JPH0713292B2 - Composite thermal spray coating with excellent resistance to molten zinc - Google Patents
Composite thermal spray coating with excellent resistance to molten zincInfo
- Publication number
- JPH0713292B2 JPH0713292B2 JP3031448A JP3144891A JPH0713292B2 JP H0713292 B2 JPH0713292 B2 JP H0713292B2 JP 3031448 A JP3031448 A JP 3031448A JP 3144891 A JP3144891 A JP 3144891A JP H0713292 B2 JPH0713292 B2 JP H0713292B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- thermal spray
- aluminum
- zinc
- spray coating
- 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.)
- Expired - Lifetime
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、複合溶射皮膜, とくに
連続式溶融亜鉛めっき装置のシンクロールなどの表面に
溶射して用いるときに有用な耐溶融亜鉛性に優れる複合
溶射皮膜に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite sprayed coating, and more particularly to a composite sprayed coating having excellent hot-dip zinc resistance which is useful when sprayed onto the surface of a sink roll of a continuous galvanizing apparatus. .
【０００２】本発明にかかる複合溶射皮膜は、溶融亜鉛
−アルミニウム合金めっき装置のシリンダー, サポート
ロール, あるいはガイドロールなどのように、亜鉛−ア
ルミニウム合金溶湯と接触する部材（浴用部材）に対し
ても有用である。The composite sprayed coating according to the present invention can be applied to a member (bath member) which comes into contact with a molten zinc-aluminum alloy, such as a cylinder, a support roll, or a guide roll of a molten zinc-aluminum alloy plating apparatus. It is useful.
【０００３】[0003]
【従来の技術】さて、前記浴用部材というのは、溶融亜
鉛めっき浴中に浸漬されるか、溶融亜鉛が飛散して付着
しやすい箇所に設置してあるか、または溶融亜鉛が付着
した高温のめっき鋼板と接触する場所で使われるもので
ある。2. Description of the Related Art The above-mentioned bath members are either immersed in a hot dip galvanizing bath, installed at a location where the hot dip zinc is likely to be scattered and adhered, or hot baths to which hot dip zinc adheres. It is used in places where it comes into contact with plated steel sheets.
【０００４】このような背景から、かかる浴用部材とい
うのは、(1) 溶融亜鉛による侵食が起こり難いこと、
(2) 通板材（鋼板）と接触しても摩耗しにくいこと、
(3) 付着した溶融亜鉛の剥離ならびに保守点検が容易な
こと、(4) ロールとしての寿命が長く低いコストである
こと、そして、(5) 高温の溶融亜鉛浴中に浸漬した際の
熱衝撃によく耐えること、などの性能が要求されるもの
である。From such a background, such a bath member is (1) that corrosion by molten zinc is unlikely to occur,
(2) It is hard to wear even if it comes into contact with the strip material (steel plate),
(3) Easy removal of molten zinc adhered and maintenance inspection, (4) Long life as a roll and low cost, and (5) Thermal shock when immersed in hot molten zinc bath. It is required to withstand such a problem well.
【０００５】ところで、従来使用されているめっき浴用
ロールや軸受構成部品、例えばブッシュ, ベアリング,
カラー, エンドボールなどの部材としては、(1) 表面に
JIS H8303 (1976) 制定のCo基自溶性合金を溶射したも
の、(2) 特開昭61−117260号公報に開示のような、ZrO2
とAl2O3からなるセラミックス皮膜を溶射したもの、(3)
特公昭58−37386 号公報に開示のように、WC, Cr3C2,T
iC の１種または２種以上に対し、Ni, Siの如き熱間耐
食性金属またはこれらの酸化物を共存させてなる 0.1〜
2.4 mm厚さの皮膜を主として溶射したもの、などがあ
る。By the way, conventionally used plating bath rolls and bearing components such as bushes, bearings,
As a member such as color and end ball, (1) on the surface
A sprayed Co-based self-fluxing alloy established by JIS H8303 (1976), (2) ZrO 2 as disclosed in JP-A-61-117260
And a ceramic coating consisting of Al 2 O 3 and (3)
As disclosed in Japanese Patent Publication No. 58-37386, WC, Cr 3 C 2 , T
0.1 to 1 in which a hot-corrosion resistant metal such as Ni or Si or an oxide thereof is coexistent with one or more kinds of iC.
For example, a coating with a thickness of 2.4 mm is mainly sprayed.
【０００６】[0006]
【発明が解決しようとする課題】前述の例示から判るよ
うに、従来の溶融亜鉛めっき浴用部材、とくにその表面
に被覆した皮膜は、耐溶融亜鉛性に優れた皮膜材料の
改良、皮膜密着性の向上、皮膜の緻密性の向上、
皮膜表面粗さの制御、などを研究開発の対象としてお
り、もちろんそれらの皮膜についても十分に改善の効果
があった。As can be seen from the above-mentioned examples, conventional members for hot dip galvanizing baths, in particular, films coated on the surface of the members are improved in film material excellent in hot dip galvanization resistance and improved in film adhesion. Improvement, improvement of film denseness,
The target of research and development is the control of film surface roughness, and of course, these films were also sufficiently improved.
【０００７】しかしながら、前記各従来技術は、昨今の
溶融亜鉛めっき鋼板の需要拡大に伴うめっきプラントの
稼働率の向上、およびめっき鋼板自身の品質向上の要求
により、より一層耐溶融亜鉛性能に優れた皮膜の開発要
請に対して、十分に応えられるものと言えるまでには至
っていないのが実情である。However, the above-mentioned respective prior arts are more excellent in the hot-dip galvanizing performance because of the demand for the improvement of the operating rate of the plating plant accompanying the recent increase in demand for hot-dip galvanized steel sheets and the quality improvement of the galvanized steel sheets themselves. The reality is that we have not yet been able to say that we can fully meet the demand for film development.
【０００８】本発明の目的は、めっき浴用部材などに被
覆して用いられ溶射皮膜について、それの耐溶融亜鉛性
や耐熱衝撃性を改善することにある。An object of the present invention is to improve the hot-dip zinc resistance and thermal shock resistance of a sprayed coating used by coating a member for a plating bath or the like.
【０００９】[0009]
【課題を解決するための手段】本発明者らの研究による
と、Alを含む溶融亜鉛めっき浴中へ非酸化物系セラミッ
クスの溶射皮膜を浸漬すると、セラミックス溶射皮膜の
表面層付近にAlが選択的に濃縮し、高濃度のAl−Zn合金
層を形成することが判った。そして、溶射皮膜表面にか
ような高濃度Al−Zn合金層が形成されると、皮膜内部へ
のめっき浴中からの亜鉛の拡散速度が極端に低下する現
象を発見した。According to the research conducted by the present inventors, when a thermal spray coating of a non-oxide ceramic is immersed in a hot dip galvanizing bath containing Al, Al is selected near the surface layer of the ceramic thermal spray coating. It was found that the Al-Zn alloy layer of high concentration was formed by the effective concentration. Then, when such a high-concentration Al-Zn alloy layer was formed on the surface of the sprayed coating, a phenomenon that the diffusion rate of zinc from the plating bath into the coating was extremely decreased was discovered.
【００１０】このことから本発明者らは、溶射皮膜にあ
らかじめ高濃度Al層を形成させておけば、優れた耐溶融
亜鉛皮膜となるのではないかと考え、非酸化物系セラミ
ックスの溶射皮膜形成後、溶射法あるいは蒸着法など
によってAlあるいはAl−Zn合金を被覆させた後これを加
熱拡散させる、Al粉末あるいはAl−Zn合金粉末を主成
分とする粉体中で加熱拡散する、高濃度Al−Zn合金溶
湯中に一定時間浸漬させること、などの方法によって、
溶射皮膜の表面に高濃度Al層を形成させ、いわゆる皮膜
構造を複合化させることによって耐溶融亜鉛性に優れた
皮膜構造を形成させることとしたのである。From this, the present inventors believe that if a high-concentration Al layer is formed in advance on the thermal spray coating, it will be an excellent molten zinc resistant coating, and the thermal spray coating of non-oxide ceramics is formed. After that, by coating the Al or Al-Zn alloy by a thermal spraying method or a vapor deposition method and then diffusing it by heating, by heat diffusing in a powder containing Al powder or Al-Zn alloy powder as a main component, high concentration Al -By immersing it in the molten Zn alloy for a certain time,
A high-concentration Al layer was formed on the surface of the thermal spray coating, and a so-called coating structure was compounded to form a coating structure excellent in molten zinc resistance.
【００１１】[0011]
【作用】本発明は、鉄系基材の表面に溶射被覆して用い
る皮膜、例えば非酸化物系セラミックスを主成分として
金属を混合してなるサーメット、または非酸化物系セラ
ミックスの溶射皮膜について、これらの溶射皮膜表面に
AlまたはAl−Zn合金を拡散浸透させて複合溶射皮膜とし
たものである。すなわち、炭化物, 硼化物およびそれら
を含むサーメットの溶射皮膜の表面に、次のような方法
によってAlまたはAl−Zn合金の拡散浸透層を形成させる
ものである。The present invention relates to a coating used by thermal spray coating on the surface of an iron-based base material, for example, a cermet obtained by mixing a metal containing a non-oxide ceramic as a main component, or a thermal spray coating of a non-oxide ceramic. On the surface of these spray coatings
A composite thermal spray coating is obtained by diffusing and penetrating Al or Al-Zn alloy. That is, a diffusion permeation layer of Al or Al-Zn alloy is formed on the surface of carbide, boride and the sprayed coating of cermet containing them by the following method.
【００１２】(1) 非酸化物系セラミックスまたはそれに
金属を混合してなるサーメットの溶射皮膜上に、Alまた
はAl−Zn合金を溶射した後、これを高温で加熱すること
によってAlまたはAl−Zn合金を内部へ拡散浸透させる、
(2) 非酸化物系セラミックスまたは同系のサーメットの
溶射皮膜を、Alを含む（例えば５％）亜鉛浴中に２〜３
日程度浸漬し、皮膜表面にAlを濃縮させてから、本来の
亜鉛浴（通常Alを 0.1〜0.3 ％を含む) 中で使用する、
(3) 非酸化物系セラミックスまたは同系のサーメットの
溶射皮膜を、Al粉末を主成分とする粉体中( 例えばAl粉
末60重量％, Al2O3 粉末40重量％) またはAl−Zn合金粉
末を主成分とする粉体中（例えばAl50−Zn50重量％合金
粉末60重量％, Al2O3 粉末38重量％, NH4Cl ２重量％）
に埋没させ、アルゴンガス雰囲気中で 300〜700 ℃で数
時間加熱する。(1) After spraying an Al or Al-Zn alloy on a sprayed coating of a cermet obtained by mixing a non-oxide ceramic or a metal with the same, heating the Al or Al-Zn alloy at a high temperature to produce Al or Al-Zn. Diffuse and penetrate the alloy inside,
(2) Apply a non-oxide ceramics or thermal spray coating of cermet of the same type in a zinc bath containing Al (for example, 5%) for 2-3 times.
After soaking for about a day to concentrate Al on the surface of the film, use it in the original zinc bath (usually containing 0.1 to 0.3% Al),
(3) Non-oxide ceramics or thermal spray coating of cermet of the same type, in powder containing Al powder as the main component (for example, Al powder 60% by weight, Al 2 O 3 powder 40% by weight) or Al-Zn alloy powder. powder in which a main component (for example, Al50-Zn50 wt% alloy powder 60 wt%, Al 2 O 3 powder 38 wt%, NH 4 Cl 2 wt%)
Immerse it in a vacuum bath and heat it in an argon gas atmosphere at 300 to 700 ° C for several hours.
【００１３】このような方法によって、非酸化物系セラ
ミックスなどの溶射皮膜表面層付近には、AlあるいはAl
−Zn合金の拡散浸透層およびAlが付着しただけの未拡散
層が形成される。特に、前記(2) の方法では高濃度Al−
Zn合金の拡散層とともに多量のZnも付着した付着Zn層も
形成される。なお、前記Al未拡散層や付着Zn層について
は、機械的に除去してもよいが、そのままの状態で溶融
亜鉛浴中で使用したとしても、表面のAlやZn成分は浴中
へ直ちに拡散消滅するので、めっき作業に支障を来すよ
うなことはない。By such a method, Al or Al is formed near the surface layer of the sprayed coating of non-oxide ceramics or the like.
-A diffused permeation layer of Zn alloy and an undiffused layer with only Al attached are formed. Particularly, in the method of (2) above, high concentration Al-
An attached Zn layer in which a large amount of Zn is also attached is formed together with the diffusion layer of the Zn alloy. The Al non-diffused layer and the adhered Zn layer may be mechanically removed, but even if they are used in the molten zinc bath as they are, the Al and Zn components on the surface immediately diffuse into the bath. Since it disappears, it does not hinder the plating work.
【００１４】さて、このようにして形成された複合溶射
皮膜中のAl拡散層は、溶融亜鉛浴中に浸漬されると、亜
鉛の侵入によって直ちに高濃度Al−Zn合金層に変化す
る。このAl−Zn合金層の融点は、溶融亜鉛めっきの操業
温度（通常 460〜490 ℃) より高いため、常に固相状態
で存在し、以後の亜鉛の拡散浸透速度を極端に遅らすよ
うに作用する。また、複合溶射皮膜中のAl−Zn合金拡散
層は、溶融亜鉛浴中に浸漬されると、高濃度Al−Zn合金
層の状態を維持して常に固相状態で存在し、以後の亜鉛
の拡散浸透速度を遅らすように作用する。Now, when the Al diffusion layer in the composite sprayed coating thus formed is immersed in the molten zinc bath, it immediately changes into a high-concentration Al-Zn alloy layer due to the penetration of zinc. Since the melting point of this Al-Zn alloy layer is higher than the operating temperature of hot dip galvanizing (usually 460 to 490 ° C), it always exists in the solid state and acts to extremely slow the diffusion and penetration rate of zinc thereafter. . Further, the Al-Zn alloy diffusion layer in the composite sprayed coating, when immersed in the molten zinc bath, maintains the state of the high-concentration Al-Zn alloy layer and always exists in the solid phase state. It acts to slow the rate of diffusion and penetration.
【００１５】本発明者らの知見によれば、 480℃の純亜
鉛中に、WC(88 wt%)−Co(12wt%) 溶射皮膜 100μｍ厚の
部材を浸漬すると、亜鉛は約10日で皮膜を貫通するが、
溶射皮膜表面にAl濃度が10〜20wt％であるAl拡散層を形
成しておくと、上記皮膜貫通期間は 130〜150 日に達
し、Al濃度が30〜40％のAl拡散層ができていると1000日
以上にもなる。According to the knowledge of the present inventors, when a WC (88 wt%)-Co (12 wt%) thermal spray coating 100 μm thick member is immersed in pure zinc at 480 ° C., the zinc film is formed in about 10 days. Through the
If an Al diffusion layer with an Al concentration of 10 to 20 wt% is formed on the surface of the thermal spray coating, the coating penetration period reaches 130 to 150 days, and an Al diffusion layer with an Al concentration of 30 to 40% is formed. And more than 1000 days.
【００１６】本発明の前記複合溶射皮膜への溶融亜鉛の
拡散は、主としてこの溶射皮膜を構成している金属成分
(この場合はCo) を溶解しながら、溶射に伴う積層粒子
の粒界をぬって侵入するが、その侵入経路にAl (あらか
じめ拡散させておいた）が存在していると、上記溶融亜
鉛は容易にAlと合金化する。このことは、上述の亜鉛の
侵入を妨げ、その侵入の速度を著しく遅らせることにな
る。なお、非酸化物系セラミックス粒子そのものは、溶
融亜鉛に対し強い抵抗力を有しており、侵食されること
のないものである。Diffusion of molten zinc into the composite sprayed coating of the present invention is mainly due to the metal components constituting this sprayed coating.
While melting (Co in this case), it penetrates through the grain boundaries of the laminated particles due to thermal spraying, but if Al (previously diffused) exists in the penetration path, the above-mentioned molten zinc will Easily alloys with Al. This hinders the penetration of zinc mentioned above and significantly slows down its penetration rate. The non-oxide ceramic particles themselves have a strong resistance to molten zinc and are not corroded.
【００１７】また、前述のようにしてAlまたはAl−Zn合
金を拡散浸透させた非酸化物系セラミックスなどの複合
溶射皮膜は、靭性にも優れるので、溶融亜鉛浴への浸漬
や引き上げ時に受ける熱衝撃に対しても強く、溶射皮膜
特有の局部剥離現象が改善される効果がある。Further, since the composite thermal spray coating of non-oxide ceramics or the like in which Al or Al-Zn alloy is diffused and permeated as described above is excellent in toughness, heat applied during immersion in the molten zinc bath or pulling up It is also resistant to impact and has the effect of improving the local delamination phenomenon peculiar to thermal spray coatings.
【００１８】本発明の複合溶射皮膜を形成するのに用い
られる溶射材料は、非酸化物系セラミックスが好適であ
り、例えば、Cr3C2 やTiC, ZrC, WC, WTiC2, B4C, NbC
などの炭化物、また、CrB2, TiB2あるいはZrB2などの硼
化物が好適である。The thermal spray material used to form the composite thermal spray coating of the present invention is preferably a non-oxide ceramic, such as Cr 3 C 2 or TiC, ZrC, WC, WTiC 2 , B 4 C, NbC
Carbides such as, and boride such as CrB 2 , TiB 2 or ZrB 2 are suitable.
【００１９】その他、本発明で用いる溶射材料として
は、サーメットも有効であり、例えば炭化物や硼化物
に、Co, NiおよびCrなどの一種以上の金属を混合したも
のが有効である。In addition, as the thermal spray material used in the present invention, cermet is also effective, for example, a material in which one or more metals such as Co, Ni and Cr are mixed with carbide or boride is effective.
【００２０】次に、鉄系基材, 例えば鋼製のめっき浴シ
ンクロールの表面に、本発明の前記溶射皮膜を形成する
には、酸素−水素, 酸素−炭化水素などの燃焼または爆
発エネルギーを利用する溶射法、Ar, H2,N2, Heなどの
ガスプラズマを熱源とする溶射法などが好適である。Next, in order to form the thermal spray coating of the present invention on the surface of a ferrous base material, for example, a steel plating bath sink roll, combustion or explosion energy of oxygen-hydrogen, oxygen-hydrocarbon, etc. is used. A spraying method to be used, a spraying method using a gas plasma of Ar, H 2 , N 2 , He or the like as a heat source are suitable.
【００２１】なお、前述のようにしてシンクロール表面
に溶射被覆した溶射皮膜に対して、本発明では上述のよ
うな方法によってAlの拡散浸透を行うが、この処理につ
いてはAlの純度に特に制約はなく、Al−Ni, Al−Si, Al
−Fe, Al−Znなどの合金を用いても、本発明の意図する
Alの拡散浸透層が得られる。In the present invention, Al is diffused and permeated by the above-described method with respect to the thermal spray coating formed by thermal spray coating on the surface of the sink roll as described above, but the purity of Al is limited in this treatment. Not Al-Ni, Al-Si, Al
The use of alloys such as --Fe and Al--Zn is not intended to
An Al diffusion layer is obtained.
【００２２】[0022]
【実施例】実施例１ 本発明にかかる複合溶射皮膜の耐溶融亜鉛性を調査する
ため、軟鋼試験片（直径15mm×長さ 200mm) の表面に 1
00μｍ厚溶射皮膜を形成し、これを 480℃の溶融亜鉛浴
中に10日間浸漬して引き上げることにより、皮膜の外観
変化および皮膜への亜鉛の侵入深さ試験を行った。比較
のため、単なる溶射皮膜, 自溶合金皮膜(JIS 8303,ＭＳ
ＦCo１）、Al2O3 を 100μｍ厚に溶射した皮膜について
も併せて調査した。各供試皮膜の組成は次のとおりであ
る。（ ）内の数字は重量％を示す。 (1) WC(88)−Co(12) (2) WC(83)−Co(17) (3) WTiC2(85) −Ni(10)−Co(5) (4) WC(63)−Cr3C2(20) −Co(17) (5) Cr3C2(75) −Ni(20)−Cr(5) Example 1 In order to investigate the molten zinc resistance of the composite thermal spray coating according to the present invention, a 1 piece was applied to the surface of a mild steel test piece (diameter 15 mm × length 200 mm).
A 00 μm thick sprayed coating was formed, and this was immersed in a molten zinc bath at 480 ° C. for 10 days and then pulled up to perform a change in the appearance of the coating and a penetration depth test of zinc into the coating. For comparison, mere thermal spray coating, self-fluxing alloy coating (JIS 8303, MS
The coatings of FCo1) and Al 2 O 3 sprayed to a thickness of 100 μm were also investigated. The composition of each test film is as follows. Numbers in parentheses indicate% by weight. (1) WC (88) −Co (12) (2) WC (83) −Co (17) (3) WTiC 2 (85) −Ni (10) −Co (5) (4) WC (63) − Cr 3 C 2 (20) −Co (17) (5) Cr 3 C 2 (75) −Ni (20) −Cr (5)
【００２３】試験は、上記の(1) 〜(5) の組成の溶射皮
膜を形成した後、次のようなAlの拡散処理を施すことに
より、本発明複合溶射皮膜を得て行った。 (1) 溶射皮膜上に30μｍのAlを溶射し、これをアルゴン
ガス雰囲気中で 700℃, ２時間加熱した。（以下、これ
を「Al拡散法」という） (2) Alを５％含む溶融亜鉛浴(490℃) 中に３日間浸漬し
て引き上げた。（以下、これを「浸漬法」という） (3) Al粉体中に試験片を埋没させ、アルゴンガス雰囲気
中で 700℃, ２時間加熱した。（以下、これを「パック
法」という）The test was carried out by forming a sprayed coating having the above-mentioned compositions (1) to (5) and then subjecting it to the following diffusion treatment of Al to obtain the composite sprayed coating of the present invention. (1) 30 μm of Al was sprayed on the sprayed coating, and this was heated in an argon gas atmosphere at 700 ° C. for 2 hours. (Hereinafter, this is referred to as "Al diffusion method".) (2) Immersed in a molten zinc bath (490 ° C) containing 5% of Al for 3 days and pulled up. (Hereinafter, this is referred to as “immersion method”.) (3) A test piece was immersed in Al powder and heated in an argon gas atmosphere at 700 ° C. for 2 hours. (Hereinafter, this is called the "pack method")
【００２４】表１は、これらの供試皮膜の実験結果を要
約したものである。比較例の自溶合金皮膜( No.11)は、
局部的に溶融亜鉛による侵食を受けて母材が露出し、母
材成分と亜鉛の反応生成物（Fe−Zn合金）が成長し、こ
れにさらに亜鉛が付着し、コブ状を呈していた。Al2O3
皮膜（No.12)も、溶融亜鉛が完全に貫通するとともに、
皮膜が局部的に破壊されていた。また、炭化物サーメッ
トの溶射皮膜 (No.6〜No.10)は、溶融亜鉛の侵食による
破壊は認められないものの、亜鉛は完全に皮膜を貫通
し、その先端は母材の表面に達していた。Table 1 summarizes the experimental results for these test coatings. The self-fluxing alloy film (No. 11) of the comparative example is
The base material was locally exposed to corrosion by molten zinc, and a reaction product of the base material component and zinc (Fe-Zn alloy) grew, and further zinc adhered to the base material, forming a bump shape. Al 2 O 3
The coating (No. 12) also penetrates the molten zinc completely,
The film was locally destroyed. In addition, although the thermal spray coating of carbide cermet (No.6 to No.10) did not show any damage due to the erosion of molten zinc, zinc completely penetrated the coating and the tip reached the surface of the base metal. ..
【００２５】これに対し本発明に係る複合溶射皮膜の場
合は、いずれも亜鉛の侵入は表面から10μｍ程度にとど
まり、外観状態に全く異常は認められず、健全であっ
た。On the other hand, in the case of the composite thermal spray coating according to the present invention, the penetration of zinc was only about 10 μm from the surface, and no abnormality was observed in the external appearance, which was sound.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例２ 実施例１で供試した溶射皮膜試験片（本発明例, 比較
例）を用いて、 480℃に維持した溶融亜鉛浴中へ１時間
浸漬し、その後これを引き上げて圧縮空気を溶射皮膜面
へ吹付けて室温 (25℃) まで冷却した。この操作を20回
繰返した後の各溶射皮膜の外観状況、特に皮膜の剥離状
況を調べ、それぞれの溶射皮膜の熱衝撃性能の比較試験
を行った。Example 2 Using the thermal spray coating test piece (invention example, comparative example) tested in Example 1, it was immersed in a molten zinc bath maintained at 480 ° C. for 1 hour and then pulled up and compressed. Air was blown onto the surface of the thermal spray coating to cool it to room temperature (25 ° C). After repeating this operation 20 times, the appearance of each spray coating, especially the peeling status of the coating, was examined, and a comparative test of the thermal shock performance of each spray coating was performed.
【００２８】表２は、その試験結果をまとめたものであ
る。比較例の皮膜（No.6〜No.12)では、熱衝撃によって
皮膜が母材から局部的に剥離するものが多く、特にAl2O
3 (No.12) は全体の32％にもおよび、炭化物サーメット
皮膜(No.６〜No.10)でも4.0〜7.9 ％の剥離が認めら
れ、耐溶融亜鉛性にすぐれていても、母材との密着性に
乏しいという一般的な溶射皮膜の特性がよく顕れてい
る。この点、自溶合金皮膜(No.11) については、その剥
離が３％にとどまっているが、亜鉛浴から引き上げた際
に多量の亜鉛が皮膜成分との合金化反応によって表面に
付着し、これによって皮膜の剥離が抑制されていたにす
ぎず、このことは表面の清浄化が要求される溶融亜鉛め
っき用の皮膜としては適当でないことを意味している。Table 2 is a summary of the test results. Many of the films (No. 6 to No. 12) of the comparative example are locally peeled from the base material due to thermal shock, especially Al 2 O.
3 (No. 12) accounts for 32% of the total, and 4.0 to 7.9% of peeling is observed even in the carbide cermet coating (No. 6 to No. 10), and even if it has excellent molten zinc resistance, it is a base material. The characteristic of a general thermal spray coating, which is poor in adhesion with, is well manifested. In this respect, the self-fluxing alloy film (No. 11) had only 3% peeling, but when pulled up from the zinc bath, a large amount of zinc adhered to the surface due to the alloying reaction with the film components, This only suppressed the peeling of the coating, which means that it is not suitable as a coating for hot dip galvanizing where surface cleaning is required.
【００２９】これに対し、本発明複合溶射皮膜は、いず
れも炭化物サーメット溶射皮膜へのAlの拡散によって母
材との密着性が向上し、殆ど剥離するものがなく、良好
な状態を維持しており、耐熱衝撃性に優れていることが
判明した。On the other hand, in all of the composite thermal spray coatings of the present invention, the adhesion to the base material is improved due to the diffusion of Al into the carbide cermet thermal spray coating, and there is almost no peeling and a good state is maintained. It was found that the thermal shock resistance was excellent.
【００３０】[0030]
【表２】 [Table 2]
【００３１】実施例３ この実施例では、軟鋼試験片（直径15×長さ 200mm) 上
に、CrB2, ZrB2, TiB2, Cr3C2 を、それぞれ 100μｍに
なるように、アルゴンガス雰囲気中でプラズマ溶射し、
その後この試験片をAl拡散法、Al浸漬法、Alパッ
ク法によって、それぞれAlを拡散浸透させ、 480℃の亜
鉛浴中で20日間浸漬する試験を行った。その後、各試験
片を引き上げ、実施例１と同じ要領によって複合溶射皮
膜の耐溶融亜鉛性を調査した。また、比較例として、Al
を拡散させないCrB2, ZrB2, TiB2, Cr3C2 溶射皮膜を用
いた。その結果を表３に示すが、比較例の CrB2, ZrB2,
TiB2, Cr3C2 溶射皮膜（No.6〜No.10)でも良好な耐溶融
亜鉛性を示すが、皮膜の欠陥部( 貫通孔) から亜鉛が侵
入し、皮膜の局部剥離が散見された。Example 3 In this example, CrB 2 , ZrB 2 , TiB 2 and Cr 3 C 2 were each placed on a mild steel test piece (diameter 15 × length 200 mm) in an argon gas atmosphere so as to have a thickness of 100 μm. Plasma sprayed inside,
Then, a test was conducted in which this test piece was diffusively impregnated with Al by the Al diffusion method, the Al dipping method, and the Al pack method, and immersed in a zinc bath at 480 ° C for 20 days. Then, each test piece was pulled up, and the molten zinc resistance of the composite sprayed coating was investigated in the same manner as in Example 1. As a comparative example, Al
We used CrB 2 , ZrB 2 , TiB 2 , and Cr 3 C 2 sprayed coatings that do not diffuse the alloy. The results are shown in Table 3, and the results of the comparative examples CrB 2 , ZrB 2 ,
The TiB 2 and Cr 3 C 2 sprayed coatings (No. 6 to No. 10) also show good resistance to molten zinc, but zinc penetrates through defective portions (through holes) of the coating, and localized peeling of the coating is observed. It was
【００３２】これに対し、本発明の複合溶射皮膜は、い
ずれも亜鉛の侵入が少ない上、皮膜の外観は全く変化せ
ず、良好な状態を維持していた。On the other hand, in each of the composite sprayed coatings of the present invention, the zinc penetration was small, and the appearance of the coating did not change at all, maintaining a good state.
【００３３】[0033]
【表３】 [Table 3]
【００３４】実施例４ 軟鋼試験片（直径15×長さ200mm)上に、WC(88)−Co(12)
材料を 200μｍ厚に溶射して溶射試験片とし、その後こ
の溶射試験片をアルミニウム含有量を５〜95wt％の範囲
内で変化させたAl−Zn合金粉末中( ただし、その他の成
分としてAl2O3 39wt％, NH4Cl １wt％を含む）に埋没さ
せ、アルゴンガス雰囲気中の 630℃２時間の条件で加熱
するパック法により、試験片の前記溶射皮膜表面にAl−
Zn合金拡散層を形成させた。その後、 0.1重量％のAlを
含む溶融亜鉛(480℃) 中に30日間浸漬した後、引き上
げ、皮膜表面の外観を観察することによって耐溶融亜鉛
性を評価した。また、実施例１と同じ比較例の皮膜を同
時に調査した。Example 4 WC (88) -Co (12) was placed on a mild steel test piece (diameter 15 x length 200 mm).
And spraying the test piece by spraying the material into 200μm thickness, after which the spraying test piece in Al-Zn alloy powder was varied in the range of aluminum content of 5 to 95 wt% (however, Al 2 O Other components ( Including 39 wt% and NH 4 Cl 1 wt%), and heat-treated under the condition of 630 ° C. for 2 hours in an argon gas atmosphere by a pack method, and the Al-
A Zn alloy diffusion layer was formed. After that, the molten zinc resistance was evaluated by immersing it in molten zinc (480 ° C.) containing 0.1% by weight of Al for 30 days, then pulling it up and observing the appearance of the coating surface. In addition, the films of the same comparative examples as in Example 1 were simultaneously investigated.
【００３５】表４は、これらの供試溶射皮膜の実験結果
を示したものである。比較例の自溶合金（No.13)は、局
部的に亜鉛の侵食を激しく受けて母材が露出し、母材成
分と亜鉛の反応生成物（Fe−Zn合金）が成長し、さらに
これに亜鉛が多量に付着し、自溶合金皮膜を直接観察す
ることができなかった。そこで、試験片を切断し、皮膜
を断面から観察したところ、溶射皮膜は局部的に完全に
消失し、その部分では母材自体も深く侵食されていた。
Al2O3 皮膜（No.14)は完全に消失し、炭化物サーメット
皮膜( No.8〜12) にも、溶融亜鉛の侵食による微小な局
部的破壊が認められた。Table 4 shows the experimental results of these test spray coatings. In the self-fluxing alloy of the comparative example (No. 13), the base metal was exposed by the strong local erosion of zinc, and the reaction product of the base metal component and zinc (Fe-Zn alloy) grew. It was impossible to directly observe the self-fluxing alloy film because a large amount of zinc adhered to the. Then, when the test piece was cut and the coating was observed from the cross section, the spray coating locally disappeared completely, and the base metal itself was deeply eroded at that portion.
The Al 2 O 3 coating (No. 14) disappeared completely, and the carbide cermet coating (No. 8 to 12) was also found to have minute local destruction due to the erosion of molten zinc.
【００３６】これに対し、本発明の複合溶射皮膜は、亜
鉛の付着は認められるものの、皮膜そのものは健全な状
態を維持していた。特にAl(10)−Zn(90)合金以上のAlを
含むものは外観は極めて平滑であった。このような結果
から、Al−Zn合金におけるAl含有量は10％以上の合金が
適切であることが判明した。On the other hand, in the composite sprayed coating of the present invention, although the adhesion of zinc was recognized, the coating itself maintained a healthy state. In particular, the appearance of Al (10) -Zn (90) alloys or more containing Al was extremely smooth. From these results, it was found that an Al-Zn alloy having an Al content of 10% or more is suitable.
【００３７】[0037]
【表４】 [Table 4]
【００３８】実施例５ 図１に示した連続溶融亜鉛めっき装置（１…溶融亜鉛
浴, ２…シンクロール, ３…サポートロール, ４…めっ
き用鋼板, ５…ガイドロール, ６…噴射ノズル）のシン
クロール（材質 JIS G3445 (1983) ＳＴＫＭ13Ａ）に、
高速ガス炎溶射法によってWC(88)−Co(12)皮膜を 150μ
ｍ形成し、その後Alパック法, Al浸漬法によって本
発明の複合溶射皮膜を形成したロール各１本を準備し
た。Example 5 of the continuous hot-dip galvanizing apparatus (1 ... hot-dip zinc bath, 2 ... sink roll, 3 ... support roll, 4 ... plating steel plate, 5 ... guide roll, 6 ... jet nozzle) shown in FIG. To the sink roll (material JIS G3445 (1983) STKM13A),
WC (88) -Co (12) coating 150μ by high speed gas flame spraying method
Then, one roll each having the composite sprayed coating of the present invention formed thereon by the Al pack method and the Al dipping method was prepared.
【００３９】その後、本発明の複合溶射皮膜形成ロール
を、Alを0.11％含む 480℃の溶融亜鉛浴を用いて連続溶
融亜鉛めっき鋼板の製造に供し、2 カ月間使用した。そ
の結果、本発明の複合溶射皮膜形成ロールは、めっき鋼
板の品質に悪影響を与えず、長期連続運転に耐え、皮膜
も健全であった。After that, the composite sprayed coating forming roll of the present invention was used for the production of continuous hot-dip galvanized steel sheet using a hot dip galvanizing bath containing 0.11% Al at 480 ° C. and used for 2 months. As a result, the composite sprayed coating forming roll of the present invention did not adversely affect the quality of the plated steel sheet, withstood long-term continuous operation, and the coating was sound.
【００４０】なお、従来のWC(88)−Co(12)の溶射皮膜だ
けの実績では、１カ月程度の連続運転には耐えるが、皮
膜の局部剥離や、剥離部における母材質の溶融亜鉛によ
る侵食現象が認められており、この意味で本発明の複合
溶射皮膜形成ロールの優位性が確認できた。In the past, only the conventional sprayed coating of WC (88) -Co (12) can withstand continuous operation for about one month, but local peeling of the coating and molten zinc as the base material in the peeling portion An erosion phenomenon was recognized, and in this sense, the superiority of the composite sprayed coating forming roll of the present invention could be confirmed.
【００４１】[0041]
【発明の効果】以上説明したように本発明複合溶射皮膜
は、炭化物, 硼化物およびそれらのサーメット溶射皮膜
表面に対し、拡散浸透法や溶融金属中浸漬法などによっ
てAl成分を拡散させることによって、溶融亜鉛中におい
て優れた耐溶融亜鉛性と耐熱衝撃性とを発揮した。その
結果、溶融亜鉛めっき鋼板の長期連続製造作業が可能と
なり、設備の保守点検費の節減, 生産コストの低減が期
待できる。しかも、皮膜のロール材質の保護作用によっ
て、ロール成分の溶融亜鉛中への溶出を防ぐことができ
るため、溶融金属の汚染が防止でき、品質のよいめっき
鋼板の生産に大きな効果が期待できる。As described above, the composite sprayed coating of the present invention is obtained by diffusing an Al component by a diffusion infiltration method or a molten metal dipping method with respect to carbide, boride and their cermet sprayed coating surfaces. Excellent molten zinc resistance and thermal shock resistance were exhibited in molten zinc. As a result, long-term continuous production of hot-dip galvanized steel sheet becomes possible, which can be expected to reduce equipment maintenance and inspection costs and production costs. Moreover, the protective action of the roll material of the film can prevent the roll components from being eluted into the molten zinc, so that the contamination of the molten metal can be prevented, and a great effect can be expected in the production of a plated steel sheet of good quality.
【図１】図１は、溶融亜鉛めっき浴槽およびこれに付属
する各種ロール類、部材の配設状態の模式図である。FIG. 1 is a schematic view of a hot dip galvanizing bath and various rolls and members attached thereto, which are arranged.
１ 溶融亜鉛浴 ２ シンクロール ３ サポートロール ４ めっき用鋼板 ５ ガイドロール ６ 噴射ノズル 1 molten zinc bath 2 sink roll 3 support roll 4 steel plate for plating 5 guide roll 6 injection nozzle
Claims (4)
覆して用いる溶射被膜表面に、アルミニウムまたはアル
ミニウム−亜鉛合金の拡散浸透層を設けてなる耐溶融亜
鉛性に優れる複合溶射皮膜。1. A composite thermal spray coating having excellent resistance to molten zinc, which is formed by providing a diffusion coating layer of aluminum or an aluminum-zinc alloy on the surface of the thermal spray coating that is used by coating the surface of an iron-based substrate that is brought into contact with molten zinc.
皮膜は、WC, Cr3C2,TiC, WTiC2, B4C, NbC, およびZrC
のいずれか１種以上の炭化物、CrB2, TiB2, およびZrB2
のいずれか１種以上である硼化物、または炭化物もしく
は硼化物にCo, NiおよびCrのいずれか１種以上の金属を
混合してなるサーメットである請求項１に記載の複合溶
射皮膜。2. The sprayed coating for diffusing and penetrating aluminum comprises WC, Cr 3 C 2 , TiC, WTiC 2 , B 4 C, NbC, and ZrC.
Any one or more of carbides, CrB 2 , TiB 2 , and ZrB 2
2. The composite thermal spray coating according to claim 1, which is a cermet obtained by mixing any one or more kinds of boride, or a carbide or boride with one or more kinds of metals of Co, Ni and Cr.
アルミニウム−亜鉛合金成分の拡散が、アルミニウムま
たはアルミニウム−亜鉛合金を含む金属の加熱拡散、ア
ルミニウムを含む溶融亜鉛中への浸漬、もしくはアルミ
ニウムまたはアルミニウム−亜鉛合金を含む粉体中にお
ける加熱拡散処理によって得られたものであることを特
徴とする請求項１に記載の複合溶射皮膜。3. The diffusion of aluminum or an aluminum-zinc alloy component into the thermal spray coating is carried out by heat diffusion of a metal containing aluminum or an aluminum-zinc alloy, immersion in molten zinc containing aluminum, or aluminum or aluminum-zinc. The composite thermal spray coating according to claim 1, which is obtained by a heat diffusion treatment in a powder containing an alloy.
アルミニウムを重量％で10％以上含むものである請求項
１に記載の拡散浸透層である複合溶射皮膜。4. The composition of the aluminum-zinc alloy is:
The composite thermal spray coating as a diffusion / permeation layer according to claim 1, which contains 10% by weight or more of aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3031448A JPH0713292B2 (en) | 1991-02-01 | 1991-02-01 | Composite thermal spray coating with excellent resistance to molten zinc |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3031448A JPH0713292B2 (en) | 1991-02-01 | 1991-02-01 | Composite thermal spray coating with excellent resistance to molten zinc |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04254571A JPH04254571A (en) | 1992-09-09 |
| JPH0713292B2 true JPH0713292B2 (en) | 1995-02-15 |
Family
ID=12331540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3031448A Expired - Lifetime JPH0713292B2 (en) | 1991-02-01 | 1991-02-01 | Composite thermal spray coating with excellent resistance to molten zinc |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713292B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2962973B2 (en) * | 1993-08-09 | 1999-10-12 | 滲透工業株式会社 | Hot dip galvanizing equipment materials |
| GB2313847B (en) * | 1995-03-08 | 1998-12-09 | Tocalo Co Ltd | Member having composite coating and process for producing the same |
| JP2004346395A (en) * | 2003-05-23 | 2004-12-09 | Praxair St Technology Inc | Thermal spraying material of excellent molten metal erosion resistance, and member for molten metal bath |
| ITRM20030602A1 (en) * | 2003-12-24 | 2005-06-25 | Ct Sviluppo Materiali Spa | MULTILAYER COATING PRODUCTION PROCEDURE |
-
1991
- 1991-02-01 JP JP3031448A patent/JPH0713292B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04254571A (en) | 1992-09-09 |
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