热处理温度对磷渣-煤矸石微晶玻璃结构和性能的影响
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摘要
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-Al_2O_3-SiO_2(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Ca_3(Si_3O_9)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,566.9HV和2.75 g/cm3。随热处理温度升高,微晶玻璃主晶相由Ca_3(Si_3O_9)相转变为硅灰石CaSiO_3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 andenvironmental 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 1 250℃ for 2 h. The results indicated that the sintered glass-ceramics with pseudo wollastonite Ca_3(Si_3 O_9) 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/cm~3, respectively. In addition, with the increase of heat treatment temperature, the main crystalline phase of the glass-ceramics changed from Ca_3(Si_3 O_9) to wollastonite(CaSiO_3), 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.
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 andenvironmental 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 1 250℃ for 2 h. The results indicated that the sintered glass-ceramics with pseudo wollastonite Ca_3(Si_3 O_9) 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/cm~3, respectively. In addition, with the increase of heat treatment temperature, the main crystalline phase of the glass-ceramics changed from Ca_3(Si_3 O_9) to wollastonite(CaSiO_3), 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.
引文
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[15]杨芃,黄永前,孙慧,等.晶化温度对R2O-MgO-Al2O3-SiO2系微晶玻璃析晶和力学性能的影响[J].硅酸盐通报,2015,34(4):985-988.Yang P,Huang Y Q,Sun H,et al.Effect of crystallization temperature on the crystallization and mechanical properties of R2O-MgO-Al2O3-SiO2 system glass-ceramics[J].Bulletin of The Chinese Ceramic Society,2015,34(4):985-988.
[16]罗智宏,何峰,张文涛,等.熔融法转炉钢渣微晶玻璃的结构与性能研究[J].人工晶体学报,2018,47(3):514-521.Luo Z H,He F,Zhang W T,et al.Study on the structure and properties of glass slag glass-ceramics in melting process converter[J].Journal of Synthetic Crystals,2018,47(3):514-521.
[17]Avrami M.Kinetics of phase change:I.general theory[J].The Journal of Chemical Physics,1939,7(12):1103-1112.
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[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 S Y,Yao Y S,Han Y,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,2017,53(11):63-68.Li B Q,Guo Y P,Dang H F,et al.Effect of crystallization temperature on crystallization properties of tungsten tailings glass-ceramics[J].China Ceramics,2017,53(11):63-68.
[2]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 Y H,Wang H P,Li Z G,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.
[3]Saadaldin S A,Rizkalla A S.Synthesis and characterization of wollastonite glass-ceramics for dental implant applications[J].Dental Materials,2014,30(3):364-371.
[4]游世海,郑化安,付东升,等.粉煤灰制备微晶玻璃研究进展[J].硅酸盐通报,2014,33(11):2902-2907.You S H,Zheng H A,Fu D S,et al.Research progress in the preparation of glass-ceramics from fly ash[J].Bulletin of Silicate,2014,33(11):2902-2907.
[5]白杨.高透性齿科二硅酸锂微晶玻璃的设计与开发[D].北京:中国科学院大学,2017:1-2.Bai Y.Design and development of high permeability dental lithium disilicate glass-ceramics[D].Beijing:University of Chinese Academy of Sciences,2017:1-2.
[6]龚星晨,陈其伟,国宏伟,等.以高炉渣与废玻璃制备烧结微晶玻璃[J].金属世界,2018,(3):13-17.Gong X C,Chen Q W,Guo H W,et al.Preparation of sintered glass-ceramics from blast furnace slag and waste glass[J].Metal World,2018,(3):13-17.
[7]邓磊波,张雪峰,张明星,等.熔制保温时间对CAMS系矿渣微晶玻璃结构与性能的影响[J].材料导报,2017,31(18):125-130.Deng L B,Zhang X F,Zhang M X,et al.Effect of melting insulation time on structure and properties of CAMS slag glass-ceramics[J].Material Review,2017,31(18):125-130.
[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 Z B,Huang X F,Ma L P,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]殷琪,杨军,陈昌锋,等.钢渣微晶玻璃材料的制备与性能表征[J].铸造技术,2017,38(1):54-59.Yin Q,Yang J,Chen C F,et al.Preparation and characterization of steel slag glass-ceramic materials[J].Foundry Technology,2017,38(1):54-59.
[10]胡兰,何峰,张文涛,等.烧结法制备高炉渣CMAS系统微晶玻璃的研究[J].人工晶体学报,2017,46(7):1267-1273.Hu L,He F,Zhang W T,et al.Preparation of glass-ceramics for blast furnace slag CMAS system by sintering method[J].Journal of Synthetic Crystals,2017,46(7):1267-1273.
[11]戚昊,何峰,严芳玲,等.利用钼尾矿制备微晶泡沫玻璃[J].陶瓷学报,2017,38(1):76-81.Qi H,He F,Yan F L,et al.Preparation of microcrystalline foam glass using molybdenum tailings[J].Journal of Ceramics,2017,38(1):76-81.
[12]廖力.利用铜矿尾矿制备微晶玻璃试验研究[J].矿产综合利用,2017,(6):82-85.Liao L.Experimental study on preparation of glass-ceramics from copper mine tailings[J].Mineral Resources Utilization,2017,(6):82-85.
[13]闫鑫坤,黄永前,万里佳.Al2O3对R2O-CaO-SiO2-F系废渣微晶玻璃析晶与性能的影响[J].玻璃,2018,45(3):1-5.Yan X K,Huang Y Q,Wan L J.Influence of Al2O3 on the crystallization and properties of R2O-CaO-SiO2-F system glass-ceramics made from residual[J].Glass,2018,45(3):1-5.
[14]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 S M,Zhang W,Dai Y.Study on preparation of glass-ceramics from Xinjiang blast furnace slag[J].Bulletin of Silicate,2014,33(1):48-53.
[15]杨芃,黄永前,孙慧,等.晶化温度对R2O-MgO-Al2O3-SiO2系微晶玻璃析晶和力学性能的影响[J].硅酸盐通报,2015,34(4):985-988.Yang P,Huang Y Q,Sun H,et al.Effect of crystallization temperature on the crystallization and mechanical properties of R2O-MgO-Al2O3-SiO2 system glass-ceramics[J].Bulletin of The Chinese Ceramic Society,2015,34(4):985-988.
[16]罗智宏,何峰,张文涛,等.熔融法转炉钢渣微晶玻璃的结构与性能研究[J].人工晶体学报,2018,47(3):514-521.Luo Z H,He F,Zhang W T,et al.Study on the structure and properties of glass slag glass-ceramics in melting process converter[J].Journal of Synthetic Crystals,2018,47(3):514-521.
[17]Avrami M.Kinetics of phase change:I.general theory[J].The Journal of Chemical Physics,1939,7(12):1103-1112.
[18]Johnson W A.Reaction kinetics in process of nucleation and growth[J].Transaction of Aime,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 S Y,Yao Y S,Han Y,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,2017,53(11):63-68.Li B Q,Guo Y P,Dang H F,et al.Effect of crystallization temperature on crystallization properties of tungsten tailings glass-ceramics[J].China Ceramics,2017,53(11):63-68.
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