低温快烧钡镁无光釉的研制
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摘要
作者开发了二种低温快烧亚光熔块釉，其中一种用在炻质墙地砖上，另一种用在精陶质内墙砖上。采用DTA、DDTA、XRD、OM、SEM和高温显微镜，研究了CaO—MgO—SiO_2系统熔块的晶化行为，计算了熔块中晶体的生长活化能，分析了热处理过程中烧结与晶化的关系。对该种熔块用在上述二种亚光釉中的作用进行了介绍和验证。同时研究和分析了上述两种亚光釉的性能、组成和显微结构，探讨了亚光釉的形成机理，并对其生产工艺作了介绍和分析，结果表明
(1)不同程度地引入了MgO、BaO、CaO、Li_2O_3、ZnO它们起到了无光剂的作用，这二类亚光釉中析出的晶相以透辉石为主(CaMg(Si_2O_7))，此外还有锂辉石(LiAl(Si_2O_6))、钡长石、(CaO·Al_2O_3·2SiO_2)、钡铁钛石(BaFe_2Ti[O_3|Si_2O_6])、钙长石(CaO·Al_2O_3·2SiO_2)、α-石英。晶粒尺寸大部分在3～10μm它们在釉表层的均匀堆叠和对可见光的散射使釉面产生了亚光效果。
(2)在CaO—MgO—SiO_2三元相图中的透辉石析晶区中，选取了一个合理的熔块组成，在此基础上以BaO取代相当量的CaO，并引入了ZnO、LiO_2等组分，构成熔块配方在1560℃下熔制，熔块中的主晶相为透辉石晶粒，尺寸大部分在3～10μm，该晶相可以在较宽的温度范围内析出，是热力学角度上能稳定存在的晶相。
(3)亚光釉的Al_2O_3/SiO_2比靠近1/6这个界限，无光釉的则靠近1/3这个界限。
(4)亚光釉的形成除了要有合理的配方外，烧成制度是个关键，烧成温度过高，会导致早期析出的晶体重新溶解，这样釉中玻璃相增加，物相以玻璃相为主，亚光釉变成光泽釉；反之烧成温度过低，则会导致生烧，造成
武汉理工大学硕士学位论文
非均匀成核，釉面晶粒过细过多、光泽暗淡失去亚光效果。此外合理的保温
时间和冷却制度也是烧成制度的重要组成部分，是形成优质、无光釉效果不
可缺少的保证。
（5）低温快烧亚光、无光釉最好以熔块釉的形式生产。与生料釉相比
熔块釉的适应范围宽、生产较稳定、釉面质感也好。
Two kinds of low-temperature fast firing mat frit glazes were developed, of which one was used in stone tile, and the other was used in fine pottery tile. The crystallization of the diopside in the CaO-MgO-SiC2 frit was studied by means of DTA, DDTA, XRA, OM, SEM and high-temperature microscope. The activation energy of the crystal growth was calculated. The relationship between sintering and crystallization in the heat treatment process was analyzed. Effects of the frit used in the above two kinds of mat glazes were investigated. The properties, compositions and micro-structures of mat glazes were studied. The forming mechanism and process conditions of mat glazes were discussed. The results show that as follow.
(1) MgO, BaO, CaO, Li2O3, ZnO introduce perform a function as non-1 ight agent, the main crystal phase of two kinds of mat glazes is diopside. In addition, there are many phases such as lithium silicate, barium feldspar, anorthite, a -quartz. Crystal grain size is 3~10 u m mostly, piling equally at the glaze and scattering to visible light which make a semi- light effect.
(2) Selecting proper compositions of the frit in crystallization section of diopside from CaO-MgO-SiO2 three phase diagram, we replace quite quantities of CaO by BaO and induced composition such as ZnO, LiO2. Proposition of the frit is melted at a temperature of 1560癈, the main crystal phase of the frit is diopside, crystal grain size is 3~10u m mostly. The crystal phase could analyze at a broad extension temperature, which is stable crystal phase according to thermodynamics.
(3) The proportion of Al2O3:SiO2of the mat glaze is near to 1:6, while that
of non-light glaze is near to 1:3.
(4) Firing schedule is a key to formation of the mat glaze besides proper proposition, extremely high firing temperature may lead to early crystallization to dissolve again, which make the glass phase increasable. The mat glaze become to the blare glaze, the main phase is the glass phase. Contrarily, low-temperature firing may lead to non-equal grown of nucleus; the grain is too thin and excessive which make semi-light effect is lost. Proper heat preservation and cooling schedule are the important composition and indispensable assure to form excellent non-light glaze.
(5) The semi-light glaze and the matt glaze in a fast-firing condition at a low temperature produce in form of the fritted glaze, compared to the raw glaze, the fritted glaze have broad adaptability and stable manufacture and good surface feeling of glaze.
(1)不同程度地引入了MgO、BaO、CaO、Li_2O_3、ZnO它们起到了无光剂的作用，这二类亚光釉中析出的晶相以透辉石为主(CaMg(Si_2O_7))，此外还有锂辉石(LiAl(Si_2O_6))、钡长石、(CaO·Al_2O_3·2SiO_2)、钡铁钛石(BaFe_2Ti[O_3|Si_2O_6])、钙长石(CaO·Al_2O_3·2SiO_2)、α-石英。晶粒尺寸大部分在3～10μm它们在釉表层的均匀堆叠和对可见光的散射使釉面产生了亚光效果。
(2)在CaO—MgO—SiO_2三元相图中的透辉石析晶区中，选取了一个合理的熔块组成，在此基础上以BaO取代相当量的CaO，并引入了ZnO、LiO_2等组分，构成熔块配方在1560℃下熔制，熔块中的主晶相为透辉石晶粒，尺寸大部分在3～10μm，该晶相可以在较宽的温度范围内析出，是热力学角度上能稳定存在的晶相。
(3)亚光釉的Al_2O_3/SiO_2比靠近1/6这个界限，无光釉的则靠近1/3这个界限。
(4)亚光釉的形成除了要有合理的配方外，烧成制度是个关键，烧成温度过高，会导致早期析出的晶体重新溶解，这样釉中玻璃相增加，物相以玻璃相为主，亚光釉变成光泽釉；反之烧成温度过低，则会导致生烧，造成
武汉理工大学硕士学位论文
非均匀成核，釉面晶粒过细过多、光泽暗淡失去亚光效果。此外合理的保温
时间和冷却制度也是烧成制度的重要组成部分，是形成优质、无光釉效果不
可缺少的保证。
（5）低温快烧亚光、无光釉最好以熔块釉的形式生产。与生料釉相比
熔块釉的适应范围宽、生产较稳定、釉面质感也好。
Two kinds of low-temperature fast firing mat frit glazes were developed, of which one was used in stone tile, and the other was used in fine pottery tile. The crystallization of the diopside in the CaO-MgO-SiC2 frit was studied by means of DTA, DDTA, XRA, OM, SEM and high-temperature microscope. The activation energy of the crystal growth was calculated. The relationship between sintering and crystallization in the heat treatment process was analyzed. Effects of the frit used in the above two kinds of mat glazes were investigated. The properties, compositions and micro-structures of mat glazes were studied. The forming mechanism and process conditions of mat glazes were discussed. The results show that as follow.
(1) MgO, BaO, CaO, Li2O3, ZnO introduce perform a function as non-1 ight agent, the main crystal phase of two kinds of mat glazes is diopside. In addition, there are many phases such as lithium silicate, barium feldspar, anorthite, a -quartz. Crystal grain size is 3~10 u m mostly, piling equally at the glaze and scattering to visible light which make a semi- light effect.
(2) Selecting proper compositions of the frit in crystallization section of diopside from CaO-MgO-SiO2 three phase diagram, we replace quite quantities of CaO by BaO and induced composition such as ZnO, LiO2. Proposition of the frit is melted at a temperature of 1560癈, the main crystal phase of the frit is diopside, crystal grain size is 3~10u m mostly. The crystal phase could analyze at a broad extension temperature, which is stable crystal phase according to thermodynamics.
(3) The proportion of Al2O3:SiO2of the mat glaze is near to 1:6, while that
of non-light glaze is near to 1:3.
(4) Firing schedule is a key to formation of the mat glaze besides proper proposition, extremely high firing temperature may lead to early crystallization to dissolve again, which make the glass phase increasable. The mat glaze become to the blare glaze, the main phase is the glass phase. Contrarily, low-temperature firing may lead to non-equal grown of nucleus; the grain is too thin and excessive which make semi-light effect is lost. Proper heat preservation and cooling schedule are the important composition and indispensable assure to form excellent non-light glaze.
(5) The semi-light glaze and the matt glaze in a fast-firing condition at a low temperature produce in form of the fritted glaze, compared to the raw glaze, the fritted glaze have broad adaptability and stable manufacture and good surface feeling of glaze.
引文
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[27]耿谦，从玻璃结构分析釉的性质，陶瓷研究，2002，17(1)：1～4
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[2]俞康泰，陶瓷色釉料与装饰导论，武汉工业大学出版社，1998
[3]俞康泰、赵宗昱、高升洲等，现代陶瓷色釉料与装饰技术手册，武汉工业大学出版社，1999
[4]祝桂洪、周健儿、曹春娥等，陶瓷釉配制基础，轻工业出版社，1989
[5]素木洋一，釉及色料，中国建筑工业出版社，1979
[6]伊曼纽尔·库珀，陶瓷釉配方，中国建筑工业出版社，1986
[7]苏展平，釉药原理与实务，台湾陶业研究学会，2000
[8]俞康泰，陶瓷添加剂实用新技术，陶瓷增刊，2001
[9]建筑工程部技术情报局，陶瓷釉料，内部资料，1963
[10]吴艺宛，陶瓷墙地砖生产，北京：中国建材工业出版社，1982
[11]于丽达，陶瓷墙地砖生产，西安：国际出版社，1992
[12]中国(台湾)生产力中心，釉及色料配方手册，1970
[13]加藤悦三，釉调合的基本，日本窑业协会，1973
[14]全国建筑材料工业陶瓷专业情报信息网，国外陶瓷釉配方手册，色釉料配方集，2001
[15]轻工业部第一轻工业局，日用陶瓷工业手册，北京：轻工业出版社，1984
[16]中国硅酸盐学会，中国陶瓷史，北京：文物出版社，1982
[17]魏忠汉，陶瓷装饰材料学，南昌：江西科学技术出版社，1985
[18]张玉春，艺术釉，北京：轻工业出版社，1976
[19]叶吉民，中国古陶瓷材料浅说，北京：轻工业出版社，1960
[20]郭靖远、相清清，日用精陶，北京：轻工业出版社，1984
[21]王成兴，硅酸盐工业矿物原料基础知识，北京：轻工业出版社，1984
[22]沈鹤年，怎样看硅酸盐相图，北京：中国建筑工业出版社，1974
[23]张师、俞建长，硼砂及熔块配合料，不同温度焙烧物相变化的X射线研究，中国陶瓷，1996，32(6)：5～8
[24]余广镇，低成本无光釉的试制及生产，佛山陶瓷，2000，4：20～22
[25]李小雷，用硼镁矿代替含硼化工原料制备陶瓷熔块的试验研究，佛山陶瓷，2000，6：8～10
[26]刘培德、俞平利，钙镁硅酸盐系列结晶釉的研究，佛山陶瓷，2002：29～32
[27]耿谦，从玻璃结构分析釉的性质，陶瓷研究，2002，17(1)：1～4
[28]吕旺、罗宏杰，透辉石系统微晶玻璃釉用熔块的晶化行为，中国陶瓷，2002，38(2)：15～19
[29]张世英、赖腾、章秦娟，炻器亚光釉的研究，中国陶瓷，2002，38(5)，22～24
[30]陈平，低温快烧炻器亚光釉的研究，中国陶瓷工业，2002，9(1)：5～9
[31]宁青菊、张世英，建筑外墙砖镁无光釉的研制，陶瓷工程，2001(2)
[32]汪良贤，关于无光釉几个问题的探讨，中国陶瓷工业，2001，8(1)，40～45
[33]何寿生，卫生陶瓷快速烧成制度探讨，陶瓷，2000，147(5)：34～35
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