高炉渣和低碳铬铁合金渣协同制备微晶玻璃

王一帆; 王艺慈; 王瑞鑫; 赵凤光; 柴轶凡; 罗果萍

doi:10.3969/j.issn.1000-6532.2024.06.003

高炉渣和低碳铬铁合金渣协同制备微晶玻璃

内蒙古科技大学材料与冶金学院，内蒙古　包头　014010

基金项目: 内蒙古科技成果转化专项项目（2019CG073）；“固废资源化”国家重点研发计划项目（2020YFC1909105）；白云鄂博稀土矿产资源基地固废循环利用集成示范（2021ZD0016）

详细信息

作者简介: 王一帆（1998-），女，硕士研究生，主要从事冶金资源综合利用方面的研究

中图分类号: TD989;TQ171

收稿日期: 2022-04-09

刊出日期: 2024-12-25

Cooperative Preparation of Glass-ceramics by Blast Furnace Slag and Low-carbon Chromium Iron Alloy Slag

School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China

Received Date: 09 April 2022

Publish Date: 25 December 2024

摘要

摘要:
这是一篇矿物材料领域的论文。为对大宗工业固废进行高值化利用和无害化处理，以包钢高炉渣、低碳铬铁合金渣和石英砂为原料熔融法制备CaO-MgO-Al₂O₃-SiO₂-Cr₂O₃体系微晶玻璃。并通过差热分析(DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)等分析手段探究较优原料配比。结果表明：当高炉渣、低碳铬铁合金渣、石英砂质量比例为60∶40∶31时，制得微晶玻璃的晶相为透辉石和绿辉石，此时微晶玻璃性能较优，抗折强度达到126.25 MPa，晶化度达到89.19%，显微结构较理想。较优原料配比条件下制备的微晶玻璃满足国家A类装饰装修材料IRa≤1.0和Iγ≤1.3的要求，且微晶玻璃中重金属铬的浸出浓度符合国家标准，表明采用高炉渣和低碳铬铁合金渣制备微晶玻璃具有可行性。
- 矿物材料 /
- 高炉渣 /
- 低碳铬铁合金渣 /
- 微晶玻璃 /
- 较优配比
Abstract:
This is an article in the field of mineral materials. In order to make high-value utilization and harmless treatment of bulk industrial solid waste, CaO-MgO-Al₂O₃-SiO₂-Cr₂O₃ system glass-ceramics were prepared by melting method with Baotou Steel blast furnace slag, low-carbon chromium iron alloy slag and quartz sand as the raw materials. The optimum ratio of raw materials was explored by means of differential thermal analysis (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that when the mass ratio of blast furnace slag, low-carbon chromium iron alloy slag and quartz sand was 60∶40∶31, the crystalline phases of glass-ceramics were diopside and omphacite. At this time, the performance of glass-ceramics was the best, the flexural strength reached 126.25 MPa, the crystallinity reached 89.19%, and the microstructure was ideal. The glass-ceramics prepared under the optimal raw material ratio met the requirements for national class A decoration materials, i.e. IRa≤1.0 and Iγ≤1.3, and the leaching concentration of heavy metal chromium in the glass-ceramics met the national standard, indicating that it is feasible to prepare glass-ceramics with blast furnace slag and low-carbon chromium iron alloy slag.
- Mineral materials /
- Blast furnace slag /
- Low-carbon chromium iron alloy slag /
- Glass-ceramics /
- Optimal ratio

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图 1 含MgO 5%的CaO-Al₂O₃-SiO₂三元相

Figure 1.

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图 2 基础玻璃DSC曲线

Figure 2.

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图 3 3^#微晶玻璃样品A、B的XRD

Figure 3.

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图 4 微晶玻璃样品的XRD

Figure 4.

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图 5 3^#和6^#微晶玻璃样品的SEM

Figure 5.

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表 1 各原料化学组成(质量分数)/%

Table 1. Chemical composition of raw materials (mass fraction)

成分	CaO	Fe₂O₃	FeO	SiO₂	K₂O	Na₂O	Al₂O₃	MgO	Cr₂O₃	CaF₂	TiO₂	CaS	MnO	其他
高炉渣	34.43	-	0.69	34.21	0.48	0.54	13.84	9.15	-	0.78	0.89	3.2	0.52	1.27
低碳铬铁合金渣	48.64	0.58	0.5	29.46	-	-	7.36	7.23	3.48	-	-	-	-	2.75
石英砂	0.029	0.037	-	98.200	-	0.018	0.120	0.005	-	-	-	-	-	1.591

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表 2 基础玻璃原料质量比例(质量分数)/%

Table 2. Quality of ratio base glass raw materials

组别	低碳铬铁合金渣：高炉渣：石英砂：纯化学试剂Al₂O₃	原料中固废占比
1^#	40∶60 ∶ 26.23∶ 0	79
2^#	50∶50 ∶ 28.78∶ 0	78
3^#	60∶40 ∶31.33∶ 0	76
4^#	70∶30 ∶ 33.88∶ 0	75
5^#	80∶20 ∶ 36.44∶0.23	73
6^#	90∶10 ∶38.99∶1.16	72

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表 3 1 500 ℃时粘度实测值/（Pa·s）

Table 3. Measured viscosity at 1 500 ℃

温度/℃	1^#	2^#	3^#	4^#	5^#	6^#
1 500	0.613	0.579	0.561	0.493	0.492	0.435

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表 4 3^#基础玻璃在不同晶化温度下的热处理制度

Table 4. 3^# Base glass heat treatment system at different crystallization temperatures

样品	核化温度/℃	核化时间/min	晶化温度/℃	晶化时间/min
A	830	90	960	90
B	830	90	1 024	90

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表 5 热处理核化温度和晶化温度

Table 5. Nucleation temperature and crystallization temperature of heat treatment

组别	核化温度/℃	晶化温度/℃
1^#	828	954
2^#	830	963
3^#	830	960
4^#	830	957
5^#	838	953
6^#	836	953

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表 6 微晶玻璃样品晶化度计算值

Table 6. Calculated crystallinity of glass-ceramics samples

组别	1^#	2^#	3^#	4^#	5^#	6^#
Cr₂O₃含量（质量分数）/%	1.11	1.36	1.60	1.83	2.05	2.25
晶化度/%	69.53	81.91	89.19	72.97	78.95	64.92

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表 7 微晶玻璃样品与大理石、花岗岩理化性能对比

Table 7. Comparison of physical and chemical properties of glass ceramics samples with marble and granite

组别	抗折强度/MPa	莫氏硬度	密度/(g/cm³)	耐酸性/%	耐碱性/%	吸水率/%
1^#	86.09	6～7	2.70	0.60	0.12	0.20
2^#	107.24	6～7	2.93	0.38	0.06	0.12
3^#	126.25	6～7	3.81	0.37	0.06	0.06
4^#	94.74	6～7	3.10	0.44	0.07	0.04
5^#	87.79	6～7	2.70	0.59	0.04	0.04
6^#	35.80	6～7	2.68	0.52	0.07	0.18
大理石	13～15	2.5～5	2.6～2.7	10.3～12.3	0.3	≤0.3
花岗岩	15～38	6～7	2.5～2.7	0.91	0.08	0.5～0.8

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表 8 3^#和4^#微晶玻璃样品放射性核素检测结果

Table 8. Radionuclide detection results of 3^#and 4^# glass-ceramics samples

组别	内照射指数IRa	外照射指数Iγ
3^#	0.30	0.88
4^#	0.19	0.70

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参考文献(24)

[1]	郝百川, 李子越, 贾东方, 等. 含钛高炉渣的综合利用[J]. 矿产综合利用, 2020(6):1-6.HAO B C, LI Z Y, JIA D F, et al. Comprehensive utilization of titanium bearing blast furnace slag[J]. Multipurpose Utilization of Mineral Resources, 2020(6):1-6. doi: 10.3969/j.issn.1000-6532.2020.06.001 HAO B C, LI Z Y, JIA D F, et al. Comprehensive utilization of titanium bearing blast furnace slag[J]. Multipurpose Utilization of Mineral Resources, 2020(6):1-6. doi: 10.3969/j.issn.1000-6532.2020.06.001
[2]	苗希望, 白智韬, 卢光华, 等. 典型铁合金渣的资源化综合利用研究现状与发展趋势[J]. 工程科学学报, 2020, 42(6):663-679.MIAO X W, BAI Z T, LU G H, et al. Research status and development trend of resource comprehensive utilization of typicalferroalloy slag[J]. Chinese Journal of Engineering, 2020, 42(6):663-679. MIAO X W, BAI Z T, LU G H, et al. Research status and development trend of resource comprehensive utilization of typicalferroalloy slag[J]. Chinese Journal of Engineering, 2020, 42(6):663-679.
[3]	Yekta B E, Alizadeh P. The effect of CaF₂ and Cr₂O₃ on the crystallisation and mechanical properties of SiO₂-CaO- Fe₂O₃-(Al₂O₃) glasses[J]. Glass Technology, 2005, 46(5):347-348.
[4]	杨焕银, 郭红力. 工业固体废物制备微晶玻璃研究进展[J]. 科技资讯, 2020, 18(33):53-55.YANG H Y, GUO H L. Research progress in preparation of glass ceramics from industrial solid waste[J]. Science & Technology Information, 2020, 18(33):53-55. YANG H Y, GUO H L. Research progress in preparation of glass ceramics from industrial solid waste[J]. Science & Technology Information, 2020, 18(33):53-55.
[5]	孙强强, 亢小红. 钙长石系尾矿微晶玻璃的制备及发光性能[J]. 矿产综合利用, 2020(4):152-155+151.SUN Q Q, KANG X H. Preparation and luminescent properties of anorthite tailings glass ceramics[J]. Multipurpose Utilization of Mineral Resources, 2020(4):152-155+151. doi: 10.3969/j.issn.1000-6532.2020.04.026 SUN Q Q, KANG X H. Preparation and luminescent properties of anorthite tailings glass ceramics[J]. Multipurpose Utilization of Mineral Resources, 2020(4):152-155+151. doi: 10.3969/j.issn.1000-6532.2020.04.026
[6]	王亚文, 贵永亮, 宋春燕, 等. 高炉渣制备微晶玻璃的研究进展[J]. 矿产综合利用, 2018(2):1-6.WANG Y W, GUI Y L, SONG C Y, et al. Research progress in preparation of glass ceramics from blast furnace slag[J]. Multipurpose Utilization of Mineral Resources, 2018(2):1-6. doi: 10.3969/j.issn.1000-6532.2018.02.001 WANG Y W, GUI Y L, SONG C Y, et al. Research progress in preparation of glass ceramics from blast furnace slag[J]. Multipurpose Utilization of Mineral Resources, 2018(2):1-6. doi: 10.3969/j.issn.1000-6532.2018.02.001
[7]	文璐, 国宏伟, 李鹏, 等. 中钛型含钛高炉渣与铬铁合金渣制备微晶玻璃[J]. 金属世界, 2020(2):68-72.WEN L, GUO H W, LI P, et al. Preparation of glass ceramics from medium titanium type blast furnace slag containing titanium and ferrochromium alloy slag[J]. Metal World, 2020(2):68-72. doi: 10.3969/j.issn.1000-6826.2020.02.018 WEN L, GUO H W, LI P, et al. Preparation of glass ceramics from medium titanium type blast furnace slag containing titanium and ferrochromium alloy slag[J]. Metal World, 2020(2):68-72. doi: 10.3969/j.issn.1000-6826.2020.02.018
[8]	王亚文, 贵永亮, 宋春燕, 等. CaO/SiO₂质量比对CaO-MgO-SiO₂-Al₂O₃系微晶玻璃析晶行为的影响[J]. 矿产综合利用, 2018(1):137-141.WANG Y W, GUI Y L, SONG C Y, et al. Effect of CaO/SiO₂ mass ratio on crystallization behavior of CaO-MgO-SiO₂- Al₂O₃ glass ceramics[J]. Multipurpose Utilization of Mineral Resources, 2018(1):137-141. doi: 10.3969/j.issn.1000-6532.2018.01.030 WANG Y W, GUI Y L, SONG C Y, et al. Effect of CaO/SiO₂ mass ratio on crystallization behavior of CaO-MgO-SiO₂- Al₂O₃ glass ceramics[J]. Multipurpose Utilization of Mineral Resources, 2018(1):137-141. doi: 10.3969/j.issn.1000-6532.2018.01.030
[9]	Deng L B, Lu W W, Zhang Z. Crystallization behavior and structure of CaO-MgO-Al₂O₃-SiO₂ glass-ceramics prepared from Cr-bearing slag[J]. Materials chemistry and physics, 2021, 261:124249. doi: 10.1016/j.matchemphys.2021.124249
[10]	Li BW, Deng L B, Zhang X F. Structure and performance of glass-ceramics obtained by Bayan Obo tailing and fly ash[J]. Journal of Non-Crystalline Solids, 2013, 380:103-108. doi: 10.1016/j.jnoncrysol.2013.09.012
[11]	Rao M V S, Rajyasree C, Narendrudu T. Physical and spectroscopic properties of multi-component Na₂O-PbO-Bi₂O₃-SiO₂ glass-ceramics with Cr₂O₃ as nucleating agent[J]. Optical materials, 2015, 47:315-322. doi: 10.1016/j.optmat.2015.05.048
[12]	王瑞鑫, 王艺慈, 曹鹏飞, 等. 高炉渣和粉煤灰制备微晶玻璃晶核剂的优化[J]. 中国陶瓷, 2020, 56(11):44-49.WANG R X, WANG Y C, CAO P F, et al. Optimization of nucleating agent for glass ceramics prepared from blast furnace slag and fly ash[J]. China Ceramics, 2020, 56(11):44-49. WANG R X, WANG Y C, CAO P F, et al. Optimization of nucleating agent for glass ceramics prepared from blast furnace slag and fly ash[J]. China Ceramics, 2020, 56(11):44-49.
[13]	陈莹, 陆雷, 王永志. 云母/β-锂辉石系可加工微晶玻璃热处理工艺的优化研究[J]. 中国陶瓷, 2011, 47(9):27-30.CHEN Y, LU L, WANG Y Z. Mica/ β-Optimization of heat treatment process of spodumene machinable glass ceramics[J]. China Ceramics, 2011, 47(9):27-30. CHEN Y, LU L, WANG Y Z. Mica/ β-Optimization of heat treatment process of spodumene machinable glass ceramics[J]. China Ceramics, 2011, 47(9):27-30.
[14]	刘晓光. Cr₂O₃对万通钢铁公司高炉渣冶金性能的影响[D]. 唐山: 华北理工大学, 2016.LIU X G. Effect of Cr₂O₃ on metallurgical properties of blast furnace slag in Wantong iron and Steel Company[D]. Tangshan: North China University of Science and Technology, 2016. LIU X G. Effect of Cr₂O₃ on metallurgical properties of blast furnace slag in Wantong iron and Steel Company[D]. Tangshan: North China University of Science and Technology, 2016.
[15]	Zhang S, Zhang Y L, Wu T. Effect of Cr₂O₃ on the crystallization behavior of synthetic diopside and characterization of Cr-doped diopside glass-ceramics[J]. Ceramics International, 2018, 44(9):10119-10129. doi: 10.1016/j.ceramint.2018.02.231
[16]	Li H R, Liu S Y, Xu W C, et al. The mechanism of the crystalline characteristics of spinel-induced epitaxial growth of diopside in CMAS glass-ceramics[J]. Journal of the European Ceramic Society, 2021, 41(2):1603-1612. doi: 10.1016/j.jeurceramsoc.2020.09.037
[17]	雷岩, 汪琦, 刘焕春, 等. 铁尾矿、菱镁石尾矿制备微晶玻璃的研究[J]. 矿产综合利用, 2011(2):41-44.LEI Y, WANG Q, LIU H C, et al. Study on preparation of glass ceramics from iron tailings and magnesite tailings[J]. Multipurpose Utilization of Mineral Resources, 2011(2):41-44. doi: 10.3969/j.issn.1000-6532.2011.02.012 LEI Y, WANG Q, LIU H C, et al. Study on preparation of glass ceramics from iron tailings and magnesite tailings[J]. Multipurpose Utilization of Mineral Resources, 2011(2):41-44. doi: 10.3969/j.issn.1000-6532.2011.02.012
[18]	刘靖靖, 肖汉宁. 晶核剂对高炉渣微晶玻璃晶化行为的影响[J]. 硅酸盐学报, 2016, 44(6):878-883.LIU J J, XIAO H N. Effect of nucleating agent on crystallization behavior of blast furnace slag glass ceramics[J]. Journal of the Chinese Ceramic Society, 2016, 44(6):878-883. LIU J J, XIAO H N. Effect of nucleating agent on crystallization behavior of blast furnace slag glass ceramics[J]. Journal of the Chinese Ceramic Society, 2016, 44(6):878-883.
[19]	陈国华, 刘心宇. 矿渣微晶玻璃的制备及展望[J]. 陶瓷, 2002(4):16-20.CHEN G H, LIU X Y. Preparation and prospect of slag glass ceramics[J]. Ceramics, 2002(4):16-20. doi: 10.3969/j.issn.1002-2872.2002.04.003 CHEN G H, LIU X Y. Preparation and prospect of slag glass ceramics[J]. Ceramics, 2002(4):16-20. doi: 10.3969/j.issn.1002-2872.2002.04.003
[20]	贾志恒. 含铬微晶玻璃制备过程中铬的赋存状态及分布行为研究[D]. 赣州: 江西理工大学, 2020.JIA Z H. Study on the existing state and distribution behavior of chromium in the preparation of chromium containing glass ceramics[D]. Ganzhou: Jiangxi University of Science and Technology, 2020. JIA Z H. Study on the existing state and distribution behavior of chromium in the preparation of chromium containing glass ceramics[D]. Ganzhou: Jiangxi University of Science and Technology, 2020.
[21]	杨健. 含铬钢渣制备微晶玻璃及一步热处理研究[D]. 北京: 北京科技大学, 2016.YANG J. Preparation of glass ceramics from chromium containing steel slag and one-step heat treatment[D]. Beijing: University of Science and Technology Beijing, 2016. YANG J. Preparation of glass ceramics from chromium containing steel slag and one-step heat treatment[D]. Beijing: University of Science and Technology Beijing, 2016.
[22]	袁少伟, 戴新荣, 贺传友, 等. 浅谈建筑装饰装修材料中放射性危害及检测方法[J]. 建材与装饰, 2017(48):42-43.YUAN S W, DAI X R, HE C Y, et al. Discussion on radioactive hazards and detection methods in building decoration materials[J]. Construction Materials & Decoration, 2017(48):42-43. doi: 10.3969/j.issn.1673-0038.2017.48.035 YUAN S W, DAI X R, HE C Y, et al. Discussion on radioactive hazards and detection methods in building decoration materials[J]. Construction Materials & Decoration, 2017(48):42-43. doi: 10.3969/j.issn.1673-0038.2017.48.035
[23]	裘慧广, 沈强, 王传彬, 等. 微晶玻璃的种类、制备及其应用[J]. 中国建材科技, 2005(1):15-19.QIU H G, SHEN Q, WANG C B, et al. Types, preparation and application of glass ceramics[J]. China Building Materials Science and Technology, 2005(1):15-19. doi: 10.3969/j.issn.1003-8965.2005.01.005 QIU H G, SHEN Q, WANG C B, et al. Types, preparation and application of glass ceramics[J]. China Building Materials Science and Technology, 2005(1):15-19. doi: 10.3969/j.issn.1003-8965.2005.01.005
[24]	李保庆, 郭艳平, 党海峰. MgO对飞灰屏玻璃协同制备微晶玻璃析晶及性能的影响[J]. 矿产综合利用, 2020(1):135-139+134.LI B Q, GUO Y P, DANG H F. Effect of MgO on crystallization and properties of glass ceramics prepared by fly ash screen glass[J]. Multipurpose Utilization of Mineral Resources, 2020(1):135-139+134. doi: 10.3969/j.issn.1000-6532.2020.01.028 LI B Q, GUO Y P, DANG H F. Effect of MgO on crystallization and properties of glass ceramics prepared by fly ash screen glass[J]. Multipurpose Utilization of Mineral Resources, 2020(1):135-139+134. doi: 10.3969/j.issn.1000-6532.2020.01.028

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高炉渣和低碳铬铁合金渣协同制备微晶玻璃

内蒙古科技大学材料与冶金学院，内蒙古 包头 014010

作者简介: 王一帆（1998-），女，硕士研究生，主要从事冶金资源综合利用方面的研究

Cooperative Preparation of Glass-ceramics by Blast Furnace Slag and Low-carbon Chromium Iron Alloy Slag

School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China

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内蒙古科技大学材料与冶金学院，内蒙古　包头　014010