WO2011071124A1 - Sliding member and manufacturing method thereof - Google Patents

Sliding member and manufacturing method thereof Download PDF

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Publication number
WO2011071124A1
WO2011071124A1 PCT/JP2010/072162 JP2010072162W WO2011071124A1 WO 2011071124 A1 WO2011071124 A1 WO 2011071124A1 JP 2010072162 W JP2010072162 W JP 2010072162W WO 2011071124 A1 WO2011071124 A1 WO 2011071124A1
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intermediate layer
layer
sliding member
carbide
chromium
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PCT/JP2010/072162
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French (fr)
Japanese (ja)
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昭 藤原
和久 古田
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本田技研工業株式会社
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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • C23C10/32—Chromising
    • 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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces

Definitions

  • the present invention relates to a metal surface treatment technology for sliding members used in camshaft drive chains, oil pump drive chains, balancer shaft drive chains and the like in automobiles and industrial machines, and in particular, cracking of a carbide film on the surface of the slide members. Prevention technology.
  • Patent Document 1 includes vanadium carbide as a main component and a small amount of chromium carbide on the surface of a steel serving as a base material of a connecting pin for a chain in order to realize excellent wear resistance even under high surface pressure.
  • a technique for forming a carbide layer by diffusion infiltration processing is disclosed.
  • the intermediate layer in Patent Document 1 is formed by interposing a Cr film having an intermediate hardness between the base material (Fe) and the film type (V).
  • the hardness of the base material (Fe) is HV500
  • the hardness of the V coating is HMV2200
  • the hardness of the Cr coating is HMV1500
  • the Cr coating has an intermediate hardness and is applied.
  • an object of the present invention is to provide a sliding member capable of preventing coating cracking caused by a difference in thermal expansion coefficient between a base material and a chromium carbide coating, and a method for manufacturing the same, taking a Cr coating as an example. It is said. These techniques can also be applied to other film types.
  • the sliding member of the present invention comprises a composite carbide (Fe,) consisting of a base element (Fe) and a coating type: A (A is one or more of Cr, V, Ti, Nb) on an iron base. A) A carbide layer is covered with an intermediate layer made of C.
  • the sliding member of the present invention is characterized in that a chromium carbide layer is coated on a steel member via an intermediate layer made of a composite carbide (Fe, Cr) C of iron and chromium.
  • a chromium carbide layer is coated on a steel member via an intermediate layer made of a composite carbide (Fe, Cr) C of iron and chromium.
  • the intermediate layer is composed of a base material (Fe) and a coating type (Cr), and can have intermediate characteristics between the two layers.
  • the stress resulting from the difference in thermal expansion coefficient between the carbide layer and the steel member can be relaxed.
  • the thickness of the intermediate layer is preferably 16% or more with respect to the thickness of (chromium carbide layer + intermediate layer).
  • the thickness of the intermediate layer is less than 16%, it is difficult to sufficiently relieve the stress caused by the difference in thermal expansion coefficient described above, and the coating on the steel member is likely to crack.
  • the Cr concentration in the intermediate layer is preferably gradually increased toward the chromium carbide layer, and the Fe concentration is preferably decreased.
  • the hardness of the intermediate layer shows an intermediate value between the hardness of the chromium carbide layer and the steel member, that is, it has intermediate characteristics and can sufficiently relax the stress concentration on the chromium carbide coating, Can be prevented.
  • the layer structure (V, Nb, Ti) other than the Cr film is shown in FIG. In this case, film cracking can be prevented under 16% or more of the same conditions as the Cr film.
  • the present invention is a method for producing a sliding member in which a chromium carbide layer is coated on a steel member through an intermediate layer made of a composite carbide of iron and chromium (Fe, Cr) C by diffusion permeation treatment. It is characterized by containing cementite in advance and performing diffusion and permeation treatment in the austenite + cementite region on the Fe—C phase diagram.
  • Fe 3 C is stably present in the austenite + cementite region. Therefore, by supplying Cr from the outside and reacting with Fe 3 C, it is shown in FIG.
  • Such an intermediate layer made of (Fe, Cr) C can be reliably generated on the surface of the steel member.
  • the chromium carbide layer is coated on the steel member via the intermediate layer made of the composite carbide (Fe, Cr) C of iron and chromium. For this reason, the stress resulting from the difference in thermal expansion coefficient between the steel member and the chromium carbide layer can be relaxed by the intermediate layer, and cracking of the coating on the steel member can be prevented.
  • the present invention will be described in more detail with reference to specific examples.
  • Treats penetrants consisting of steel materials containing 0.6% or more of C, chromium-containing powders (for example, metallic chromium), sintering inhibitors (for example, alumina) and accelerators (for example, halides such as ammonium chloride).
  • the apparatus was filled, diffusion diffusion treatment was performed under inert gas inflow conditions, and the steel member was coated with chromium carbide.
  • Table 1 and FIG. 2 summarize the results of the surface carbon concentration after the carburizing process, the diffusion infiltration temperature, and whether an intermediate layer was formed between the steel member and the chromium carbide layer during the diffusion infiltration process. .
  • FIG. 2 is a graph showing the relationship between the surface carbon concentration of each steel member and the presence or absence of an intermediate layer. From Table 1 and FIG. 2, in Examples 1 to 13 of the present invention in which the diffusion and permeation treatment was performed in a state where the surface carbon concentration of the steel member showed a predetermined value and the surface structure was in or near the austenite + cementite region, The intermediate layer was confirmed at any temperature during the permeation treatment. This is because cementite (Fe 3 C) is stably present in the austenite + cementite region, and Cr from the chromium carbide layer coated on the outermost surface reacts with Fe 3 C on the surface of the base material, so (Fe, Cr) C It is thought that an intermediate layer was formed.
  • cementite Fe 3 C
  • Comparative Examples 1 to 8 in which the diffusion permeation treatment was performed in a state where the structure of the steel member surface was in the austenite region, no intermediate layer was formed. From this, it has been confirmed that the intermediate layer can be obtained reliably if the diffusion permeation treatment is performed in a state where the structure of the steel member surface is austenite + cementite.
  • FIG. 3 shows the result of examining whether or not the intermediate layer has been generated by microscopic observation.
  • FIG. 4 shows the EPMA analysis result of the coating film of Example 16 of the present invention.
  • the intermediate layer has a surface CrC layer and components (Fe, Cr, C) contained in the base material, and the intermediate layer Cr concentration gradually increases toward the surface layer. Recognize.
  • the CrC layer was HV1626
  • the intermediate layer was HV889
  • the base material was HV526. Therefore, it was confirmed that the intermediate layer had an intermediate composition and hardness between the CrC layer and the base material.
  • the steel material subjected to the diffusion permeation treatment was subjected to an austemper treatment (holding at 830 ° C. for 60 minutes and then quenched in a salt bath at 310 ° C.) for strengthening the base material.
  • an austemper treatment holding at 830 ° C. for 60 minutes and then quenched in a salt bath at 310 ° C.
  • the cross section of each sample was observed with a microscope, and the relationship between the presence or absence of film cracking and the intermediate layer ratio was examined.
  • the results are shown in Table 2 and FIG.
  • the intermediate layer ratio is the ratio of the intermediate layer to the thickness of the entire coating on the base material. From Table 2 and FIG.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Disclosed is a sliding member which prevents film cracking due to differences in thermal expansion. A complex carbide (Fe,Cr)C containing a base material element (Fe) and a covering element (Cr) is formed between a base material and a covering layer.

Description

摺動部材およびその製造方法Sliding member and manufacturing method thereof
　本発明は、自動車及び産業用機械におけるカムシャフト駆動チェーン、オイルポンプ駆動チェーン、バランサーシャフト駆動チェーン等に用いられる摺動部材の金属表面処理技術に係り、特に、摺動部材表面の炭化物皮膜の割れ防止技術に関する。 The present invention relates to a metal surface treatment technology for sliding members used in camshaft drive chains, oil pump drive chains, balancer shaft drive chains and the like in automobiles and industrial machines, and in particular, cracking of a carbide film on the surface of the slide members. Prevention technology.
　自動車及び産業機械等には各種のチェーンが使用されており、カムシャフト駆動チェーン、オイルポンプ駆動チェーン、バランサーシャフト駆動チェーン等が挙げられる。これらチェーンにおいては、運転中にリンクがピンの周りを往復摺動するため、ピンが摩耗する。このため、チェーン用ピン等の摺動部材の耐摩耗性向上に関し様々な技術開発がなされている。例えば、特許文献１には、高面圧下においても優れた耐摩耗性を実現すべく、チェーン用連結ピンの母材となる鋼の表面に、バナジウム炭化物を主成分としかつ少量のクロム炭化物を含む炭化物層を拡散浸透処理によって形成する技術が開示されている。 Various chains are used in automobiles and industrial machines, such as camshaft drive chains, oil pump drive chains, balancer shaft drive chains, and the like. In these chains, the link wears back and forth around the pin during operation, so the pin wears. For this reason, various technical developments have been made for improving the wear resistance of sliding members such as chain pins. For example, Patent Document 1 includes vanadium carbide as a main component and a small amount of chromium carbide on the surface of a steel serving as a base material of a connecting pin for a chain in order to realize excellent wear resistance even under high surface pressure. A technique for forming a carbide layer by diffusion infiltration processing is disclosed.
特開２００２－１９５３５６号公報JP 2002-195356 A
　特許文献１における中間層は母材（Ｆｅ）と皮膜種（Ｖ）の間に中間的な硬度を持つＣｒ被膜を介装して中間層としたものである。ここで、母材（Ｆｅ）の硬度はＨＭＶ５００、Ｖ被膜の硬度はＨＭＶ２２００で、Ｃｒ被膜の硬度がＨＭＶ１５００であることから、Ｃｒ皮膜が中間的な硬度を持ち適用されている。しかしながら、母材（Ｆｅ）にＨＭＶ１５００のＣｒ皮膜を適用して焼き入れ処理を実施すると、熱膨張係数差によりＣｒ皮膜が割れることが知られているが、中間層として用いることができる適当な被膜は現在のところ提供されていないのが実情である。同様に、コーティング種としては前述のＣｒ（ＨＭＶ１５００）、Ｖ（ＨＭＶ２２００）の他にもＮｂ、Ｔｉ（ＨＭＶ３２００）等の高硬度で耐久性に優れた皮膜はあるが、皮膜処理後の焼き入れ処理（基材強化）において割れるため、量産化が困難であるのが実情である。 The intermediate layer in Patent Document 1 is formed by interposing a Cr film having an intermediate hardness between the base material (Fe) and the film type (V). Here, since the hardness of the base material (Fe) is HV500, the hardness of the V coating is HMV2200, and the hardness of the Cr coating is HMV1500, the Cr coating has an intermediate hardness and is applied. However, it is known that when the HV1500 Cr coating is applied to the base material (Fe) and the quenching treatment is performed, the Cr coating is cracked due to a difference in thermal expansion coefficient, but an appropriate coating that can be used as an intermediate layer. Is currently not provided. Similarly, there are coatings with high hardness and durability such as Nb and Ti (HMV3200) in addition to the aforementioned Cr (HMV1500) and V (HMV2200), but quenching treatment after coating treatment. Actually, it is difficult to mass-produce because it breaks in (strengthening the base material).
　したがって、本発明は、Ｃｒ皮膜を例に取り、母材とクロム炭化物被膜との熱膨張係数の差に起因する被膜割れを防止することができる摺動部材およびその製造方法を提供することを目的としている。また、これらの技術は他皮膜種にも適用できるものである。 Accordingly, an object of the present invention is to provide a sliding member capable of preventing coating cracking caused by a difference in thermal expansion coefficient between a base material and a chromium carbide coating, and a method for manufacturing the same, taking a Cr coating as an example. It is said. These techniques can also be applied to other film types.
　本発明の摺動部材は、鉄系母材に、母材元素（Ｆｅ）と被覆種:Ａ（ＡはＣｒ，Ｖ，Ｔｉ，Ｎｂの１種または２種以上）からなる複合炭化物　(Ｆｅ，Ａ)Ｃからなる中間層を介してＡ炭化物層が被覆されていることを特徴とする。 The sliding member of the present invention comprises a composite carbide (Fe,) consisting of a base element (Fe) and a coating type: A (A is one or more of Cr, V, Ti, Nb) on an iron base. A) A carbide layer is covered with an intermediate layer made of C.
　Ｃｒ皮膜を例に取ると、本発明の摺動部材は、鋼部材に、鉄とクロムの複合炭化物（Ｆｅ，Ｃｒ）Ｃからなる中間層を介してクロム炭化物層が被覆されていることを特徴とする。この層構造を図１（ａ）に示す。図１（ａ）に示すようにこの層構造によれば、中間層の構成が母材（Ｆｅ）と皮膜種（Ｃｒ）からなり、両層の中間的な特性を持たすことが可能となり、クロム炭化物層と鋼部材の熱膨張係数の差に起因する応力を緩和することができる。この場合、（クロム炭化物層＋中間層）の厚さに対し、中間層の厚さが１６％以上であることが好ましい。中間層の厚さが１６％未満であると、前述の熱膨張係数の差に起因する応力を十分に緩和し難く、鋼部材上の被膜が割れ易くなる。また、中間層のＣｒ濃度が、クロム炭化物層へ向けて徐々に増加することが好ましく、又、Ｆｅ濃度は逆に減少することが好ましい。これにより、中間層の硬度はクロム炭化物層と鋼部材の硬度の中間程度の値を示し、すなわち中間的な特性を持ち、クロム炭化物被膜への応力集中を十分に緩和することができ、被膜割れを防止することができる。 Taking a Cr film as an example, the sliding member of the present invention is characterized in that a chromium carbide layer is coated on a steel member via an intermediate layer made of a composite carbide (Fe, Cr) C of iron and chromium. And This layer structure is shown in FIG. As shown in FIG. 1 (a), according to this layer structure, the intermediate layer is composed of a base material (Fe) and a coating type (Cr), and can have intermediate characteristics between the two layers. The stress resulting from the difference in thermal expansion coefficient between the carbide layer and the steel member can be relaxed. In this case, the thickness of the intermediate layer is preferably 16% or more with respect to the thickness of (chromium carbide layer + intermediate layer). When the thickness of the intermediate layer is less than 16%, it is difficult to sufficiently relieve the stress caused by the difference in thermal expansion coefficient described above, and the coating on the steel member is likely to crack. Further, the Cr concentration in the intermediate layer is preferably gradually increased toward the chromium carbide layer, and the Fe concentration is preferably decreased. As a result, the hardness of the intermediate layer shows an intermediate value between the hardness of the chromium carbide layer and the steel member, that is, it has intermediate characteristics and can sufficiently relax the stress concentration on the chromium carbide coating, Can be prevented.
　また、Ｃｒ皮膜以外の層構造（Ｖ，Ｎｂ，Ｔｉ）を図１（ｂ）に示した。この場合には、Ｃｒ皮膜と同様の条件の１６％以上にて皮膜割れを防止することができる。 Also, the layer structure (V, Nb, Ti) other than the Cr film is shown in FIG. In this case, film cracking can be prevented under 16% or more of the same conditions as the Cr film.
　また、本発明は、拡散浸透処理によって鉄とクロムの複合炭化物（Ｆｅ，Ｃｒ）Ｃからなる中間層を介してクロム炭化物層を鋼部材に被覆する摺動部材の製造方法であり、鋼材組織はセメンタイトをあらかじめ含み、Ｆｅ－Ｃ系状態図上のオーステナイト＋セメンタイト領域で拡散浸透処理を行うことを特徴とする。鋼部材表面の組織がオーステナイト＋セメンタイトの状態であると、オーステナイト＋セメンタイト領域ではＦｅ３Ｃが安定に存在するため、外部からＣｒを供給してＦｅ３Ｃと反応させることにより、図１に示すような（Ｆｅ，Ｃｒ）Ｃからなる中間層を鋼部材表面に確実に生成することができる。 Further, the present invention is a method for producing a sliding member in which a chromium carbide layer is coated on a steel member through an intermediate layer made of a composite carbide of iron and chromium (Fe, Cr) C by diffusion permeation treatment. It is characterized by containing cementite in advance and performing diffusion and permeation treatment in the austenite + cementite region on the Fe—C phase diagram. When the structure of the steel member surface is in the austenite + cementite state, Fe 3 C is stably present in the austenite + cementite region. Therefore, by supplying Cr from the outside and reacting with Fe 3 C, it is shown in FIG. Such an intermediate layer made of (Fe, Cr) C can be reliably generated on the surface of the steel member.
　本発明によれば、鋼部材に、鉄とクロムの複合炭化物（Ｆｅ，Ｃｒ）Ｃからなる中間層を介してクロム炭化物層の被覆を行う。このため、鋼部材とクロム炭化物層の熱膨張係数差に起因する応力を中間層により緩和することができ、鋼部材上の被膜の割れを防ぐことができる。 According to the present invention, the chromium carbide layer is coated on the steel member via the intermediate layer made of the composite carbide (Fe, Cr) C of iron and chromium. For this reason, the stress resulting from the difference in thermal expansion coefficient between the steel member and the chromium carbide layer can be relaxed by the intermediate layer, and cracking of the coating on the steel member can be prevented.
本発明の摺動部材の層構造を示す図である。It is a figure which shows the layer structure of the sliding member of this invention. 実施例における各鋼部材の炭素濃度と中間層の有無との関係を示すグラフである。It is a graph which shows the relationship between the carbon concentration of each steel member in an Example, and the presence or absence of an intermediate | middle layer. 実施例における各鋼部材の被膜の断面図である。It is sectional drawing of the film of each steel member in an Example. 実施例における本発明の被膜のＥＰＭＡ分析結果を示す図である。It is a figure which shows the EPMA analysis result of the film of this invention in an Example. 鋼部材上の被膜に対する中間層の割合と被膜厚さとの関係を示すグラフである。It is a graph which shows the relationship between the ratio of the intermediate | middle layer with respect to the film on a steel member, and a film thickness.
　以下、具体的な実施例により本発明をさらに詳細に説明する。
　はじめに、本発明の中間層の生成条件について検討を行った。０．６％以上のＣを含む鉄鋼材料、クロム含有粉末（例えば、金属クロム）、焼結防止剤（例えば、アルミナ）および促進剤（例えば、塩化アンモニウム等のハロゲン化物）からなる浸透剤を処理装置に充填し、不活性ガス流入条件下にて拡散浸透処理を行い、鋼部材にクロム炭化物を被覆した。浸炭処理後の表面炭素濃度と、拡散浸透処理温度と、この拡散浸透処理の際に鋼部材とクロム炭化物層との間に中間層が生成したかどうかの結果を表１および図２にまとめた。 Hereinafter, the present invention will be described in more detail with reference to specific examples.
First, the conditions for forming the intermediate layer of the present invention were examined. Treats penetrants consisting of steel materials containing 0.6% or more of C, chromium-containing powders (for example, metallic chromium), sintering inhibitors (for example, alumina) and accelerators (for example, halides such as ammonium chloride). The apparatus was filled, diffusion diffusion treatment was performed under inert gas inflow conditions, and the steel member was coated with chromium carbide. Table 1 and FIG. 2 summarize the results of the surface carbon concentration after the carburizing process, the diffusion infiltration temperature, and whether an intermediate layer was formed between the steel member and the chromium carbide layer during the diffusion infiltration process. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　図２は、各鋼部材の表面炭素濃度と中間層の有無との関係を示すグラフである。表１および図２より、鋼部材の表面炭素濃度が所定の値を示し、表面組織がオーステナイト＋セメンタイト領域内またはその付近にある状態で拡散浸透処理を行った本発明例１～１３では、拡散浸透処理時の温度がいずれの場合においても中間層が確認された。これは、オーステナイト＋セメンタイト領域ではセメンタイト（Ｆｅ３Ｃ）が安定に存在し、最表面に被覆したクロム炭化物層からのＣｒと母材表面のＦｅ３Ｃが反応したため、（Ｆｅ，Ｃｒ）Ｃからなる中間層が生成したと考えられる。一方、鋼部材表面の組織がオーステナイト領域にある状態で拡散浸透処理を行った比較例１～８では、中間層は生成しなかった。このことから、鋼部材表面の組織がオーステナイト＋セメンタイトの状態において拡散浸透処理を行えば中間層を確実に得られることを確認できた。 FIG. 2 is a graph showing the relationship between the surface carbon concentration of each steel member and the presence or absence of an intermediate layer. From Table 1 and FIG. 2, in Examples 1 to 13 of the present invention in which the diffusion and permeation treatment was performed in a state where the surface carbon concentration of the steel member showed a predetermined value and the surface structure was in or near the austenite + cementite region, The intermediate layer was confirmed at any temperature during the permeation treatment. This is because cementite (Fe 3 C) is stably present in the austenite + cementite region, and Cr from the chromium carbide layer coated on the outermost surface reacts with Fe 3 C on the surface of the base material, so (Fe, Cr) C It is thought that an intermediate layer was formed. On the other hand, in Comparative Examples 1 to 8 in which the diffusion permeation treatment was performed in a state where the structure of the steel member surface was in the austenite region, no intermediate layer was formed. From this, it has been confirmed that the intermediate layer can be obtained reliably if the diffusion permeation treatment is performed in a state where the structure of the steel member surface is austenite + cementite.
　そして、中間層が生成したかどうかを顕微鏡観察で調べた結果を図３に示す。また、一例として、本発明例１６の被膜のＥＰＭＡ分析結果を図４に示す。 FIG. 3 shows the result of examining whether or not the intermediate layer has been generated by microscopic observation. As an example, FIG. 4 shows the EPMA analysis result of the coating film of Example 16 of the present invention.
　図４より、中間層は表層のＣｒＣ層と母材に含有される成分（Ｆｅ，Ｃｒ，Ｃ）を有しており、中間層のＣｒ濃度が表層へ向けて徐々に増加していることがわかる。また、この試料の各層および母材のビッカース硬度を調べたところ、ＣｒＣ層はＨＶ１６２６、中間層はＨＶ８８９、母材はＨＶ５２６であった。したがって、中間層はＣｒＣ層と母材の中間の組成および硬度を有していることを確認できた。 From FIG. 4, the intermediate layer has a surface CrC layer and components (Fe, Cr, C) contained in the base material, and the intermediate layer Cr concentration gradually increases toward the surface layer. Recognize. When the Vickers hardness of each layer and the base material of this sample was examined, the CrC layer was HV1626, the intermediate layer was HV889, and the base material was HV526. Therefore, it was confirmed that the intermediate layer had an intermediate composition and hardness between the CrC layer and the base material.
　次に、本発明の中間層の厚さとその効果について検討を行った。
　拡散浸透処理を行った鋼材を母材強化のためオーステンパー処理（８３０℃・６０分保持後、３１０℃の塩浴に焼入れ）を行った。熱処理後、各試料の断面を顕微鏡により観察し、被膜割れの有無と中間層比率との関係について調べた。その結果を表２および図５に示す。なお、中間層比率は、母材上の全被膜の厚さに対する中間層の割合である。表２および図５より、中間層比率が１６％以上の本発明例１４～２０では、中間層による応力緩和の効果が十分であるため被膜の割れは確認されなかった。一方、中間層比率が１６％未満の比較例９～１２では、中間層による応力緩和の効果が小さいため被膜が割れている。したがって、母材上の全被膜厚さに対し中間層の厚さが１６％以上であれば、被膜の割れを防ぐことができることが判った。 Next, the thickness of the intermediate layer of the present invention and its effect were examined.
The steel material subjected to the diffusion permeation treatment was subjected to an austemper treatment (holding at 830 ° C. for 60 minutes and then quenched in a salt bath at 310 ° C.) for strengthening the base material. After the heat treatment, the cross section of each sample was observed with a microscope, and the relationship between the presence or absence of film cracking and the intermediate layer ratio was examined. The results are shown in Table 2 and FIG. The intermediate layer ratio is the ratio of the intermediate layer to the thickness of the entire coating on the base material. From Table 2 and FIG. 5, in Examples 14 to 20 of the present invention in which the intermediate layer ratio was 16% or more, the effect of stress relaxation by the intermediate layer was sufficient, and no cracking of the coating was confirmed. On the other hand, in Comparative Examples 9 to 12 in which the intermediate layer ratio is less than 16%, the coating is cracked because the effect of stress relaxation by the intermediate layer is small. Therefore, it was found that the crack of the coating can be prevented if the thickness of the intermediate layer is 16% or more with respect to the total film thickness on the base material.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (5)

  1. 　鉄系母材に、母材元素（Ｆｅ）と被覆種:Ａ（ＡはＣｒ，Ｖ，Ｔｉ，Ｎｂの１種または２種以上）からなる複合炭化物　(Ｆｅ，Ａ)Ｃからなる中間層を介してＡ炭化物層が被覆されていることを特徴とする摺動部材。 An intermediate layer composed of a composite carbide (Fe, A) C composed of a base element (Fe) and a coating type: A (A is one or more of Cr, V, Ti, Nb) is formed on an iron-based matrix. A sliding member, characterized in that the A carbide layer is covered therewith.
  2. 　鋼部材に、鉄とクロムの複合炭化物（Ｆｅ，Ｃｒ）Ｃからなる中間層を介してクロム炭化物層が被覆されていることを特徴とする摺動部材。 A sliding member characterized in that a chromium carbide layer is coated on a steel member via an intermediate layer made of a composite carbide (Fe, Cr) C of iron and chromium.
  3. 　（クロム炭化物層＋中間層）の厚さに対し、中間層の厚さが１６％以上であることを特徴とする請求項２に記載の摺動部材。 The sliding member according to claim 2, wherein the thickness of the intermediate layer is 16% or more with respect to the thickness of the (chrome carbide layer + intermediate layer).
  4. 　前記中間層のＣｒ濃度はクロム炭化物層へ向けて徐々に増加することを特徴とする請求項２または３に記載の摺動部材。 The sliding member according to claim 2 or 3, wherein the Cr concentration of the intermediate layer gradually increases toward the chromium carbide layer.
  5. 　拡散浸透処理によって、鉄とクロムの複合炭化物（Ｆｅ，Ｃｒ）Ｃからなる中間層を介してクロム炭化物層を鋼部材に被覆する摺動部材の製造方法において、
    　鋼部材表面の組織がオーステナイト＋セメンタイトの状態において前記拡散浸透処理を行うことを特徴とする摺動部材の製造方法。     In the manufacturing method of the sliding member which coats the chromium carbide layer to the steel member through the intermediate layer made of the composite carbide of iron and chromium (Fe, Cr) C by the diffusion penetration treatment,
    The manufacturing method of the sliding member characterized by performing the said diffusion penetration process in the state of the structure | tissue of a steel member surface austenite + cementite.
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CN114657558A (en) * 2022-04-22 2022-06-24 济宁矿业集团海纳科技机电股份有限公司 Coal mining machine transmission shaft with modified surface and processing method

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