃迁,X射线衍射表明样品为金红石单一相,红外吸收光谱证实了[MoO₄]^2-的存在,由光电子能谱推测体系中还含有低价态的Mo离子,它们提供了上转换得以进行的中间态,高温下的氧化还原处理会改变低价Mo的数量,从而严重影响样品的发光行为。     

新型固体润滑及油品添加剂-硫代钼酸盐的制备

研究了在水溶液中合成新型固体润滑兼油品添加剂一ＮｉＭｏＯ_２Ｓ_２及其原料（ＮＨ_４）_２ＭｏＯ_２Ｓ_２的条件,其最佳参数为ｐＨ＝４～５,温度为３０℃左右和ｐＨ＝７～９;温度为－５～０℃．还对产品的组成、结构及形貌进行了分析观察,并验证了ＮｉＭｏＯ_２Ｓ_２作为油品添加剂和固体润滑剂从２０～６００℃的减摩性能;证实硫代钼酸镍是一种宽温度范围的润滑剂．     

Bridgman法生长的MnxCd1-xIn2Te4晶体相形成规律和物理性能研究

采用Bridgman法生长了x为0.1,0.22和0.4的四元稀磁半导体化合物Mn_xCd_1-xIn₂Te₄晶体.研究了三根晶体中相的形貌、结构、成分和Mn_0.1Cd_0.9In₂Te₄晶体中各组元沿轴向和径向的成分分布.晶体生长初始端的组织为α+β+β₁,随着生长的进行,形成β相的单相区.在晶锭末端,形成In₂Te₃类面心立方结构化合物.组分x增大后,Mn_xCd_1-xIn₂Te₄晶体的吸收边向短波方向移动,禁带宽度则线性增大.磁化率测量结果表明:晶体在高温区的x^-1-T曲线服从居里-外斯定律,在低温区(<50K)则表现出顺磁增强现象.     

飞秒激光诱导玻璃内Ba2TiSi2O8晶体的析出

使用聚焦后的800nm,150fs,250kHz的高重复频率飞秒脉冲激光器能够在BaO-TiO₂-SiO₂组分的玻璃内部三维选择性地诱导Ba₂TiSi₂O₈晶体的析出. 发光光谱显示这种晶体把入射的800nm光转化成了400nm的蓝光,因此这种析出的晶体具有非线性倍频特性. 通过拉曼光谱测定,在当前的玻璃组分中析出的晶体是Ba₂TiSi₂O₈. 研究表明,经250kHz的飞秒激光辐照一段时间后,在玻璃内部由于脉冲能量的连续沉积会使得激光辐照区域出现热积累效应,因此,该辐照区域的温度会不断升高以致超过玻璃析晶温度,最终诱导玻璃熔融析晶. 此外,对飞秒激光辐照区域不同部位进行拉曼光谱检测,结果表明：在整个区域Ba₂TiSi₂O₈晶体的析出呈现中间比外围明显的分布特点,因此晶体析出与辐照形成的温度梯度场有密切关系.     

SnO2-Sb2O3基压敏陶瓷致密化及脉冲电流耐受特性

实验研究了TiO₂、Co₃O₄、Cr₂O₃、Ni₂O₃和MnO掺杂对SnO₂-Sb₂O₃基压敏陶瓷材料微观结构和电性能的影响. 研究结果表明, TiO₂和Co₃O₄促进SnO₂陶瓷烧结致密化, 根据XRD图谱分析结果, Co₃O₄与SnO₂反应形成了Co₂SnO₄晶相, TiO₂则固溶于SnO₂晶相;Sb元素的引入能够促进SnO₂晶粒的半导化;复合添加Cr₂O₃、Ni₂O₃和MnO可以有效提高材料的电压非线性特性和脉冲电流冲击耐受能力. 获得电性能接近实用化的SnO₂压敏陶瓷样品, 其压敏电压V_1mA约为350V/mm, 非线性系数α达到50, 漏电流小于5μA, 并且在8/20μs脉冲电流冲击试验中,直径14mm的样品能够经受2kA的脉冲峰值电流.     

KZrQ6(Q=Se,Te)的中温固相合成

采用反应性熔盐法,以K₂Se₃：Zr：Q（Q＝Se,Te）＝1：1：5的摩尔比,在500℃下反应五天,生成黑色针状晶体（a）和（b）．元素分析结果表明晶体（a）和（b）分别为新的三元金属硫族化合物KZrSe₆和KZrTe₆,KZrSe₆和KZrTe₆晶体具有热力学介稳相的某些结构特征．     

高温氧化物晶体界面非稳定性研究

设计了一套模拟实验,以获得关于晶体形态和界面非稳定性的差异的可靠数据,如高温溶液生长的骸晶和枝蔓晶．这些实验是在高温实时观察装置（ＨＩＴＩＳＯＴ）内进行的．高温溶液晶体生长实验是在环形铂金丝炉圈内进行的．炉圈直径为２ｍｍ．铂金丝既起加热又起支撑熔体的作用．选用ＫＮｂＯ_３和Ｌｉ_２Ｂ_４Ｏ_７的混合物进行晶体生长实验．在只存在扩散机制的快速生长过程中,会形成不同的晶体不完整性,如晶面凹坑、骸晶和枝蔓晶．采用淬火实验以分辨不同的ＫＮｂＯ_３晶体形态,并用扫描电镜研究Ｌｉ_２Ｂ_４Ｏ_７溶体中ＫＮｂＯ_３晶体生长的形貌．在一般情况下,当晶体在气液界面附近液相区成核时,会产生晶体界面非稳定性．导致晶体形状不稳定的溶液层的厚度为６０μｍ．通过扫描电镜观察,发现晶体在这一溶液层中由多面体晶变为枝蔓晶．骸晶和枝蔓晶的各向异性反映了ＫＮｂＯ_３的立方特性,也反映了界面非稳定性是沿［１１０］晶棱扩大的,［１１０］晶棱方向的分支证实了晶体生长形状的各向异性·形成界面非稳定性的临界尺寸为１０μｍ．与此相反,中持稳定的晶面形状是通过６０μｍ厚度以下的溶液内的晶体生长来实现的．晶体生长过程是由高温实时观察装置进行实时观察和记录的,并能观察到晶体固液     

硬盘基板用微晶玻璃的析晶过程研究

利用差热分析、热膨胀曲线与Ｘ射线衍射等方法研究了含ＴｉＯ_２和ＺｒＯ_２的 ＭｇＯ－Ａｌ_２Ｏ_３－ＳｉＯ_２玻璃的析晶过程．７８０℃时玻璃中析出的镁铝钛酸盐促使玻璃在８００℃析出Ｍｇ－透辉石,随后在 ９３０℃Ｍｇ－透辉石和镁铝钛酸盐开始向假蓝宝石、金红石和Ｚｒ／Ｔｉ固溶体转变;１０３０℃假蓝宝石开始转变为β－石英固溶体,而在１１２５℃以上温度,β－石英固溶体转化为α－堇青石、方石英和顽火辉石,同时金红石和Ｚｒ／Ｔｉ固溶体向锆英石和钛酸镁转变．依据玻璃析晶序列,选择在９３０～１０５０℃间温度下对玻璃进行热处理,制得以假蓝宝石为主晶相的微晶玻璃．此微晶玻璃具有细小均匀的晶粒结构,具有高的弹性模量（１２０ＧＰａ）和良好的表面性能,是适宜的硬盘基板材料．     

The quantitative effects of crystal habit change on the film surface form and the preferred orientation during the growth of vacuum-condensed films

Our recent systematic observations by reflection electron diffraction showed that a basic feature of film growth of high melting point materials condensed in vacuum on substrates initially at room temperature is that, after the initial thin film of randomly oriented crystals, and the growth of faces and preferred orientation of a particular type at the film surface, a new type of face and preferred orientation is often developed in further strata of deposit growth.Calculations are made showing the effect of a change in crystal habit on the film surface element distribution and the nature of the new preferred orientation which is developed.The {211} habit and orientation in gold films, in further growth after the first-developed {111} habit and orientation, is discussed as an example of the calculations, which indicate a tilt δ of approximately 25° for the {211} orientation when the vapour angle of incidence i is 45°. This agrees with our observations, confirming that the {211} orientation arises from the habit change and not from nucleation by secondary {111} twinning.     

Morphology, Growth Process and Symmetry of {0001} Face on Yb：YAl3（BO3）4 Crystal

The {0001} face develops on the habit of self-frequency doubling laser crystal Yb: YAl3(BO3)4 (YbYAB) only under high growth rate condition, and its morphology is rough. To study the growth mechanism of {0001} face, we have observed the growth morphology on {0001} polishing section by atomic force microscopy (AFM). A series of AFM images captured in different growth durations on the {0001} polishing section reflect the crystal growth process. It is shown that the growth morphology on the {0001} polishing section was rough with many hillocks at the first growth stage, and it can become smooth finally, although the growth morphology on the {0001} face develoFed naturally on YbYAB crystal habit is always rough. On the smooth {0001} surface formed at the last growth stage, there aresome triangular pits. This fact is different from that of hillocks in most crystal growth morphologies. AFM can easilydistinguish the pits or hillocks on the surface, but differential interfere contrast microscopy (DIC) can not do. Theorientation of the triangular pits is just the opposite to the triangular {0001} faces. The chemical etching patternis also composed of this kind of triangular pits. These growth morphology and etching pattern of the {0001} facesshow 3m symmetry, but the point group of YbYAB crystal is 32. The symmetric contradiction between morphologyand point group does not exist for quartz, although whichsurface morphology we can distinguish the right form ormorphology we can not do. The reason for the symmetricand its point group is not known yet.has the same point group as YbYAB. From quartz {0001}left form of the crystal, but from YbYAB {0001} surfacecontradiction between YbYAB {0001} surface morphology and its point group is not known yet.     

Synthesis of cross-shaped PbS nanostructures by a surfactant-assisted reflux process

Cross-shaped PbS crystals composed of six pods were prepared by a reflux process using CTAB as the surfactant. Parameters affecting the morphology of PbS have been investigated systematically. Results reveal that various PbS structures including cubic, truncated octahedral, flower-shaped and dendritic crystals can be obtained by changing the sulfur and lead source, the solvent or the surfactant. The difference of the morphology was explained to be closely related to the change of the relative growth rate in the 〈100〉 direction to that in the 〈111〉 direction.     

Crystal Growth Modification of AgCl in an Aqueous Gelatin Medium by Incorporating Br- and I- Ions

The habit of {110} AgCl crystals changes by incorporation of Br^- or I^- ions during crystal growth. At high Br content the {110} habit of AgCl turns into an irregular {100} habit in the presence of the growth modifying agent. The incorporation of a rather low amount of I^- ions causes the {110} habit of AgCl to disappear and to be modified into a {100} habit. Adsorption of 3,3’-diethyl-9-methyl thiocarbocyanine on the crystals follows very well the aggregation rule found previously.     

Crystal growth of the primary silicon in an Al-16 wt % Si alloy

Studies on the crystallographic growth habit of primary silicon crystals in an Al-16 wt% Si alloy were carried out by X-ray micro focus Laue analysis and ECP (electron channelling pattern) analysis. The plate-like primary silicon crystals grow by the same mechanism as that for germanium dendrites, i.e. the TPRE (twin plane re-entrant edges) mechanism. The spherical primary silicon crystal in sodium treated melts is composed of several pyramidal grains with tops at the centre of the sphere. Many of these grains have a twin relation to each other. The sodium enriched regions are found at the boundaries of these pyramidal silicon grains. The external surfaces of the spherical primary crystals exhibit regular crystal facets. The surface facets are most frequently parallel to {111} plane but there are also some facets parallel to other less densely packed planes such as {100}, {211} and so on.     

Hybrid Electrolyte Design for High-Performance Zinc–Sulfur Battery

Rechargeable aqueous Zn/S batteries exhibit high capacity and energy density. However, the long-term battery performance is bottlenecked by the sulfur side reactions and serious Zn anode dendritic growth in the aqueous electrolyte medium. This work addresses the problem of sulfur side reactions and zinc dendrite growth simultaneously by developing a unique hybrid aqueous electrolyte using ethylene glycol as a co-solvent. The designed hybrid electrolyte enables the fabricated Zn/S battery to deliver an unprecedented capacity of 1435 mAh g⁻¹ and an excellent energy density of 730 Wh kg⁻¹ at 0.1 Ag⁻¹. In addition, the battery exhibits capacity retention of 70% after 250 cycles even at 3 Ag⁻¹. Moreover, the cathode charge–discharge mechanism studies demonstrate a multi-step conversion reaction. During discharge, the elemental sulfur is sequentially reduced by Zn to S²⁻ (${\mathrm{S}}_8\to {\mathrm{S}}_{\mathrm{x}}^{2-}\to {\mathrm{S}}_2^{2-}+{\mathrm{S}}^{2-})$, forming ZnS. On charging, the ZnS and short-chain polysulfides will oxidize back to elemental sulfur. This electrolyte design strategy and unique multi-step electrochemistry of the Zn/S system provide a new pathway in tackling both key issues of Zn dendritic growth and sulfur side reactions, and also in designing better Zn/S batteries in the future.     

TEM observation of liquid-phase bonded aluminum–silicon/aluminum nitride hetero interface

Liquid-phase bonded aluminum–silicon/aluminum nitride interface structure was investigated using high-resolution transmission electron microscopy. A textured layer of aluminum formed a stable orientation relationship with aluminum nitride, which showed Al(111) to be tilted by about 4° with respect to the AlN(0001) interface plane. The unique orientation relationship between Al and AlN was predicted as one of the stable orientation relationships using coincidence of reciprocal lattice point method, which surveys the degree of geometrical coherency between two crystals in three-dimensional space. A stable orientation relationship was found to be (001)[1_boxclose \bar{1} 0]Al//(2[`2] \bar{2} 03)[11[`2] \bar{2} 0]AlN.     

Crystallographic facet-dependent stress responses by polyhedral lead sulfide nanocrystals and the potential “safe-by-design” approach

The particular physicochemical properties of nanomaterials are able to elicit unique biological responses. The property activity relationship is usually established for in-depth understanding of toxicity mechanisms and designing safer nanomaterials. In this study, the toxic role of specific crystallographic facets of a series of polyhedral lead sulfide (PbS) nanocrystals, including truncated octahedrons, cuboctahedrons, truncated cubes, and cubes, was investigated in human bronchial epithelial cells (BEAS-2B) and murine alveolar macrophages (RAW 264.7) cells. {100} facets were found capable of triggering facet-dependent cellular oxidative stress and heavy metal stress responses, such as glutathione depletion, lipid peroxidation, reactive oxygen species (ROS) production, heme oxygenase-1 (HO-1) and metallothionein (MT) expression, and mitochondrial dysfunction, while {111} facets remained inert under biological conditions. The {100}-facet-dependent toxicity was ascribed to {100}-facet-dependent lead dissolution, while the low lead dissolution of {111} facets was due to the strong protection afforded by poly(vinyl pyrrolidone) during synthesis. Based on this facet-toxicity relationship, a “safe-by-design” strategy was designed to prevent lead dissolution from {100} facets through the formation of atomically thin lead-chloride adlayers, resulting in safer polyhedral PbS nanocrystals.

Open image in new window

     

Growth mechanism of NaBrO3 crystals from aqueous solutions

To study the growth mechanism of {111} faces of NaBrO₃, crystals were grown at different supersaturations ranging from 2% to 8%. The growth mechanisms were investigated based on the growth rate versus supersaturation relation and from the surface features observed on {111} faces. The growth mechanism of these crystals appear to be due to 2D nucleation. The growth rate curve has been further investigated using Ohara and Reid equations. Polynucleation model in two-dimensional nucleation growth theory is suggested as the most possible growth mechanism for these crystals in the present supersaturation range.