JPH05209259A - Member for molten metal bath with coating film excellent in corrosion resistance to molten metal and exfoliation resistance and its production - Google Patents
Member for molten metal bath with coating film excellent in corrosion resistance to molten metal and exfoliation resistance and its productionInfo
- Publication number
- JPH05209259A JPH05209259A JP1435792A JP1435792A JPH05209259A JP H05209259 A JPH05209259 A JP H05209259A JP 1435792 A JP1435792 A JP 1435792A JP 1435792 A JP1435792 A JP 1435792A JP H05209259 A JPH05209259 A JP H05209259A
- Authority
- JP
- Japan
- Prior art keywords
- molten metal
- resistance
- corrosion resistance
- metal bath
- sprayed
- 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.)
- Granted
Links
Landscapes
- Coating With Molten Metal (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製鉄機械、特に溶融亜
鉛めっきライン等において用いられる溶融金属浴用部材
およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a member for a molten metal bath used in an iron making machine, particularly a hot dip galvanizing line, and a method for producing the member.
【０００２】[0002]
【従来の技術】溶融亜鉛めっきライン用金属浴中ロール
等としては、各種サーメット系材料を溶射したり、酸化
物セラミックス系材料を溶射したものが使われてきた
が、サーメット系溶射皮膜は溶融金属耐食性に乏しく、
セラミックス系溶射皮膜は剥離しやすいという難点があ
った。2. Description of the Related Art As a roll in a metal bath for a hot dip galvanizing line, various cermet materials or thermal sprayed oxide ceramic materials have been used. Poor corrosion resistance,
The ceramic-based sprayed coating has a drawback that it is easily peeled off.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、溶融金属耐
食性および耐剥離性に優れた溶融金属浴用部材およびそ
の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a molten metal bath member excellent in molten metal corrosion resistance and peeling resistance, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】前記の課題は、下記要旨
の本発明によって解決される。 （１） 基材表面に５〜６０％の硼化物とＣｏ、Ｃｒ、
Ｍｏ、Ｗの１種又は２種以上を５〜３０％含有し、残部
炭化物および不可避不純物よりなるサーメット材料を溶
射した上に、酸化物系セラミックスを厚さ２００μｍ以
下溶射してなることを特徴とする溶融金属耐食性および
耐剥離性に優れた皮膜を有する溶融金属浴用部材。The above-mentioned problems can be solved by the present invention as summarized below. (1) 5-60% boride and Co, Cr on the surface of the base material
5 to 30% of one or more of Mo and W are contained, and a cermet material composed of the balance carbide and unavoidable impurities is thermally sprayed, and then oxide ceramics is thermally sprayed to a thickness of 200 μm or less. A molten metal bath member having a film excellent in corrosion resistance and peeling resistance.
【０００５】（２） 基材表面に５〜６０％の硼化物と
Ｃｏ、Ｃｒ、Ｍｏ、Ｗの１種又は２種以上を５〜３０％
含有し、残部炭化物および不可避不純物よりなるサーメ
ット材料を溶射した上に、酸化物系セラミックスを厚さ
２００μｍ以下溶射後、クロム酸（Ｈ2 ＣｒＯ4 および
Ｈ2 Ｃｒ2 Ｏ7 ）を主成分とする水溶液で含浸処理し、
次いで焼成することを特徴とする溶融金属耐食性および
耐剥離性に優れた皮膜を有する溶融金属浴用部材の製造
方法。(2) 5 to 60% of boride and 5 to 30% of one or more of Co, Cr, Mo and W on the surface of the substrate.
After spraying a cermet material containing the remainder and carbide and unavoidable impurities, and then spraying oxide ceramics to a thickness of 200 μm or less, chromic acid (H 2 CrO 4 and H 2 Cr 2 O 7 ) is the main component Impregnated with an aqueous solution,
A method for producing a member for molten metal bath having a coating film excellent in corrosion resistance and peeling resistance of molten metal, which is characterized by firing.
【０００６】本発明者らはさきにタングステン硼化物等
の硼化物を含有する皮膜は溶融金属耐食性に極めて優れ
ていることを確認した。又ＷＢ等はＷＣより若干熱膨脹
係数が高いようで溶射皮膜は熱衝撃性にも強いことが考
えられる。又、硼化物は酸化性雰囲気ではＢ2 Ｏ3 を表
面に生成し、一部表面に残存することが認められた。さ
らにこの生成Ｂ2 Ｏ3 は低温でガラス化し、溶融温度も
低いため、セラミックスが溶射された場合、ソルダー化
し、セラミックスとのなじみがよくなると考えられる。
本発明者らは、ＷＢ等硼化物を含有したサーメット皮膜
の上に酸化物系セラミックス溶射を行った皮膜は溶融金
属耐食性に優れるばかりでなく、基材との密着性が高
く、剥離し難いことを確認した。The present inventors have previously confirmed that a film containing a boride such as tungsten boride is extremely excellent in molten metal corrosion resistance. Further, WB and the like seem to have a coefficient of thermal expansion slightly higher than that of WC, and it is considered that the thermal spray coating is also strong in thermal shock resistance. Further, it was confirmed that the boride forms B 2 O 3 on the surface in the oxidizing atmosphere and partially remains on the surface. Further, since the produced B 2 O 3 is vitrified at a low temperature and has a low melting temperature, it is considered that when the ceramic is sprayed, it becomes a solder and becomes well compatible with the ceramic.
The inventors of the present invention have found that a coating obtained by spraying oxide-based ceramics on a cermet coating containing a boride such as WB is not only excellent in molten metal corrosion resistance, but also has high adhesion to a substrate and is difficult to peel off. It was confirmed.
【０００７】このためボンドコート材料へのＷＢ等硼化
物の添加は必須であるが、含有量が少ない場合には、密
着強度改善効果がなく、多すぎる時は大気中での良好な
溶射は難しくなる。よって硼化物添加量は５〜６０％に
限定する。サーメットとしての金属相としてはＣｏ、Ｃ
ｒ、Ｍｏ、Ｗが選定されるが、ボンドコートサーメット
の金属成分としては、これら元素の１種又は２種以上を
５〜３０％添加する。金属成分は、少なすぎると皮膜粒
子の結合力を弱めるため、最低５％は添加する。又、必
要以上に添加すると、皮膜の溶融金属による侵食性が増
すため、添加量は３０％までとする。For this reason, it is essential to add boride such as WB to the bond coat material, but if the content is too small, there is no effect of improving the adhesion strength, and if it is too large, good thermal spraying in air is difficult. Become. Therefore, the boride addition amount is limited to 5 to 60%. Co, C as the metal phase as cermet
Although r, Mo, and W are selected, as a metal component of the bond coat cermet, one or more of these elements are added in an amount of 5 to 30%. If the amount of the metal component is too small, the binding force of the coating particles is weakened, so at least 5% is added. If added more than necessary, the corrosiveness of the coating film due to molten metal increases, so the addition amount is limited to 30%.
【０００８】なお、残部はＷＣ等の炭化物であるが、こ
れら炭化物は硼化物の作用効果を補完し、ボンドコート
自体に溶融金属耐食性を与えるものである。トップコー
トセラミックスとしては、基材である金属部と熱膨脹率
の差が大きくないセラミックスが良好であり、出来るだ
け線膨脹係数の大きい材料を選択するのがよい。本発明
の実施例では膨脹係数の大きいクロミアを適用してい
る。The balance is carbide such as WC. These carbides complement the action and effect of boride and give the bond coat itself molten metal corrosion resistance. As the top coat ceramics, ceramics having a large difference in coefficient of thermal expansion from the metal part as a base material are preferable, and it is preferable to select a material having a linear expansion coefficient as large as possible. In the embodiment of the present invention, chromia having a large expansion coefficient is applied.
【０００９】トップコート皮膜厚みについては、皮膜厚
が過大になると残留応力が増し、セラミックス皮膜内部
やボンドコートとトップコートセラミックス界面で剥離
しやすくなるので、最大２００μｍに限定する（実施例
参照）。又、ボンドコート表面に生成しているＢ2 Ｏ3
は、セラミックス界面でガラス化し、強い密着力を呈す
るようになる。すなわち本発明はボンドコートの硼化物
系サーメットにより硼酸を含むガラス質をつくり、強い
密着力をトップコートに与えるものである。The topcoat film thickness is limited to 200 μm at the maximum because the residual stress increases if the film thickness becomes too large and peeling easily occurs inside the ceramic film or at the interface between the bond coat and the topcoat ceramics (see Examples). In addition, B 2 O 3 generated on the surface of the bond coat
Becomes vitrified at the ceramic interface and exhibits strong adhesion. That is, the present invention forms a glassy material containing boric acid by the boride-based cermet of the bond coat and gives a strong adhesion to the top coat.
【００１０】又、請求項２においてクロム酸を主成分と
する水溶液で含浸処理を行い、焼成処理を行うのは、セ
ラミックス皮膜を緻密化し、皮膜粒子の脱落を抑制する
ためである。主成分であるＨ2 ＣｒＯ4 、Ｈ2 Ｃｒ2 Ｏ
7 等は含浸後の加熱で脱水反応を起し、ＣｒＯ3 化す
る。ＣｒＯ3 は２００℃程度から溶融し、皮膜を酸化し
ながらＣｒ2 Ｏ3 化し、封孔が行われる。この場合Ｃｒ
Ｏ3 の酸化でＣｒ2 Ｏ3は皮膜に密着し、皮膜強度を上
げることになる。又、モリブデン酸アンモニウムを添加
した液ではpH調整と、酸化モリブデンによる封孔を行わ
せ、封孔効果を補完することができる。Further, in the second aspect, the reason why the impregnation treatment is performed with the aqueous solution containing chromic acid as a main component and the firing treatment is performed is for the purpose of densifying the ceramic coating and suppressing the fall of coating particles. H 2 CrO 4 and H 2 Cr 2 O which are the main components
7 etc. undergoes a dehydration reaction by heating after impregnation to form CrO 3 . CrO 3 is melted from about 200 ° C. and converted into Cr 2 O 3 while oxidizing the film, and sealing is performed. In this case Cr
Cr 2 O 3 in the oxidation of O 3 is in close contact with the film, thus increasing the film strength. In addition, with a liquid containing ammonium molybdate added, pH adjustment and sealing with molybdenum oxide are performed to complement the sealing effect.
【００１１】[0011]
【実施例】本発明の実施例および比較例を表１（トップ
コートおよびボンドコート成分）および表２（トップコ
ート溶射後の侵食熱衝撃試験結果）に示す。Ｎｏ．１〜
Ｎｏ．８は本発明の実施例、Ｎｏ．９〜１２は比較例で
ある。Ｎｏ．１〜Ｎｏ．８の実施例においては、ボンド
コートとして硼化物を含むサーメットを溶射して皮膜を
形成した。トップコートとしてＣｒ2 Ｏ3 を５０μｍ、
１００μｍおよび２００μｍ溶射した皮膜は、侵食熱衝
撃試験で全く剥離していない。２５０μｍ厚トップコー
トを溶射した場合に、はじめて皮膜中残留応力のため一
部部分剥離を生じた。EXAMPLES Examples and comparative examples of the present invention are shown in Table 1 (topcoat and bondcoat components) and Table 2 (results of erosion thermal shock test after topcoat thermal spraying). No. 1 to
No. No. 8 is an example of the present invention. 9-12 are comparative examples. No. 1-No. In Example No. 8, a coating was formed by spraying a cermet containing boride as a bond coat. Cr 2 O 3 is 50 μm as a top coat,
The coatings sprayed at 100 μm and 200 μm did not peel at all in the erosion thermal shock test. When the 250 μm thick top coat was sprayed, partial peeling occurred for the first time due to residual stress in the coating.
【００１２】これに対して、ボンドコートがＷＣ系であ
る比較例Ｎｏ．９およびＮｉ−Ａｌ系である比較例Ｎ
ｏ．１０の皮膜の場合は、膜厚２００μｍ以下ですでに
部分剥離が認められた。又、ボンドコートなしで、セラ
ミックスを溶射した比較例Ｎｏ．１１および１２の皮膜
の場合には、膜厚に関係なくすべて剥離した。これより
本発明の部材は溶融金属浴に対する耐食性および耐剥離
性の点で優れたものであることが分る。On the other hand, Comparative Example No. 1 in which the bond coat is WC type. 9 and Comparative Example N which is a Ni-Al system
o. In the case of the film of No. 10, partial peeling was already observed at a film thickness of 200 μm or less. Further, Comparative Example No. 1 in which ceramics were sprayed without a bond coat. In the case of the films of 11 and 12, they were all peeled off regardless of the film thickness. From this, it can be seen that the member of the present invention is excellent in corrosion resistance and peeling resistance to the molten metal bath.
【００１３】なお、本実施例ではトップコート材料とし
てクロミアのみを使用した結果であるが、他の実施例で
はアルミナ、ジルコニア・イットリア、スピネル等で同
様の結果が得られており、本発明の効果が確認されてい
る。The results of using only chromia as the top coat material in this example are the same as those of other examples, such as alumina, zirconia-yttria, and spinel. Has been confirmed.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【発明の効果】本発明によれば、溶融金属耐食性および
耐剥離性の優れた溶融金属浴用部材を提供することがで
きる。According to the present invention, it is possible to provide a molten metal bath member having excellent molten metal corrosion resistance and peeling resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内山 輝之 愛知県東海市東海町５−３ 新日本製鐵株 式会社名古屋製鐵所構内日鉄ハード株式会 社名古屋事業所内 (72)発明者 垂水 清弘 福岡県北九州市戸畑区大字中原先の浜46 日鉄ハード株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Teruyuki Uchiyama 5-3 Tokai-cho, Tokai City, Aichi Prefecture Nippon Steel Co., Ltd. Nagoya Steel Works premises Nittetsu Hard Co., Ltd. Nagoya Office (72) Inventor Tarumi Kiyohiro, Tobata-ku, Kitakyushu-shi, Fukuoka, Nakahama 46, Nakahara-mae, Nittetsu Hard Co.
Claims (2)
Ｃｒ、Ｍｏ、Ｗの１種又は２種以上を５〜３０％含有
し、残部炭化物および不可避不純物よりなるサーメット
材料を溶射した上に、酸化物系セラミックスを厚さ２０
０μｍ以下溶射してなることを特徴とする溶融金属耐食
性および耐剥離性に優れた皮膜を有する溶融金属浴用部
材。1. A substrate surface containing 5 to 60% of boride and Co,
A cermet material containing 5 to 30% of one or two or more of Cr, Mo, and W and having a balance of carbide and unavoidable impurities is sprayed, and an oxide ceramics having a thickness of 20
A member for a molten metal bath having a coating excellent in molten metal corrosion resistance and peeling resistance, characterized by being sprayed to a thickness of 0 μm or less.
Ｃｒ、Ｍｏ、Ｗの１種又は２種以上を５〜３０％含有
し、残部炭化物および不可避不純物よりなるサーメット
材料を溶射した上に、酸化物系セラミックスを厚さ２０
０μｍ以下溶射後、クロム酸（Ｈ2 ＣｒＯ4 およびＨ2
Ｃｒ2 Ｏ7 ）を主成分とする水溶液で含浸処理し、次い
で焼成することを特徴とする溶融金属耐食性および耐剥
離性に優れた皮膜を有する溶融金属浴用部材の製造方
法。2. Boron and Co of 5 to 60% on the surface of the substrate,
A cermet material containing 5 to 30% of one or two or more of Cr, Mo, and W and having a balance of carbide and unavoidable impurities is sprayed, and an oxide ceramics having a thickness of 20
Chromic acid (H 2 CrO 4 and H 2
A method for producing a member for molten metal bath having a coating film excellent in corrosion resistance and peeling resistance of molten metal, which comprises impregnating with an aqueous solution containing Cr 2 O 7 ) as a main component and then firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01435792A JP3577598B2 (en) | 1992-01-29 | 1992-01-29 | Method for producing molten metal bath member having coating excellent in molten metal corrosion resistance and peeling resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01435792A JP3577598B2 (en) | 1992-01-29 | 1992-01-29 | Method for producing molten metal bath member having coating excellent in molten metal corrosion resistance and peeling resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05209259A true JPH05209259A (en) | 1993-08-20 |
| JP3577598B2 JP3577598B2 (en) | 2004-10-13 |
Family
ID=11858824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01435792A Expired - Lifetime JP3577598B2 (en) | 1992-01-29 | 1992-01-29 | Method for producing molten metal bath member having coating excellent in molten metal corrosion resistance and peeling resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3577598B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0712939A3 (en) * | 1994-10-24 | 1996-05-29 | Praxair S.T. Technology, Inc. | Pot roll for continuous hot-dip galvanizing |
| WO1998049364A1 (en) * | 1997-04-28 | 1998-11-05 | Nippon Steel Hardfacing Co., Ltd. | Member for molten metal bath, provided with composite sprayed coating having excellent corrosion resistance and peeling resistance against molten metal |
| KR20030052921A (en) * | 2001-12-21 | 2003-06-27 | 재단법인 포항산업과학연구원 | Thermal spray coated rolls used in an aluminum pot of a continuous aluminum plating line |
| JP2004331995A (en) * | 2003-04-30 | 2004-11-25 | Jfe Steel Kk | Material for coating surface of dipping member into hot dip metal plating bath, and dipping member for hot dip metal plating bath having excellent dross sticking resistance |
| WO2020136719A1 (en) * | 2018-12-25 | 2020-07-02 | 日鉄住金ハード株式会社 | Sink roll and method for manufacturing sink roll |
-
1992
- 1992-01-29 JP JP01435792A patent/JP3577598B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0712939A3 (en) * | 1994-10-24 | 1996-05-29 | Praxair S.T. Technology, Inc. | Pot roll for continuous hot-dip galvanizing |
| WO1998049364A1 (en) * | 1997-04-28 | 1998-11-05 | Nippon Steel Hardfacing Co., Ltd. | Member for molten metal bath, provided with composite sprayed coating having excellent corrosion resistance and peeling resistance against molten metal |
| EP0927774A1 (en) * | 1997-04-28 | 1999-07-07 | Nippon Steel Hardfacing Co., Ltd. | Member for molten metal bath, provided with composite sprayed coating having excellent corrosion resistance and peeling resistance against molten metal |
| EP0927774A4 (en) * | 1997-04-28 | 2003-06-04 | Nippon Steel Hardfacing | Member for molten metal bath, provided with composite sprayed coating having excellent corrosion resistance and peeling resistance against molten metal |
| KR20030052921A (en) * | 2001-12-21 | 2003-06-27 | 재단법인 포항산업과학연구원 | Thermal spray coated rolls used in an aluminum pot of a continuous aluminum plating line |
| JP2004331995A (en) * | 2003-04-30 | 2004-11-25 | Jfe Steel Kk | Material for coating surface of dipping member into hot dip metal plating bath, and dipping member for hot dip metal plating bath having excellent dross sticking resistance |
| WO2020136719A1 (en) * | 2018-12-25 | 2020-07-02 | 日鉄住金ハード株式会社 | Sink roll and method for manufacturing sink roll |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3577598B2 (en) | 2004-10-13 |
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