JP2988281B2 - Ceramic / metal composite powder for thermal spraying and method for forming thermal spray coating - Google Patents
Ceramic / metal composite powder for thermal spraying and method for forming thermal spray coatingInfo
- Publication number
- JP2988281B2 JP2988281B2 JP6268398A JP26839894A JP2988281B2 JP 2988281 B2 JP2988281 B2 JP 2988281B2 JP 6268398 A JP6268398 A JP 6268398A JP 26839894 A JP26839894 A JP 26839894A JP 2988281 B2 JP2988281 B2 JP 2988281B2
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- powder
- ceramic
- thermal spraying
- weight
- metal
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Description
【０００１】[0001]
【産業上の利用分野】本発明は溶射用セラミックス・金
属複合粉末及び溶射被膜に関し、特に金属部材の表面
に、耐磨耗性、耐熱性、耐溶融金属性などを向上させる
目的で実施される溶射用粉末及び溶射被膜に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic / metal composite powder for thermal spraying and a thermal spray coating, and more particularly, to the purpose of improving the abrasion resistance, heat resistance, molten metal resistance and the like on the surface of a metal member. The present invention relates to a thermal spraying powder and a thermal spray coating.
【０００２】[0002]
【従来の技術】各種産業機械や治工具から一般向け機械
に至るまでの金属製部品には、用途にあわせて様々な特
性が求められている。求められている特性は多岐にわた
るが、耐磨耗性、耐熱性や耐溶融金属性などは代表的な
ものであり、特に近年では金属自体ではその要求特性が
満たされない場合が多く、各種の表面改質により問題を
解決しようとすることが多い。表面改質の方法としては
溶射法、物理的蒸着法や化学的蒸着法などが実用化され
ているが、このうち溶射法は比較的容易に厚膜が形成で
きることや、溶射できる材料の種類が豊富で選択の幅が
広いことから多用されている。2. Description of the Related Art Various characteristics are required for metal parts ranging from various industrial machines and jigs to general-purpose machines in accordance with applications. Although the required characteristics are diverse, the wear resistance, heat resistance, and resistance to molten metal are typical. Often, reforming attempts to solve the problem. As methods for surface modification, thermal spraying, physical vapor deposition, chemical vapor deposition, etc. have been put to practical use. Among these, thermal spraying is relatively easy to form a thick film, and the type of material that can be sprayed is It is widely used because of its abundance and wide selection.
【０００３】溶射材料としては、ワイヤー状や棒状とし
た金属の他、金属、セラミックス及びこれらの複合材料
の粉末が用いられている。これらの溶射材の内いずれを
選ぶかは、その使用目的による。例えば、耐磨耗、耐食
の両特性が同時に求められる用途にはニッケル−クロム
合金などの自溶性合金がよく用いられており、さらに磨
耗の激しい用途にはセラミックスと金属の複合材料が有
効である。また、製鋼プロセス材料のように鉄との凝着
を防ぎたい用途では、溶鋼との反応性が低いセラミック
スを選択する。[0003] As the thermal spraying material, powders of metals, ceramics, and composite materials thereof are used in addition to metal in a wire or rod shape. Which of these thermal spray materials is selected depends on the purpose of use. For example, self-fluxing alloys such as nickel-chromium alloys are often used for applications where both abrasion resistance and corrosion resistance are required at the same time, and ceramic-metal composite materials are effective for applications with severe wear. . In applications where it is desired to prevent adhesion with iron, such as steelmaking process materials, ceramics having low reactivity with molten steel are selected.
【０００４】セラミックスと金属の複合材料としては耐
磨耗性の用途に用いられる代表的な炭化タングステンと
コバルトの複合材料（超硬合金）の他に、耐熱性の用途
に炭化クロムとニッケル−コバルト合金の複合材料が実
用化されている。これらの複合材料を溶射する場合には
プラズマ溶射法や高速フレーム溶射法が適用されている
が、プラズマは温度が極めて高いために炭化物が分解さ
れ易いなどの問題がありプラズマ溶射法では良好な被膜
が得られ難いので、高速フレーム溶射法を用いるのが一
般的である。As a composite material of ceramics and metal, in addition to a typical tungsten carbide and cobalt composite material (hard metal) used for wear resistance, chromium carbide and nickel-cobalt are used for heat resistance. Alloy composite materials have been put to practical use. Plasma spraying and high-speed flame spraying are applied when spraying these composite materials.However, the plasma temperature is so high that carbides are easily decomposed. Is generally difficult to obtain, so that a high-speed flame spraying method is generally used.
【０００５】超硬合金や炭化クロムとニッケル−クロム
合金との複合材料の溶射は実用化されてはいるが、その
目的に対し十分な特性の良質な溶射被膜を得るために
は、次の二つの条件が満たされなくてはならない。先
ず、これらの合金で用いている炭化物は高温の酸化雰囲
気下においては比較的不安定で、酸化物や他の炭化物等
が生成しやすいため、過剰の熱エネルギーを付与するこ
とを避ける必要がある。次に、緻密な被膜を形成するに
不可欠な炭化物と金属の共晶による液相を出現させるた
めには必ず一定以上の温度（超硬合金では約１３２０℃
以上）に一定時間以上さらす必要がある。この相反する
二つの条件を、極めて短時間の超高温処理である溶射の
プロセスにおいて、再現性よく両立させることは困難で
あり、多くの場合溶射被膜中に意図しない酸化物などが
混入していたり、気孔が多く介在するため、十分な特性
の被膜が得られないのが実状である。[0005] Although thermal spraying of cemented carbide or a composite material of chromium carbide and a nickel-chromium alloy has been put to practical use, in order to obtain a high-quality thermal spray coating having sufficient characteristics for the purpose, the following two methods are required. Two conditions must be met. First, the carbides used in these alloys are relatively unstable in a high-temperature oxidizing atmosphere, and oxides and other carbides are easily formed, so it is necessary to avoid applying excessive heat energy. . Next, in order to produce a liquid phase due to the eutectic of carbide and metal, which is indispensable for forming a dense film, the temperature must be at least a certain level (about 1320 ° C. for cemented carbide).
Above) for a certain period of time. It is difficult to reconcile these two contradictory conditions with good reproducibility in the thermal spraying process, which is an ultra-high-temperature treatment for a very short time.In many cases, unintended oxides and the like are mixed in the thermal spray coating. In fact, since a large number of pores are present, a film having sufficient characteristics cannot be obtained.
【０００６】また、溶射被膜の特性を向上させるには、
溶射粉末の粒子径や形態を厳密に制御する必要がある。
たとえば、超硬合金においては一旦、真空中などで十分
に焼結させたものを粉砕し、適当な粒子径範囲にある粒
子のみをふるい分けした粉末が最適と言われているが、
このような工程に要するコストが決して小さくはないの
は当然であり、また形態などを含めた均質性にも問題が
ある。超硬合金の溶射粉末で、このような工程が要求さ
れるのは、溶射作業においては十分な流動性を獲得する
ことが必要であることの他に、前述したような材料種固
有の問題点、即ち溶射作業中に付与される熱エネルギー
の厳密な制御が必要である事に起因する。さらに一旦焼
結し、粉砕した粉末であっても、一般に数十μｍ以上の
粒子径である溶射用粉末においては、個々の粒子の各部
に付与される熱エネルギー量は期待した一定の値とはな
らず、結果として得られる溶射被膜は均質性の点で満足
できるものでない場合が多い。In order to improve the properties of the thermal spray coating,
It is necessary to strictly control the particle diameter and form of the thermal spray powder.
For example, in the case of cemented carbide, once it has been sufficiently sintered in a vacuum or the like, pulverized and sieved only particles within an appropriate particle size range are said to be optimal,
Naturally, the cost required for such a process is not small, and there is also a problem in homogeneity including the form. Such a process is required for the sprayed powder of cemented carbide in addition to the fact that it is necessary to obtain sufficient fluidity in the spraying operation, and the problems inherent to the material types as described above. That is, strict control of the thermal energy applied during the thermal spraying operation is required. Furthermore, even if the powder is once sintered and pulverized, in the case of a thermal spraying powder having a particle diameter of generally several tens of μm or more, the amount of heat energy applied to each part of each individual particle is a certain expected value. Rather, the resulting thermal spray coating is often not satisfactory in terms of homogeneity.
【０００７】また、セラミックスと金属の複合材料の溶
射に適するとされている高速フレーム溶射法により、超
硬合金の溶射被膜を形成する場合の最大膜厚は一般には
２００〜３００μｍ程度である。これは、基板である鉄
鋼材料の熱膨張係数に比較して超硬合金の熱膨張係数が
小さく、これらの材料の熱膨張係数の間には相当な差が
あり、被膜が厚くなると剥離が生じるためである。従っ
て形成できる最大膜厚は超硬合金の溶射被膜が緻密にな
ればなるほど小さくなり、耐磨耗性の向上等を目的とし
て溶射を行う場合には大きな欠点である。[0007] When forming a sprayed coating of cemented carbide by a high-speed flame spraying method, which is considered to be suitable for spraying a composite material of ceramic and metal, the maximum thickness is generally about 200 to 300 µm. This is because the thermal expansion coefficient of cemented carbide is small compared to the thermal expansion coefficient of the steel material that is the substrate, there is a considerable difference between the thermal expansion coefficients of these materials, and peeling occurs when the coating becomes thicker That's why. Therefore, the maximum film thickness that can be formed becomes smaller as the sprayed coating of cemented carbide becomes denser, which is a major drawback when spraying for the purpose of improving abrasion resistance and the like.
【０００８】特開昭６３−１９５２５４では、鉄鋼材料
の上にＦｅ−ＢまたはＦｅ−Ｂ系合金粉末などの金属を
溶射し加熱処理を行うことにより複ホウ化物と金属から
構成される被膜を形成し、耐磨耗性などが向上した被覆
鉄鋼材料を得ることを提言している。しかし、当該発明
では溶射粉末が複ホウ化物系の材料でなく、溶射された
被膜の均質性や特性が劣り、均質性や特性の向上には高
温での再加熱処理が必要であるが、再加熱処理による鉄
鋼材料の寸法変化や変質は無視できない。In Japanese Patent Application Laid-Open No. 63-195254, a metal film such as Fe-B or an Fe-B-based alloy powder is sprayed on a steel material and subjected to a heat treatment to form a film composed of a double boride and a metal. It is proposed to obtain a coated steel material with improved abrasion resistance and the like. However, in the present invention, the sprayed powder is not a double boride-based material, and the uniformity and properties of the sprayed coating are inferior. To improve the homogeneity and properties, a reheating treatment at a high temperature is necessary. The dimensional change and deterioration of the steel material due to the heat treatment cannot be ignored.
【０００９】また、特開平１−２５９１１７には、Ｃｒ
Ｂ、ＭｏＢ、ＷＢ、ＴｉＢ2 、ＺｒＢ2 のいずれかと金
属とからなる溶射サーメット被膜が開示されているが、
これらの材料を用いても、超硬合金の場合と同様な問題
があり十分な特性の被膜が得られない。Japanese Patent Application Laid-Open No. 1-259117 discloses Cr
B, MoB, WB, TiB 2 , ZrB 2 any of the thermal spray coating cermet coating comprising a metal is disclosed,
Even if these materials are used, the same problem as in the case of cemented carbide cannot be obtained, and a film having sufficient characteristics cannot be obtained.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、上記従来技
術における問題点を解決し、均質性や特性に優れた溶射
被膜を形成でき、膜厚を厚くしても溶射被膜の剥離が生
じ難い新規なセラミックス・金属複合材料の溶射用粉末
およびそれを用いた溶射方法を提供することを目的とす
る。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the prior art and can form a sprayed coating having excellent uniformity and characteristics. Even when the thickness is large, the sprayed coating is hardly peeled off. An object of the present invention is to provide a novel ceramic / metal composite material thermal spraying powder and a thermal spraying method using the same.
【００１１】[0011]
【課題を解決するための手段】本発明は、前述の課題を
達成すべくなされたものであり、本発明が提供する溶射
用粉末は、Ｆｅ、Ｎｉ及びＣｏから選ばれる一種以上の
元素とＭｏ及び／又はＷとの複合ホウ化物を主体とする
セラミックス相と、Ｆｅ、Ｎｉ及びＣｏから選ばれる一
種以上の元素を主体とする金属結合相とで構成されてい
る粒子からなることを特徴とする溶射用セラミックス・
金属複合粉末である。SUMMARY OF THE INVENTION The present invention has been made to achieve the above-mentioned object, and a thermal spraying powder provided by the present invention contains one or more elements selected from Fe, Ni and Co and Mo. And / or particles composed of a ceramic phase mainly composed of a composite boride with W and a metal binding phase mainly composed of one or more elements selected from Fe, Ni and Co. Ceramics for thermal spraying
It is a metal composite powder.
【００１２】[0012]
【００１３】Ｆｅ、Ｎｉ、Ｃｏから選ばれる１種以上の
元素とＭｏ及び／又はＷとの複合ホウ化物を主体とする
セラミックス相と、Ｆｅ、Ｎｉ、Ｃｏから選ばれる一種
以上の元素を主体とする金属結合相から構成される複合
材料は、様々な用途分野において、特に高温で使用され
る用途において、超硬合金に代わり得る、または凌駕す
る材料である（特公昭６０−５７４９９、特開昭６３−
１４３２３６参照）。A ceramic phase mainly composed of a complex boride of one or more elements selected from Fe, Ni and Co and Mo and / or W, and a ceramic phase mainly composed of one or more elements selected from Fe, Ni and Co A composite material composed of a metal binder phase is a material that can replace or surpass a cemented carbide in various application fields, particularly in applications used at high temperatures (Japanese Patent Publication No. 60-57499, Japanese Patent Application Laid-Open No. 63-
143236).
【００１４】すなわち、この複合ホウ化物を主体とする
材料の熱膨張係数は鉄鋼材料と超硬合金との中間に有
り、溶射法によりその被膜を鉄鋼材料の上に形成すれば
超硬合金よりも剥離は生じ難い。このため、Ｆｅ、Ｎ
ｉ、Ｃｏから選ばれる一種以上の元素とＭｏ及び／又は
Ｗとの複合ホウ化物を主体とするセラミックス相と、Ｆ
ｅ、Ｎｉ、Ｃｏから選ばれる一種以上の元素を主体とす
る金属結合相とから構成される良質で厚さのある被膜を
形成する事ができ、耐磨耗性や耐食性の向上を目的とし
た鉄鋼材料の表面処理として十分に有効な手段となる。That is, the thermal expansion coefficient of the material mainly composed of the composite boride is between the steel material and the cemented carbide, and if the coating is formed on the steel material by the thermal spraying method, the thermal expansion coefficient is higher than that of the cemented carbide. Peeling is unlikely to occur. Therefore, Fe, N
a ceramic phase mainly composed of a complex boride of one or more elements selected from i and Co and Mo and / or W;
It is possible to form a high-quality and thick coating composed of a metal binder phase mainly composed of one or more elements selected from e, Ni, and Co, and to improve abrasion resistance and corrosion resistance. This is a sufficiently effective means for surface treatment of steel materials.
【００１５】また、特にＮｉ及び／又はＣｏとＭｏ及び
／又はＷとの複合ホウ化物を主体とするセラミックス相
と、Ｎｉ及び／又はＣｏを主体とする金属結合相との複
合溶射被膜は、耐磨耗性の用途に一般に用いられている
自溶性合金などの溶射被膜よりも硬度や耐食性が高く、
超硬合金やクロム炭化物／金属複合材の溶射被膜に比べ
て密着性と耐熱性にも優れている。In particular, the composite sprayed coating of a ceramic phase mainly composed of a composite boride of Ni and / or Co and Mo and / or W and a metal bonding phase mainly composed of Ni and / or Co is resistant to thermal spraying. Hardness and corrosion resistance are higher than thermal spray coatings such as self-fluxing alloys generally used for abrasion applications,
Excellent adhesion and heat resistance compared to sprayed coatings of cemented carbides and chromium carbide / metal composites.
【００１６】この溶射用セラミックス・金属複合粉末
は、好ましくは、造粒後に焼結された多孔質で概ね球形
の粒子からなっている。このような粒子の粉末とするこ
とで、流動性が優れる（たとえば安息角が３０゜以下）
とともに、溶射時に粒子の中心部まで均等に熱を受けて
半溶融状態となる粒子の粉末が提供される。The ceramic / metal composite powder for thermal spraying preferably comprises porous and generally spherical particles sintered after granulation. By using powder of such particles, fluidity is excellent (for example, the angle of repose is 30 ° or less).
At the same time, a powder of the particles which are uniformly heated to the center of the particles during the thermal spraying to be in a semi-molten state is provided.
【００１７】本発明において、セラミックス相は溶射用
セラミックス・金属複合粉末全体の５０重量％以上、９
０重量％以下を占めることが好ましい。５０重量％未満
では複合ホウ化物の有する好ましい物性を溶射被膜に付
与することが困難となり、９０重量％を超えると金属結
合相が少なくなって溶射被膜の強度が小さくなり、密着
性が低下するからである。In the present invention, the ceramic phase comprises 50% by weight or more of the entire ceramic / metal composite powder for thermal spraying.
Preferably, it accounts for 0% by weight or less. If the amount is less than 50% by weight, it is difficult to impart desirable physical properties of the composite boride to the sprayed coating. It is.
【００１８】本発明の溶射用セラミックス・金属複合粉
末におけるＦｅ、Ｎｉ、Ｃｏから選ばれる１種以上の元
素とＭｏ及び／又はＷとの複合ホウ化物のセラミックス
相全体に対する割合は好ましくは７０重量％以上であ
り、より好ましくは８５重量％以上である。７０重量％
以上とすれば複合ホウ化物の好ましい特性が発現され、
８５重量％以上とすることで一層優れた特性を確保でき
る。In the ceramic / metal composite powder for thermal spraying of the present invention, the ratio of the composite boride of one or more elements selected from Fe, Ni and Co and Mo and / or W to the entire ceramic phase is preferably 70% by weight. And more preferably at least 85% by weight. 70% by weight
With the above, preferable characteristics of the complex boride are expressed,
By setting the content to 85% by weight or more, more excellent characteristics can be secured.
【００１９】また、好ましくは、金属結合相全体の６５
重量％以上が、より好ましくは７０重量％以上がＦｅ、
Ｎｉ、Ｃｏから選ばれる１種以上の金属である。これら
の金属元素が６５重量％以上であると好ましからざる特
性を付与する第３相の生成を抑制できるからであり、さ
らに７０重量％以上であると安定して優れた特性を有す
る溶射被膜が得られるからである。Also, preferably, 65% of the entire metal binding phase is used.
% By weight or more, more preferably 70% by weight or more of Fe,
One or more metals selected from Ni and Co. When the content of these metal elements is 65% by weight or more, the formation of the third phase imparting undesired properties can be suppressed, and when the content is 70% by weight or more, a thermal spray coating having stable and excellent properties can be obtained. Because it can be done.
【００２０】複合ホウ化物中においてＷはＭｏと任意の
割り合いで置換でき、Ｗが含まれていることによって被
膜の硬度と強度が向上する。しかしＷは比重が大きく高
価な原料でもあるので、粉末中のＷの含有量は２５重量
％以下とするのが好ましい。硬度と強度を向上せしめる
効果を得るには粉末中にＷを５重量％以上含有せしめる
のが好ましい。In the composite boride , W can be replaced with Mo at any ratio, and the inclusion of W improves the hardness and strength of the coating. However, since W is also an expensive raw material having a large specific gravity, the content of W in the powder is preferably set to 25% by weight or less. In order to obtain the effect of improving the hardness and strength, it is preferable that W is contained in the powder in an amount of 5% by weight or more.
【００２１】本発明の溶射用セラミックス・金属複合粉
末を構成する主たるセラミックス相と金属結合相の好ま
しい組合せは、Ｍｏ2 ＦｅＢ2 型セラミックスとＦｅ基
合金との組合せ、Ｍｏ2 ＮｉＢ2 型セラミックスとＮｉ
基合金との組合せ、およびＭｏＣｏＢ型セラミックスと
Ｃｏ基合金との組合せである。Ｍｏ2 ＦｅＢ2 型セラミ
ックスとＦｅ基合金とを組合せた材質は比較的安価であ
り、Ｍｏ2 ＮｉＢ2 型セラミックスとＮｉ基合金とを組
合せた材質は総合的に優れた特性を示し、ＭｏＣｏＢ型
セラミックスとＣｏ基合金とを組合せた材質は溶融アル
ミニウム、溶融亜鉛に対して耐食性が良好である。The preferred combination of the main ceramic phase and the metal binding phase constituting the ceramic / metal composite powder for thermal spraying of the present invention is a combination of a Mo 2 FeB 2 type ceramic and an Fe-based alloy, a Mo 2 NiB 2 type ceramic and a Ni
A combination with a base alloy, and a combination of a MoCoB type ceramic with a Co base alloy. The material combining Mo 2 FeB 2 type ceramics and an Fe-based alloy is relatively inexpensive, and the material combining Mo 2 NiB 2 type ceramics and a Ni-based alloy exhibits excellent overall properties. A material obtained by combining and a Co-based alloy has good corrosion resistance to molten aluminum and molten zinc.
【００２２】そして、本発明の好ましい粉末は、セラミ
ックス相の７０重量％以上が（Ｍｏ，Ｗ）ＸＦｅＹＢＺ
（但しＸ＝１．８〜２．２、Ｙ＝０．９〜１．１）であ
り、金属結合相の７０重量％以上がＦｅである。また、
他の好ましい粉末は、セラミックス相の７０重量％以上
が（Ｍｏ，Ｗ）ＸＮｉＹＢＺ（但しＸ＝１．８〜２．
２、Ｙ＝０．９〜１．１）であり、金属結合相の７０重
量％以上がＮｉである。また、さらに他の好ましい粉末
は、セラミックス相の７０重量％以上が（Ｍｏ，Ｗ） Ｘ
Ｃｏ Ｙ Ｂ（但しＸ＝０．９〜１．１、Ｙ＝０．９〜１．
１）であり、金属結合相の７０重量％以上がＣｏであ
る。In the preferred powder of the present invention, 70% by weight or more of the ceramic phase is (Mo, W) X Fe Y B Z.
(Where X = 1.8 to 2.2, Y = 0.9 to 1.1), and 70% by weight or more of the metal binding phase is Fe. Also,
In another preferred powder, 70% by weight or more of the ceramic phase is (Mo, W) X Ni Y B Z (where X = 1.8 to 2.
2, Y = 0.9 to 1.1), and 70% by weight or more of the metal binding phase is Ni. In still another preferred powder, 70% by weight or more of the ceramic phase is (Mo, W) X
Co Y B (where X = 0.9~1.1, Y = 0.9~1.
1), wherein 70% by weight or more of the metal binding phase is Co.
【００２３】本発明の溶射用粉末を得るには、例えば、
ＭｏＢ、ＷＢ等の各ホウ化物粉末及びＮｉ、Ｍｏ、Ｃｒ
等の金属粉末を秤量し、回転ボールミルや振動ボールミ
ル等を用いて、エタノール等の有機溶媒中で混合粉砕し
た後有機バインダーを添加し、このスラリーを非酸化性
雰囲気中でスプレードライヤー等を用いて造粒し、好ま
しくは真空、Ａｒ等の非酸化性雰囲気中において９００
〜１１００℃でゆるく焼結した後、解砕して概ね球形の
粒子とする。In order to obtain the thermal spray powder of the present invention, for example,
Each boride powder such as MoB, WB, and Ni, Mo, Cr
Weigh metal powder such as, using a rotary ball mill or vibration ball mill, etc., mixed and pulverized in an organic solvent such as ethanol, and then added an organic binder, and the slurry using a spray dryer or the like in a non-oxidizing atmosphere Granulated, preferably in a non-oxidizing atmosphere such as vacuum, Ar or the like.
After loosely sintering at １1100 ° C., it is crushed into roughly spherical particles.
【００２４】用いる原料粉末は必ずしも前述のようにホ
ウ化物と金属の形である必要はなく、例えばＮｉ−Ｂ合
金とＭｏ粉、Ｗ粉及びＮｉ粉との組み合わせ、あるいは
予めアトマイズ法やその他の方法で合成した複合ホウ化
物粉末と金属粉末との組合せ、さらにはＮｉ、Ｍｏ、Ｗ
等の単体の金属粉末とＢ粉末の組合せでもよい。一般的
にこれらの原料粉末は出来るかぎり純度が高く、微細で
ある方が優れた特性の粉末を得る上で有利であることは
言うまでもない。特に溶射粉末の均質性を確保するため
に、ホウ化物の粒径は平均で１０μｍ以下とするのが好
ましい。The raw material powder used need not necessarily be in the form of a boride and a metal, as described above. For example, a combination of a Ni—B alloy with Mo powder, W powder and Ni powder, or an atomizing method or another method Complex boriding synthesized by
Combination of material powder and metal powder, and also Ni, Mo, W
Or a combination of a single metal powder and B powder. In general, it is needless to say that these raw material powders are as pure as possible, and that finer powders are more advantageous in obtaining powders having excellent characteristics. In particular, in order to ensure the uniformity of the thermal spray powder, the boride preferably has an average particle size of 10 μm or less.
【００２５】回転ボールミルで粉砕混合した粉末は微細
であり、そのままでは溶射粉末としては不適であるた
め、有機バインダーを添加して造粒処理を行う。用いる
有機バインダーは焼結時に除去され易いものを選ぶこと
が好ましく、アクリル樹脂やポリエチレングリコール等
を用いることができる。造粒処理を行った粉末は一般に
球形であり、流動性は良いが、加圧ガスによる搬送に耐
えるに十分なほど固くはない。Since the powder pulverized and mixed by the rotary ball mill is fine and unsuitable as a sprayed powder as it is, an organic binder is added to perform a granulation treatment. It is preferable to select an organic binder to be easily removed during sintering, and an acrylic resin, polyethylene glycol, or the like can be used. The granulated powder is generally spherical and has good fluidity, but is not hard enough to withstand transport by pressurized gas.
【００２６】この造粒粉を真空中などにおいて９００〜
１１００℃で焼結すると、有機バインダーが除去される
と共に、球形を保ったまま造粒粉内の一次粒子同士が焼
結して概ね球状の多孔質粒子となり、加圧ガスによる搬
送を行っても容易に崩れない（図１参照）。緻密質の粒
子では溶射作業時の短時間の熱付与では中心部と外縁部
で溶け方に差が生じやすいのに対し、粉末が多孔質であ
ると中心部まで均等に熱を受けて溶融する効果がある。
この場合多孔質粒子の気孔率が２０〜６０％であること
が好ましい。２０％未満では粒子内部への熱の通りが悪
くなり、６０％を超えると粒子の強度が小さくて搬送時
に微粉となりやすいからである。また、この焼結を行う
と、当初の混合原料として予め合成した複合ホウ化物を
用いない場合も溶射用粉末の結晶組成が複合ホウ化物と
鉄族金属の合金を主体としたものとなる。極めて短時間
の加熱処理でしかない溶射時の熱履歴では、複合ホウ化
物の生成を十分に進行させることが困難であるため、溶
射用粉末とする段階で複合ホウ化物を生成させておく効
果は大きい。The granulated powder is 900 to 900
When sintering at 1100 ° C., the organic binder is removed, and the primary particles in the granulated powder are sintered to form substantially spherical porous particles while maintaining a spherical shape. Does not collapse easily (see FIG. 1). In the case of dense particles, if the heat is applied for a short time during the spraying operation, a difference tends to occur between the center and the outer edge, whereas if the powder is porous, the powder is uniformly heated to the center and melts effective.
In this case, the porosity of the porous particles is preferably 20 to 60%. If it is less than 20%, the heat flow into the inside of the particles will be poor, and if it exceeds 60%, the strength of the particles will be small and it will be easy to become fine powder during transportation. In addition, when this sintering is performed, the crystal composition of the thermal spraying powder is mainly composed of the alloy of the composite boride and the iron group metal even when the composite boride synthesized in advance is not used as the initial mixed raw material. In the thermal history during spraying is only a very short time of heat treatment, the composite boride
Since it is difficult to sufficiently advance the formation of the product, the effect of forming the composite boride at the stage of forming the powder for thermal spraying is great.
【００２７】ここで、好ましい加熱温度を９００〜１１
００℃としたのは、９００℃未満では複合ホウ化物の生
成が十分ではなく、更に造粒粉内の一次粒子同士の焼結
も弱く粉末の粒子が崩れやすいためであり、１１００℃
を越えると一次粒子同士の焼結のみではなく造粒粉同士
の焼結も生じ始め、解砕作業が困難となり、粒子の気孔
率が２０％未満になるためである。Here, the preferable heating temperature is 900-11.
The reason for setting the temperature to 00 ° C. is that if the temperature is lower than 900 ° C., the formation of the complex boride is not sufficient, and the sintering of the primary particles in the granulated powder is weak, and the particles of the powder are easily broken.
When the ratio exceeds sintering, not only sintering of the primary particles but also sintering of the granulated powders starts to occur, so that the crushing operation becomes difficult and the porosity of the particles becomes less than 20%.
【００２８】本発明の溶射用セラミックス・金属複合粉
末の好ましい粒子径は平均粒径で２０〜７０μｍであ
る。粉末の平均粒径が２０〜７０μｍであることが好ま
しいのは、平均粒径が２０μｍ未満では流動性が小さく
なくなるためであり、７０μｍを超えると溶射時の粒子
速度が小さくなるためと多孔質であっても中心部の溶融
が不十分となり均質な溶射被膜の形成が困難となるため
である。The preferred particle size of the ceramic / metal composite powder for thermal spraying of the present invention is 20 to 70 μm in average particle size. The average particle diameter of the powder is preferably 20 to 70 μm because if the average particle diameter is less than 20 μm, the fluidity is not reduced. If the average particle diameter is more than 70 μm, the particle velocity at the time of thermal spraying is reduced, and the powder is porous. This is because even at this point, the melting at the central portion becomes insufficient and it becomes difficult to form a uniform thermal spray coating.
【００２９】[0029]
【実施例】以下に本発明の実施例および比較例を説明す
るが、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES Examples and comparative examples of the present invention will be described below, but the present invention is not limited to these examples.
【００３０】実施例１ ＭｏＢ（純度約９９．５％、平均粒径約６μｍ）４９重
量％、ＷＢ（純度約９９．４％、平均粒径約４μｍ）９
重量％、Ｍｏ（純度約９９．８％、平均粒径約８μｍ）
７重量％、Ｎｉ（純度約９９．５％、平均粒径約３μ
ｍ）３５重量％の４種類の粉末を混合し、有機溶媒とし
てエチルアルコールを用い回転ボールミルにて４８時間
粉砕を行った。得られたスラリーにポリエチレングリコ
ールを３％添加し粘度調整を行った後、ディスクアトマ
イザー式スプレードライヤーを用いて造粒処理を行い平
均粒径が約４６μｍの造粒粉を作製した。この造粒粉を
Ａｒ雰囲気中１１００℃で１時間焼結した後、解砕し
て、分級を行い粒径２６〜５０μｍの溶射用粉末を得
た。得られた溶射用粉末は概ね球形の多孔質粒子からな
り（図１参照）、気孔率は約４０％であり、平均粒径は
約４１μｍであった。Example 1 MoB (purity: about 99.5%, average particle size: about 6 μm) 49% by weight, WB (purity: about 99.4%, average particle size: about 4 μm) 9
% By weight, Mo (purity: about 99.8%, average particle size: about 8 μm)
7% by weight, Ni (purity: about 99.5%, average particle size: about 3μ)
m) Four kinds of powders of 35% by weight were mixed and pulverized for 48 hours by a rotary ball mill using ethyl alcohol as an organic solvent. After adding 3% of polyethylene glycol to the obtained slurry and adjusting the viscosity, a granulation treatment was performed using a disk atomizer type spray dryer to produce granulated powder having an average particle size of about 46 μm. After sintering this granulated powder at 1100 ° C. for 1 hour in an Ar atmosphere, it was crushed and classified to obtain a thermal spraying powder having a particle size of 26 to 50 μm. The obtained thermal spraying powder was composed of substantially spherical porous particles (see FIG. 1), the porosity was about 40%, and the average particle size was about 41 μm.
【００３１】この溶射用粉末をサンドブラスト処理を行
った厚さ６ｍｍの炭素鋼（Ｓ４５Ｃ）の基板の上に、メ
テコ社製ダイヤモンドジェット式の溶射機を用い、膜厚
が約１００μｍになるように溶射した。得られた基板２
０上の溶射被膜１０は図２の顕微鏡写真に示したように
緻密で均質であり、気孔率（断面写真より画像解析によ
り求めた、以下同じ）が０．２％、平均硬度（断面に荷
重３００ｇのマイクロビッカースを打ちこんで測定し
た）Ｈｖ３００が１０１０ｋｇ／ｍｍ２の特性を示し
た。ＣｕＫα線を用いるＸ線回折法によって得られた溶
射被膜中の生成相を同定したところ、複合ホウ化物相の
回折ピークは顕著に現れた（図３の回折ピーク１）が、
Ｎｉ基合金相の回折ピークは認められなかった。別にＥ
ＰＭＡで調べたところ、Ｎｉ基合金相の存在が認められ
たので、Ｎｉ基合金相は非晶質化しているものと考えら
れる。The powder for thermal spraying is sprayed onto a 6 mm-thick carbon steel (S45C) substrate that has been subjected to sandblasting, using a diamond jet type thermal spraying machine manufactured by Meteco Co., Ltd. so as to have a film thickness of about 100 μm. did. Obtained substrate 2
As shown in the photomicrograph of FIG. 2, the thermal sprayed coating 10 is dense and homogeneous, has a porosity (determined by image analysis from a cross-sectional photograph, the same applies hereinafter), and an average hardness (load on the cross-section). Hv 300 showed a characteristic of 1010 kg / mm 2 (measured by injecting 300 g of micro Vickers). When the generated phase in the thermal sprayed coating obtained by the X-ray diffraction method using CuKα ray was identified, the diffraction peak of the composite boride phase remarkably appeared (diffraction peak 1 in FIG. 3).
No diffraction peak of the Ni-based alloy phase was observed. Separately E
When examined by PMA, the presence of the Ni-based alloy phase was recognized, and it is considered that the Ni-based alloy phase was amorphous.
【００３２】実施例２ Ｆｅ−１５重量％Ｂ合金（純度約９９％、平均粒径約１
０μｍ）を２８重量％、Ｆｅ−１３重量％Ｃｒ合金（純
度約９９．５％、平均粒径約６μｍ）を３２．３重量
％、前記Ｍｏを３５．５重量％、前記Ｎｉを２．１重量
％、カーボニルＦｅ（純度約９９．６％、平均粒径約
２．５μｍ）を１．８重量％、Ｃ（純度約９９．５％、
平均粒径約５μｍ）を０．３重量％の６種類の粉末を混
合し、焼結温度を１１５０℃とし、他は実施例１に準じ
た条件で溶射用粉末を作製した。この溶射原料を実施例
１と同様に溶射したところ、気孔率が０．３％、平均硬
度がＨｖ30 0 ＝８５０ｋｇ／ｍｍ2 の緻密かつ均質な溶
射被膜を得た。Example 2 Fe-15 wt% B alloy (purity: about 99%, average particle size: about 1
0 μm), 32.3% by weight of an Fe-13% by weight Cr alloy (purity: about 99.5%, average particle size: about 6 μm), 35.5% by weight of Mo, and 2.1% by weight of Ni. 1.8% by weight of carbonyl Fe (purity: about 99.6%, average particle size: about 2.5 μm), C (purity: about 99.5%,
Six kinds of powders having an average particle size of about 5 μm) and 0.3% by weight were mixed, the sintering temperature was set at 1150 ° C., and the other conditions were the same as in Example 1 to prepare thermal spraying powders. The thermal spray material was sprayed in the same manner as in Example 1, a porosity of 0.3%, an average hardness was obtained dense and uniform spray coating of Hv 30 0 = 850kg / mm 2 .
【００３３】実施例３ 前記ＭｏＢ合金を５４重量％、Ｃｏ（純度約９９．６
％、平均粒径約５μｍ）を４５重量％、前記Ｍｏを１重
量％の３種類の粉末を混合し、焼結温度を１０００℃と
し、他は実施例１に準じた条件で溶射用粉末を作製し
た。この溶射粉末を実施例１と同様に溶射したところ、
気孔率１．０％、平均硬度Ｈｖ300 ＝１２００ｋｇ／ｍ
ｍ2 で緻密かつ均質な溶射被膜を得た。Example 3 The above MoB alloy was composed of 54% by weight of Co (purity of about 99.6).
%, An average particle size of about 5 μm), and three kinds of powders of 45% by weight of Mo and 1% by weight of Mo were mixed, the sintering temperature was set to 1000 ° C., and the other powders were sprayed under the same conditions as in Example 1. Produced. When this sprayed powder was sprayed in the same manner as in Example 1,
Porosity 1.0%, average hardness Hv 300 = 1200 kg / m
With m 2 , a dense and uniform sprayed coating was obtained.
【００３４】実施例４ 実施例１と同様にして処理した原料粉末のスラリーを減
圧下で乾燥した。この乾燥粉末を０．１Ｔｏｒｒの真空
中において１２００℃で５時間乾燥したものを粉砕して
分級し、粒径１０μｍ以下と粒径４０μｍ以上を除いて
平均粒径２５μｍの粒子からなる粉末を得た。この粉末
を用いて、実施例１と同じ条件で溶射を行ったところ、
気孔率１．２％、平均硬度Ｈｖ300 が８８０ｋｇ／ｍｍ
2 の溶射被膜が得られた。この溶射被膜をＸ線回折で調
べたところ、実施例１の場合と同様の回折図を得た。Example 4 A slurry of the raw material powder treated in the same manner as in Example 1 was dried under reduced pressure. The dried powder was dried at 1200 ° C. for 5 hours in a vacuum of 0.1 Torr and pulverized and classified to obtain a powder having an average particle diameter of 25 μm except for a particle diameter of 10 μm or less and a particle diameter of 40 μm or more. . When thermal spraying was performed under the same conditions as in Example 1 using this powder,
Porosity 1.2%, average hardness Hv 300 is 880 kg / mm
2 sprayed coatings were obtained. When the sprayed coating was examined by X-ray diffraction, a diffraction pattern similar to that of Example 1 was obtained.
【００３５】なお、これらの実施例において調合した原
料の化学組成と得られた溶射被膜の化学組成の間の有意
差は化学分析の精度と同程度であった。In these examples, the significant difference between the chemical composition of the prepared raw materials and the chemical composition of the obtained sprayed coating was almost equal to the precision of the chemical analysis.
【００３６】比較例１、２ 実施例１において作製した造粒粉末を比較例１ではその
まま、比較例２では７５０℃で焼結した後解砕し、実施
例１と同様に分級を行って溶射用粉末とした。得られた
溶射用粉末は比較例１と比較例２では球形で多孔質であ
ったが、比較例２では解砕時に球形が崩れたものが多く
なった。Comparative Examples 1 and 2 The granulated powder produced in Example 1 was directly sintered in 750 ° C. in Comparative Example 2 after being sintered at 750 ° C. In Comparative Example 2, the powder was classified and sprayed in the same manner as in Example 1. Powder. The obtained thermal spraying powder was spherical and porous in Comparative Examples 1 and 2, but in Comparative Example 2, many of the spherical particles were broken during crushing.
【００３７】これらの溶射用粉末を実施例１と同様に溶
射しようとしたが、比較例１では微粉が発生して粉末の
流動性が悪いため粉末供給装置が粉末で閉塞し溶射被膜
を形成できなかった。また、比較例２でも膜厚約１００
μｍまで溶射したとき、粉末供給装置が粉末で閉塞して
溶射不能となった。この比較例２で得られた溶射被膜は
気孔率が６％、平均硬度がＨｖ300 ＝６５０ｋｇ／ｍｍ
2 であり、非常に不均質な組織を有していた。この溶射
被膜の生成相中には相当量のＭｏＢが含まれたいた。The thermal spraying of these powders was attempted in the same manner as in Example 1. However, in Comparative Example 1, fine powder was generated and the fluidity of the powder was poor. Did not. In Comparative Example 2, the film thickness was about 100.
When thermal spraying was performed down to μm, the powder supply device was clogged with the powder and could not be sprayed. The sprayed coating obtained in Comparative Example 2 has a porosity of 6% and an average hardness of Hv 300 = 650 kg / mm.
2 and had a very heterogeneous tissue. A considerable amount of MoB was contained in the formation phase of this thermal spray coating.
【００３８】比較例３ 平均粒径が２０〜５０μｍの範囲にあるＭｏＢ、ＷＢ、
ＭｏおよびＮｉの粉末を準備し実施例１と同じ組成に混
合し、これをそのまま溶射用粉末として実施例１に準じ
た条件で溶射を行った。得られた溶射被膜は気孔率が７
％、平均硬度がＨｖ３００＝６５０を示し、不均質な組
織を有していた。また、被膜内に含まれている（Ｍｏ，
Ｗ）２ＮｉＢ２相は重量比で４０％未満であった。Comparative Example 3 MoB, WB, and MoB having an average particle size in the range of 20 to 50 μm
Mo and Ni powders were prepared and mixed to have the same composition as in Example 1, and this was directly used as a thermal spraying powder and subjected to thermal spraying under the same conditions as in Example 1. The resulting sprayed coating has a porosity of 7
%, The average hardness was Hv 300 = 650, and the sample had an inhomogeneous structure. It is also contained in the coating (Mo,
W) 2 NiB 2 phase was less than 40% by weight.
【００３９】[0039]
【発明の効果】本発明のＦｅ、Ｎｉ、Ｃｏから選ばれる
１種以上の元素とＭｏ及び／又はＷとの複合ホウ化物を
主体とするセラミックスと、Ｆｅ、Ｎｉ、Ｃｏから選ば
れる１種以上の元素を主体とする金属との複合粉末を用
いて形成した溶射被膜は、耐磨耗性用途に従来用いられ
ている自溶性合金などの溶射被膜よりも硬度と耐食性が
高く、超硬合金やクロム炭化物／金属複合耐の溶射被膜
に比べて密着性と耐熱性に優れている。また、鋼材に対
して熱膨張率の差が小さいため溶射被膜の膜厚も厚くで
きる。従って、本発明が提供する溶射粉末による溶射被
膜は、耐食性、硬度、耐熱性が同時に要求される温間ま
たは熱間鍛造用の金型類やアルミニウム鋳造用の金型類
に用いるとこれらの金型類の寿命が大幅に向上すると共
に、加工される製品の歩留まりや品質も向上する。さら
に、より一般的な摺動や粒子に対する耐磨耗性が求めら
れる部材に、この溶射被膜を形成しても部材の寿命延長
等に大きな効果があるので、その産業上の利用価値は多
大である。According to the present invention, a ceramic mainly composed of a complex boride of one or more elements selected from Fe, Ni and Co and Mo and / or W, and one or more elements selected from Fe, Ni and Co Sprayed coatings formed using composite powders with metals mainly composed of elements have higher hardness and corrosion resistance than sprayed coatings such as self-fluxing alloys conventionally used for wear-resistant applications, Excellent adhesion and heat resistance compared to thermal spray coating of chromium carbide / metal composite. Further, since the difference in the coefficient of thermal expansion is smaller than that of steel, the thickness of the thermal spray coating can be increased. Therefore, the thermal spray coating by the thermal spray powder provided by the present invention, when used in molds for warm or hot forging and molds for aluminum casting, which require corrosion resistance, hardness and heat resistance at the same time. The life of the molds is greatly improved, and the yield and quality of the processed product are also improved. Further, even if this thermal spray coating is formed on a member requiring more general sliding and abrasion resistance to particles, it has a great effect on extending the life of the member and the like, and its industrial utility value is great. is there.
【００４０】本発明のＦｅ、Ｎｉ、Ｃｏから選ばれる１
種以上の元素とＭｏ及び／又はＷとの複合ホウ化物を主
体とするセラミックスと、Ｆｅ、Ｎｉ、Ｃｏから選ばれ
る１種以上の元素を主体とする金属との溶射用セラミッ
クス・金属複合粉末は、原料粉末の造粒処理を行った後
に一定の条件で焼結することによって、組織的に均質で
一次粒子同士が多孔質に焼結した球状の粒子とされる。
この粒子からなる溶射用粉末は好ましくは概ね球形とす
ることによって流動性に優れ、さらに多孔質とすること
によって高速フレーム溶射の熱源により十分に溶融する
ため、気孔率が小さい、均質な組織を有する複合ホウ化
物・金属複合溶射被膜を容易に得ることができる。1 selected from Fe, Ni and Co of the present invention
Ceramic / metal composite powder for thermal spraying of a ceramic mainly composed of a complex boride of at least one element with Mo and / or W and a metal mainly composed of one or more elements selected from Fe, Ni and Co By performing sintering under a certain condition after performing the granulation treatment of the raw material powder, spherical particles in which the primary particles are systematically uniform and the primary particles are sintered to be porous.
The thermal spray powder composed of these particles is preferably excellent in fluidity by preferably being substantially spherical, and is sufficiently porous to be sufficiently melted by the heat source of high-speed flame spraying, so that it has a small porosity and a homogeneous structure. Compound boring
An article / metal composite sprayed coating can be easily obtained.
【図１】本発明の溶射用セラミックス・金属複合粉末の
外観を示す顕微鏡写真である。FIG. 1 is a micrograph showing the appearance of a ceramic / metal composite powder for thermal spraying of the present invention.
【図２】本発明の溶射用セラミックス・金属複合粉末を
用いて得た溶射被膜の断面を示す顕微鏡写真である。。FIG. 2 is a photomicrograph showing a cross section of a thermal spray coating obtained by using the ceramic / metal composite powder for thermal spraying of the present invention. .
【図３】本発明の溶射用セラミックス・金属複合粉末を
用いて得た溶射被膜中の生成相を示すＸ線回折図であ
る。FIG. 3 is an X-ray diffraction diagram showing a generated phase in a thermal spray coating obtained by using the ceramic / metal composite powder for thermal spraying of the present invention.
１０…セラミックス・金属複合溶射被膜 ２０…炭素鋼の基板 １…（Ｍｏ，Ｗ）2 ＮｉＢ2 相の回折ピーク10: Ceramic / metal composite thermal spray coating 20: Carbon steel substrate 1: (Mo, W) 2 NiB 2 phase diffraction peak
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 公彦 兵庫県高砂市梅井５丁目６番１号 旭硝 子株式会社高砂工場内 (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 4/10 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kimihiko Sato 5-6-1 Umei, Takasago City, Hyogo Prefecture Inside the Takasago Plant, Asahi Glass Co., Ltd. (58) Field surveyed (Int. Cl. 6 , DB name) C23C 4/10
Claims (6)
の元素とＭｏ及び／又はＷとの複合ホウ化物を主体とす
るセラミックス相と、Ｆｅ、Ｎｉ及びＣｏから選ばれる
一種以上の元素を主体とする金属結合相とで構成されて
いる粒子からなることを特徴とする溶射用セラミックス
・金属複合粉末。1. A ceramic phase mainly composed of a complex boride of one or more elements selected from Fe, Ni and Co and Mo and / or W, and a ceramic phase mainly composed of one or more elements selected from Fe, Ni and Co. A ceramic / metal composite powder for thermal spraying, comprising particles composed of a metal binder phase described below.
む請求項１記載の溶射用セラミックス・金属複合粉末。 2. The ceramic / metal composite powder for thermal spraying according to claim 1, wherein said ceramic phase contains 50 to 90% by weight.
（Ｍｏ，Ｗ）ＸＦｅＹＢＺ（但しＸ＝１．８〜２．２、
Ｙ＝０．９〜１．１）であり、前記金属結合相の７０重
量％以上がＦｅである請求項１または２記載の溶射用セ
ラミックス・金属複合粉末。 3. The method according to claim 1, wherein 70% by weight or more of the ceramic phase is (Mo, W) X Fe Y B Z (where X = 1.8 to 2.2,
3. The ceramic / metal composite powder for thermal spraying according to claim 1 , wherein Y = 0.9 to 1.1), and 70% by weight or more of the metal binder phase is Fe.
（Ｍｏ，Ｗ）ＸＮｉＹＢＺ（但しＸ＝１．８〜２．２、
Ｙ＝０．９〜１．１）であり、前記金属結合相の７０重
量％以上がＮｉである請求項１または２記載の溶射用セ
ラミックス・金属複合粉末。4. The method according to claim 1, wherein 70% by weight or more of the ceramic phase is (Mo, W) X Ni Y B Z (where X = 1.8 to 2.2,
3. The ceramic / metal composite powder for thermal spraying according to claim 1 , wherein Y = 0.9 to 1.1), and 70% by weight or more of the metal binder phase is Ni.
（Ｍｏ，Ｗ） Ｘ Ｃｏ Ｙ Ｂ（但しＸ＝０．９〜１．１、Ｙ
＝０．９〜１．１）であり、前記金属結合相の７０重量
％以上がＣｏである請求項１または２記載の溶射用セラ
ミックス・金属複合粉末。5. The method according to claim 1, wherein at least 70% by weight of said ceramic phase is
(Mo, W) X Co Y B (where X = 0.9 to 1.1, Y
3. The ceramic-metal composite powder for thermal spraying according to claim 1 , wherein Co is 0.9 to 1.1), and 70% by weight or more of the metal binder phase is Co.
ミックス・金属複合粉末を用いて溶射を行うことを特徴
とする溶射被膜の形成方法。 6. A method for forming a thermal sprayed coating, comprising performing thermal spraying using the ceramic / metal composite powder for thermal spraying according to claim 1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6268398A JP2988281B2 (en) | 1994-10-05 | 1994-10-05 | Ceramic / metal composite powder for thermal spraying and method for forming thermal spray coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6268398A JP2988281B2 (en) | 1994-10-05 | 1994-10-05 | Ceramic / metal composite powder for thermal spraying and method for forming thermal spray coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08104969A JPH08104969A (en) | 1996-04-23 |
| JP2988281B2 true JP2988281B2 (en) | 1999-12-13 |
Family
ID=17457928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6268398A Expired - Fee Related JP2988281B2 (en) | 1994-10-05 | 1994-10-05 | Ceramic / metal composite powder for thermal spraying and method for forming thermal spray coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2988281B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004196608A (en) * | 2002-12-19 | 2004-07-15 | Asahi Glass Co Ltd | Glass shaping tool and its manufacturing method |
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| JP2007211293A (en) | 2006-02-09 | 2007-08-23 | Fujimi Inc | Spray deposit film, and powder for thermal spraying |
| EP2407573A4 (en) * | 2009-03-10 | 2016-07-13 | Toyo Kohan Co Ltd | Highly corrosion-resistant and wearing-resistant member with thermal-spraying deposit and powder for thermal-spraying deposit formation for forming the same |
| TW201116794A (en) * | 2009-11-10 | 2011-05-16 | Pegatron Corp | Vapor chamber and manufacturing method thereof |
| JP6185047B2 (en) * | 2013-03-13 | 2017-08-23 | 株式会社フジミインコーポレーテッド | Thermal spray slurry and method of forming thermal spray coating |
| KR101727848B1 (en) | 2013-03-13 | 2017-04-17 | 가부시키가이샤 후지미인코퍼레이티드 | Slurry for thermal spraying, thermal sprayed coating, and method for forming thermal sprayed coating |
| KR102419886B1 (en) | 2014-09-03 | 2022-07-12 | 가부시키가이샤 후지미인코퍼레이티드 | Slurry for thermal spraying, thermal sprayed film and thermal sprayed film formation method |
| JP6741410B2 (en) | 2015-09-25 | 2020-08-19 | 株式会社フジミインコーポレーテッド | Spraying slurry, sprayed coating and method for forming sprayed coating |
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-
1994
- 1994-10-05 JP JP6268398A patent/JP2988281B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004196608A (en) * | 2002-12-19 | 2004-07-15 | Asahi Glass Co Ltd | Glass shaping tool and its manufacturing method |
| JP4725000B2 (en) * | 2002-12-19 | 2011-07-13 | 旭硝子株式会社 | Glass forming jig and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08104969A (en) | 1996-04-23 |
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