Mechanism of Compound Refining Agents for TFT Substrate Glass Melting Process

Abstract

Abstract: Aiming to better understand the mechanism of refining agents for thin film transistor (TFT) substrate glass melting process, the proper temperature and refining effect of SnO₂, CaSO₄, NaCl and their compounds in melting process were studied by simulating float melting technology of TFT substrate glass. A high temperature melting dynamic observation was also used to study the detailed melting process. The effect of the NaCl amount used on the thermal properties of glass and the residual Na⁺ content in glass was discussed. The results show that the appropriate amount of SnO₂ is 0.10% (mass fraction) as a single refining agent. The further investigations on the compound refining agents indicate that the gradient clarification composed of 0.10% (mass fraction) SnO₂ and 0.35% (mass fraction) CaSO₄ has the best refining performance. For the synergy clarification composed of SnO₂ and NaCl, the refining performance increases with the increase of the amount of NaCl, but it should not exceed 0.076 3% (mass fraction) to satisfy the strict requirements of TFT substrate glass. The above research results offer important information for improving melting technology and product quality of TFT substrate glass, and they are beneficial to reduce cost and increase efficiency for the related industrial production.

Key words: compound refining agent, substrate glass, float melting technology, high temperature melting dynamic observation, gradient clarification, synergy clarification

CLC Number:

TQ171

HUANG Yiping, SHU Zhongzhong, CAO Zhiqiang, ZHANG Xiaodong, ZHANG Chong, JIN Liangmao, SHEN Yuguo. Mechanism of Compound Refining Agents for TFT Substrate Glass Melting Process[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(11): 3799-3806.

References

[1] LIU C T. Revolution of the TFT LCD technology[J]. Journal of Display Technology, 2007, 3(4): 342-350.
[2] 刘建党,刘攀,肖子凡,等.TFT-LCD基板玻璃的市场现状及发展趋势[J].玻璃,2018,45(2):16-20.
LIU J D, LIU P, XIAO Z F, et al. The market present situation and technology development prospects of TFT-LCD substrate glass[J]. Glass, 2018, 45(2): 16-20 (in Chinese).
[3] CUI J D, CAO X, SHI L F, et al. Quantitative evaluation of the improvement of B₂O₃ for the melting and fining process of high aluminium silicate glass batches under reduced atmospheric pressure[J]. Journal of Asian Ceramic Societies, 2021, 9(1): 151-162.
[4] MÜLLER H, STRUBEL C, BANGE K. Characterization and identification of local defects in glass[J]. Scanning, 2001, 23(1): 14-23.
[5] 田英良,徐言超,张铁柱,等.无碱玻璃纤维的澄清方法与机理[J].玻璃与搪瓷,2010,38(5):28-32.
TIAN Y L, XU Y C, ZHANG T Z, et al. The techniques and mechanism of refining for alkali-free glass fiber[J]. Glass & Enamel, 2010, 38(5): 28-32 (in Chinese).
[6] SOLVANG M, YUE Y Z, JENSEN S L, et al. Rheological and thermodynamic behaviors of different calcium aluminosilicate melts with the same non-bridging oxygen content[J]. Journal of Non-Crystalline Solids, 2004, 336(3): 179-188.
[7] 李青,王步洲,张占永,等.TFT-LCD基板玻璃粘附缺陷成因及控制[J].玻璃,2020,47(11):27-31.
LI Q, WANG B Z, ZHANG Z Y, et al. Causes and control of glass adhesion defects in TFT-LCD substrate glass[J]. Glass, 2020, 47(11): 27-31 (in Chinese).
[8] 靳一铁.玻璃制品的气泡缺陷[J].玻璃与搪瓷,2019,47(1):36-43.
JIN Y T. Bubble defect in glass products[J]. Glass & Enamel, 2019, 47(1): 36-43 (in Chinese).
[9] 杜燕军,路有昌.澄清剂对消除玻璃液气泡的机理研究[J].安阳师范学院学报,2003(5):65-66.
DU Y J, LU Y C. Study on mechanism of clarification and clarificant of the liquified glass[J]. Journal of Anyang Teachers College, 2003(5): 65-66 (in Chinese).
[10] WOOD J G, PRABAKAR S, MUELLER K T, et al. The effects of antimony oxide on the structure of alkaline-earth alumino borosilicate glasses[J]. Journal of Non-Crystalline Solids, 2004, 349: 276-284.
[11] VON DER GÖNNA G, RÜSSEL C. Voltammetric studies on redox equilibria of various polyvalent elements in CaO/BaO/Al₂O₃/SiO₂-melts[J]. Journal of Non-Crystalline Solids, 2001, 288(1/2/3): 175-183.
[12] BENNE D, RÜSSEL C, MENZEL M, et al. The effect of alumina on the Sn²⁺/Sn⁴⁺ redox equilibrium and the incorporation of tin in Na₂O/Al₂O₃/SiO₂ melts[J]. Journal of Non-Crystalline Solids, 2004, 337(3): 232-240.
[13] EHRT D. Redox behavior of Sn⁴⁺/Sn²⁺ in alkali free aluminosilicate glasses and melts[J]. European Journal of Glass Science and Technology Part B Physics and Chemistry of Glasses, 2013, 49(2008): 68-72.
[14] KIM K. Fining behavior in alkaline earth aluminoborosilicate melts doped with As₂O₅ and SnO₂[J]. Journal of the American Ceramic Society, 2013, 96(3): 781-786.
[15] HE X, SHEN X F, HUANG Q X, et al. Study on the structure, fining and properties of non-alkali aluminoborosilicate glasses containing SnO₂[J]. Journal of Non-Crystalline Solids, 2021, 559: 120670.
[16] HUJOVA M. Influence of fining agents on glass melting: a review, part 1[J]. Ceramics-Silikaty, 2017: 119-126.
[17] 王倩,应浩,韩高荣.高硼硅玻璃的复合澄清剂研究[J].玻璃,2006,33(1):6-10.
WANG Q, YING H, HAN G R. Investigation on compound refining agent of borosilicate glass[J]. Glass, 2006, 33(1): 6-10 (in Chinese).
[18] HUJOVA M. Influence of fining agents on glass melting: a review, part 2[J]. Ceramics-Silikaty, 2017: 202-208.
[19] ZHERNOVAYA N F, MIN'KO N I, ONISHCHUK V I, et al. Effectiveness of sulfate clarification of type E alkali-free glass[J]. Glass and Ceramics, 2008, 65(3/4): 109-112.
[20] CORNING. Method of fining borosilicate glasses: US 2035318[P]. 1936-03-24.
[21] 程继健,吕梦龙.提高玻璃澄清剂效果的研究[J].硅酸盐学报,1979,7(4):370-379+413.
CHENG J J, LÜ M L. A research on increasing the effect of refining agents for glass melting[J]. Journal of the Chinese Ceramic Society, 1979, 7(4): 370-379+413 (in Chinese).
[22] 李铭涵,赵会峰,代干,等.高铝硅酸盐玻璃的复合澄清剂研究[J].硅酸盐通报,2018,37(3):1053-1058.
LI M H, ZHAO H F, DAI G, et al. Compound fining agents of high aluminosilicate glass[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(3): 1053-1058 (in Chinese).
[23] 彭寿,赵凤阳,曹欣,等.澄清剂氧化锡对TFT-LCD基板玻璃澄清效果的影响[J].材料导报,2019,33(s1):195-198.
PENG S, ZHAO F Y, CAO X, et al. Impact of clarification of stannic oxide on TFT-LCD substrate glass[J]. Materials Reports, 2019, 33(s1): 195-198 (in Chinese).
[24] 陶东平,杨显万.氧化亚锡氧化还原动力学和二氧化锡还原机理[J].中国有色金属学报,1998,8(1):126-130.
TAO D P, YANG X W. Kinetics of disproportionation and reduction of stannous oxide and mechanism of reduction of stannic oxide[J]. The Chinese Journal of Nonferrous Metals, 1998, 8(1): 126-130 (in Chinese).
[25] 李铭涵,赵会峰,潘国志,等.不同澄清剂对高铝硅玻璃的澄清作用[J].材料科学与工程学报,2018,36(6):998-1002.
LI M H, ZHAO H F, PAN G Z, et al. High aluminosilicate glass fining with various fining agent[J]. Journal of Materials Science and Engineering, 2018, 36(6): 998-1002 (in Chinese).
[26] 司敏杰,郭卫,王艳霞,等.浮法玻璃锡缺陷治理的研究及进展[J].玻璃,2017,44(7):20-22.
SI M J, GUO W, WANG Y X, et al. Research status and development of float glass tin defect treatment[J]. Glass, 2017, 44(7): 20-22 (in Chinese).
[27] 刘志刚,任红灿,杨俊超,等.LCD玻璃基板表面锡缺陷的形成和控制[J].玻璃,2007,34(1):50-53.
LIU Z G, REN H C, YANG J C, et al. Formation and control about tin mixed flaw of the LCD glass surface[J]. Glass, 2007, 34(1): 50-53 (in Chinese).
[28] 田英良,程金树,梁新辉,等.高碱铝硅酸盐玻璃澄清剂与澄清效果研究[C]//2011中国硅酸盐学会电子玻璃分会论文选编.2011:112-126.
TIAN Y L, CHENG J S, LIANG X H, et al. Fining effect and fining agents in high alkali alumino-sllicate glasses[C]//Selected Papers from the Chinese Ceramic Society Electronic Glass Branch in 2011. 2011: 112-126 (in Chinese).
[29] 田路线,李国富,吴光文.TFT-LCD玻璃基板简介[J].玻璃,2009,36(5):46-49.
TIAN L X, LI G F, WU G W. Summary of TFT-LCD glass substrate[J]. Glass, 2009, 36(5): 46-49 (in Chinese).
[30] 王德宪,才秀琴.硫酸盐在玻璃澄清中的若干问题探讨[J].玻璃,2009,36(11):3-7.
WANG D X, CAI X Q. Discussion on some issues of sulfate as fining agent in glass melting[J]. Glass, 2009, 36(11): 3-7 (in Chinese).
[31] 王倩.澄清剂对高硼硅平板玻璃结构与性能的影响研究[D].杭州:浙江大学,2006.
WANG Q. Effect of fining agents on structure and property of Pyrex flat glass[D]. Hangzhou: Zhejiang University, 2006 (in Chinese).
[32] 冯明良,郭利娅.氟和氯在玻璃生产中的应用[J].玻璃,2002,29(6):22-24.
FENG M L, GUO L Y. Application of fluorine and chlorine in glass production[J]. Glass, 2002, 29(6): 22-24 (in Chinese).
[33] 张磊.TFT-LCD基板玻璃配方及工艺性能研究[D].北京:北京工业大学,2011.
ZHANG L. Study on the composition and technical properties of substrate glasses for TFT-LCD[D]. Beijing: Beijing University of Technology, 2011 (in Chinese).
[34] 田民波,叶锋.TFT-LCD面板设计与构装技术[M].北京:科学出版社,2010:201-217.
TIAN M B, YE F. Design and packaging technology of TFT-LCD panel[M]. Beijing: Science Press, 2010: 201-217 (in Chinese).