花岗岩废渣微晶玻璃的析晶过程

以花岗岩废渣为主要原料制备了微晶玻璃。采用差示量热扫描分析、X射线衍射分析、扫描和透射电子显微镜、能量色散X射线谱等分析技术,对其析晶过程进行了研究。结果表明:基础玻璃中发生液液分相,呈现微乳浊状,形成了富Si~(4+)、Al~(3+)相和富P~(5+)、Ca~(2+)、Mg~(2+)、Ti~(4+)相。基础玻璃经740℃核化处理60 min后,两相之间离子发生迁移,Ti~(4+)含量比由1.96变为2.85,P~(5+)、Ca~(2+)、Mg~(2+)均富集于富Ti~(4+)相,为Ti O_2晶核剂在相界面处的成核以及含钛辉石初晶相的析出提供了有利的先驱条件。晶化过程中,玻璃依次析出亚稳的含钛辉石相和镁橄榄石;延长晶化时间,主晶相由亚稳的含钛辉石逐渐向稳定的透辉石转变。740℃核化60 min、950℃晶化120 min的样品,其四点抗弯强度达70.19 MPa。     

SiO_2—Al_2O_3—MgO—K_2O—MgF_2系玻璃陶瓷析晶机理及断裂机制

以SiO2—Al2O3—MgO—K2O—MgF2体系玻璃为基础,采用整体析晶法,在高温条件下制备出堇青石/氟金云母玻璃陶瓷。借助于综合热分析仪、X射线衍射仪和扫描电子显微镜等分析手段,研究了玻璃陶瓷的析晶机制、显微形貌和断裂机制。结果表明:所制备的玻璃陶瓷主晶相为板条状氟金云母和β-堇青石,经1 000℃保温3h热处理后,主晶相转变为镁橄榄石;以堇青石和氟金云母为主晶相的玻璃陶瓷断裂机理为穿晶断裂,以镁橄榄石为主晶相的玻璃陶瓷为沿晶断裂。在基础玻璃中添加5%B2O3,可抑制氟金云母相的析出,并提高玻璃陶瓷的致密度。     

低热膨胀系数堇青石微晶玻璃的制备

采用传统熔体冷却法制备了Mg O-A1_2O_3-Si O_2玻璃,并通过热处理进一步获得了堇青石基微晶玻璃。探索了Zr O_2/Ti O_2复合成核剂及热处理制度对微晶玻璃析晶性能及热膨胀系数的影响规律。结果表明,Mg O-A1_2O_3-Si O_2体系有较强的表面析晶倾向,晶核剂的加入能降低析晶温度,同时有利于诱导样品发生均匀析晶,并能促进低温型堇青石相向膨胀系数更低的高温型堇青石相转变,有利于降低堇青石微晶玻璃材料的膨胀系数。在复合晶核剂作用下,当析晶温度为1050℃,保温时间为60 min时,可获得最低热膨胀系数为1.03×10~(-6)/℃的堇青石微晶玻璃材料。     

镁铝硅系堇青石基微晶玻璃的制备及性能研究

采用高温熔融法制备了MgO-Al2O3-SiO2 (MAS)系堇青石基微晶玻璃.借助X射线衍射仪(XRD)、扫描电镜(SEM)及热膨胀系数仪研究了晶化热处理工艺、MgO/Al2O3质量比以及晶核剂种类(TiO2/ZrO2)与含量对MAS系堇青石基微晶玻璃理化性能和晶化特性的影响.结果表明:在核化温度750℃、保温时间1h,晶化温度1050℃、保温时间2.5h,升温速率5 ℃/min时,微晶玻璃中堇青石含量最高,析晶性能最好;当MgO/Al2O3质量比为1左右时,在30 ～ 700℃温度范围内,平均热膨胀系数最小,在4.4 ～4.8×10-6K-1范围内可调;TiO2是MAS系堇青石基微晶玻璃的有效晶核剂,而ZrO2的加入并不利于基础玻璃的晶化.     

反应析晶烧结法制备透辉石-钠长石玻璃陶瓷

以滑石、高岭土和化学试剂合成了两种析晶促进剂,加入到废玻璃粉末中烧结制备成透辉石-钠长石玻璃陶瓷。研究了析晶促进剂的组成和加入量对玻璃陶瓷析晶和性能的影响。结果表明,在烧结过程中,析晶促进剂和玻璃发生反应,析出透辉石和钠长石。析晶促进剂的组成和加入量对反应析晶有一定影响,随析晶促进剂加入量的增加,玻璃陶瓷密度和强度先增后降,存在一最佳加入量,这时烧结的玻璃陶瓷有较高的密度和强度。     

熔制法制备不同晶相的钙镁铝硅微晶玻璃

采用熔制法制备两种可析出不同晶相的CaO-MgO-Al2O3-SiO(2CMAS)玻璃,研究了不同原料组成下CMAS玻璃的析晶行为和显微结构。研究结果表明,CMAS玻璃A在986℃下热处理4 h,能析出钙长石和透辉石主晶相;CMAS玻璃B在950℃下热处理4h,可获得堇青石晶相及少量金红石型TiO2晶相。     

花岗岩废渣微晶玻璃晶化工艺研究

用差示扫描量热法(DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试方法研究了晶化工艺对R_2O-CaO-MgO-Al_2O_3-SiO_2-F系废渣微晶玻璃晶相组成、显微结构和力学性能的影响。结果表明:873℃晶化1 h,试样主晶相为斜顽辉石;随着晶化温度升高斜顽辉石向透辉石转变,1010℃晶化1 h,试样主晶相为透辉石和斜顽辉石,三点抗弯强度和显微硬度达最大值,分别为125 MPa、5.21 GPa;1 080℃晶化1 h,出现氟闪石新相,力学性能开始下降。     

MgO-Al2O3-SiO2系高强度微晶玻璃的晶化行为与力学性能

通过DTA，XRD，SEM等技术，对以TiO2作为晶核利的堇青石基微晶玻璃的晶化过程和力学性能进行了研究。对晶化过程中晶体类型、热处理工艺与力学性能之间的关系作了讨论。结果表明：随温度升高，玻璃中依次析出镁铝钛酸盐、β-石英固溶体、假蓝宝石、尖晶石、α-堇青石、α-石英、方石英、顽辉石等晶体。材料力学性能取决于热处理工艺，经850℃，2h和1200℃，2h处理后，所制备的玻璃具有良好的力学性能，其弯曲强度可稳定在340MPa以上。     

晶化时间对MgO-Al2O3-SiO2微晶玻璃相转变及热膨胀性能的影响

采用XRD、DTA、SEM等测试方法,对MgO-Al2O3-SiO2（MAS）系微晶玻璃的析晶和微观结构进行了研究,讨论了不同的晶化时间对MAS微晶玻璃析晶行为及其热膨胀性能的影响。结果表明：在1050℃保温,堇青石能快速地晶化析出。随着晶化时间的增长,堇青石相逐渐增多,当晶化2h时几乎完全析出,析出晶粒大小约为2～5um。MAS系微晶玻璃的热膨胀系数与相组成有着密切的关系,随着晶化时间的延长,热膨胀系数逐渐减小。     

晶化处理对堇青石微晶玻璃晶相及其性能影响的研究

以堇青石的理论化学组成为基础玻璃配方,采用熔融法制备堇青石微晶玻璃。利用DSC-TG、XRD、SEM研究堇青石微晶玻璃的析晶特性和微观形貌,并对其热膨胀性能以及烧结性能进行测试。结果表明:微晶玻璃初晶相为亚稳MgAl_2Si_3O_(10)相,终晶相为α-堇青石相,随着热处理温度升高,亚稳MgAl_2Si_3O_(10)相向α-堇青石相转变。在1000～1200℃的温度范围内,堇青石微晶玻璃的结构和性能较为稳定。     

Crystallization behavior and mechanical properties of high strength mica-containing glass-ceramics from granite wastes

The high-strength mica-containing glass-ceramics were prepared from granite wastes by bulk crystallization. The influences of SiO₂/Al₂O₃ molar ratio (S/A = 7.72, 9.62, 12.58, 17.82 and 29.67) on the crystallization behavior, microstructure, mechanical properties and machinability of glass-ceramics were investigated. The results demonstrated that the polymerization degree of the glass network decreased with the S/A ratio increasing, which further caused the decrease in glass transition temperature and crystallization temperatures. The increase in the S/A ratio promoted the precipitation of diopside, hectorite, kalsilite and tainiolite in glass-ceramics when the samples were heated at 750 °C, while inhibiting the precipitation of forsterite. For the glass-ceramics crystallized at 800 and 900 °C, the main crystalline phases transformed from diopside, forsterite, and nepheline to diopside, kalsilite, and tainiolite, with the S/A ratio increasing. As the SiO₂ gradually replaced Al₂O₃, the morphology of crystals changed from lamellar to granular, while the mean size of crystals reduced. The Vickers-Hardness values of glass-ceramics crystallized at 800 and 900 °C ascended with S/A ratio rising, and the values were above 6.30 GPa. The bending strength of most glass-ceramics is stable between 90 and 140 MPa, among which the maximum bending strength is 133.28 ± 14.81 MPa. The fracture toughness of the glass-ceramic crystallized at 800 and 900 °C declined, while that at 700 °C increased with a larger S/A ratio. Glass-ceramics after heat-treated at 900 °C with S/A ratio of 9.62 had the largest fracture toughness of 3.28 ± 0.15 MPa m^1/2. In preliminary tests of machinability, glass-ceramic after heat-treated at 900 °C with S/A ratio of 9.62 showed better results.     

Crystallization pathways in glass-ceramics by sintering cathode ray tube (CRT) glass with kaolin-based precursors

The crystallization mechanisms for the formation of glass-ceramics by sintering CRT glass with kaolin-based precursors were investigated by quantitatively determining the crystalline and amorphous phases in the products. Amorphization of sintered products was observed in CRT/kaolinite and CRT/mullite glass-ceramics systems at 700–900?°C. With the increase of temperature, the crystallochemical formation of lead feldspar and orthoclase was detected. Orthoclase was found to be the major crystalline phase in both CRT/kaolinite and CRT/mullite systems at 1000–1100?°C. When the temperature increased to 1000–1100?°C, lead feldspar was formed as the only crystalline phase to host Pb. The leaching tests suggested that the glass-ceramic product sintered by CRT/kaolin-based precursors has stronger resistance against acid attack because of the incorporation of lead into lead feldspar crystal protected by glass matrix. The incorporation of CRT glass into glass-ceramics provides a promising strategy for reducing the environmental hazard of CRT glass.     

Preparation of translucent YAG glass/ceramic at temperatures below 900 °C

The work presented here deals with the preparation of bulk yttrium aluminium garnet (YAG) glass-ceramics and YAG ceramics from glass microspheres with a YAG composition. Sol-gel prepared YAG powder was fed into a high temperature methane-oxygen flame where the particles melted and glass microspheres, with a YAG composition, were formed. Viscous flow sintering of the microspheres was then performed to prepare bulk YAG glass-ceramics or ceramics in a hot press.Rapid crystallization of YAG glass was traced during hot pressing through a change in the heating rate slope due to release of latent (crystallization) heat. This allowed control of crystallization and enabled preparation of YAG-based materials with different amounts of residual glass. YAG ceramic with relative density of 94.2 % was prepared at 891 °C without isothermal heating; additionally, YAG glass-ceramic reached relative density > 99 % at temperature 815 °C without isothermal heating.     

Synthesis of glass-ceramics in the Na2O/K2O-CaO-MgO-SiO2-P2O5-CaF2 system as candidate materials for dental applications

This study reports on the sintering behavior, crystallization process, and mechanical properties of novel glass-ceramics (CGs) produced by the glass powder compact consolidation method. Substitution of K₂O for Na₂O and MgO for CaO was attempted in the parent glasses belonging to Na₂O-CaO-MgO-SiO₂-P₂O₅-CaF₂ system. Glass powder compacts were heat treated at various temperatures between 700°C and 900°C, taking under consideration the glass transition (T_g) and the crystallization peak (T_p) temperatures, which were experimentally determined for each investigated glass by thermal analysis (dilatometry and differential scanning calorimetry). The experimental results showed that sintering always preceded crystallization, regardless of the type of substitution. In the case of MgO substitution for CaO, crystallization was advanced in the range of 800°C-850°C, resulting in the formation of an assembly of crystalline phases, such as diopside, fluorapatite, and wollastonite. The substitution of K₂O for Na₂O increased the activation energy for crystallization, shifting crystallization process to a high temperature region, with the formation of alpha-potassium magnesium silicate, instead of wollastonite. The GCs produced had values of 22-31 GPa regarding the modulus of elasticity, 5.0-6.1 GPa concerning the microhardness, and 1.4-1.9 MPa⋅m^0.5 as regard the fracture toughness, which are similar to those of the human jawbone.     

Synthesis,phase composition and characterization of Co-diopside ceramic pigments

Ceramic pigments in the system CaO – CoO – MgO – 2SiO₂ were synthesized through solid-state high temperature sintering at 1000, 1100 and 1200 °C. The starting compositions were determined from the stoichiometric mineral diopside, following the expression CaO.xCoO.(1-x)MgO·2SiO₂, where x = 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 0.7 and 0.9. The effect of sintering temperature and initial cobalt concentration on the phase composition and colour were studied by powder X-ray diffraction analysis, scanning electron microscopy (SEM), infrared (FT-IR), ultraviolet–visible - (UV–Vis) and electron paramagnetic resonance (EPR) spectroscopy. Poly-phase ceramics were obtained depending on synthesis parameters, which in addition to Co-diopside, may contain wollastonite, Co-åckermanite – Ca₂(Co, Mg)Si₂O₇, Co-olivine – CoMgSiO₄, Co-monticellite – Ca(Mg, Co) SiO₄, and cristobalite. Quantitative ratios of detected mineral phases and the degree of cobalt isomorphic substitution were determined by applying Rietveld refinement approach. Trends and consistencies were outlined revealing that concentration of cobalt in the initial synthesis batch and its isomorphous incorporation in the crystal structure of diopside affect the structural perfection of the cation polyhedra. This fact obviously plays a key role in controlling the amount of the main constituent phase in the run-product. Ceramics of highest diopside content and lowest measured degree of structural distortion were only formed at 1200 °C and initial cobalt concentration in the range x = 0.2–0.3. These samples are pink in colour and have the highest value of red coordinate in the CIELab system due to Co²⁺ ions in octahedral coordination in diopside structure.     

Promoting spinel formation and growth for preparation of refractory materials from ferronickel slag

The study provides a method for improving the quality of the refractory material prepared from ferronickel slag by promoting the spinel formation and growth in the slag which was sintered with sintered magnesia and chromium oxide in a broad sintering temperature range from 1200°C to 1500°C. According to the thermodynamic analysis, except for forsterite due to the addition of sintered magnesia, a number of high-melting point spinel phases can also be formed in the presence of chromium oxide and this trend becomes more apparent with increasing sintering temperature, along with declined presence of low-melting point clinopyroxene, mainly enstatite. This expectation was verified by conversion of a part of the original phase of ferronickel slag, olivine, to two main spinel phases, including magnesium aluminate spinel and donathite which was produced by the replacement of nontoxic Cr³⁺ ions with Fe³⁺ ions in the octahedral vacancies of magnesium chromate spinel. The formation and growth of these spinel phases were promoted by elevating temperature from 1200°C to 1500°C, which accelerated the transition of initially generated enstatite to a glassy phase, in favor of densification. The formation and growth of spinel during sintering contributed to high refractoriness and compressive strength of the resulting refractory materials     

Synthesis of glass-ceramic glazes in the ZnO–Al2O3–SiO2–ZrO2 system

Glazes in the ZnO–Al₂O₃–SiO₂–ZrO₂ system with crystallization ability of gahnite (ZnO·Al₂O₃) and β-quartz solid solution (βqss) were synthesized. The compositions were designed based on calcium and magnesium oxide replacement (from a CaO–MgO–Al₂O₃–SiO₂ glass-ceramic glaze system) with zinc oxide and simultaneous increasing aluminum oxide. By this replacement, diopside eliminated and co-precipitation of gahnite and zirconium silicate observed. However, a little addition of Li₂O changes the crystallization path by precipitation of βq_ss and willemite (2ZnO·SiO₂) at low temperatures (800–900 °C) which dissolved into glaze by development of firing temperature. The experiments showed that while the micro-hardness of gahnite-based glass-ceramic glazes is almost equal with the diopside based one, it is more than the traditional floor tile glazes.     

Influence of Al2O3 and B2O3 on Sintering and Crystallization of Lithium Silicate Glass System

This article reports on the effect of Al₂O₃ and B₂O₃ added as dopants on the preparation of glass‐ceramics (GCs) belonging to the lithium silicate glass system. The GCs are prepared by sintering route using glass powders. The reasons for the crystallization of the metastable crystalline phase lithium metasilicate (LS) are discussed and the impact of the dopants on the thermodynamics and kinetics of crystallization is investigated. The addition of dopants modifies the thermodynamic equilibrium of the system and this change is mainly entropy driven and also slowdown the kinetics of crystallization. Differential thermal analysis and hot‐stage microscopy are employed to investigate the glass‐forming ability, sintering, and crystallization behavior of the studied glasses. The crystalline phase assemblage studied under nonisothermal heating conditions in the temperature range of 800°C–900°C in air. Well sintered and dense glass‐ceramics are obtained after sintering of glass powders at 850°C–900°C for 1 h featuring crystalline phase assemblage dominated by lithium disilicate (LS₂).     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

Structural and magnetic properties of steel slag based glass–ceramics

Crystallisation of magnetite in multicomponent glass melts was investigated. Structural features and magnetic properties were tested using X-ray diffraction, scanning electron microscope techniques, vibrating sample magnetometer and Mössbauer spectroscopy at room temperature. The results show that the magnetite phase was detected in the glass–ceramic samples after heat treatment at higher crystallisation temperature (over 900°C). Fe²⁺ and Fe³⁺ ions contribute to the formation of magnetite crystal. Various crystal morphologies were observed. Isomer shift values suggest that Fe³⁺ and Fe²⁺ are in tetrahedral and octahedral coordination respectively. The saturation magnetisation tends to increase with the crystallisation temperature.