金红玻璃化还原状态对其着色的影响
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摘要
金对玻璃的着色属于最漂亮最优雅的颜色,即美丽的紫红色,在加工高级工艺品时要用这种颜色,也常用于生产高级器皿玻璃和装饰艺术玻璃。
玻璃在高温熔制时,金以Au+离子状态溶解于熔体之中。玻璃冷却后是无色的,经热处理(显色),Au+离子被还原为金原子,并聚集长大成具有一定数量的胶体大小粒子,而呈现紫红色。
本文对Au+掺杂R20—SnO—SnO—PbO—B2O3—Sb2O3—SiO2系统金红玻璃的制备工艺与着色机理进行了探讨。本文利用分光光度法测量掺杂铁的金红玻璃中Fe2+和Fe3+的含量,进行监测玻璃氧化还原性的方法,以及紫外-可见光-红外分光光度仪、扫描电镜形貌分析等方法,研究了在一定的热处理工艺制度下,玻璃的氧化还原状态变化对金红玻璃光谱、微观形貌等的影响,从晶核的形成及长大等方面对金红玻璃氧化还原状态与其着色过程进行了理论分析。
当本文所研究的金红玻璃系统的Fe2+/Fe3+比值在0.0708～0.0742的范围时,可以得到吸收峰在520nm左右而呈紫红色的金红玻璃。
The glass colored with Au particles is the most beautiful and refined, and the color is fuchsia. This color glass is usually used in processing the high-level craftwork, the exclusive vessel glasses and decorative art glasses.
When the glass is melt under high temperature, the gold is dissolved in the fusibility by Au+ions. After cooling the glass is achromatous, but through heat treatment which is the course of showing colors, the glass shows fuchsia. During the heat treatment Au+ions are deoxidize to Au atoms, and the atoms are congregated together to certain number colloid.
This paper mainly covers the fundamental and experimental researches of R2O—SnO—ZnO—PbO—B2O3—Sb2O3—SiO2 system glass containing the Au. The method of analyze the oxidation-reduction state in glass by measuring the content of Fe2+and Fe3+is studied in this paper. By means of UV—VIS—IR, SEM, the size and the number of Au colloid which were processed by nucleating were observed and analyzed.
The result show that the system can be applied in practice, and get gold ruby glass whose the absorb spectra is at about 520nm and the suitable Au particles can be obtained by controlling the value of Fe2+/Fe3+between 0.0708 and 0.0742.
玻璃在高温熔制时,金以Au+离子状态溶解于熔体之中。玻璃冷却后是无色的,经热处理(显色),Au+离子被还原为金原子,并聚集长大成具有一定数量的胶体大小粒子,而呈现紫红色。
本文对Au+掺杂R20—SnO—SnO—PbO—B2O3—Sb2O3—SiO2系统金红玻璃的制备工艺与着色机理进行了探讨。本文利用分光光度法测量掺杂铁的金红玻璃中Fe2+和Fe3+的含量,进行监测玻璃氧化还原性的方法,以及紫外-可见光-红外分光光度仪、扫描电镜形貌分析等方法,研究了在一定的热处理工艺制度下,玻璃的氧化还原状态变化对金红玻璃光谱、微观形貌等的影响,从晶核的形成及长大等方面对金红玻璃氧化还原状态与其着色过程进行了理论分析。
当本文所研究的金红玻璃系统的Fe2+/Fe3+比值在0.0708～0.0742的范围时,可以得到吸收峰在520nm左右而呈紫红色的金红玻璃。
The glass colored with Au particles is the most beautiful and refined, and the color is fuchsia. This color glass is usually used in processing the high-level craftwork, the exclusive vessel glasses and decorative art glasses.
When the glass is melt under high temperature, the gold is dissolved in the fusibility by Au+ions. After cooling the glass is achromatous, but through heat treatment which is the course of showing colors, the glass shows fuchsia. During the heat treatment Au+ions are deoxidize to Au atoms, and the atoms are congregated together to certain number colloid.
This paper mainly covers the fundamental and experimental researches of R2O—SnO—ZnO—PbO—B2O3—Sb2O3—SiO2 system glass containing the Au. The method of analyze the oxidation-reduction state in glass by measuring the content of Fe2+and Fe3+is studied in this paper. By means of UV—VIS—IR, SEM, the size and the number of Au colloid which were processed by nucleating were observed and analyzed.
The result show that the system can be applied in practice, and get gold ruby glass whose the absorb spectra is at about 520nm and the suitable Au particles can be obtained by controlling the value of Fe2+/Fe3+between 0.0708 and 0.0742.
引文
[1]王承遇,陶瑛.艺术玻璃与装饰玻璃[M].北京：化学工业出版社,2008.
[2]曹振亚,张泽田编译.有色玻璃与特种玻璃[M].成都：四川科学技术出版社,1987：76-79.
[3]袁怡宋,吴柏诚,罗红旗编著.颜色玻璃[M].北京：轻工业出版社,1987：185-186.
[4]郑国培.有色光学玻璃及应用[M].北京：中国轻工业出版社,1990：144-146.
[5]袁怡松.颜色玻璃(六)一银和金的着色[J].玻璃与搪瓷,1997,25(3)：56-61.
[6]Weyl WA. Coloured Glasses [M]. London:Dawsons of Pall Mall,1959:37(1).
[7]Banford CR. Colour Generation and Control in Glass [M]. New York:1977:4(8).
[8]BISHAY A. Radiation induced color centers in multicomponent glasses [J]. Non-Cryst Solids,1970, (3):54-114.
[9]Henry D. Schreiber. Redox processes in glass-forming melts [J]. Journal of Non-Crystalline Solids,1986,84:129-141.
[10]H. Mertens, A. Polman. Depth-resolved nanostructure and refractive index of borosilicate glass doped with Ag nanocrystals [J]. Optical Materials,2005,64(3):24-26.
[11]Kaminsky N,Kaminsky F. Features of Producing Novel Colorful Self-striking Gold and Copper Ruby Glasses [J]. Sci Israel Technol Adv,2004,6 (3-4):53-65.
[12]西北轻工业学院.玻璃工艺学[M].北京：中国轻工业出版社,1995：182-184.
[13]浙江大学主编.玻璃工艺原理[M].北京：中国建筑工业出版社,1981.
[14]徐恒钧主编.材料科学基础[M].北京：北京工业大学出版社,2001.
[15]浙江大学等合编.硅酸盐物理化学[M].北京：中国建筑出版社,1980.
[16]J.扎齐斯基主编.玻璃与非晶态材料[M].北京：科学出版社,2001.
[17]邱美明,黄良制.玻璃形成学[M].北京：兵器工业出版社,1987.
[18]伍宏标主编.玻璃测试原理及方法[M].湖北：武汉工业大学出版社,2002.
[19]杨南如编.无机非金属材料测试方法[M].湖北：武汉工业大学出版社,1998.
[20]杨淑珍,周和平编.无机非金属材料测试实验[M].湖北：武汉工业大学出版社,2002.
[21]汤顺青.色度学[M].北京：北京理工大学出版社,1990.
[22]P.W.麦克米论著,王仞干译.微晶玻璃[M].北京：中国建筑工业出版社,1988：42-51.
[23]任海兰,岳勇,叶朝辉等.钠硼硅酸盐玻璃分相过程的NMR研究[J].无机材料学报,1998,13(3)：419-423.
[24]肖卓豪,卢安贤.R2O-MO-Al2O3-SiO2玻璃的组成与其热膨胀系数的关系[J].中南大学学报,2005,36(4)：566-570.
[25]张丽娟,温广武.K20一B203一SiO2玻璃成分对析晶性能的影响[J].材料科学与工艺,1996,4(1)：39-42.
[26]杨秋红,姜中宏.玻璃析晶动力学判据研究[J].硅酸盐学报,1994,22(5)：419-426.
[27]M.M. L ima, R.Monteiro. Characterisation and thermal behavior of a borosilicate glass [J]. Thermochimica Acta,2001,373:69-74.
[28]Yu Baolong, Zhu Congshan, Xia Haiping. Opticalnonirnerity of PbSe Microcrystallite doped in glass [J].Master Scr Lett,1997,16:2001.
[29]QIU J, SHIRAI M, NAKAYA T, et al. Space selective precipitation of metal nanoparticles inside glasses [J]. Appl Phys Lett,2002,81(16):3040-3042.
[30]C.-P. Peter Choul, David Turnbulla. Transformation behavior of Pd---Au ---Si metallic glasses [J]. Journal of Non-Crystalline Solids,1975,17(2):169-188.
[31]Yasuo Hayashi, Yasuo Fukuda, Masahiro Kudo. Investigation on changes in surface composition of float glass—mechanisms and effects on the mechanical properties. Surface Science,2002,507-510:872-876
[32]Woo-Sung Kim, Do-Hyung Cho, Sung-Ki Lim. The activity of sodium oxide in molten float glass by EMF measurements [J]. Thermochimica Acta,2004,414:191-195.
[33]杨锦才,孙方明.热处理制度对微晶玻璃颜色的影响[J].玻璃与搪瓷,1996,25(5).
[34]夏海平,章践立,王金浩,茅森.高折射率红玻璃的研制及吸收特性[J].材料导报,2002,16(8)：71-73.
[35]程金树,赵前,王怀德,等.红色微晶玻璃装饰板材的研究[J].玻璃,1996,23(5)：9-11.
[36]印保忠,郭常霖,陆昌大.金红玻璃显色过程的研究[J].硅酸盐学报,1986,14(1)：88-96.
[37]曾惠丹,邱建荣,姜雄伟,等.透明玻璃内部金纳米颗粒的空间选择性析出控制[J].硅酸盐学报,2004,32(3)：270-279.
[38]姜妍彦,王承遇,王璐,汤华娟.金红玻璃显色条件及其溶解度研究.2009年全国玻璃科学技术年会论文集[C].武汉：武汉理工大学出版社,2009.
[39]J SASAI J, HIRAO K. Relaxation behavior of nonlinear optical response in borate glasses containing gold nanoparticles [J]. Appl Phys Lett,2001,89(8):4548-4553.
[40]CHEN S, AKAI T, KADONO K, et al. Reversible control of silver nanoparticle generation and dissolution in soda lime silicate glass through X2ray irradiation and heat treatment[J]. Appl Phys Lett,2001,79(22):3687-3689.
[41]SHENGJ, KADONO K, YAZAWA T. Nanosized gold clusters formation in selected areas of soda lime silicate glass [J]. Journal of Non-Crystalline Solids,2003,324:295-299.
[42]Yin Baozhonga, Guo Changlina and Lu Changweia. Studies on the development process of gold ruby glasses [J]. Journal of Non-Crystalline Solids.1987,95-96,725-731.
[43]B.G. Varshal. Viscosity of alumino silicate glassesof R2O (RO) ·A12O3·6SiO2 composition [J]. Journal of Non-Crystalline Solids,1990,123:344-348.
[44]Leslie B. Hunt M.Sc., Ph.D. Gold based glass and enamel colours [J]. Endeavour,1981, 5(2):61-67.
[45]Glen B. Cook, Reid F. Cooper. Redox dynamics in the high-temperature float processing of glasses. I. Reaction between undoped and iron-doped borosilicate glassmelts and a gold-tin alloy [J]. Journal of Non-Crystalline Solids,1999,249:210-227.
[46]M. K. Tiwari a, M. H. Modi. Non-destructive surface characterization of float glass: X-ray reflectivity and grazing incidence X-ray fluorescence analysis [J]. Journal of Non-Crystalline Solids,2005,351:2341-2347.
[47]Kocarek J. The Shade Stabilization of Gold-coloured Glasses [J]. Inter Cong Glass,1989, 26:147-150.
[48]B. Svecova, P. Nekvindova, A. Mackova, et al. Study of Cu+, Ag+ and Au+ion implantation into silicate glasses[J]. Journal of Non-Crystalline Solids,2010,3:31-38.
[49]P. Malinsky, A. Mackova, J. Boc"an, B. Svecova, P. Nekvindova. Au implantation into various types of silicate glasses[J]. Journal of Non-Crystalline Solids,2009,267: 1575-1578.
[50]Andreia Ruivo, Cristina Gomes. Gold nanoparticles in ancient and contemporary ruby glass[J]. Journal of Cultural Heritage,2008,9:134-137.
[51]Edmond Iancua. The Colour Glass Condensate [J]. Nuclear Physics,2003,715:219-232.
[52]Lidia Armelao, Davide Barreca, et al. Recent trends on nanocomposites based on Cu, Ag and Au clusters:A closer look [J]. Coordination Chemistry Reviews,2006,250: 1294-1314.
[53]Dmitri Kharzeev, Yuri V. Kovchegov, Kirill Tuchin. Nuclear modification factor in d+Au collisions:onset of suppression in the color glass condensate [J]. Physics Letters B,2004. 599:23-31.
[54]Shiliang Qu, Yawen Zhang, Huajun Li, Jianrong Qiu, Congshan Zhu. Nanosecond nonlinear absorption in Au and Ag nanoparticles precipitated glasses induced by a femtosecond laser [J]. Optical Materials,2006,28:259-265.
[2]曹振亚,张泽田编译.有色玻璃与特种玻璃[M].成都：四川科学技术出版社,1987：76-79.
[3]袁怡宋,吴柏诚,罗红旗编著.颜色玻璃[M].北京：轻工业出版社,1987：185-186.
[4]郑国培.有色光学玻璃及应用[M].北京：中国轻工业出版社,1990：144-146.
[5]袁怡松.颜色玻璃(六)一银和金的着色[J].玻璃与搪瓷,1997,25(3)：56-61.
[6]Weyl WA. Coloured Glasses [M]. London:Dawsons of Pall Mall,1959:37(1).
[7]Banford CR. Colour Generation and Control in Glass [M]. New York:1977:4(8).
[8]BISHAY A. Radiation induced color centers in multicomponent glasses [J]. Non-Cryst Solids,1970, (3):54-114.
[9]Henry D. Schreiber. Redox processes in glass-forming melts [J]. Journal of Non-Crystalline Solids,1986,84:129-141.
[10]H. Mertens, A. Polman. Depth-resolved nanostructure and refractive index of borosilicate glass doped with Ag nanocrystals [J]. Optical Materials,2005,64(3):24-26.
[11]Kaminsky N,Kaminsky F. Features of Producing Novel Colorful Self-striking Gold and Copper Ruby Glasses [J]. Sci Israel Technol Adv,2004,6 (3-4):53-65.
[12]西北轻工业学院.玻璃工艺学[M].北京：中国轻工业出版社,1995：182-184.
[13]浙江大学主编.玻璃工艺原理[M].北京：中国建筑工业出版社,1981.
[14]徐恒钧主编.材料科学基础[M].北京：北京工业大学出版社,2001.
[15]浙江大学等合编.硅酸盐物理化学[M].北京：中国建筑出版社,1980.
[16]J.扎齐斯基主编.玻璃与非晶态材料[M].北京：科学出版社,2001.
[17]邱美明,黄良制.玻璃形成学[M].北京：兵器工业出版社,1987.
[18]伍宏标主编.玻璃测试原理及方法[M].湖北：武汉工业大学出版社,2002.
[19]杨南如编.无机非金属材料测试方法[M].湖北：武汉工业大学出版社,1998.
[20]杨淑珍,周和平编.无机非金属材料测试实验[M].湖北：武汉工业大学出版社,2002.
[21]汤顺青.色度学[M].北京：北京理工大学出版社,1990.
[22]P.W.麦克米论著,王仞干译.微晶玻璃[M].北京：中国建筑工业出版社,1988：42-51.
[23]任海兰,岳勇,叶朝辉等.钠硼硅酸盐玻璃分相过程的NMR研究[J].无机材料学报,1998,13(3)：419-423.
[24]肖卓豪,卢安贤.R2O-MO-Al2O3-SiO2玻璃的组成与其热膨胀系数的关系[J].中南大学学报,2005,36(4)：566-570.
[25]张丽娟,温广武.K20一B203一SiO2玻璃成分对析晶性能的影响[J].材料科学与工艺,1996,4(1)：39-42.
[26]杨秋红,姜中宏.玻璃析晶动力学判据研究[J].硅酸盐学报,1994,22(5)：419-426.
[27]M.M. L ima, R.Monteiro. Characterisation and thermal behavior of a borosilicate glass [J]. Thermochimica Acta,2001,373:69-74.
[28]Yu Baolong, Zhu Congshan, Xia Haiping. Opticalnonirnerity of PbSe Microcrystallite doped in glass [J].Master Scr Lett,1997,16:2001.
[29]QIU J, SHIRAI M, NAKAYA T, et al. Space selective precipitation of metal nanoparticles inside glasses [J]. Appl Phys Lett,2002,81(16):3040-3042.
[30]C.-P. Peter Choul, David Turnbulla. Transformation behavior of Pd---Au ---Si metallic glasses [J]. Journal of Non-Crystalline Solids,1975,17(2):169-188.
[31]Yasuo Hayashi, Yasuo Fukuda, Masahiro Kudo. Investigation on changes in surface composition of float glass—mechanisms and effects on the mechanical properties. Surface Science,2002,507-510:872-876
[32]Woo-Sung Kim, Do-Hyung Cho, Sung-Ki Lim. The activity of sodium oxide in molten float glass by EMF measurements [J]. Thermochimica Acta,2004,414:191-195.
[33]杨锦才,孙方明.热处理制度对微晶玻璃颜色的影响[J].玻璃与搪瓷,1996,25(5).
[34]夏海平,章践立,王金浩,茅森.高折射率红玻璃的研制及吸收特性[J].材料导报,2002,16(8)：71-73.
[35]程金树,赵前,王怀德,等.红色微晶玻璃装饰板材的研究[J].玻璃,1996,23(5)：9-11.
[36]印保忠,郭常霖,陆昌大.金红玻璃显色过程的研究[J].硅酸盐学报,1986,14(1)：88-96.
[37]曾惠丹,邱建荣,姜雄伟,等.透明玻璃内部金纳米颗粒的空间选择性析出控制[J].硅酸盐学报,2004,32(3)：270-279.
[38]姜妍彦,王承遇,王璐,汤华娟.金红玻璃显色条件及其溶解度研究.2009年全国玻璃科学技术年会论文集[C].武汉：武汉理工大学出版社,2009.
[39]J SASAI J, HIRAO K. Relaxation behavior of nonlinear optical response in borate glasses containing gold nanoparticles [J]. Appl Phys Lett,2001,89(8):4548-4553.
[40]CHEN S, AKAI T, KADONO K, et al. Reversible control of silver nanoparticle generation and dissolution in soda lime silicate glass through X2ray irradiation and heat treatment[J]. Appl Phys Lett,2001,79(22):3687-3689.
[41]SHENGJ, KADONO K, YAZAWA T. Nanosized gold clusters formation in selected areas of soda lime silicate glass [J]. Journal of Non-Crystalline Solids,2003,324:295-299.
[42]Yin Baozhonga, Guo Changlina and Lu Changweia. Studies on the development process of gold ruby glasses [J]. Journal of Non-Crystalline Solids.1987,95-96,725-731.
[43]B.G. Varshal. Viscosity of alumino silicate glassesof R2O (RO) ·A12O3·6SiO2 composition [J]. Journal of Non-Crystalline Solids,1990,123:344-348.
[44]Leslie B. Hunt M.Sc., Ph.D. Gold based glass and enamel colours [J]. Endeavour,1981, 5(2):61-67.
[45]Glen B. Cook, Reid F. Cooper. Redox dynamics in the high-temperature float processing of glasses. I. Reaction between undoped and iron-doped borosilicate glassmelts and a gold-tin alloy [J]. Journal of Non-Crystalline Solids,1999,249:210-227.
[46]M. K. Tiwari a, M. H. Modi. Non-destructive surface characterization of float glass: X-ray reflectivity and grazing incidence X-ray fluorescence analysis [J]. Journal of Non-Crystalline Solids,2005,351:2341-2347.
[47]Kocarek J. The Shade Stabilization of Gold-coloured Glasses [J]. Inter Cong Glass,1989, 26:147-150.
[48]B. Svecova, P. Nekvindova, A. Mackova, et al. Study of Cu+, Ag+ and Au+ion implantation into silicate glasses[J]. Journal of Non-Crystalline Solids,2010,3:31-38.
[49]P. Malinsky, A. Mackova, J. Boc"an, B. Svecova, P. Nekvindova. Au implantation into various types of silicate glasses[J]. Journal of Non-Crystalline Solids,2009,267: 1575-1578.
[50]Andreia Ruivo, Cristina Gomes. Gold nanoparticles in ancient and contemporary ruby glass[J]. Journal of Cultural Heritage,2008,9:134-137.
[51]Edmond Iancua. The Colour Glass Condensate [J]. Nuclear Physics,2003,715:219-232.
[52]Lidia Armelao, Davide Barreca, et al. Recent trends on nanocomposites based on Cu, Ag and Au clusters:A closer look [J]. Coordination Chemistry Reviews,2006,250: 1294-1314.
[53]Dmitri Kharzeev, Yuri V. Kovchegov, Kirill Tuchin. Nuclear modification factor in d+Au collisions:onset of suppression in the color glass condensate [J]. Physics Letters B,2004. 599:23-31.
[54]Shiliang Qu, Yawen Zhang, Huajun Li, Jianrong Qiu, Congshan Zhu. Nanosecond nonlinear absorption in Au and Ag nanoparticles precipitated glasses induced by a femtosecond laser [J]. Optical Materials,2006,28:259-265.