以磷渣和煤矸石为原料，采用一步烧结法制备了性能优良的CaO?Al2O3?SiO2(CAS)系微晶玻璃，用差示扫描量热法(DSC)，X射线衍射(XRD)和扫描电子显微镜(SEM)等对其进行分析和表征，研究了热处理温度对微晶玻璃晶相组成、微观结构和宏观性能的影响规律。结果表明，固废利用率达100%，微晶玻璃性能良好；以磷渣和煤矸石为原料在1250℃下熔融2 h、于850℃热处理保温2 h可制备主晶相为假硅灰石Ca3(Si3O9)的微晶玻璃，其抗折强度、显微硬度和体积密度分别为74.4 MPa，566.9 HV和2.75 g/cm3。随热处理温度升高，微晶玻璃主晶相由Ca3(Si3O9)相转变为硅灰石CaSiO3相，晶体形态由球状向针状、短柱状改变，对提高微晶玻璃抗折性能有利，而显微硬度和体积密度均先增加后降低。
Phosphorus slag is an industrial waste produced in the production of yellow phosphorus by the electric furnace method. For each 1 t of yellow phosphorus produced, it is necessary to discharge 8~10 t of phosphorus slag. Coal gangue is a solid waste produced in the coal industry. It is discharged from 10% to 15% of annual coal production. It has accumulated more than 4.5 billion tons of storage, which is the largest solid waste in China. Since a large amount of unexploited solid waste occupied industrial and agricultural land, safety problems and environmental pressures are presented. The disposal of solid waste is an urgent task. Therefore, the effective use of the solid waste resources and turning waste into treasure have important practical significance. In recent years, the glass-ceramics based on solid waste has been widely used in building decoration field. However, the technology has not been widely used due to high cost and defects in the preparation process. In this work, the feasibility of preparing glass-ceramics by the combination of phosphorus slag and coal gangue was studied. The effects of heat treatment temperature on the crystalline phase composition, microstructure and properties of the glass-ceramics were also discussed via differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Powder base glass was obtained by melting phosphorus slag with coal gangue at 1250℃ for 2 h. The results indicated that the sintered glass-ceramics with pseudo wollastonite Ca3(Si3O9) as the main crystallization phase could be prepared after heat treatment at 850℃ for 2 h. The flexural strength, microscopic strength and bulk density of the sample were 74.4 MPa, 566.9 HV and 2.75 g/cm3, respectively. In addition, with the increase of heat treatment temperature, the main crystalline phase of the glass-ceramics changed from Ca3(Si3O9) to wollastonite (CaSiO3), the morphology of the crystal developed from spherical to the needle-like and short column, which were beneficial for improving the flexural strength. Both the microscopic strength and bulk density increased first and then decreased with the increase of heat treatment temperature.
[1] 方一航, 王焕平, 李志刚,等. Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃-陶瓷复合材料性能的影响[J]. 复合材料学报, 2014, 31(6):1509-1515.
Fang Yihang, Wang Huanping, Li Zhigang, et al. Effect of Bi2O3 flux on properties of CaO-B2O3-SiO2/Al2O3 glass-ceramic composites[J]. Acta Materiae Compositae Sinica, 2014, 31(6):1509-1515.
[2] Saadaldin S A, Rizkalla A S. Synthesis and characterization of wollastonite glass–ceramics for dental implant applications[J]. Dental Materials, 2014, 30:364-371.
[3] Toya T, Kameshima Y, Yasumori A, et al. Preparation and properties of glass-ceramics from wastes (Kira) of silica sand and kaolin clay refining[J]. Journal of the European Ceramic Society, 2004, 24:2367-2372.．
[4] 杜瑞材, 倪似愚, 常江,等. 含Zn生物玻璃、玻璃陶瓷与聚酯复合骨组织工程支架的制备及性能[J]. 复合材料学报, 2008(6):123-129.
Du Ruicai, Ni Xiangyu, Chang Jiang, et al. Preparation and properties of Zn-containing bioglass, glass-ceramic and polyester composite bone tissue engineering scaffolds[J]. Acta Materiae Compositae Sinica, 2008(6):123-129.
[5] WOLFRAM H, GEORGE B. Glass-Ceramic Technology [M]. The American Ceramic Society, 2002:1–4.
[6] 史培阳, 张影, 张大勇, 等. 矿渣微晶玻璃的析晶行为与性能[J].中国有色金属学报, 2007, 17(2):341–347.
SHI Peiyang, ZHANG Yi, ZHANG Dayong, et al. Chin J NonferrousMetals, 2007, 17(2):341–347.
[7] 程金树, 李宏, 汤李缨, 等. 微晶玻璃[M]. 北京: 化学工业出版社,2006:1–6.
Cheng Jinshu, Li Hong, Tang Lizhen, et al. Glass-ceramics [M]. Beijing: Chemical Industry Press, 2006:1–6.
[8] 尚志标, 黄小凤, 马丽萍,等. 粉煤灰和自然冷却黄磷炉渣协同制备微晶玻璃[J]. 硅酸盐通报, 2017, 36(2):533-538.
Shang Zhibiao, Huang Xiaofeng, Ma Liping, et al. Synergistic preparation of glass-ceramics from fly ash and naturally cooled yellow phosphorus furnace slag [J]. Bulletin of Silicate, 2017, 36(2): 533-538.
[9] Soon-Do, Yoon, Jong-Un, et al. Characterization of Wollastonite Glass-ceramics Made from Waste Glass and Coal Fly Ash[J]. Journal of Materials Science & Technology, 2013, 29(2):149-153.
[10] 杨淑敏, 张伟, 戴晔. 利用新疆高炉渣制备微晶玻璃的研究[J]. 硅酸盐通报, 2014, 33(1):48-53.
Yang Shumin, Zhang Wei, Dai Wei. Study on Preparation of Glass-ceramics from Xinjiang Blast Furnace Slag[J]. Bulletin of Silicate, 2014, 33(1): 48-53.
[11] 岳钦艳, 张升晓, 于慧,等. TiO2加入量对高炉渣微晶玻璃析晶的影响[J]. 过程工程学报, 2007, 7(2):327-331.
Yue Qinyan, Zhang Shengxiao, Yu Hui, et al. Effect of TiO2 Addition on Crystallization of Blast Furnace Slag Glass-Ceramics[J]. Chinese Journal of Process Engineering, 2007, 7(2):327-331.
[12] 史培阳, 姜茂发, 刘承军,等. 热处理对硼泥微晶玻璃微观结构的影响[J]. 过程工程学报, 2005, 5(2):175-178.
Shi Peiyang, Jiang Maofa, Liu Chengjun, et al. Effect of heat treatment on microstructure of boron mud glass-ceramics[J]. Chinese Journal of Process Engineering, 2005, 5(2): 175-178.
[13] Gomes V, Borba C D G D, Riella H G. Production and characterization of glass ceramics from steelwork slag[J]. Journal of Materials Science, 2002,12:2581-2585.
[14] 中国国家建材工业局标准化研究所.C/T 872-2000[S].北京：机械科学研究院标准出版中心,2001.
Institute of Standardization, China National Building Material Industry Bureau. C/T 872-2000[S]. Beijing: Standard Publishing Center of Mechanical Science Research Institute ,2001.
[15] Kissinger H E. Variation of Peak Temperature with Heating Rate in Differential Thermal Analysis[J]. Journal of Research of the National Bureau of Standards, 1956:217-221.
[16] Kissinger H E. Reaction Kinetics in Differential Thermal Analysis[J]. Analytical Chemistry, 1957, 29(11):1702-1706.
[17] Avrami M. Kinetics of Phase Change．I General theory［J］．The Journal of Chemical Physics，1939，7:1103-1112．
[18] Johnson W A. Reaction Kinetics in Processes of Nucleation and Growth[J]. Am.inst.min.metal.petro.eng, 1939, 135(8): 396-415．
[19] 姚树玉, 姚玉随, 韩野,等. CaO-Al2O3-SiO2系粉煤灰微晶玻璃的析晶动力学及电子探针分析[J]. 硅酸盐学报, 2012, 40(1):170-174.
YAO Shu-yu, YAO Yu-sui, HAN Ye, et al. Crystallization kinetics and electron probe analysis of CaO-Al2O3-SiO2 fly ash glass-ceramics[J]. Journal of The Chinese Ceramic Society, 2012, 40(1): 170-174 .
[20] 李保庆, 郭艳平, 党海峰,等. 晶化温度对钨尾矿微晶玻璃析晶性能的影响[J]. 中国陶瓷, 2017(11):63-68.
Bao Qing, Guo Yanping, Dang Haifeng, et al. Effect of Crystallization Temperature on Crystallization Properties of Tungsten Tailings Glass-Ceramics[J]. China Ceramics, 2017(11): 63-68.
