Transparent Nano Crystalline Glass-Ceramics by Interface Controlled Crystallization

A prerequisite for the preparation of nano glass-ceramics is an increase in viscosity of the residual glassy matrix phase during the course of the crystallization process. This results in a deceleration of the crystal growth process due to increasing stresses, which finally may lead to a total freezing of the crystallization process. In principle, two routes for the preparation of nano glass-ceramics exist: in one of these routes, the first step is a phase separation in which a droplet phase is formed. Inside this droplet phase, the crystals are precipitated. In the other route, a preceding phase separation does not occur and the nucleation takes place in a homogeneous glassy phase. In both cases, the crystal growth velocity is high until the crystals reach a size of some nanometers or some ten nanometers, then the crystal growth velocity decreases strongly.     

核化及晶化温度对微晶玻璃性能的影响

本文以95％炼铁高炉渣和5％钾长石为原料,采用简易的烧结法制备出炉渣微晶玻璃。利用DSC、XRD等分析手段研究了不同核化晶化温度对矿渣微晶玻璃性能的影响。研究表明：不同的核化晶化温度对高炉渣微晶玻璃的性能有较大的影响;最后得出最佳核化温度为760℃、最佳晶化温度为960℃。     

Crystallization Mechanisms in Glass-Ceramics

Transmission electron microscopy, electron diffraction, and microprobe X-ray analysis were used to study crystallization of glasses in the systems Li₂O-SiO₂, BaO-SiO₂, and Li₂O-A1₂O₃-SO₂. The ternary system, with 4 mol% TiO₂ added to an Li₂O-Al₂O₃-4SiO₂ composition, crystallizes with a simple morphology of equiaxed grains of the β-quartz metastable phase which transforms at higher temperatures to the stable β-spodumene structure. The binary systems exhibit a more complex crystallization morphology dictated by crystal anisotropy, temperature, impurity content, and susceptibility either to intermediate-phase formation (BaO-SiO₂) or to liquid immiscibility (Li₂O-SiO₂). The initial crystal growth units formed in these systems are frequently two-phase branched morphologies many micrometers in diameter. They may be recrystallized to form polycrystalline glass-ceramics with submicrometer grain sizes.     

Controlled Crystallization in Lead Zirconate Titanate Glass-Ceramics Prepared by the Sol-Gel Process

Lead titanate and lead zirconate titanate grains were grown in situ from lead-titanium-boron-silicon and lead-zirconium-titanium-boron-silicon gels prepared via the sol-gel method. The lead zirconate titanate grains were much smaller and more uniform than lead titanate grains grown from gels of similar composition. The crystallization mechanisms of the two systems were studied via scanning electron microscopy, X-ray diffractometry, Raman spectroscopy, and differential thermal analysis. Crystallization had a tendency to begin near the surface or at defects in the lead titanate system, whereas it was controlled by the original precipitated nuclei of tetragonal zirconia particles in the lead zirconate titanate system. Controlled bulk crystallization may explain the finer structure of the resultant lead zirconate titanate glass-ceramic.     

热处理制度对RCS系着色微晶玻璃析晶性能的影响

采用不同热处理制度对掺加硫硒化镉的R2O-CaO-SiO2 (RCS,R为Na,K)系玻璃进行显色处理得到着色微晶玻璃.通过X射线衍射、场发射扫描电镜及紫外可见分光光度计等测试分析手段研究不同热处理制度对RCS系着色微晶玻璃析晶性能的影响.结果表明:在700℃进行显色热处理,微晶玻璃的主晶相为柱状的硬硅钙石[Ca6Si...     

废玻璃粉反应析晶制备枪晶石玻璃陶瓷性能研究

将废玻璃粉与钙铝黄长石、氟化钙混合,使用反应析晶烧结法制备出主晶相为枪晶石的玻璃陶瓷.研究了钙铝黄长石和氟化钙含量、烧结温度对玻璃陶瓷晶相、相对密度、烧结率、吸水率及力学性能的影响.结果表明,加入15％(质量分数,下同)钙铝黄长石和6％氟化钙时,玻璃陶瓷中析出的主晶相为枪晶石.提高钙铝黄长石或氟化钙含量有硅灰石析出.在850℃和900℃烧结后,玻璃陶瓷的相对密度和烧结率都随钙铝黄长石或氟化钙含量的升高而降低,其中,提高氟化钙含量比提高钙铝黄长石含量对烧结阻碍作用更大;吸水率随钙铝黄长石或氟化钙含量的升高而升高;玻璃陶瓷的强度随钙铝黄长石或氟化钙含量提高而降低,随温度升高而变大.和850℃相比,900℃烧结后,枪晶石玻璃陶瓷的强度最大可提高51％.     

LAS微晶玻璃在离子交换后的去结晶相变化及机械性能表征

Li2 O-Al2 O3-SiO2(LAS)系微晶玻璃是一种高性能的实用微晶玻璃体系,以Li2 O、Al2 O3和SiO2作为主要原料,采用整体析晶法制备了以透锂长石(LiAlSi4 O10)为主晶相的微晶玻璃,并采用低温离子交换单元盐浴的方法,对其进行化学强化.利用X射线衍射仪、扫描电子显微镜等设备研究了LAS系微晶...     

Crystallization and Chemical Strengthening of Nepheline Glass-Ceramics

Electron micrographic and X-ray diffraction techniques were used to study the nucleation and growth of titania-nucleated nepheline in glass. On heating, the glasses phase-separated as a prelude to the crystallization sequence. The first crystalline phase identified was the metastable phase, carnegieite. With time, the equilibrium phase, nepheline, crystallized and the titania crystallized to anatase. The resulting materials were nonporous and largely crystalline. These nepheline glass-ceramics were chemically strengthened by treatments in molten potassium salts. A K⁺→ Na⁺ exchange took place and effected transformation of nepheline to kalsilite. This transformation was a function not only of the exchange treatment, but of the composition of the initial nepheline crystals. Confining the kalsilite surface against a volume increase during the phase transformation created a surface compressive stress. Glass-ceramics containing nepheline crystals with an appropriate structure were chemically strengthened in this manner to yield bulk, abraded modulus of rupture values above 200,000 psi.     

钙铝酸盐红外玻璃的微晶化

采用真空熔制方法制备出钙铝酸盐红外玻璃,通过热处理方法对玻璃进行微晶化获得钙铝酸盐微晶玻璃。研究了晶核剂ZrO_2对钙铝酸盐玻璃析晶机制的影响,以及不同微晶化条件下钙铝酸盐玻璃的析晶情况和红外透过性能。结果表明:晶核剂的引入改变了钙铝酸盐玻璃的析晶机制,未添加ZrO_2的铝酸钙玻璃的析晶主要为表面析晶,析出晶相主要是BaAl_2O_4、Ba_3Al_2O_6;添加ZrO_2后,玻璃向整体析晶转化,析出晶相以Ca_3Al_2O_6为主;在930~970℃范围内,通过控制处理温度和时间可以获得透明的含ZrO_2铝酸钙微晶玻璃,在3~5μm波段具有良好的红外透过性能,玻璃硬度达到8.04 GPa以上。     

一步法热处理对复合尾矿微晶玻璃晶化过程及性能的影响

以金尾矿和铁尾矿为主要原料,采用熔融法制备了CaO-Al2O,-SiO2 (CAS)系微晶玻璃,利用差热分析(DSC)、X射线衍射分析(XRD)、扫描电镜(SEM)和综合力学性能仪等测试手段,研究了一步法热处理制度中不同温度对CAS系尾矿微晶玻璃显微结构及性能的影响.结果表明:采用一步法热处理制度可以成功制备出以透辉石(Mg0.6Fe0.2Al0.2)Ca(Si1.5Al0.5)O6为主晶相的微晶玻璃,且随着热处理温度的升高,所制备的微晶玻璃的综合性能有所提高.确定最佳的热处理制度为870℃保温2h,所制备的微晶玻璃的密度为2.97 g/cm3,抗折强度为230.33 MPa,耐酸性99.38％,耐碱性99.25％,弹性模量、剪切模量分别为118.19 GPa和47.9 GPa.     

透辉石玻璃陶瓷的制备及其析晶特性研究

以废玻璃粉为原料,采用反应析晶烧结法制备了透辉石玻璃陶瓷。采用差热分析、X射线衍射分析、扫描电镜、能谱、高分辨透射电镜等方法研究了顽辉石-堇青石粉和废玻璃粉混合样品等温烧结过程中顽辉石-堇青石向透辉石转变的演变过程。结果表明:顽辉石-堇青石与玻璃粉在815°C下即可发生反应析晶;900°C保温2 h可获得透辉石为主晶相的玻璃陶瓷。在保温过程中,顽辉石的Mg~(2+)和O~(2-)向玻璃中扩散,玻璃中的Si~(4+)和Ca~(2+)向顽辉石中移动,使顽辉石晶体在b轴方向交替排列的两条链沿c轴方向断开,转变成单链,由Mg~(2+)和Ca~(2+)连接生成透辉石。保温0 h时,由于堇青石[MgO_6]八面体膨胀较小,玻璃中的Si~(4+)、Ca~(2+)、Na~+向堇青石中移动,反应析晶生成钠长石与透辉石;当保温时间延长至2 h时,堇青石[MgO_6]八面体骨架进一步扭曲,生成主晶相为透辉石的玻璃陶瓷。     

钙钛锆石玻璃陶瓷体的晶化和抗浸出性能

以SiO2、A12O3、B2O3、CaO、TiO2和ZrO2为原料,加入3％CeO2（质量分数,下同）作为模拟核素,利用熔融法制备钙钛锆石基玻璃陶瓷体,对含锕系元素的放射性废物进行固化处置。通过X射线衍射仪和场发射扫描电子显微镜等对热处理后玻璃陶瓷体进行表征。以电感耦合等离子体质谱测试玻璃陶瓷体抗浸出性能。结果表明：在晶化温度为1050℃,B203掺量为12．5％时,玻璃陶瓷体中低质量分数的TiO2和ZrO2更易参与生成钙钛锆石晶体,但固化体中仍有其他晶相存在;在同样晶化温度下,B203掺量为8．33％时对玻璃陶瓷体形成钙钛锆石单一晶相较为有利,且具有较好的抗浸出性能,其中Ce在产品一致性测试法下元素标准化浸出率7d后维持在10^-6数量级,固化效果明显。     

添加剂对铜渣还原尾渣微晶玻璃析晶行为及性能的影响

铜渣还原尾渣与CaO-Al₂O₃-SiO₂系微晶玻璃的化学组成相似,采用熔融法以铜渣还原尾渣为主要原料制备微晶玻璃可为铜渣的高效利用提供一种有效途径。通过DSC、XRD和SEM-EDS等技术研究了不同添加剂(B₂O₃、CaF₂、TiO₂和Cr₂O₃)对微晶玻璃物相组成、抗折强度、体密度、吸水率和显气孔率等性能的影响。结果表明:无论添加哪种添加剂,微晶玻璃均能析出力学性能较好的钙长石和钙铝黄长石,且能使晶体析晶方式转化为整体析晶;添加B₂O₃可使微晶玻璃性能最优,其次是TiO₂与CaF₂。     

氟化钙对钠钙玻璃反应析晶制备玻璃陶瓷性能的影响

用X射线衍射、Fourier变换红外光谱、扫描电子显微镜研究了不同氟化钙加入量的钠钙玻璃粉末在烧结过程中的反应析晶。结果表明:未加入氟化钙时,以钙铝黄长石作为析晶促进剂,在850℃反应析晶生成硅灰石玻璃陶瓷;当析晶促进剂含量低于15%(质量分数,下同)时,添加6%氟化钙在850℃反应析晶生成枪晶石玻璃陶瓷。随氟化钙添加量增加,制备的枪晶石玻璃陶瓷气孔率逐渐增大,体积密度减小,抗弯强度降低。当氟化钙添加量为6%时,制得的枪晶石玻璃陶瓷抗弯强度达到68MPa。     

Tribological Properties of Glass-Ceramics

Tribological properties of five glass-ceramics are reported. The materials were tested unlubricated against themselves. Testing was performed using a simulated inertial sample dynamometer. Sliding speeds were between 0.5 and 1.8 m /S with an applied load of 225 N. Average friction coefficients were in the range 0.07 to 0.5. The wear rate of a lithium aluminosilicate was 43 ×10–14 m3/N.m, in good agreemen2 with previous pin-on-disk results. Wear surfaces exhibited cracking, ploughing, delamination, and viscous flow or plastic deformation.     

锂铝硅透明微晶玻璃析晶动力学研究

本文利用经典方程(Johnson-Mehl-Avrami)分析了非化学计量的锂铝硅Li₂O-Al₂O₃-SiO₂-ZrO₂-P₂O₅透明微晶玻璃的析晶动力学,采用DSC、XRD和SEM研究了晶化温度对玻璃析晶行为的影响。结果表明:在较低的起始析晶温度下Li₂Si₂O₅和Li₂SiO₃析出,随晶化温度的升高,主晶相转变为LiAlSi₄O₁₀,Li₂SiO₃晶相消失,晶体尺寸变小,在550 nm处微晶玻璃透过率由89.3%升高到90.6%;利用Kissinger方法计算出的Li₂Si₂O₅和LiAlSi₄O₁₀的析晶活化能分别为349.5 kJ/mol和184.2 kJ/mol,平均晶体生长指数分别为3.05和1.42。     

The Effects of Co2O3 Addition on Crystallization,Microstructure and Properties of Cordierite-Based Glass-Ceramics

The Co₂O₃ doped MgO-Al₂O₃-SiO₂-B₂O₃ (MASB) glass-ceramics were successfully fabricated by traditional melt quenching method and the following heat treatment. The effect of Co₂O₃ addition on crystallization behavior, glass networks, microstructure and physical properties was investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier transform infrared absorption spectra (FTIR) and scanning electron microscopy (SEM) measurements. The results show that the metastable phase μ-cordierite and α-cordierite precipitated from the parent glass during the thermal treatment process. With the increase of Co₂O₃ content, the crystallization tendency of the parent glass increased, and the addition Co₂O₃ favored the transformation from μ-cordierite to α-cordierite. Meanwhile, the grain size of glass-ceramics increased obviously, Simultaneously, the mechanical strength of glass-ceramics increased first and then decreased, while the thermal expansion coefficient decreased. Glass-ceramic with excellent thermal and physical properties were prepared by adding 0.1 mol% Co₂O₃ content and then crystallizing it at 1020 ^∘C for 3 h.

     

氟硅酸盐微晶玻璃的结构和性能

本文介绍了氟硅酸盐微晶玻璃的结构和性能,并指出了当前存在的几个问题。     

Preparation of High-Strength Calcium Phosphate Glass-Ceramics by Unidirectional Crystallization

Unidirectionally crystallized CaO-P₂O₅ glass-ceramics were produced by reheating glass rods between 450° and 580°C (glass transition temperature ∼500°C) under a temperature gradient of 30°C/cm. These glass-ceramics exhibit high bending strength (∼650MN/m²) and toughness. Sample preparation is described and compared with conventional unidirectional solidification of melts. The characteristic mechanical properties are discussed in terms of the texture of the glass-ceramics.