JPH0874071A - Structure with glass film fused to thermally sprayed layer - Google Patents
Structure with glass film fused to thermally sprayed layerInfo
- Publication number
- JPH0874071A JPH0874071A JP25265794A JP25265794A JPH0874071A JP H0874071 A JPH0874071 A JP H0874071A JP 25265794 A JP25265794 A JP 25265794A JP 25265794 A JP25265794 A JP 25265794A JP H0874071 A JPH0874071 A JP H0874071A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fused
- sprayed layer
- film
- glass film
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 44
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011651 chromium Substances 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 229910019830 Cr2 O3 Inorganic materials 0.000 abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000156 glass melt Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶射層にガラス膜が融
着した構造体に関わり、さらに詳しくは、腐食性の液
体、あるいは高温の腐食性ガス、酸化性ガスが不透過性
の溶射被膜構造体に係わるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure in which a glass film is fused to a sprayed layer. More specifically, the sprayed film is impermeable to corrosive liquids, high temperature corrosive gases, or oxidizing gases. It relates to a coating structure.
【０００２】[0002]
【従来の技術】溶射被膜には本来気孔が存在する。いか
に密度の高い方法でも気孔は存在する。したがってでき
た気孔をいかに封孔するか、これが今までの課題であ
る。封孔の有力な手段としてガラスがけがある。これは
溶射面にガラス粉末を溶射して溶融する方法、あるいは
ホーローの様にガラス粉末を塗布して溶融する方法であ
る。従来の方法の問題点は、溶射膜には本来気孔が存在
するために、このガスが抜けずに残って、ここから被膜
が剥離したり、あるいはピンホールとなったり、あるい
は大きな寸法のものでは熱膨張の調整がうまく行かずに
ガラス膜に割れが発生することである。したがって、こ
の結果、ガラス被膜が腐食、酸化に対して保護被膜とし
て作用し得ず、溶射膜あるいは溶射膜の下の母材が根こ
そぎ腐食して剥離するような事態が発生している。2. Description of the Related Art Porosity is inherent in a thermal spray coating. Pores are present no matter how dense the method is. Therefore, how to seal the created pores has been a challenge so far. Glass glazing is a powerful means of sealing. This is a method of spraying and melting glass powder on the sprayed surface, or a method of coating and melting glass powder like enamel. The problem with the conventional method is that since the sprayed film originally has pores, this gas does not escape and the film peels off from this, or becomes a pinhole, or in the case of a large size. This means that the thermal expansion cannot be adjusted properly and cracks occur in the glass film. Therefore, as a result, the glass coating cannot act as a protective coating against corrosion and oxidation, and the sprayed coating or the base material under the sprayed coating is uprooted and peeled off.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、かかる状況
に鑑みてなされたもので、その目的とするところは、溶
射層に対して腐食、酸化に対して十分な保護機能を持
つ、しかも大きな寸法のものにも十分な保護機能を持つ
溶射層とガラスの新しい融着構造体を提供せんとするも
のである。SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object thereof is to have a sufficient protection function against corrosion and oxidation with respect to a thermal sprayed layer, and yet to provide a large scale. It is intended to provide a new fused structure of a sprayed layer and glass having a sufficient protection function even for a size.
【０００４】[0004]
【課題を解決するための手段】上記問題点は次の手段に
よって解決できる。すなわち、The above problems can be solved by the following means. That is,
【０００５】１．金属あるいはセラミックの溶射層の上
にガラス膜が融着した構造体であって、該ガラス膜はガ
ラス融着時に加熱生成されたＣｒ２Ｏ３、あるいはＣｒ
２Ｏ３の複酸化物を含んでなることを特徴とする溶射層
にガラス膜が融着した構造体。1. A structure in which a glass film is fused on a metal or ceramic sprayed layer, the glass film being Cr 2 O 3 or Cr produced by heating during glass fusion.
A structure in which a glass film is fused to a thermal sprayed layer, which comprises a double oxide of 2 O 3 .
【０００６】[0006]
【作用】本来溶射膜には無数の気孔が存在し、ガラスが
溶融するさい、気孔に閉じ込められた空気は完全に抜け
難い。また、凹凸が激しくて表面積が大きいために、被
膜が厚くなる欠点がある。また、溶融ガラスの溶射膜に
対する濡れ性にも問題がある。この結果、被膜の中に気
泡が残り、これが膜の剥離、あるいはピンホールを誘発
し、従来からの溶射膜にガラス掛けするのは難しい問題
である。Function: There are innumerable pores in the sprayed film, and when the glass melts, the air trapped in the pores is difficult to completely escape. In addition, there is a drawback that the coating becomes thick due to the large unevenness and the large surface area. There is also a problem in the wettability of the molten glass with respect to the sprayed film. As a result, air bubbles remain in the coating, which induces peeling of the coating or pinholes, and it is a difficult problem to glass the conventional sprayed coating.
【０００７】本発明者は、ガラス被膜の中に、ガラス融
着時にＣｒ２Ｏ３、あるいはＣｒ２Ｏ３の複酸化物を生
成する成分を添加すると、薄くて気泡のない、連続被膜
が形成されることを見出だした。The present inventor adds a component which forms Cr 2 O 3 or a double oxide of Cr 2 O 3 during glass fusion to the glass coating to form a thin and bubble-free continuous coating. I was found to be done.
【０００８】Ｃｒ２Ｏ３あるいはＣｒ２Ｏ３の複酸化物
を生成する成分は、可溶性クロム化合物が最も好まし
い。つまり上記Ｃｒ２Ｏ３あるいはＣｒ２Ｏ３の複酸化
物の供給源として使用した、クロム酸、クロム塩酸、二
クロム塩酸、クロム塩および可溶性錯体クロム化合物等
であり、これらは水等の溶媒にとかして使用する。例え
ば、ＣｒＯ３の水溶液、ＣｒＯ３の水溶液にＺｎＯ、Ｍ
ｇＯ、ＣａＯ等の酸化物を溶解した形で、ＣｒＣｌ２、
Ｃｒ２（ＳＯ４）３等の水溶液の形で使用できる。これ
らの中では、ＣｒＯ３の水溶液、ＣｒＯ３の水溶液にＺ
ｎＯ、ＭｇＯ、ＣａＯ等酸化物を溶解した水溶液が最も
好ましい結果をもたらす。とりわけＣｒＯ３の水溶液に
ＺｎＯあるいはＣａＯを加えたもの、あるいはＺｎＯと
ＣａＯを混合して加えたものが良い。The component which forms Cr 2 O 3 or the double oxide of Cr 2 O 3 is most preferably a soluble chromium compound. That is, chromic acid, chromic hydrochloric acid, dichromic hydrochloric acid, chrome salts and soluble complex chrome compounds, etc. used as the source of the above-mentioned Cr 2 O 3 or Cr 2 O 3 complex oxides, which are used in a solvent such as water. Use it as a comb. For example, an aqueous solution of CrO 3, ZnO in an aqueous solution of CrO 3, M
In a form in which oxides such as gO and CaO are dissolved, CrCl 2 ,
It can be used in the form of an aqueous solution of Cr 2 (SO 4 ) 3 . Among these, ZO was added to the CrO 3 aqueous solution and CrO 3 aqueous solution.
Aqueous solutions of oxides such as nO, MgO and CaO provide the most favorable results. Particularly, a solution obtained by adding ZnO or CaO to an aqueous solution of CrO 3 or a mixture obtained by mixing ZnO and CaO is preferable.
【０００９】添加割合は、微量から飽和状態まで適宜添
加してよいが最も好ましいのは、ＣｒＯ３１モルに対し
てＺｎＯを０．２モルから溶解限度まで添加したもの、
あるいはＺｎＯとＣａＯを混ぜて０．２モルから溶解限
度まで添加したものである。The addition ratio may be appropriately added from a trace amount to a saturated state, but the most preferable one is ZnO added from 0.2 mol to the solubility limit with respect to 1 mol of CrO 3 .
Alternatively, ZnO and CaO are mixed and added from 0.2 mol to the solubility limit.
【００１０】上記したような可溶性クロム化合物の添加
により、ガラスは溶射膜の凹凸面に沿って濡れて、極め
て薄い連続膜を形成する。これは微量添加（ガラスに対
して１％程度の添加）でも効果が現れる。濡れがよく、
薄い被膜を形成できることにより、中に気泡の残存もな
く、欠陥のない連続膜が形成されるものと推察される。By the addition of the soluble chromium compound as described above, the glass gets wet along the uneven surface of the sprayed film to form an extremely thin continuous film. This is effective even when added in a small amount (about 1% to glass). Well wet,
It is speculated that the ability to form a thin coating allows the formation of a continuous film having no defects and no defects inside.
【００１１】ガラス層は溶射の凹凸面をすべて埋め尽く
す程厚くする必要はない。本発明では、凹凸の谷の一部
が埋まり峰の突起部が一部残っていても、この突起部も
ガラスで濡れて薄い連続被膜で被覆されており十分な耐
蝕性がある。熱疲労、熱応力および大型の寸法のものに
はこの被膜のほうが好ましい。The glass layer does not have to be thick enough to completely fill the uneven surface of the thermal spray. In the present invention, even if a part of the valleys of the unevenness is buried and a part of the protrusion of the peak remains, this protrusion is also wet with glass and covered with a thin continuous film, and thus has sufficient corrosion resistance. This coating is preferred for thermal fatigue, thermal stress and large dimensions.
【００１２】なお、ここで溶射材料にはセラミック、金
属いずれも使用でき特別な制約はないが、金属を使用す
る場合、本発明の溶射膜は少なくともガラス溶融時の酸
化を防ぐことが目的であり、この目的のためにはＡＬ、
Ｃｒ、Ｓｉ、Ｙ等に代表される耐酸化性元素を含有する
合金が好ましい。Ｆｅ、Ｎｉ、Ｃｏ基で、必須成分とし
てＡＬ、Ｃｒ、Ｓｉ、Ｙ等の耐酸化性元素の一種あるい
は二種以上を含む合金が好ましい。本発明のガラス成分
はこれらの元素を含む溶射合金に対して極めて濡れが良
く、緻密で密着性の良いガラス膜の連続膜が形成され
る。It should be noted that ceramics or metals can be used as the thermal spraying material and there is no particular limitation. However, when a metal is used, the thermal spraying film of the present invention is intended to prevent at least oxidation during glass melting. , For this purpose AL,
An alloy containing an oxidation resistant element represented by Cr, Si, Y or the like is preferable. An alloy containing Fe, Ni, and Co bases and containing one or more of oxidation resistant elements such as AL, Cr, Si, and Y as essential components is preferable. The glass component of the present invention has extremely good wettability with respect to the thermal spray alloy containing these elements, and forms a continuous film of a glass film that is dense and has good adhesion.
【００１３】ガラス膜の形成には目標成分に溶製した粉
末あるいは各成分の粉末を調合して混合したものを結合
剤の溶液と混ぜてスラリーあるいはペースト状にしたも
のを基材に塗布して加熱する。使用するガラスの成分
は、目的用途に応じて適宜色々な成分を選択できるが、
ただ、使用に際して融着させる基材の熱膨張係数と同じ
か、あるいは若干小さめに調整することが好ましい。In order to form a glass film, powder prepared by melting the target components or powders of each component are mixed and mixed with a binder solution to form a slurry or paste, which is applied to a substrate. To heat. The components of the glass used can be appropriately selected from various components according to the intended use,
However, it is preferable to adjust the thermal expansion coefficient to be the same as or slightly smaller than the thermal expansion coefficient of the base material to be fused during use.
【００１４】本発明のガラス融着膜は低温から高温まで
の腐食性ガス、および腐食性液体に対して十分な抵抗力
を有するので、これらの雰囲気で使用される部材には特
に威力を発揮する。Since the glass fusing film of the present invention has sufficient resistance to corrosive gases and corrosive liquids from low temperatures to high temperatures, it is particularly effective for members used in these atmospheres. .
【００１５】[0015]
【実施例】実施例によって本発明を説明する。The present invention will be described with reference to examples.
【００１６】 基材：φ２０×５０ｍｍの軟鋼の表面をショットブラス
トして粗面化した後、下記成分（ｗｔ．％）の合金粉末
を０．３ｍｍの厚さで溶射した。 Ｃ ： ０．１５ Ｓｉ： ２．０ Ｍｎ： １．０ Ｎｉ： ０．５ Ｃｒ：２７．０ Ｍｏ： ３．０ ＡＬ： ７．０ Ｆｅ：Ｂａｌ． ＜ガラス被膜＞線膨張係数１０．５×１０−６、適性焼
成温度が８５０℃のガラスフリット粉末に下記組成のバ
インダーを混ぜて作ったペーストを溶射膜の上に下地が
透けて見えるほど薄く塗布した。 ＜バインダーの組成＞水４重量部にＣｒＯ３５重量部を
加えて作ったクロム酸溶液にＺｎＯを飽和状態まで溶か
した溶液。 ＜ペーストの組成＞ガラス粉末１．５重量部、上記バイ
ンダー１．０重量部を混合したもの。常温で乾燥した
後、９００℃まで５時間かけて昇温、９００℃で３０分
保持して炉冷した。溶射の凹凸面は茶褐色の薄いガラス
膜でコートされ、谷の部分が一部ガラスで埋まってい
た。 ＜評価テスト＞ガラスの被覆されたサンプルの両端面に
樹脂を塗布してマスキングしたものを１０％塩酸溶液に
浸漬した。１０日間放置したが液はまったく着色しなか
った。比較のために上記した溶射のみのサンプルについ
てもテストした。この場合、浸漬と同時に溶解が始ま
り、１日で液が濃い緑色に変色し、５日後は真っ黒くな
った。溶射膜も手でぼろぼろ剥げた。Base material: A surface of mild steel of φ20 × 50 mm was shot-blasted to roughen it, and then alloy powder of the following components (wt.%) Was sprayed to a thickness of 0.3 mm. C: 0.15 Si: 2.0 Mn: 1.0 Ni: 0.5 Cr: 27.0 Mo: 3.0 AL: 7.0 Fe: Bal. <Glass coating> A paste made by mixing a glass frit powder with a linear expansion coefficient of 10.5 x 10 -6 and an appropriate firing temperature of 850 ° C with a binder having the following composition is applied thinly on the thermal spray coating so that the underlying layer can be seen through. did. <Binder composition> A solution in which ZnO is dissolved to a saturated state in a chromic acid solution prepared by adding 5 parts by weight of CrO 3 to 4 parts by weight of water. <Composition of paste> A mixture of 1.5 parts by weight of glass powder and 1.0 part by weight of the binder. After drying at room temperature, the temperature was raised to 900 ° C. over 5 hours, and the temperature was kept at 900 ° C. for 30 minutes to cool the furnace. The uneven surface of the thermal spray was coated with a thin brown glass film, and the valleys were partially filled with glass. <Evaluation Test> The glass-covered sample was dipped in a 10% hydrochloric acid solution which was coated with resin and masked. After leaving for 10 days, the liquid was not colored at all. For comparison, the spray only sample described above was also tested. In this case, dissolution started at the same time as immersion, and the liquid turned dark green in one day, and became black after 5 days. The sprayed film was also shaved off by hand.
【００１７】（急速加熱、急速冷却の例） ＜基材＞φ２０×５０ｍｍの軟鋼の表面をブラストで粗
化し、Ｎｉ−７％ＡＬ合金を０．３ｍｍの厚さで溶射し
たもの。 ＜ガラス被覆＞実施例のガラスペーストを溶射膜の上
にやや厚め（実施例よりは）に塗布し、乾燥後、９０
０℃に加熱した電気炉の中に入れて３０分保持し、ただ
ちに炉から外に取り出した。ガラス溶融被膜が形成され
た。ガラス膜に割れはなかった。 ＜評価テスト＞実施例と同じく、サンプルの両端面に
樹脂を塗布してマスキングしたものを濃塩酸の蒸気が充
満した密閉容器の中につるし、３ケ月放置したが、まっ
たく腐食されなかった。(Example of rapid heating and rapid cooling) <Substrate> A surface of mild steel of φ20 × 50 mm is roughened by blasting, and a Ni-7% AL alloy is sprayed to a thickness of 0.3 mm. <Glass coating> The glass paste of the example is applied on the sprayed film to be slightly thicker (than the example), and after drying, 90
It was placed in an electric furnace heated to 0 ° C., held for 30 minutes, and immediately taken out of the furnace. A glass melt coating was formed. There was no crack in the glass film. <Evaluation Test> As in the example, the sample was coated with resin on both end faces and masked, and the sample was hung in a closed container filled with vapor of concentrated hydrochloric acid and left for 3 months, but was not corroded at all.
【００１８】[0018]
【発明の効果】以上詳記したように本発明は溶射膜の上
に欠陥のないガラスの溶融膜を形成したものであり、腐
食性ガス、腐食性液体に対して顕著な耐蝕性を発揮す
る。高価な材料を使用しなくても高度な耐蝕性が期待で
き、腐食部材の分野で多大な貢献が期待できるものであ
る。As described above in detail, the present invention forms a defect-free glass melt film on a sprayed film, and exhibits remarkable corrosion resistance to corrosive gas and corrosive liquid. . A high degree of corrosion resistance can be expected without using expensive materials, and a great contribution can be expected in the field of corrosive members.
Claims (1)
ガラス膜が融着した構造体であって、該ガラス膜はガラ
ス融着時に加熱生成されたＣｒ２Ｏ３、あるいはＣｒ２
Ｏ３の複酸化物を含んでなることを特徴とする溶射層に
ガラス膜が融着した構造体。1. A structure in which a glass film is fusion-bonded on a metal or ceramic sprayed layer, the glass film being Cr 2 O 3 or Cr 2 generated by heating during glass fusion.
A structure in which a glass film is fusion-bonded to a thermal sprayed layer, which is characterized by containing a double oxide of O 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25265794A JPH0874071A (en) | 1994-09-09 | 1994-09-09 | Structure with glass film fused to thermally sprayed layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25265794A JPH0874071A (en) | 1994-09-09 | 1994-09-09 | Structure with glass film fused to thermally sprayed layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0874071A true JPH0874071A (en) | 1996-03-19 |
Family
ID=17240412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25265794A Pending JPH0874071A (en) | 1994-09-09 | 1994-09-09 | Structure with glass film fused to thermally sprayed layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0874071A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007242668A (en) * | 2006-03-06 | 2007-09-20 | Tokyo Electron Ltd | Processing equipment |
-
1994
- 1994-09-09 JP JP25265794A patent/JPH0874071A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007242668A (en) * | 2006-03-06 | 2007-09-20 | Tokyo Electron Ltd | Processing equipment |
| US8173928B2 (en) | 2006-03-06 | 2012-05-08 | Tokyo Electron Limited | Processing device |
| US8785809B2 (en) | 2006-03-06 | 2014-07-22 | Tokyo Electron Limited | Processing device |
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