CN102015564B - 涂覆玻璃的制备 - Google Patents
涂覆玻璃的制备 Download PDFInfo
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- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
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- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3655—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing at least one conducting layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
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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
本发明公开了一种用于涂覆浮法玻璃带的方法。其包括步骤：形成玻璃带，在该带的主表面上沉积第一透明导电涂层，所述涂层不延伸到该带的边缘，而该带处于提高的温度，在受控条件下在退火炉中冷却所述涂覆玻璃带并切掉该带的边缘，以便产生具有均匀涂层的带，该涂层在切割带的全部宽度中延伸，其特征在于，将第二导电涂层沉积在带的未涂覆边缘，而边缘处于高于环境温度的温度下。本发明在生产涂覆玻璃产品方面获得了特别的应用，其中玻璃带的厚度至少为8mm，最特别地，其中玻璃的厚度至少为10mm。
Description
本发明涉及一种在浮法玻璃生产过程中用于生产涂覆玻璃的新方法。
1952年由Pilkington开发的浮法玻璃方法，现在是用于高品质玻璃生产的世界标准。在装入建筑物和交通工具之前，通常将浮法玻璃进一步处理。
将该方法用于制造薄至0.4mm和厚至25mm的玻璃。在炉中将准确混合的原料的“批料”熔融。在大约1000℃下，在化学上受控的气氛下连续地将熔融的玻璃从炉内浇注到熔融锡的浅(shallow)浴槽上。玻璃在锡上漂浮，展开并形成水平表面。通过将固化的玻璃带拉离浴槽的速度来控制厚度。在受控条件下将所生产的玻璃带传送到退火炉，其在该炉中冷却。退火后，玻璃以具有实质上平行表面的“火”抛光产品的形式形成。
可以通过在玻璃带的至少一个表面上沉积透明涂层来改变玻璃的热和光的透射性能。可以在浮法玻璃的生产过程中沉积这些涂层。通常将用来沉积这样的涂层的方法称为在线涂覆方法。这样的方法在商业生产中得到良好确立，并且可以使用常压化学气相沉积方法(下文中简写为APCVD方法)来进行。在APCVD方法中，将流体混合物引向玻璃带表面的一定位置处，在该位置处该带处于提高的温度下，且玻璃的热量引起流体混合物中的组分反应以及在玻璃带表面上的涂层沉积。这样的方法在浮法浴槽中尤其有用。为了避免锡氧化，将浮法浴槽保持在还原气氛中并且保持在基本常压下。玻璃处于高的温度下，典型为750℃到400℃。
可以使用公知的方法和设备进行这样的方法，例如在EP 785868中描述的那些。该设备典型地包括一个或几个分配柱(distributorbeam)，所述分配柱延伸横穿过浮法浴槽截面。将该方法设计为涂覆玻璃带的全部宽度，分配柱典型地呈现为延伸横穿该带的全部宽度。然而，实际上分配柱并不延伸到该带的边缘，这是因为流体混合物组分与浮法浴槽里面的锡反应和/或使其污染的可能性。该带的端部并没有涂覆，并且在该带离开退火炉后将其切掉。
在浮法玻璃生产过程中通常遇到的问题是玻璃带在通过退火炉时的破损。这些破损是不可预知的事件，这降低了可用玻璃的产率并降低该方法的经济性。它们出现在生产未涂覆玻璃期间，可能因为通常称为硬节(knurl)的玻璃带端部比该带的中心薄，这导致在该带中产生热应力和机械应力。当生产涂覆玻璃带时，该带中的破损问题恶化。该带的未涂覆边缘中的热损失速率比带的涂覆部分大。当该带通过退火炉时，这导致在该带中的这两个部位之间的温差，该温差引起热应力，该热应力可导致带的不希望的破损。
已经尝试了通过提供加热装置来升高未涂覆的带边缘的方法来降低破损量。这些尝试都并非完全成功的，尤其是当玻璃带的涂覆部分具有大于4mm的厚度时。
现在发现，可通过在玻璃带的未涂覆边缘上沉积包含导电材料的层来缓解在退火炉中出现破损的该问题。因而，本发明第一方面提供了一种生产涂覆玻璃带的方法，包括步骤：形成玻璃带，在该带的主表面上沉积第一透明导电涂层，所述涂层不延伸到该带的边缘，而该带处于提高的温度，在受控条件下在退火炉中冷却所述涂覆带并切掉该带的边缘，以便产生具有均匀涂层的带，该涂层在切割带的全部宽度上延伸，其特征在于，将第二导电涂层沉积在带的未涂覆边缘，而边缘处于高于环境温度的温度下。施加边缘涂层处的玻璃带的温度优选为至少300℃，更优选为至少400℃，最优选为至少500℃。在提高的温度下施加边缘涂层意味着该带较少地得到冷却因而较少地受应力。在这些温度下还可以较容易和较快地沉积边缘涂层。当带从浮法浴槽中形成时，该带的温度通常约为600℃，由于在浮法浴槽中沉积第二边缘涂层存在着污染浴槽的风险，因此优选在带从浮法浴槽中形成后沉积第二边缘涂层。在优选的实施方案中，在通过浮法浴槽和退火炉之间的间隙时沉积第二涂层。也可以在带处于退火炉中时沉积第二涂层。
在浮法玻璃处理中，已经将APCVD方法用于在玻璃带上沉积多种氧化物。在浮法浴槽中，使用多个分配柱沉积多层涂层。提供的多个涂层柱还使涂层的厚度或者涂层内单个层的厚度能得到增加。
这种方法制备的涂覆玻璃表现出多种性能，尤其包括热绝缘性能、阳光控制性能、自清洁性能以及减反射性能。导电涂层可以以这种方式沉积，且这些涂覆的产品在很多用途中得到应用，包括CRT和平板显示器以及加热的玻璃产品例如冰箱门。
相对于带边缘处的未涂覆玻璃，涂层的施加降低了热损失速率。这对于低发射率涂层尤为如此，将该涂层设计用于反射长波红外线辐射。浮法玻璃的发射率大约是0.84，而具有低发射率涂层的玻璃的发射率典型处于0.15-0.25的范围内。特定涂层的发射率ε，是指该涂层相对于黑体所吸收和辐射能量的趋势，所述黑体是理想辐射体并且被定义为具有为一的发射率(ε＝1)。发射率随着辐射波长的变化而变化，且申报(declared)值是典型5-55微米的波长范围内的平均值。在该全部说明书中提到的低发射率涂层是较长波长热能的不良吸收体和辐射体，并且其ε＜1。
在本发明的方法中，边缘涂层优选为具有与带中心的涂覆玻璃相似的发射率值的涂层。在带边缘处的涂层可以与中心处的涂层相同，但是通常因为经济和实用性的原因，其并不相同。例如，提供多层涂层可能是昂贵的并且可能是不切实际的。此外，APCVD方法使用玻璃的热量来驱动沉积反应，且当玻璃温度较低时，形成的涂层可能与当玻璃处于较高温度时通过相同反应沉积的涂层不同。
在玻璃带边缘处的涂层厚度可以是变化的，以便为玻璃带的涂覆边缘提供与在该带中心的涂覆玻璃的发射率接近的发射率。涂层和它的厚度优选使得涂覆的带边缘的发射率从0.8降低到0.2-0.7的范围内的值。
已将多种导电透明涂层施加于玻璃基材，且这些中的任何对于本发明的方法中涂覆带的边缘都是潜在可用的。一组这样的涂层包括金属氧化物和掺杂的金属氧化物，例如掺杂氟的氧化锡、氧化锡、掺杂锑的氧化锡、氧化铟、氧化锌、铟氧化锌(ITO)、掺杂铝的氧化锌和掺杂镓的氧化锌。
包含这些材料中的多于一种的多层涂层(其中层厚受控)为涂覆玻璃提供了多种有用的性能。这样的产品在市场上是可得到的，并且通常称作硬涂覆产品。这使得它们区别于由离线涂覆方法例如是真空溅射制备的所谓软涂覆产品。
可以使用公知的方法和公知的化学物质沉积这些边缘涂层。例如，可以使用如下的体系通过APCVD方法沉积氧化锡涂层：例如四氯化锡和水、四氯化锡低醇和水、二甲基二氯化锡和水、二甲基二氯化锡和水及氧、一丁基四氯化锡和水及氧，或者一丁基三氯化锡和乙酸乙酯及氧。可以通过在用于沉积氧化锡的APCVD方法中引入挥发性的氟前体来沉积掺杂氟的氧化锡涂层，所述氟前体例如氢氟酸、三氟乙酸或者六氟环氧丙烷。用于沉积掺杂氟的氧化锡涂层的优选化学物质包括一丁基三氯化锡、乙酸乙酯和氢氟酸以及氯化锡、甲醇、水和氢氟酸。氧化锌涂层可以使用挥发性有机锌化合物沉积，例如二甲基锌、二乙基锌和带有酯例如乙酸乙酯或带有氧的仲丁醇锌。
可能使用的另一公知方法是喷涂系统，其中将包含金属前体的液体喷在带边缘的表面上。还可将任何上述化学物质用于喷涂方法中。特别优选的喷涂方法是使用一丁基三氯化锡、乙酸乙酯和氢氟酸以沉积掺杂氟的氧化锌涂层的喷涂方法。
另外类型的公知方法是燃烧化学气相沉积(CCVD)方法，其中在接近要涂覆的表面的火焰中燃烧蒸气或液体。同样，可以将上述的化学物质用于CCVD方法中。在CCVD方法中，前体在火焰中分解，这意味着在APCVD方法中无用的前体例如乙酸锡或者乙酸锌可为有用的。当玻璃的温度相对低时，CCVD方法可能较APCVD方法更为有效。
可以用于涂覆玻璃带边缘的其它类型的涂覆方法是溶胶凝胶涂覆方法。在溶胶凝胶方法中，将液态载体涂覆在表面上，然后加热从而蒸发溶剂并形成涂层。
边缘涂层的厚度典型为5-500nm，更通常为100nm-300nm。
在将玻璃穿过浮法浴槽时，可以将这些方法用于涂覆玻璃边缘，但是优选地将它们在退火炉间隙中涂覆玻璃，也就是当该带穿过浮法浴槽到退火炉中或者在退火炉浴槽本身内时。当涂覆玻璃已穿过退火炉时，切掉涂覆边缘并丢弃。施加在边缘的涂层品质不是重要的，并且其均匀性的变化一般不影响该方法的性能。类似地，在玻璃带的涂覆边缘处的可见光透射率可能小于在该带中心处的涂覆玻璃的透射率。
本发明的方法在生产涂覆玻璃产品中得到特别应用，其中玻璃带的厚度至少为8mm，且最特别地，其中玻璃的厚度至少为10mm。本发明使这种厚度的涂覆玻璃成为可能，尤其是在浮法玻璃生产过程中在线制备低e涂覆玻璃，而在该带中具有较少的破损。
Claims (16)
1.在浮法玻璃生产过程中用于生产涂覆玻璃带的方法，其包括步骤：形成玻璃带，在该带的主表面上沉积第一透明导电涂层，所述涂层不延伸到该带的边缘，而该带处于提高的温度下，在受控条件下在退火炉中冷却所述涂覆带并切掉该带的边缘，以便产生具有均匀涂层的带，该涂层在切割带的全部宽度上延伸，其特征在于，将第二导电涂层沉积在该带的未涂覆边缘，而边缘处于高于环境温度的温度下。
2.权利要求1所述的方法，其特征在于是以浮法玻璃生产方法中的一部分生产该带。
3.权利要求1或2所述的方法，其特征在于该带具有至少8mm的厚度。
4.权利要求1或2所述的方法，其特征在于第一透明涂层具有10nm-500nm的厚度。
5.权利要求1或2所述的方法，其特征在于使用化学气相沉积方法在浮法浴槽中沉积第一透明导电涂层。
6.权利要求1或2所述的方法，其特征在于将第二涂层施加到玻璃带的边缘并且该带的温度至少为300℃。
7.权利要求6所述的方法，其特征在于该带的温度为500℃-600℃。
8.权利要求1或2所述的方法，其特征在于浮法浴槽和退火炉之间的间隙处将第二涂层施加于玻璃带。
9.权利要求1、2或7所述的方法，其特征在于使用热解喷涂沉积方法施加第二涂层。
10.权利要求1、2或7中任一项所述的方法，其特征在于使用化学气相沉积方法施加第二涂层。
11.权利要求1、2或7中任一项所述的方法，其特征在于使用燃烧化学气相沉积方法施加第二涂层。
12.权利要求1、2或7所述的方法，其特征在于第一透明涂层是低发射率涂层。
13.权利要求12所述的方法，其特征在于涂覆有第一导电涂层的玻璃的发射率与涂覆有第二导电涂层的玻璃的发射率相同。
14.权利要求12所述的方法，其特征在于第二导电涂层的发射率为0.2-0.7。
15.权利要求1、2、7或13中任一项所述的方法，其特征在于第二导电涂层包括氧化锡。
16.权利要求15所述的方法，其特征在于第二导电涂层包括掺杂氟的氧化锡。
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| GB0808338.8 | 2008-05-08 | ||
| GBGB0808338.8A GB0808338D0 (en) | 2008-05-08 | 2008-05-08 | Production of coated glass |
| PCT/GB2009/050479 WO2009136201A1 (en) | 2008-05-08 | 2009-05-07 | Production of coated glass |
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| CN102015564A CN102015564A (zh) | 2011-04-13 |
| CN102015564B true CN102015564B (zh) | 2013-09-11 |
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| WO2013008895A1 (ja) * | 2011-07-12 | 2013-01-17 | 旭硝子株式会社 | 積層膜付きガラス基板の製造方法 |
| JP2016047775A (ja) * | 2013-01-16 | 2016-04-07 | 旭硝子株式会社 | 積層膜付きフロートガラス及びその製造方法 |
| WO2017137773A1 (en) * | 2016-02-12 | 2017-08-17 | Pilkington Group Limited | Chemical vapor deposition process for depositing a mixed metal oxide coating and the coated article formed thereby |
| ES3008700A1 (es) * | 2024-12-03 | 2025-03-24 | Luca Margherito | Procedimiento de fabricacion de laminas de vidrio plano decorado para arquitectura e interiorismo |
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- 2009-05-07 WO PCT/GB2009/050479 patent/WO2009136201A1/en active Application Filing
- 2009-05-07 JP JP2011507996A patent/JP5484446B2/ja active Active
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| US4100330A (en) * | 1977-03-28 | 1978-07-11 | Ppg Industries, Inc. | Method for coating glass with silicon and a metal oxide and resulting product |
| CN1228067A (zh) * | 1996-08-13 | 1999-09-08 | 皮尔金顿公共有限公司 | 在平板玻璃上沉积氧化锡和二氧化钛涂层的方法及所获得的涂覆玻璃 |
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| GB0808338D0 (en) | 2008-06-18 |
| JP5484446B2 (ja) | 2014-05-07 |
| EP2285747A1 (en) | 2011-02-23 |
| WO2009136201A1 (en) | 2009-11-12 |
| EP2285747B1 (en) | 2017-09-20 |
| CN102015564A (zh) | 2011-04-13 |
| US8733130B2 (en) | 2014-05-27 |
| US20110083472A1 (en) | 2011-04-14 |
| JP2011519813A (ja) | 2011-07-14 |
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