低成本无钴黑色色料的制备研究
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摘要
通过Ni_2O_3、Cr_2O_3、Fe_2O_3、CuO、MnO_2等化工原料引入的优化实验,初步研制了一种1280℃温度下呈色较纯正的低成本Cr-Fe-Ni-Cu-Mn系无钴黑色色料。该色料色度指数为: L*=27.49,a*=1.21,b*=1.45。黑色色料的组成是:氧化铬31、氧化铁42、氧化镍37、氧化铜7、氧化锰7、外加氧化镁3wt%。为了进一步降低成本,在保证色料品质的前提下,进而引入工业废料铜尾砂、铬铁矿取代部分化工原料制备低成本无钴黑色颜料。制得该颜料色度指数为:L*=28.26,a*=1.82,b*=1.35。该黑色色料的组成范围是:氧化铬21～26、氧化铁33.4～35.2、氧化镍37、氧化铜7、氧化锰7、铜尾砂11.8～23.6、铬铁矿10.2～20.4。
通过XRD、紫外可见光吸收光谱等测试手段研究分析表明:色料呈现黑色是由于过渡金属离子生成了混合尖晶石晶相所致。铜尾砂、铬铁矿引入杂质离子导致晶相的平均晶胞常数和晶胞体积变化是影响色料的吸光强度和色调变化的主要原因。冷却方式对色料的呈色有影响,按黑度大小排列:水中淬冷>空气中急冷>随炉缓冷。水中淬冷保持了高温时过渡金属离子杂乱无序的分布及晶格畸变增大是吸光强度大的主要原因。保温时间对色料呈色也有影响,随着保温时间的延长,晶体的结晶程度越好,结晶越完整,色料的L*值增大,而a*、b*值减小。所以,此色料的保温时间为60min即可,不需要太长时间。
Using nickel sesqui oxide、chromic oxide、ferric oxide、copper oxide、manganese dioxide as raw materials, a kind of low-cost black pigments, which presents pure relatively black color at high temperature, is obtained through a series of optiumization experiments. It’s a type of ceramic pigments which shows color indensity data L*=27.49,a*=1.21,b*=1.45. This type of pigments which can present pure relatively black color at high temperature with its compositional ranges as follows: nickel sesqui oxide 37, chromic oxide 31, ferric oxide 42, copper oxide 7, manganese dioxide 7 and magnesium oxide 3wt%. In order to further reduce the cost, a kind of lower cost coblat free black pigments, which also presents pure relatively black color at high temperature, is obtained through introducing the industrial waste including copper cement-tailings and chromite replacing part of chemical raw materials. It’s a type of ceramic pigments which shows color indensity data L*=28.26,a*=1.82,b*=1.35. This type of pigments which can present pure relatively black color at high temperature with its compositional ranges as follows: nickel sesqui oxide 37, chromic oxide 21～26, ferric oxide 33.4～35.2, copper oxide 7, manganese dioxide 7 ,copper cement-tailings 11.8～23.6, chromite 10.2～20.4 and magnesium oxide 3wt%.
X-ray diffraction (XRD) and uv vis absorption spectrum(UV )analysis show that type ceramic pigments which present black color is due to transition metal ions forming complex spinel phases. Introducing copper cement-tailings and chromite to the samples leads to the changes of unit cell constant and unit cell volume, which cause the changes of photon absorbing intensity and hue. Cooling ways act on pigment color performance, according to the degree of size: quenching-in water > air quenching > furnace cooling. Quenching-in water keeping the transition metal ions sprawling distribution at high temperature and lattice distortion increasing is the main reason of light intensity. The color indensity data are also affected by soaking time. With extending soaking time, the degree of crystal is better and L* value is increscent while a*and b* is lower. So, the optimal soaking time was 60 minutes in this study.
通过XRD、紫外可见光吸收光谱等测试手段研究分析表明:色料呈现黑色是由于过渡金属离子生成了混合尖晶石晶相所致。铜尾砂、铬铁矿引入杂质离子导致晶相的平均晶胞常数和晶胞体积变化是影响色料的吸光强度和色调变化的主要原因。冷却方式对色料的呈色有影响,按黑度大小排列:水中淬冷>空气中急冷>随炉缓冷。水中淬冷保持了高温时过渡金属离子杂乱无序的分布及晶格畸变增大是吸光强度大的主要原因。保温时间对色料呈色也有影响,随着保温时间的延长,晶体的结晶程度越好,结晶越完整,色料的L*值增大,而a*、b*值减小。所以,此色料的保温时间为60min即可,不需要太长时间。
Using nickel sesqui oxide、chromic oxide、ferric oxide、copper oxide、manganese dioxide as raw materials, a kind of low-cost black pigments, which presents pure relatively black color at high temperature, is obtained through a series of optiumization experiments. It’s a type of ceramic pigments which shows color indensity data L*=27.49,a*=1.21,b*=1.45. This type of pigments which can present pure relatively black color at high temperature with its compositional ranges as follows: nickel sesqui oxide 37, chromic oxide 31, ferric oxide 42, copper oxide 7, manganese dioxide 7 and magnesium oxide 3wt%. In order to further reduce the cost, a kind of lower cost coblat free black pigments, which also presents pure relatively black color at high temperature, is obtained through introducing the industrial waste including copper cement-tailings and chromite replacing part of chemical raw materials. It’s a type of ceramic pigments which shows color indensity data L*=28.26,a*=1.82,b*=1.35. This type of pigments which can present pure relatively black color at high temperature with its compositional ranges as follows: nickel sesqui oxide 37, chromic oxide 21～26, ferric oxide 33.4～35.2, copper oxide 7, manganese dioxide 7 ,copper cement-tailings 11.8～23.6, chromite 10.2～20.4 and magnesium oxide 3wt%.
X-ray diffraction (XRD) and uv vis absorption spectrum(UV )analysis show that type ceramic pigments which present black color is due to transition metal ions forming complex spinel phases. Introducing copper cement-tailings and chromite to the samples leads to the changes of unit cell constant and unit cell volume, which cause the changes of photon absorbing intensity and hue. Cooling ways act on pigment color performance, according to the degree of size: quenching-in water > air quenching > furnace cooling. Quenching-in water keeping the transition metal ions sprawling distribution at high temperature and lattice distortion increasing is the main reason of light intensity. The color indensity data are also affected by soaking time. With extending soaking time, the degree of crystal is better and L* value is increscent while a*and b* is lower. So, the optimal soaking time was 60 minutes in this study.
引文
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[20]谢春波.纯正黑色釉的研制.河北陶瓷.1997.3.
[21]张弦.铬铁矿基低成本色料的研制及着色机理分析.2006.
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[24] A.B.Corradi等著.袁国华译.含天然铬铁矿瓷化砖的快速烧成、制备与特性.国外建材科技,15(3):15～20.
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[28]刘宇等.工业废料和稀土化合物合成黑色陶瓷颜料.陶瓷研究,1993,8(l).
[29]管志斌.稀土氧化物在金光釉中的应用研究.中国陶瓷.1995(2).
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[35]方容川.固体光谱学.合肥:中国科技大学出版社.2001.5.71～82.
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[37]罗谷风.《结晶学导论》.第一版.北京:地质出版社,1984.195～201
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[39]曹春娥,顾幸勇.无机材料测试技术.武汉:武汉理工大学出版社. 2001.
[40]张有纲,黄永杰,罗迪民.磁性材料.成都电讯工程学院出版社.1988.
[41] Schneider H. J.Am.Ceram.Soc.[J]. 1993,76(11): 289299.
[42] Schneider H. J.Am.Ceram.Soc.[J]. 1988,71(3): C162～C175.
[43]吴育全.氧化铬绿性状特征及生产工艺改进研究.重庆大学工程硕士论文
[44]徐梁才. CIE系统颜色参数的阅读和分析方法.上海计量测试. 1992,19(1):34-35.
[45]邱海波等.Cr2O3在α-Fe2O3中固溶量的测定.中国陶瓷,2003(2):52
[46]杨于兴等. X射线衍射分析(修订版).上海:上海交通大学出版社. 1994.155.
[47]姚建曦等.无钻黑色陶瓷颜料的研究及应用现状.陶瓷工程.1999.10(3)
[48]武汉大学化学系.仪器分析.北京:高等教育出版社. 2000.
[49]刘维良,喻佑华.先进陶瓷工艺学.武汉:武汉理工大学出版社. 2004.
[50]李玉书等.棕色尖晶石颜料的合成.湖南大学学报(自然科学版).2003(2):33
[51] A.A.Fotiev,L.L.Surat,G.A.Korablev,and A.I Tret’yakov zh.Neorg khim,Russ.J. Iorg.Chem.26[1]:242～248(1981)
[52]刘延祥等.棕红色颜料的制备及呈色机理研究.佛山陶瓷.2003(8):12
[53]王忠兵. Fe-Mn-Ni-O尖晶石型负温度系数热敏陶瓷的制备和老化性能研究.2005.4
[54]杨治虎.铁、镍、硒类钠离子的跃迁几率研究.原子和分子物理学报. 1994.4
[55] W.H.Hall, J.Inst.Met. 1949, (75): 1127.
[2] W·D·金格瑞等著.陶瓷导论.北京:中国建筑工业出版社. 1982:682-695.
[3]孙再清,刘属兴.陶瓷色料生产及应用.北京:化学工业出版社. 2006:1-8.
[4]俞康泰.现代陶瓷色釉料与装饰技术手册.武汉:武汉工业大学出版社. 1999:1-38.
[5]朱骥良.颜料工艺学.北京:化学工业出版社. 1989:8-20.
[6]胡志强.无机材料科学基础教程.第1版.北京:化学工业出版社. 2005:26-30,54-58,71-79,286-289.
[7]任引哲,王玉湘等.物质的颜色与结构.北京:北京师范大学出版社. 1991,12-21.
[8] [美]Roy S.Berns编著,李小梅等译.颜色技术原理.北京:化学工业出版社. 2002.9:289.
[9]吴立峰,陈信华等.颜色的物理学原理.第1版.北京:化学工业. 2003:2003.
[10]俞康泰.陶瓷色釉料研究开发的的现状及进展.佛山陶瓷. 2000(4):1-4.
[11]张有纲,黄永杰,罗迪民.磁性材料.成都电讯工程学院出版社.1988.
[12]徐庆,陈文,袁润章. Fe-Mn-Co-Cu体系尖晶石的结构和红外辐射特性.矿物学报. 2001, 9(3): 385～387.
[13]张宇宏,张鹏等.陶瓷色剂的应用及其最新发展.陶瓷. 2000 (5):25-27.
[14]张文丽.色料的呈色机理、生产及应用[J]. Document Summary:10-16.
[15]杨萍.陶瓷颜料颜色与结构关系的探讨.中国陶瓷. 1998,34(6):18-20.
[16]刘建路,张其春等.纳米粒子的平均晶粒尺寸和晶格畸变的同时测定.现代技术陶瓷. 2002.1
[17]张旭东等.Co-Cr-Fe-Mn系黑颜料呈色机理的研究.佛山陶瓷.1996.3.12-15.
[18]吴建锋,徐晓虹.Fe-Mn-Cr-Ni系黑色料制备工艺的研究.陶瓷学报.1999.3.
[19]司志胜.廉价黑色色剂的研究.陶瓷工程,1998.2
[20]谢春波.纯正黑色釉的研制.河北陶瓷.1997.3.
[21]张弦.铬铁矿基低成本色料的研制及着色机理分析.2006.
[22]中国专利CN86104984A.
[23]中国专利CN1064471A.
[24] A.B.Corradi等著.袁国华译.含天然铬铁矿瓷化砖的快速烧成、制备与特性.国外建材科技,15(3):15～20.
[25]乔艳.铬铁矿在陶瓷颜料中的应用.山东陶瓷,1998(6).
[26]朱振锋等.工艺参数与铬铁矿系无钴黑色料呈色性能关系的研究.2002(8).
[27]赵峰等.利用工业尾渣制备黑色颜料的研究.山东陶瓷,1997,20(2):26.
[28]刘宇等.工业废料和稀土化合物合成黑色陶瓷颜料.陶瓷研究,1993,8(l).
[29]管志斌.稀土氧化物在金光釉中的应用研究.中国陶瓷.1995(2).
[30]李春文等.析晶虹彩釉的研制.陶瓷,1995(2):41.
[31] RICHARD.A.EPPLER.AmerieanCerahaeSoeietyBulltin.1981,60(5):562.
[32] RICHARD.A.EPPLER.AmerieanCeramieSoeietyBulltin.1981,11(8):847.
[33]边华英.利用含钴工业废料研制黑色陶瓷颜料.佛山陶瓷.2003(12).15-18.
[34] Richard C S,Lu J,Beranger G et al.Study of Cr2O3 Coating[J].Journal of Thermal Spray Technology,1995,4(4):342～352.
[35]方容川.固体光谱学.合肥:中国科技大学出版社.2001.5.71～82.
[36]方容川.固体光谱学.合肥:中国科技大学出版社.2001.5.68～70.
[37]罗谷风.《结晶学导论》.第一版.北京:地质出版社,1984.195～201
[38]周公度.结构和物性化学原理的应用(第二版).北京:高等教育出版社.2000.291～299
[39]曹春娥,顾幸勇.无机材料测试技术.武汉:武汉理工大学出版社. 2001.
[40]张有纲,黄永杰,罗迪民.磁性材料.成都电讯工程学院出版社.1988.
[41] Schneider H. J.Am.Ceram.Soc.[J]. 1993,76(11): 289299.
[42] Schneider H. J.Am.Ceram.Soc.[J]. 1988,71(3): C162～C175.
[43]吴育全.氧化铬绿性状特征及生产工艺改进研究.重庆大学工程硕士论文
[44]徐梁才. CIE系统颜色参数的阅读和分析方法.上海计量测试. 1992,19(1):34-35.
[45]邱海波等.Cr2O3在α-Fe2O3中固溶量的测定.中国陶瓷,2003(2):52
[46]杨于兴等. X射线衍射分析(修订版).上海:上海交通大学出版社. 1994.155.
[47]姚建曦等.无钻黑色陶瓷颜料的研究及应用现状.陶瓷工程.1999.10(3)
[48]武汉大学化学系.仪器分析.北京:高等教育出版社. 2000.
[49]刘维良,喻佑华.先进陶瓷工艺学.武汉:武汉理工大学出版社. 2004.
[50]李玉书等.棕色尖晶石颜料的合成.湖南大学学报(自然科学版).2003(2):33
[51] A.A.Fotiev,L.L.Surat,G.A.Korablev,and A.I Tret’yakov zh.Neorg khim,Russ.J. Iorg.Chem.26[1]:242～248(1981)
[52]刘延祥等.棕红色颜料的制备及呈色机理研究.佛山陶瓷.2003(8):12
[53]王忠兵. Fe-Mn-Ni-O尖晶石型负温度系数热敏陶瓷的制备和老化性能研究.2005.4
[54]杨治虎.铁、镍、硒类钠离子的跃迁几率研究.原子和分子物理学报. 1994.4
[55] W.H.Hall, J.Inst.Met. 1949, (75): 1127.