JP2955625B2 - Material for molten metal bath - Google Patents
Material for molten metal bathInfo
- Publication number
- JP2955625B2 JP2955625B2 JP14934691A JP14934691A JP2955625B2 JP 2955625 B2 JP2955625 B2 JP 2955625B2 JP 14934691 A JP14934691 A JP 14934691A JP 14934691 A JP14934691 A JP 14934691A JP 2955625 B2 JP2955625 B2 JP 2955625B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- molten metal
- bath
- carbide
- metal bath
- 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
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 62
- 239000002184 metal Substances 0.000 title claims description 62
- 239000000463 material Substances 0.000 title description 23
- 239000010410 layer Substances 0.000 claims description 40
- 239000011247 coating layer Substances 0.000 claims description 26
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 25
- 239000011224 oxide ceramic Substances 0.000 claims description 24
- 238000005524 ceramic coating Methods 0.000 claims description 19
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- 238000005260 corrosion Methods 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 13
- 239000011195 cermet Substances 0.000 claims description 11
- 150000001247 metal acetylides Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005246 galvanizing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 229910000746 Structural steel Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 101100017046 Caenorhabditis elegans hira-1 gene Proteins 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Coating By Spraying Or Casting (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶融金属浴用部材に関
し、特に溶融アルミニウムめっき浴や溶融亜鉛めっき浴
の浴用部材としての特性, すなわち熱間耐食性、耐熱衝
撃性および耐剥離性などに優れた複層溶射皮膜を設けて
なる溶融金属浴用部材についての提案である。また、本
発明は、溶融アルミニウムや溶融亜鉛めっき浴中に浸漬
して用いるロール類や各種部材（軸受部など）のみなら
ず、これらの溶融金属が飛散付着する各種の溶融めっき
浴付帯の部材としても適用されるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-dip metal bath member, and more particularly to a hot-dip aluminum plating bath or a hot-dip galvanizing bath having excellent properties as a bath member, that is, excellent hot corrosion resistance, thermal shock resistance, and peeling resistance. This is a proposal for a member for a molten metal bath having a multilayer sprayed coating. In addition, the present invention is applicable not only to rolls and various members (such as bearings) used by dipping in a hot-dip aluminum or hot-dip galvanizing bath, but also to various hot-dip bath accessories to which these molten metals are scattered and adhered. Is also applicable.
【０００２】[0002]
【従来の技術】溶融アルミニウムおよび溶融亜鉛めっき
鋼板は、自動車や建築資材用の耐熱,耐食部材として賞
用されているが、これらは主として連続めっき処理によ
って製造されている。2. Description of the Related Art Hot-dip aluminum and hot-dip galvanized steel sheets have been used as heat-resistant and corrosion-resistant members for automobiles and building materials, but they are mainly produced by continuous plating.
【０００３】その連続めっき処理装置には、溶融金属中
に浸漬されている浸漬ロールや溶融金属表面近傍に設置
されているめっきロール、あるいはこれらのロールを通
過した後のめっき鋼板をガイドするためのガイドロール
などが配設してある。これらのロール類は、溶融金属中
に浸漬されているが、溶融金属を被覆した高温の鋼板と
接触するため、次に示すような性能が要求されるもので
ある。 (1) 溶融金属による侵食が起こりにくいこと、(2) 通板
する鋼板と接触しても摩耗しにくいこと、(3) 付着した
溶融金属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いこと、(5) 低コストであるこ
と。[0003] The continuous plating apparatus includes a dipping roll immersed in the molten metal, a plating roll placed near the surface of the molten metal, or a guide for guiding a plated steel sheet after passing through these rolls. Guide rolls are provided. Although these rolls are immersed in the molten metal, they come into contact with a high-temperature steel sheet coated with the molten metal, so that the following performance is required. (1) Erosion by molten metal is unlikely to occur, (2) It is hard to be worn even when it comes in contact with the steel sheet to be passed, (3) It is easy to remove adhered molten metal and maintenance and inspection is easy, (4) Roll (5) low cost.
【０００４】これらの要求に応えられるロール、すなわ
ちめっき浴用部材の提供を目的にした従来技術として
は、ロール表面にJIS H8303 (1976)制定の自溶合金を
溶射したもの、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被覆層を施したも
の、特公昭57−174440号公報に開示のようなSiO2 15
〜45重量％, MgO 5 〜40重量％、残部ZrO2からなるセラ
ミック被覆層を施したもの、特公昭58−37386 号公報
に開示のようなWC, CrC, TiC の１種または２種以上で
残部が熱間耐食性金属またはその酸化物からなる 0.1〜
2.4 mm厚さの表面被覆層を形成させたロール、特公平
１−225761号公報に開示のようなWC−Coサーメットを
1.8％以下の気孔率で溶射被覆したもの、などが提案さ
れている。As a prior art for providing a roll which can meet these requirements, that is, for providing a member for a plating bath, a roll sprayed with a self-fluxing alloy established in JIS H8303 (1976) is disclosed in JP-A-61-117260. JP those subjected to ceramic coating layer made of ZrO 2 and Al 2 O 3 as disclosed, SiO 2 15 as disclosed in JP-B-57-174440
WC, CrC, TiC or the like as disclosed in JP-B-58-37386, which is provided with a ceramic coating layer comprising 〜45% by weight, MgO 5 4040% by weight and the balance ZrO 2. The balance consists of hot corrosion resistant metal or its oxide 0.1 ~
A roll having a surface coating layer having a thickness of 2.4 mm, a WC-Co cermet as disclosed in Japanese Patent Publication No. 1-25761.
Thermal spray coating with a porosity of 1.8% or less has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】上掲の各従来技術につ
いては、の技術の場合、それ以前の無処理ロールに比
べると寿命は長くなっているものの、自溶合金皮膜が溶
融金属に腐食されて２週間程度でもロール表面が凹凸状
となり、通板材の表面に疵を発生させるという欠点があ
った。In each of the above prior arts, the self-fluxing alloy film is corroded by the molten metal in the case of the prior art, although the life is longer than that of the untreated roll before that. Even for about two weeks, the roll surface becomes uneven, and there is a defect that a flaw is generated on the surface of the sheet passing material.
【０００６】また、の技術の場合は、セラミック皮膜
自体は腐食を受けることがないものの、素材との熱膨張
差に起因する貫通クラックや局部的剥離を発生しやす
く、その部分から侵入する溶融金属により、アンダーコ
ートの金属溶射層や素材が腐食する。その結果、上記セ
ラミック皮膜が剥離し、長期間の繰り返し使用が困難に
なるという欠点があった。In the case of the technique described above, the ceramic coating itself is not corroded, but penetrating cracks and local exfoliation due to a difference in thermal expansion from the material are liable to occur. As a result, the metal spray layer and the material of the undercoat are corroded. As a result, there is a drawback that the ceramic coating peels off, making it difficult to use repeatedly for a long period of time.
【０００７】また、の技術の場合は、SiO2を15〜45重
量％含有するセラミック皮膜を用いたことから、溶射層
中に熱応力を吸収するのに好適な微細な縦割れが存在す
るため、耐熱衝撃性に優れている。しかしながら、溶融
亜鉛めっき浴や溶融アルミニウム浴で長期間使用した場
合、上記の微細な縦割れ部やセラミック皮膜の気孔部を
通じて溶融金属の侵入や拡散浸透を受けやすく、そのた
めにセラミックスと素材の熱膨張差を緩和する目的で設
けられた中間金属層や素材を著しく腐食する。その結
果、セラミック皮膜の剥離が発生し、比較的頻繁にロー
ル交換が必要となり、ラインの休止に伴う生産性の低下
を余儀無くされ、実用に供し得ないという欠点があっ
た。In the case of the technique described above, since a ceramic coating containing 15 to 45% by weight of SiO 2 is used, fine vertical cracks suitable for absorbing thermal stress exist in the sprayed layer. Excellent heat shock resistance. However, when used for a long time in a hot-dip galvanizing bath or a hot-dip aluminum bath, the molten metal easily penetrates or diffuses and penetrates through the fine vertical cracks and the pores of the ceramic film. Significantly corrodes intermediate metal layers and materials provided to mitigate the difference. As a result, peeling of the ceramic film occurs, and the roll needs to be replaced relatively frequently, which inevitably causes a reduction in productivity due to the suspension of the line, and has a disadvantage that it cannot be put to practical use.
【０００８】また、特公昭57−174440号公報に開示の
の技術の場合は、セラミック被覆層と基材の熱膨張差を
緩和するために、セラミック被覆層と基材の間に１層ま
たは２層以上の中間層を設けてなるものであるが、この
ような熱膨張差を緩和する目的でNi−Cr系合金やCo系合
金を中間層として使用した場合でも、この中間層がセラ
ミック皮膜の粒界からの溶融金属の侵入や拡散浸透によ
って腐食され、セラミック被覆層の剥離を生じること
が、本発明者らの実験によって確認されている。In the case of the technique disclosed in Japanese Patent Publication No. 57-174440, one layer or two layers are provided between the ceramic coating layer and the substrate in order to reduce the difference in thermal expansion between the ceramic coating layer and the substrate. Although an intermediate layer of at least one layer is provided, even if a Ni-Cr alloy or a Co alloy is used as the intermediate layer for the purpose of reducing such a difference in thermal expansion, the intermediate layer is formed of a ceramic film. It has been confirmed by the experiments of the present inventors that they are corroded by intrusion of molten metal from the grain boundaries or by diffusion and infiltration, thereby causing peeling of the ceramic coating layer.
【０００９】一方、, に挙げた各従来技術の場合、
炭化物および炭化物サーメット被覆層を用いるので、溶
融金属に比較的優れた耐食性を示すものの、それでも、
溶融めっき浴で長期間にわたって使用した場合、皮膜粒
界から溶融金属の侵入を受けて表面が微細な凹凸状とな
り、これがめっき鋼板表面に変色模様として転写され、
その結果、商品価値を著しく低下させるという欠点があ
った。[0009] On the other hand, in the case of each of the prior arts mentioned above,
Because of the use of carbide and carbide cermet coating layers, while exhibiting relatively good corrosion resistance to molten metal,
When used in a hot-dip plating bath for a long time, the surface becomes fine irregularities due to the intrusion of molten metal from the film grain boundaries, and this is transferred as a discolored pattern on the surface of the plated steel sheet,
As a result, there is a disadvantage that the commercial value is significantly reduced.
【００１０】以上説明したように、上記各従来技術は、
それぞれに改善の効果はあったものの、最近の厳しい操
業条件や品質要求を考慮したときにはなお不十分であ
り、例えば溶融金属の侵食や被覆層自体の剥離によるめ
っき製品への疵の発生および生産性の低下等に対しては
十分な効果が顕れてはいない。このことから従来、溶融
金属に対する耐食性に優れ、かつ溶融金属浴用部材の母
材となる鉄鋼部材に適用しても、剥離などの皮膜不具合
を生じない浴用部材の開発が強く望まれていた。As described above, each of the above prior arts is:
Although each of them had an effect of improvement, it was still insufficient when considering recent severe operating conditions and quality requirements.For example, the occurrence of scratches on plated products due to the erosion of the molten metal and the peeling of the coating layer itself and the productivity However, no sufficient effect has been found on the decrease in water content. For this reason, there has been a strong demand for a bath member which is excellent in corrosion resistance to molten metal and which does not cause coating defects such as peeling even when applied to a steel member as a base material of a molten metal bath member.
【００１１】本発明の目的は、溶融金属浴用部材, 特に
その表面にセラミック材料を溶射被覆してなる従来浴用
部材が抱えている上述した欠点を克服し、斯界の要請に
応えられる溶融金属浴用部材を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned drawbacks of a molten metal bath member, particularly a conventional bath member having a surface sprayed with a ceramic material, and to meet the demands of the art. Is to provide.
【００１２】[0012]
【課題を解決するための手段】酸化物セラミック材料を
被覆した従来技術の欠点を克服すべく鋭意研究した結
果、本発明者らは、酸化物セラミック皮膜剥離現象に関
する次のような知見を得た。すなわち、このセラミック
皮膜の剥離現象は、酸化物セラミック被覆層を溶融金
属浴中に浸漬したり引き上げたりする際に、被覆層と素
材との熱膨張係数の差に起因して起るもの、酸化物セ
ラミック被覆層と素材との間の、上記熱膨張差から生じ
た貫通クラックを通じて溶融金属が侵入し、その結果と
して下盛金属被覆層や素材を腐食することにより起るも
の、長期間の使用に際して、溶融金属が溶射皮膜を構
成する微小な粒子の粒界を通じて侵入したり、溶融金属
の拡散浸透によって下盛金属被覆層や素材を腐食するこ
とにより起るもの、であることが明らかとなった。As a result of intensive studies to overcome the disadvantages of the prior art coated with an oxide ceramic material, the present inventors have obtained the following knowledge on the oxide ceramic film peeling phenomenon. . That is, the peeling phenomenon of the ceramic coating is caused by a difference in thermal expansion coefficient between the coating layer and the material when the oxide ceramic coating layer is immersed in a molten metal bath or lifted up, and oxidation occurs. Molten metal penetrates through the cracks caused by the difference in thermal expansion between the ceramic coating layer and the material, resulting in corrosion of the underlying metal coating layer and the material, resulting in long-term use. It is evident that the molten metal invades through the grain boundaries of the fine particles that make up the sprayed coating, or that the molten metal diffuses and penetrates to corrode the underlying metal coating layer and material. Was.
【００１３】このことから、上述した本発明の目的を実
現するには、溶融金属浴用部材の表面構造としては、耐
熱衝撃性に優れるとともに、長期間の使用に際して、酸
化物セラミック層中の溶融金属の侵入や拡散浸透に対し
て、優れた耐食性を有する下盛層が必要であることが判
った。From the above, in order to realize the above-mentioned object of the present invention, the surface structure of the molten metal bath member has excellent thermal shock resistance and, when used for a long time, the molten metal in the oxide ceramic layer. It has been found that an underlay layer having excellent corrosion resistance is required for penetration and diffusion infiltration.
【００１４】そこで本発明は、耐溶融金属侵食性に優
れ、かつ耐熱衝撃性にも優れた特性を示す酸化物セラミ
ックスを上盛層として採用することを基本とし、これに
加えて長期間の繰り返し使用に当たって、溶融金属が酸
化物セラミック皮膜中を拡散侵入しても、なお耐食性を
維持できるようにするための下盛層を設けたものであっ
て、これによって溶融金属の侵食を抑制し、しかも上記
酸化物セラミックスの剥離を防止して、長期間繰り返し
安定使用可能な溶融金属浴用部材を完成したものであ
る。Accordingly, the present invention is based on the fact that an oxide ceramic having excellent resistance to molten metal erosion and excellent thermal shock resistance is employed as an upper layer, and in addition to this, a repetition for a long time is required. In use, even if the molten metal diffuses and penetrates through the oxide ceramic coating, it is provided with an underlayer to maintain the corrosion resistance, thereby suppressing the erosion of the molten metal, and Thus, a member for a molten metal bath that can be used repeatedly and stably for a long period of time is completed by preventing the oxide ceramics from peeling off.
【００１５】このような知見に基づいて開発した本発明
は、鉄鋼部材の表面に、下盛層が炭化物または熱間耐食
性金属の炭化物サーメット被覆層で構成され、上盛層が
10〜40重量％のSiO2を含む酸化物セラミック被覆層で構
成された２層溶射皮膜を設けてなる溶融金属浴用部材、
を基本構成とし、さらに鉄鋼部材の表面に、下盛層とし
て、Cr3C2, NbC,TiC, WC, WTiC, ZrCおよびSiC のうち
から選ばれる１種以上の炭化物、またはそれらの炭化物
を50％以上含有し、かつ残部がCo, Ni, Cr, Moのなかか
ら選ばれる１つ以上の熱間耐食性金属からなる炭化物サ
ーメットの溶射被覆層を有し、そして上盛層が10〜40重
量％のSiO2を含み、残部が MgO, CaO, ZrO2, Al2O3, Y2
O3およびTiO2のうちから選ばれる少なくとも１種を含む
酸化物セラミックス溶射被覆層から構成された２層構造
の溶射皮膜を設ける溶融金属浴用部材である。According to the present invention developed based on such knowledge, the underlay layer is formed of a carbide or cermet coating layer of a hot corrosion-resistant metal on the surface of the steel member, and the overlay layer is formed of
A member for a molten metal bath provided with a two-layer thermal spray coating composed of an oxide ceramic coating layer containing 10 to 40% by weight of SiO 2 ,
In addition, one or more carbides selected from Cr 3 C 2 , NbC, TiC, WC, WTiC, ZrC, and SiC, or carbides thereof, are formed on the surface of the steel member as an underlaying layer. %, With the balance being a spray coating of a carbide cermet consisting of one or more hot corrosion resistant metals selected from the group consisting of Co, Ni, Cr and Mo. Of SiO 2 , the remainder being MgO, CaO, ZrO 2 , Al 2 O 3 , Y 2
This is a molten metal bath member provided with a sprayed coating having a two-layer structure composed of a sprayed oxide ceramics coating layer containing at least one selected from O 3 and TiO 2 .
【００１６】[0016]
【作用】本発明において、上盛層を構成させる酸化物セ
ラミックスとしては、SiO2を10〜40重量％含有する酸化
物セラミックスを用いる。本来、酸化物セラミックス
は、溶融金属との間で反応することがなく、濡れ性も極
めて小さい材料である。とくにSiO2を10重量％以上含有
させると、溶射被覆層に微細な縦割れを発生し、これが
熱応力を吸収する作用を示して耐熱衝撃性を著しく向上
させる。しかし、このSiO2含有量が40重量％を超える
と、このような酸化物セラミック皮膜は多孔質となるた
めに、溶融金属の侵入が顕著となり、溶融金属に対して
耐食性を有する下盛層であっても腐食を受けて剥離を生
じやすくなる。すなわち、本発明において上盛層に用い
る酸化物セラミックスは、SiO2を10〜40重量％含有する
ことが必要である。 本発明において、このSiO2の他に
加えるその他のセラミックス成分としては、MgO, CaO,
ZrO2, Al2O3, Y2O3 およびTiO2のいずれか少なくとも１
種以上を加えて用いる。[Action] In the present invention, the oxide ceramic which constitutes the upper-up layers, an oxide ceramic containing SiO 2 10 to 40 wt%. Originally, oxide ceramics are materials that do not react with molten metal and have extremely low wettability. In particular, when SiO 2 is contained in an amount of 10% by weight or more, fine vertical cracks are generated in the thermal spray coating layer, which exhibits an action of absorbing thermal stress, and significantly improves thermal shock resistance. However, when the SiO 2 content exceeds 40% by weight, such an oxide ceramic coating becomes porous, so that the penetration of the molten metal becomes remarkable, and the undercoat layer having corrosion resistance to the molten metal is formed. Even if it is present, it is susceptible to peeling due to corrosion. That is, oxide ceramics used in the above-up layer in the present invention, it is necessary to contain SiO 2 10 to 40 wt%. In the present invention, other ceramic components added in addition to this SiO 2 include MgO, CaO,
At least one of ZrO 2 , Al 2 O 3 , Y 2 O 3 and TiO 2
Add more than seeds.
【００１７】一方、本発明における下盛層は、Cr3C2, N
bC, TiC, WC, WTiC, ZrCおよびSiCのうちから選ばれる
１種以上の炭化物, またはかかる炭化物を50重量％以上
含有し残部がCo, Ni, Cr, Moのなかから選ばれる１種以
上の熱間耐食性金属との混合物からなる炭化物サーメッ
トを溶射して用いる。Cr3C2, NbC, TiC, WC, WTiC,ZrC
およびSiC などの炭化物セラミックスは、溶融金属に対
して濡れにくく、かつ溶融金属と反応しない材料であ
り、しかも鉄鋼材料素材に対して優れた密着性を示すの
で、セラミックスの上盛層のアンダーコート用材料とし
て最適である。On the other hand, the underlayer according to the present invention is composed of Cr 3 C 2 , N
one or more carbides selected from bC, TiC, WC, WTiC, ZrC and SiC, or one or more carbides containing 50% by weight or more of such carbides and the balance being Co, Ni, Cr, Mo A carbide cermet made of a mixture with a hot corrosion resistant metal is sprayed and used. Cr 3 C 2 , NbC, TiC, WC, WTiC, ZrC
And carbide ceramics such as SiC are materials that are difficult to wet with molten metal and do not react with molten metal, and show excellent adhesion to steel materials. Ideal as a material.
【００１８】特に、Co, Ni, Cr, Moなどの耐熱金属を混
合してなる炭化物サーメットは、鉄鋼材料素材に対して
高い密着性を有し、さらに鉄鋼素材と酸化物セラミック
スの熱膨張差を漸次的に緩和する皮膜構造効果を併せも
つため、酸化物セラミック被覆層の下盛層として極めて
優れた効果を示す。しかし、酸化物セラミック被覆層中
を浸透する溶融金属によって下盛層が侵食されることに
よる酸化物セラミック層の剥離を防止するには、この炭
化物サーメット中には50重量％以上の炭化物を含有させ
ることが必要である。In particular, a carbide cermet obtained by mixing a heat-resistant metal such as Co, Ni, Cr, and Mo has a high adhesiveness to a steel material, and further has a difference in thermal expansion between the steel material and the oxide ceramic. Since it also has a film structure effect of gradually relaxing, it exhibits an extremely excellent effect as an underlayer of the oxide ceramic coating layer. However, in order to prevent the oxide ceramic layer from being peeled off due to the erosion of the underlying layer by the molten metal penetrating into the oxide ceramic coating layer, the carbide cermet should contain at least 50% by weight of carbide. It is necessary.
【００１９】[0019]
実施例１ 以上説明したように、溶融金属部材における酸化物セラ
ミック層の剥離の主因は、鉄鋼素材とセラミック層の熱
膨張係数の相違に基づく熱応力によって発生したクラッ
クおよび溶融金属の拡散浸透による金属溶射層や鉄鋼素
材の侵食であると考えられる。そこで、以下にこれらの
ことを確かめるために、素材には熱膨張係数の大きいSU
S 304 鋼を使用し、幾つかの溶射材料を溶射処理したテ
ストピースを製作し、これを溶融アルミニウム浴に浸漬
する試験および熱サイクル試験を実施した。Example 1 As described above, the main causes of the separation of the oxide ceramic layer in the molten metal member are cracks generated by thermal stress based on the difference in the thermal expansion coefficient between the steel material and the ceramic layer, and metal diffusion and diffusion of the molten metal. This is considered to be the erosion of the thermal spray layer and the steel material. Therefore, in order to confirm these points below, the material must be made of SU with a large coefficient of thermal expansion.
Using S 304 steel, test pieces were prepared by spraying several sprayed materials, and the test pieces were immersed in a molten aluminum bath and subjected to a thermal cycle test.
【００２０】すなわち、溶射被覆した上記テストピース
を 700℃の溶融アルミニウム浴に浸漬し、30分後に引き
上げて冷却した後アルカリ洗浄するまでを１サイクルと
する試験を50回繰り返した。この試験には、直径30×長
さ300 のSUS 304 鋼基材に、アルミナ砥粒でブラスト処
理した後、表１に示す下盛層を各々 100μｍ溶射し、さ
らにその上に各種酸化物セラミック被覆層を 300μｍに
プラズマ溶射したテストピースを使用した。その結果を
表１に示す。That is, the test piece coated with the thermal spray coating was immersed in a molten aluminum bath at 700 ° C., pulled up 30 minutes later, cooled, and then washed with an alkali one cycle, and the test was repeated 50 times. In this test, a SUS 304 steel base material having a diameter of 30 x length of 300 was blasted with alumina abrasive grains, and the underlaying layers shown in Table 1 were sprayed at 100 µm each, and further coated with various oxide ceramics. A test piece whose layer was plasma-sprayed to 300 μm was used. Table 1 shows the results.
【００２１】 [0021]
【００２２】表１に示す結果から明らかなように、下盛
層として炭化物被覆層または炭化物を50重量％以上含有
し残部がCo, Ni, Cr, Moのなかから選ばれる１種以上の
熱間耐食性金属からなる炭化物サーメット被覆層を有
し、その上に上盛層として10〜40重量％のSiO2を含む酸
化物セラミック被覆層から構成された溶射皮膜は、耐剥
離性, 耐反応性に優れ、抜群の耐用性を有することが判
明した。As is apparent from the results shown in Table 1, at least 50% by weight of a carbide coating layer or carbide is contained as an underlaying layer, and the balance is at least one selected from the group consisting of Co, Ni, Cr and Mo. The thermal spray coating, which has a carbide cermet coating layer composed of a corrosion-resistant metal and an oxide ceramic coating layer containing 10 to 40% by weight of SiO 2 as an overlayer on the coating layer, has excellent resistance to peeling and reaction. It was found to be excellent and had excellent durability.
【００２３】実施例２ 次に、連続亜鉛めっき装置の浸漬ロールおよびサポート
ロールに、本発明皮膜であるWC−12Coを80μｍ下盛溶射
し、上盛層に 250μｍの30重量％SiO2−65重量％ CaO−
５重量％ZrO2溶射皮膜をプラズマ溶射法にて施工し、常
法により構造用鋼板を通過させる溶融亜鉛めっき処理試
験を行った。この溶射ロールは、亜鉛めっき浴装置の保
守点検のために、10日間（１チャージ）毎に溶融亜鉛浴
から引き上げた後、再び使用することを繰り返し、述べ
100日（10チャージ) の間、局部的な剥離やクラックも
なく、もちろん溶融亜鉛との反応もなく良好に使用でき
た。この点、従来の溶射皮膜の場合、３〜４チャージで
溶融亜鉛との反応や局部的剥離を生じていたことからみ
て、本発明皮膜は数倍の寿命延長が可能となったばかり
でなく、溶融亜鉛めっき鋼板の品質を向上させ、高級鋼
板の製造を可能とした。Example 2 Next, WC-12Co, which is a film of the present invention, was spray-sprayed on a lower layer of 80 μm on a dipping roll and a support roll of a continuous galvanizing apparatus, and 250 μm of 30% by weight SiO 2 -65 weight on the upper layer. % CaO-
A 5 wt% ZrO 2 thermal spray coating was applied by a plasma spraying method, and a hot-dip galvanizing treatment test for passing a structural steel sheet by a conventional method was performed. This spraying roll was repeatedly withdrawn from the molten zinc bath every 10 days (one charge) for maintenance and inspection of the galvanizing bath equipment, and was repeatedly used.
During 100 days (10 charges), it could be used without any local peeling or cracking and, of course, no reaction with molten zinc. In this respect, in the case of the conventional thermal spray coating, the coating of the present invention can not only extend the service life by several times, The quality of galvanized steel sheets has been improved, and high-grade steel sheets can be manufactured.
【００２４】実施例３ ロール基材表面に Cr3C2−20重量％NiCrの下盛層を 100
μｍ溶射被覆し、その上に300 μｍの10重量％SiO2−70
重量％MgO −20重量％ZrO2成分からなる酸化物セラミッ
クの超高速ガス炎溶射皮膜を形成したポットロール（浸
漬ロール）を連続溶融アルミニウムめっき装置のアルミ
ニウム浴中に取付けて使用した。溶融アルミニウムめっ
き装置の保守点検のために７日間（１チャージ）毎にめ
っき浴から引き上げた後、再使用するサイクルを繰返し
たが、延べ70日間 (10チャージ)の間、局部的な剥離や
クラックもなく、さらに溶融アルミニウムとの反応や摩
耗もなく、良好に使用できていた。この点、従来の溶射
被覆ロールは、１〜３チャージで溶融アルミニウムとの
反応や剥離によって取替えていたことから、本発明の皮
膜つき浴用部材は、数倍の耐用性を有することが判明し
た。Example 3 An underlayer of Cr 3 C 2 -20% by weight NiCr was applied to a roll base material surface by 100
μm spray-coated and 300 μm of 10% by weight SiO 2 -70
A pot roll (immersion roll) on which an ultrahigh-speed gas flame sprayed coating of an oxide ceramic composed of 2 % by weight of MgO-20% by weight of ZrO was mounted and used in an aluminum bath of a continuous hot-dip aluminum plating apparatus. After being lifted out of the plating bath every seven days (one charge) for maintenance and inspection of the hot-dip aluminum plating equipment, the cycle of reuse was repeated, but local peeling and cracking occurred for a total of 70 days (10 charges). There was no reaction and no abrasion with the molten aluminum. In this regard, since the conventional thermal spray coating roll was replaced by reaction with molten aluminum or exfoliation at 1 to 3 charges, it was found that the bath member with a coating of the present invention had several times the durability.
【００２５】実施例４ 連続亜鉛−55重量％アルミニウム合金めっき装置のサポ
ートロールに、本発明の皮膜つき浴用部材であるCr3C2
を70μｍ下盛溶射した後、上盛層に 250μｍの35重量％
SiO2−45重量％MgO −20重量％ZrO2材料をプラズマ溶射
法にて施工し、常法により構造用鋼板を通過させる溶融
亜鉛−45重量％アルミニウム合金めっき処理試験を行っ
た。この溶射ロールは、亜鉛−アルミニウム合金めっき
浴装置の保守点検のために、７日間（１チャージ）毎に
溶融めっき浴から引き上げた後、再び使用することを繰
返し、延べ77日間 (11チャージ) の間、局部的な剥離や
クラック、また溶融金属との反応もなく、良好に使用で
きていた。この点、従来の溶射皮膜やSUS 316Lステンレ
ス鋼製ロールは、２〜４チャージで局部的剥離や溶融金
属との反応を生じていたことから、本発明の浴用部材は
数倍の寿命延長が可能となった。Example 4 Cr 3 C 2 which is a bath member with a film of the present invention was applied to a support roll of a continuous zinc-55 wt% aluminum alloy plating apparatus.
After spraying 70 μm underlay, 35% by weight of 250 μm
A SiO 2 -45 wt% MgO-20 wt% ZrO 2 material was applied by a plasma spraying method, and a hot zinc-45 wt% aluminum alloy plating test was performed by passing through a structural steel sheet by a conventional method. The thermal spraying roll is pulled up from the hot-dip plating bath every seven days (one charge) for maintenance and inspection of the zinc-aluminum alloy plating bath equipment, and then repeatedly used, for a total of 77 days (11 charges). During the operation, there was no local peeling or cracking and no reaction with the molten metal. In this regard, the conventional sprayed coating and SUS 316L stainless steel roll have caused local exfoliation and reaction with the molten metal in 2 to 4 charges, so that the life of the bath member of the present invention can be extended several times. It became.
【００２６】[0026]
【発明の効果】以上の説明ならびに実施例での検証結果
から明らかなように、炭化物の下盛被覆層または50重量
％以上の炭化物と熱間耐食性金属からなる炭化物サーメ
ットの下盛層と、10〜40重量％のSiO2を含有する酸化物
セラミック被覆層による上盛層から構成された溶射皮膜
を有する本発明溶融金属部材は、亜鉛めっき浴だけでな
く、処理温度が高いアルミニウム浴でも耐侵食性に優
れ、十分に満足する寿命を発揮する。また、本発明の浴
用部材は、安定した溶融金属めっき作用と高い生産性な
らびにめっき鋼板の品質改善に効果を発揮する。As is evident from the above description and the verification results in the examples, it is clear that the underlayer coating layer of carbide or the underlayer layer of carbide cermet composed of at least 50% by weight of carbide and hot corrosion resistant metal, The molten metal member of the present invention having a sprayed coating composed of an overlaid layer of an oxide ceramic coating layer containing 4040% by weight of SiO 2 is not only erosion-resistant in a zinc plating bath but also in an aluminum bath having a high processing temperature. It has excellent properties and exhibits a satisfactory life. Further, the bath member of the present invention exerts an effect on a stable hot-dip metal plating action, high productivity, and quality improvement of a plated steel sheet.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三船 法行 兵庫県神戸市垂水区学が丘６丁目１− 3031 (72)発明者 平 初雄 兵庫県姫路市広畑区富士町１番地 新日 本製鐵株式会社 広畑製鉄所内 (72)発明者 今若 寛 兵庫県姫路市広畑区富士町１番地 新日 本製鐵株式会社 広畑製鉄所内 (72)発明者 余頃 孝之 東京都江東区豊洲１丁目１番７号 小野 田セメント株式会社 セラミックス研究 所内 (72)発明者 山根 洋 山口県小野田市大字小野田6276番地 小 野田セメント株式会社 セラミックス小 野田工場内 (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 4/04 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Noriyuki Mifune 6-303-1 Gakugaoka, Tarumizu-ku, Kobe-shi, Hyogo (72) Inventor Hatsuo Hira 1 Fujimachi, Hirohata-ku, Himeji-shi, Hyogo Nippon Steel Corporation Hirohata Works (72) Inventor Hiroshi Imawaka 1 Fuji-machi, Hirohata-ku, Himeji-shi, Hyogo Nippon Steel Corporation Inside Hirohata Works (72) Inventor Takayuki Yorochi 1-7-1 Toyosu, Koto-ku, Tokyo No. Onoda Cement Co., Ltd. Ceramics Research Institute (72) Inventor Hiroshi Yamane 6276 Onoda, Onoda-shi, Yamaguchi Prefecture Onoda Cement Co., Ltd. Ceramics Onoda Factory (58) Field surveyed (Int.Cl. 6 , DB name) C23C 4/04
Claims (4)
は熱間耐食性金属の炭化物サーメット被覆層で構成さ
れ、上盛層が10〜40重量％のSiO2を含む酸化物セラミッ
ク被覆層で構成された２層溶射皮膜を設けてなる溶融金
属浴用部材。On the surface of the 1. A steel member, avaiable layer is made of a carbide cermet coating layer of a carbide or hot corrosion resistant metal, on up layer is oxide ceramic coating layer containing 10 to 40 wt% of SiO 2 A member for a molten metal bath provided with the constituted two-layer thermal spray coating.
TiC, ZrCおよび SiCのなかから選ばれる１種以上の炭化
物からなる溶射層で構成することを特徴とする請求項１
に記載の溶融金属浴用部材。2. The underlaying layer is made of Cr 3 C 2 , NbC, TiC, WC, W
2. A thermal spraying layer comprising at least one carbide selected from TiC, ZrC and SiC.
3. The member for a molten metal bath according to item 1.
TiC, ZrCおよび SiCのなかから選ばれる１種以上の炭化
物を50重量％以上含有し、残部がCo, Ni, Cr, Moのうち
いずれか１種以上の金属または合金である熱間耐食性金
属である炭化物サーメットの溶射層で構成することを特
徴とする請求項１に記載の溶融金属浴用部材。3. The method according to claim 1, wherein the underlayer is made of Cr 3 C 2 , NbC, TiC, WC, W
A hot corrosion resistant metal containing at least 50% by weight of one or more carbides selected from TiC, ZrC and SiC, with the balance being one or more metals or alloys of Co, Ni, Cr and Mo 2. The member for a molten metal bath according to claim 1, wherein the member is formed of a sprayed layer of a certain carbide cermet.
に、MgO, CaO, ZrO2, Al2O3, Y2O3 およびTiO2のうちい
ずれか１種以上の酸化物セラミックスを含む複合物の溶
射層で構成することを特徴とする請求項１に記載の溶融
金属浴用部材。4. The above-mentioned overlaid layer comprises, in addition to 10 to 40% by weight of SiO 2 , at least one of MgO, CaO, ZrO 2 , Al 2 O 3 , Y 2 O 3 and TiO 2 . The member for a molten metal bath according to claim 1, wherein the member is formed of a composite thermal sprayed layer containing an oxide ceramic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14934691A JP2955625B2 (en) | 1991-05-27 | 1991-05-27 | Material for molten metal bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14934691A JP2955625B2 (en) | 1991-05-27 | 1991-05-27 | Material for molten metal bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04350154A JPH04350154A (en) | 1992-12-04 |
| JP2955625B2 true JP2955625B2 (en) | 1999-10-04 |
Family
ID=15473114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14934691A Expired - Lifetime JP2955625B2 (en) | 1991-05-27 | 1991-05-27 | Material for molten metal bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2955625B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000096204A (en) * | 1998-09-19 | 2000-04-04 | Nippon Steel Hardfacing Co Ltd | Manufacture of member for molten metal bath having film excellent in corrosion resistance to molten metal |
| KR20020051089A (en) * | 2000-12-22 | 2002-06-28 | 이구택 | Thermal Spray Method of Oxide Coatings for Rolls used in Molten Zinc Pot |
| JP2005179766A (en) * | 2003-12-19 | 2005-07-07 | Murata Boring Giken Kk | Corrosion resistant and insulative material, and manufacturing method therefor |
| DE102007012635A1 (en) * | 2007-03-16 | 2008-09-18 | Alfred Flamang | Flame spraying material for flame-sprayed high-speed coatings comprises zirconium carbide as hardening material, and binding agent, which has nickel or copper |
| CN106929844B (en) * | 2017-03-29 | 2019-04-23 | 大连理工大学 | The method that a kind of pair of shielding tunnel excavator hobboing cutter cutter ring carries out surface laser Alloying Treatment |
| KR102266655B1 (en) * | 2020-12-10 | 2021-06-18 | (주)코미코 | The method of producing thermal spray coating using the yittrium powder and the yittrium coating produced by the mothod |
-
1991
- 1991-05-27 JP JP14934691A patent/JP2955625B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04350154A (en) | 1992-12-04 |
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