耐火材料发展概述

doi:10.15541/jim20170582

摘要/Abstract

摘要：

本文简要介绍了中国耐火材料现状, 结合高温工业技术发展需求, 阐述了耐火材料的发展态势和发展方向。指出结构功能一体化设计与制备是以长寿化、功能化、轻量化、智能化、绿色化为特征的先进耐火材料发展的核心。结合新型高效隔热耐火材料、钢铁冶金连铸用先进功能耐火材料的研究, 介绍了先进耐火材料的组成-结构-性能-功能一体化设计理念与制备技术, 采用有限元数值模拟、融合先进陶瓷技术及梯度多层复合设计, 实现了关键服役性能的最优化设计与制备。

关键词: 先进耐火材料, 结构功能一体化设计, 隔热耐火材料, 功能耐火材料, 综述

Abstract:

In this paper, current situation of refractory industry in China is introduced briefly. Developing tendency of refractory materials is remarked based on the technical development of high temperature industries. Advanced refractory materials, characterized by long service life, functionalization, lightweight and ecological-friendly design, play very important roles in sustainable development of high temperature industries. Since the key service properties of advanced refractories constrain each other in traditional material design and fabrication, new design methods are developed to optimize the key service properties simultaneously. Combined with the development of new insulating materials, and functional refractories used in steel-making industry, structure-function combining design concept and new fabrication technologies are introduced by applying FEM analysis, bridging of advance ceramic technologies, and multilayered/gradient composite structure.

Key words: advanced refractories, structure-function combining design, insulating materials, functional refractories, review

中图分类号:

TQ175

李红霞. 耐火材料发展概述[J]. 无机材料学报, 2018, 33(2): 198-205.

LI Hong-Xia. Development Overview of Refractory Materials[J]. Journal of Inorganic Materials, 2018, 33(2): 198-205.

图/表 10

图1 纤维增强二氧化硅-高温烟尘复合隔热材料的微结构及热导率随温度的变化[41]

Fig. 1 Microstructure and effects of temperature on thermal conductivity of developed ceramic fiber enforced nano-SiO2- fumed-corundum insulation composite materials[41]

图2 微纳米孔复合隔热材料的厚度与隔热效果[41]

Fig. 2 Insulting effect versus the thickness of developed insulation composite materials with micro/nano-sized pores[41]

表1 纳/微米多孔隔热材料的性能[42]

Table 1 Properties of developed insulation composite material with micro/nano-sized pores[42]

	Developed composite plate	Developed plate with nano-sized pores	A Company	B Company	Porextherm plate with nano-sized pores
Thermal conductivity (1000℃)/(W·m^-1·K^-1)	0.087	0.063	0.050(800℃)	—	0.062
Bulk density/(g·cm^-3)	0.55-0.65	0.35-0.4	0.30-0.35	—	0.35-0.45
Service temperature/℃	1800	1100	850	650	1100
Linear change/% (1000℃, 24 h)	~1.5	<2	—	—	<2

图3 氮化硅/碳化硅复相多孔陶瓷的产品(a)和SEM照片(b)[42]

Fig. 3 The product photo and SEM image of porous silicon nitride-silicon carbide composites[42] (a) Product(STIC-n); (b) SEM photograph

图4 几种隔热材料侵蚀实验前(a)后(b)外观对比[43]

Fig. 4 Comparison of erosion resistance of several insulation materials (a) before and (b) after test[43]

图5 Al-Si复合粉抗氧化剂对低碳Al2O3-C材料微结构和性能的影响[44]

Fig. 5 The influence of Al-Si alloy antioxidant additives on the microstructure and properties of Al2O3-C refractories[44] (a) Fibrous substance formed by antioxidant reaction; (b) Narrowing influence on the pores distribution; (c) Effect on HMOR

图6 (a)不同催化树脂的残碳率, (b)裂解生成的纤维碳SEM照片和(c)纤维碳TEM照片[45]

Fig. 6 (a) Char yield of phenolic resins, (b) SEM image of carbon fiber and (c)TEM image of carbon fiber[45]

图7 (a)膨胀石墨的SEM照片, (b)纳米碳包覆氧化铝复合粉体的SEM照片和(c)形成的纳米碳的TEM照片[4]

Fig. 7 (a) SEM image of expanded graphite, (b) SEM image of alumina composite powder covered by nano-carbon and (c) TEM image of nano-carbon[4]

图8 长水口功能分区示意图[42]

Fig. 8 Schematic diagram of the long nozzle with composite structure[42]

图9 应力缓释区对温度场和最大热应力的影响[42]

Fig. 9 Effects of stress buffer release area with micro-porous structure on temperature field and maximum thermal stress[42]

参考文献 45

[1]	李红霞. 高温工业的发展与耐火材料的技术进步. 耐火材料, 2006, 40(增刊): 4-8.
[2]	陈肇友, 李红霞. 镁资源的综合利用及镁质耐火材料的发展. 耐火材料, 2005, 39(1): 6-15.
[3]	LI H X, LIU G Q.Current situation and development of refractories for clean steel production.China’s Refractories, 2013, 22(3): 1-6.
[4]	吴小贤, 李红霞, 刘国齐, 等. 高能球磨合成纳米碳包覆α-Al2O3复合粉体. 无机材料学报, 2013, 28(3): 261-266.
[5]	刘辉敏, 李红霞, 洪彦若, 等. 复合结构长水口热应力有限元分析. 硅酸盐学报, 2009, 31(12): 2000-2006.
[6]	SONG Y Y, LIU G Q, LI H X, et al. Influence of ladle purging plug airway on flow properties of liquid steel. Advanced Materials Research, 2012, 472-475: 2581-2587.
[7]	LI H X, YANG B, LIU G Q, et al.Gradient Functional Refractories for High Efficient Con-casting (invited). Proceedings of the 6th International Congress on the Science and Technology of Steelmaking(I), Beijing, China, 2015: 4-8.
[8]	张洪哲, 李富朝, 孙庚辰, 等. 高风温长寿热风炉用高效小孔径格子砖的设计及选材. 耐火材料, 2015, 49(5): 376-380.
[9]	王佳平, 金广湘, 王勇峰, 等.新型复相氮化物结合碳化硅耐火材料在干熄炉斜道区的应用和分析. 西安: 2016年(第十届)焦化节能环保及干熄焦技术研讨会论文集, 2016: 96-101.
[10]	YIN H J, ZHANG T, WU A J, et al. Effect of M-ZrO2 on sintering behavior and thermal shock resistance of dense Cr2O3 material. Advanced Materials Research, 2011, 199-200: 1928-1931.
[11]	孙红刚, 陈杰, 范志辉, 等. 新型高铬砖在GE气化炉的试用研究. 大氮肥, 2011, 34(增刊2): 108-111.
[12]	耿可明, 王金相. Cr2O3在水煤浆气化炉过程中的行为. 耐火材料, 2015, 49(1): 68-71.
[13]	李红霞, 王金相. 水泥窑用碱性耐火材料无铬化的技术进展. 中国水泥, 2004, 10: 79-82.
[14]	LI H X, LIU J, FENG H X, et al.Development and application of chrome-free refractory materials for RH degasser.China's Refractories, 2014, 23(4): 1-5, 12.
[15]	GE H B, WANG G, YUAN B, et al.Fabrication and microstructure of porous SiC ceramics using suspension emulsions as pore-forming agents.Ceramics International, 2014, 40(8): 11705-11711.
[16]	WU H B, HUANG Z R, WANG G, et al.Alumina heat insulator through composite poring mechanisms.International Journal of Applied Ceramic Technology, 2015, 11(6): 1061-1067.
[17]	徐殿利. 2016年全国耐火材料行业生产运行情况及2017年耐火材料市场预测分析. 北京: 2017年耐火材料行业协会年会报告会, 2017: 1-8.
[18]	江东亮, 袁渭康, 钱锋, 等. 我国高耗能工业高温热工装备节能科技发展战略研究. 北京: 科学出版社, 2017: 50-55.
[19]	李红霞, 杨彬. 中国石墨资源和产业状况概述. 郑州: 耐火原料学术交流会论文集, 2011: 1-11.
[20]	刘俊光, 魏同. 我国耐火材料工业节能降耗技术及发展方向. 太原: 新形势下全国耐火原料发展战略研讨会论文集, 2014: 193-194.
[21]	HEMRICK J G, HAYDE H W, ANGELINI, et al. Refractories for industrial processing: opportunities for improved energy efficiency.Industrial Technologies Program, 2005, 1: 4-6.
[22]	HEMRICK J G.Improved refractories=energy saving.American Ceramic Society Bulletin, 2013, 92(7): 32-35.
[23]	HEADRICK W L.Towards a “greener” future with advanced refractories.American Ceramic Society Bulletin, 2013, 92(7): 28-31.
[24]	SEMLER C E.Refractories—the world most important but least known products.American Ceramic Society Bulletin, 2014, 93(2): 34-39.
[25]	GUIRE E D.State raw materials 2013-overview and frontiers.American Ceramic Society Bulletin, 2013, 92(6): 24-28.
[26]	CERAME-UNIE.The Ceramic Industry Roadmap. Paving the Way to 2050, 2012, 1: 40-45.
[27]	COHEN L.Challenge and opportunities for refractory manufacturers in the UK.Refractories Engineer, 2013, 11: 12-17.
[28]	JARVIS D R.An overview of the current 2013 global refractories industry.International Ceramic Review, 2013, 62(4): 262-266.
[29]	XU D L, CUI Y S, YANG K, et al.On the future of Chinese cement industry.Cement and Concrete Research, 2015, 78: 2-13.
[30]	殷瑞钰. 高效率、低成本洁净钢“制造平台”集成技术及其动态运行. 钢铁, 2012, 47(1): 1-12.
[31]	LI HONGXIA.Development of Refractory Industry in China with Restricts of Resource, Energy and Environment Factors. Proceedings of UNITECR 2011, Kyoto, Japan, 2011: 122-123.
[32]	李红霞. 经济下行时中国耐火材料行业发展的思考. 耐火材料, 2012, 46(5): 321-324.
[33]	JAKOBSEN D, GOTSCHEL I, ROOSEN A.Manufacture of multilayer composite with optimized thermal and chemical properties via the tape casting process.Refractories Worldforum, 2016, 8(2): 86-94.
[34]	蔡斌利, 李红霞, 赵世贤, 等. 水煤浆气化炉中O2分压和Cr2O3稳定性的热力学计算. 耐火材料, 2016, 50(6): 411-415.
[35]	YANG W G, LIU G Q, LI H X, et al.Thermal Stress Distribution in Stopper by Finite Element Analysis. Proceedings of UNITECR 2013, Columbia, Canada, 2013: 154-158.
[36]	李红霞. 对耐火材料的性能调控及设计的一些思考. 耐火材料, 2013, 47(增刊1): 1-2.
[37]	SEMLER C E.Review of advances in refractories.International Ceramic Review, 2011, 2: 77-81.
[38]	SUGITA K.The past and future of refractories technology.International Ceramic Review, 2012, 1: 8-12.
[39]	SEMLER C E.The advancement of refractories technology never stops.Refractories Worldforum, 2014, 6(4): 27-31.
[40]	PHILIP A.An introduction to Alkaline Silicate wool products. Proceedings of the Institute of Industrial Engineers Asian Conference 2013, Taipei, 2013: 100-105.
[41]	孙小飞, 王刚, 袁波. 高铝纤维复合SiO2质纳米微孔隔热材料研究. 耐火材料, 2014, 48(6): 406-408.
[42]	LI H X.Some design consideration of advanced refractories.Refractories Worldforum, 2017, 9(4): 99-105.
[43]	张琪. 隔热材料抗冰晶石蒸汽侵蚀机理研究. 洛阳: 中钢集团洛阳耐火材料研究院硕士学位论文, 2016.
[44]	刘国齐. Al2O3-Al-C功能耐火材料的热变化和应用研究. 北京: 北京科技大学博士学位论文, 2006.
[45]	吴小贤. 含纳米碳新型低碳铝碳耐火材料研究. 北京: 北京科技大学博士学位论文, 2013.