发光陶瓷的研制
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摘要
本论文对广东河台金矿的尾矿砂及高要白土进行了详细而系统的组成、工艺性能方面的测试、分析和研究，在此基础之上，以金矿尾矿砂、白土为主要原料，掺入紫木节、钾长石、少量滑石进行陶瓷坯体配料、配方和成型，通过分析坯体的矿物组成和化学成分，以及大量烧成试验，制定了较合理的烧成制度，成功制备了各种类型的陶瓷制品并详尽地讨论了素烧坯体的缺陷及形成原因，提出了合理的防范措施。
简要论述了新型发光釉的发光材料、基础熔块釉及发光釉釉浆制备诸问题。进行了多次低温釉烧试验，从坯釉组成成分、烧成工艺两个大的方面探讨了影响釉面质量和发光性能的内外因素，在合理的釉烧制度下，制得质量较好的发光釉陶瓷。
通过实验、分析、检测，得到以下结论：
1、河台金矿的尾矿砂以石英、绢云母(包括伊利石、水云母)为主要成分，其中石英占50-60％左右，绢云母占14-17％左右，斜长石、水云母、玉燧少量，其他矿物则更少。石英是陶瓷中利用的主要对象，含碱土的粘土矿物则以绢云母为主，包括伊利石、水云母类，均可用于制备陶瓷坯体。除了尾矿砂中含有的铁质成分外，其余矿物成分均可应用于陶瓷坯料中而在烧成过程中没有什么影响。从陶瓷原料的类型来说尾矿砂可为瘠性物料，但含有可利用的粘土类矿物成分及熔剂性成分(方解石、白云石等)。尾砂粒度细，矿物组成简单，有害杂质矿物少，化学成分较纯，是一优良的陶瓷工业原料。
2、高要白土是当地地表风化残留型粘土，石英含量高，粘土类矿物高岭石、多水高岭石含量相对较低，整体可塑性中偏低，耐火度低。有害杂质矿物含量少，烧后灰白色，为一优质复合型陶瓷原料，可与尾矿砂一起加以利用以降低利用成本。
3、以金矿尾矿砂、高要白土、紫木节、钾长石和少量滑石为原料，根据参考坯体成分、经验数据进行配料、配方、成型、烧成，得到素烧程度不同的陶瓷制品。实验中1#、2#、3#配方生坯成瓷烧成温度低，在1130-1170℃，高火保温时间30-40分钟，烧成周期5h左右。
4、实验中使用的发光釉是一种性能优良的低温快烧釉。发光材料是碱土铝酸锶Eu~(2+)Dy~(3+)晶体材料，基础釉料为熔块，熔块釉熔融温度800℃。
5、发光陶瓷釉面质量和发光性能烧成工艺方面的影响因素有：烧成温度和烧成周期。在确保发光釉熔融的条件下，釉烧温度愈低，烧成周期愈短，发光陶瓷的发光性能愈好。实验中在氧化气氛中烧成，釉烧温度一般在850℃左右，烧成周期30-60分钟，高火保温时间2-3分钟。
6、坯、釉成分和性质是影响发光陶瓷釉面质量和发光性能的又一因素。发光釉中发光粉的含量、粒度及釉层厚度均对发光陶瓷的质量的有所影响：发光粉含量以30％，粒度200目为宜，釉层厚度则在一定范围内越大则发光性能更好。素烧坯的成分、素烧程度对坯、釉的适应性有影响并进而影响到发光釉的釉面质量和发光性能。一般情况下，以坯、釉成分相近、坯体素烧到一定程度，吸水率稍大而不瓷化为更有利于发光陶瓷釉烧质量的提高。
This paper makes particular and systemic tests,analyses,investigations of composition and technical capability on HETAI gold mine gangue and GAOYAO white earth in GUANGDONG province.On these basis,mainly taking gold mine gangue and white earth as primary materials and mixing into camwood earth.kaliumfelspar and a ounce steatite to manufacture ceramics.By analyzing mineral and chemical elements of original ceramic bricks,with a great deal of burning experiments,to get a rationly burning regulation.Successfully produce many kinds of ceramics and discuss disfigurements of burned brick and put forward good measures to avoid these to happen.
Briefly discuss various issues of luminescent material,basic melted block and luminescent glaze plasm preparation and glazing of new luminescent glaze.Time after time to do low temperature glaze burning experimentations to investigate the inside and outside factors of glaze's quality and luminescent capability.In logical glaze burning regulations to produce very better luminescent glaze ceramics.
These are some conclusions through a series of experiments, analyses and surveys:
One,quartz,sericite including Eriestone and water mica are main elements in HETAI gold mine gangue.In this material quartz occupies 50-60% around,sericite 14-17% around,else materials much less.Quartz is main object.Containing alkaline clay minerals can be used in ceramics.In exception of iron element,rest mineral elements have nothing to influence the burning regulations.As raw material,gangue is a barren material,containing useable clay and dolomite.Gangue's granularity is very small.mineral makeup single,maleficent impurity minerals little and chemical elements are relatively pure.So gangue is a fine ceramic material.
Two,in GAOYAO white earth ,a incompletely airslaked clay on the earth's surface,quartz content is high ,clay minerals such as kaolinite, water kaotinite are relatively lower ,the whole plasticity middle class,fire enduring capability low. After burning,this material takes on hoar color, is a high quality compound ceramics materials,can be used with gangue to reduce manufacture costs.
Three,taking gold mine gangue, GAOYAO white earth,camwood earth,kaliumfelspar and little steatite as primary materials.in reference of experiments,receive all kinds of products. 1#.2#.3# prescription bricks' burning temperatures are low, 1130-1170 degree around,high temperature preservation only 30-40 minutes.the whole burning period is 3 hours long.
Four.luminescent glaze in experiments is a excellent low temperature rapidly burning glaze.Luminescent material is alkali aluminium acid strontiumEu2+Dy3+ crystals.Basic glaze material is melted block and its melting temperature is 800 degrees.
Five,the surface quality and luminescent capability of luminescent ceramics have two aspect effects:buming temperature and burning period.As far as luminescent glaze melts,burning temperature can be lower and burning period can be short.Experiments doing in oxygen gases.has a burning temperature ordinary 850 degree about,Burning period 30-60 minutes,high temperature preservation 2-3 minutes.
Six.the elements and natures of brick and glaze affect luminescent glaze ceramics.the containing ratio of luminescent powdery,granularity and glaze thickness all have effects on luminescent ceramics:luminescent powders' quantity 30%,Granularity 200 order.in certain range big thickness can make luminescent capability better.the elements and burning degree affect adjustability between brick and glaze and at the same time to affect glaze surface quality and luminescent capability.Ordinary,brick,glaze's elements very near,burned to some degree.sop ratio a little great can put up luminescent ceramics quality.
简要论述了新型发光釉的发光材料、基础熔块釉及发光釉釉浆制备诸问题。进行了多次低温釉烧试验，从坯釉组成成分、烧成工艺两个大的方面探讨了影响釉面质量和发光性能的内外因素，在合理的釉烧制度下，制得质量较好的发光釉陶瓷。
通过实验、分析、检测，得到以下结论：
1、河台金矿的尾矿砂以石英、绢云母(包括伊利石、水云母)为主要成分，其中石英占50-60％左右，绢云母占14-17％左右，斜长石、水云母、玉燧少量，其他矿物则更少。石英是陶瓷中利用的主要对象，含碱土的粘土矿物则以绢云母为主，包括伊利石、水云母类，均可用于制备陶瓷坯体。除了尾矿砂中含有的铁质成分外，其余矿物成分均可应用于陶瓷坯料中而在烧成过程中没有什么影响。从陶瓷原料的类型来说尾矿砂可为瘠性物料，但含有可利用的粘土类矿物成分及熔剂性成分(方解石、白云石等)。尾砂粒度细，矿物组成简单，有害杂质矿物少，化学成分较纯，是一优良的陶瓷工业原料。
2、高要白土是当地地表风化残留型粘土，石英含量高，粘土类矿物高岭石、多水高岭石含量相对较低，整体可塑性中偏低，耐火度低。有害杂质矿物含量少，烧后灰白色，为一优质复合型陶瓷原料，可与尾矿砂一起加以利用以降低利用成本。
3、以金矿尾矿砂、高要白土、紫木节、钾长石和少量滑石为原料，根据参考坯体成分、经验数据进行配料、配方、成型、烧成，得到素烧程度不同的陶瓷制品。实验中1#、2#、3#配方生坯成瓷烧成温度低，在1130-1170℃，高火保温时间30-40分钟，烧成周期5h左右。
4、实验中使用的发光釉是一种性能优良的低温快烧釉。发光材料是碱土铝酸锶Eu~(2+)Dy~(3+)晶体材料，基础釉料为熔块，熔块釉熔融温度800℃。
5、发光陶瓷釉面质量和发光性能烧成工艺方面的影响因素有：烧成温度和烧成周期。在确保发光釉熔融的条件下，釉烧温度愈低，烧成周期愈短，发光陶瓷的发光性能愈好。实验中在氧化气氛中烧成，釉烧温度一般在850℃左右，烧成周期30-60分钟，高火保温时间2-3分钟。
6、坯、釉成分和性质是影响发光陶瓷釉面质量和发光性能的又一因素。发光釉中发光粉的含量、粒度及釉层厚度均对发光陶瓷的质量的有所影响：发光粉含量以30％，粒度200目为宜，釉层厚度则在一定范围内越大则发光性能更好。素烧坯的成分、素烧程度对坯、釉的适应性有影响并进而影响到发光釉的釉面质量和发光性能。一般情况下，以坯、釉成分相近、坯体素烧到一定程度，吸水率稍大而不瓷化为更有利于发光陶瓷釉烧质量的提高。
This paper makes particular and systemic tests,analyses,investigations of composition and technical capability on HETAI gold mine gangue and GAOYAO white earth in GUANGDONG province.On these basis,mainly taking gold mine gangue and white earth as primary materials and mixing into camwood earth.kaliumfelspar and a ounce steatite to manufacture ceramics.By analyzing mineral and chemical elements of original ceramic bricks,with a great deal of burning experiments,to get a rationly burning regulation.Successfully produce many kinds of ceramics and discuss disfigurements of burned brick and put forward good measures to avoid these to happen.
Briefly discuss various issues of luminescent material,basic melted block and luminescent glaze plasm preparation and glazing of new luminescent glaze.Time after time to do low temperature glaze burning experimentations to investigate the inside and outside factors of glaze's quality and luminescent capability.In logical glaze burning regulations to produce very better luminescent glaze ceramics.
These are some conclusions through a series of experiments, analyses and surveys:
One,quartz,sericite including Eriestone and water mica are main elements in HETAI gold mine gangue.In this material quartz occupies 50-60% around,sericite 14-17% around,else materials much less.Quartz is main object.Containing alkaline clay minerals can be used in ceramics.In exception of iron element,rest mineral elements have nothing to influence the burning regulations.As raw material,gangue is a barren material,containing useable clay and dolomite.Gangue's granularity is very small.mineral makeup single,maleficent impurity minerals little and chemical elements are relatively pure.So gangue is a fine ceramic material.
Two,in GAOYAO white earth ,a incompletely airslaked clay on the earth's surface,quartz content is high ,clay minerals such as kaolinite, water kaotinite are relatively lower ,the whole plasticity middle class,fire enduring capability low. After burning,this material takes on hoar color, is a high quality compound ceramics materials,can be used with gangue to reduce manufacture costs.
Three,taking gold mine gangue, GAOYAO white earth,camwood earth,kaliumfelspar and little steatite as primary materials.in reference of experiments,receive all kinds of products. 1#.2#.3# prescription bricks' burning temperatures are low, 1130-1170 degree around,high temperature preservation only 30-40 minutes.the whole burning period is 3 hours long.
Four.luminescent glaze in experiments is a excellent low temperature rapidly burning glaze.Luminescent material is alkali aluminium acid strontiumEu2+Dy3+ crystals.Basic glaze material is melted block and its melting temperature is 800 degrees.
Five,the surface quality and luminescent capability of luminescent ceramics have two aspect effects:buming temperature and burning period.As far as luminescent glaze melts,burning temperature can be lower and burning period can be short.Experiments doing in oxygen gases.has a burning temperature ordinary 850 degree about,Burning period 30-60 minutes,high temperature preservation 2-3 minutes.
Six.the elements and natures of brick and glaze affect luminescent glaze ceramics.the containing ratio of luminescent powdery,granularity and glaze thickness all have effects on luminescent ceramics:luminescent powders' quantity 30%,Granularity 200 order.in certain range big thickness can make luminescent capability better.the elements and burning degree affect adjustability between brick and glaze and at the same time to affect glaze surface quality and luminescent capability.Ordinary,brick,glaze's elements very near,burned to some degree.sop ratio a little great can put up luminescent ceramics quality.
引文
1、邹力行编著 陶瓷生产技术问答 北京 中国建筑工业出版社 1993、2
2、钟旭尔 胡智荣 坯釉配方对陶瓷烧成及质量的影响 江苏陶瓷 2000、6 15-17
3、周正付 缩釉的成因及解决方法 佛山陶瓷 2001、10 7-11
4、董大静 低温一次快烧釉面砖坯釉料的选择及其相互适应性 河北陶瓷 2000、3 36-37
5、牟善彬 扫描电子显微镜在陶瓷材料中的应用 佛山陶瓷 2001、9 27-29
6、李惠玲 高石英陶瓷坯体的研究 佛山陶瓷 2001、8、12-15
7、黄汉生编译 新型蓄光性材料 化工新型材料 1999、27：28
8、余宪恩编著 实用发光材料与光致发光机理 北京中国轻工业出版社 1997、1
9、杨南如主编 无机非金属材料测试方法 武汉工业大学出版社 1993修订本
10、Weiyi Jia, Huabiao Yuan, Lizhu Lu, Huimin Liu, W. M. Yen Phosphorescent dynamics in SrAl_2O_4: Eu~(2+), Dy~(3+) single crystal fibers Journal of Luminescence 76&76(1998): 424-428
11、W. Jia. H.yuan,S.Holmstrom,H.Liu,W.M.Yen, Photo-stimulated luminescence in SrAl_2O_4: Eu~(2+),Dy~(3+) single crystal fibers, Journal of Luminescence 83-84(1999): 463-469
12、John Wiley, Crystal structure of Calcium Monoaluminate, Nature, August 10, 1957 vol. 180: 292-293
13、F.P. Glasser and L.S. Dent Glasse, Crystal Chemistry of some AB204 Compounds Journal of The American Ceramic Society, August 1963, Vol. 46, No.8
14、潘兆橹主编 结晶学及矿物学 北京 地质出版社 1985、第一版
15、黄勇、崔国文 相图与相变 清华大学材料科学与工程系 1984、3
16、杨萍 金矿尾砂代替长石用于陶瓷墙地砖的研究 中国陶瓷 1999、4
17、吕荣、宋守志 金属尾矿资源化利用前景中国矿业 1998、1 25-27
18、徐惠忠 利用选金尾砂生产系列硅酸盐墙体材料的工艺技术研究 黄金 1997、1
19、徐惠忠 黄金尾砂用于生产建筑材料的技术和经济可行性研究 黄金 1996、3
20、陈刚、刘奎仁、赵翠微 黄金矿山尾渣尾液综合利用及无害化处理 黄金学报 1999、9176-182
21、杨雄 利用金矿尾砂作建陶长石原料的研究 陶瓷研究 1999、6 11-14
22、张顺堂、张金龙 利用金矿尾砂烧制陶瓷墙地砖试验研究 1999、12 34-37
23、徐林 石英砂的工业利用及加工技术 1992、1 21-24
24、孙继寿 双王金矿尾矿的综合利用 1998、3 36-38
25、石大鑫、于桂莲 云母的加工技术 矿产保护和利用 1991、1 28-35
26、杨少明 南安绢云母深加工及综合利用 非金属矿 1999、11 13-14
27、SrAl_2O_4: Eu~(2+), Dy~(3+)荧光材料的发光性质 光散射学报 1999，6：35-38
28、宋庆梅 黄锦斐 吴茂钧 铝酸锶铕的合成与发光研究 发光学报 June 1991，12(2)：4-149
29、天之等 MAl_2O_4: Eu~(2+), RE~(3+)长余辉发光性质的研究 发光学报 June 1999, 20(2)：170-174
30、张中太，张枫，唐子龙，孙红飞 长余辉蓄光陶瓷 SrAl_2O_4：Eu，Dy的性能及发光机理功能材料 1999，30(3)：295-296
31、林元华，张中太，陈清明，唐子龙等 长余辉光致发光玻璃的制备及其性能研究 材料科学与工艺 2000，8(1)：1-5
32、张玉军，尹衍升，谭砂砾等 蓄能发光搪瓷牌的试制 玻璃与搪瓷 1998，27(2)：12-14
33、袁莹 赵彦军 长余辉荧光涂料 化学建材 1993，(4)：146-148
34、E. Nakazawa, T. Mochida,Traps in SrAl_2O_4: Eu~(2+) Phosphor with rare-earth ion doping, Journal of Luminescence 72-74(1997): 236-237
35、Hajime Yamamoto, Takashi Matsuzawa, Mechanism of long phosphorescence of SrAl_2O_4: Eu~(2+),Dy~(3+) and CaAl_2O_4:Eu~(2+),Nd~(3+), Journal of Luminescence 72-74(1997): 287-289
36、Katsumata, T. Nabate, K. Sasajima, T. Matsuzawa, Growth and characteristics of long persistent SrAl_2O_4 and CaAl_2O_4-based phosphor crystals by floating zone technique Journal of Crystal Growth 183(1998): 363-365
2、钟旭尔 胡智荣 坯釉配方对陶瓷烧成及质量的影响 江苏陶瓷 2000、6 15-17
3、周正付 缩釉的成因及解决方法 佛山陶瓷 2001、10 7-11
4、董大静 低温一次快烧釉面砖坯釉料的选择及其相互适应性 河北陶瓷 2000、3 36-37
5、牟善彬 扫描电子显微镜在陶瓷材料中的应用 佛山陶瓷 2001、9 27-29
6、李惠玲 高石英陶瓷坯体的研究 佛山陶瓷 2001、8、12-15
7、黄汉生编译 新型蓄光性材料 化工新型材料 1999、27：28
8、余宪恩编著 实用发光材料与光致发光机理 北京中国轻工业出版社 1997、1
9、杨南如主编 无机非金属材料测试方法 武汉工业大学出版社 1993修订本
10、Weiyi Jia, Huabiao Yuan, Lizhu Lu, Huimin Liu, W. M. Yen Phosphorescent dynamics in SrAl_2O_4: Eu~(2+), Dy~(3+) single crystal fibers Journal of Luminescence 76&76(1998): 424-428
11、W. Jia. H.yuan,S.Holmstrom,H.Liu,W.M.Yen, Photo-stimulated luminescence in SrAl_2O_4: Eu~(2+),Dy~(3+) single crystal fibers, Journal of Luminescence 83-84(1999): 463-469
12、John Wiley, Crystal structure of Calcium Monoaluminate, Nature, August 10, 1957 vol. 180: 292-293
13、F.P. Glasser and L.S. Dent Glasse, Crystal Chemistry of some AB204 Compounds Journal of The American Ceramic Society, August 1963, Vol. 46, No.8
14、潘兆橹主编 结晶学及矿物学 北京 地质出版社 1985、第一版
15、黄勇、崔国文 相图与相变 清华大学材料科学与工程系 1984、3
16、杨萍 金矿尾砂代替长石用于陶瓷墙地砖的研究 中国陶瓷 1999、4
17、吕荣、宋守志 金属尾矿资源化利用前景中国矿业 1998、1 25-27
18、徐惠忠 利用选金尾砂生产系列硅酸盐墙体材料的工艺技术研究 黄金 1997、1
19、徐惠忠 黄金尾砂用于生产建筑材料的技术和经济可行性研究 黄金 1996、3
20、陈刚、刘奎仁、赵翠微 黄金矿山尾渣尾液综合利用及无害化处理 黄金学报 1999、9176-182
21、杨雄 利用金矿尾砂作建陶长石原料的研究 陶瓷研究 1999、6 11-14
22、张顺堂、张金龙 利用金矿尾砂烧制陶瓷墙地砖试验研究 1999、12 34-37
23、徐林 石英砂的工业利用及加工技术 1992、1 21-24
24、孙继寿 双王金矿尾矿的综合利用 1998、3 36-38
25、石大鑫、于桂莲 云母的加工技术 矿产保护和利用 1991、1 28-35
26、杨少明 南安绢云母深加工及综合利用 非金属矿 1999、11 13-14
27、SrAl_2O_4: Eu~(2+), Dy~(3+)荧光材料的发光性质 光散射学报 1999，6：35-38
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