JPWO2013058376A1 - Mo powder for thermal spraying, Mo sprayed film using the same, and Mo sprayed film parts - Google Patents
Mo powder for thermal spraying, Mo sprayed film using the same, and Mo sprayed film parts Download PDFInfo
- Publication number
- JPWO2013058376A1 JPWO2013058376A1 JP2013539707A JP2013539707A JPWO2013058376A1 JP WO2013058376 A1 JPWO2013058376 A1 JP WO2013058376A1 JP 2013539707 A JP2013539707 A JP 2013539707A JP 2013539707 A JP2013539707 A JP 2013539707A JP WO2013058376 A1 JPWO2013058376 A1 JP WO2013058376A1
- Authority
- JP
- Japan
- Prior art keywords
- powder
- thermal spraying
- component
- particles
- sprayed 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
Abstract
取扱い性が良好で成膜性のよい溶射用Ｍｏ粉末を提供する。一次粒子の平均粒径が１μｍ以上、１０μｍ以下、二次粒子の平均粒径が２０μｍ以上、２００μｍ以下である溶射用Ｍｏ粉末において、アスペクト比１．０〜１．５を有する二次粒子が含まれる割合が、８０質量％以上、１００質量％以下である溶射用Ｍｏ粉末とする。Provided is a thermal spraying Mo powder having good handleability and good film formability. In the thermal spraying Mo powder having an average primary particle size of 1 μm or more and 10 μm or less, and an average secondary particle size of 20 μm or more and 200 μm or less, secondary particles having an aspect ratio of 1.0 to 1.5 are included. It is set as the Mo powder for thermal spraying whose ratio is 80 mass% or more and 100 mass% or less.
Description
本発明は、溶射用Ｍｏ粉末およびそれを用いたＭｏ溶射膜並びにＭｏ溶射膜部品に関する。 The present invention relates to a thermal spraying Mo powder, a Mo sprayed film using the same, and a Mo sprayed film component.
溶射とは、材料を加熱・溶融して、基材（被施工物）に吹き付けて被膜を形成する成膜方法である。加熱の熱源としては、燃焼炎やプラズマなどが使われている。溶射方式は、フレーム溶射、爆発溶射、電気式溶射、高速フレーム溶射などがあり、近年は材料を溶融しないで被膜を形成するコールドスプレー法も開発されている。 Thermal spraying is a film forming method in which a material is heated and melted and sprayed onto a substrate (workpiece) to form a film. A combustion flame or plasma is used as a heat source for heating. Thermal spraying methods include flame spraying, explosion spraying, electric spraying, high-speed flame spraying, and the like. In recent years, a cold spray method for forming a film without melting a material has been developed.
溶射は、溶融する材料であれば適用できるため、金属、セラミックス、サーメットやプラスチックなどの様々の材料が使われている。そのため、その用途も様々であり、耐摩耗性膜、耐食性膜、耐熱性膜などが挙げられ、自動車部品、産業機械部品、成膜装置用部品など種々の分野に適用されている。 Since thermal spraying can be applied to any material that melts, various materials such as metals, ceramics, cermets, and plastics are used. Therefore, the use is also various, and an abrasion-resistant film | membrane, a corrosion-resistant film | membrane, a heat resistant film | membrane etc. are mentioned, and it is applied to various fields, such as a motor vehicle part, an industrial machine part, and parts for film-forming apparatuses.
ところで、溶射は、溶射材料を粉末または線材（ワイヤー状、棒状）に加工して、加熱源に供給することにより行われる。フレーム溶射を例に挙げると、線状の溶射材料を使う方式を、溶線式フレーム溶射（ｗｉｒｅ ｆｌａｍｅ ｓｐｒａｙｉｎｇ）と呼び、粉末状の溶融材料を使う方式を、粉末式フレーム溶射（ｐｏｗｄｅｒ ｆｌａｍｅ ｓｐｒａｙｉｎｇ）と呼んでいる。溶線式フレーム溶射法は、燃焼炎に線状溶射材料を連続的に供給できることから、供給量を一定にコントロールし易く、均一な溶射膜が得易いといった利点がある。 By the way, thermal spraying is performed by processing the thermal spray material into powder or wire (wire shape, rod shape) and supplying it to a heating source. Taking flame spraying as an example, a method using a linear thermal spray material is called “wire flame spraying”, and a method using a powdered molten material is called “powder flame spraying”. I'm calling. The hot wire flame spraying method has an advantage that a linear spray material can be continuously supplied to the combustion flame, so that the supply amount can be easily controlled to be uniform and a uniform sprayed film can be easily obtained.
しかしながら、溶射材料を線材に加工しなければならないことから、炭素鋼、アルミニウムや亜鉛など比較的加工し易い材料には向くが、モリブデンやタングステンなどの硬い高融点金属に適用する場合はコストアップの要因となっていた。 However, since the thermal spray material must be processed into a wire, it is suitable for materials that are relatively easy to process such as carbon steel, aluminum, and zinc. However, when applied to hard refractory metals such as molybdenum and tungsten, the cost increases. It was a factor.
このため、高融点金属を溶射するときは粉末式フレーム溶射が適用されることが多かった。溶射用粉末として、例えば、特開２００４−３００５５５号公報（特許文献１）が開示されている。特許文献１では、平均粒径１０μｍ以下のＭｏ粉末を、造粒焼結法によって５〜７５μｍや４５〜２５０μｍの溶射用粉末を得ている。 For this reason, when flame spraying a refractory metal, powder flame spraying is often applied. For example, Japanese Patent Application Laid-Open No. 2004-300555 (Patent Document 1) is disclosed as a thermal spraying powder. In patent document 1, the powder for thermal spraying of 5-75 micrometers or 45-250 micrometers is obtained for the Mo powder with an average particle diameter of 10 micrometers or less by the granulation sintering method.
造粒焼結法により粒径を大きくすることにより、溶射ノズル（燃焼炎）への供給量を増やすことができるため、成膜量を増やすことはできる。しかしながら、単に造粒焼結法により得られた粒子はアスペクト比が２〜３程度の大きな粒子（二次粒子）であった。アスペクト比の大きな二次粒子は、流動性が悪く、溶射ノズルに供給する際に、瞬間的な溶射用粉末の供給量にバラツキが生じてしまうため、厚さが均一な膜が得られ難いといった問題が生じていた。 By increasing the particle size by the granulation sintering method, the amount supplied to the thermal spray nozzle (combustion flame) can be increased, so the amount of film formation can be increased. However, the particles obtained simply by the granulation sintering method were large particles (secondary particles) having an aspect ratio of about 2 to 3. Secondary particles with a large aspect ratio have poor fluidity, and when supplied to a thermal spray nozzle, the amount of instantaneous spray powder supplied varies, making it difficult to obtain a film with a uniform thickness. There was a problem.
本発明は、このような問題を解決するためのもので、均一な溶射膜を得ることができる溶射用Ｍｏ粉末およびそれを用いたＭｏ膜、並びにＭｏ膜部品を提供することを目的としている。 The present invention is intended to solve such problems, and an object of the present invention is to provide a thermal spraying Mo powder capable of obtaining a uniform thermal sprayed film, an Mo film using the same, and an Mo film component.
本発明による溶射用Ｍｏ粉末は、一次粒子の平均粒径が１μｍ以上、１０μｍ以下、二次粒子の平均粒径が２０μｍ以上、２００μｍ以下である溶射用Ｍｏ粉末において、アスペクト比１．０〜１．５を有する二次粒子が含まれる割合が、８０質量％以上、１００質量％以下であることを特徴とするものである。 The Mo powder for thermal spraying according to the present invention is an Mo powder for thermal spraying in which the average particle size of primary particles is 1 μm or more and 10 μm or less, and the average particle size of secondary particles is 20 μm or more and 200 μm or less. The ratio of the secondary particles having .5 is 80% by mass or more and 100% by mass or less.
また、本発明の態様においては、単位面積１０００μｍ×１０００μｍのＳＥＭ写真において、面積比（長径５μｍ以下の粒子の合計面積比／５μｍを超える粒子の合計面積比）が０〜１０％であってもよい。 In the aspect of the present invention, in an SEM photograph having a unit area of 1000 μm × 1000 μm, even if the area ratio (total area ratio of particles having a major axis of 5 μm or less / 5% total area ratio of particles exceeding 5 μm) is 0 to 10%. Good.
また、本発明の態様においては、二次粒子の密度が５．０ｋｇ／ｃｍ３以下であってもよい。In the embodiment of the present invention, the density of the secondary particles may be 5.0 kg / cm 3 or less.
また、本発明の態様においては、Ｍｏ純度が９９．０％以上であってもよい。 In the embodiment of the present invention, the Mo purity may be 99.0% or more.
また、本発明の態様においては、前記溶射用Ｍｏ粉末が、Ｍｏ粉末と第二成分粉末とを混合したものであってもよい。 In the aspect of the present invention, the thermal spraying Mo powder may be a mixture of Mo powder and second component powder.
また、本発明の態様においては、前記第二成分粉末が炭化物成分またはＮｉ成分であってもよい。 In the embodiment of the present invention, the second component powder may be a carbide component or a Ni component.
また、本発明の態様においては、前記第二成分粉末が１〜３５質量％含まれていてもよい。 Moreover, in the aspect of this invention, 1-35 mass% of said 2nd component powder may be contained.
また、本発明の態様においては、前記溶射用Ｍｏ粉末が、脱脂処理または焼結処理が施されていてもよい。 In the aspect of the present invention, the thermal spraying Mo powder may be subjected to a degreasing process or a sintering process.
また、本発明の態様においては、前記溶射用Ｍｏ粉末の流動性が５０ｓｅｃ／５０ｇ以下であってもよい。 In the embodiment of the present invention, the fluidity of the thermal spraying Mo powder may be 50 sec / 50 g or less.
また、本発明の態様においては、二次粒子の断面は二次粒子の断面は、Ｍｏ粉末および／または第二成分粉末が連なっている構造を有していてもよい。 In the embodiment of the present invention, the cross section of the secondary particles may have a structure in which the cross section of the secondary particles is continuous with the Mo powder and / or the second component powder.
本発明の別の態様にいては、上記溶射用Ｍｏ粉末を用いて溶射して形成されたＭｏ溶射膜も提供される。 In another aspect of the present invention, there is also provided a Mo spray coating formed by thermal spraying using the thermal spraying Mo powder.
また、本発明の別の態様においては、上記Ｍｏ溶射膜を備えたＭｏ溶射膜部品も提供される。 Moreover, in another aspect of the present invention, a Mo sprayed film component including the Mo sprayed film is also provided.
また、本発明の態様においては、Ｍｏ溶射膜部品が、自動車用部品、航空機用部品、発電機器力用部品、Ｘ線管用部品、熱電変換機器、および金型からなる群より選択される少なくとも１種であってよい。 In the aspect of the present invention, the Mo sprayed film component is at least one selected from the group consisting of an automotive component, an aircraft component, a power generator component, an X-ray tube component, a thermoelectric conversion device, and a mold. It can be a seed.
また、本発明の態様においては、前記Ｍｏ溶射膜の平均膜厚が５〜５００μｍであってもよい。 Moreover, in the aspect of this invention, 5-500 micrometers may be sufficient as the average film thickness of the said Mo sprayed film.
本発明による溶射用Ｍｏ粉末は、アスペクト比が１．０〜１．５の範囲にある二次粒子の割合を多くすることにより、溶射ノズルへの溶射用粉末の供給量を一定に管理し易くなるため、均一な高融点金属溶射膜を得ることができる。また、一次粒子を接着した二次粒子を使うことにより、コストアップを防ぐこともできる。 The Mo powder for thermal spraying according to the present invention can easily manage the supply amount of the thermal spraying powder to the thermal spray nozzle by increasing the ratio of secondary particles having an aspect ratio in the range of 1.0 to 1.5. Therefore, a uniform high melting point metal sprayed film can be obtained. In addition, the use of secondary particles to which primary particles are bonded can prevent an increase in cost.
本発明による溶射用Ｍｏ粉末は、一次粒子の平均粒径が１μｍ以上、１０μｍ以下、二次粒子の平均粒径が２０μｍ以上、２００μｍ以下である溶射用Ｍｏ粉末において、アスペクト比１．０〜１．５を有する二次粒子が含まれる割合が、８０質量％以上、１００質量％以下であることを特徴とするものである。 The Mo powder for thermal spraying according to the present invention is an Mo powder for thermal spraying in which the average particle size of primary particles is 1 μm or more and 10 μm or less, and the average particle size of secondary particles is 20 μm or more and 200 μm or less. The ratio of the secondary particles having .5 is 80% by mass or more and 100% by mass or less.
本発明において、一次粒子とは、Ｍｏ粉末１個（一粒）または第二成分粉末１個（一粒）のことを示し、二次粒子とは、複数の一次粒子が固まった粒子のことを示す。一次粒子が固まるとは、凝集して固まった状態や、接着剤またはバインダなどを介して接着した状態や、一次粒子を造粒したものを示す。 In the present invention, primary particles indicate one Mo powder (one grain) or one second component powder (one grain), and secondary particles are particles in which a plurality of primary particles are solidified. Show. The term “primary particles are solidified” indicates a state in which the particles are aggregated and solidified, a state in which the particles are bonded via an adhesive or a binder, or a case where primary particles are granulated.
図１は、一次粒子と二次粒子とが混在した状態の一例を示したものである。図中、符号１が溶射用Ｍｏ粉末の一次粒子であり、符号２が溶射用Ｍｏ粉末の二次粒子である。
FIG. 1 shows an example of a state in which primary particles and secondary particles are mixed. In the figure, reference numeral 1 denotes primary particles of the thermal spraying Mo powder, and
本発明による溶射用Ｍｏ粉末は、Ｍｏ金属単体からなるものであってもよく、また、Ｍｏ粉末と第二成分粉末とを混合したものであってもよい。溶射用Ｍｏ粉末に第二成分粉末が含まれる場合、第二成分粉末としては、金属Ｍｏ以外であれば特に限定されるものではなく、炭化物粉末、Ｎｉ成分粉末、Ｃｏ成分粉末、希土類元素成分粉末などが挙げられる。また、炭化物としては、炭化モリブデン、炭化タングステン、炭化珪素などが挙げられる。また、Ｎｉ成分粉末、Ｃｏ成分粉末、希土類元素成分粉末としては、金属単体、合金、化合物など様々なものが含まれる。これらのなかでも、第二成分粉末としては、炭化モリブデンまたはＮｉ成分が好ましい。炭化モリブデンは、溶射工程において不純物酸素（大気中で溶射した際の酸素を含む）を吸着する効果がある。また、炭化モリブデンは潤滑剤としての効果もあることから溶射膜の耐摩耗性を向上させることもできる。また、Ｎｉ成分は、耐食性が良いことから溶射膜の耐食性を向上させることができる。また、第二成分粉末は１種のみに限らず、２種以上であってもよい。また、第二成分粉末の混合量は、Ｍｏ粉末と第二成分粉末の合計値を１００質量％としたとき、１〜３５質量％の範囲であることが好ましい。この範囲であれば、溶射膜におけるＭｏの良さを活かして第二成分の特性を付与することができる。以下、単に「Ｍｏ粉末」と記載する場合は、Ｍｏ粉末単体からなるものの他、Ｍｏ粉末と第二成分粉末とを混合したものも含む意味とする。 The Mo powder for thermal spraying according to the present invention may be composed of Mo metal alone, or may be a mixture of Mo powder and second component powder. When the second component powder is included in the thermal spraying Mo powder, the second component powder is not particularly limited as long as it is other than metal Mo. Carbide powder, Ni component powder, Co component powder, rare earth element component powder Etc. Examples of the carbide include molybdenum carbide, tungsten carbide, and silicon carbide. The Ni component powder, the Co component powder, and the rare earth element component powder include various metals such as simple metals, alloys, and compounds. Among these, molybdenum carbide or Ni component is preferable as the second component powder. Molybdenum carbide has an effect of adsorbing impurity oxygen (including oxygen at the time of thermal spraying in the atmosphere) in the thermal spraying process. Further, since molybdenum carbide also has an effect as a lubricant, it is possible to improve the wear resistance of the sprayed film. Further, since the Ni component has good corrosion resistance, the corrosion resistance of the sprayed film can be improved. Further, the second component powder is not limited to one type, and may be two or more types. Moreover, it is preferable that the mixing amount of 2nd component powder is the range of 1-35 mass% when the sum total value of Mo powder and 2nd component powder is 100 mass%. If it is this range, the characteristic of 2nd component can be provided taking advantage of the goodness of Mo in a sprayed film. Hereinafter, when it is simply described as “Mo powder”, it is meant to include a mixture of Mo powder and a second component powder in addition to those composed of Mo powder alone.
Ｍｏ純度は９９．０％以上（質量％）であることが好ましい。Ｍｏ純度が９９．０％未満であると不純物の存在によりＭｏ粉末の融点にばらつきが生じてしまうおそれがある。 The Mo purity is preferably 99.0% or more (mass%). If the Mo purity is less than 99.0%, the melting point of the Mo powder may vary due to the presence of impurities.
本発明においては、一次粒子の平均粒径が１μｍ未満では粉末が細かすぎて取扱い性が悪くなり、１０μｍを超えて大きいと二次粒子のサイズが必要以上に大きくなってしまうおそれがある。また、二次粒子の平均粒径が２０μｍ未満では二次粒子とする効果が小さく、２００μｍを超えるとサイズが大きすぎるため溶射工程における材料供給量のばらつきを招く。また、溶射フレーム炎は、炎の表面と中心とでは温度が異なっており、同じフレーム炎にＭｏ粉末を供給しても、大きな粉末と小さな粉末とでは溶け方が異なる。Ｍｏ粉末（および第二成分粉末）の溶け方が均一でないと得られる溶射膜に未溶融組織ができ膜質にばらつきが生じる。そのため、あまり大きな粒子がない方が好ましい。 In the present invention, if the average particle size of the primary particles is less than 1 μm, the powder is too fine and the handleability is poor, and if it exceeds 10 μm, the size of the secondary particles may be unnecessarily large. Further, when the average particle size of the secondary particles is less than 20 μm, the effect of forming the secondary particles is small. When the average particle size exceeds 200 μm, the size is too large, resulting in variations in the material supply amount in the thermal spraying process. In addition, the temperature of the flame flame is different between the surface and the center of the flame, and even if the Mo powder is supplied to the same flame flame, the melting method is different between the large powder and the small powder. If the melting of the Mo powder (and the second component powder) is not uniform, an unmelted structure is formed in the obtained sprayed film, and the film quality varies. Therefore, it is preferable that there are no very large particles.
また本発明においては、アスペクト比１．０〜１．５を有する二次粒子が８０質量％以上、１００質量％以下含まれるものである。アスペクト比の測定は、拡大写真を使い、図１に示したように拡大写真（ＳＥＭ写真）に写る二次粒子の縦と横の最大長さを、それぞれＡ、Ｂとする。縦最大長さＡと、横最大長さＢとの小さい方を分母、大きい方を分子として（Ａ／ＢまたはＢ／Ａ）にてアスペクト比を求めるものとする。縦最大長さＡと横最大長さＢとの小さい方を分母にするので最小値は１．０となる。アスペクト比が１．５以下であるということは、二次粒子がほぼ球体であることを示している。アスペクト比が１．５を超えて大きいと、個々の二次粒子のサイズのばらつきが大きくなる。サイズばらつきが大きいと溶射フレーム炎への材料供給量にばらつきが生じ、溶射膜の膜厚にばらつきが生じて均一な膜が形成し難くなる。また、前述の通り、溶射フレーム炎は表面と中心では温度が異なるため、あまりアスペクト比の大きな二次粒子があると二次粒子の溶け方にばらつきが生じ、溶射膜中に未溶融組織ができて膜質に不均一な部分ができてしまう。そのため、本発明においては、アスペクト比１．０〜１．５を有する二次粒子が含まれる割合を８０質量％以上にしている。すべての二次粒子がアスペクト比１．０〜１．５の範囲であることが好ましい。 In the present invention, secondary particles having an aspect ratio of 1.0 to 1.5 are contained in an amount of 80% by mass to 100% by mass. For the measurement of the aspect ratio, an enlarged photograph is used, and the vertical and horizontal maximum lengths of secondary particles appearing in the enlarged photograph (SEM photograph) as shown in FIG. The aspect ratio is obtained by (A / B or B / A), where the smaller of the maximum vertical length A and the maximum horizontal length B is the denominator and the larger is the numerator. Since the smaller one of the maximum vertical length A and the maximum horizontal length B is used as the denominator, the minimum value is 1.0. An aspect ratio of 1.5 or less indicates that the secondary particles are almost spherical. When the aspect ratio is larger than 1.5, the size of individual secondary particles varies greatly. If the size variation is large, the amount of material supplied to the spray flame flame varies, and the film thickness of the sprayed film varies, making it difficult to form a uniform film. In addition, as described above, the temperature of the spray flame flame differs between the surface and the center, so if there are secondary particles with a very large aspect ratio, the secondary particles will be melted differently, and an unmelted structure will be formed in the sprayed film. As a result, the film quality is uneven. Therefore, in the present invention, the ratio of secondary particles having an aspect ratio of 1.0 to 1.5 is 80% by mass or more. It is preferable that all the secondary particles have an aspect ratio in the range of 1.0 to 1.5.
以上のように、Ｍｏ粉末単体からなるＭｏ溶射膜、またはＭｏ溶射膜の特性を維持しながら第二成分粉末の特性を付与したＭｏ溶射膜は、その膜質が均一な溶射膜である必要がある。均一な溶射膜を形成するために二次粒子を用い、その二次粒子のアスペクト比を制御することが重要である。さらに均一な溶射膜を得るためには、小さな粒子の存在をできるだけ少なくすることも必要である。溶射膜は、Ｍｏ粉末をフレーム炎で溶かして高速で噴射して成膜する技術である。本発明においては、溶射フレーム炎で溶射用Ｍｏ粉末を溶かすため、Ｍｏ粉末のサイズがばらつくと、Ｍｏ粉末の溶け方にばらつきが生じるため、あまり小さなＭｏ粉も少ない方がよい。小さなＭｏ粉末とは、二次粒子にならなかった一次粒子や、二次粒子であっても小さな二次粒子である。 As described above, the Mo sprayed film composed of the Mo powder alone or the Mo sprayed film provided with the characteristics of the second component powder while maintaining the characteristics of the Mo sprayed film needs to be a sprayed film having a uniform film quality. . In order to form a uniform sprayed film, it is important to use secondary particles and control the aspect ratio of the secondary particles. In order to obtain a more uniform sprayed film, it is also necessary to minimize the presence of small particles. The sprayed film is a technique for forming a film by melting Mo powder with a flame flame and spraying it at a high speed. In the present invention, since the thermal spraying Mo powder is melted by the thermal spray flame, if the size of the Mo powder varies, the method of melting the Mo powder varies. A small Mo powder is a primary particle which did not become a secondary particle, or a small secondary particle even if it is a secondary particle.
そのため、単位面積１０００μｍ×１０００μｍのＳＥＭ写真において、面積比（長径５μｍ以下の粒子の合計面積比／５μｍを超える粒子の合計面積比）が０〜１０％であることが好ましい。面積比は、まず、単位面積１０００μｍ×１０００μｍのＳＥＭ写真（拡大写真）を撮り、個々の粉末の最も長い対角線を長径Ｌとして測定する。図２に長径を測定する一例を示した。拡大写真を使うことにより、粉末を二次元で捉えることができる。そこに写る一次粒子または二次粒子の長径Ｌを測定する。長径Ｌが５μｍ以下と５μｍを超える粒子に振り分け、それぞれの面積を求め合計する。合計２００粒以上の粒子について長径Ｌ、面積を求めて面積比（長径５μｍ以下の粒子の合計面積比／５μｍを超える粒子の合計面積比）を求める。 Therefore, in the SEM photograph having a unit area of 1000 μm × 1000 μm, it is preferable that the area ratio (total area ratio of particles having a major axis of 5 μm or less / total area ratio of particles exceeding 5 μm) is 0 to 10%. For the area ratio, first, an SEM photograph (enlarged photograph) having a unit area of 1000 μm × 1000 μm is taken, and the longest diagonal line of each powder is measured as the major axis L. FIG. 2 shows an example of measuring the major axis. By using the enlarged photo, the powder can be captured in two dimensions. The major axis L of the primary particle or secondary particle reflected there is measured. The major axis L is distributed to particles of 5 μm or less and more than 5 μm, and the respective areas are obtained and totaled. The major axis L and the area are determined for a total of 200 or more particles to determine the area ratio (total area ratio of particles having a major axis of 5 μm or less / 5% total area ratio of particles exceeding 5 μm).
長径Ｌが５μｍ以下の小さな粒子（二次粒子にならなかった一次粒子または小さな二次粒子）が面積比で１０％以下と少なくすることにより、溶射フレーム炎に投入したときの溶融ばらつきを低減することができる。溶融ばらつきを低減するためには、面積比を１０％以下、さらには５％以下、最も好ましくは０％にすることである。つまり、すべての粒子を長径Ｌが５μｍを超える二次粒子にすることである。 By reducing the area ratio of small particles (primary particles that did not become secondary particles or small secondary particles) having a major axis L of 5 μm or less to 10% or less, variation in melting when injected into a spray flame flame is reduced. be able to. In order to reduce the melting variation, the area ratio should be 10% or less, further 5% or less, and most preferably 0%. In other words, all the particles are made into secondary particles having a major axis L exceeding 5 μm.
また、二次粒子の密度が５．０ｋｇ／ｃｍ３以下であることが好ましい。これまでは、一次粒子および二次粒子の粒径やアスペクト比などの外観形状による制御について説明してきた。しかしながら、二次粒子は一次粒子が立体的に結合して形成されたものである。そのため、二次粒子の密度を制御することも重要である。Moreover, it is preferable that the density of a secondary particle is 5.0 kg / cm < 3 > or less. So far, the control by the external shape such as the particle size and aspect ratio of the primary particles and the secondary particles has been described. However, the secondary particles are formed by sterically bonding the primary particles. Therefore, it is also important to control the density of secondary particles.
溶射用Ｍｏ粉末の二次粒子は、溶射フレーム炎に投入したとき、一次粒子にばらける。ばらけた一次粒子が溶融し、高速で噴射されて基材上に堆積され溶射膜となる。そのため、二次粒子の密度があまり高いと溶射フレーム炎に投入した際に一次粒子にばらけて分散し難くなる。二次粒子のまま溶射膜として堆積されると、未溶融組織ができて膜質の異なるものとなってしまう。そのため、二次粒子の密度は５．０ｋｇ／ｃｍ３以下、さらには３．０ｋｇ／ｃｍ３以下であることが好ましい。密度の下限値は特に限定されるものではないが、あまり密度が低いと二次粒子の形状維持性が悪くなり、溶射フレーム炎に供給する前に一次粒子にばらけてしまう。また、密度があまり低いと内部が空洞の二次粒子となる。あまり空洞が多いと材料供給量のばらつきがおきてしまう。つまり、粒径やアスペクト比が同じ二次粒子であっても、密度が異なれば、二次粒子を形成する一次粒子の量が異なり、結果として材料供給量のばらつきを生じてしまう。そのため、二次粒子の密度は１．０ｇ／ｃｍ３以上であることが好ましい。二次粒子の密度はより好ましくは１．０〜３．０ｇ／ｃｍ３である。なお、二次粒子の密度はアルキメデス法にて行うものとする。The secondary particles of the thermal spraying Mo powder are dispersed into primary particles when put into the thermal spray flame. The scattered primary particles are melted, sprayed at a high speed, and deposited on the substrate to form a sprayed film. For this reason, if the density of the secondary particles is too high, it will be difficult to disperse by being scattered to the primary particles when put into the spray flame flame. When the secondary particles are deposited as a sprayed film, an unmelted structure is formed and the film quality is different. Therefore, the density of the secondary particles is preferably 5.0 kg / cm 3 or less, more preferably 3.0 kg / cm 3 or less. The lower limit value of the density is not particularly limited, but if the density is too low, the shape maintaining property of the secondary particles is deteriorated and the primary particles are scattered before being supplied to the flame spray flame. On the other hand, when the density is too low, secondary particles with hollow inside are formed. If there are too many cavities, the material supply will vary. That is, even if the secondary particles have the same particle size and aspect ratio, if the density is different, the amount of primary particles forming the secondary particles is different, resulting in variations in the amount of material supply. Therefore, the density of the secondary particles is preferably 1.0 g / cm 3 or more. The density of the secondary particles is more preferably 1.0 to 3.0 g / cm 3 . In addition, the density of secondary particles shall be performed by the Archimedes method.
また、二次粒子の断面は、Ｍｏ粉末および／または第二成分粉末が連なっている構造であることが好ましい。前述のとおり、二次粒子は溶射フレーム炎に供給された際に一次粒子にばらけて、ばらけた一次粒子が溶融し、基材に堆積され溶射膜となる。二次粒子の断面が一次粒子の連なった構造となることにより、ばらけた一次粒子が基材に噴射されていく工程において一次粒子の存在割合を均一にすることができる。基材に噴射される工程で一次粒子の存在割合が均一であると、できあがった溶射膜の膜質を均一にすることができる。図３は、Ｍｏ粉末（および第二成分粉末）が連なった構造の一例を示したものである。二次粒子の断面を見たときに、端からもう一方の端までＭｏ粉末ないし、Ｍｏ粉末および第二成分粉末（一次粒子）が連なった構造を具備するものである。 Moreover, it is preferable that the cross section of a secondary particle is a structure where Mo powder and / or 2nd component powder are continuing. As described above, when the secondary particles are supplied to the spray flame flame, the secondary particles are scattered to the primary particles, and the scattered primary particles are melted and deposited on the base material to form a sprayed film. Since the cross-section of the secondary particles has a structure in which the primary particles are continuous, the ratio of the primary particles can be made uniform in the process in which the scattered primary particles are sprayed onto the base material. If the ratio of the primary particles is uniform in the step of spraying onto the base material, the film quality of the finished sprayed film can be made uniform. FIG. 3 shows an example of a structure in which Mo powders (and second component powders) are connected. When the cross section of the secondary particle is viewed, it has a structure in which Mo powder or Mo powder and second component powder (primary particles) are connected from one end to the other end.
また、本発明による溶射用Ｍｏ粉末は、脱脂処理または焼結処理が施されていることが好ましい。本発明の溶射用Ｍｏ粉末であれば流動性を５０ｓｅｃ／５０ｇ以下にすることができる。脱脂処理または焼結処理をすることにより、流動性を３０ｓｅｃ／５０ｇ以下と向上させることができる。なお、本発明において、流動性の測定は、ＪＩＳ−Ｋ−６７６０に準じた押し出し形プラストメーターを用い、溶射用Ｍｏ粉末５０ｇが押し出されるまでに何秒かかるかで測定するものとする。 Further, the thermal spraying Mo powder according to the present invention is preferably subjected to a degreasing treatment or a sintering treatment. If it is Mo powder for thermal spraying of this invention, fluidity | liquidity can be 50 sec / 50g or less. By performing the degreasing process or the sintering process, the fluidity can be improved to 30 sec / 50 g or less. In the present invention, the fluidity is measured by using an extruded plastometer according to JIS-K-6760 and measuring how many seconds it takes for 50 g of the thermal spraying Mo powder to be extruded.
脱脂処理は、６００〜１０００℃未満にて熱処理して、二次粒子中の樹脂バインダを焼失させる処理である。また、焼結処理は１０００〜１４００℃に加熱して樹脂バインダを焼失させると共に一次粒子同士の結合力を強化させる方法である。脱脂処理温度が６００℃未満では脱脂処理に時間がかかりすぎて製造性が低下する。一方、焼結処理温度が１４００℃を超えて高いと、一次粒子の結合力が強くなりすぎて溶射フレーム炎に投入した際に、二次粒子が一次粒子にばらけ難くなる。 A degreasing process is a process which heat-processes at less than 600-1000 degreeC, and burns down the resin binder in a secondary particle. In addition, the sintering process is a method of heating to 1000 to 1400 ° C. to burn out the resin binder and strengthen the bonding force between the primary particles. If the degreasing treatment temperature is less than 600 ° C., the degreasing treatment takes too much time and the productivity is lowered. On the other hand, when the sintering temperature is higher than 1400 ° C., the binding force of the primary particles becomes too strong, and the secondary particles are difficult to be dispersed into the primary particles when put into the spray flame flame.
以上のように、本発明による溶射用Ｍｏ粉末であれば、細かい一次粒子を二次粒子に加工した上で、その二次粒子のアスペクト比を所定のサイズにしているので取扱い性が良好である。そのため、溶射フレーム炎への供給量を安定的にすることができる。さらに、溶射フレーム炎に供給して、二次粒子が一次粒子にばらけて基材上に成膜される際に、基材への一次粒子の供給量を安定化させることができる。そのため、均一なＭｏ溶射膜を得ることができる。また、従来のようにＭｏ線材やＭｏ棒材よりもＭｏ粉末の方が溶融しやすいので同じ溶射フレーム炎であれば成膜速度も上げることができる。 As described above, with the thermal spraying Mo powder according to the present invention, fine primary particles are processed into secondary particles, and the aspect ratio of the secondary particles is set to a predetermined size, so that the handleability is good. . Therefore, the supply amount to the thermal spray flame can be stabilized. Furthermore, when the secondary particles are supplied to the spray flame flame and dispersed on the base material to form a film on the base material, the supply amount of the primary particles to the base material can be stabilized. Therefore, a uniform Mo sprayed film can be obtained. In addition, since Mo powder is more easily melted than Mo wire and Mo rod as in the prior art, the film deposition rate can be increased with the same flame spray flame.
また、本発明の溶射用Ｍｏ粉末を用いれば、線材を用いるよりも大幅なコストダウンを可能とした上で、成膜量の均一化が図れる。また、密度や流動性の制御により成膜量の均一化のみならず、成膜工程の自動化など取扱い性も向上する。 Moreover, if the thermal spraying Mo powder of the present invention is used, the film formation amount can be made uniform while enabling a significant cost reduction compared to the case of using a wire. In addition, by controlling the density and fluidity, not only the film formation amount can be made uniform, but also handleability such as automation of the film formation process can be improved.
このような溶射用Ｍｏ粉末を溶射して基材上に成膜することにより、様々なＭｏ溶射膜を得ることができる。また、このような溶射膜を備えた様々な溶射部品に適用できる。図４に溶射部品の一例を示した。図中、符号４は溶射膜、符号５は基材、を表す。溶射部品は、溶射膜を有する部品であれば特に限定されるものではないが、耐摩耗性膜、耐食性膜、耐熱性膜などが挙げられ、自動車部品、産業機械部品、成膜装置用部品など種々の分野に適用可能である。また、溶射膜の膜厚は、特に限定されるものではなく、１０〜５００μｍが例示される。
By spraying such a thermal spraying Mo powder and forming a film on the substrate, various Mo sprayed films can be obtained. Further, the present invention can be applied to various sprayed parts provided with such a sprayed film. FIG. 4 shows an example of a thermal sprayed part. In the figure,
次に、本発明による溶射用Ｍｏ粉末の製造方法について説明する。本発明の溶射用Ｍｏ粉末は、上記構成を具備すれば、その製造方法は特に限定されるものではないが、歩留まり良くえるための製法として次の方法が挙げられる。 Next, the manufacturing method of the thermal spraying Mo powder by this invention is demonstrated. If the Mo powder for thermal spraying of this invention comprises the said structure, the manufacturing method will not be specifically limited, However, The following method is mentioned as a manufacturing method for improving a yield.
まず、一次粒子径が平均粒径１〜１０μｍのＭｏ粉末を用意する。また、溶射用Ｍｏ粉末としてＭｏ粉末と第二成分粉末とを混合したものを得る場合には、一次粒子径が平均粒径１〜１０μｍのＭｏ粉末および第二成分粉末を用意する。一次粒子径はＦＳＳＳ粒径とする。また、Ｍｏ粉末の純度は９９．０ｗｔ％以上、さらには９９．９ｗｔ％以上であることが好ましい。用意したＭｏ粉末（および第二成分粉末）を回転式アトマイザーなどの攪拌装置に入れて十分な攪拌を行う。なお、以下、単に「Ｍｏ粉末」と記載する場合は、Ｍｏ粉末単体からなるものの他、Ｍｏ粉末と第二成分粉末とを混合したものも含む意味とする。 First, Mo powder having a primary particle diameter of 1 to 10 μm is prepared. Moreover, when obtaining what mixed Mo powder and 2nd component powder as Mo powder for thermal spraying, Mo powder and 2nd component powder whose primary particle diameters are 1-10 micrometers in average particle diameter are prepared. The primary particle size is the FSSS particle size. The purity of the Mo powder is preferably 99.0 wt% or more, more preferably 99.9 wt% or more. The prepared Mo powder (and the second component powder) is put into a stirring device such as a rotary atomizer and sufficiently stirred. In addition, hereinafter, when simply described as “Mo powder”, it is meant to include a mixture of a Mo powder and a second component powder in addition to a Mo powder alone.
次に、樹脂バインダを添加して造粒工程を行う。樹脂バインダは、ポリビニルアルコール粉末、ポリエチンレングリコール粉末またはカルボメキシメチルセルロース粉末の少なくとも１種以上が好ましい。これら樹脂バインダは６００℃以上に加熱すると焼失するので二次粒子の密度を制御し易い。また、粉末状でＭｏ粉末と混合することができるので均一に混合することができる。造粒工程は、スプレードライヤー方式や転動造粒方式などを適用することが好ましい。造粒工程を行うことにより、一次粒子を二次粒子に加工することができる。 Next, a resin binder is added and a granulation process is performed. The resin binder is preferably at least one of polyvinyl alcohol powder, polyethylene glycol powder or carbomethylmethylcellulose powder. Since these resin binders are burned off when heated to 600 ° C. or higher, it is easy to control the density of secondary particles. Moreover, since it can be mixed with Mo powder in powder form, it can mix uniformly. It is preferable to apply a spray dryer system, a rolling granulation system, etc. to a granulation process. By performing the granulation step, the primary particles can be processed into secondary particles.
また、必要に応じ、脱脂処理または焼結処理を行う。脱脂処理は、６００〜１０００℃未満にて熱処理して、二次粒子中の樹脂バインダを焼失させる処理である。また、焼結処理は１０００〜１４００℃に加熱して樹脂バインダを焼失させると共に一次粒子同士の結合力を強化させる方法である。このような処理を行うと二次粒子の密度を調製した上で、その断面がＭｏ粉末（一次粒子）が連なった構造とすることができる。 また、二次粒子のアスペクト比は、造粒工程の条件を適正化することによりアスペクト比１．０〜１．５の割合を向上させることができる。また、必要に応じ、ふるい分け等により形状分級することも効果的である。特に、アスペクト比が１．５以下と１．６以上では傾斜面を転がる速度が異なるので、この現象を利用して形状分級する方法も効果的である。このような製造方法により得られた溶射用Ｍｏ粉末は、流動性に優れることから取り扱い性が良好である。 Moreover, a degreasing process or a sintering process is performed as needed. A degreasing process is a process which heat-processes at less than 600-1000 degreeC, and burns down the resin binder in a secondary particle. In addition, the sintering process is a method of heating to 1000 to 1400 ° C. to burn out the resin binder and strengthen the bonding force between the primary particles. When such a treatment is performed, the density of the secondary particles can be adjusted, and the cross section can be made to have a structure in which Mo powders (primary particles) are connected. Moreover, the aspect ratio of secondary particles can improve the ratio of aspect ratio 1.0-1.5 by optimizing the conditions of a granulation process. It is also effective to classify the shape by sieving or the like as necessary. In particular, since the rolling speed of the inclined surface is different when the aspect ratio is 1.5 or less and 1.6 or more, the shape classification method using this phenomenon is also effective. The thermal spraying Mo powder obtained by such a production method is excellent in handling properties because of its excellent fluidity.
本発明を、実施例によりさらに詳細に説明するが、本発明がこれら実施例の内容に限定されるものではない。 Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to the contents of these examples.
＜実施例Ａ１〜Ａ５、比較例Ａ１＞
原料粉末として純度９９．９質量％以上のモリブデン粉末（一次粒子径は表１に示す）を用意した。モリブデン粉末を回転式アトマイザーにより粉砕工程を行った。次に、樹脂バインダ（ポリビニルアルコール樹脂バインダ）と混合して、Ｍｏ粉末スラリーを調製した。<Examples A1 to A5, Comparative Example A1>
A molybdenum powder having a purity of 99.9% by mass or more (primary particle diameter is shown in Table 1) was prepared as a raw material powder. The molybdenum powder was pulverized by a rotary atomizer. Next, it was mixed with a resin binder (polyvinyl alcohol resin binder) to prepare a Mo powder slurry.
次に、Ｍｏ粉末スラリーをスプレードライヤーを使って造粒することにより、Ｍｏ粉末の二次粒子を得た。また、表に示すように脱脂処理または焼結処理を行った。スプレードライヤーの条件（回転速度、供給量など）を変えて、アスペクト比１．０〜１．５の二次粒子の割合を変えたものを用意した。 Next, secondary particles of Mo powder were obtained by granulating the Mo powder slurry using a spray dryer. In addition, degreasing treatment or sintering treatment was performed as shown in the table. What changed the ratio of the secondary particle of aspect ratio 1.0-1.5 by changing the conditions (rotation speed, supply amount, etc.) of the spray dryer was prepared.
各実施例および比較例の溶射用Ｍｏ粉末に関して、面積比（長径５μｍ以下の粒子の合計面積比／５μｍを超える粒子の合計面積比）、二次粒子の密度、二次粒子の断面はＭｏ粉末が連なっているか否か、流動性を調べた。その結果を表１、２に示す。 Regarding the Mo powder for thermal spraying of each Example and Comparative Example, the area ratio (total area ratio of particles having a major axis of 5 μm or less / 5% total area ratio of particles exceeding 5 μm), the density of secondary particles, and the cross section of the secondary particles are Mo powder. The fluidity was examined to see if they were connected. The results are shown in Tables 1 and 2.
なお、面積比（長径５μｍ以下の粒子の合計面積比／５μｍを超える粒子の合計面積比）は、以下のようにして求めた。先ず、溶射用Ｍｏ粉末をガラス板上に広げ、単位面積１０００μｍ×１０００μｍの拡大写真を撮った。その拡大写真に写る個々の溶射用Ｍｏ粉末の最大径を測定し、その最大径が５μ以下と５μｍを超えるもので分けて面積比を求めた。 In addition, the area ratio (total area ratio of particles having a major axis of 5 μm or less / total area ratio of particles exceeding 5 μm) was determined as follows. First, the thermal spraying Mo powder was spread on a glass plate, and an enlarged photograph having a unit area of 1000 μm × 1000 μm was taken. The maximum diameter of each thermal spraying Mo powder shown in the enlarged photograph was measured, and the area ratio was determined by dividing the maximum diameter into those having a maximum diameter of 5 μm or less and exceeding 5 μm.
また、二次粒子の密度はアルキメデス法にて分析したものである。また、二次粒子の断面はＭｏ粉末が連なっているか否かは、二次粒子を切断して断面写真を撮り、任意の対角線にてＭｏ粉末（一次粒子）が連なっているか否かを問測定した。また、流動性はＪＩＳ−Ｋ−６７６０に準じた押し出し形プラストメーターを用い、溶射用Ｍｏ粉末５０ｇが押し出されるまでに何秒かかるかで測定した。 The density of secondary particles was analyzed by Archimedes method. In addition, the cross-section of the secondary particles is determined by checking whether the Mo powders are connected to each other by cutting the secondary particles and taking a cross-sectional photograph to determine whether the Mo powders (primary particles) are connected at an arbitrary diagonal line. did. The fluidity was measured by using an extruded plastometer according to JIS-K-6760, and how many seconds it took for 50 g of the thermal spraying Mo powder to be extruded.
表１および２に示される通り、実施例Ａ１〜Ａ５の溶射用Ｍｏ粉末は流動性が優れていた。 As shown in Tables 1 and 2, the thermal spraying Mo powders of Examples A1 to A5 were excellent in fluidity.
次に、上記のようにして得られた実施例Ａ１〜Ａ５および比較例Ａ１の溶射用Ｍｏ粉末を用いて溶射膜を形成した。粉末式フレーム溶射装置（ｐｏｗｄｅｒ ｆｌａｍｅ ｓｐｒａｙｉｎｇ ｄｅｖｉｃｅ）を用いて大気中にて成膜した。基材として縦１０ｃｍ×横１０ｃｍ×厚さ１ｍｍのＭｏ板を用いた。基材上に縦２ｃｍ×横２ｃｍの溶射膜を一定時間かけて溶射処理をしたときの膜厚のバラツキを調べた。２×２ｃｍの溶射膜を３か所設け、下記のように、膜厚の最大値と最小値の差を求めこれを溶射膜のバラツキとした。
溶射膜のバラツキ（％）＝［（膜厚の最大値−膜厚の最小値）／（膜厚の最大値＋膜厚の最小値）］×１００（％）
また、各溶射膜の表面粗さＲａを求めた。その結果を表３に示す。Next, a thermal spray film was formed using the thermal spraying Mo powders of Examples A1 to A5 and Comparative Example A1 obtained as described above. A film was formed in the atmosphere using a powder frame spraying device. A Mo plate having a length of 10 cm, a width of 10 cm, and a thickness of 1 mm was used as the substrate. The variation in film thickness was examined when a sprayed film of 2 cm in length and 2 cm in width was sprayed over a certain time on a substrate. Three 2 × 2 cm sprayed films were provided, and the difference between the maximum value and the minimum value of the film thickness was determined as follows, and this was used as the dispersion of the sprayed film.
Dispersion of sprayed film (%) = [(maximum value of film thickness−minimum value of film thickness) / (maximum value of film thickness + minimum value of film thickness)] × 100 (%)
Further, the surface roughness Ra of each sprayed film was obtained. The results are shown in Table 3.
表３から分かる通り、実施例Ａ１〜Ａ５の溶射用Ｍｏ粉末を用いた溶射膜は、溶射膜のバラツキが６％以下と小さかった。また、表面粗さ（Ｒａ）が小さく、大気中で成膜したにも関わらず膜質が均一なものが得られた。特に脱脂処理や焼結処理したものは優れた特性を示した。 As can be seen from Table 3, the sprayed film using the thermal spraying Mo powders of Examples A1 to A5 had a dispersion of the sprayed film as small as 6% or less. Moreover, the surface roughness (Ra) was small, and a film with uniform film quality was obtained despite the film formation in the atmosphere. In particular, those subjected to degreasing treatment and sintering treatment exhibited excellent characteristics.
＜実施例Ｂ１〜Ｂ５、比較例Ｂ１＞
原料粉末として、純度９９．９質量％以上のモリブデン粉末と、表４に示す各第二成分粉末（一次粒子径および配合比率は表４に示す）とを混合したものを使用した以外は、実施例Ａ１と同様にして溶射用Ｍｏ粉末を作製した。得られた溶射用Ｍｏ粉末について、実施例Ａ１と同様にして、面積比（長径５μｍ以下の粒子の合計面積比／５μｍを超える粒子の合計面積比）、二次粒子の密度、二次粒子の断面はＭｏ粉末が連なっているか否か、流動性を調べた。その結果を表４、５に示す。<Examples B1 to B5, Comparative Example B1>
Implementation was carried out except that the raw material powder used was a mixture of molybdenum powder having a purity of 99.9% by mass or more and each second component powder shown in Table 4 (primary particle diameter and blending ratio are shown in Table 4). In the same manner as in Example A1, Mo powder for thermal spraying was produced. About the obtained Mo powder for thermal spraying, in the same manner as in Example A1, the area ratio (total area ratio of particles having a major axis of 5 μm or less / total area ratio of particles exceeding 5 μm), the density of secondary particles, and the secondary particles The cross section was examined for fluidity as to whether or not the Mo powder was continuous. The results are shown in Tables 4 and 5.
表４および５に示される通り、実施例Ｂ１〜Ｂ５の溶射用Ｍｏ粉末は流動性が優れていた。 As shown in Tables 4 and 5, the thermal spraying Mo powders of Examples B1 to B5 were excellent in fluidity.
次に、得られた実施例Ｂ１〜Ｂ５および比較例Ｂ１の溶射用Ｍｏ粉末を用いて、実施例Ａ１と同様にして溶射膜を形成し、溶射膜のバラツキ（％）および溶射膜の表面粗さＲａを求めた。その結果を表６に示す。 Next, using the obtained thermal spraying Mo powders of Examples B1 to B5 and Comparative Example B1, a thermal spray film was formed in the same manner as in Example A1, and the variation (%) of the thermal spray film and the surface roughness of the thermal spray film were measured. Ra was determined. The results are shown in Table 6.
表６から分かる通り、実施例Ｂ１〜Ｂ５の溶射用Ｍｏ粉末を用いた溶射膜は、溶射膜のバラツキが６％以下と小さかった。また、表面粗さ（Ｒａ）が小さく、大気中で成膜したにも関わらず膜質が均一なものが得られた。特に脱脂処理や焼結処理したものは優れた特性を示した。 As can be seen from Table 6, the sprayed film using the thermal spraying Mo powders of Examples B1 to B5 had a dispersion of the sprayed film as small as 6% or less. Moreover, the surface roughness (Ra) was small, and a film with uniform film quality was obtained despite the film formation in the atmosphere. In particular, those subjected to degreasing treatment and sintering treatment exhibited excellent characteristics.
１…溶射用Ｍｏ粉末（一次粒子）
２…溶射用Ｍｏ粉末（二次粒子）
Ｌ…溶射用Ｍｏ粉末（二次粒子）の粒径
３…Ｍｏ粉末および／または第二成分粉末が連なった部分
４…溶射膜
５…基材1 ... Mo powder for spraying (primary particles)
2 ... Mo powder for thermal spraying (secondary particles)
L: Particle size of Mo powder for spraying (secondary particles) 3 ... Part where Mo powder and / or second component powder are connected 4 ... Sprayed
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013539707A JP5890843B2 (en) | 2011-10-20 | 2012-10-19 | Mo powder for thermal spraying, Mo sprayed film using the same, and Mo sprayed film parts |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011230621 | 2011-10-20 | ||
| JP2011230621 | 2011-10-20 | ||
| JP2011230620 | 2011-10-20 | ||
| JP2011230620 | 2011-10-20 | ||
| JP2013539707A JP5890843B2 (en) | 2011-10-20 | 2012-10-19 | Mo powder for thermal spraying, Mo sprayed film using the same, and Mo sprayed film parts |
| PCT/JP2012/077146 WO2013058376A1 (en) | 2011-10-20 | 2012-10-19 | Mo POWDER FOR THERMAL SPRAYING, Mo THERMAL SPRAY COATING FILM USING SAME, AND COMPONENT WITH Mo THERMAL SPRAY COATING FILM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2013058376A1 true JPWO2013058376A1 (en) | 2015-04-02 |
| JP5890843B2 JP5890843B2 (en) | 2016-03-22 |
Family
ID=48141019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013539707A Active JP5890843B2 (en) | 2011-10-20 | 2012-10-19 | Mo powder for thermal spraying, Mo sprayed film using the same, and Mo sprayed film parts |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5890843B2 (en) |
| CN (1) | CN103781934B (en) |
| WO (1) | WO2013058376A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015194678A1 (en) * | 2014-06-20 | 2015-12-23 | 株式会社フジミインコーポレーテッド | Powder material to be used in powder lamination shaping and powder lamination shaping method using same |
| KR101890507B1 (en) * | 2014-07-03 | 2018-08-21 | 플란제 에스이 | Method for producing a layer |
| CN108342677A (en) * | 2018-03-13 | 2018-07-31 | 中国神华能源股份有限公司 | The wheel and its manufacturing method of rolling stock |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113369A (en) * | 1981-12-28 | 1983-07-06 | Showa Denko Kk | Powder material for melt-spraying and its production |
| JPH04231450A (en) * | 1990-05-23 | 1992-08-20 | Gte Prod Corp | Improved method for processing spray coating nickel alloy and molybdenum powder |
| JP2004300555A (en) * | 2003-03-31 | 2004-10-28 | Fujimi Inc | Thermal spraying powder, and method for forming thermal sprayed film using he same |
| WO2012008413A1 (en) * | 2010-07-12 | 2012-01-19 | 株式会社東芝 | Refractory metal powder for thermal spraying, and refractory metal thermally-sprayed film and thermally-sprayed components using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5690716A (en) * | 1994-09-09 | 1997-11-25 | Osram Sylvania Inc. | Thermal spray powder |
-
2012
- 2012-10-19 CN CN201280042145.7A patent/CN103781934B/en active Active
- 2012-10-19 WO PCT/JP2012/077146 patent/WO2013058376A1/en active Application Filing
- 2012-10-19 JP JP2013539707A patent/JP5890843B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113369A (en) * | 1981-12-28 | 1983-07-06 | Showa Denko Kk | Powder material for melt-spraying and its production |
| JPH04231450A (en) * | 1990-05-23 | 1992-08-20 | Gte Prod Corp | Improved method for processing spray coating nickel alloy and molybdenum powder |
| JP2004300555A (en) * | 2003-03-31 | 2004-10-28 | Fujimi Inc | Thermal spraying powder, and method for forming thermal sprayed film using he same |
| WO2012008413A1 (en) * | 2010-07-12 | 2012-01-19 | 株式会社東芝 | Refractory metal powder for thermal spraying, and refractory metal thermally-sprayed film and thermally-sprayed components using same |
Non-Patent Citations (1)
| Title |
|---|
| JPN6011064649; 馬込正勝: ＪＩＳ使い方シリーズ 溶射技術マニュアル 第１版 第１刷, 19981030, ｐ．３２-３３, 財団法人 日本規格協会 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5890843B2 (en) | 2016-03-22 |
| CN103781934A (en) | 2014-05-07 |
| WO2013058376A1 (en) | 2013-04-25 |
| CN103781934B (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Review of the methods for production of spherical Ti and Ti alloy powder | |
| KR102048062B1 (en) | Titanium powder, its products, and sintered products | |
| CN108103499A (en) | A kind of particle for ultrahigh speed laser melting coating enhances iron-based metal powder | |
| CN109338137B (en) | Method for producing chromium nitride-containing spray powders | |
| JP4602401B2 (en) | Discharge surface treatment electrode manufacturing method and discharge surface treatment electrode | |
| CN101223294A (en) | Method for the manufacture of titanium alloy structure | |
| KR102432787B1 (en) | ODS alloy powder, production method thereof by plasma treatment, and use thereof | |
| WO2017073487A1 (en) | Sputtering target and method for producing sputtering target | |
| JP2009293108A (en) | METHOD FOR PRODUCING Al-BASED ALLOY SPUTTERING TARGET MATERIAL | |
| JP5890843B2 (en) | Mo powder for thermal spraying, Mo sprayed film using the same, and Mo sprayed film parts | |
| KR20150123219A (en) | Aluminum material for sintering, method for producing aluminum material for sintering, and method for producing porous aluminum sintered compact | |
| US20080293558A1 (en) | Wear Resistant Materials | |
| EP2505689A1 (en) | Cermet coating, spraying particles for forming same, method for forming cermet coating, and article with coating | |
| JP5881605B2 (en) | High melting point metal powder for thermal spraying, high melting point metal sprayed film using the same, and thermal sprayed parts | |
| Eguiluz et al. | Dispersion of Ni nanoparticles into Ti (C, N) colloidal filaments for 3D printing by FFF | |
| JP2012112012A (en) | Powder for hvaf thermal spraying, and method for forming thermal-sprayed film | |
| JP2006176818A (en) | Powder for thermal spraying | |
| JPWO2019123989A1 (en) | Powder material, powder material for additional manufacturing, and method of manufacturing powder material | |
| JP6520523B2 (en) | Oxide sintered body, method for producing the same, and sputtering target | |
| WO2021214106A1 (en) | Additive manufacturing powders for use in additive manufacturing processes resulting in improved stability of steel melt-track | |
| JP2012188677A (en) | Powder for thermal spraying | |
| KR101280285B1 (en) | Spherical tungsten composite powders and manufacturing method thereof | |
| JP6618749B2 (en) | Thermal spray powder and method of forming thermal spray coating | |
| JP2004124259A (en) | METHOD FOR PRODUCING W-Cu COMPOSITE MATERIAL THIN SHEET | |
| JP2004218004A (en) | Lubrication coating sprayed body, and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150602 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150803 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160122 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160219 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5890843 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |