JP3160387B2 - Composite thermal spray material and composite thermal spray coating excellent in molten metal resistance - Google Patents
Composite thermal spray material and composite thermal spray coating excellent in molten metal resistanceInfo
- Publication number
- JP3160387B2 JP3160387B2 JP26342892A JP26342892A JP3160387B2 JP 3160387 B2 JP3160387 B2 JP 3160387B2 JP 26342892 A JP26342892 A JP 26342892A JP 26342892 A JP26342892 A JP 26342892A JP 3160387 B2 JP3160387 B2 JP 3160387B2
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- Prior art keywords
- boride
- composite
- thermal spray
- carbide
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐溶融金属性に優れ
る、粉状もしくは粒状の複合溶射材料とこの材料の溶射
によって形成さ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 powdery or granular composite sprayed material having excellent resistance to molten metal and a composite sprayed coating formed by spraying the material.
【０００２】[0002]
【従来の技術】溶融亜鉛めっき、溶融アルミニウムめっ
き、溶融亜鉛−アルミニウム合金めっきなどのめっき層
は、優れた防錆、防食力を発揮することから、かかるめ
っき技術は、自動車、航空機、車輌、建築、家電製品な
どの主要部材に古くから使用されており、現在でもなお
主要な役割りを果している有用な表面処理技術である。2. Description of the Related Art Plating layers such as hot-dip galvanizing, hot-dip aluminum plating, hot-dip zinc-aluminum alloy plating exhibit excellent rust and corrosion resistance. It is a useful surface treatment technology that has been used for a long time in main components such as home appliances and still plays a major role even today.
【０００３】なかでも、特に大量に生産されている溶融
亜鉛めっき鋼板のめっき処理は、多くの場合、図１に示
すような連続めっき処理によって行われている。この連
続式溶融亜鉛めっき装置には、めっき浴１中に浸漬され
ているシンクロール２、めっき浴中の表面近傍に配設さ
れるサポートロール３及びこれらのロールを通過した後
のめっき鋼板４を案内するガイドロール５、鋼板に付着
した過剰の亜鉛を窒素ガスや水蒸気で吹き飛ばすための
噴射ノズル６などが配設されている。ここで、本発明に
係る複合溶射材料の溶射対象となるめっき用部材は、め
っき浴中に浸漬されるか、溶融亜鉛が飛散付着するか、
あるいは鋼板上にめっきされた亜鉛が軟化状態にある条
件下でそれに接触する箇所に配設され、(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) めっき用部材とし
ての寿命が長く低コストであること、(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が要
求されるものである。[0003] In particular, plating of hot-dip galvanized steel sheets, which are produced in large quantities, is often performed by continuous plating as shown in FIG. This continuous hot-dip galvanizing apparatus includes a sink roll 2 immersed in a plating bath 1, a support roll 3 disposed near the surface in the plating bath, and a plated steel sheet 4 after passing through these rolls. A guide roll 5 for guiding, an injection nozzle 6 for blowing off excess zinc attached to the steel plate with nitrogen gas or water vapor, and the like are provided. Here, the plating member to be sprayed with the composite sprayed material according to the present invention is immersed in a plating bath, or molten zinc is scattered and adhered,
Alternatively, the zinc plated on the steel sheet is placed at the place where it comes into contact with the softened condition, and (1) the erosion by molten zinc is unlikely to occur, (2) even if it comes in contact with the threading material (steel sheet) (3) Easy removal of adhered molten zinc and easy maintenance and inspection, (4) Long life as a plating member and low cost, (5) Immersion in hot zinc bath It is required to well withstand the thermal shock when it is performed.
【０００４】このような要求に応えるため、シンクロー
ル用皮膜を例にとれば、(1) 特公昭58−11507 号公報に
記載のJIS H8303 (1976)制定のCo基自溶合金に準拠した
合金組成の皮膜を形成したもの。(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
クス皮膜を溶射形成したもの、(3) 特公昭58−37386 号
公報に開示のように、WC, Cr3C2, TiCの一種または二種
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 〜2.4mm 厚さの皮膜
を、主として溶射法によって形成したもの、などが提案
されており、以上のような技術に対し、発明者らも同種
技術の開発研究を行なって、(4) 特願昭63−49846 号
（特開平１−225761号) で、WCサーメットにおいて、Co
を５〜28％含み、その皮膜の気孔率を1.8 ％以下、膜厚
を 0.040〜0.10mm未満とした溶射皮膜、(5) 特願昭63−
192753号（特開平２−43352 号) において、硼化物また
はこれにCoを５〜28％含ませた材料を減圧プラズマ溶射
法によって形成させたもの、(6) 特願平１−54883 号
（特開平２−236266号) において、ZrB2, TiB2及び各種
炭化物に５〜40％のTa, Nbを含ませた材料を用い、減圧
プラズマ溶射法によってその皮膜表面粗さをRa 0.01 〜
５μm 、気孔率1.8 ％以下の皮膜を形成させたもの、
(7) 実願平１−124010号（実開平３−63565 号) におい
て、炭化物を主体とするサーメット溶射皮膜上に、化学
的緻密化法によってCr3O3 を形成した皮膜、(8) 特願平
２−201187号（特開平４−88159 号) において、炭化物
溶射皮膜の一部を硼化処理によって硼化物に変化させた
皮膜、(9) 特願平３−31448 号（出願日 平成3.2.1)に
おいて各種炭化物、硼化物またはそのサーメット溶射皮
膜にAlまたはAl−Zn合金を加熱拡散することによって、
耐溶融亜鉛性を向上させる、などの諸技術および皮膜を
提案してきた。[0004] In order to meet such a demand, taking a film for a sink roll as an example, (1) An alloy based on a Co-based self-fluxing alloy specified in JIS H8303 (1976) described in Japanese Patent Publication No. 58-11507. A film with a composition formed. (2) JP-A-61-117260
As disclosed in Japanese Unexamined Patent Publication (Kokai) Publication No. H8-78, a ceramic coating composed of ZrO 2 and Al 2 O 3 is spray-formed, (3) As disclosed in Japanese Patent Publication No. 58-37386, WC, Cr 3 C 2 , TiC For one or two or more types, a hot corrosion resistant metal such as Ni or Si, or a 0.1 to 2.4 mm thick film formed by coexisting these oxides, mainly formed by a thermal spraying method, has been proposed. With respect to the above-mentioned technologies, the inventors have also conducted research on the development of similar technologies. (4) In Japanese Patent Application No. 63-49846 (Japanese Patent Application Laid-Open No.
Thermal spray coating having a porosity of 1.8% or less and a film thickness of 0.040 to less than 0.10 mm.
No. 192753 (Japanese Unexamined Patent Publication No. 2-43352), a method in which a boride or a material containing 5 to 28% of Co is formed by a low pressure plasma spraying method. No. 2-236266), using a material in which ZrB 2 , TiB 2 and various carbides contain 5 to 40% of Ta and Nb were used, and the coating surface roughness was reduced to Ra 0.01 to
5 μm, having a film with a porosity of 1.8% or less,
(7) In Japanese Utility Model Application No. 1-124010 (Japanese Utility Model Application Laid-Open No. 3-63565), a film in which Cr 3 O 3 is formed by a chemical densification method on a cermet sprayed coating mainly composed of carbide; Japanese Unexamined Patent Application No. Hei 2-201187 (Japanese Patent Application Laid-Open No. 4-88159) discloses a coating obtained by converting a part of a carbide sprayed coating into a boride by boride treatment. .1) by heating and diffusing Al or Al-Zn alloy to various carbides, borides or their cermet sprayed coatings,
Various technologies and films have been proposed, such as improving the resistance to molten zinc.
【０００５】[0005]
【発明が解決しようとする課題】以上の例示から判るよ
うに、従来の溶融亜鉛めっき用部材に形成する溶射皮膜
についての研究課題は、耐溶融亜鉛性皮膜材料の選
定、皮膜の密着性の改善、皮膜の表面粗さと緻密性
の改善、などが主体を占めており、それぞれ改善効果が
認められている。しかしながら、昨今の溶融亜鉛めっき
鋼板の需要の拡大に伴って、めっきプラントの稼動率の
向上および、めっき鋼板の品質向上に対する要求が極め
て強くなり、耐溶融亜鉛性はもとより、めっき浴中に浮
遊する微細なドロス成分 (Zn−Fe, Zn−Fe−Al合金) の
溶射皮膜表面への付着ひいては、付着したそのドロスに
よって鋼板に極微小な押傷が発生することさえも嫌忌す
るような状況となってきた。そこで、本発明では、これ
らの要求を十分に満たすことができる、耐溶融金属性に
優れる複合溶射材料およびこの材料を用いて溶射形成し
た複合溶射皮膜を提供することを目的とする。As can be seen from the above examples, the research issues regarding the thermal spray coating formed on the conventional hot-dip galvanized member are to select a hot-dip galvanizing coating material and to improve the adhesion of the coating. In addition, improvement of the surface roughness and denseness of the film is mainly occupied, and the improvement effect is recognized respectively. However, with the recent increase in the demand for hot-dip galvanized steel sheets, the demand for improving the operation rate of the plating plant and the quality of the coated steel sheets has become extremely strong. Adhesion of the fine dross component (Zn-Fe, Zn-Fe-Al alloy) to the sprayed coating surface It has become. Therefore, an object of the present invention is to provide a composite sprayed material which can sufficiently satisfy these requirements and has excellent resistance to molten metal, and a composite sprayed coating formed by spraying using this material.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、種々の実
験研究を行った結果、溶射皮膜中への溶融亜鉛の侵入に
ついては、緻密な炭化物あるいは炭化物サーメット皮膜
を採用することによって阻止する一方、ドロス成分の付
着については、溶融亜鉛と冶金反応しない硼化物を使用
することによって防止することが有効であることを知見
した。これがため、本発明の、耐溶融金属性に優れる複
合溶射材料では、炭化物あるいは炭化物サーメットの各
粒子と硼化物とからなる混合溶射材料の粒子を、予め複
合一体化させておき、これにより、溶射作業中において
両成分が分離することなく、複合状態のままで溶射され
て成膜化されるように構成した。即ち、本発明は、炭化
物あるいは炭化物サーメットの各粒子と、硼化物とを混
合してなる複合溶射材料において、上記炭化物または炭
化物サーメットの各粒子と硼化物とが予め複合一体化し
ていることを特徴とする耐溶融金属性に優れる複合溶射
材料を、提案する。また、本発明は、予め硼化物と溶融
結合させるかまたは表面に予め硼化物の被覆層を設けて
なる炭化物、あるいは同じ処理を施してなる炭化物サー
メットの溶射材料を溶射して形成される複合溶射皮膜
を、提案する。なお、上記複合溶射材料を溶射して形成
した複合溶射皮膜は、炭化物や炭化物サーメットの特性
である溶融亜鉛の内部侵入防止特性と、硼化物が具える
ドロス成分付着防止特性を兼備した皮膜となる。As a result of various experiments and studies, the present inventors have found that the penetration of molten zinc into a sprayed coating can be prevented by employing a dense carbide or carbide cermet coating. On the other hand, it has been found that it is effective to prevent the adhesion of the dross component by using a boride that does not react with the molten zinc by metallurgy. For this reason, in the composite thermal spraying material of the present invention, which is excellent in molten metal resistance, the particles of the mixed thermal spraying material composed of carbide or carbide cermet particles and boride are preliminarily composite-integrated, whereby the thermal spraying is performed. During the operation, the two components were sprayed and formed into a film in a composite state without separation. That is, the present invention is characterized in that, in a composite thermal spray material obtained by mixing each particle of carbide or carbide cermet and boride, each of the above-mentioned particles of carbide or carbide cermet and boride are preliminarily compositely integrated. We propose a composite sprayed material that is excellent in molten metal resistance. Further, the present invention provides a composite spray formed by spraying a sprayed material of a carbide which is preliminarily melt-bonded with a boride or provided with a boride coating layer on the surface or a carbide cermet sprayed material which is subjected to the same treatment. Suggest a coating. The composite thermal spray coating formed by thermal spraying the composite thermal spray material is a film having both the property of preventing intrusion of molten zinc, which is a property of carbide and carbide cermet, and the property of preventing dross component adhesion of boride. .
【０００７】[0007]
【作用】本発明の溶射材料を構成する主要成分は、炭化
物、硼化物およびサーメットを構成する金属であり、か
かる炭化物としては、TiC, NbC, WC, Cr3C2, B4C, TaC,
BiC, ZrC, HfCもしくはVCなどが有利に適合し、かかる
硼化物としては、TiB2, ZrB2, HfB2, VB2, TaB2, NbB2,
W2B5 もしくはCrB2などが有利に適合し、そして、上記
の炭化物サーメットを構成する金属成分としては、Co,
Ni, Cr,Al, Feのいずれか一種または二種以上のものが
用いられる。The main components constituting the thermal sprayed material of the present invention are carbides, borides and metals constituting cermets. Such carbides include TiC, NbC, WC, Cr 3 C 2 , B 4 C, TaC,
BiC, ZrC, etc. are advantageously adapted HfC or VC, as such boride, TiB 2, ZrB 2, HfB 2, VB 2, TaB 2, NbB 2,
W 2 B 5 or CrB 2 or the like is advantageously suitable, and as a metal component constituting the above-mentioned carbide cermet, Co,
Any one or more of Ni, Cr, Al, and Fe are used.
【０００８】これらのそれぞれの主要構成成分は、次に
示すような特性を有する。炭化物は、溶融金属に対して
強い侵食抵抗力, 即ち溶融亜鉛の内部侵入防止特性を示
すが、それ単独では溶融しにくい。しかし、金属が共存
すると、これがバインダーとなって溶射皮膜の形成を容
易にする。硼化物は、炭化物以上に溶融金属に対する侵
食抵抗力が高く、しかも本質的に溶融金属との接触角が
大きく、濡れ難く、溶融金属と合金反応をしない特徴が
ある。本発明は、この特性を、溶融亜鉛浴中に浮遊する
ドロス成分の付着防止の目的に利用しようとするもので
ある。また、硼化物は安定した溶融状態を呈するためそ
の溶射成膜が容易である。金属成分は、本質的に溶融亜
鉛と反応して合金をつくるが、一方では炭化物や硼化物
とも反応して金属間化合物をつくることができる。この
金属間化合物は、溶射皮膜の形成を容易にするほか、金
属単体よりも耐溶融亜鉛性を向上させる特徴がある。Each of these main components has the following characteristics. Carbide exhibits strong erosion resistance to molten metal, that is, the property of preventing molten zinc from entering the inside, but is not easily melted by itself. However, when a metal coexists, this acts as a binder to facilitate the formation of a thermal spray coating. Borides are characterized by having a higher erosion resistance to molten metal than carbides, and have a substantially large contact angle with molten metal, are hardly wet, and do not react with the molten metal. The present invention intends to utilize this property for the purpose of preventing the dross component floating in the molten zinc bath from adhering. Further, the boride exhibits a stable molten state, so that thermal spray deposition is easy. The metal component essentially reacts with the molten zinc to form an alloy, while it can also react with carbides and borides to form intermetallic compounds. This intermetallic compound is characterized by facilitating the formation of a thermal spray coating and improving the resistance to molten zinc as compared with a single metal.
【０００９】なお、市販の炭化物のなかには、製造条件
によって遊離の炭素を含むことがあり、また金属材料中
にもＣ，Si, Mn, Ｐ，Ｓその他の不純物を含むことがあ
るが、これらの成分の混入量については本発明の目的に
対し、妨げとなる現象が認められないので、特に規定し
ないことを付記しておく。[0009] Some of the commercially available carbides may contain free carbon depending on the production conditions, and the metal material may contain C, Si, Mn, P, S and other impurities. It should be noted that the amount of the components to be mixed is not particularly specified because no phenomena that hinder the object of the present invention are observed.
【００１０】以上の材料を用いて、本発明の溶射材料の
製造例を説明する。 (1) 市販の炭化物サーメット粉末に、硼化物粉末を混合
し、メカニカルアロイング法またはメカノフュージング
法によって両成分の少なくとも一部を溶融させて複合一
体化させる。なお、このとき高分子バインダーを添加す
ることによって両粉末の結合を促進させることもできる
（機械的複合法）。 (2) 市販の炭化物サーメット粉末を、硼化物の蒸気、特
にハロゲン硼化物の蒸気中に曝露させることによって、
炭化物サーメット粉末の表面に硼素または硼化物を析出
させて蒸着被覆する（CVD 法）。 (3) 真空容器中の硼素又は硼化物に電子ビームを照射し
てこれを蒸気化させ、炭化物サーメット粉末をこの蒸気
に曝露させることによって、その表面に硼化物を析出付
着させて被覆する（PVD 法）。 (4) 市販の炭化物サーメットを溶融状の硼砂 (Na2B2O7)
中に浸漬含浸させることにより、炭化物サーメット粉末
の表面を硼化物化させる。なお、この硼砂に代えて、NH
4Cl ＋B4C 混合粉末中に炭化物サーメット粉末を添加し
て600 ℃〜800℃で１〜３時間加熱することにより、硼
化物を含浸させる方法でもよい（熱拡散法）。An example of manufacturing the thermal spray material of the present invention using the above materials will be described. (1) A boride powder is mixed with a commercially available carbide cermet powder, and at least a part of both components is melted by a mechanical alloying method or a mechanofusing method so as to be integrated. At this time, the binding of both powders can be promoted by adding a polymer binder (mechanical composite method). (2) by exposing a commercial carbide cermet powder to boride vapors, in particular halogen boride vapors,
Boron or boride is deposited on the surface of the carbide cermet powder and coated by vapor deposition (CVD method). (3) Boron or boride in a vacuum vessel is irradiated with an electron beam to vaporize it, and a carbide cermet powder is exposed to the vapor to deposit and coat boride on the surface (PVD). Law). (4) Commercially available carbide cermet is melted borax (Na 2 B 2 O 7 )
The surface of the carbide cermet powder is boridified by immersion and impregnation therein. Instead of this borax, NH
A method in which a carbide cermet powder is added to a 4 Cl + B 4 C mixed powder and heated at 600 ° C. to 800 ° C. for 1 to 3 hours to impregnate a boride may be used (thermal diffusion method).
【００１１】このようにして製造した溶射粉末材料は、
比重の著しく異なる材料たとえばWC（約15.6) 、TiB2
(約4.4)を一つの粉末粒子（複合粒子）として取扱うこ
とができるので、一旦複合一体化すれば、溶射作業中に
おいてもこの両成分が分離するようなことがない。な
お、複合一体化した粒子は、必要に応じ溶射に適した粒
度に粉砕調整する。すなわち、溶射用としては直径５〜
50μm が好ましく、これ未満では溶射時にフューム化
し、またそれを越えると、皮膜を構成した際に、未溶融
粒子となって混在し、空隙の発生や粒子間結合力の低下
をもたらすので好ましくない。[0011] The thermal spray powder material produced in this way is:
Materials with significantly different specific gravities such as WC (about 15.6), TiB 2
(Approximately 4.4) can be handled as one powder particle (composite particle). Therefore, once the composite is integrated, these two components do not separate during the thermal spraying operation. The particles integrated into a composite are pulverized and adjusted to a particle size suitable for thermal spraying, if necessary. That is, for thermal spraying, diameter 5
If it is less than 50 μm, fumes are formed during thermal spraying, and if it is more than 50 μm, undesired particles are mixed and formed when forming a coating film, which is not preferable because voids are generated and the interparticle bonding force is reduced.
【００１２】次に、上述した複合溶射材料を用いて溶射
成膜を形成する方法について具体的に説明する。さきに
述べたように、本発明の溶射材料は、そのすべてが粉末
状態であるため、成膜に当っては、プラズマ溶射法、可
燃性ガスの燃焼炎を熱源とするフレーム溶射法あるいは
爆発溶射法によって成膜することが好適である。また、
かかる溶射皮膜の形成に際しては、炭化物、硼化物、こ
れらのサーメットあるいは複合粒子などを使用目的に応
じて任意に選定できるため、それらの溶射材料を層状構
造にしたり、傾斜構造に成膜することも可能である。た
とえば(1) 炭化物サーメットを50μm 厚にフレーム溶射
法によって形成し、さらにその上に複合材料粒子を50μ
m 厚にプラズマ溶射法によって積層すること、(2) 炭化
物サーメット材料と複合粉末材料の混合割合を種々変化
させ、鉄鋼母材側ほど炭化物サーメット含有量を多く
し、上層部ほど複合材料の比率が高くなるような構造に
成膜すること、など成膜構成成分の割合いを自由に選定
することができる。Next, a method of forming a thermal sprayed film using the above-described composite thermal spray material will be specifically described. As described above, since the sprayed material of the present invention is all in a powder state, the film is formed by a plasma spraying method, a flame spraying method using a combustible gas combustion flame as a heat source, or an explosive spraying method. It is preferable to form a film by a method. Also,
In forming such a thermal spray coating, carbides, borides, cermets or composite particles thereof can be arbitrarily selected according to the purpose of use, so that those thermal spray materials can be formed into a layered structure or formed into a gradient structure. It is possible. For example, (1) a carbide cermet is formed to a thickness of 50 μm by flame spraying, and composite material particles are further
(2) Varying the mixing ratio between the carbide cermet material and the composite powder material, increasing the carbide cermet content toward the steel base material and increasing the composite material ratio toward the upper layer. It is possible to freely select the proportion of the constituent components of the film formation, such as formation of a film having a high structure.
【００１３】ところで、このようにして形成される溶射
皮膜は、緻密な状態にすることが大切であり、多孔質な
皮膜では、溶融亜鉛が気孔部を通って内部へ侵入するた
め、如何に耐溶融亜鉛性に優れた溶融材料を用いて成膜
しても、その機能を十分に発揮させることができない。
これがため、溶射成膜時においては、溶射粉末の、溶射
ガンへの供給量を調整して１パス当り３〜30μm の皮膜
厚みが得られるように、複数回の溶射を重ねて所定の膜
厚となるようにするのが好ましい。なお、１パス当りの
膜厚が上述したより薄い場合には、より緻密な皮膜が得
られるものの、実用的な膜厚たとえば100 μm を得るの
に長時間を要し経済的でない。一方、１パス当りの皮膜
厚さが30μm を越える場合には、皮膜の気孔率が高くな
るとともに、皮膜を構成する粒子相互の結合力が弱くな
り、剥離しやすくなる欠点がある。By the way, it is important that the thermal sprayed coating formed in this way is made dense, and in the case of a porous coating, the molten zinc penetrates through the pores and enters the inside, so that it has no problem. Even if a film is formed using a molten material having excellent molten zinc properties, its function cannot be sufficiently exhibited.
For this reason, at the time of thermal spray deposition, a plurality of thermal sprays are repeated to obtain a predetermined film thickness so as to obtain a film thickness of 3 to 30 μm per pass by adjusting the supply amount of the thermal spray powder to the thermal spray gun. It is preferable that When the film thickness per pass is thinner than described above, a denser film can be obtained, but it takes a long time to obtain a practical film thickness of, for example, 100 μm, which is not economical. On the other hand, when the film thickness per pass exceeds 30 μm, the porosity of the film becomes high, and the bonding force between the particles constituting the film becomes weak, so that there is a disadvantage that the film is easily peeled.
【００１４】以上のような方法で製造した本発明の溶射
材料およびこの材料を用いて形成される溶射皮膜の最大
の特徴は、耐溶融金属性に優れた炭化物あるいは炭化物
サーメットの粒子、硼化物がそれぞれ一個の粒子として
完全に複合一体化していることにある。このため、本発
明の溶射材料によって形成した皮膜表面は、炭化物、硼
化物、金属などから成る複合化粒子が均等に分布した状
態を呈するとともに、粒子の表面には常に、硼化物が存
在する確率が高い。これに対し、炭化物、硼化物、金属
などを単に混合状態にしたままで、または、炭化物サー
メットと硼化物とを単に混合させただけの状態で溶射を
行うと、高速の粒子となって、飛行中にそれぞれの材料
の比重（例えば、WCの比重約15、TiB2の比重約4.4 、Ti
C の比重約4.9 、CrB2の比重約5.2)の差、粒径差などに
よって分離現象が発生する。このため、如何に均等に混
合した溶射材料を用いても、それを溶射成膜した表面で
は粉末材料成分の分布は極めて不均等となり、この結
果、溶融金属の内部侵入速度が速くなったり、ドロス成
分が付着しやすくなる欠陥がある。すなわち、ドロス成
分の付着は、溶射皮膜表面に存在する金属質部を核とし
て成長することが多く、単なる混合粉末の溶射面では、
ドロスの付着を防ぐことはできない。この点、本発明の
複合溶射材料では、前述の粉末加工例に示すように、硼
化物が常に金属質を被覆した状態にしてあるので、皮膜
表面には、ドロス成分の付着の核となる部分が殆んど存
在しない状態となる。The most significant feature of the thermal sprayed material of the present invention produced by the above-described method and the thermal sprayed coating formed by using this material is that carbide or carbide cermet particles and boride having excellent molten metal resistance are used. The point is that they are completely integrated into a single particle. For this reason, the surface of the coating formed by the thermal spray material of the present invention exhibits a state in which the composite particles composed of carbide, boride, metal, etc. are uniformly distributed, and the probability that boride is always present on the surface of the particles. Is high. On the other hand, if thermal spraying is performed with carbides, borides, metals, etc. simply kept in a mixed state, or simply with carbide cermets and borides mixed, high-speed particles will be formed and fly. The specific gravity of each material (for example, WC specific gravity about 15, TiB 2 specific gravity about 4.4, Ti
Separation phenomena occur due to a difference in specific gravity of C of about 4.9, a specific gravity of CrB 2 of about 5.2), a difference in particle size, and the like. For this reason, no matter how even the sprayed material is mixed, the distribution of the powder material components becomes extremely uneven on the surface on which the sprayed film is formed, and as a result, the penetration rate of the molten metal into the inside becomes high, There is a defect that makes it easy for components to adhere. That is, the adhesion of the dross component often grows with the metal part existing on the surface of the sprayed coating as a nucleus.
Dross adhesion cannot be prevented. In this regard, in the composite sprayed material of the present invention, as shown in the above-mentioned powder processing example, since the boride is always in a state of being coated with the metal, a portion serving as a nucleus of the adhesion of the dross component is formed on the film surface. Is almost nonexistent.
【００１５】[0015]
（実施例１）本発明に係る材料を溶射して形成した溶射
皮膜の耐溶融亜鉛性を調査するため、次のような実験を
行った。先ず、構造用炭素鋼 (SS400)直径15×長さ200m
m を母材とし、その表面に下記(1) 〜(13)の粉末材料を
用いて厚さ100 μm の皮膜を、高速ガス炎溶射法および
プラズマ溶射法によって形成した。なお(1) 〜(9) の材
料は機械的複合法によって製造したものであり、その他
の材料は、(10),(11)の材料は機械的混合法により、(1
3),(14) の材料は溶融粉砕法により、また(12)の材料は
噴霧法によってそれぞれ製造されたものである。(Example 1) The following experiment was conducted in order to investigate the molten zinc resistance of a thermal spray coating formed by thermal spraying the material according to the present invention. First, structural carbon steel (SS400) diameter 15 x length 200m
m was used as a base material, and a film having a thickness of 100 μm was formed on the surface thereof using the powder materials (1) to (13) below by a high-speed gas flame spraying method and a plasma spraying method. The materials (1) to (9) were manufactured by a mechanical composite method, and the other materials (10) and (11) were manufactured by a mechanical mixing method.
The materials (3) and (14) were produced by the melt-pulverization method, and the material (12) was produced by the spray method.
【００１６】(1) (85WC−11Co) −4TiB2 (2) (80TiC −1Ni −2Cr −10Al) −7TiB2 (3) 80Cr3C2−20ZrB2 (4) (84WC−10Co−2Al)−4CrB2 (5) (90TiC −5Al −2Fe)−3TiB2 (6) (88WC−12Co) 50μm その上に(1) を50μm (7) (83WC−17Co) 70μm その上に(2) を30μm (8) (88WC−12Co) 80μm その上に(3) を20μm (9) (83WC−17Co) 50μm その上に(4) を50μm (10) (88WC−12Co) (11) (83WC−17Co) (12)自溶合金 (JIS H8303, MSFCo1) (13) 100Al2O3 (14) 8Y2O3−92ZrO2 以上の材料のうち(10)〜(14)は比較用として準備したも
のであり、括弧内はサーメット１個の粉末粒子を示す。[0016] (1) (85WC-11Co) -4TiB 2 (2) (80TiC -1Ni -2Cr -10Al) -7TiB 2 (3) 80Cr 3 C 2 -20ZrB 2 (4) (84WC-10Co-2Al) - 4CrB 2 (5) (90TiC −5Al −2Fe) −3TiB 2 (6) (88WC−12Co) 50μm (1) 50μm (7) (83WC−17Co) 70μm (2) 30μm ( 8) (88WC-12Co) 80μm (3) 20μm (9) (83WC-17Co) 50μm (4) 50μm (10) (88WC-12Co) (11) (83WC-17Co) ( 12) self-fluxing alloy (JIS H8303, MSFCo1) (13 ) 100Al 2 O 3 (14) 8Y 2 O 3 of -92ZrO 2 or more materials (10) to (14) are those prepared for comparison, The numbers in parentheses indicate powder particles of one cermet.
【００１７】次に、上記複合溶射材料を溶射した溶射皮
膜つき材料を溶融亜鉛浴中に浸漬した。その条件は下記
の通りである。 (1) 亜鉛浴組成 純亜鉛中に、ドロス成分として0.05
％の鉄粉を添加 (2) 温 度 480 ℃ (3) 浸漬時間 10日間 浸漬後の皮膜は、外観観察するとともに、試験片皮膜を
切断してその断面を光学顕微鏡およびＸ線マイクロアナ
ライザによって、亜鉛の皮膜内部への侵入状況を観察し
た。Next, the material having a sprayed coating obtained by spraying the composite sprayed material was immersed in a molten zinc bath. The conditions are as follows. (1) Zinc bath composition 0.05 as dross component in pure zinc
(2) Temperature 480 ° C (3) Immersion time 10 days Observation of the appearance of the film after immersion, cutting of the test piece film, and cross-section of the film with an optical microscope and an X-ray microanalyzer. The state of penetration of zinc into the coating was observed.
【００１８】表１は、この結果を要約したものである。
No.12 の比較材料の自溶合金表面には、多量の亜鉛が付
着するとともに、自溶合金皮膜が亜鉛によって侵食さ
れ、局部的に母材が露出していた。また、No.13 の100A
l2O3皮膜およびNo.14 の8Y2O3・92ZrO2皮膜はいずれ
も、皮膜の50％以上が剥離し、ここでも母材が亜鉛によ
って甚しく侵食されていた。ただ、No.10 およびNo.11
のWC−Co皮膜は、亜鉛の侵食は認められるものの、皮膜
それ自体は破壊されなかった。しかし皮膜表面にはドロ
ス成分の付着が認められた。これに対し、本発明の材料
による皮膜では、その内部への亜鉛の侵入深さが３〜10
μm の範囲にあることに加え、ドロス成分の付着も認め
られず極めて清浄かつ健全な状態を維持していた。Table 1 summarizes the results.
A large amount of zinc adhered to the surface of the self-fluxing alloy of the No. 12 comparative material, and the self-fluxing alloy film was eroded by zinc, exposing the base metal locally. No.13 100A
Both l 2 O 3 film and 8Y 2 O 3 · 92ZrO 2 film of No.14 is peeled off more than 50% of the coating, even the base material has been甚properly eroded by zinc here. However, No.10 and No.11
In the WC-Co film, although the zinc was eroded, the film itself was not destroyed. However, adhesion of dross components was observed on the film surface. On the other hand, in the film made of the material of the present invention, the penetration depth of zinc into the inside thereof is 3 to 10%.
In addition to being in the μm range, no dross component was found to adhere and the condition was extremely clean and healthy.
【００１９】[0019]
【表１】 [Table 1]
【００２０】（実施例２）本実施例では、本発明の複合
溶射材料と化学成分的には同一ながら、炭化物（炭化物
サーメットを含む）、硼化物、金属などの粒子を単に混
合した状態で、プラズマ溶射法によって100 μm 厚に溶
射成膜したものの耐溶融亜鉛性とドロス成分の付着状況
を調査した。(Example 2) In this example, while being identical in chemical composition to the composite thermal spray material of the present invention, particles of carbide (including carbide cermet), boride, metal and the like are simply mixed. We investigated the molten zinc resistance and the adhesion of dross components of the 100-μm-thick film formed by plasma spraying.
【００２１】・本発明の複合溶射材料（全成分が一体化
している） (1) (85WC −11Co) −4TiB2 (2) (80TiC−1Ni −2Cr −10Al) −7TiB2 (3) 80Cr3C2 −20ZrB2 (4) (84WC −10Co−2Al)−4CrB2 (5) (90TiC−5Al −2Fe)−3TiB2 ・比較のための溶射材料 (6) (85WC-11Co) に4TiB2 を機械的に混合 (7) (80TiC−1Ni −2Cr −10Al) に7TiB2 を機械的に混
合 (8) 80Cr3C2 と20ZrB2を機械的に混合 (9) (84WC −10Co−2Al)に4CrB2 を機械的に混合 (10)(90TiC−5Al −2Fe)に3TiB2 を機械的に混合 なおここで、溶射皮膜浸漬用亜鉛浴組成、温度、浸漬時
間及び浸漬後の皮膜の調査要領などは実施例１と同様と
した。[0021] - composite spray material (all components are integrated) of the present invention (1) (85WC -11Co) -4TiB 2 (2) (80TiC-1Ni -2Cr -10Al) -7TiB 2 (3) 80Cr 3 the C 2 -20ZrB 2 (4) ( 84WC -10Co-2Al) -4CrB 2 (5) (90TiC-5Al -2Fe) -3TiB 2 · spray material for comparison (6) (85WC-11Co) in 4TiB 2 mechanically mixing (7) (80TiC-1Ni -2Cr -10Al) mechanically mixing mechanically mixed (8) 80Cr 3 C 2 and 20ZrB 2 the 7TiB 2 (9) (84WC -10Co -2Al) 4CrB 2 is mechanically mixed (10) (90TiC-5Al-2Fe) is mechanically mixed with 3TiB 2 Here, the zinc bath composition for spray coating immersion, temperature, immersion time, and procedures for investigating the coating after immersion, etc. Was the same as in Example 1.
【００２２】調査結果を要約すると表２に示す通りであ
る。この結果から明らかなように、比較用の溶射材料で
成膜したNo.6〜No.10 の皮膜でもその表面からの亜鉛の
侵入深さは30μm 以内にとどまっており、この点では耐
溶融亜鉛性は認められる。しかし皮膜の表面にはドロス
成分が点々と付着成長していた。ドロス成分が付着して
いる皮膜表面部をミクロ的に観察すると、その部分には
金属成分が存在し、これを核としてドロスが付着してい
ることが判明した。これに対し、本発明の複合溶射材料
で形成されたNo.1〜No.5の皮膜では亜鉛の侵入深さが５
μm 以下であるうえ、ドロス成分の付着もなく、極めて
健全かつ清浄な状態を呈していた。なお、皮膜の表面を
拡大鏡及びEPMAで調査すると硼化物がほぼ全面を被覆し
た状態となっており、このためドロス成分の付着現象が
なかったものと考えられる。The results of the survey are summarized in Table 2. As is evident from these results, the penetration depth of zinc from the surface of the No. 6 to No. 10 coatings formed with the comparative sprayed material was within 30 μm, and in this respect, the zinc Sex is recognized. However, dross components adhered and grew on the surface of the film. Microscopic observation of the surface of the film to which the dross component adhered revealed that a metal component was present at that portion, and dross was adhered to the metal component. On the other hand, in the No. 1 to No. 5 coatings formed of the composite thermal spray material of the present invention, the penetration depth of zinc was 5
It was not more than μm, and there was no dross component attached, showing an extremely healthy and clean state. When the surface of the film was examined with a magnifying glass and EPMA, it was in a state where boride was covered almost entirely, and it is considered that there was no adhesion phenomenon of the dross component.
【００２３】[0023]
【表２】 [Table 2]
【００２４】（実施例３）本実施例では、アルミニウム
(55)−亜鉛(45)合金浴への本発明の複合溶射材料を用い
たプラズマ溶射皮膜の適用性を実験的に調査した。ここ
でも溶射皮膜の厚さは 100μm とし、比較材料は実施例
２と同じものを用いた。(Embodiment 3) In this embodiment, aluminum
The applicability of the plasma sprayed coating using the composite sprayed material of the present invention to a (55) -zinc (45) alloy bath was experimentally investigated. Also here, the thickness of the thermal spray coating was 100 μm, and the same comparative material as in Example 2 was used.
【００２５】・本発明の複合溶射材料 (1) (85WC −11Co) −4TiB4 (2) (80TiC−1Ni −2Cr −10Al) −7TiB4 (3) 80Cr3C2 −20ZrB2 (4) (84WC −10Co−2Al)−4CrB2 (5) (90TiC−5Al −2Fe)−3TiB2 ・比較のための溶射材料 (6) (85WC-11Co) に4TiB4 を機械的に混合 (7) (80TiC−1Ni −2Cr −10Al) に7TiB2 を機械的に混
合 (8) 80Cr3C2 と20ZrB2を機械的に混合 (9) (84WC −10Co−2Al)に4CrB2 を機械的に混合 (10)(90TiC−5Al −2Fe)に3TiB2 を機械的に混合 ・アルミニウム−亜鉛合金浴への浸漬条件 (1) 浴組成 アルミニウム55重量％−亜鉛45重量％にFe
粉0.05％添加 (2) 温 度 605℃ (3) 浸漬時間 10 日間 浸漬後の皮膜は実施例１及び２と同様な方法によって評
価した。[0025] - composite thermal spray material of the present invention (1) (85WC -11Co) -4TiB 4 (2) (80TiC-1Ni -2Cr -10Al) -7TiB 4 (3) 80Cr 3 C 2 -20ZrB 2 (4) ( 84WC −10Co−2Al) −4CrB 2 (5) (90TiC−5Al −2Fe) −3TiB 2・ Spray material for comparison (6) 4TiB 4 is mechanically mixed with (85WC-11Co) (7) (80TiC -1Ni -2Cr -10Al) mechanically mixing 7TiB 2 to (8) 80Cr 3 C 2 and 20ZrB 2 mechanically mixed (9) (84WC -10Co-2Al ) mechanically mixing 4CrB 2 (10 ) (90TiC-5Al -2Fe) mechanically mixing and aluminum 3TiB 2 - immersion conditions to zinc alloy bath (1) bath composition aluminum 55 wt% - Fe zinc 45 weight%
(2) Temperature 605 ° C (3) Immersion time 10 days The film after immersion was evaluated in the same manner as in Examples 1 and 2.
【００２６】表３はこれらの結果を要約したものであ
る。この結果から明らかなように、比較用の溶射材料で
形成したNo.6〜No.10 の皮膜は、外観的には破壊は認め
られないものの、ドロス成分が多量に付着するととも
に、その断面を調査すると亜鉛の一部は完全に皮膜 (10
0 μm 厚) を貫通し、母材に達していた。これに対し本
発明の複合溶射材料を用いて形成した溶射皮膜は、亜鉛
の侵入が30〜60μm の深さにとどまるとともに、ドロス
成分の付着も軽微であり、特にNo.1, No.2およびNo.5の
皮膜にはほとんど認められず、良好な外観状態を示し
た。Table 3 summarizes these results. As is clear from the results, the coatings of No. 6 to No. 10 formed with the comparative thermal spray material did not show any destruction in appearance, but a large amount of dross component adhered and the cross section was Inspection revealed that some of the zinc was completely coated (10
0 μm thick) and reached the base metal. On the other hand, in the thermal spray coating formed using the composite thermal spray material of the present invention, penetration of zinc is limited to a depth of 30 to 60 μm, and adhesion of dross component is slight. The film of No. 5 was hardly recognized and showed a good appearance.
【００２７】[0027]
【表３】 [Table 3]
【００２８】（実施例４） 本実施例では、本発明の溶射材料で形成した皮膜の耐溶
融アルミニウム性を調査するため、実施例１と同質, 同
寸法の構造用炭素鋼を母材とし、その表面に、下記(1)
〜(12 よの粉末材料を用いて厚さ 150μm の皮膜を高速
ガス炎溶射法およびプラズマ溶射法で形成した。なお、
(1) 〜(7) の材料は機械的複合法によって製造したもの
であり、(8) と(9) は機械的混合法、(10)は噴霧法、(1
1)と(12)は溶融粉砕法によって製造された市販品であ
る。 (1) (84NbC−5Al −4Fe)−5NbB２−2TiB２ (2) (90B４C−3Al −3Fe −1Co)−3TiB２ (3) (84TaC−8Al −3Fe −2Co)−3VB２ (4) (85SiC−7Al −1Fe −2Co)−5HfB２ (5) (87ZrC−7Cr −2Al)−4W ２ B ５ (6) (80Cr３C２−10VC−5Ni −2Co)−3NbB２ (7) (80WC −5TiC−10Co) −5TiB２ (8) (80WC −12Co) (9) (83WC −17Co) (10)自溶合金 (JIS H8303, MSFCo1) (11) 100Al２O３ (12) 8Y２O３−92ZrO２ 以上の材料のうち (8)〜(12)は、比較用として準備した
ものであり、また括弧内はサーメット材料として１個の
粒子を示す。次に、これらの溶射皮膜を溶融アルミニウ
ム中に浸漬したが、その条件は下記の通りである。 (1) アルミニウム浴組成 純アルミニウム浴中に、ドロス成分として 0.1％の 鉄粉を添加 (2) 温 度 720 ℃ (3) 浸漬時間 4 日間 浸漬後の皮膜は、外観を観察するとともに皮膜を切断
し、光学顕微鏡およびＸ線マイクロアナライザーによっ
て、アルミニウムの皮膜内部への侵入状況を観察した。Example 4 In this example, the resistance of the coating formed from the thermal sprayed material of the present invention to melting was evaluated.
In order to investigate the molten aluminum properties,
Structural carbon steel of dimensions is used as a base material, and the following (1)
~ (High-speed coating of 150μm thick using powder material of 12
It was formed by gas flame spraying and plasma spraying. In addition,
Materials (1) to (7) are manufactured by the mechanical composite method
(8) and (9) are mechanical mixing, (10) is spraying, (1)
1) and (12) are commercial products manufactured by the melt pulverization method.
You. (1) (84NbC-5Al-4Fe) -5NbB2−2TiB2 (2) (90B4C-3Al-3Fe-1Co) -3TiB2 (3) (84TaC-8Al-3Fe-2Co) -3VB2 (4) (85SiC-7Al-1Fe-2Co) -5HfB2 (5) (87ZrC-7Cr-2Al)-4W 2 B 5 (6) (80Cr3C2−10VC−5Ni −2Co) −3NbB2 (7) (80WC −5TiC−10Co) −5TiB2 (8) (80WC −12Co) (9) (83WC −17Co) (10) Self-fluxing alloy (JIS H8303, MSFCo1) (11) 100Al2O3 (12) 8Y2O3−92ZrO2 Of the above materials, (8) to (12) were prepared for comparison
In the parentheses, one piece of cermet material is used.
Show particles. Next, these thermal spray coatings were
The condition was as follows. (1) Aluminum bath composition 0.1% iron powder added as a dross component to a pure aluminum bath. (2) Temperature 720 ° C (3) Immersion time 4 days.
Using an optical microscope and an X-ray microanalyzer.
Then, the state of penetration of aluminum into the inside of the film was observed.
【００２９】表４は、この結果を要約したものである。
No.10 の自溶合金皮膜は溶融アルミニウムによって侵食
されて、母材の侵食も顕著であった。No.11 の100 Al2O
3 皮膜およびNo.12 の８Y2O3−92ZrO2皮膜は、ともに溶
射皮膜の気孔から侵入したアルミニウムによって母材が
選択的に侵食され、これに伴って皮膜は剥離と破壊して
いた。また、No.8, 9 のWC−Coサーメット皮膜でも、溶
融亜鉛の内部侵入が激しく、その先端は母材近くにまで
達するとともに、ドロス成分が付着していた。また、皮
膜の一部にチッピング現象も認められた。これに対し、
本発明の材料で形成した皮膜は、アルミニウムの皮膜内
部への侵入深さは10〜20μm の範囲にとどまるととも
に、ドロス成分の付着が認められないか、あるいはドロ
スの付着が軽微であるうえ、その除去が極めて容易であ
った。Table 4 summarizes the results.
The self-fluxing alloy film of No. 10 was eroded by the molten aluminum, and the erosion of the base metal was remarkable. No.11 100 Al 2 O
3 coatings and 8Y 2 O 3 -92ZrO 2 film of No.12, the base material is selectively eroded by aluminum together entering from the pores of the thermal spray coating, the coating was destroyed with peeling accordingly. Also, in the WC-Co cermet films of Nos. 8 and 9, the penetration of the molten zinc was severe, and the tip reached the vicinity of the base metal and dross components were attached. In addition, a chipping phenomenon was observed in a part of the film. In contrast,
In the film formed of the material of the present invention, the penetration depth of aluminum into the film remains within the range of 10 to 20 μm, and there is no adhesion of dross component, or the adhesion of dross is slight. Removal was very easy.
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【発明の効果】以上の実施例から明らかなように、本発
明にかかる、炭化物あるいは炭化物サーメットの粒子と
硼化物とを複合一体化してなる複合溶射材料を用いて形
成した溶射皮膜は、溶融亜鉛および溶融亜鉛−アルミニ
ウム合金浴およびアルミニウム浴中において、優れた耐
溶融金属性を発揮できるにとどまらず、浴中に浮遊する
ドロス成分の付着をも防止し得ることが判明した。この
結果、溶融めっき鋼板の長期連続生産が可能となり、設
備の保守点検費用の節減、生産コストの低減などと共
に、ドロスの付着のない高品質めっき鋼板の安定生産に
大きな効果が期待できる。また、本発明の複合材料によ
って溶射皮膜を形成したシンクロールは、溶融亜鉛によ
る侵食が防止されるため、ロール材質の、亜鉛浴中への
溶出による、亜鉛浴の純度低下が発生せず、この面から
も高品質めっき鋼板の生産を期待することができる。As is apparent from the above examples, the thermal spray coating formed by using the composite thermal spray material according to the present invention, which is obtained by integrally integrating carbide or carbide cermet particles and boride, is formed of molten zinc. In addition, it has been found that not only the excellent molten metal resistance can be exhibited in the molten zinc-aluminum alloy bath and the aluminum bath, but also the adhesion of dross components floating in the bath can be prevented. As a result, a long-term continuous production of hot-dip coated steel sheets becomes possible, and it is possible to reduce the maintenance and inspection costs of equipment and production costs, and to expect a great effect on stable production of high-quality coated steel sheets without dross adhesion. Further, the sink roll having a sprayed coating formed by the composite material of the present invention is prevented from being eroded by the molten zinc, so that the roll material does not decrease in purity of the zinc bath due to elution into the zinc bath. Production of high-quality plated steel sheets can be expected from the aspect as well.
【図１】溶融亜鉛めっき浴槽およびそれに付属する各種
ロールその他の配設状態を示す模式図である。FIG. 1 is a schematic diagram showing a hot-dip galvanizing bath, various rolls attached thereto, and other arrangement states.
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 Reference Signs List 1 molten zinc bath 2 sink roll 3 support roll 4 steel plate for plating 5 guide roll 6 injection nozzle
Claims (6)
子と、硼化物とを混合してなる複合溶射材料において、
上記炭化物または炭化物サーメットの各粒子と硼化物と
が予め複合一体化していることを特徴とする耐溶融金属
性に優れる複合溶射材料。1. A composite spray material comprising a mixture of carbide or carbide cermet particles and boride,
A composite sprayed material having excellent resistance to molten metal, wherein each of the above-mentioned carbides or carbide cermet particles and a boride are compositely integrated in advance.
化物との複合一体化は、各粒子と硼化物との機械的結
合, 溶融結合、もしくは該粒子表面に硼化物を蒸気被覆
または含浸させることにより得られたものである請求項
１に記載の複合溶射材料。2. The composite integration of carbide particles or carbide cermet particles with boride is carried out by mechanical bonding, fusion bonding of each particle and boride, or by vapor coating or impregnation of boride on the particle surface. The composite thermal spray material according to claim 1, which is obtained.
4C, TaC, SiC, ZrC,HfCおよびVCのいずれか１種以上か
らなる請求項１に記載の複合溶射材料。3. The method according to claim 1, wherein the carbide is TiC, NbC, WC, Cr 3 C 2 , B
2. The composite thermal spray material according to claim 1, comprising at least one of 4 C, TaC, SiC, ZrC, HfC and VC.
TaB2, NbB2, W2B5およびCrB2のいずれか１種以上から
なる請求項１に記載の複合溶射材料。4. The method according to claim 1, wherein the boride is TiB 2 , ZrB 2 , HfB 2 , VB 2 ,
2. The composite thermal spray material according to claim 1, comprising at least one of TaB 2 , NbB 2 , W 2 B 5 and CrB 2 .
分が、Co, Ni, Cr,Al, Feのいずれか一種または二種以
上のものである請求項１に記載の複合溶射材料。5. The composite thermal spray material according to claim 1, wherein the metal component constituting the carbide cermet is one or more of Co, Ni, Cr, Al, and Fe.
面に予め硼化物の被覆層を設けて複合一体化させてなる
炭化物、あるいは同じ処理を施してなる炭化物サーメッ
トの溶射材料を溶射して形成される複合溶射皮膜。6. A sprayed material of a carbide which has been previously melt-bonded with a boride or has a boride coating layer formed on its surface and which has been combined and integrated, or a carbide cermet which has been subjected to the same treatment. Composite spray coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26342892A JP3160387B2 (en) | 1992-10-01 | 1992-10-01 | Composite thermal spray material and composite thermal spray coating excellent in molten metal resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26342892A JP3160387B2 (en) | 1992-10-01 | 1992-10-01 | Composite thermal spray material and composite thermal spray coating excellent in molten metal resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06116702A JPH06116702A (en) | 1994-04-26 |
| JP3160387B2 true JP3160387B2 (en) | 2001-04-25 |
Family
ID=17389364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26342892A Expired - Lifetime JP3160387B2 (en) | 1992-10-01 | 1992-10-01 | Composite thermal spray material and composite thermal spray coating excellent in molten metal resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3160387B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100487490B1 (en) * | 2000-12-22 | 2005-05-03 | 주식회사 포스코 | Powder making method of wc-based for thermal spray coating which has high corrosion resistance against molten zinc |
| CN100427635C (en) * | 2006-06-30 | 2008-10-22 | 北京工业大学 | Powder cored wire for NiB-containing amorphous coating prepared by electric arc spraying |
| CN108424174B (en) * | 2018-04-18 | 2020-03-20 | 北京矿冶科技集团有限公司 | Multi-element complex phase nano boride, corresponding ultrahigh temperature oxidation resistant coating and preparation method |
| AT16480U1 (en) * | 2018-04-20 | 2019-10-15 | Plansee Composite Mat Gmbh | Target and method of making a target |
| CN110904375A (en) * | 2019-12-10 | 2020-03-24 | 泰州永航精密铸造有限公司 | Alloy with good corrosion resistance for yacht and preparation method thereof |
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1992
- 1992-10-01 JP JP26342892A patent/JP3160387B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH06116702A (en) | 1994-04-26 |
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