JP2002294430A - Wear-resistant iron-based coating superior in toughness, and manufacturing method therefor - Google Patents
Wear-resistant iron-based coating superior in toughness, and manufacturing method thereforInfo
- Publication number
- JP2002294430A JP2002294430A JP2001096872A JP2001096872A JP2002294430A JP 2002294430 A JP2002294430 A JP 2002294430A JP 2001096872 A JP2001096872 A JP 2001096872A JP 2001096872 A JP2001096872 A JP 2001096872A JP 2002294430 A JP2002294430 A JP 2002294430A
- Authority
- JP
- Japan
- Prior art keywords
- film
- coating
- based coating
- wear
- area
- 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
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は優れた靭性と耐摩耗
性を兼ね備えた鉄系皮膜及びその製造方法に関し、詳細
には輸送機，産業機械，レジャー用品などの分野におい
て、高い耐摩耗性が要求される治工具，車軸，軸受け，
等速ジョイント，レールガイド等の各種摺動，転動の要
素を含んだ機械部品の靭性及び耐摩耗性向上に有用な鉄
系皮膜、およびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an iron-based coating having excellent toughness and abrasion resistance and a method for producing the same, and more particularly, to a high abrasion resistance in the fields of transportation, industrial machinery, leisure equipment and the like. Required tools, axles, bearings,
The present invention relates to an iron-based coating useful for improving the toughness and abrasion resistance of mechanical parts including various sliding and rolling elements such as constant velocity joints and rail guides, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年の過酷な使用環境に対応すべく、摺
動部材や転動部材などの各種機械部品には、硬度のみな
らず高い靭性が要求されている。この様な技術として例
えば特開平５−７８８２１号には、Ｃｏ，Ｎｉ及びＭｏ
から選ばれる１種以上の金属と、Ｓｉ，Ｔｉ，Ｖ，Ｃ
ｒ，Ｆｅ，Ｚｒ，Ｎｂ及びＷから選ばれる１種以上の金
属の炭化物又は窒化物との混合組織からなる被膜をイオ
ンプレーティング法によって母材表面に被覆することに
より耐摩耗性，被膜靭性を向上させる技術が提案されて
いる。また特開平５−１２５５２１号には、ＴｉＮとＮ
ｉからなる被膜をイオンプレーティング法によって母材
表面に被覆して密着性を向上させる技術が開示されてい
る。更に特開平９−７１８５６号にはＡｌ，Ｓｉ，Ｆ
ｅ，Ｔｉ，Ｖ，Ｃｒ，Ｚｒ，Ｎｂ，Ｈｆ及びＷよりなる
群から選択される１種以上の金属の炭化物，窒化物また
は炭窒化物中にＣｏ，Ｎｉ，Ｍｏ及びＣｕよりなる群か
ら選択される１種以上の金属を含む被膜をイオンプレー
ティング法によって母材表面に被覆すして靭性及び密着
性を改善する方法が提案されている。2. Description of the Related Art In order to cope with severe use environments in recent years, various mechanical parts such as sliding members and rolling members are required to have not only hardness but also high toughness. As such a technique, for example, Japanese Patent Laid-Open No. 5-78821 discloses Co, Ni and Mo.
At least one metal selected from the group consisting of Si, Ti, V, and C
Abrasion resistance and film toughness are improved by coating a film composed of a mixed structure of at least one metal selected from the group consisting of r, Fe, Zr, Nb and W with a carbide or nitride of the metal by ion plating. Techniques for improving have been proposed. Japanese Patent Application Laid-Open No. 5-125521 discloses that TiN and N
A technique has been disclosed in which a coating made of i is coated on the surface of a base material by an ion plating method to improve adhesion. Japanese Patent Application Laid-Open No. Hei 9-71856 discloses Al, Si, F
e, at least one metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Hf and W, selected from the group consisting of Co, Ni, Mo and Cu in carbides, nitrides or carbonitrides A method of improving the toughness and adhesion by coating a coating containing at least one kind of metal on the surface of a base material by an ion plating method has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】これら提案されている
技術は十分な靭性を確保するためにＮｉ，Ｃｏ，Ｍｏ，
Ｃｕ等の高価な金属を多量に添加する必要があり、高コ
ストの要因となっていた。特に成膜にイオンプレーティ
ング法などの気相コーティング法を用いる場合、特殊な
組成のターゲット材を溶製したり、或いは複数種のター
ゲットを用いるような複雑な成膜操作が必要となり、製
造コストが大幅に上昇するため、その適用は一部の高級
品に限られていた。SUMMARY OF THE INVENTION These proposed techniques are based on Ni, Co, Mo, and Ni in order to secure sufficient toughness.
It is necessary to add a large amount of expensive metal such as Cu, which is a factor of high cost. In particular, when a gas phase coating method such as an ion plating method is used for film formation, a complicated film formation operation such as melting a target material having a special composition or using a plurality of types of targets is required, and the manufacturing cost is increased. , So its application was limited to some luxury goods.
【０００４】また従来技術の皮膜を施した耐摩耗部材は
潤滑油存在下で使用されるため、潤滑油は鋼製部品への
適用を前提に添加剤などの成分設計が行なわれている。
しかしながら皮膜を構成する主成分がＦｅ以外である
と、潤滑油と膜との相性が悪く、潤滑油が劣化するとい
う問題が生じていた。例えば皮膜にＮｉが多量に含有さ
れているとＮｉは潤滑油中のＳ系極圧剤と反応し、Ｎｉ
硫化物を生成して潤滑油を黒変させると共に、極圧剤を
消費するため、潤滑油の寿命が著しく低下するという問
題が生じている。[0004] Further, since a wear-resistant member provided with a film according to the prior art is used in the presence of a lubricating oil, the lubricating oil is designed for components such as additives on the assumption that the lubricating oil is applied to steel parts.
However, if the main component of the coating is other than Fe, the compatibility between the lubricating oil and the film is poor, and the lubricating oil is degraded. For example, if the film contains a large amount of Ni, Ni reacts with the S-based extreme pressure agent in the lubricating oil, and Ni
Since sulfides are generated to blacken the lubricating oil and the extreme pressure agent is consumed, there is a problem that the life of the lubricating oil is significantly reduced.
【０００５】本発明は上記問題を鑑みなされたものであ
って、その目的は優れた靭性と耐摩耗性を有する鉄系皮
膜を提供すること、およびその成膜方法を提供すること
である。The present invention has been made in view of the above problems, and an object of the present invention is to provide an iron-based coating having excellent toughness and wear resistance, and to provide a method for forming the same.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決し得た本
発明の皮膜とは、母材表面に形成される少なくともＮ
ｉ，Ｃｒ，Ｎを含有する鉄系皮膜において、該皮膜を厚
さ方向に垂直に切断して鏡面研磨した断面を、電解放射
型走査電子顕微鏡を用いて倍率１０００倍で反射電子像
にて観察したとき、各反射電子像の皮膜部分に存在する
マトリックスより輝度が高く、且つ面積が０．０５μｍ
2以上の不連続領域を合計した面積が、全面積の１５％
以下（但し、５視野を観察したときの平均値）であるこ
とに要旨する。また透過型電子顕微鏡を用いて倍率１５
０００倍で前記断面の５視野（各５μｍ2）を観察した
とき、マトリックスと不連続領域の境界に存在する空隙
であって、その長さが０．１μｍ以上である空隙の数が
平均３以下であることが推奨され、更に前記皮膜が窒化
物を有するオーステナイト相を含むものであることが望
ましい。Means for Solving the Problems The film of the present invention which can solve the above-mentioned problems includes at least N 2 formed on the surface of the base material.
In an iron-based coating containing i, Cr, and N, a section cut perpendicular to the thickness direction and mirror-polished is observed as a reflected electron image at a magnification of 1000 using an electro-emission scanning electron microscope. The brightness is higher than the matrix present in the film portion of each reflected electron image and the area is 0.05 μm
2 or more summed area discontinuous regions of 15% of the total area
The gist is as follows (however, an average value when five visual fields are observed). Using a transmission electron microscope, a magnification of 15
When observing five visual fields (5 μm 2 each) of the cross section at 000 ×, the number of voids existing at the boundary between the matrix and the discontinuous region and having a length of 0.1 μm or more is 3 or less on average. And it is desirable that the film contains an austenitic phase having a nitride.
【０００７】本発明の皮膜を母材に形成する方法として
は、Ｆｅ，Ｎｉ，Ｃｒを含む合金ターゲットを用い、窒
素を含むプラズマ雰囲気中で磁場誘導型フィルタードア
ーク法にて成膜するか、あるいは皮膜を母材に形成する
にあたり、Ｆｅ，Ｎｉ，Ｃｒを含む合金ターゲットを用
い、窒素を含むプラズマ雰囲気中でスパッタリング法に
て成膜することが推奨される。As a method of forming the coating of the present invention on a base material, a film is formed by a magnetic field induction type filtered arc method in a plasma atmosphere containing nitrogen using an alloy target containing Fe, Ni, and Cr. Alternatively, when forming the film on the base material, it is recommended to use an alloy target containing Fe, Ni, and Cr and form the film by a sputtering method in a plasma atmosphere containing nitrogen.
【０００８】[0008]
【発明の実施の形態】本発明者らは、前記従来技術の問
題点を解決すべく、鋭意研究を重ねた結果、皮膜組織に
不連続部分が存在すると、使用中における外部応力に対
して該不連続部分とマトリックスとの界面部分が起点と
なってクラックが生じてしまうことを見出した。そして
Ｆｅ−Ｃｒ−Ｎｉ系窒素皮膜における微細構造を特定す
ることによって皮膜の靭性及び密着性を著しく向上でき
ることを知得し、本発明の皮膜を完成するに至った。以
下本発明について詳述する。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems of the prior art. It has been found that cracks occur from the interface between the discontinuous portion and the matrix as a starting point. Then, it was found that the toughness and adhesion of the film can be remarkably improved by specifying the microstructure of the Fe—Cr—Ni-based nitrogen film, and the film of the present invention was completed. Hereinafter, the present invention will be described in detail.
【０００９】本発明の対象とする皮膜は母材に形成する
皮膜であって、Ｃｒ，Ｎｉ，Ｎ，及び残部は実質的にＦ
ｅからなる皮膜であるが、残部が「実質的にＦｅ」とは
Ｆｅ系合金中に通常含まれているＣ，Ｂ，Ｐ，Ｓｉ，
Ｓ，Ｎｂ等やその他金属元素等が皮膜の特性に大きな影
響を与えない範囲で含まれていても良い趣旨であり、ま
た酸化物や硼化物などを混入させる場合も同様の趣旨で
あれば本発明の範囲内とする意味である。The film of the present invention is a film formed on a base material, and Cr, Ni, N, and the balance are substantially F
e, but the balance “substantially Fe” means that C, B, P, Si,
This means that S, Nb, and other metal elements may be contained within a range that does not greatly affect the properties of the film. Also, when oxides or borides are mixed, the same effect can be obtained. This is within the scope of the invention.
【００１０】尚、皮膜を構成するＣｒ，Ｎｉ，Ｎ，Ｆｅ
の成分比については特に限定されないが、Ｆｅの含有量
が多いほど皮膜と潤滑油との相性を向上させることがで
きるので皮膜中のＦｅ含有率は少なくとも５０質量％と
することが推奨される。Ｃｒ，Ｎｉ，Ｎは皮膜靭性・耐
摩耗性を向上させるのに有効な成分であるが、これらの
含有量は特に限定されず、目的に応じて適宜調節すれば
よい。例えばＮｉは高価な元素であるため多量に添加す
るとコスト上昇の要因となり、また添加効果も飽和する
傾向にあるので、上限は３０質量％とすることが好まし
い。この際、潤滑油劣化を防止しつつ、十分なＮｉ添加
効果を発揮させるという観点からＮｉ含有量上限を１０
質量％としてもよい。Ｃｒが多量に含有されると膜自体
が脆くなることがあるので好ましくは２５質量％以下、
より好ましくは２０質量％以下とすることが望ましい。
またＮは皮膜特性劣化防止の観点から好ましくは２０質
量％以下，より好ましくは１５質量％以下とすることが
望ましい。The Cr, Ni, N, Fe constituting the coating
The component ratio of is not particularly limited, but the greater the Fe content, the more the compatibility between the film and the lubricating oil can be improved. Therefore, it is recommended that the Fe content in the film be at least 50% by mass. Cr, Ni, and N are effective components for improving the film toughness and wear resistance, but their contents are not particularly limited, and may be appropriately adjusted according to the purpose. For example, Ni is an expensive element and if added in a large amount, it causes a cost increase, and the effect of addition tends to be saturated. Therefore, the upper limit is preferably set to 30% by mass. At this time, the upper limit of the Ni content is set at 10 from the viewpoint of exerting a sufficient Ni addition effect while preventing deterioration of the lubricating oil.
% By mass. When a large amount of Cr is contained, the film itself may become brittle.
More preferably, it is desirably 20% by mass or less.
N is preferably 20% by mass or less, and more preferably 15% by mass or less, from the viewpoint of preventing deterioration of film characteristics.
【００１１】本発明は上記した様な少なくともＮｉ，Ｃ
ｒ，Ｎを含有する鉄系皮膜において、該皮膜を厚さ方向
に垂直に切断して鏡面研磨した断面を、電解放射型走査
電子顕微鏡を用いて倍率１０００倍で反射電子像にて５
視野観察したとき、各反射電子像の皮膜部分に存在する
マトリックスより輝度が高く、且つ面積が０．０５μｍ
2以上の不連続領域を合計した面積が、全面積の１５％
以下（５視野の平均値）であることに要旨を有する皮膜
である。The present invention provides at least Ni, C
In an iron-based coating containing r and N, the coating was cut perpendicularly to the thickness direction and mirror-polished.
When observed in a visual field, the brightness is higher than the matrix existing in the film portion of each reflected electron image, and the area is 0.05 μm.
The total area of two or more discontinuous areas is 15% of the total area
This is a film having the gist of the following (average value of 5 visual fields).
【００１２】本発明において「不連続領域」とは、母材
に形成した皮膜を厚さ方向に垂直に切断して鏡面研磨し
た断面を、電解放射型走査電子顕微鏡を用いて倍率１０
００倍で反射電子像にて観察したときに、該反射電子像
の皮膜部分に存在するマトリックスと明度が異なる粒子
部分をいう。図３ｂは本発明に係る皮膜の反射電子像
（１０００倍）である。マトリックスと明度が異なる粒
子部分とは該写真１に示される如く、明度の異なる粒子
状の部分（例えば図３ｂにおける数字が付与された白抜
き部分）であって、マトリックスよりも輝度が高い部分
が組織的に不連続な領域である。In the present invention, the term "discontinuous region" means that a film formed on a base material is cut perpendicularly to the thickness direction and mirror-polished, and a section of 10 magnifications is obtained using a field emission scanning electron microscope.
When observed with a reflected electron image at a magnification of 00, it refers to a particle portion having a different brightness from the matrix existing in the film portion of the reflected electron image. FIG. 3b is a backscattered electron image (× 1000) of the coating according to the present invention. As shown in the photograph 1, the particle portion having a different brightness from the matrix is a particle portion having a different brightness (for example, a white portion provided with a number in FIG. 3B), and a portion having a higher brightness than the matrix is a portion having a brightness. It is an area that is discontinuously organized.
【００１３】尚、不連続領域の構造は必ずしも明確では
ないが、不連続領域はマトリックスよりも窒素の固溶度
が小さく、マトリックスと機械的特性（硬度，ヤング率
など）が異なるα相、あるいはマトリックスと比較して
窒素量の少ないγ相などの相を含む組織であって、マト
リックスと機械的特性が異なる構造を有する領域であ
る。Although the structure of the discontinuous region is not always clear, the discontinuous region has a lower solid solubility of nitrogen than the matrix, and has an α phase having different mechanical properties (hardness, Young's modulus, etc.) from the matrix, or A structure containing a phase such as a γ phase having a smaller amount of nitrogen as compared with a matrix, and is a region having a structure having different mechanical properties from the matrix.
【００１４】皮膜ミクロ組織に不連続領域が存在する
と、使用中における外部応力に対して該不連続領域とマ
トリックスとの界面部分が起点となってクラックが生じ
るが、皮膜マトリックス中の不連続領域が占める割合
（面積総計比率）を１５％以下とすれば、不連続領域に
起因するクラックの発生を抑止することができる。した
がって同一の成分組成を有する皮膜と比べても不連続領
域が１５％以下である皮膜は、不連続領域が１５％を超
える皮膜と比べて密着性，靭性に優れている。If a discontinuous region exists in the coating microstructure, cracks occur at the interface between the discontinuous region and the matrix due to external stress during use, but cracks occur in the coating matrix. When the occupying ratio (total area ratio) is 15% or less, generation of cracks due to the discontinuous region can be suppressed. Therefore, a film having a discontinuous region of 15% or less as compared with a film having the same component composition has better adhesion and toughness than a film having a discontinuous region of more than 15%.
【００１５】尚、１個の不連続領域の面積が０．０５μ
ｍ2未満である場合は、靭性や密着性などの各種皮膜特
性への影響が小さいことから、本発明における「不連続
領域」とは、１個の不連続領域の面積が０．０５μｍ2
以上である領域を意味する。本発明においては、皮膜を
厚さ方向に垂直に切断し、更に切断面を鏡面研磨して得
られた断面を電解放射型示差電子顕微鏡（日立製作所
製，電解放射型走査電子顕微鏡Ｓ４５００）を用いて該
断面の反射電子像（１０００倍）を５視野観察したとき
の皮膜部分に存在するマトリックスより輝度が高く、且
つ面積が０．０５μｍ2以上の不連続領域を合計した面
積が、全面積の１５％以下（但し、５視野を観察したと
きの平均値）であることが推奨され、好ましくは１０％
以下、より好ましくは５％以下である。特に使用条件が
過酷な部材においては３％以下であることが望ましい。The area of one discontinuous region is 0.05 μm.
When the area is less than m 2 , the effect on various film properties such as toughness and adhesion is small. Therefore, the “discontinuous area” in the present invention is defined as an area of one discontinuous area of 0.05 μm 2
It means the above-mentioned area. In the present invention, the coating is cut perpendicularly to the thickness direction, and the cut surface is mirror-polished, and the cross section obtained is used with an electrolytic emission differential electron microscope (S4500, manufactured by Hitachi, Ltd.). When the reflected electron image (1000 times) of the cross section is observed in five fields of view, the brightness is higher than the matrix existing in the coating portion and the total area of the discontinuous regions having an area of 0.05 μm 2 or more is the total area. It is recommended to be 15% or less (however, an average value when observing 5 visual fields), and preferably 10%
Or less, more preferably 5% or less. In particular, it is desirable to be 3% or less for a member under severe use conditions.
【００１６】また該不連続領域とマトリックスとの境界
部分に空隙（図４参照）が存在していると、該空隙部分
が起点となって皮膜クラックの原因となることがあり、
上記不連続領域の面積が１５％以下であっても空隙が存
在するとクラックが発生することがある。特に１個の空
隙の長さ（空隙の長さとは、空隙２点間の最大長さであ
る。）が０．１μｍ以上とクラック発生に与える影響も
大きいため、本発明においてはマトリックスと不連続領
域の境界部分に存在する空隙の長さは０．１μｍ未満で
あることが皮膜膜靭性劣化抑止の観点からも望ましい。
また空隙の長さが０．１μｍ未満であれば、靭性や密着
性などの各種皮膜特性への影響が小さく、またクラック
発生に与える影響も小さい。If there is a void (see FIG. 4) at the boundary between the discontinuous region and the matrix, the void may serve as a starting point and cause a crack in the film.
Even if the area of the discontinuous region is 15% or less, cracks may occur if voids are present. In particular, when the length of one void (the length of the void is the maximum length between two voids) is 0.1 μm or more, the influence on crack generation is great. It is desirable that the length of the void existing at the boundary between the regions is less than 0.1 μm also from the viewpoint of suppressing the deterioration of the coating film toughness.
When the length of the void is less than 0.1 μm, the influence on various film properties such as toughness and adhesion is small, and the influence on crack generation is small.
【００１７】したがって本発明においては、不連続領域
の面積比率を小さくすると共に空隙が少ないことが推奨
され、透過型電子顕微鏡（日立製作所製ＨＦ２０００）
を用いて倍率１５０００倍にて皮膜を厚さ方向に切断し
た断面（鏡面研磨せず）の５視野（各５μｍ2）を観察
したとき、マトリックスと不連続領域の境界に存在する
０．１μｍ以上の長さを有する空隙の数が平均３以下で
あれば、空隙がクラック，靭性，密着性へ及ぼす影響が
ほとんどないので好ましい。より好ましくは１以下であ
って、最も好ましくは０である。Therefore, in the present invention, it is recommended that the area ratio of the discontinuous region be reduced and the voids be reduced, and a transmission electron microscope (HF2000 manufactured by Hitachi, Ltd.)
Observation of 5 visual fields (each 5 μm 2 ) of a cross section (not mirror-polished) obtained by cutting the film in the thickness direction at a magnification of 15000 times using a microscope, 0.1 μm or more existing at the boundary between the matrix and the discontinuous region The average number of voids having a length of 3 or less is preferable because the voids have almost no effect on cracks, toughness, and adhesion. It is more preferably 1 or less, and most preferably 0.
【００１８】上記した様な組織を有する皮膜であれば、
皮膜のＦｅ組織については特に限定されず、例えばフェ
ライト相（以下、「α相」ということがある。）主体で
あってもよく、あるいはオーステナイト相（以下、「γ
相」ということがある。）主体であってもよいが、皮膜
が窒化物を有するγ相で構成されていると、皮膜の靭性
が更に改善されるので望ましい。特に皮膜中に含まれる
窒化物を有するγ相の割合（体積率（％）、以下同じ）
が好ましくは１０％以上であれば優れた靭性を示す。よ
り好ましくは２０％以上、最も好ましくは１００％であ
る。この様なγ相を有する皮膜とするためには、例えば
Ｎｉ，Ｎ，Ｃｒ含有量を適宜調節すればよく、Ｎｉはγ
相の生成を促進させると共に、靭性を確保するという観
点から好ましくは２．５質量％以上含有させることが望
ましい。Ｎはγ相の生成を促進させると共に、皮膜硬
度，靭性を向上させるという観点から好ましくは４質量
％以上含有させることが望ましく、Ｃｒはγ相の生成を
阻害させずに皮膜硬度，耐摩耗性，皮膜靭性などの皮膜
特性を向上させるという観点から好ましくは５質量％以
上含有させることが望ましい。γ相，窒化物の有無並び
に体積比率はリートベルト法を用いたＸ線回折（ＸＲ
Ｄ）により皮膜中に含まれるγ相、α相及び窒化物の比
率により測定することができる。If the film has the structure as described above,
The Fe structure of the film is not particularly limited. For example, the film may be mainly composed of a ferrite phase (hereinafter, sometimes referred to as “α phase”) or an austenite phase (hereinafter, “γ phase”).
Phase. " ) It may be a main component, but it is desirable that the film is composed of a γ phase having a nitride, because the toughness of the film is further improved. In particular, the ratio of the gamma phase containing nitride contained in the film (volume ratio (%), the same applies hereinafter)
However, if it is 10% or more, excellent toughness is exhibited. It is more preferably at least 20%, most preferably 100%. In order to form a film having such a γ phase, for example, the contents of Ni, N, and Cr may be appropriately adjusted.
From the viewpoint of promoting the formation of a phase and securing toughness, it is desirable that the content is preferably 2.5% by mass or more. From the viewpoint of promoting the formation of the γ phase and improving the film hardness and toughness, it is desirable that N be contained in an amount of preferably 4% by mass or more. From the viewpoint of improving film properties such as film toughness and the like, the content is preferably 5% by mass or more. The presence / absence and volume ratio of the γ-phase and nitride are determined by X-ray diffraction (XR
It can be measured by the ratio of γ phase, α phase and nitride contained in the film according to D).
【００１９】本発明において皮膜の硬度は少なくともＨ
ｖ９００を有することが好ましい。Ｈｖ９００以上であ
れば、耐摩耗性部材として窒化処理鋼や浸炭窒化処理鋼
を用いた場合、母材硬度として同程度の硬度を有する皮
膜を施すことができ、広範な用途に用いることができ
る。より優れた耐摩耗性が要求される分野に適用するた
めには皮膜の硬度はＨｖ１０００以上であることが好ま
しい。この様な硬度を有する皮膜とするためには皮膜の
組成を適宜調節すればよい。In the present invention, the hardness of the film is at least H
Preferably it has a v900. When Hv900 or more, when nitriding steel or carbonitriding steel is used as the wear-resistant member, a coating having the same hardness as the base material hardness can be applied, and can be used in a wide range of applications. The hardness of the coating is preferably Hv1000 or more in order to be applied to a field requiring more excellent wear resistance. In order to obtain a film having such hardness, the composition of the film may be appropriately adjusted.
【００２０】本発明に係る皮膜が被覆される母材の種類
は特に限定されず、Ｔｉ合金，Ａｌ合金，Ｍｇ合金など
の軽量材料；機械構造用鋼、工具用鋼，軸受け鋼などの
Ｆｅ基合金；超硬材料；セラミックスなどを用いること
ができる。これらのうち高い硬度を有する素材が好まし
く、高い硬度を有していれば局部的な面圧がかかる環境
下で使用しても、皮膜及び母材自身の変形量を軽減し、
母材の変形に伴う皮膜の破壊，剥離を防止することがで
きる。特にＦｅ基合金は耐摩耗部品としても優れてお
り、しかも本発明の皮膜とのヤング率差が小さくＦｅ基
合金であれば皮膜／母材界面に生じる剪断応力を抑える
ことができると共に、密着性を維持することができる。
この様な観点から硬度の高いＦｅ基合金が好ましく、Ｈ
ｖ６００以上を有するものがより好ましく、より好まし
くはＨｖ９００以上、最も好ましくは１０００Ｈｖ以上
を有するＦｅ基合金である。The type of the base material to be coated with the coating according to the present invention is not particularly limited, and is a light-weight material such as a Ti alloy, an Al alloy, or a Mg alloy; and an Fe-based material such as steel for machine structures, steel for tools, and bearing steel. Alloys, super hard materials, ceramics and the like can be used. Of these, materials having high hardness are preferable, and even if used in an environment where local surface pressure is applied if they have high hardness, the amount of deformation of the coating and the base material itself is reduced,
Destruction and peeling of the film due to deformation of the base material can be prevented. In particular, an Fe-based alloy is excellent as a wear-resistant part. In addition, a difference in Young's modulus from the coating of the present invention is small. Can be maintained.
From such a viewpoint, an Fe-based alloy having high hardness is preferable.
Those having v600 or more are more preferable, and those based on Hb are more preferably Hv900 or more, and most preferably 1000 Hv or more.
【００２１】本発明に係る皮膜の膜厚は特に限定され
ず、使用環境，適用部材，要求される寸法精度等の種々
の要因に基づいて必要な膜厚を選定すればよい。極端に
膜厚が薄い場合や逆に厚い場合は、皮膜の十分な効果が
得られなくなることがある。したがって膜厚は通常、好
ましくは２μｍ以上、より好ましくは５μｍ以上であっ
て、好ましくは５０μｍ以下、より好ましくは２０μｍ
以下の範囲で用いることが推奨される。The film thickness of the film according to the present invention is not particularly limited, and the necessary film thickness may be selected based on various factors such as the use environment, applicable members, and required dimensional accuracy. When the film thickness is extremely thin or conversely, when the film thickness is extremely large, a sufficient effect of the film may not be obtained. Therefore, the film thickness is usually preferably 2 μm or more, more preferably 5 μm or more, preferably 50 μm or less, more preferably 20 μm or less.
It is recommended to use in the following range.
【００２２】上記皮膜を母材に形成するにあたり、Ｆ
ｅ，Ｎｉ，Ｃｒを含む合金ターゲットを用いて、窒素を
含むプラズマ雰囲気中で磁場誘導型フィルタードアーク
法、あるいはスパッタリング法にて成膜することが推奨
される。また成膜時のプロセスガスとして窒素以外にも
窒素−メタン混合ガスなどの窒素含有ガスを用いてもよ
い。該プロセスガス雰囲気中でプラズマを発生させ、母
材に向って蒸発もしくは飛散させたターゲット材料とプ
ラズマを反応させながら磁場誘導型フィルタードアーク
（図１参照，尚、図中１は電磁コイル，２はプラズマ，
３は母材，４はターゲット，ＭＰはマクロパーティクル
である）、或いはスパッタリング法によって成膜すれ
ば、ターゲット材に起因する不連続領域の発生、及びマ
トリックスと不連続領域との界面における空隙の発生を
抑制することができると共に、マトリックスをγ相＋窒
化物とすることができる。In forming the above-mentioned film on the base material, F
It is recommended to use an alloy target containing e, Ni, and Cr to form a film by a magnetic field induction type filtered arc method or a sputtering method in a plasma atmosphere containing nitrogen. A nitrogen-containing gas such as a mixed gas of nitrogen and methane may be used as a process gas at the time of film formation in addition to nitrogen. A plasma is generated in the process gas atmosphere, and a magnetic field induction type filtered arc is generated while reacting the plasma with the target material evaporated or scattered toward the base material (see FIG. 1, where 1 is an electromagnetic coil and 2 is an electromagnetic coil. Is plasma,
3 is a base material, 4 is a target, MP is a macro particle), or if a film is formed by a sputtering method, a discontinuous region due to the target material and a void at an interface between the matrix and the discontinuous region are generated. Can be suppressed, and the matrix can be γ phase + nitride.
【００２３】本発明で採用している磁場誘導型フィルタ
ードアーク法とは図１に例示される様な直線型フィルタ
ードアーク法、或いは９０°偏向型フィルタードアーク
法のいずれであってもよいが、カソード型アークイオン
プレーティング法の様にフィルターを用いないで成膜す
ると、皮膜組織中に不可避的に不連続領域が混入してし
まうと共に、マトリックスと不連続領域との界面に空隙
が形成されてしまい本発明の上記皮膜が得られないので
好ましくない。The magnetic field induction type filtered arc method employed in the present invention may be either a linear type filtered arc method as illustrated in FIG. 1 or a 90 ° deflection type filtered arc method. However, if a film is formed without using a filter as in the cathode-type arc ion plating method, discontinuous regions are inevitably mixed into the coating structure, and voids are formed at the interface between the matrix and the discontinuous regions. It is not preferable because the above-mentioned film of the present invention cannot be obtained.
【００２４】成膜時のバイアス電圧としては十分な皮膜
硬度を得るために好ましくは１０Ｖ以上、より好ましく
は３０Ｖ以上とすることが望ましいが、電圧上昇に伴っ
て温度が上昇し過ぎると所望のγ層等が得られなくなる
ことがあるので好ましくは２００Ｖ以下、より好ましく
は１００Ｖ以下とすることが望ましい。母材の温度はタ
ーゲット合金の組成や成膜条件によって異なるが、温度
が高くなりすぎると皮膜特性が劣化することがあるので
成膜時の最高温度を好ましくは３００℃以下、より好ま
しくは２００℃以下とすることが望ましいが、十分な皮
膜−母材間の密着性を得るためには好ましくは１００℃
以上、より好ましくは１５０℃以上である。The bias voltage at the time of film formation is preferably 10 V or more, more preferably 30 V or more, in order to obtain a sufficient film hardness. However, if the temperature rises too much as the voltage rises, the desired γ It is desirable that the voltage be 200 V or less, more preferably 100 V or less, since a layer or the like may not be obtained. The temperature of the base material varies depending on the composition of the target alloy and the film forming conditions. However, if the temperature is too high, the film characteristics may deteriorate. Therefore, the maximum temperature during film formation is preferably 300 ° C. or less, more preferably 200 ° C. Although it is desirable to set it as follows, in order to obtain sufficient adhesion between the film and the base material, it is preferably 100 ° C.
The temperature is more preferably 150 ° C. or more.
【００２５】また成膜時のカソード電流は効率的に所望
の皮膜を成膜するためには好ましくは４０Ａ以上、より
好ましくは５０Ａ以上とすることが望ましく、温度上昇
に伴う皮膜特性劣化抑止の観点から好ましくは２００Ａ
以下、より好ましくは１００Ａ以下である。The cathode current at the time of film formation is preferably 40 A or more, more preferably 50 A or more, in order to efficiently form a desired film. From the viewpoint of suppressing deterioration of film characteristics due to temperature rise. To preferably 200A
Or less, more preferably 100A or less.
【００２６】プロセスガス導入後の圧力は窒素を十分含
有させると共に、所望の皮膜硬度を得るためには少なく
とも０．５Ｐａとなる様に制御することが好ましく、よ
り好ましくは１Ｐａ以上であることが望ましい。上限に
ついては特に限定されないが、ある程度の高圧で効果も
飽和することから生産性の観点から好ましくは５Ｐａ以
下、より好ましくは３Ｐａ以下である。The pressure after the introduction of the process gas is preferably controlled to be at least 0.5 Pa, more preferably 1 Pa or more, in order to sufficiently contain nitrogen and obtain a desired film hardness. . Although the upper limit is not particularly limited, it is preferably 5 Pa or less, more preferably 3 Pa or less from the viewpoint of productivity since the effect is saturated at a certain high pressure.
【００２７】本発明で用いることのできるターゲット材
としては、Ｆｅ，Ｎｉ，Ｃｒを含有するものであればよ
く、例えば市販のオーステナイト系ステンレス若しくは
ニッケルクロムモリブデン鋼等の合金鋼をターゲットと
して用いることができる。本発明では市販の鉄系合金を
ターゲット材料として用いることができるので、特殊な
合金の溶製を必要とせず、また複数種のターゲットを用
いた複雑な成膜操作を必要としないので経済性にも優れ
ている。The target material that can be used in the present invention may be any material containing Fe, Ni, and Cr. For example, commercially available austenitic stainless steel or alloy steel such as nickel-chromium molybdenum steel may be used as the target. it can. In the present invention, a commercially available iron-based alloy can be used as a target material, so that it is not necessary to melt a special alloy, and it is not necessary to perform a complicated film forming operation using a plurality of types of targets, which leads to economical efficiency. Is also excellent.
【００２８】以下実施例に基づいて本発明を詳述する。
尚、下記実施例は本発明を限定する趣旨のものではな
く、前・後記の趣旨を逸脱しない範囲で変更を加えて実
施することは全て本発明の技術範囲に包含される。Hereinafter, the present invention will be described in detail with reference to examples.
It should be noted that the following examples are not intended to limit the present invention, and all modifications and implementations without departing from the spirit of the preceding and the following are included in the technical scope of the present invention.
【００２９】[0029]
【実施例】母材としてクロムモリブデン浸炭窒化鋼を用
い、この母材表面に図２（図中１，２，３，４，ＭＰは
図１と同じ）に示す様な９０°偏向型フィルタードアー
ク法（Ｎｏ．１〜４）、スパッタリング法（Ｎｏ．５〜
７）、或いはカソード型アークイオンプレーティング法
（Ｎｏ．８〜１２）を用いて下記表１に示す条件で被覆
（膜厚については全試験材共に同一）した。この際、導
入ガスとして窒素を用いるとともに圧力調整用にＡｒガ
スを必要に応じて適宜混入させた。また成膜温度を抑え
るために必要に応じて間欠成膜を行なった。EXAMPLE A chromium molybdenum carbonitrided steel was used as a base material, and a 90 ° deflection type filter as shown in FIG. 2 (1, 2, 3, 4, MP in FIG. Arc method (Nos. 1 to 4), sputtering method (Nos. 5 to 5)
7) Alternatively, coating was performed using the cathode-type arc ion plating method (Nos. 8 to 12) under the conditions shown in Table 1 below (the film thickness was the same for all test materials). At this time, nitrogen was used as an introduction gas, and Ar gas was appropriately mixed for pressure adjustment as needed. In addition, intermittent film formation was performed as necessary to suppress the film formation temperature.
【００３０】 ＜９０°偏向型フィルタードアーク法成膜条件＞ ガス導入前真空度 ：１×１０-3〜５×１０-5Ｐａ スパッタクリーニング：−５００×―８００Ｖ ガス導入後圧力 ：０．５〜３Ｐａ 成膜時カソード電流 ：１００〜２００Ａ 成膜時バイアス電圧 ：−５〜−１００Ｖ 成膜前温度 ：１００〜１５０℃ ＜スパッタリング成膜条件＞ ガス導入前真空度 ：５×１０-4〜５×１０-5Ｐａ スパッタクリーニング：−７００Ｖ，２ｍｉｎ（間欠） ガス導入後圧力 ：０．１〜０．５Ｐａ 成膜時バイアス電圧 ：−５０〜−２００Ｖ ＲＦ出力 ：５００〜２０００Ｗ 成膜前温度 ：１００〜１５０℃ ＜カソード型アークイオンプレーティング成膜条件＞ ガス導入前真空度 ：５×１０-3〜１×１０-2Ｐａ スパッタクリーニング：４００Ｖ，５ｍｉｎ（間欠） ガス導入後圧力 ：１〜３Ｐａ 成膜時バイアス電圧 ：１０〜１００Ｖ 成膜前温度 ：１００〜３００℃ 皮膜組織における不連続領域面積比率及び空隙部の評価
方法を以下に示す。<Film formation conditions for 90 ° deflection type filtered arc method> Vacuum degree before gas introduction: 1 × 10 −3 to 5 × 10 −5 Pa Sputter cleaning: −500 × −800 V Pressure after gas introduction: 0.5 ３3 Pa Cathode current during film formation: 100 to 200 A Bias voltage during film formation: -5 to -100 V Temperature before film formation: 100 to 150 ° C. <Sputtering film formation conditions> Degree of vacuum before gas introduction: 5 × 10 -4 -5 × 10 −5 Pa Sputter cleaning: −700 V, 2 min (intermittent) Pressure after gas introduction: 0.1 to 0.5 Pa Bias voltage during film formation: −50 to −200 V RF output: 500 to 2000 W Temperature before film formation: 100 to 150 DEG ° C. <cathode arc ion plating film forming conditions> gas introduced before vacuum: 5 × 10 -3 ~1 × 10 -2 Pa sputter cleaning: 400V, 5 m n (intermittent) gas pressure after introducing: 1-3 Pa during deposition the bias voltage: 10～100V before film formation temperature: shows a discontinuous region area ratio and the evaluation method of the gap portion at 100 to 300 ° C. coating the tissue below.
【００３１】＜膜中粒状部面積比測定方法＞ 皮膜厚み ：１０μｍ 切断研磨 ：基板面に対して垂直に切断，鏡面研磨 観察方法 ：日立製作所製電解放射型走査電子顕微鏡Ｓ
４５００（加速電圧２０ｋＶ） 観察像 ：反射電子像 観察倍率 ：１００００倍（５視野で粒状部の面積を測
定） その他 ：反射電子像観察時に不連続領域と周辺部
（マトリックス）のコントラストが最大となる様に観察
条件を設定し、得られた像に対して画像処理を行い、周
囲より輝度の高い部分を粒状部として面積比率を計算し
た。<Measuring method of area ratio of granular portion in film> Film thickness: 10 μm Cutting polishing: Cutting perpendicular to substrate surface, mirror polishing Observation method: Electrolytic emission scanning electron microscope S manufactured by Hitachi, Ltd.
4500 (acceleration voltage: 20 kV) Observed image: backscattered electron image Observation magnification: 10,000 times (measured the area of the granular portion in 5 fields of view) Other: The contrast between the discontinuous region and the peripheral portion (matrix) is maximized during the backscattered electron image observation Observation conditions were set as described above, image processing was performed on the obtained image, and an area ratio was calculated with a portion having higher luminance than the surroundings as a granular portion.
【００３２】＜空隙部測定方法＞ 皮膜厚み ：４μｍ 切断研磨 ：基板面に対して垂直に切断，ＴＥＭ試料
用に薄片化 観察方法 ：電解放射型透過電子顕微鏡（日立製作所
製ＨＦ２０００） 観察倍率 ：１５０００倍 観察視野 ：５μｍ角 観察視野数 ：５視野 膜の靭性は異化のスクラッチ試験機を用いて試験した。<Void measurement method> Film thickness: 4 μm Cutting / polishing: Cutting perpendicular to the substrate surface, thinning for TEM samples Observation method: Electron emission type transmission electron microscope (HF2000, manufactured by Hitachi, Ltd.) Observation magnification: 15000 × Observation field: 5 μm square Number of observation fields: 5 fields The toughness of the membrane was tested using a catabolic scratch tester.
【００３３】＜靭性評価方法＞ 圧子 ：ダイヤモンド，先端径１００μｍＲ 速度 ：１０ｎｍ／ｍｉｎ 荷重 ：１００Ｎ／ｍｉｎ 評価基準 ：靭性 → チッピング発生荷重 ＜硬度評価方法＞ 装置 ：マイクロビッカース硬度計 荷重 ：２５ｇｆ 採用値 ：３点測定平均 ＜ＸＲＤによる定量条件＞ γ相量 ：使用ピークγ（１１１），（２９９），（２２０）の強度総和 α（２００）の強度 窒化物（１１０）の強度 相対感度係数 γ相 ０．１５２３ α相 １．０ Ｆｅ3Ｎ １．５７５５ （Ｃｒ，Ｆｅ）2Ｎ1-X １．５２２３<Toughness evaluation method> Indenter: diamond, tip diameter 100 μmR Speed: 10 nm / min Load: 100 N / min Evaluation criteria: toughness → chipping occurrence load <Hardness evaluation method> Apparatus: Micro Vickers hardness meter Load: 25 gf Adopted value: Three-point measurement average <Quantitative conditions by XRD> γ phase amount: Total intensity of peaks used γ (111), (299), and (220) Intensity of α (200) Intensity of nitride (110) Relative sensitivity coefficient γ phase 0 .1523 α-phase 1.0 Fe 3 N 1.5755 (Cr, Fe) 2 N 1-X 1.5223
【００３４】γ相および析出相以外に同定された相は主
にα相である。その他同定不能相が見られる場合があっ
たが、量的にはわずかであるために定量する際は無視し
た。また相対感度係数はリートベルト法によるシュミレ
ーションで分離ピークにフィットする値を計算して求め
た。 γ相中Ｎ量：使用ピークγ（１１１），（２２０）より
格子定数を算出した平均 Ｎ（質量％）＝−１１６．２５２＋３２．６１８×平均
格子定数（Å） ＜皮膜中Ｎ含有量測定＞ 面分析 ：１００μｍφ領域の表面から分析 定量 ：ＳＵＳ３０４合金を使用して感度微調整The phases identified other than the γ phase and the precipitated phase are mainly the α phase. Other unidentifiable phases were observed in some cases, but they were ignored when quantifying due to their small quantity. The relative sensitivity coefficient was determined by calculating a value that fits the separation peak by simulation using the Rietveld method. N content in γ phase: average N (mass%) calculated from lattice peaks used (γ) (111) and (220) N (% by mass) = − 116.252 + 32.618 × average lattice constant (Å) <Measurement of N content in film> Surface analysis: Analyzed from the surface in the 100 μmφ area Quantitative analysis: Fine adjustment of sensitivity using SUS304 alloy
【００３５】[0035]
【表１】 [Table 1]
【００３６】９０°偏向型フィルタードアーク法及びス
パッタリングで成膜したＮｏ．１〜７は、皮膜の靭性と
硬度（耐摩耗性）に特に優れている。No. 9 formed by the 90 ° deflection type filtered arc method and sputtering. Nos. 1 to 7 are particularly excellent in the toughness and hardness (wear resistance) of the film.
【００３７】[0037]
【発明の効果】本発明によれば、優れた靭性と耐摩耗性
に優れた皮膜を提供することができる。また本発明の成
膜方法によれば優れた耐摩耗性を有する表面処理膜を安
価で簡便な方法によって施すことが可能であり、結果と
して実用性に優れた耐摩耗性部品を得ることが可能であ
る。According to the present invention, a film having excellent toughness and abrasion resistance can be provided. Further, according to the film forming method of the present invention, it is possible to apply a surface treatment film having excellent wear resistance by an inexpensive and simple method, and as a result, it is possible to obtain a wear resistant part having excellent practicality. It is.
【図１】本発明で用いることができる直線型フィルター
ドアーク法を示す一概念図である。FIG. 1 is a conceptual diagram showing a linear filtered arc method that can be used in the present invention.
【図２】本発明で用いることができる９０°偏向型フィ
ルタードアーク法を示す一概念図である。FIG. 2 is a conceptual diagram showing a 90 ° deflection type filtered arc method that can be used in the present invention.
【図３】電解放射型走査電子顕微鏡を用いた皮膜断面の
反射電子像である。FIG. 3 is a backscattered electron image of a cross section of a film using a field emission scanning electron microscope.
【図４】電解放射型透過電子顕微鏡を用いた皮膜写真で
ある。FIG. 4 is a photograph of a film using a field emission transmission electron microscope.
１．電磁コイル ２．プラズマ ３．母材 ４．ターゲット ＭＰ．マクロパーティクル 1. 1. electromagnetic coil Plasma 3. Base material 4. Target MP. Macro particles
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 俊樹 神戸市西区高塚台１丁目５番５号 株式会 社神戸製鋼所神戸総合技術研究所内 Ｆターム(参考） 4K029 AA02 BA26 BA58 BC02 BD03 CA04 CA06 DC04 DD06 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Toshiki Sato 1-5-5 Takatsukadai, Nishi-ku, Kobe F-term in Kobe Steel Research Institute, Kobe Research Institute Co., Ltd. 4K029 AA02 BA26 BA58 BC02 BD03 CA04 CA06 DC04 DD06
Claims (5)
Ｃｒ，Ｎを含有する鉄系皮膜において、該皮膜を厚さ方
向に垂直に切断して鏡面研磨した断面を、電解放射型走
査電子顕微鏡を用いて倍率１０００倍で反射電子像にて
観察したとき、各反射電子像の皮膜部分に存在するマト
リックスより輝度が高く、且つ面積が０．０５μｍ2以
上の不連続領域を合計した面積が、全面積の１５％以下
（但し、５視野を観察したときの平均値）であることを
特徴とする靭性に優れた耐摩耗性鉄系皮膜。At least Ni, formed on a surface of a base material,
When an iron-based coating containing Cr and N is cut perpendicularly to the thickness direction and mirror-polished, the cross section is observed as a backscattered electron image using a field emission scanning electron microscope at a magnification of 1000 times. The total area of discontinuous regions having a higher luminance than the matrix existing in the film portion of each reflected electron image and having an area of 0.05 μm 2 or more is 15% or less of the entire area (however, when five visual fields are observed). Abrasion-resistant iron-based coating with excellent toughness.
０倍で前記断面の５視野（各５μｍ2）を観察したと
き、マトリックスと不連続領域の境界に存在する空隙で
あって、その長さが０．１μｍ以上である空隙の数が平
均３以下である請求項１に記載の耐摩耗性鉄系皮膜。2. A magnification of 1500 using a transmission electron microscope.
When observing 5 visual fields (each 5 μm 2 ) of the cross section at 0 ×, the number of voids existing at the boundary between the matrix and the discontinuous region and having a length of 0.1 μm or more is 3 or less on average. The wear-resistant iron-based coating according to claim 1, which is:
ト相を含むものである請求項１または２に記載の耐摩耗
性鉄系皮膜。3. The wear-resistant iron-based coating according to claim 1, wherein the coating contains an austenitic phase having a nitride.
母材に形成するにあたり、Ｆｅ，Ｎｉ，Ｃｒを含む合金
ターゲットを用い、窒素を含むプラズマ雰囲気中で磁場
誘導型フィルタードアーク法にて成膜することを特徴と
する耐摩耗性鉄系皮膜の製造方法。4. A magnetic field-induced filtered arc in a plasma atmosphere containing nitrogen, using an alloy target containing Fe, Ni, and Cr for forming the film according to claim 1 on a base material. A method for producing a wear-resistant iron-based film, characterized by being formed by a method.
母材に形成するにあたり、Ｆｅ，Ｎｉ，Ｃｒを含む合金
ターゲットを用い、窒素を含むプラズマ雰囲気中でスパ
ッタリング法にて成膜することを特徴とする耐摩耗性鉄
系皮膜の製造方法。5. A method for forming a film according to claim 1 on a base material using a sputtering method in a plasma atmosphere containing nitrogen using an alloy target containing Fe, Ni, and Cr. A method for producing a wear-resistant iron-based coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001096872A JP4112814B2 (en) | 2001-03-29 | 2001-03-29 | Wear-resistant iron-based coating with excellent toughness and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001096872A JP4112814B2 (en) | 2001-03-29 | 2001-03-29 | Wear-resistant iron-based coating with excellent toughness and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002294430A true JP2002294430A (en) | 2002-10-09 |
| JP4112814B2 JP4112814B2 (en) | 2008-07-02 |
Family
ID=18950740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001096872A Expired - Lifetime JP4112814B2 (en) | 2001-03-29 | 2001-03-29 | Wear-resistant iron-based coating with excellent toughness and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4112814B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007077494A (en) * | 2005-08-08 | 2007-03-29 | Nanofilm Technologies Internatl Pte Ltd | Metal coating |
| WO2008114561A1 (en) * | 2007-02-22 | 2008-09-25 | Toyota Jidosha Kabushiki Kaisha | Fuel cell separator, fuel cell separator manufacturing method and fuel cell |
| CN103298967A (en) * | 2010-12-08 | 2013-09-11 | 盖伦国际公司 | Hard and low friction nitride coatings |
-
2001
- 2001-03-29 JP JP2001096872A patent/JP4112814B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007077494A (en) * | 2005-08-08 | 2007-03-29 | Nanofilm Technologies Internatl Pte Ltd | Metal coating |
| WO2008114561A1 (en) * | 2007-02-22 | 2008-09-25 | Toyota Jidosha Kabushiki Kaisha | Fuel cell separator, fuel cell separator manufacturing method and fuel cell |
| US8906571B2 (en) | 2007-02-22 | 2014-12-09 | Toyota Jidosha Kabushiki Kaisha | Fuel cell separator, manufacturing method of the fuel cell separator, and fuel cell |
| CN103298967A (en) * | 2010-12-08 | 2013-09-11 | 盖伦国际公司 | Hard and low friction nitride coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4112814B2 (en) | 2008-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meghwal et al. | Thermal spray high-entropy alloy coatings: a review | |
| US11293548B2 (en) | Sliding member and coating film | |
| JP4400603B2 (en) | Member with hard carbon coating | |
| Puchi-Cabrera et al. | On the fatigue behavior of an AISI 316L stainless steel coated with a PVD TiN deposit | |
| WO2013137060A1 (en) | Combination of cylinder and piston ring | |
| Piasecki et al. | Wear behavior of self-lubricating boride layers produced on Inconel 600-alloy by laser alloying | |
| Gunen et al. | Microstructure and mechanical properties of borided inconel 625 superalloy | |
| EP4039846A1 (en) | Sliding member and method for producing same, and coating film | |
| Kumar et al. | Characterization of HiPIMS and DCMS deposited TiAlN coatings and machining performance evaluation in high speed dry machining of low and high carbon steel | |
| Haus et al. | Wear properties of carbon-rich tungsten carbide films | |
| Chen et al. | A comparative investigation on bi-layer Al–Cr/Al–Si coating and mono-layer Al–Cr–Si coating synthesized on Ti–6Al–4V alloy substrate by mechanical alloying method | |
| JP2002294430A (en) | Wear-resistant iron-based coating superior in toughness, and manufacturing method therefor | |
| Kahraman et al. | Characterization and wear behavior of plasma nitrided nickel based dental alloy | |
| Hovsepian et al. | Combined steered cathodic arc/unbalanced magnetron grown C/Cr nanoscale multilayer coatings for tribological applications | |
| CN115094416B (en) | Method for preparing stainless steel-based high-hardness wear-resistant corrosion-resistant alloy and product thereof | |
| Kim et al. | Mechanical and friction behavior of sputtered Mo–Cu–(N) coatings under various N2 gas flow using a multicomponent single alloy target | |
| Kao et al. | Optimum MoS2–Cr coating for sliding against copper, steel and ceramic balls | |
| Bakhytuly et al. | Microstructure and tribological study of TiAlCN and TiTaCN coatings | |
| Lothrop et al. | Characterization of (AlCrTiVZr) N High-Entropy Coating Produced by Cathodic Arc Evaporation | |
| JP3993391B2 (en) | Abrasion-resistant iron-based coating with excellent toughness and method for forming the same | |
| Atapour et al. | Tribology and cyclic oxidation behavior of plasma nitrided valve steel | |
| JP2001107221A (en) | Wear resistant film coating material and production method thereof | |
| Meghwal | Thermal Spray Coatings for Extreme Engineering Environments | |
| Wei et al. | Microstructural characterization and tribological behavior of surface plasma Zr-Er alloying on TC11 alloy | |
| Akhter | Microstructure, Mechanical and Tribological Properties of Ternary Transition Metal Nitride Coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040401 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040806 |
|
| A977 | Report on retrieval |
Effective date: 20060801 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070814 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071015 |
|
| A02 | Decision of refusal |
Effective date: 20071218 Free format text: JAPANESE INTERMEDIATE CODE: A02 |
|
| A521 | Written amendment |
Effective date: 20080201 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Effective date: 20080311 Free format text: JAPANESE INTERMEDIATE CODE: A911 |
|
| 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: 20080408 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080410 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 3 Free format text: PAYMENT UNTIL: 20110418 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 4 Free format text: PAYMENT UNTIL: 20120418 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130418 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20130418 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20140418 |