闪光釉的研制
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摘要
闪光釉是近几年发展起来的一种装饰艺术釉。用它可以在墙地砖上印制各种花色图案，烧成后具有镜面般的反光效果，能迎合一部分用户的欣赏要求。本论文对闪光釉的配方组成、制备工艺、闪光釉中CeO_2晶体的析晶过程及闪光机理作了比较系统的试验和研究。
通过大量的配方试验，确定了较佳的四个配方组成及相应的工艺条件。对各项工艺因素的试验表明：烧成温度影响釉熔体中析出的CeO_2晶粒的大小和数量，因而对闪光效果影响很大；闪光釉的烧成宜于快速冷却；闪光釉可以在一定的温度范围内熔制成功，但熔制温度的高低会对烧成温度造成影响，一般地，烧成温度随熔制温度的降低而升高；闪光釉熔块以按料:球:水=1:3:5球磨1h为宜，过度细磨会加剧闪光釉与底釉的反应，于烧成不利，球磨时外加少量的CMC和乙二醇有助于提高球磨效率，并改善烧成釉面的闪光效果；合适的釉层厚度为0.3～0.4mm。
从对国外闪光釉粉烧釉时CeO_2析晶过程的试验和分析可以发现：釉熔体中CeO_2晶体的晶核生成范围大约在950～1040℃，最大成核速度在1010℃附近，1040～1100℃位于CeO_2晶体的生长范围之内，最大生长速度大致介于1070～1100℃之间。
对闪光机理的分析表明：CeO_2晶粒的反射和釉面镜反射是造成闪光效果的直接原因，而釉层折射率、釉面平整度、CeO_2晶粒的取向度、颗粒度及其在釉层中的铺盖面积则是影响闪光效果的重要因素，改善工艺可从这些因素着手。
Glisten glaze, developed in recent years, is a kind of ornamental artistic glaze. It can be used to print all kinds of the design and color patterns on tiles with specular reflection when sintered, which may cater to some customers' appetite. In this paper, the formula and producing process of the glisten glaze are discussed systematically, as well as the crystallization of CeO2 in the glisten glaze and the glistening mechanism.
Four formulas and their corresponding technical processing are determined by large numbers of formula experiments. The test of all kinds of factors shows that the sintering temperature affects the size and quantity of the grain of CeO2 crystallized from the glaze melt so as to influence the glistening effect dramatically; the glisten glaze should be cooled quickly after sintering ; the glisten glaze can be successfully melted in a certain temperature range, but the melting temperature can affect the sintering temperature to some extend. Generally, the sintering temperature will rise with the falling of the melting temperature. The clinker of the glisten glaze is grinded for an hour with such a proportion ?powder:ball:water = 1:3:5. The extreme grinding will accelerate the reaction between the glisten glaze and the based glaze, which is not good for sintering. While grinding, a small quantity of CMC and ethylene glycol are added to improve the grinding efficiency and the glistening effect of glaze surface. The finable thickness of glaze layer is 0.3-0.4mm.
Testing and analyzing the crystallization process of CeO2 when the glisten glaze powders from foreign countries were sintered, we find that the crystal nucleus of CeO2 in the glaze form in 950-1040℃, and the maxical velocity of nucleation is near 1010℃. 1040-1100 ℃ is located in the temperature range of the growing of CeO2 crystal and the temperature of the maxical growing velocity is nearly between 1070℃ and 1100℃.
The analysis of the glistening mechanism shows that the reflection of crystal grain of CeO2 and the specular reflection of glaze surface directly affect the glazing effect. The refractive index of glaze layer, the smoothness of glaze surface, the orientation, size and covering area in the glaze of CeO2 are the important factors influencing the glistening effect We may begin with these factors to improve the technology.
通过大量的配方试验，确定了较佳的四个配方组成及相应的工艺条件。对各项工艺因素的试验表明：烧成温度影响釉熔体中析出的CeO_2晶粒的大小和数量，因而对闪光效果影响很大；闪光釉的烧成宜于快速冷却；闪光釉可以在一定的温度范围内熔制成功，但熔制温度的高低会对烧成温度造成影响，一般地，烧成温度随熔制温度的降低而升高；闪光釉熔块以按料:球:水=1:3:5球磨1h为宜，过度细磨会加剧闪光釉与底釉的反应，于烧成不利，球磨时外加少量的CMC和乙二醇有助于提高球磨效率，并改善烧成釉面的闪光效果；合适的釉层厚度为0.3～0.4mm。
从对国外闪光釉粉烧釉时CeO_2析晶过程的试验和分析可以发现：釉熔体中CeO_2晶体的晶核生成范围大约在950～1040℃，最大成核速度在1010℃附近，1040～1100℃位于CeO_2晶体的生长范围之内，最大生长速度大致介于1070～1100℃之间。
对闪光机理的分析表明：CeO_2晶粒的反射和釉面镜反射是造成闪光效果的直接原因，而釉层折射率、釉面平整度、CeO_2晶粒的取向度、颗粒度及其在釉层中的铺盖面积则是影响闪光效果的重要因素，改善工艺可从这些因素着手。
Glisten glaze, developed in recent years, is a kind of ornamental artistic glaze. It can be used to print all kinds of the design and color patterns on tiles with specular reflection when sintered, which may cater to some customers' appetite. In this paper, the formula and producing process of the glisten glaze are discussed systematically, as well as the crystallization of CeO2 in the glisten glaze and the glistening mechanism.
Four formulas and their corresponding technical processing are determined by large numbers of formula experiments. The test of all kinds of factors shows that the sintering temperature affects the size and quantity of the grain of CeO2 crystallized from the glaze melt so as to influence the glistening effect dramatically; the glisten glaze should be cooled quickly after sintering ; the glisten glaze can be successfully melted in a certain temperature range, but the melting temperature can affect the sintering temperature to some extend. Generally, the sintering temperature will rise with the falling of the melting temperature. The clinker of the glisten glaze is grinded for an hour with such a proportion ?powder:ball:water = 1:3:5. The extreme grinding will accelerate the reaction between the glisten glaze and the based glaze, which is not good for sintering. While grinding, a small quantity of CMC and ethylene glycol are added to improve the grinding efficiency and the glistening effect of glaze surface. The finable thickness of glaze layer is 0.3-0.4mm.
Testing and analyzing the crystallization process of CeO2 when the glisten glaze powders from foreign countries were sintered, we find that the crystal nucleus of CeO2 in the glaze form in 950-1040℃, and the maxical velocity of nucleation is near 1010℃. 1040-1100 ℃ is located in the temperature range of the growing of CeO2 crystal and the temperature of the maxical growing velocity is nearly between 1070℃ and 1100℃.
The analysis of the glistening mechanism shows that the reflection of crystal grain of CeO2 and the specular reflection of glaze surface directly affect the glazing effect. The refractive index of glaze layer, the smoothness of glaze surface, the orientation, size and covering area in the glaze of CeO2 are the important factors influencing the glistening effect We may begin with these factors to improve the technology.
引文
[1]张凤岐，魏忠汉著．结晶釉工艺．上海：上海科学技术出版社．1981
[2][日]素木洋一著．釉及色料．(刘习栋、刘光跃译)．北京：中国建筑工业出版社．1979
[3]刘康时等编著．陶瓷工艺原理．广州：华南理工大学出版社．1990
[4]李家驹主编．日用陶瓷工艺学．武汉：武汉工业大学出版社．1992
[5]西北轻工业学院等编．陶瓷工艺学．北京：中国轻工业出版社．1997
[6]解春波．硅酸锌结晶釉的生产特点．河北陶瓷．1997，25(3)：37
[7]陈文钦，林珠金．再论结晶晶花釉的研究．陶瓷研究．2000，15(4)：13
[8]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
[9]牟国栋等．煤矸石的纳米结构研究及用其烧制结晶釉的试验．矿物岩石．2000，20(1)：98
[10]赵效忠．我国硅锌矿结晶釉研究进展．硅酸盐学报．1994，22(3)：270-271
[11]李斌，李方勇等．彩釉瓷质地砖的研制．山东陶瓷．1997，20(3)：27-29
[12]韩顺良，杨增林．锆熔块无光釉的研制．江苏陶瓷．1995(2)：25
[13]司志胜，马桂红．低温快烧无光釉的研制．山东陶瓷．1996，19(3)：23
[14]张玉南．正三角形取值试验法及其应用．陶瓷研究．2000，15(4)：21
[15]黄剑峰，曹丽云．CuO-MnO-V_2O_5-Fe_2O_3系金属光泽釉的研究．陶瓷．2001(4)：22-23
[16]刘德明．对中医方剂学基础理论在调整陶瓷配方中的应用初探．陶瓷研究．2001，16(1)：15-16，18
[17]田斌守，王花枝．绿色银光釉的研制．陶瓷．1995(4)：35，19
[18]陆小荣．变色结晶釉的研制．江苏陶瓷．1997，30(4)：4
[19]邵明梁，付兴华，章希胜．低温快烧结晶釉的研制．河北陶瓷．1998，26(1)：3
[20]赵鸿声著．陶瓷制作．北京：印刷工业出版社，1994
[21]天津大学物理化学教研室编．物理化学(下册)．北京：高等教育出版社．1993
[22]张忠铭编．日用陶瓷原料的分析及坯釉配方．上海：上海交通大学出版社．1986
[23]赵效忠，张桂英等．结晶釉中硅锌矿的析晶．硅酸盐通报．1984，3(5)：15-16，12-13
[24]关振铎，张中太，焦金生编著．无机材料物理性能．北京：清华大学出版社．1992
[25]李春蓉，刘纯．熔块釉制备过程中应如何进行质量控制．陶瓷．2001(4)：48-49
[26]俞康泰编著．陶瓷色釉料与装饰导论．武汉：武汉工业大学出版社．1998
[27]李如生著．有序与无序的奥秘．北京；人民教育出版社．1984
[28]罗谷风编．结晶学导论．北京：地质出版社．1984
[29]浙江大学等四校合编．硅酸盐物理化学．北京：中国建筑工业出版社．1998
[30]黄昆原著，韩汝琦改编．固体物理学．北京：高等教育出版社．1988
[31]王秀文，董秀珍．MnO-PbO-ZnO系统虹彩釉工艺过程的探讨冲国陶瓷．2001，37(2)：34-35
[32]大连理工大学无机化学教研室编．无机化学(下册)．北京：高等教育出版社．1990。
[33]SACMI Experimental center. Technological notes on the Manufacture of ceramic tiles.
1988
[34]S. R. Scholes.Modern Glass Practice. Cahners Books. 1975
[35]F. H. Norton. Fine Ceramics, Tchnology and Applications.R.E. Krieger Pub. Co. New York. 1978
[36]Terence J. Clark. JAMES. REED. Kinetic Processes involved in the sintering and crystallization of glass powders. J. Am. Ceram. Soc. 1986,69(11): 837-846
[37]J. Chappel. The potter's complete book of clay and glazes. Watson. Guptil. New York. 1977
[38]F. Singer and S. S. Singer. Industrial ceramics. Chamman and Hall.1963
[39]K. Teuchert etc. Formation of glazes of different chemical compositions at different temperatures. Interceram. 1995,44(4)
[40]F.H.Norton. The Control of Crystalline Glazes. J .Am,Ceram. Soc. 1937,20: 217-224
[41]H.D.K.eith and F.J. Padden. A Phenomenological Theory of Spherulitic Crystallization. J.Appl.Phys. 1963,34(8):2409
[42]M,Avrami. Granulation,Phase Change, And Microstructure.Kinetics of Phase Change. J, Chem. Phys. 1941,9:177
[43]E.A.Guggenheim. Grand Partition Functions and Socalled Thermodynamic Probability.J.Chem Phys. 1939,7:103
[44]M.Avrami. Kinetics of Phase Change Transformation-time Relations for Random Distribution of Nuclei. J.Chem.Phys. 1940,8:212
[45]G.Yoldjian. The Use of Rare Earths In Ceramics. J. Less-Common Met. 1985,111(1-2):17-22
[46]I.Gutzow. Kinetics of Crystallization Processes in Glass Forming Melts. J.Cryst. Growth. 1979,48: 589-599
[47]Z.E.Holland and E.R.Segnit The Ternary System Na_2O-ZnO-SiO_2.Australia J.Chem. 1966,19(6): 905-913
[48]S.Kanakamju, S.Mohan, A.K. Sood,Optical and Structural Properties of Reactive Ion Beam Sputter Deposited CeO_2 Films. Thin Solid Films. 1997,305(1-2): 191-195
[49]10.Jin S,et al. Melt-textured Growth of Polycrystalline YBa_2Cu3O_(7-(?)) With High Transport J_c at 77k. Phys. Rev. 1988,B37:7850
[50]徐建华．仿茶叶末釉的研制及其机理探讨．江苏陶瓷．1994(2)：14
[51]王迎军，刘康时．结晶釉中硅锌矿晶体的核化与生长．中国陶瓷．1986(6)：4
[52]闵乃本．晶体生长的物理基础．上海：上海科学技术出版社．1982
[53][比]G·尼科利斯，I.普里戈京著．非平衡系统的自组织．(徐锡申译)．北京：清华大学出版社．1986
[54]李晓云，陆天长．闪光釉闪光机理的研究．中国陶瓷．2001，(37)1：15
[2][日]素木洋一著．釉及色料．(刘习栋、刘光跃译)．北京：中国建筑工业出版社．1979
[3]刘康时等编著．陶瓷工艺原理．广州：华南理工大学出版社．1990
[4]李家驹主编．日用陶瓷工艺学．武汉：武汉工业大学出版社．1992
[5]西北轻工业学院等编．陶瓷工艺学．北京：中国轻工业出版社．1997
[6]解春波．硅酸锌结晶釉的生产特点．河北陶瓷．1997，25(3)：37
[7]陈文钦，林珠金．再论结晶晶花釉的研究．陶瓷研究．2000，15(4)：13
[8]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
[9]牟国栋等．煤矸石的纳米结构研究及用其烧制结晶釉的试验．矿物岩石．2000，20(1)：98
[10]赵效忠．我国硅锌矿结晶釉研究进展．硅酸盐学报．1994，22(3)：270-271
[11]李斌，李方勇等．彩釉瓷质地砖的研制．山东陶瓷．1997，20(3)：27-29
[12]韩顺良，杨增林．锆熔块无光釉的研制．江苏陶瓷．1995(2)：25
[13]司志胜，马桂红．低温快烧无光釉的研制．山东陶瓷．1996，19(3)：23
[14]张玉南．正三角形取值试验法及其应用．陶瓷研究．2000，15(4)：21
[15]黄剑峰，曹丽云．CuO-MnO-V_2O_5-Fe_2O_3系金属光泽釉的研究．陶瓷．2001(4)：22-23
[16]刘德明．对中医方剂学基础理论在调整陶瓷配方中的应用初探．陶瓷研究．2001，16(1)：15-16，18
[17]田斌守，王花枝．绿色银光釉的研制．陶瓷．1995(4)：35，19
[18]陆小荣．变色结晶釉的研制．江苏陶瓷．1997，30(4)：4
[19]邵明梁，付兴华，章希胜．低温快烧结晶釉的研制．河北陶瓷．1998，26(1)：3
[20]赵鸿声著．陶瓷制作．北京：印刷工业出版社，1994
[21]天津大学物理化学教研室编．物理化学(下册)．北京：高等教育出版社．1993
[22]张忠铭编．日用陶瓷原料的分析及坯釉配方．上海：上海交通大学出版社．1986
[23]赵效忠，张桂英等．结晶釉中硅锌矿的析晶．硅酸盐通报．1984，3(5)：15-16，12-13
[24]关振铎，张中太，焦金生编著．无机材料物理性能．北京：清华大学出版社．1992
[25]李春蓉，刘纯．熔块釉制备过程中应如何进行质量控制．陶瓷．2001(4)：48-49
[26]俞康泰编著．陶瓷色釉料与装饰导论．武汉：武汉工业大学出版社．1998
[27]李如生著．有序与无序的奥秘．北京；人民教育出版社．1984
[28]罗谷风编．结晶学导论．北京：地质出版社．1984
[29]浙江大学等四校合编．硅酸盐物理化学．北京：中国建筑工业出版社．1998
[30]黄昆原著，韩汝琦改编．固体物理学．北京：高等教育出版社．1988
[31]王秀文，董秀珍．MnO-PbO-ZnO系统虹彩釉工艺过程的探讨冲国陶瓷．2001，37(2)：34-35
[32]大连理工大学无机化学教研室编．无机化学(下册)．北京：高等教育出版社．1990。
[33]SACMI Experimental center. Technological notes on the Manufacture of ceramic tiles.
1988
[34]S. R. Scholes.Modern Glass Practice. Cahners Books. 1975
[35]F. H. Norton. Fine Ceramics, Tchnology and Applications.R.E. Krieger Pub. Co. New York. 1978
[36]Terence J. Clark. JAMES. REED. Kinetic Processes involved in the sintering and crystallization of glass powders. J. Am. Ceram. Soc. 1986,69(11): 837-846
[37]J. Chappel. The potter's complete book of clay and glazes. Watson. Guptil. New York. 1977
[38]F. Singer and S. S. Singer. Industrial ceramics. Chamman and Hall.1963
[39]K. Teuchert etc. Formation of glazes of different chemical compositions at different temperatures. Interceram. 1995,44(4)
[40]F.H.Norton. The Control of Crystalline Glazes. J .Am,Ceram. Soc. 1937,20: 217-224
[41]H.D.K.eith and F.J. Padden. A Phenomenological Theory of Spherulitic Crystallization. J.Appl.Phys. 1963,34(8):2409
[42]M,Avrami. Granulation,Phase Change, And Microstructure.Kinetics of Phase Change. J, Chem. Phys. 1941,9:177
[43]E.A.Guggenheim. Grand Partition Functions and Socalled Thermodynamic Probability.J.Chem Phys. 1939,7:103
[44]M.Avrami. Kinetics of Phase Change Transformation-time Relations for Random Distribution of Nuclei. J.Chem.Phys. 1940,8:212
[45]G.Yoldjian. The Use of Rare Earths In Ceramics. J. Less-Common Met. 1985,111(1-2):17-22
[46]I.Gutzow. Kinetics of Crystallization Processes in Glass Forming Melts. J.Cryst. Growth. 1979,48: 589-599
[47]Z.E.Holland and E.R.Segnit The Ternary System Na_2O-ZnO-SiO_2.Australia J.Chem. 1966,19(6): 905-913
[48]S.Kanakamju, S.Mohan, A.K. Sood,Optical and Structural Properties of Reactive Ion Beam Sputter Deposited CeO_2 Films. Thin Solid Films. 1997,305(1-2): 191-195
[49]10.Jin S,et al. Melt-textured Growth of Polycrystalline YBa_2Cu3O_(7-(?)) With High Transport J_c at 77k. Phys. Rev. 1988,B37:7850
[50]徐建华．仿茶叶末釉的研制及其机理探讨．江苏陶瓷．1994(2)：14
[51]王迎军，刘康时．结晶釉中硅锌矿晶体的核化与生长．中国陶瓷．1986(6)：4
[52]闵乃本．晶体生长的物理基础．上海：上海科学技术出版社．1982
[53][比]G·尼科利斯，I.普里戈京著．非平衡系统的自组织．(徐锡申译)．北京：清华大学出版社．1986
[54]李晓云，陆天长．闪光釉闪光机理的研究．中国陶瓷．2001，(37)1：15