铁在锡槽中的氧化还原反应及对玻璃表面锡扩散影响的研究
发布时间：2018-10-14 09:53
【摘要】：我国浮法玻璃普遍存在渗锡量大,虹彩严重的情况,制约了我国玻璃制品的精深加工。为了解决这一问题,提升我国浮法玻璃的市场竞争力,必须针对该问题进行研究,提出降低渗锡量和减轻玻璃虹彩的有效措施。研究发现,往锡液中加金属铁能有效的降低玻璃表面的渗锡量,进而降低玻璃钢化虹彩出现的概率。 本课题利用x射线荧光分析仪(XRF)、电子探针(EPMA、X射线光电子能谱(XPS)研究锡液中加铁对玻璃表面锡扩散的影响。研究从两个方面展开：一是直接对生产线上的玻璃样品进行分析研究；另一方面是利用自行搭建的模拟浮法玻璃成型装置制样,对玻璃样品进行分析研究。实验中还对锡槽加铁引起玻璃下表面微泡的原因进行了简单的分析。 研究发现实际生产中往锡液中加适量的金属铁,不仅能有效的降低玻璃表面的渗锡量、锡的渗入深度及玻璃表面Sn2+的相对含量,还能有效的降低玻璃钢化虹彩等级。锡液中加金属铁能促使玻璃下表层渗入铁增多,渗入的铁主要以Fe3+的形式存在。铁不仅能优先与氧气反应,还能把锡氧化物还原回锡单质,从而降低玻璃表面锡的渗入量和渗入深度。同时锡液中反应生成的Fe3+还能把Sn2+氧化成Sn4+,扩散到玻璃表层的Fe3+也能把渗入玻璃表层的Sn2+氧化成Sn4+,从而增加玻璃表层中Sn4+的相对含量。对实验室制样分析研究发现,往锡液中加金属铁时,随着加铁量(0%-0.8%)的增加,玻璃表层渗锡量先减少后增大,进入玻璃表层中的Sn2+相对含量也是先减少后增大,而Sn4+相对含量增加先增大后减少。加铁量为0.4%时,渗锡量最小,约为17.30ug/cm2,进入玻璃表层的Sn4+的相对含量最大,约为96.12%；玻璃下表面铁渗入量随着锡液中加铁量的增多而增多；加铁量相同,延长玻璃与锡液的接触时间,渗锡量增多,进入玻璃中的铁含量反而降低。 实际生产中发现,往锡液中加铁控制玻璃钢化虹彩,加入铁的量有一个最优范围,当锡液中铁含量控制在0.03%左右时,生产出的玻璃钢化虹彩等级低；当锡液中加入的铁的量太少或过多时,生产出的玻璃进行钢化后虹彩严重。这一生产实践正好验证了前面的研究成果：生产中加入适量的铁不仅减少了玻璃表面渗锡量和Sn2+的相对含量,还减轻了玻璃虹彩,少加或多加都不利于玻璃表面渗锡量的减少。实践中还发现采取少量多次的方式往锡液中加铁能大大降低玻璃下表面气泡的产生。
[Abstract]:The high tin permeation and iridescent are common in float glass in China, which restricts the deep processing of glass products in China. In order to solve this problem and improve the market competitiveness of float glass in China, it is necessary to study the problem and put forward effective measures to reduce the amount of tin permeation and lighten the iris of glass. It is found that the addition of metal iron to the tin solution can effectively reduce the amount of tin permeation on the glass surface and thus reduce the probability of the appearance of the glass tempered iris. The effect of iron addition on tin diffusion on glass surface was studied by using X-ray fluorescence analyzer (XRF),) electron probe (EPMA,X) photoelectron spectroscopy (XPS). The research is carried out from two aspects: one is to analyze the glass samples in the production line directly; the other is to analyze and study the glass samples by using the self-built simulated float glass forming device. The causes of the microbubbles on the glass surface caused by the addition of iron in the tin bath were also analyzed. It is found that adding appropriate amount of metal iron to the tin solution in actual production can not only effectively reduce the amount of tin permeation on the glass surface, the penetration depth of tin and the relative content of Sn2 on the glass surface, but also effectively reduce the grade of glass tempered iridescent. The addition of metal iron in the tin solution can increase the amount of iron infiltrated in the surface layer of glass, and the infiltrated iron mainly exists in the form of Fe3. Iron can not only preferentially react with oxygen, but also reduce tin oxide back to tin element, thus reducing the amount and depth of tin infiltration on glass surface. At the same time, Fe3 can oxidize the Sn2 to Sn4, and the Fe3 diffused to the glass surface can also oxidize the Sn2 infiltrated into the glass surface to Sn4, thus increasing the relative content of Sn4 in the glass surface. It is found that with the increase of iron content (0% -0.8%), the amount of tin permeated in the glass surface decreases first and then increases, and the relative content of Sn2 entering the glass surface decreases first and then increases when the metal iron is added to the tin solution. The relative content of Sn4 increased first and then decreased. When the amount of iron added is 0.4, the amount of tin permeation is the smallest, about 17.30ugr / cm ~ 2, and the relative content of Sn4 entering the surface of glass is the largest, about 96.12.The amount of iron infiltration on the surface of the glass increases with the increase of the amount of iron added into the tin solution; the amount of iron added is the same. When the contact time between glass and tin solution is prolonged, the amount of tin permeation increases and the content of iron entering the glass decreases. In practical production, it is found that adding iron to the molten tin to control the glass tempered iridescent has an optimal range. When the iron content in the molten tin is controlled at about 0.03%, the grade of the glass tempered iridescent is low. When too little or too much iron is added to the molten tin, the resulting glass is tempered and ironed seriously. This production practice just verifies the previous research results: the addition of appropriate amount of iron in production not only reduces the amount of tin permeation on glass surface and the relative content of Sn2, but also lightens the glass iris, and less or more addition is not conducive to the reduction of the amount of tin permeation on glass surface. It is also found that adding iron to the tin solution in a small amount of time can greatly reduce the formation of bubbles on the surface of the glass.
【学位授予单位】：海南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ171.721
本文编号：2270107
[Abstract]:The high tin permeation and iridescent are common in float glass in China, which restricts the deep processing of glass products in China. In order to solve this problem and improve the market competitiveness of float glass in China, it is necessary to study the problem and put forward effective measures to reduce the amount of tin permeation and lighten the iris of glass. It is found that the addition of metal iron to the tin solution can effectively reduce the amount of tin permeation on the glass surface and thus reduce the probability of the appearance of the glass tempered iris. The effect of iron addition on tin diffusion on glass surface was studied by using X-ray fluorescence analyzer (XRF),) electron probe (EPMA,X) photoelectron spectroscopy (XPS). The research is carried out from two aspects: one is to analyze the glass samples in the production line directly; the other is to analyze and study the glass samples by using the self-built simulated float glass forming device. The causes of the microbubbles on the glass surface caused by the addition of iron in the tin bath were also analyzed. It is found that adding appropriate amount of metal iron to the tin solution in actual production can not only effectively reduce the amount of tin permeation on the glass surface, the penetration depth of tin and the relative content of Sn2 on the glass surface, but also effectively reduce the grade of glass tempered iridescent. The addition of metal iron in the tin solution can increase the amount of iron infiltrated in the surface layer of glass, and the infiltrated iron mainly exists in the form of Fe3. Iron can not only preferentially react with oxygen, but also reduce tin oxide back to tin element, thus reducing the amount and depth of tin infiltration on glass surface. At the same time, Fe3 can oxidize the Sn2 to Sn4, and the Fe3 diffused to the glass surface can also oxidize the Sn2 infiltrated into the glass surface to Sn4, thus increasing the relative content of Sn4 in the glass surface. It is found that with the increase of iron content (0% -0.8%), the amount of tin permeated in the glass surface decreases first and then increases, and the relative content of Sn2 entering the glass surface decreases first and then increases when the metal iron is added to the tin solution. The relative content of Sn4 increased first and then decreased. When the amount of iron added is 0.4, the amount of tin permeation is the smallest, about 17.30ugr / cm ~ 2, and the relative content of Sn4 entering the surface of glass is the largest, about 96.12.The amount of iron infiltration on the surface of the glass increases with the increase of the amount of iron added into the tin solution; the amount of iron added is the same. When the contact time between glass and tin solution is prolonged, the amount of tin permeation increases and the content of iron entering the glass decreases. In practical production, it is found that adding iron to the molten tin to control the glass tempered iridescent has an optimal range. When the iron content in the molten tin is controlled at about 0.03%, the grade of the glass tempered iridescent is low. When too little or too much iron is added to the molten tin, the resulting glass is tempered and ironed seriously. This production practice just verifies the previous research results: the addition of appropriate amount of iron in production not only reduces the amount of tin permeation on glass surface and the relative content of Sn2, but also lightens the glass iris, and less or more addition is not conducive to the reduction of the amount of tin permeation on glass surface. It is also found that adding iron to the tin solution in a small amount of time can greatly reduce the formation of bubbles on the surface of the glass.
【学位授予单位】：海南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ171.721
【参考文献】
相关期刊论文 前10条
1 姜宏,赵会峰,王廷籍;浮法玻璃表面渗锡与工艺诊断[J];玻璃与搪瓷;2000年03期
2 金明坤;X射线荧光分析在测定浮法玻璃表面渗锡量中的应用[J];玻璃;1998年06期
3 宋炯生,嵇书伟;浮法玻璃虹彩的检验及消除[J];玻璃;1999年02期
4 纪福顺;;浮法玻璃锡缺陷的预防与控制[J];玻璃;2008年02期
5 陈芳;王德宪;;浮法玻璃表面渗锡与渗锡量测定[J];玻璃;2008年02期
6 张贤华;浮法玻璃的锡缺陷[J];玻璃;1997年02期
7 刘芬;赵志娟;邱丽美;赵良仲;;XPS光电子峰和俄歇电子峰峰位表[J];分析测试技术与仪器;2009年01期
8 陆平;程金树;刘清;万军鹏;;降温速率对浮法硼硅酸盐玻璃下表面渗锡的影响(英文)[J];硅酸盐学报;2008年04期
9 孙文明;;降低浮法玻璃下表面渗锡量的体会[J];玻璃;2012年08期
10 王文泽;卢占国;;浮法锡槽常见质量缺陷及解决方法[J];玻璃;2008年09期
相关博士学位论文 前1条
1 孟政;浮法玻璃成型过程中硫的形态变化及扩散机理研究[D];中国建筑材料科学研究总院;2013年
相关硕士学位论文 前1条
1 秦国强;浮法玻璃表面渗锡的XPS与UV-PL研究[D];燕山大学;2006年
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