CN1369449A - 一种玻璃综合增强方法 - Google Patents

一种玻璃综合增强方法 Download PDF

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CN1369449A
CN1369449A CN 02116248 CN02116248A CN1369449A CN 1369449 A CN1369449 A CN 1369449A CN 02116248 CN02116248 CN 02116248 CN 02116248 A CN02116248 A CN 02116248A CN 1369449 A CN1369449 A CN 1369449A
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glass
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chemical tempering
acid
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CN1161298C (zh
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苗向阳
张保军
龚方田
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China Building Materials Academy CBMA
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/31Pre-treatment

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

采用化学钢化与表面处理、表面保护相结合,来增强平板玻璃或玻璃制品的方法。它包括玻璃表面预处理、化学钢化、表面后处理、表面保护四个过程,可以将普通平板玻璃的弯曲强度提高到1000MPa以上。

Description

一种玻璃综合增强方法
本发明阐述一种能够大幅度提高玻璃弯曲强度的增强方法,它的特征是采用化学钢化、化学腐蚀和涂层保护相结合的综合途径,来增强玻璃的韧性和强度。
普通平板玻璃实际强度只有50~80Mpa左右,而玻璃的理论强度可达到10000~20000Mpa。这之间2~3个数量级的巨大差异,主要是由于玻璃内、外部的缺陷造成的,其中表面缺陷特别是裂纹的影响更为显著。目前,玻璃增强主要采取在表面造成压缩应力层的方法,如风钢化、液体钢化、固体微粒钢化、化学钢化等,已取得广泛的实际应用。表面压应力增强方法的局限在于表层产生压缩应力的同时,在玻璃内部产生相应的与之平衡的张应力,因而,引入的压应力值不能过高,增强效果受到限制。依据工艺方法的不同,玻璃弯曲强度一般可提高到150~450MPa之间;化学腐蚀也是玻璃增强的一种方法,它是通过化学处理,去除玻璃表面缺陷层,使表面趋于“无缺陷”的理想状态,从而恢复玻璃固有的高强度。化学腐蚀存在的主要问题,一是腐蚀过程经常引起玻璃表面光学性能的降低;二是恢复的强度不能持久,衰减十分严重。
为提高玻璃强度,前人在综合增强方面做过一些探索。US3287200,采用风钢化结合化学钢化的方式。风钢化形成的压缩应力层厚但表面应力小;化学钢化的表面应力层薄但表面应力大。该专利希望能够综合两种钢化增强方法的优点,形成表面应力大并且应力层厚的制品。但实际上,该专利的可行性存在问题,实践表明,在450℃的化学钢化温度下,风钢化产生的应力会迅速松弛,失去增强效果,无法形成复合应力层。
用化学溶液特别是酸溶液如HF酸腐蚀增强玻璃的案例更多的见于实验室结果,实际商业应用很少。主要原因是表面腐蚀增强虽然暂时都能得到较高的强度值,但玻璃表面由于环境作用产生缺陷后,强度会急剧丧失,失去增强效果。即便在玻璃腐蚀后用有机涂层形成保护,这种单纯依靠表面增强的结构仍然具有很大的脆弱性,强度值分散程度较大。RU649672提供一种用HF酸和熔盐先后腐蚀、再进行化学钢化的综合增强方法,可以提高增强后制品强度的高温稳定性。从数据看,其强度仅能提高3~4倍,与单纯化学钢化的效果相差不大。
本专利更加完善地提出表面预处理、钢化、表面后处理、表面保护的综合增强方法。其目的就是稳定地大幅度提高并保持玻璃(制品)的强度。
本发明的具体描述如下:
玻璃的预处理。目的是为了在钢化前最大程度去除玻璃表面的微裂纹、划伤等微观宏观缺陷,提高玻璃强度,并且增加表面离子可交换性,促进化学钢化。预处理液的适宜组分为:HF酸浓度6.0N~8.5N,磷酸和硫酸分别占总溶液总重的5~8%,起缓冲作用的NH4F加入量8~10%。表面处理时间是室温下5~15分钟,表面去除厚度50~90微米。以下是最佳参数:
                             表1
HF酸浓度 磷酸浓度 硫酸浓度 NH4F浓度 表面处理时间 表面去除厚度
  7.2N   5%   8%     8.5%     12分钟     80微米
化学钢化。表面预处理后的制品用去离子水洗净,在无尘的洁净环境下自然干燥后进行钢化增强。化学钢化的最佳工艺参数控制为:交换温度420~480℃,交换时间6~30小时。推荐参数为交换温度450℃,交换时间20小时。
表面后处理。目的是在已形成应力层的玻璃表面进一步消除缺陷。后处理液可以与预处理液成分相同,但处理时间要短。表面腐蚀深度不能超过钢化应力层的厚度。最佳的条件是在室温下处理1~2分钟,腐蚀深度5~15微米。表面后处理后的制品用无水乙醇或异丙醇脱水10~20分钟,在无尘的洁净环境下自然干燥。
表面保护。表面保护的目的是保持酸液后处理的效果,防止在外界影响下制品强度的下降。形成保护层的材料为有机涂料,特别推荐有机硅改性丙烯酸、改性环氧树脂和PVB醇溶液。保护层的施加方法为喷涂或浸渍。涂层后的制品在红外干燥箱于60~100℃下干燥。
本发明与已知的玻璃增强或综合增强方法相比,显著优点是解决了增强后的玻璃制品强度衰减问题,降低了强度分散性,能够大幅度提高普通平板玻璃或制品的强度,玻璃双环抗弯强度可以稳定地提高到800~1000Mpa,最大达到1400Mpa。
实施例:
100×100×3mm浮法玻璃样品,成分如下:
                            表2
    SiO2     Al2O3     CaO     MgO     Na2O     K2O
    72     1.8     7.2     4.0     14.5     0.5
用去离子水清洗干净自然干燥,在环境温度25℃,湿度40%条件下,在表1所示地腐蚀液中处理12分钟,其中前10分钟用洁净气体鼓泡搅拌,后2分钟停止搅拌。处理后的样品在25℃的洁净环境自然干燥1小时,之后在450℃的KNO3熔盐中离子交换增强(化学钢化)20小时。钢化后的制品用清水和去离子水洗净,在同样成分的处理液中处理1分钟。处理后的样品在25℃的洁净环境自然干燥0.5小时,之后用有机硅改性丙烯酸液浸涂两次。涂层后的制品在红外干燥箱80℃下干燥24小时。
干燥后的样品用WD-5A万能材料试验机采用双环抗弯方法测试。原片玻璃及增强后的玻璃强度测试结果分别见表3和表4:
                                   表3
样品编号  1  2  3  4  5  6  7  8  9  10 平均强度
强度MPa  80  77  85  92  71  104  124  65  73  62  83
                                   表4
样品编号  1  2  3  4  5  6  7  8  9  10 平均强度
强度MPa  956  1031  982  1153  947  978  1205  994  1298  1194  1058

Claims (8)

1、一种大幅度提高玻璃强度的增强方法,该方法包括以下步骤:
(a)用腐蚀性溶液对玻璃进行表面处理;
(b)对处理过的玻璃进行化学钢化增强;
(c)对化学钢化后的玻璃进行表面后处理;
(d)在处理后玻璃表面形成保护层。
2、按权利要求1的方法,玻璃是指普通Na-Ca-Si平板玻璃或玻璃制品。
3、按权利要求1的方法,其中步骤(a)和步骤(c)所指表面处理液是以HF酸为主的对玻璃表面具有腐蚀性的液体。
4、按权利要求1的方法,玻璃在表面处理后要经过一个溶剂脱水过程。
5、按权利要求1的方法,其中步骤(d)是指用有机硅改性丙烯酸涂料在玻璃表面形成保护涂层。
6、按权利要求3的方法,处理液中的其它组分为磷酸、盐酸和NH4F。
7、按权利要求4的方法,脱水溶剂为无水乙醇或异丙醇。
8、按权利要求5的方法,有机保护涂层是在新形成的无损伤的玻璃表面形成。
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