金红石结晶釉的制备及析晶机制的研究
|
摘要
结晶釉是一种装饰效果明显的艺术釉,现有的结晶釉主要是硅锌矿系结晶釉,体系较为单一,缺少其晶体生长的理论分析。本文研究了添加TiO_2加入对硅锌矿系结晶釉中对析出晶体物相的影响,探讨了TiO_2加入量和工艺条件对制备的结晶釉晶花形貌的影响规律,研究了用煤矸石替代粘土制备结晶釉艺术瓷坯体的可行性。
研究结果表明,在1250℃熔融1130℃析晶工艺条件下可成功制备出有较强美感的金红石结晶釉,结晶釉中晶体能自发生长且能铺满整个釉面,结晶釉中析出晶体的数量随析晶温度的升高而增大。XRD和光学显微分析结果表明析出的晶体为长柱状的金红石,优化的结晶釉的最佳原料配方为14.5%TiO_2、10.1%ZnO、11.6%焦宝石、63.5%玻璃粉和0.3%CuO。
结晶釉中引入稀土氧化物作为着色剂,研究结果表明:CeO_2能使结晶釉高温下呈现稳定的黄色,而Er2O3能使结晶釉高温下呈现稳定的红色。添加稀土氧化物使结晶釉中析出的柱状晶体直径变细,但没有改变析出晶体的晶型。
采用煤矸石代替粘土制备结晶釉坯体的研究表明,煤矸石替代粘土对坯体的吸水率、气孔率、抗折强度、抗压强度和坯釉结合的影响较小。当煤矸石替代量达46%时,结晶釉坯体的气孔率、抗折强度、抗压强度和坯釉结合等性能几乎没有发生改变,以煤矸石代替粘土作为结晶釉艺术瓷坯体的原料是完全可行的。
本课题的研究成果不仅有重要的理论意义还有更重要的应用前景。
Crystalline glaze is a kind of art glaze with excellent decorative performance. Now, the system of willemite crystalline glaze as the most common crystalline glaze is single. Little theoretical analysis on the crystal growth has been reported. In this paper, TiO_2 was introduced into willemite crystalline glaze. The influence of TiO_2 addition and processing conditions on the phase constitution and patterns of crystal flowers of the crystalline glaze was studied. Also, the feasibility of using coal gangue as a substitute for clay to prepare crystalline glaze was investigated.
The results showed that a rutile crystalline glaze with better aesthetic appearance was prepared under the conditions of melting temperature of 1250℃and crystallization temperature of 1130℃. The crystals in the crystalline glaze could self-grow and overspread the whole surface of the glaze. The amount of the crystals increased with the increase of the crystallization temperatures. XRD and optical microscope results indicated that the precipitated crystals were long columnar rutile crystals. The optimizing raw materials formula for the crystalline glaze was as follows: 14.5%TiO_2, 10.1%ZnO, 11.6%flint clay, 63.5%glass frit and 0.3%CuO. This paper also showed that.
Rare earth oxides were also introduced into the crystalline gaze as colorant. The results showed that CeO_2 could make the crystalline glaze present steady yellowness and Er2O3 could make crystalline glaze present steady redness at high temperature. The addition of rare earth oxides made the long columnar crystals in the crystalline glaze became thinne. The crystal structure did not changed.
Using coal gangue as a substitute for clay to prepare crystalline glaze body showed has little effect on the hygroscopic coefficient, the porosity, volume concentration, flexural strength and the bonding between the crystalline glaze and the body. When the rate of the coal gangue reached 46%, the performances mentioned above had little changes. The results indicated that it is completely feasible to use coal gangue as a substitute for clay to prepare crystalline glaze ceramic body.
研究结果表明,在1250℃熔融1130℃析晶工艺条件下可成功制备出有较强美感的金红石结晶釉,结晶釉中晶体能自发生长且能铺满整个釉面,结晶釉中析出晶体的数量随析晶温度的升高而增大。XRD和光学显微分析结果表明析出的晶体为长柱状的金红石,优化的结晶釉的最佳原料配方为14.5%TiO_2、10.1%ZnO、11.6%焦宝石、63.5%玻璃粉和0.3%CuO。
结晶釉中引入稀土氧化物作为着色剂,研究结果表明:CeO_2能使结晶釉高温下呈现稳定的黄色,而Er2O3能使结晶釉高温下呈现稳定的红色。添加稀土氧化物使结晶釉中析出的柱状晶体直径变细,但没有改变析出晶体的晶型。
采用煤矸石代替粘土制备结晶釉坯体的研究表明,煤矸石替代粘土对坯体的吸水率、气孔率、抗折强度、抗压强度和坯釉结合的影响较小。当煤矸石替代量达46%时,结晶釉坯体的气孔率、抗折强度、抗压强度和坯釉结合等性能几乎没有发生改变,以煤矸石代替粘土作为结晶釉艺术瓷坯体的原料是完全可行的。
本课题的研究成果不仅有重要的理论意义还有更重要的应用前景。
Crystalline glaze is a kind of art glaze with excellent decorative performance. Now, the system of willemite crystalline glaze as the most common crystalline glaze is single. Little theoretical analysis on the crystal growth has been reported. In this paper, TiO_2 was introduced into willemite crystalline glaze. The influence of TiO_2 addition and processing conditions on the phase constitution and patterns of crystal flowers of the crystalline glaze was studied. Also, the feasibility of using coal gangue as a substitute for clay to prepare crystalline glaze was investigated.
The results showed that a rutile crystalline glaze with better aesthetic appearance was prepared under the conditions of melting temperature of 1250℃and crystallization temperature of 1130℃. The crystals in the crystalline glaze could self-grow and overspread the whole surface of the glaze. The amount of the crystals increased with the increase of the crystallization temperatures. XRD and optical microscope results indicated that the precipitated crystals were long columnar rutile crystals. The optimizing raw materials formula for the crystalline glaze was as follows: 14.5%TiO_2, 10.1%ZnO, 11.6%flint clay, 63.5%glass frit and 0.3%CuO. This paper also showed that.
Rare earth oxides were also introduced into the crystalline gaze as colorant. The results showed that CeO_2 could make the crystalline glaze present steady yellowness and Er2O3 could make crystalline glaze present steady redness at high temperature. The addition of rare earth oxides made the long columnar crystals in the crystalline glaze became thinne. The crystal structure did not changed.
Using coal gangue as a substitute for clay to prepare crystalline glaze body showed has little effect on the hygroscopic coefficient, the porosity, volume concentration, flexural strength and the bonding between the crystalline glaze and the body. When the rate of the coal gangue reached 46%, the performances mentioned above had little changes. The results indicated that it is completely feasible to use coal gangue as a substitute for clay to prepare crystalline glaze ceramic body.
引文
[1] 李家驹. 陶瓷工艺学. 中国轻工业出版社. 2004. 151～153
[2] 王芬,张超武,黄剑锋. 硅酸盐制品的装饰及装饰材料. 北京:化学工业出版社,2004. 255～257
[3] 赵世学. 古瓷釉的形成和发展. 安阳师专学报. 1999
[4] Dond M,Francesco M. High-performance yellow ceramic pigments Zr. Crystal structure,colouring mechanism and technological properties. Materials Research Bulletin,2007.42(1):64～76.
[5] Molera J. The growth of sanidine crystals in the lead of glazes of Hispano-Moresque pottery. Applied Clay Science. 1993(3):483～491.
[6] Hetherington A L. Chiaese Ceramic Glazes. Cambridge at the University. 1937.
[7] 武秀兰,陈国平. 硅酸盐生产配方设计与工艺控制. 化学工业出版社. 2004. 56～58
[8] Turan,B.Effects of cobalt,copper. Manganese and titanium oxide additions on the microstructures of zinc containing soft porcelain glazes. Journal of the European Ceramic Society. 2002. 22(9-10):206～216.
[9] 颜汉军. 试论陶瓷结晶釉的应用. 陶瓷科学与艺术. 2002.6:26～30.
[10] Encarna Bou,Arnaldo Moreno. Microstructure study of opaque glazes obtained from frits of the system:SiO2- Al2O3-B2O3- P2O5 –CaO- K2O- TiO2. Journal of the European Ceramic Society. 2007. 27:1791～1796.
[11] 马鸿文. 工业矿物与岩石. 地质出版社. 2002.8 181～183
[12] 潘兆橹. 结晶学与矿物学(下册). 地质出版社. 1994.11 60～62
[13] 周亚栋. 无机材料物理化学. 武汉工业大学出版社.2003 147～149
[14] 刘河洲,胡文彬,顾明元等. 纳米 TiO2 晶粒生长动力学的研究. 无机材料学报. 2002.5,17(3):429～436.
[15] 毕孝国,修稚萌,孙旭东等. 大尺寸金红石(TiO2)单晶体生长条件的实验研究. 人工晶体学报. 2004.4,33(2):244～249.
[16] 潘兆橹. 结晶学与矿物学(上册). 地质出版社. 2003 10～13
[17] 赵效忠,苏良赫等.硅锌矿结晶釉中氧化锌的核化作用.硅酸盐通报,1983,2(3):16
[18] 刘康时,黄励知等.硅锌矿熔块结晶釉的析晶过程.广州,华南工学院,1980.
[19] 赵效忠.硅锌矿的生长形态学研究.硅酸盐学报,1993;21(1):38.
[20] 赵效忠,张桂英等. 氧化铝对结晶釉工艺性能的影响. 辽宁陶瓷. 1983,(2):37
[21] 孙洪巍,王淑玲,封鉴秋. 组成和温度制度对硅锌矿析晶的影响. 郑州大学学报. 2000.12,32(4):88～92.
[22] 李家驹. 陶瓷工艺学. 中国轻工业出版社. 2004. 224～225
[23] 程金树,李宏等. 微晶玻璃. 化学工业出版社. 2006.1 22～27
[24] 朱小平,于长风,凌清等. 辊道窑快烧结晶釉的制备与晶体形貌分析. 中国陶瓷. 2005.6,3(41):21～25.
[25] 郑少华,姜奉华. 试验设计与数据处理. 中国建材工业出版社,2004. 80～87
[26] 叶巧明,张其春. 烧成制度与结晶釉相关性的研究. 陶瓷. 2002,1:37～38.
[27] 潘兆橹. 结晶学与矿物学(上册). 地质出版社. 187～191
[28] 张克从,张乐潓. 晶体生长科学与技术. 科学出版社. 1997. 174～196.
[29] 伊赫桑·巴伦. 纯物质热化学数据手册(Thermochemical Data of Pure Substance). 科学出版社. 2003.10 1837～1838、1836、1505、1692、1693
[30] 李如璧,徐培苍. 硅酸盐熔体粘度理论计算模式的研究. 江苏技术师范学院学报. 2004.12,10(4):33～37.
[31] 张青红,高濂,孙静. 煅烧温度对二氧化钛纳米晶性能的影响. 无机材料学报. 2001.9,16(5):833～838.
[32] 毕胜. 中国二氧化钛和钛矿工业的形势及发展分析. 现代涂料与涂装. 2005.2:44～47.
[33] 于长风,朱小平,张脉官. 稀土氧化物对变色结晶釉呈色的影响. 中国陶瓷工业. 2002.10,9(5):9～14.
[34] Bekir Karasu. The Development and Characterisation of Zinc Crystal Glazes Used for Amakusa-like Soft Porcelains. Journal of the European Ceramic Society, 2000
[35] 吴贤,张健. 中国的钛资源分布及特点. 钛工业进展. 2006.12,23(6):8～12.
[36] 井立强. 孙晓君. 辛柏福等. 掺杂镧和铈的TiO2纳米粒子的结构相变. 材料科学与工程. 2004.4,12(2):148～152.
[37] 高荣杰,史可信,王之昌. 金红石型二氧化钛粒子成长动力学. 无机材料学报. 1998.10,13(5):729～732.
[38] 赵鸿胜,张雄. 煤矸石作水泥混合材的活化方法. 新世纪水泥导报.2004,4:23-27.
[39] 张凤辰. 煤矸石及其综合利用. 中国环保产业. 2004,10:14-20.
[40] 马鸿文. 工业矿物与岩石. 北京:地质出版社,2002. 456～458
[41] 江嘉运,盖广清,金玉杰. 煤矸石页岩烧结砖的原料制备工艺. 新型墙体材料与施工. 2004,49-51.
[42] 刘家第,刘凤春等. 煤矸石烧结空心砖的原料选择和生产工艺影响因素研究. 非金属矿. 2004,7:18-20.
[43] 赵效忠.硅锌矿的生长形态学研究.硅酸盐学报,1993;21(1):38.
[44] 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):1
[45] 胡志强.无机材料科学基础.化学工业出版社.2003 37～39
[46] 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):12
[47] 伍洪标. 无机非金属材料实验. 化学工业出版社. 2002 154～167
[2] 王芬,张超武,黄剑锋. 硅酸盐制品的装饰及装饰材料. 北京:化学工业出版社,2004. 255～257
[3] 赵世学. 古瓷釉的形成和发展. 安阳师专学报. 1999
[4] Dond M,Francesco M. High-performance yellow ceramic pigments Zr. Crystal structure,colouring mechanism and technological properties. Materials Research Bulletin,2007.42(1):64～76.
[5] Molera J. The growth of sanidine crystals in the lead of glazes of Hispano-Moresque pottery. Applied Clay Science. 1993(3):483～491.
[6] Hetherington A L. Chiaese Ceramic Glazes. Cambridge at the University. 1937.
[7] 武秀兰,陈国平. 硅酸盐生产配方设计与工艺控制. 化学工业出版社. 2004. 56～58
[8] Turan,B.Effects of cobalt,copper. Manganese and titanium oxide additions on the microstructures of zinc containing soft porcelain glazes. Journal of the European Ceramic Society. 2002. 22(9-10):206～216.
[9] 颜汉军. 试论陶瓷结晶釉的应用. 陶瓷科学与艺术. 2002.6:26～30.
[10] Encarna Bou,Arnaldo Moreno. Microstructure study of opaque glazes obtained from frits of the system:SiO2- Al2O3-B2O3- P2O5 –CaO- K2O- TiO2. Journal of the European Ceramic Society. 2007. 27:1791～1796.
[11] 马鸿文. 工业矿物与岩石. 地质出版社. 2002.8 181～183
[12] 潘兆橹. 结晶学与矿物学(下册). 地质出版社. 1994.11 60～62
[13] 周亚栋. 无机材料物理化学. 武汉工业大学出版社.2003 147～149
[14] 刘河洲,胡文彬,顾明元等. 纳米 TiO2 晶粒生长动力学的研究. 无机材料学报. 2002.5,17(3):429～436.
[15] 毕孝国,修稚萌,孙旭东等. 大尺寸金红石(TiO2)单晶体生长条件的实验研究. 人工晶体学报. 2004.4,33(2):244～249.
[16] 潘兆橹. 结晶学与矿物学(上册). 地质出版社. 2003 10～13
[17] 赵效忠,苏良赫等.硅锌矿结晶釉中氧化锌的核化作用.硅酸盐通报,1983,2(3):16
[18] 刘康时,黄励知等.硅锌矿熔块结晶釉的析晶过程.广州,华南工学院,1980.
[19] 赵效忠.硅锌矿的生长形态学研究.硅酸盐学报,1993;21(1):38.
[20] 赵效忠,张桂英等. 氧化铝对结晶釉工艺性能的影响. 辽宁陶瓷. 1983,(2):37
[21] 孙洪巍,王淑玲,封鉴秋. 组成和温度制度对硅锌矿析晶的影响. 郑州大学学报. 2000.12,32(4):88～92.
[22] 李家驹. 陶瓷工艺学. 中国轻工业出版社. 2004. 224～225
[23] 程金树,李宏等. 微晶玻璃. 化学工业出版社. 2006.1 22～27
[24] 朱小平,于长风,凌清等. 辊道窑快烧结晶釉的制备与晶体形貌分析. 中国陶瓷. 2005.6,3(41):21～25.
[25] 郑少华,姜奉华. 试验设计与数据处理. 中国建材工业出版社,2004. 80～87
[26] 叶巧明,张其春. 烧成制度与结晶釉相关性的研究. 陶瓷. 2002,1:37～38.
[27] 潘兆橹. 结晶学与矿物学(上册). 地质出版社. 187～191
[28] 张克从,张乐潓. 晶体生长科学与技术. 科学出版社. 1997. 174～196.
[29] 伊赫桑·巴伦. 纯物质热化学数据手册(Thermochemical Data of Pure Substance). 科学出版社. 2003.10 1837～1838、1836、1505、1692、1693
[30] 李如璧,徐培苍. 硅酸盐熔体粘度理论计算模式的研究. 江苏技术师范学院学报. 2004.12,10(4):33～37.
[31] 张青红,高濂,孙静. 煅烧温度对二氧化钛纳米晶性能的影响. 无机材料学报. 2001.9,16(5):833～838.
[32] 毕胜. 中国二氧化钛和钛矿工业的形势及发展分析. 现代涂料与涂装. 2005.2:44～47.
[33] 于长风,朱小平,张脉官. 稀土氧化物对变色结晶釉呈色的影响. 中国陶瓷工业. 2002.10,9(5):9～14.
[34] Bekir Karasu. The Development and Characterisation of Zinc Crystal Glazes Used for Amakusa-like Soft Porcelains. Journal of the European Ceramic Society, 2000
[35] 吴贤,张健. 中国的钛资源分布及特点. 钛工业进展. 2006.12,23(6):8～12.
[36] 井立强. 孙晓君. 辛柏福等. 掺杂镧和铈的TiO2纳米粒子的结构相变. 材料科学与工程. 2004.4,12(2):148～152.
[37] 高荣杰,史可信,王之昌. 金红石型二氧化钛粒子成长动力学. 无机材料学报. 1998.10,13(5):729～732.
[38] 赵鸿胜,张雄. 煤矸石作水泥混合材的活化方法. 新世纪水泥导报.2004,4:23-27.
[39] 张凤辰. 煤矸石及其综合利用. 中国环保产业. 2004,10:14-20.
[40] 马鸿文. 工业矿物与岩石. 北京:地质出版社,2002. 456～458
[41] 江嘉运,盖广清,金玉杰. 煤矸石页岩烧结砖的原料制备工艺. 新型墙体材料与施工. 2004,49-51.
[42] 刘家第,刘凤春等. 煤矸石烧结空心砖的原料选择和生产工艺影响因素研究. 非金属矿. 2004,7:18-20.
[43] 赵效忠.硅锌矿的生长形态学研究.硅酸盐学报,1993;21(1):38.
[44] 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):1
[45] 胡志强.无机材料科学基础.化学工业出版社.2003 37～39
[46] 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):12
[47] 伍洪标. 无机非金属材料实验. 化学工业出版社. 2002 154～167