CN1039625A - 氧化铋的化学气相沉积 - Google Patents
氧化铋的化学气相沉积 Download PDFInfo
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- CN1039625A CN1039625A CN89104552A CN89104552A CN1039625A CN 1039625 A CN1039625 A CN 1039625A CN 89104552 A CN89104552 A CN 89104552A CN 89104552 A CN89104552 A CN 89104552A CN 1039625 A CN1039625 A CN 1039625A
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- CN
- China
- Prior art keywords
- bismuth
- glass
- matrix
- organic compound
- triphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
-
- 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/228—Other specific oxides
-
- 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
Abstract
本发明公开了一种含有有机铋化合物的新型的有机金属涂层组合物,以及一种用于在基体(如玻璃)表面上形成氧化铋膜的化学气相沉积方法。
Description
本发明是关于反红外涂层玻璃产品技术,更具体地说,是关于无彩虹色的、高透射率、低辐射率的反红外涂层玻璃产品。
可以通过各种方法使氧化锡之类的透明反红外薄膜沉积在玻璃之类的基体上,所说的各种方法包括将能热分解的化合物施用到加热的表面上的方法。成形透明反红外氧化锡薄膜的有用方法公开于Saunders等人的U.S.Patent No.3,107,177,Gillery的U.S.Patent No.3,677,814和Wagner等人的U.S.Patent No.4,263,335。
厚度约为1000~8000埃的氧化锡膜为特别有效的红外反射层。但是,这一厚度下的薄膜趋向于表现出干涉的效果,即通常称为彩虹色的多种可见颜色。这种干涉效果使这种涂层玻璃对大多数建筑应用不符合美学要求。在比较薄的薄膜中观察不到彩虹色;但是,这些薄膜的红外反射率不足以满足实际应用。同样,在较厚的薄膜中观察不到彩虹色;但是,这些薄膜趋于混浊并且难于均匀沉积。因此,研制了各种掩盖干涉作用的方法。
Stewart的U.S.Patent No.3,710,074公开了一种电加热多层玻璃窗构件,该构件在封闭的表面上具有导电涂层,和具有至少0.7的绝对红外反射率的选择性反射薄膜,以改进该构件的热绝缘性能和减少导电膜的可见彩虹。
Chess等人的U.S.Patent No.4,069,630公开了一种热反射多层釉面窗,该窗包括一个着色的内表面具有反热氧化锡膜的吸热外部玻璃板,和一个内层玻璃板,该板可以是无色玻璃也可以是着色的。这种氧化锡薄膜典型地具有从第一级红到第四级红的干涉色,这种可见的效应可以通过着色的吸热玻璃降低。
Gordon的U.S.Patent Nos.4,187,336;4,206,252和4,308,316公开了透明玻璃窗结构,该结构包括一个具有反红外的第一涂层的玻璃板,其中由该第一涂层引起的虹彩可由具有特殊反射指数和厚度的第二涂层来减少,该第二涂层有至少两个形成反射和折射光线的界面,以干扰惯常的彩虹。
Gordon的U.S.Patent No.4,377,613公开了一种透明窗结构,该窗结构由一种带红外反射材料涂层的玻璃板组成,在其中,惯常的彩虹通过在红外反射涂层下面的一种很薄的涂层系统构造而减少,该涂层系统构造反射和折射光线以干扰惯常的彩虹。
1985年8月23日V.A.Hevery等人的U.S.申请系列号768,922公开另一种在窗构件上掩蔽红外反射膜可见虹彩效应的方法。该方法是通过一种第二层膜的方法掩蔽红外反射膜的可见干涉效应,该第二层膜具有在可见波长范围的均匀反射率,并具有显著高于红外反射膜光反射率的光反射率。为产生一种高透明性、低辐射性的构件,最好选择与反射曲线上第一个最低点相应的红外反射膜厚度。
屏蔽可见干涉效应的红外反射薄膜在一种单片薄板上可能是有用的。按照本发明的最好制品是多层釉面玻璃构件,该构件包括至少两层板,最好都是玻璃的。传统的玻璃组份是有效的,尤其是典型浮法线生产的钠-钙-硅玻璃。吸热着色玻璃可以采用,但对高透明的应用来说,最好是透明玻璃。
可对太阳能控制有用的各种红外反射薄膜的成份最好是氧化锡。氧化锡膜可通过各种不同的方法沉积在玻璃表面上,比如热解沉淀、粉末涂层、化学气相沉积和阴极溅射。适宜的方法有Gillery的U.S.Patent Nos.3,677,814和Wagner等人的4,263,335中所述的氟化烷基锡热解、Sopko的U.S.Patent No.3,850,679所述的化学气相沉淀、Wagner的U.S.Patent No.4,325,988和Hevery的No.4,344,986所述的粉末涂层,以及Gillery的U.S.Petent Nos.3,477,936和3,506,556所述的阴极溅射。
优选的氧化锡红外反射膜具有低于约50Ω/平方的电阻率,最好的是在20~30Ω/平方的范围,并具低辐射率,最好的低于0.4。膜的厚度选择与光反射率曲线上最低点相适。最好,薄厚度相应于第一最低点,因为该点代表对氧化锡膜来说可得到的最低可见反射率。该点相应于在约1400 的厚度上第二级兰干涉效应。把涂层工艺参数控制到对已知厚度产生最低的阻抗,以提供最大红外反射率和最小辐射率。如果较高的太阳能性能要求较低的阻抗,则可形成一种较厚的红外反射氧化锡膜,其厚度最好接近于光反射曲线上第二个最低点,厚度相应于第三级兰干涉效应则极好,约2750埃。
在氧化锡红外反射膜的厚度相应于光反射曲线上第一个最低点的优选具体实例中,膜由于干涉效应一般呈兰色,可见反射率约10%,阻抗通常约45~50Ω/平方。
当氧化锡除其红外反射性质外还因其耐久性而得到广泛应用时,在某些光学应用中就要求较高的红外折射指数(即大于0.2)的涂层。两种众所周知的高折射指数涂层是硫酸锌和氧化钛,但各有其严重的缺陷。硫酸锌对许多应用不够耐久,而氧化钛则具有吸收的特性而产生一种兰色。折射指数为2.4的氧化铋是无色的,但当用溅射法制作时是不耐久的。按照本发明由化学气相沉积制作氧化铋则耐久而无色,并具有2.4的高折射指数。
按照本发明用于氧化铋化学气相沉积的优选的有机铋化合物为芳基 ,较好的是三芳基 ,最好的是三苯基 。然而其它具有适当的热稳定性和热解性的有机铋如烷基、链烯基、烷氧基、芳烷基及其氟衍生物也可使用。最好的有机铋化合物包括对空气和水稳定、无色、无毒和相对无味的结晶化合物。
例1
用一个实验室规模的动力涂敷器、改良的冷壁反应器制做涂层玻璃试样。将该玻璃试样置于通过感应加热到约950°F(约510℃)的金属块上。将具有约0.01摩尔%三苯基 的空气载体流以10cm/秒的流速在试样上面通过约8分钟。积沉淀成约150 厚的氧化铋膜。
例2
将一玻璃基体置于直径约1英寸、长约8英寸的陶瓷管中,将一高温加热带置于基体所在区域的周围。将一带进气口的聚四氟乙烯(Teflon)阀装在陶瓷管的一端。将一个出气口连同热偶装在陶瓷管的另一端。将基体加热到约1200°F(约649℃)。将带有约0.1mole%三苯基铋的空气载体流以约5cm/秒的流速通过该陶瓷管。用此方法制成五个试样,膜厚度从100到1200 。
上述实例只用于说明本发明。希望涂层装置、工艺参数及组份的优化提供改善的耐久、无色、高折射指数的氧化铋膜,并包括在本发明中。其它芳基、烷氧基和链烯基的铋化合物,基于其热稳定性和热解性,可用于按照本发明制作氧化铋膜。本发明范围由以下权利要求书来限定。
Claims (10)
1、一种通过化学气相沉积而形成氧化铋涂层的方法,该方法包括在一种氧化气氛中用一种有机铋化合物接触一基体的表面,接触时的温度足以使所说的有机铋化合物发生热反应,在所说的表面上沉积一层氧化铋膜。
2、一种按照权利要求1的方法,其中所说的基体是玻璃。
3、一种按照权利要求2的方法,其中所说的有机铋化合物与载体气体结合形成混合物。
4、一种按照权利要求3的方法,其中所说的载体气体是空气。
5、一种按照权利要求4的方法,其中所说的有机铋化合物选自包括芳基 和链烯基 。
9、一种按照权利要求8的方法,其中所说的基体在至少350℃的温度下和三苯基 接触。
10、一种按照权利要求9的方法,其中所说的基体在500~650℃范围的温度下与三苯基 接触。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/219,693 | 1988-07-05 | ||
US07/219,693 US4965093A (en) | 1988-07-05 | 1988-07-05 | Chemical vapor deposition of bismuth oxide |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1039625A true CN1039625A (zh) | 1990-02-14 |
Family
ID=22820367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN89104552A Pending CN1039625A (zh) | 1988-07-05 | 1989-07-05 | 氧化铋的化学气相沉积 |
Country Status (8)
Country | Link |
---|---|
US (1) | US4965093A (zh) |
EP (1) | EP0353461B1 (zh) |
JP (1) | JPH0255245A (zh) |
KR (1) | KR900001612A (zh) |
CN (1) | CN1039625A (zh) |
DE (1) | DE68908505T2 (zh) |
ES (1) | ES2045275T3 (zh) |
ZA (1) | ZA894576B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110305354A (zh) * | 2019-07-08 | 2019-10-08 | 安徽省蚌埠华益导电膜玻璃有限公司 | 一种pet膜形成炫彩膜的镀膜方法及其在玻璃盖板中的应用 |
CN110420650A (zh) * | 2019-07-26 | 2019-11-08 | 北京理工大学 | 一种核壳结构Bi/BiOBr复合材料的制备方法 |
CN112323143A (zh) * | 2020-10-14 | 2021-02-05 | 南京理工大学 | 一种化学气相沉积制备二维氧化铋纳米片的方法 |
Families Citing this family (9)
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US5237447A (en) * | 1992-08-27 | 1993-08-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Alkali metal for ultraviolet band-pass filter |
US5344211A (en) * | 1993-08-05 | 1994-09-06 | Riyaz Adat | Adjustable backrest |
US5811191A (en) * | 1994-12-27 | 1998-09-22 | Ppg Industries, Inc. | Multilayer antireflective coating with a graded base layer |
US5744215A (en) * | 1996-01-04 | 1998-04-28 | Ppg Industries, Inc. | Reduction of haze in transparent coatings |
US7118726B2 (en) * | 2002-12-13 | 2006-10-10 | Clark Manufacturing, Llc | Method for making oxide compounds |
JP2007063095A (ja) * | 2005-09-01 | 2007-03-15 | Sumitomo Electric Ind Ltd | ガラス体製造方法及び光ファイバ |
US8199264B2 (en) * | 2007-11-26 | 2012-06-12 | Guardian Industries Corp. | Ruggedized switchable glazing comprising a liquid crystal inclusive layer and a multi-layer low-E ultraviolet blocking coating |
US9333728B2 (en) * | 2007-11-06 | 2016-05-10 | Guardian Industries Corp. | Ruggedized switchable glazing, and/or method of making the same |
US9517721B2 (en) | 2014-08-22 | 2016-12-13 | Guardian Industries Corp. | Vehicle sunroof with switchable glazing and side-firing light emitting diodes |
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USRE25767E (en) * | 1958-03-05 | 1965-04-27 | Treating glass sheets | |
US3107177A (en) * | 1960-01-29 | 1963-10-15 | Pittsburgh Plate Glass Co | Method of applying an electroconductive tin oxide film and composition therefor |
US3710074A (en) * | 1970-10-08 | 1973-01-09 | Ppg Industries Inc | Electrically heated multiple glazed window having an iridescence masking film |
US3677814A (en) * | 1970-10-26 | 1972-07-18 | Ppg Industries Inc | Process for forming electroconductive tin oxide films by pyrolyzation of alkyl and aryl tin fluorides |
US3808035A (en) * | 1970-12-09 | 1974-04-30 | M Stelter | Deposition of single or multiple layers on substrates from dilute gas sweep to produce optical components, electro-optical components, and the like |
US4069630A (en) * | 1976-03-31 | 1978-01-24 | Ppg Industries, Inc. | Heat reflecting window |
US4206252A (en) * | 1977-04-04 | 1980-06-03 | Gordon Roy G | Deposition method for coating glass and the like |
US4187336A (en) * | 1977-04-04 | 1980-02-05 | Gordon Roy G | Non-iridescent glass structures |
US4308316A (en) * | 1977-04-04 | 1981-12-29 | Gordon Roy G | Non-iridescent glass structures |
US4263335A (en) * | 1978-07-26 | 1981-04-21 | Ppg Industries, Inc. | Airless spray method for depositing electroconductive tin oxide coatings |
JPS5841720A (ja) * | 1981-09-02 | 1983-03-11 | Nippon Soda Co Ltd | 金属酸化被膜形成組成物 |
US4377613A (en) * | 1981-09-14 | 1983-03-22 | Gordon Roy G | Non-iridescent glass structures |
DE3211753C2 (de) * | 1982-03-30 | 1985-03-28 | Interpane Entwicklungs- und Beratungsgesellschaft mbH & Co. KG, 3471 Lauenförde | Hochtransparenter, in Durch- als auch Außenansicht neutral wirkender und wärmedämmender Belag für ein Substrat aus transparentem Material sowie Verwendung des Belages |
JPS6217099A (ja) * | 1985-07-16 | 1987-01-26 | Kokusai Denshin Denwa Co Ltd <Kdd> | ビスマス含有酸化物単結晶の製造方法 |
JPH068509B2 (ja) * | 1985-09-17 | 1994-02-02 | 勝 岡田 | 強誘電体薄膜の製造方法 |
-
1988
- 1988-07-05 US US07/219,693 patent/US4965093A/en not_active Expired - Fee Related
-
1989
- 1989-06-15 ZA ZA894576A patent/ZA894576B/xx unknown
- 1989-06-30 EP EP89111888A patent/EP0353461B1/en not_active Expired - Lifetime
- 1989-06-30 DE DE89111888T patent/DE68908505T2/de not_active Expired - Fee Related
- 1989-06-30 ES ES89111888T patent/ES2045275T3/es not_active Expired - Lifetime
- 1989-07-04 KR KR1019890009505A patent/KR900001612A/ko not_active Application Discontinuation
- 1989-07-04 JP JP1171344A patent/JPH0255245A/ja active Pending
- 1989-07-05 CN CN89104552A patent/CN1039625A/zh active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110305354A (zh) * | 2019-07-08 | 2019-10-08 | 安徽省蚌埠华益导电膜玻璃有限公司 | 一种pet膜形成炫彩膜的镀膜方法及其在玻璃盖板中的应用 |
CN110305354B (zh) * | 2019-07-08 | 2021-10-01 | 凯盛科技股份有限公司蚌埠华益分公司 | 一种pet膜形成炫彩膜的镀膜方法及其在玻璃盖板中的应用 |
CN110420650A (zh) * | 2019-07-26 | 2019-11-08 | 北京理工大学 | 一种核壳结构Bi/BiOBr复合材料的制备方法 |
CN112323143A (zh) * | 2020-10-14 | 2021-02-05 | 南京理工大学 | 一种化学气相沉积制备二维氧化铋纳米片的方法 |
CN112323143B (zh) * | 2020-10-14 | 2021-12-28 | 南京理工大学 | 一种化学气相沉积制备二维氧化铋纳米片的方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH0255245A (ja) | 1990-02-23 |
ZA894576B (en) | 1991-02-27 |
KR900001612A (ko) | 1990-02-27 |
US4965093A (en) | 1990-10-23 |
EP0353461B1 (en) | 1993-08-18 |
DE68908505D1 (de) | 1993-09-23 |
EP0353461A1 (en) | 1990-02-07 |
DE68908505T2 (de) | 1994-03-03 |
ES2045275T3 (es) | 1994-01-16 |
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