烧结法制备粉煤灰微晶玻璃的实验研究

以粉煤灰为主要原料,采用烧结法制备粉煤灰建筑微晶玻璃.运用差热分析(DTA)、扫描电镜(SEM)、X射线衍射(XRD)等技术对粉煤灰微晶玻璃性能、微观结构进行了研究,并测试了粉煤灰微晶玻璃的物化力学性能.研究表明,粉煤灰微晶玻璃的主晶相为副硅灰石,副晶相为钙长石;CaO/SiO2为0.33时,微晶玻璃的理化力学性能达到最优,Al2O3/SiO2为0.19时,析晶过程相对最容易发生.     

利用高炉渣及粉煤灰制备废渣微晶玻璃的研究

利用高炉渣及粉煤灰为主要原料,采用直接烧结法制备废渣微晶玻璃,利用差热分析(DSC)、X射线衍射(XRD)、扫描电镜(SEM)等分析手段,结合力学性能测试,讨论了粉煤灰含量对微晶玻璃晶相组成和性能的影响.结果表明:当粉煤灰含量较高时,微晶玻璃的主晶相为钙镁黄长石,副品相为透辉石;较高的粉煤灰含量有利于透辉石的生成,随着粉煤灰含量的减少微晶玻璃晶相逐渐变为钙镁黄长石;由于粉煤灰引入了较多的残余碳粒及硫,当粉煤灰含量较高时会导致微晶玻璃性能下降;当高炉渣含量为90wt％,粉煤灰含量为10wt％时,制备的微晶玻璃性能最好,其主晶相为钙镁黄长石,各项性能均优于其它建材.     

晶化温度对CaO-Al2O3-SiO2-Fe2O3系粉煤灰微晶玻璃析晶及性能的影响

以粉煤灰、石灰石和无水碳酸钠为原料,通过烧结法制备了以钙长石、钙铁辉石和霞石为晶相的复合晶相微晶玻璃.借助差热分析、X射线衍射及扫描电子显微镜研究了晶化温度(850～1100℃)对微晶玻璃析晶行为、显微形貌和性能的影响.结果表明:随晶化温度的升高钙长石和霞石晶相的含量先增加后降低,钙铁辉石晶相含量逐渐增加,同时微晶玻璃中晶体形态逐渐由球形微晶发育成柱状,最后长成片状;晶化温度的升高有利于微晶玻璃的烧结致密化,1050℃时微晶玻璃的线收缩率和体积密度达到最大,分别为17.04％和2.76 g/cm3,吸水率最小,为0.01％.过高的晶化温度(1100℃)会降低其致密程度.     

Fe2O3,ZrO2及F对CaO-MgO-Al2O3-SiO2系微晶玻璃析晶行为的影响

研究了形核剂对CaO-MgO-Al2O3-SiO2系微晶玻璃析晶的影响,将形核剂掺量(质量分数)分别为1.0?2O3,2.0%ZrO2和4.0%F添加到基础玻璃中.用扫描电子显微镜和X射线衍射技术分析了微晶玻璃析晶和显微特征.不添加任何形核剂的样品以及分别添加1.0?2O3和1.0?2O3 2.0%ZrO2形核剂的样品以表面析晶为主,在1 053 ℃保温1.0 h后,析出晶体以硅灰石(CaO·SiO2)为主,同时还有少量钙长石(CaO·Al2O3·2SiO2)和透辉石(CaO·MgO·2SiO2)析出.Fe2O3的加入促进了玻璃的析晶和生长,而ZrO2的作用正好相反,抑制了玻璃的析晶.对于添加1.0?2O3 2.0%ZrO2 4.0%F形核剂的样品,在1 040 ℃保温1.0h后,其析出晶体以整体析晶为主,块状晶体均匀析出,析出主晶相为钙长石.     

SiO2/CaO质量比对白云鄂博尾矿微晶玻璃的影响研究

以白云鄂博二次选后尾矿和粉煤灰为主要原料,采用熔融法制备得到了CaO-MgO-Al2O3-SiO2系尾矿微晶玻璃.利用XRD、DTA、SEM等测试手段研究了SiO2/CaO质量比对微晶玻璃结构及物化性能的影响.结果表明:随着SiO2/CaO质量比的增加,基础玻璃放热峰右移、放热峰面积减小;微晶玻璃主晶相由辉石相转变为磁铁矿相;析出晶粒尺寸逐渐减小、晶化程度逐渐降低;微晶玻璃相关物化特性降低.     

粉煤灰和自然冷却黄磷炉渣协同制备微晶玻璃

以粉煤灰和自然冷黄磷炉渣为研究对象,采用熔融法制备CaO-Al2 O3-SiO2 (CAS)系微晶玻璃.利用Kissinger方程和Augis-Bennett方程计算了粉煤灰-自然冷却黄磷炉渣微晶玻璃玻璃析晶活化能(E)和晶化指数(n).借助差热分析(DTA),X射线衍射仪(XRD)和扫描电子显微镜(SEM)研究了晶核剂TiO2,CaF2,P2O5(由KH2 PO4引入)对粉煤灰-自然冷却黄磷炉渣微晶玻璃析晶的影响.结果表明:利用粉煤灰和自然冷却黄磷炉渣并添加一定量的辅料可以制备CAS系微晶玻璃.当分别添加2wt％的TiO2,CaF2,P2 O5时,主晶相不发生改变,均为硅灰石(CaSiO3),但添加2wt％ TiO2或2wt％ CaF2具有降低析晶活化能、促进析晶的作用,而添加2wt％P2O5具有增加析晶活化能、抑制析晶的作用.     

钙硅比对钙铁硅铁磁体微晶玻璃核化与晶化的影响

为了研制用作温热治疗癌症的铁磁体微晶玻璃热种子材料,制备了一组化学组成为40Fe2O3xCaO(60-x)SiO23B2O33P2O5玻璃(x=20、25、30、35质量分数),用XRD、DTA、VSM对其核化与晶化过程进行了研究.研究发现,钙铁硅微晶玻璃在还原气氛下热处理后,除了磁铁矿和硅灰石及少量赤铁矿晶相外,还会出现钙铁辉石、方石英晶相.钙硅比较小的玻璃,热处理温度-时间相图中钙铁辉石相区范围较大;钙硅比较大的,钙铁辉石相区范围较小.另外,钙硅比不同,玻璃的成核机理、开始析出磁铁矿的温度也不同.     

钙硅比对钙铁硅铁磁体微晶玻璃核化与晶化的影响

为了研制用作温热治疗癌症的铁磁体微晶玻璃热种子材料,制备了一组化学组成为40Fe2O3xCaO(60-x)SiO23B2O33P2O5玻璃(x=20、25、30、35质量分数),用XRD、DTA、VSM对其核化与晶化过程进行了研究.研究发现,钙铁硅微晶玻璃在还原气氛下热处理后,除了磁铁矿和硅灰石及少量赤铁矿晶相外,还会出现钙铁辉石、方石英晶相.钙硅比较小的玻璃,热处理温度-时间相图中钙铁辉石相区范围较大;钙硅比较大的,钙铁辉石相区范围较小.另外,钙硅比不同,玻璃的成核机理、开始析出磁铁矿的温度也不同.     

烧结粉煤灰微晶玻璃装饰板的研究

以粉煤灰为主要原料,采用烧结法制备粉煤灰微晶玻璃装饰板,并借助Ｘ射线衍射法鉴定材料的主晶相。测定了微晶玻璃的主要性能,研究了基础玻璃成分、热处理制度对烧结、晶化过程及样品外观的影响,确定了合理的玻璃成分范围和工艺制度。     

CaO-SiO2-R2O-F系微晶玻璃的制备

通过烧结法制备了CaO-SiO2-R2O-F系微晶玻璃,用XED、DTA方法对微晶玻璃的析晶温度、物相组成等进行了分析,并通过SEM观察了微晶玻璃的断面形貌.讨论了热处理制度对析晶的影响.结果表明:晶化温度对微晶玻璃析晶过程有显著的影响.在晶化温度为870℃时,主晶相为枪晶石,化学式为ca4(F15(OH)05)si2O7在这个温度下,析出了大量的枪晶石晶体,还有少量的硅碱钙石及ca2SiO2F2晶体.     

Current advances on titanate glass-ceramic composite materials as waste forms for actinide immobilization: A technical review

As the emerging versatile waste forms for immobilizing actinide-rich radioactive wastes, glass-ceramic composite materials based on some durable ceramic phases are being developed. They have apparent advantages over the conventional borosilicate glasses and multi- or single- phase ceramics as they essentially combine the chemical and processing flexibilities of glasses to accommodate processing impurities and excellent chemical durability of ceramic phases to host actinides. More recently, some new advances have been made on scientific and technological aspects including new glass-ceramic systems; improved understanding of ceramic phase evolution in glass; actinide validation studies and simplified processing techniques. This review is intended to cover the current advances on the development of glass-ceramic composite waste forms focusing on titanate ceramic phases (zirconolite, pyrochlore and brannerite) for immobilizing various actinide-rich radioactive wastes arising from the nuclear fuel cycle.     

Glass-ceramic from fly ash with added MgO and TiO2

The effects of the addition of MgO and TiO₂ to fly ash on the nucleation and crystal growth mechanisms of the derived glass are investigated with the aid of differential thermal analysis, dilatometry, X-ray diffraction and scanning electron microscopy (SEM). Phase separation occurs on heating the investigated glass. The glass-ceramic materials obtained contain anorthite (CaOAl₂O₃2SiO₂) and cordierite (2MgO2Al₂O₃5SiO₂) as the main crystalline phases. The morphology of the glass-ceramic material was investigated by SEM and it was consistent with the double-framework structure of the phase-separated glass and it was constituted by a low viscosity phase almost completely crystallised and high viscosity phase scarcely or not crystallised, depending on the heat-treatment.     

Resorbability of a Bioglass®-based glass-ceramic scaffold produced via a powder metallurgy approach

Consolidation processes aimed at manufacturing cellular solids from bioglasses often result in a glass-ceramic microstructure, whose response to aqueous environment affects their performance. In this study, we evaluated the microstructure and the effect of crystallization on the dissolution mechanism of a Bioglass®-based glass-ceramic scaffold, produced with a powder metallurgy inspired technology. All the experiments are conducted in a controlled aqueous environment in order to avoid nucleation of different species or unknown chemical interactions between simulated body fluids and bioglass-ceramic material.The presence of a residual silica glass embedding different phases of not fully crystallized particles is highlighted, showing a complex multiscale structure elucidated via Focused Ion Beam (FIB) preparation and Scanning Transmission Electron Microscopy (STEM) observation. Crystalline and amorphous phases dissolved both in water, with different kinetics. The dissolution appears to be a surface phenomenon, which reduces the section of the foam struts without instability of the glass-ceramic material. Amorphization of crystalline phase is observed during immersion of the glass-ceramic material in stirring conditions at room temperature from the ions dissolved in water.     

TiO2加入量对高炉渣微晶玻璃析晶的影响

以高炉渣微晶玻璃为研究对象,改变配料中晶核剂TiO2的含量,制得微晶玻璃样品. 以不同的升温速率对样品进行差热分析,根据升温速率和差热分析曲线上的晶化峰温度,采用3种不同的方法计算微晶玻璃样品的析晶活化能. 结果表明,随着TiO2含量的增加,析晶活化能呈现出先减小后增大的趋势,在TiO2的加入量为3.1%时,微晶玻璃的析晶活化能最低,此时拟合出的3种析晶活化能最小值分别为135.7, 143.9, 151.7 kJ/mol. 样品的红外谱图表明,TiO2的含量为3%~4%时析出晶体较多. TiO2含量为3%和4%的样品的X射线衍射图谱表明,样品中析出了以透辉石为主晶相、金红石为次晶相的晶体.     

CaO-Al2O3-SiO2系粉煤灰微晶玻璃的析晶动力学及电子探针分析

利用烧结法制备了CaO-Al2O3-SiO2系粉煤灰微晶玻璃。采用差热分析方法确定了析晶峰温度Tp,研究了其晶析动力学,并利用JMA方程获得的析晶动力学参数k（Tp）制备玻璃热稳定性。采用X射线衍射、电子探针-能谱分析方法研究了微晶玻璃中玻璃基体、晶相的组成。研究结果表明：析晶活化能Ea为591.5kJ/mol,指前因子A为1.87×1013min-1,k（Tp）判据表明玻璃的稳定性随升温速率的增加而降低;升温速率对主晶相的种类没有影响,即均为单一的β-硅灰石,其尺寸大小约为2～20μm;基体玻璃中原子种类十分复杂,既有网络形成体,又有网络修饰体和网络中间体,其性质与Na2O SiO2玻璃相近。     

Characterization investigations of glass-ceramics developed from Seyitömer thermal power plant fly ash

Glass-ceramic materials were produced from fly ash samples obtained from the Seyitömer thermal power plant in Turkey. Glass samples were crystallized by suitable nucleation and crystal growth heat treatments on the basis of DTA results. The microstructural analysis of glass-ceramic samples were carried out using SEM and XRD techniques. SEM investigations clearly demonstrated the presence of a tiny crystallized phase dispersed in the microstructure. XRD results revealed that the main crystalline phase was diopside [Ca(Mg,Al)(Si,Al)₂O₆]. It was observed that the mechanical properties and the thermal expansion coefficient of the glass-ceramic samples depend only on the amount of the crystalline phase. Furthermore, chemical durability of the produced glass-ceramic samples were high.     

Effect of Thermal History on the Properties of a Willemite Glass-Ceramic

The effect of time and temperature on the properties and structure of a willemite glass-ceramic were measured. -0 polymorphs of willemite were found to exist in most of the glass-ceramics. Those properties of the glass-ceramic which depend primarily on the composition of the glassy phase (helium permeation and diffusion, and chemical durability) were found to be strong functions of the thermal history of the samples, whereas those properties which depend on both the compositions and the relative amounts of both the glassy and crystalline phases (thermal expansion coefficient, density, and refractive index) were found to be relatively insensitive to thermal history. The properties of the glass-ceramics could be described by simple mixing models using the properties measured for willemite and for glasses having theoretical residual glass compositions corresponding to varying degrees of crystallinity in the glass-ceramic.     

Dissolution of a Sphene Glass-Ceramic, and of Its Component Sphene and Glass Phases, in Ca-Na-Cl Brines

Leaching experiments for up to 569 d have been performed to examine the dissolution in Ca-Na-Cl groundwater of a sphene (CaTiSiO₅)-based glass-ceramic, a candidate material for immobilizing nuclear fuel recycle wastes. The experiments involved leaching of samples of a simulated-waste-loaded glass-ceramic, doped with ²²Na or ⁴⁵Ca, in a synthetic groundwater at 25° and 100°C. The results are compared with those from separate leaching experiments with ²²Na- or ⁴⁵Ca-doped samples of aluminosilicate glass and ceramic sphene, representing the component phases of the glass-ceramic. The comparison supports a model in which the glass-ceramic dissolution rate may be approximately derived from the weighted average of the separate dissolution rates of its component glass and ceramic phases. No synergistic effects in the leaching of the glass and ceramic phases in the glass-ceramic were found.     

自洁净微晶玻璃的制备工艺研究

为了制备表面具有高疏水性的自洁净微晶玻璃,文中首先以高炉矿渣和钾长石为原料制成微晶玻璃坯体,然后利用溶胶-凝胶的工艺制备出硅溶胶/聚四氟乙烯(PTFE)有机/无机镀液,利用浸渍提拉法在微晶玻璃表面进行镀膜,最后通过热处理制成表面具有自洁净功能的微晶玻璃。分析了乙醇用量、加水量、pH值、陈化时间及温度对于溶胶形成的影响,以及硅溶胶/PTFE配比对于镀液性能和镀膜效果的影响。利用XRD、SEM、接触角测定仪等对样品进行性能检测。结果表明,制备的微晶玻璃的主晶相是镁黄长石,聚四氟乙烯对硅溶胶有良好的修饰作用,自洁净微晶玻璃的接触角已达到120°,具有较强的疏水性。     

Microporous Glass-Ceramics in NASICON-Type Copper(II) Titanium Phosphate

A novel porous glass-ceramic with a skeleton of a NASICON-type copper(II) titanium phosphate was prepared via the controlled crystallization of a glass and the subsequent chemical leaching of the resulting dense glass-ceramic. A volume-crystallized dense glass-ceramic comprised of CuTi₂(PO₄)₃ and Cu₃(PO₄)₂, whose surface was covered by a thin layer of CuO, was prepared by reheating a glass with a nominal composition of 50CuO20TiO₂30P₂O₅ (in mol%) in air. When the resulting glass-ceramic was leached with dilute HCl, the Cu₃(PO₄)₂ and CuO phases were dissolved out selectively, and a cuprous NASICON crystal of CuTi₂(PO₄)₃ was converted to its cupric type, CuTi₄(PO₄)₆, which was left as a skeleton of the porous materials. The specific surface area and the average pore radius of the porous glass-ceramic obtained were ∼70 m²/g and ∼7 nm, respectively. The porous glass-ceramic showed high catalytic activities for the dehydration of 2-propanol.