铬锡红色料的低温合成及其光学性能的研究
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摘要
本论文的主要工作是研究铬锡红色料的低温合成和光谱性能，实验中采
用了化学共沉淀法、溶胶凝胶法合成了铬锡红色料，并与固相合成法进行了比
较。
在固相法中，主要研究了铬锡红色料的矿物组成对呈色的影响，确定了
较为适宜的配方组成。首先得到了采用预先合成锡榍石制备色料效果要好于
一次性合成色料的结论，为化学共沉淀前驱体合成法找到了理论依据。
在化学共沉淀法中，得到的铬锡红色料合成温度明显低于固相法。本工
作采用SnCl2·2H2O、K2Cr2O7、Na2SiO3、CaCO3为原料，对色料的前驱物进行
了化学计算和理论设计。实验表明，实验结果和理论计算结果相吻合，且得
到的产物在较低的温度即可得到铬锡红（低于固相法100℃），较好地解决了
高档铬锡红色料的低温合成问题。
在溶胶凝胶法中，得到的锡铬红色料的合成温度明显低于固相法的（降
低150℃），也低于化学共沉淀法的。本工作采用正硅酸乙酯（TEOS）、乙醇
（EtOH）、SnCl2·2H2O、CaCO3、CrCl3·6H2O为原料，对TEOS的水解条件进
行了探索，并通过水解粘度、光谱性能的测试对TEOS的水解过程进行了表征。
借助TG-DTA、XRD等测试手段，对三种合成方法进行了比较，初步分析
了铬锡红色料低温合成机理及反应过程；测试了铬锡红色料的反射光谱，结
合载色体锡榍石的结构特点，用晶体场理论较好的解释了铬锡红色料的呈色
机理。
In this paper,chrome-tin pink pigments was synthesized by chemical cosedimentation and sol-gel method which were contrasted with solid phase reaction.
In the solid phase method, the effect of composition on colour generation was mainly studied. Firstly, the pigment prepared by presynthesized tin sphene was obtained and has a good colour development. Theorical evidence was found by coprecipitation method.
Using SnCl22H2CK K2Cr2O7, Na2SiO3 and CaCO, as materials, synthesized temperature of liquid phase method was lower than that of solid phase method. In addtion, the preparation of pigment precursor was proved by chemical calculation and designed theorically. Synthesized temperature of chrome-tin pink by coprecipitation was lower 100 than solid method.
Using TEOSx EtOFK SnCl2 2H2O CaCO and CrCl36HO as materials, synthesized temperature of sol-gel was the lowest in three methods. It is declined 150. Water solution of TEOS was expressed by hydrolysis concentration and reflection spectrum curve.
By TG-DTA and XRD , three methods was constrasted , synthetic mechanism of low temperature and reaction processing were analysed and reflection spectrum of pigments was tested. From the crystallize chemistry angle, colour gegeration mechnism of chrome-tin pink was claimed by crystalline field theory.
用了化学共沉淀法、溶胶凝胶法合成了铬锡红色料，并与固相合成法进行了比
较。
在固相法中，主要研究了铬锡红色料的矿物组成对呈色的影响，确定了
较为适宜的配方组成。首先得到了采用预先合成锡榍石制备色料效果要好于
一次性合成色料的结论，为化学共沉淀前驱体合成法找到了理论依据。
在化学共沉淀法中，得到的铬锡红色料合成温度明显低于固相法。本工
作采用SnCl2·2H2O、K2Cr2O7、Na2SiO3、CaCO3为原料，对色料的前驱物进行
了化学计算和理论设计。实验表明，实验结果和理论计算结果相吻合，且得
到的产物在较低的温度即可得到铬锡红（低于固相法100℃），较好地解决了
高档铬锡红色料的低温合成问题。
在溶胶凝胶法中，得到的锡铬红色料的合成温度明显低于固相法的（降
低150℃），也低于化学共沉淀法的。本工作采用正硅酸乙酯（TEOS）、乙醇
（EtOH）、SnCl2·2H2O、CaCO3、CrCl3·6H2O为原料，对TEOS的水解条件进
行了探索，并通过水解粘度、光谱性能的测试对TEOS的水解过程进行了表征。
借助TG-DTA、XRD等测试手段，对三种合成方法进行了比较，初步分析
了铬锡红色料低温合成机理及反应过程；测试了铬锡红色料的反射光谱，结
合载色体锡榍石的结构特点，用晶体场理论较好的解释了铬锡红色料的呈色
机理。
In this paper,chrome-tin pink pigments was synthesized by chemical cosedimentation and sol-gel method which were contrasted with solid phase reaction.
In the solid phase method, the effect of composition on colour generation was mainly studied. Firstly, the pigment prepared by presynthesized tin sphene was obtained and has a good colour development. Theorical evidence was found by coprecipitation method.
Using SnCl22H2CK K2Cr2O7, Na2SiO3 and CaCO, as materials, synthesized temperature of liquid phase method was lower than that of solid phase method. In addtion, the preparation of pigment precursor was proved by chemical calculation and designed theorically. Synthesized temperature of chrome-tin pink by coprecipitation was lower 100 than solid method.
Using TEOSx EtOFK SnCl2 2H2O CaCO and CrCl36HO as materials, synthesized temperature of sol-gel was the lowest in three methods. It is declined 150. Water solution of TEOS was expressed by hydrolysis concentration and reflection spectrum curve.
By TG-DTA and XRD , three methods was constrasted , synthetic mechanism of low temperature and reaction processing were analysed and reflection spectrum of pigments was tested. From the crystallize chemistry angle, colour gegeration mechnism of chrome-tin pink was claimed by crystalline field theory.
引文
[1]加藤悦三．陶瓷器颜料．日本：日本窑业协会，1960：19
[2]俞康泰等．铬锡红色剂中铬的价态研究．中国陶瓷，1999，35(2)：503-507
[3]RICHARD A.EPPLER.Lattice Parameters of Tin Sphene.Amer.Ceram.Soc.,1976,59(9-10):455
[4]石田信武等．Chemical state of chromium inn-sphene.窑业协会志，1986，94(5)：458
[5]Christine J.Byrne and Richad A.Pipoly.Getting the Lead Out-A Case Study,Ceram.Eng.Sci.Proc.,1993,14(1-2):472-483
[6]Richard A.Eppler.Selecting Ceramic Pigments.Ceram.Eng.Sci.Proc.,1987,8(11-12):1139
[7]Richad A.Eppler and Douglas R.Eppler.Which Colors Can and Cannot Be Produced in Ceramic Glazes,Ceram.Eng.Sci.Proc.,1994,15(1):281-288
[8]公方杰．高档卫生陶瓷玛瑙红釉研制．科研与生产．
[9]郑乃章．铬锡红色料研究的现状与展望．中国陶瓷工业，1999，6(4)：42-44
[10]何代英等．玛瑙红高温陶瓷色剂的研究与应用．陶瓷，1994，110(4)：15-17
[11]徐平等．铬锡红釉的研究．景德镇陶瓷，第51期：10-12
[12]李国盛．玫瑰紫色釉的研制．陶瓷，1988，73(3)：6-8
[13]崔文元等．玫瑰紫色釉卫生洁具的研制．陶瓷，1989，82(6)：22-24
[14]Douglas R.Eppler and Richard A.Eppler.Analyzing the Color of Reddish Glazes.Ceram.Eng.Sci.Proc.,1996,17(1):77-87
[15]Christine J.Byrne,Steve G.Kutney and Richard A.Pipoly.How Glaze Composition Affects Chrome-Tin Pinks.Am.Ceram.Soc.Bull.,1994,73(5)
[16]A.C.Airey and Wroberts.Advances in Ceramic Colors.Ceram.Eng.Sci.Proc.,1987,8(11-12):1168
[17]南京地质大学系岩矿教研室编著．结晶学与矿物学．南京：地质出版社，1978．424～426
[18]系统矿物学．地质出版社，1984．205-206
[19]Anton M.Heyns,Peter M.Harden.Evidence for the existence of Cr(IV)in chromium-doped malayaite Cr~1:CaSnOSiO_4:a reasonance Raman Study.Journal of Physics and Chemistry of Solids,1999,60:277～284
[20]高富裕，刘贤儒主编．矿物学．南京：地址出版社，1984．56
[21]素木洋一著．釉及色料．北京：中国建筑工业出版社，1986．621
[22]杨萍等．关于红色陶瓷颜料．山东陶瓷，1999，22(1)：7-10
[23]武汉大学编．分析化学．北京：高等教育出版社，2000．189
[24]薛群基，徐康．纳米化学．化学进展，2000，12(4)：431-444
[25]田玉明，黄平，冷叔炎等．沉淀法的研究及其应用现状．材料导报，2000，14(2)：47-48
[26]上海化工学院无机化学教研室编．无机化学实验．人民教育出版社，1980
[27]M.LLUSAR,J.CALBO,J.A.BADENES,et al.Synthesis of iron zircon coral by eoprecipitation routes.Mat.Sci.,2001(3):153～163
[28]E.Cordoncillo,F.del Rio,J.Carda,M.Llusar,et al.Influence of Some Mineralizers in the Synthesis of Sphene-Pink Pigments.Journal of the European Ceramic Society,1998(18):1115～1120
[29]丁子上，翁文剑．溶胶-凝胶技术制备材料的进展．硅酸盐学报，1993，21(5)：443
[30]徐莉．正硅酸乙酯-凝胶过程中催化剂的作用．南京林业大学学报，1998，22(4)：67-70
[31]R.Stefani.Developing a Pink Pigment for Glazes.The American Ceramic Society Bulletin,1997(9):61～64
[32]Masashi SHOYhMA,Hiroyuki NASU nad Kanichi KAMIYA.Preparation of Rare Earth-Zircon Pigments by the Sol-Gel Method.Ceram.Sei.of Japan,1998,106(3):279～284
[33]C.L.Estrada,L.C.Torres-Gonzalez,A.F.Fuentes,et al.Synthesis of new vanadium cordierite pigment by sol-gel processing.British Ceramic Transactions,2000,99(2):67～71
[34]Masashi SHOYAMA,Kyoko HASHIMOTO,Tadanori HASHIMOTO,et al.Iron-Zircon Pigments Prepared by the Sol-Gel Method.Journal of the Ceramic Society of Japan,1999,107(6):534～540
[35]SAMIA T.BLACHERE.Chrome-Tin Pink Glazes.Ceramic Bulletin,1989,68(1):81～84
[36]M.Muthuraman and K.C.Patil.Synthesis,Properties,Sintering and Microstructure of Sphene,CaTiSi05:A Comparative Study of Coprecipitation,Sol-Gel and Combustion Processes. Materials Research Bulletin,1998,33(4):655～661
[37]I.Ou-benmmou,H.Ahamdane,M.A.E1 idrissi Raghni,et al.Tin Sphene micron-sized powders. Journal of the European Ceramic Society,2000(20):2159～2163
[38]P.ESCRIBANO LOPEA,C.GUILLEM MONZONIS,and J.ALARCON NAVARRO.Cr-SnO_2-CaO-SiO_2-Based Ceramic Pigments. Ceramic Bulletin,1984,63(12):1492～1495
[39]陈智主编．过渡元素化学．北京：原子能出版社，1990．13
[40]K．拿骚．颜色的物理与化学．北京：科学出版社，1991．93-96
[41]郭用猷．物质结构基本原理．北京：高等教育出版社，1982．358
[42]SAMIA T.BLACHERE. Chrome-Tin Pink Glazes. Ceramic Bulletin,1989,68(1):81～84
[2]俞康泰等．铬锡红色剂中铬的价态研究．中国陶瓷，1999，35(2)：503-507
[3]RICHARD A.EPPLER.Lattice Parameters of Tin Sphene.Amer.Ceram.Soc.,1976,59(9-10):455
[4]石田信武等．Chemical state of chromium inn-sphene.窑业协会志，1986，94(5)：458
[5]Christine J.Byrne and Richad A.Pipoly.Getting the Lead Out-A Case Study,Ceram.Eng.Sci.Proc.,1993,14(1-2):472-483
[6]Richard A.Eppler.Selecting Ceramic Pigments.Ceram.Eng.Sci.Proc.,1987,8(11-12):1139
[7]Richad A.Eppler and Douglas R.Eppler.Which Colors Can and Cannot Be Produced in Ceramic Glazes,Ceram.Eng.Sci.Proc.,1994,15(1):281-288
[8]公方杰．高档卫生陶瓷玛瑙红釉研制．科研与生产．
[9]郑乃章．铬锡红色料研究的现状与展望．中国陶瓷工业，1999，6(4)：42-44
[10]何代英等．玛瑙红高温陶瓷色剂的研究与应用．陶瓷，1994，110(4)：15-17
[11]徐平等．铬锡红釉的研究．景德镇陶瓷，第51期：10-12
[12]李国盛．玫瑰紫色釉的研制．陶瓷，1988，73(3)：6-8
[13]崔文元等．玫瑰紫色釉卫生洁具的研制．陶瓷，1989，82(6)：22-24
[14]Douglas R.Eppler and Richard A.Eppler.Analyzing the Color of Reddish Glazes.Ceram.Eng.Sci.Proc.,1996,17(1):77-87
[15]Christine J.Byrne,Steve G.Kutney and Richard A.Pipoly.How Glaze Composition Affects Chrome-Tin Pinks.Am.Ceram.Soc.Bull.,1994,73(5)
[16]A.C.Airey and Wroberts.Advances in Ceramic Colors.Ceram.Eng.Sci.Proc.,1987,8(11-12):1168
[17]南京地质大学系岩矿教研室编著．结晶学与矿物学．南京：地质出版社，1978．424～426
[18]系统矿物学．地质出版社，1984．205-206
[19]Anton M.Heyns,Peter M.Harden.Evidence for the existence of Cr(IV)in chromium-doped malayaite Cr~1:CaSnOSiO_4:a reasonance Raman Study.Journal of Physics and Chemistry of Solids,1999,60:277～284
[20]高富裕，刘贤儒主编．矿物学．南京：地址出版社，1984．56
[21]素木洋一著．釉及色料．北京：中国建筑工业出版社，1986．621
[22]杨萍等．关于红色陶瓷颜料．山东陶瓷，1999，22(1)：7-10
[23]武汉大学编．分析化学．北京：高等教育出版社，2000．189
[24]薛群基，徐康．纳米化学．化学进展，2000，12(4)：431-444
[25]田玉明，黄平，冷叔炎等．沉淀法的研究及其应用现状．材料导报，2000，14(2)：47-48
[26]上海化工学院无机化学教研室编．无机化学实验．人民教育出版社，1980
[27]M.LLUSAR,J.CALBO,J.A.BADENES,et al.Synthesis of iron zircon coral by eoprecipitation routes.Mat.Sci.,2001(3):153～163
[28]E.Cordoncillo,F.del Rio,J.Carda,M.Llusar,et al.Influence of Some Mineralizers in the Synthesis of Sphene-Pink Pigments.Journal of the European Ceramic Society,1998(18):1115～1120
[29]丁子上，翁文剑．溶胶-凝胶技术制备材料的进展．硅酸盐学报，1993，21(5)：443
[30]徐莉．正硅酸乙酯-凝胶过程中催化剂的作用．南京林业大学学报，1998，22(4)：67-70
[31]R.Stefani.Developing a Pink Pigment for Glazes.The American Ceramic Society Bulletin,1997(9):61～64
[32]Masashi SHOYhMA,Hiroyuki NASU nad Kanichi KAMIYA.Preparation of Rare Earth-Zircon Pigments by the Sol-Gel Method.Ceram.Sei.of Japan,1998,106(3):279～284
[33]C.L.Estrada,L.C.Torres-Gonzalez,A.F.Fuentes,et al.Synthesis of new vanadium cordierite pigment by sol-gel processing.British Ceramic Transactions,2000,99(2):67～71
[34]Masashi SHOYAMA,Kyoko HASHIMOTO,Tadanori HASHIMOTO,et al.Iron-Zircon Pigments Prepared by the Sol-Gel Method.Journal of the Ceramic Society of Japan,1999,107(6):534～540
[35]SAMIA T.BLACHERE.Chrome-Tin Pink Glazes.Ceramic Bulletin,1989,68(1):81～84
[36]M.Muthuraman and K.C.Patil.Synthesis,Properties,Sintering and Microstructure of Sphene,CaTiSi05:A Comparative Study of Coprecipitation,Sol-Gel and Combustion Processes. Materials Research Bulletin,1998,33(4):655～661
[37]I.Ou-benmmou,H.Ahamdane,M.A.E1 idrissi Raghni,et al.Tin Sphene micron-sized powders. Journal of the European Ceramic Society,2000(20):2159～2163
[38]P.ESCRIBANO LOPEA,C.GUILLEM MONZONIS,and J.ALARCON NAVARRO.Cr-SnO_2-CaO-SiO_2-Based Ceramic Pigments. Ceramic Bulletin,1984,63(12):1492～1495
[39]陈智主编．过渡元素化学．北京：原子能出版社，1990．13
[40]K．拿骚．颜色的物理与化学．北京：科学出版社，1991．93-96
[41]郭用猷．物质结构基本原理．北京：高等教育出版社，1982．358
[42]SAMIA T.BLACHERE. Chrome-Tin Pink Glazes. Ceramic Bulletin,1989,68(1):81～84