JP4408649B2 - Dipping member for hot metal plating baths with excellent dross resistance - Google Patents
Dipping member for hot metal plating baths with excellent dross resistance Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、溶融亜鉛めっき装置に配設される溶融亜鉛めっき浴中に浸漬されて使用されるシンクロールやサポートロール等の浴中ロール等、溶融金属めっき浴浸漬部材に係り、とくに溶融金属めっき浴浸漬部材の耐ドロス付着性の改善に関する。
【０００２】
【従来の技術】
鋼材に溶融亜鉛めっき処理を行う溶融亜鉛めっき装置では、鋼材の搬送・支持のために溶融亜鉛めっき浴にシンクロールやサポートロール等の浴中ロールや溶融亜鉛を輸送するポンプ等が設けられている。これら溶融亜鉛めっき浴浸漬部材は、高温の溶融亜鉛めっき浴中に長時間浸漬状態で使用されるため、まず溶融亜鉛による侵食が起こりにくい材料であること、搬送される鋼材と接触しても摩耗しにくいこと、等が要求されている。
【０００３】
このような要求に対し、例えば浴中ロールの外周面に耐溶融亜鉛侵食性を有する被覆層を設けることが行われている。被覆層としては、ＷＣ−Coサーメットのような溶射皮膜が用いられている。ＷＣ−Coサーメット溶射皮膜は、耐溶融亜鉛侵食性を有する材料であることから、浴中ロールの保護にはある程度有効である。しかし、ＷＣ−Coサーメット溶射皮膜を表面に被覆した浴中ロールでは、広義のドロスと呼ばれる金属間化合物が付着・成長しやすいという問題があった。これは、例えば、非特許文献１に記載されているように、ＷＣ−Coサーメット溶射皮膜中に結合相として存在するβ−Co相が溶出し、溶射皮膜に亜鉛が浸入・付着しやすくなり耐久性が低下することによると推察される。
【０００４】
このような問題に対し、例えば、特許文献１には、ＷＣ−Coサーメット溶射皮膜の表面に、クロム酸化物と窒化物との混合物焼成皮膜を形成すると共に、溶射皮膜の表層付近に存在する微小気孔中にクロム酸化物と窒化物との混合物の焼成微粒子を充填した溶融金属めっき浴用ロール部材が提案されている。
また、特許文献２には、タングステンほう化物を１〜50wt％含有し、金属相としてNi、Co、Mo、Crのうち１種または２種以上を３〜25wt％含有し、残部タングステン炭化物と不可避不純物よりなる溶射皮膜を形成し、該溶射皮膜にクロム酸を主成分とした処理液で含浸処理を行い、ついで焼成処理を行う溶融金属浴用浸漬部材の製造方法が記載されている。特許文献２に記載された技術では、耐溶融金属侵食性を改善させる観点から、金属相はCo、Niを主とし、Mo、Crの１種または２種は15％以下とすることがよいとしている。
【０００５】
【特許文献１】
特開2000-54096号公報
【特許文献２】
特許第3080651 号公報
【非特許文献１】
富田友樹他４名、「溶融純亜鉛中におけるＷＣ／Ｃｏサーメット溶射皮膜の耐久性」、鉄と鋼、第７８年（1992）第４号、ｐ．608 〜615
【０００６】
【発明の解決しようとする課題】
通常、浴中ロールにドロス等が付着した場合には、浴中ロールの酸洗を実施してドロスを除去している。このため、浴中ロールには耐溶融亜鉛侵食性に加えてさらに、耐酸腐食性に優れることが要求されている。しかし、特許文献２に記載された技術で使用するＷＣ−Co系溶射皮膜は、耐酸腐食性が十分でなく、酸洗した場合、皮膜が侵食され皮膜の剥離が発生するという問題があった。
【０００７】
また、特許文献１に記載された技術では、部材表面に溶射皮膜の形成に加えて、さらに焼成皮膜を形成しており、被覆層の形成のために複雑な工程を必要とするため、製造コストの高騰を招くという問題があった。
本発明は、上記した従来技術の問題を有利に解決し、耐溶融金属侵食性、耐ドロス付着性、および耐酸腐食性に優れた溶融金属めっき浴浸漬部材を提案することを目的とする。なお、本発明でいう「耐ドロス付着性」とは、シンクロール等の溶融金属めっき浴浸漬部材表面に、溶融金属が付着・浸入し、金属間化合物を形成し成長して、ドロス付着に至ることを抑制・防止する特性をいうものとする。
【０００８】
【課題を解決するための手段】
本発明者らは、上記した課題を達成するために、溶融金属を溶融亜鉛として、溶融亜鉛めっき浴浸漬部材であるシンクロールの耐ドロス付着性に及ぼす被覆層の種類の影響について鋭意検討した。その結果、被覆層を、Coより高い融点の高融点金属または高融点金属の合金を結合相としセラミックスを含有する溶射皮膜とすることにより、耐溶融亜鉛腐食性、耐酸腐食性及び耐ドロス付着性がともに優れた被覆層となることを知見した。
【０００９】
本発明は、これらの知見に基づいて、さらに検討を加えて完成したものである。すなわち、本発明は、溶融金属めっき浴に浸漬されて使用される溶融金属めっき浴浸漬部材であって、該溶融金属めっき浴浸漬部材の表面に被覆層として、Coより高い融点を有する高融点金属に、セラミックスを50〜90質量％分散してなる皮膜を有し、前記高融点金属が、Ta、Ｖ、Mo、Zr、Nb、Hf、Ｗのうちから選ばれた１種、またはTa、Ｖ、Mo、Zr、Nb、Hf、Ｗのうちから選ばれた２種以上からなる合金であり、前記セラミックスが、酸化物、窒化物、炭化物、珪化物のうちから選ばれた１種または２種以上であることを特徴とする耐ドロス付着性に優れた溶融金属めっき浴浸漬部材であり、また、本発明では、前記セラミックスが、酸化物としてZrO2、窒化物としてNbN 、炭化物としてWC、TiC 、珪化物としてWSi のうちから選ばれた１種または２種以上であることが好ましい。また、本発明では、前記溶融金属めっき浴浸漬部材が浴中ロールであることが好ましい。
【００１１】
【発明の実施の形態】
本発明の溶融金属めっき浴浸漬部材は、溶融金属めっき浴に浸漬されて使用される、好ましくは浴中ロールであり、表面に被覆層として、Coより高い融点を有する高融点金属に、セラミックスを50〜90質量％分散してなる皮膜を有する。皮膜の形成は、プラズマ溶射法、あるいは、高速フレーム溶射法とすることが好ましい。
【００１２】
Coより高い融点の高融点金属は、非常に安定な金属または合金であり、溶融金属や酸に対し安定で腐食されにくい特性と、ドロスが付着しにくい特性を有している。そして、皮膜中の結合相としての役割を果たす。なお、Coより高い融点の高融点金属は、皮膜中で15質量％超えとすることが好ましい。15質量％以下では、結合相としての量が不足するため、被膜の密着力が低下するとともに、皮膜としての耐溶融金属腐食性、耐酸腐食性、耐ドロス付着性が低下する。
【００１３】
Coより高い融点の高融点金属としては、Ta、Ｖ、Mo、Zr、Nb、Hf、Ｗのうちから選ばれた１種、またはTa、Ｖ、Mo、Zr、Nb、Hf、Ｗのうちから選ばれた２種以上からなる合金とし、なかでもMo、Ｗとすることが好ましい。
また、皮膜中に分散するセラミックスは、酸化物、窒化物、炭化物、珪化物のうちから選ばれた１種または２種以上とすることが好ましい。これらセラミックスは、硬度が高く耐摩耗性に優れる特性を有するとともに、溶融金属との濡れ性および反応性が低く、またドロス付着性も低い。なお、酸化物としてはZrO2、Al2O3 、Y2O3等が、窒化物としてはBN、AlN 、NbN 等が、炭化物としてはCr3C2 、WC、TiC 等が、珪化物としてはTiSi、ZrSi、WSi 等が、それぞれ好ましい。
【００１４】
セラミックスは、皮膜中に、50〜90質量％分散して含有される。セラミックスの含有量が50質量％未満では、皮膜中のセラミックス量が少なく、皮膜の硬さが不足し、被めっき板との接触により皮膜の摩耗進行が著しくなり、溶融金属めっき浴浸漬部材としての耐摩耗性が低下する。一方、90質量％を超える場合には、皮膜中のセラミックス量が多くなり過ぎ耐熱衝撃性が低下し、皮膜剥離の危険性が増大する。なお、好ましくは、皮膜中のセラミックス含有量は65〜85質量％である。
【００１５】
本発明の溶融金属めっき浴浸漬部材表面の皮膜は、表面被覆用材料（溶射材料）を、好ましくは高速フレーム溶射法（HVAF(High Velocity Aero Fuel) 溶射法、HVOF(High Velocity Oxgen Fuel)溶射法）、プラズマ溶射法あるいは爆発溶射法を用い溶射して形成することが好ましい。皮膜を形成する溶融金属めっき浴浸漬部材表面は、皮膜密着性向上のために予め基材の粗面化、清浄化等の通常の処理を施すことはいうまでもない。
【００１６】
つぎに、本発明の溶融金属めっき浴浸漬部材表面の皮膜形成用として、好ましい表面被覆用材料について説明する。
本発明の溶融金属めっき浴浸漬部材表面被覆用材料は、Coより高い融点の高融点金属粉末に、セラミックス粉末を50〜90質量％混合、あるいはCoより高い融点の高融点金属粉末とセラミックス粉末とを混合し造粒してなる溶射材料である。
【００１７】
表面被覆用材料中に混合される高融点金属粉末は、溶射皮膜を形成したときにセラミックスを結合する作用を有する金属相となる粉末である。Coより高い融点の高融点金属粉末の配合量は、表面被覆用材料全量に対し15質量％超えとすることが好ましい。15質量％以下では、溶射皮膜の密着性が不足する。なお、Coより高い融点の高融点金属粉末としては、Ta、Ｖ、Mo、Zr、Nb、Hf、Ｗのうちから選ばれた１種の粉末、またはTa、Ｖ、Mo、Zr、Nb、Hf、Ｗのうちから選ばれた２種以上からなる合金粉末とすることが好ましい。なかでもMo、Ｗの粉末がより好ましい。
【００１８】
また、表面被覆用材料中に混合されるセラミックス粉末は、酸化物、窒化物、炭化物、硼化物、珪化物のうちから選ばれた１種または２種以上の粉末とすることが好ましい。セラミックス粉末は、表面被覆用材料全量に対し、50〜90質量％混合する。セラミックス粉末の混合量が50質量％未満では、溶融金属めっき浴浸漬部材の表面に形成される被覆層（溶射皮膜）中のセラミックス量が少なく、被覆層（溶射皮膜）の硬さが不足し、被めっき板との接触により被覆層（溶射皮膜）の摩耗の進行が著しくなり、溶融金属めっき浴浸漬部材としての耐摩耗性が低下する。一方、90質量％を超える混合は、形成される被覆層（溶射皮膜）中のセラミックス量が多くなり過ぎ耐熱衝撃性が低下し、被覆層の剥離の危険性が増大する。
【００１９】
なお、酸化物としてはZrO2、Al2O3 、Y2O3等が、窒化物としてはBN、AlN 、NbN 等が、炭化物としてはCr3C2 、WC、TiC 等が、珪化物としてはTiSi、ZrSi、WSi 等が、それぞれ好ましい。
【００２０】
【実施例】
溶融亜鉛めっき浴浸漬部材としてのシンクロール用試験片（材質：SUS316L ，大きさ：10mmφ×100mm 長さ）表面に、表１に示す組成の皮膜となるように、結合相としての金属（バインダー金属）粉末とセラミックス粉末とを、造粒して製造した表面被覆材料（溶射材料）を用いて、プラズマ溶射法で溶射し、皮膜（皮膜厚さ：100 μｍ）を形成した。なお、試験片No. １はＷＣ−Coサーメット溶射皮膜を形成した従来例である。
【００２１】
得られた試験片について、ドロス付着試験、溶融金属腐食試験、酸腐食試験、熱衝撃試験、硬さ試験を実施した。試験方法は次のとおりとした。
（１）ドロス付着試験
得られた試験片を、溶融亜鉛めっき浴（浴組成：Zn−２％Al、浴温度：470 ℃）中に２週間浸漬した。浸漬後、試験片の被覆断面を光学顕微鏡（倍率：200 倍）で観察し、皮膜表面に形成されたドロスの厚みを測定し、ドロス付着量（mm）として、耐ドロス付着性を評価した。なお、ドロス付着量が0.10mm以下を◎、0.10mm超〜0.30mm以下を○、0.30mm超0.50mm以下を△、0.50mm超を×とした。
（２）溶融金属腐食試験
得られた試験片を、溶融亜鉛めっき浴（浴組成：100 ％Zn、浴温度：470 ℃）中に２週間浸漬した。浸漬後、試験片の被覆断面を光学顕微鏡（倍率：1000倍）で観察し、皮膜の腐食量（μm ）を測定し、耐溶融金属腐食性を評価した。腐食量が、10μm 以下を◎、10μm 超〜20μm 以下を○、20μm 超〜30μm 以下を△、30μm 超を×とした。
（３）酸腐食試験
得られた試験片を、酸洗浴（浴組成：10％リン酸水溶液、液温：35℃）中に４週間浸漬した。浸漬後、試験片の被覆断面を光学顕微鏡（倍率：1000倍）で観察し、皮膜の腐食量（μm ）を測定し、耐酸腐食性を評価した。腐食量が、15μm 以下を◎、15μm 超〜20μm 以下を○、20μm 超〜30μm 以下を△、30μm 超を×とした。
（４）熱衝撃試験
得られた試験片に、大気雰囲気中で、300 ℃に加熱しその温度で30min 間保持し、水中投下による急冷処理を繰返し、皮膜が剥離するまでの繰返回数を求め、耐熱衝撃性を評価した。繰返回数が、15回以下を×、15回超〜25回以下を△、25回超〜35回以下を○、35回超を◎とした。
（５）硬さ試験
得られた試験片の被覆断面の膜厚中央で、皮膜の硬さを微小硬度計（荷重：2.94N ）を用いて５箇所測定し、平均値をその試験片の硬さＨｖとした。硬さが、1000以上を◎、800 以上〜1000未満を○、500 以上〜800 未満を△、500 未満を×として、皮膜硬さを評価した。
【００２２】
得られた結果を表１に併記した。なお、各特性評価を総合した総合評価も併記した。
【００２３】
【表１】
【表２】
本発明例はいずれも、従来例と同等またはそれ以上の硬さ、耐熱衝撃性を有し、従来例に比べ格段に優れた耐ドロス付着性、耐溶融金属腐食性、耐酸腐食性を同時に有している。一方、本発明の範囲を外れる比較例は、硬さが低いか、耐熱衝撃性、耐ドロス付着性、耐溶融金属腐食性、耐酸腐食性のうちのいずれかが、低下している。
【００２６】
【発明の効果】
本発明によれば、従来並の硬さ、耐熱衝撃性を有し、しかも従来に比べ格段に優れた耐溶融金属侵食性、耐ドロス付着性および耐酸腐食性を有する溶融金属めっき浴浸漬部材が容易に製造でき、溶融金属めっき浴浸漬部材の耐用期間の更なる延長が可能となり、産業上格段の効果を奏する。また、本発明は、耐溶損性にも優れており、浴中ロール( シンクロール) 等の溶融金属めっき浴浸漬部材以外に、溶融金属めっき浴中構造物としても適用が可能であり、溶融金属めっき浴中構造物の耐用期間を顕著に延長できるいう効果もある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a member immersed in a molten metal plating bath such as a sink roll or a support roll used in a hot dip galvanizing bath disposed in a hot dip galvanizing apparatus. The present invention relates to improvement of dross resistance of bath immersion members.
[0002]
[Prior art]
In a hot dip galvanizing apparatus that performs hot dip galvanizing treatment on steel materials, a pump for transporting hot galvanized rolls, sink rolls, support rolls, etc., to the hot dip galvanizing bath is provided for conveying and supporting steel materials . These hot dip galvanizing bath immersion members are used in the hot dip galvanizing bath for a long time so that they are resistant to erosion by hot dip zinc, and wear even when in contact with the steel being transported. It is difficult to do so.
[0003]
In response to such a requirement, for example, a coating layer having a molten zinc erosion resistance is provided on the outer peripheral surface of the roll in the bath. As the coating layer, a sprayed coating such as WC-Co cermet is used. Since the WC-Co cermet sprayed coating is a material having resistance to molten zinc erosion, it is effective to some extent for protecting the roll in the bath. However, a roll in bath with a WC-Co cermet sprayed coating on its surface has a problem that an intermetallic compound called dross in a broad sense is likely to adhere and grow. This is because, for example, as described in Non-Patent Document 1, the β-Co phase existing as a binder phase in the WC-Co cermet sprayed coating is eluted, and zinc easily enters and adheres to the sprayed coating. It is presumed to be due to a decline in sex.
[0004]
To deal with such a problem, for example, in Patent Document 1, a mixture fired coating of chromium oxide and nitride is formed on the surface of a WC-Co cermet sprayed coating, and a microscopic surface existing near the surface of the sprayed coating. There has been proposed a roll member for a molten metal plating bath in which pores are filled with sintered fine particles of a mixture of chromium oxide and nitride.
Patent Document 2 contains 1 to 50 wt% of tungsten boride, 3 to 25 wt% of one or more of Ni, Co, Mo, and Cr as metal phases, with the balance being tungsten carbide. There is described a method for manufacturing an immersion member for a molten metal bath in which a thermal spray coating made of impurities is formed, the thermal spray coating is impregnated with a treatment liquid containing chromic acid as a main component, and then fired. In the technique described in Patent Document 2, from the viewpoint of improving the molten metal erosion resistance, the metal phase is mainly Co and Ni, and one or two of Mo and Cr should be 15% or less. Yes.
[0005]
[Patent Document 1]
JP 2000-54096 [Patent Document 2]
Japanese Patent No. 3080651 [Non-Patent Document 1]
Yuki Tomita et al., “Durability of WC / Co cermet sprayed coating in molten pure zinc”, Iron and Steel, 78th (1992) No. 4, p. 608 to 615
[0006]
[Problem to be Solved by the Invention]
Normally, when dross or the like adheres to the roll in the bath, the dross is removed by pickling the roll in the bath. For this reason, in addition to the molten zinc erosion resistance, the roll in the bath is required to be further excellent in acid corrosion resistance. However, the WC-Co sprayed coating used in the technique described in Patent Document 2 has insufficient acid corrosion resistance, and there is a problem that when pickling, the coating is eroded and peeling of the coating occurs.
[0007]
Moreover, in the technique described in Patent Document 1, in addition to the formation of the thermal spray coating on the surface of the member, a fired coating is further formed, and a complicated process is required for forming the coating layer. There was a problem of inviting soaring.
An object of the present invention is to advantageously solve the above-described problems of the prior art and propose a molten metal plating bath immersion member having excellent resistance to molten metal erosion resistance, dross resistance, and acid corrosion resistance. In the present invention, “dross-resistant adhesion” means that molten metal adheres and penetrates on the surface of a molten metal plating bath immersion member such as a sink roll, and forms and grows an intermetallic compound, leading to dross adhesion. It shall mean the property that suppresses or prevents this.
[0008]
[Means for Solving the Problems]
In order to achieve the above-mentioned problems, the present inventors diligently studied the influence of the type of coating layer on the dross resistance of a sink roll, which is a hot dip galvanizing bath immersion member, using molten metal as molten zinc. As a result, the coating layer, by a thermal spray coating containing the ceramic and binder phase a higher melting point refractory metal or refractory metal alloy Co, anti molten zinc corrosion resistance, acid corrosion resistance and dross adhesion Are both excellent coating layers.
[0009]
The present invention has been completed by further studies based on these findings. That is, the present invention is a molten metal plating bath immersion member used by being immersed in a molten metal plating bath, and has a melting point higher than Co as a coating layer on the surface of the molten metal plating bath immersion member. And having a film in which 50 to 90% by mass of ceramic is dispersed, and the refractory metal is one selected from Ta, V, Mo, Zr, Nb, Hf, and W, or Ta , V , Mo, Zr, Nb, Hf, alloys der of two or more members selected from among W is, the ceramics, oxides, nitrides, carbides, one selected from among the silicide or 2 a molten metal plating bath immersion member excellent in resistance to dross adhesion, characterized in der Rukoto more species, and in the present invention, the ceramic, ZrO 2 as an oxide, WC as a nitride NbN, as a carbide , TiC, 1 kind selected from among WSi as silicofluoride compound or Or more at a wavelength of 550 nm. Also, in the present invention, it is preferable that the molten metal plating bath immersion member is bath roll.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The molten metal plating bath immersion member of the present invention is used by being immersed in a molten metal plating bath, preferably a roll in the bath, and a ceramic is applied to a high melting point metal having a melting point higher than Co as a coating layer on the surface. It has a film formed by dispersing 50 to 90% by mass. The film is preferably formed by plasma spraying or high-speed flame spraying.
[0012]
A refractory metal having a melting point higher than that of Co is a very stable metal or alloy, and has a characteristic that it is stable and hardly corroded against molten metal or acid, and a characteristic that dross is difficult to adhere. And it plays a role as a binder phase in the film. The refractory metal having a melting point higher than that of Co is preferably more than 15% by mass in the film. If it is 15% by mass or less, since the amount as a binder phase is insufficient, the adhesion of the coating is reduced, and the molten metal corrosion resistance, acid corrosion resistance, and dross resistance resistance as the coating are reduced.
[0013]
As the refractory metal having a melting point higher than Co, one selected from Ta , V , Mo , Zr , Nb, Hf, and W, or Ta , V , Mo , Zr , Nb, Hf, and W is used. An alloy composed of two or more selected ones is preferable, and Mo and W are particularly preferable.
Also, the ceramic dispersed in the coating, oxides, nitrides, carbides, it is preferable that the one or more selected from among silicofluoride compound. These ceramics have characteristics of high hardness and excellent wear resistance, low wettability and reactivity with molten metal, and low dross adhesion. Incidentally, like ZrO 2, Al 2 O 3, Y 2 O 3 as the oxide, the nitride BN, AlN, NbN and the like, as the carbide Cr 3 C 2, WC, TiC or the like, as silicofluoride compound Are preferably TiSi, ZrSi, WSi, and the like.
[0014]
Ceramics are contained in the film in a dispersed form of 50 to 90% by mass. If the ceramic content is less than 50% by mass, the amount of ceramic in the coating is small, the coating is insufficiently hard, and the coating progresses significantly due to contact with the plate to be plated. Wear resistance is reduced. On the other hand, if it exceeds 90% by mass, the amount of ceramics in the film increases so much that the thermal shock resistance decreases, and the risk of film peeling increases. Preferably, the ceramic content in the film is 65 to 85% by mass.
[0015]
The coating on the surface of the immersion member of the molten metal plating bath of the present invention is preferably made of a surface coating material (spraying material), preferably a high-speed flame spraying method (HVAF (High Velocity Aero Fuel) spraying method, HVOF (High Velocity Oxgen Fuel) spraying method). ), Preferably by thermal spraying using plasma spraying or explosion spraying. Needless to say, the surface of the member immersed in the molten metal plating bath for forming a film is subjected to conventional treatments such as roughening and cleaning of the substrate in advance in order to improve film adhesion.
[0016]
Next, a preferable surface coating material for forming a film on the surface of the immersion member of the molten metal plating bath of the present invention will be described.
The material for coating the surface of a molten metal plating bath immersion member of the present invention comprises a high melting point metal powder having a melting point higher than Co and a ceramic powder mixed in an amount of 50 to 90% by mass, or a high melting point metal powder having a melting point higher than Co and a ceramic powder. It is a thermal spray material formed by mixing and granulating.
[0017]
The refractory metal powder mixed in the surface coating material is a powder that becomes a metal phase having an action of bonding ceramics when a sprayed coating is formed. The blending amount of the refractory metal powder having a melting point higher than that of Co is preferably more than 15% by mass relative to the total amount of the surface coating material. If it is 15% by mass or less, the adhesion of the thermal spray coating is insufficient. The high melting point metal powder having a melting point higher than that of Co is one kind of powder selected from Ta, V, Mo, Zr, Nb, Hf, and W, or Ta , V, Mo , Zr, Nb, and Hf. , W is preferably an alloy powder composed of two or more selected from W. Of these, powders of Mo and W are more preferable.
[0018]
The ceramic powder mixed in the surface coating material is preferably one or more powders selected from oxides, nitrides, carbides, borides, and silicides. The ceramic powder is mixed in an amount of 50 to 90% by mass based on the total amount of the surface coating material. When the mixing amount of the ceramic powder is less than 50% by mass, the ceramic amount in the coating layer (spray coating) formed on the surface of the molten metal plating bath immersion member is small, and the hardness of the coating layer (spray coating) is insufficient. Due to the contact with the plate to be plated, the wear of the coating layer (sprayed coating) is remarkably progressed, and the wear resistance as a molten metal plating bath immersion member is lowered. On the other hand, when the content exceeds 90% by mass, the amount of ceramics in the coating layer (sprayed coating) to be formed increases so that the thermal shock resistance decreases and the risk of peeling of the coating layer increases.
[0019]
Incidentally, like ZrO 2, Al 2 O 3, Y 2 O 3 as the oxide, the nitride BN, AlN, NbN and the like, as the carbide Cr 3 C 2, WC, TiC or the like, as silicofluoride compound Are preferably TiSi, ZrSi, WSi, and the like.
[0020]
【Example】
Sink roll test piece (material: SUS316L, size: 10 mmφ x 100 mm length) as a hot dip galvanizing bath immersion member, metal (binder metal) as a binder phase so as to form a film having the composition shown in Table 1 ) Using a surface coating material (spraying material) produced by granulating powder and ceramic powder, the coating was sprayed by plasma spraying to form a coating (film thickness: 100 μm). Test piece No. 1 is a conventional example in which a WC-Co cermet sprayed coating is formed.
[0021]
About the obtained test piece, the dross adhesion test, the molten metal corrosion test, the acid corrosion test, the thermal shock test, and the hardness test were implemented. The test method was as follows.
(1) Dross adhesion test The obtained test piece was immersed in a hot dip galvanizing bath (bath composition: Zn-2% Al, bath temperature: 470 ° C.) for 2 weeks. After the immersion, the coated cross section of the test piece was observed with an optical microscope (magnification: 200 times), the thickness of the dross formed on the coating surface was measured, and the dross resistance was evaluated as the dross adhesion amount (mm). The dross adhesion amount was 0.10 mm or less, 以下, more than 0.10 mm to 0.30 mm or less, ◯, 0.30 mm or more and 0.50 mm or less Δ, and 0.50 mm or more ×.
(2) Molten metal corrosion test The obtained specimen was immersed in a hot dip galvanizing bath (bath composition: 100% Zn, bath temperature: 470 ° C.) for 2 weeks. After the immersion, the coated cross section of the test piece was observed with an optical microscope (magnification: 1000 times), and the corrosion amount (μm) of the film was measured to evaluate the resistance to molten metal corrosion. Corrosion amount was rated as ◎ when less than 10 μm, ◯ when more than 10 μm and less than 20 μm, Δ when more than 20 μm and less than 30 μm, and × when more than 30 μm.
(3) Acid corrosion test The obtained test piece was immersed in a pickling bath (bath composition: 10% phosphoric acid aqueous solution, liquid temperature: 35 ° C.) for 4 weeks. After the immersion, the coated cross section of the test piece was observed with an optical microscope (magnification: 1000 times), and the corrosion amount (μm) of the film was measured to evaluate the acid corrosion resistance. Corrosion amounts of 15 μm or less were evaluated as ◎, 15 μm or more to 20 μm or less as ◯, 20 μm or more and 30 μm or less as Δ, and 30 μm or more as x.
(4) Thermal shock test The obtained test piece is heated to 300 ° C in the atmosphere and held at that temperature for 30 minutes. The rapid cooling treatment by dropping in water is repeated, and the number of repetitions until the film peels is obtained. The thermal shock resistance was evaluated. The number of repetitions was set to x for 15 times or less, Δ for more than 15 to 25 times, ◯ for more than 25 to 35 times, and ◎ for more than 35 times.
(5) Hardness test The hardness of the coating was measured at five locations using a micro hardness tester (load: 2.94N) at the center of the film thickness of the coated cross section of the obtained test piece, and the average value was determined as the hardness of the test piece. Hv. The hardness of the film was evaluated with a hardness of 1000 or more, ◯, 800 or more but less than 1000, ○, 500 or more but less than 800, Δ, and less than 500, x.
[0022]
The obtained results are also shown in Table 1. In addition, the comprehensive evaluation which integrated each characteristic evaluation was also written together.
[0023]
[Table 1]
[Table 2]
All of the inventive examples have hardness and thermal shock resistance equivalent to or higher than those of the conventional examples, and at the same time have dross resistance, molten metal corrosion resistance, and acid corrosion resistance, which are much superior to the conventional examples. is doing. On the other hand, in the comparative example that is out of the scope of the present invention, the hardness is low, or any one of thermal shock resistance, dross adhesion resistance, molten metal corrosion resistance, and acid corrosion resistance is reduced.
[0026]
【The invention's effect】
According to the present invention, there is provided a molten metal plating bath immersion member having the same hardness and thermal shock resistance as in the prior art, and also having excellent resistance to molten metal erosion, dross adhesion and acid corrosion resistance compared to the prior art. It can be easily manufactured, and it is possible to further extend the service life of the molten metal plating bath immersion member. Further, the present invention is also excellent in resistance to melting, and can be applied as a structure in a molten metal plating bath in addition to a molten metal plating bath immersion member such as a roll in bath (sink roll). There is also an effect that the service life of the structure in the plating bath can be remarkably extended.
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| JP2003124797A JP4408649B2 (en) | 2003-04-30 | 2003-04-30 | Dipping member for hot metal plating baths with excellent dross resistance |
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| JP2003124797A JP4408649B2 (en) | 2003-04-30 | 2003-04-30 | Dipping member for hot metal plating baths with excellent dross resistance |
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| JP5638185B2 (en) | 2007-04-06 | 2014-12-10 | 山陽特殊製鋼株式会社 | Surface coating material for molten zinc bath member, method for producing the same, and method for producing the member |
| JP5638668B2 (en) * | 2007-04-06 | 2014-12-10 | 山陽特殊製鋼株式会社 | Surface coating material for molten zinc bath member, method for producing the same, and member |
| CN107587131B (en) * | 2017-09-25 | 2020-06-19 | 中原工学院 | Molten zinc corrosion resistant SiO2Preparation method of/NbCrMn ceramic-metal composite coating |
| CN107641805B (en) * | 2017-09-25 | 2020-06-19 | 中原工学院 | Preparation method of molten zinc corrosion resistant SiC-W-Mo-Fe ceramic metal composite coating |
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| DE69125398T2 (en) * | 1991-11-29 | 1997-07-10 | Nippon Steel Hardfacing | METHOD FOR PRODUCING AN IMMERSION PART FOR A MELT BATH |
| JP3577598B2 (en) * | 1992-01-29 | 2004-10-13 | 日鉄ハード株式会社 | Method for producing molten metal bath member having coating excellent in molten metal corrosion resistance and peeling resistance |
| JPH0776763A (en) * | 1993-09-01 | 1995-03-20 | Praxair St Technol Inc | Member for galvanization bath excellent in resistance to blocking to alloy layer, its preparation and hot dip galvanization therewith |
| JPH07138722A (en) * | 1993-11-19 | 1995-05-30 | Nippon Steel Corp | Universal shaft joint in molten metal |
| JP3134768B2 (en) * | 1996-04-03 | 2001-02-13 | 住友金属鉱山株式会社 | Boride cermet spraying powder |
| JPH1161369A (en) * | 1997-08-25 | 1999-03-05 | Nippon Steel Corp | Member for hot dip metal bath and its production |
| JPH1180917A (en) * | 1997-09-05 | 1999-03-26 | Nippon Steel Hardfacing Co Ltd | Immersion member for molten metal bath, excellent in resistance to corrosion and wear |
| JP4571250B2 (en) * | 1999-02-15 | 2010-10-27 | トーカロ株式会社 | Roll for molten metal plating bath and method for producing the same |
| JP2000248345A (en) * | 1999-03-01 | 2000-09-12 | Kawasaki Steel Corp | Sink roll for continuous hot dip metal coating |
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