JPH09170068A - High strength coated member with crystal orientational property - Google Patents
High strength coated member with crystal orientational propertyInfo
- Publication number
- JPH09170068A JPH09170068A JP34830995A JP34830995A JPH09170068A JP H09170068 A JPH09170068 A JP H09170068A JP 34830995 A JP34830995 A JP 34830995A JP 34830995 A JP34830995 A JP 34830995A JP H09170068 A JPH09170068 A JP H09170068A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- intermediate layer
- base material
- hard film
- 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
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は金属、合金またはセ
ラミックス焼結体の基材上に（ＴｉＡｌ）の化合物でな
る被膜をヘテロエピタキシャル関係に被覆してなる結晶
配向性高強度被覆部材に関し、具体的には、金属、合金
またはセラミックス焼結体の基材上に耐剥離性に優れた
高硬度、高靭性の被膜を被覆して、例えば旋削工具，フ
ライス工具，ドリル，エンドミルに代表される切削用工
具、スリッタ−などの切断刃，裁断刃とダイス，パンチ
などの型工具とノズルなどの耐腐食耐摩耗部材として代
表される耐摩耗用工具、ビットに代表される土木建設用
工具として最適な結晶配向性高強度被覆部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystallographically-oriented high-strength coating member obtained by coating a coating of a (TiAl) compound on a substrate of a metal, alloy or ceramics sintered body in a heteroepitaxial relationship. In particular, a metal, alloy or ceramics sintered base material is coated with a film of high hardness and high toughness with excellent peeling resistance, for example, cutting tools represented by turning tools, milling tools, drills and end mills. Optimal as a tool for cutting, a cutting blade such as a slitter, a cutting blade and a die, a die tool such as a punch and a wear-resistant tool represented by a corrosion-resistant wear-resistant member such as a nozzle, and a civil construction tool represented by a bit. The present invention relates to a crystal-oriented high-strength covering member.
【０００２】[0002]
【従来の技術】金属、合金およびセラミックスの基材上
に厚さが２０μｍ以下のセラミックスの被膜を被覆し、
基材と被膜とのそれぞれの特性を有効に引き出して、長
寿命を達成しようとした被覆部材が多数提案されてい
る。この被覆部材に被膜を被覆する方法は、大別すると
化学蒸着法（ＣＶＤ法）と物理蒸着法（ＰＶＤ法）があ
る。これらのうち、特にＰＶＤ法により被覆された被膜
は、基材の強度を劣化させることなく耐摩耗性を高める
利点がある。そのために、一般に強度，耐欠損性を重要
視するドリル、エンドミル、フライス用スロ−アウェイ
チップに代表される被覆切削工具の被膜は、ＰＶＤ法に
より被覆されているのが現状である。2. Description of the Related Art A ceramic film having a thickness of 20 μm or less is coated on a base material of metal, alloy and ceramics,
A large number of coating members have been proposed in which the respective characteristics of the base material and the coating film are effectively drawn to achieve a long life. The method of coating the coating on the coating member is roughly classified into a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method). Among them, a coating coated by the PVD method has an advantage of increasing abrasion resistance without deteriorating the strength of the substrate. For this reason, coatings of coated cutting tools typified by drills, end mills, and throw-away inserts for milling, which generally emphasize strength and fracture resistance, are currently coated by a PVD method.
【０００３】従来から耐摩耗性を向上させるために窒化
チタンの被膜を被覆することはよく知られている。しか
しながら、窒化チタンを代表とする金属窒化物は高温で
酸化されやすく、耐摩耗性が著しく劣化するという問題
がある。この窒化チタン被膜の酸化の問題を改善しょう
として１９８０年代中頃から提案されたものに、（Ｔｉ
Ａｌ）化合物の被膜に代表される被覆部材に関するもの
があり、その代表的なものとして特開昭６２−５６５６
５号公報，特開平６−２１０５０２号公報，特開平６−
２１０５１１号公報および特開平７−１９７２３５号公
報がある。It has been well known that a titanium nitride film is coated to improve wear resistance. However, metal nitrides typified by titanium nitride are liable to be oxidized at high temperatures, and have a problem that wear resistance is significantly deteriorated. A proposal made in the mid-1980s to improve the problem of oxidation of this titanium nitride film, (Ti
There is a coating member typified by a coating film of Al) compound, and a representative one thereof is JP-A-62-5656.
No. 5, JP-A-6-210502, JP-A-6-210502
There are JP-A-210511 and JP-A-7-197235.
【０００４】一方、基材の表面に被覆する被膜を結晶配
向させて、被膜の付着性を高めることが提案されてお
り、その代表的なものとして特開昭５６−１５６７６７
号公報，特開平２−１５９３６３号公報，特開平５−２
８７３２２号公報，特開平５−２８７３２３号公報およ
び特開平５−２９５５１７号公報がある。On the other hand, it has been proposed to improve the adhesion of a film by crystallizing a film to be coated on the surface of a substrate, as a typical example of which is disclosed in JP-A-56-156767.
JP, JP-A-2-159363, JP-A-5-2
87322, JP-A-5-287323 and JP-A-5-295517.
【０００５】[0005]
【発明が解決しようとする課題】ＴｉＡｌ化合物の被膜
に関する先行技術としての特開昭６２−５６５６５号公
報，特開平６−２１０５０２号公報，特開平６−２１０
５１１号公報および特開平７−１９７２３５号公報に
は、基体の表面に（ＴｉＡｌ）の炭化物，窒化物および
炭窒化物のうちの１種の単層または２種以上の複層でな
る硬質被覆層を形成した耐摩耗性に優れた表面被覆硬質
部材について開示されている。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention JP-A-62-56565, JP-A-6-210502 and JP-A-6-210 as prior arts relating to a TiAl compound film.
No. 511 and Japanese Patent Laid-Open No. 7-197235 disclose a hard coating layer formed on the surface of a substrate by a single layer of one or more of (TiAl) carbides, nitrides and carbonitrides or a multi-layer of two or more layers. A surface-coated hard member having excellent wear resistance is formed.
【０００６】これらの公報に開示の表面被覆硬質部材
は、開発当初の通りにＴｉ化合物の被膜に比べて耐酸化
性および耐摩耗性の向上した被覆硬質部材ではあるが、
逆に機械的性質が劣化し、工具、特に苛酷な条件で用い
られる切削工具へ適用した場合に切削性能が低下すると
いう問題がある。つまり、同公報に記載の表面被覆硬質
部材は、被膜中にＡｌを含有させることにより、Ｔｉ化
合物の被膜に比較して被膜表面の化学的性質の向上を達
成した反面、基材と被膜との界面における結晶構造的な
配慮がされていないことから、被膜の耐剥離性および強
度が劣り、表面被覆硬質部材の破壊靭性値および耐欠損
性が低下すること、特に高速切削用切削工具として用い
ると、高温による被膜の酸化，急激な摩耗の進行，熱衝
撃性による劣化および被削材との溶着により短寿命にな
るという問題がある。The surface-coated hard members disclosed in these publications are coated hard members having improved oxidation resistance and wear resistance as compared with the Ti compound coating as initially developed,
On the contrary, there is a problem that mechanical properties are deteriorated and cutting performance is lowered when applied to a tool, particularly a cutting tool used under severe conditions. That is, the surface-coated hard member described in the publication achieves an improvement in the chemical property of the coating surface as compared with the coating film of the Ti compound by including Al in the coating film, on the other hand Since no consideration is given to the crystal structure at the interface, the peeling resistance and strength of the coating are poor, and the fracture toughness value and fracture resistance of the surface-coated hard member are reduced, especially when used as a cutting tool for high-speed cutting. However, there is a problem that the life of the coating is shortened due to oxidation of the coating film due to high temperature, rapid abrasion, deterioration due to thermal shock, and welding with the work material.
【０００７】一方、結晶配向された被膜に関する先行技
術としての特開昭５６−１５６７６７号公報，特開平２
−１５９３６３号公報，特開平５−２８７３２２号公
報，特開平５−２８７３２３号公報および特開平５−２
９５５１７号公報には、Ｔｉ化合物の被膜を結晶配向し
て基材の表面に被覆した被覆硬質部材について開示され
ている。On the other hand, JP-A-56-156767 and JP-A-Hei 2 156767 as prior art relating to a crystal oriented film.
JP-A-159363, JP-A-5-287322, JP-A-5-287323 and JP-A-5-2-2
Japanese Patent No. 95517 discloses a hard coated member in which a Ti compound coating is crystallized and coated on the surface of a substrate.
【０００８】これらの結晶配向に関する公報のうち、前
２公報に開示の結晶配向性被覆硬質部材は、基材と被膜
との相互の界面においてヘテロエピタキシャル関係を保
たせていないことから、被膜の結晶配向性が弱くなり、
被膜の付着性および被膜の強度が劣るという問題があ
る。また、これらの公報のうち、後３公報に開示の結晶
配向性被覆硬質部材は、基材と被膜との界面における応
力を考慮した被膜層の構成になっていなく、かつ被膜自
体の機械的性質が低いことから、被膜の強度，硬度，耐
摩耗性，耐熱性および耐剥離性に未だ満足できないとい
う問題がある。Among the publications relating to these crystal orientations, the crystallographically coated hard members disclosed in the preceding two publications do not maintain a heteroepitaxial relationship at the interface between the base material and the coating film, so that the crystal of the coating film is formed. Orientation becomes weak,
There is a problem that the adhesion of the coating and the strength of the coating are poor. Further, among these publications, the crystallographically-coated hard members disclosed in the latter three publications do not have a coating layer configuration in consideration of stress at the interface between the base material and the coating, and the mechanical properties of the coating itself. Therefore, there is a problem that the strength, hardness, wear resistance, heat resistance and peeling resistance of the coating film cannot be satisfied yet.
【０００９】本発明は、上述のような問題点を解決した
もので、具体的には、低温領域から高温領域に至るまで
の広い領域において、高靭性，高硬度性，耐摩耗性，耐
酸化性，耐熱衝撃性，耐欠損性，耐溶着性のある被膜お
よび耐剥離性の被膜を被覆したことにより一層長寿命と
なる結晶配向性高強度被覆部材の提供を目的とする。The present invention has solved the above-mentioned problems. Specifically, it has high toughness, high hardness, wear resistance, and oxidation resistance in a wide range from a low temperature region to a high temperature region. An object of the present invention is to provide a crystal-oriented high-strength coated member having a longer life by coating with a coating having heat resistance, thermal shock resistance, fracture resistance, welding resistance, and peeling resistance.
【００１０】[0010]
【発明が解決しようとする課題】本発明者らは、超硬合
金の基材上に（ＴｉＡｌ）の化合物の硬質膜を被覆した
被覆部材が、低温領域で使用すると割合に優れた効果を
発揮するのに対し、高温領域で使用するとその効果が低
減されるという問題を検討していたところ、基材上に被
覆する（ＴｉＡｌ）の化合物でなる硬質膜との間に、周
期律表の４ａ，５ａ，６ａ金属の化合物でなる中間層を
介在し、これらの基材と中間層と硬質膜とをヘテロエピ
タキシャル関係を保つように被覆すると、高強度な被膜
となること、また低温から高温の領域に至るまで耐摩耗
性の低減が生じなく、かつ中間層および硬質膜の耐剥離
性が顕著に向上し、寿命が延長するということを見出
し、本発明を完成するに至ったものである。DISCLOSURE OF THE INVENTION The present inventors have found that a coating member obtained by coating a hard film of a (TiAl) compound on a base material of cemented carbide exhibits a relatively excellent effect when used in a low temperature range. On the other hand, when the problem that the effect is reduced when used in a high temperature region was examined, it was confirmed that the 4a of the periodic table was formed between the hard film made of the (TiAl) compound and coated on the base material. , 5a, 6a intervening an intermediate layer made of a metal compound, and covering these base material, intermediate layer, and hard film so as to maintain a heteroepitaxial relationship, a high-strength film is formed, and a low-temperature to high-temperature film is formed. The inventors have found that the wear resistance does not decrease up to the region, the peel resistance of the intermediate layer and the hard film is significantly improved, and the life is extended, and the present invention has been completed.
【００１１】本発明の高強度被覆部材は、基材上にチタ
ンとアルミニウムとを含む複合窒化物，複合炭窒化物，
複合窒酸化物，複合炭窒酸化物の中の１種以上の単層ま
たは多層でなる硬質膜が被覆された被覆部材において、
該基材と該硬質膜との間に周期律表の４ａ，５ａ，６ａ
族金属の炭化物，窒化物およびこれらの相互固溶体の中
の１種の単層または２種以上の多層でなる中間層を介在
させて、該基材と該中間層との界面または／および該中
間層と該硬質膜との界面がヘテロエピタキシャル関係を
保つように被覆されていることを特徴とするものであ
る。The high-strength coated member of the present invention is a composite nitride containing titanium and aluminum on a base material, a composite carbonitride,
In a covering member coated with a hard film consisting of a single layer or multiple layers of one or more kinds of complex nitric oxide and complex carbonitride oxide,
4a, 5a, 6a of the periodic table between the base material and the hard film
An interface between the base material and the intermediate layer and / or the intermediate, with an intermediate layer consisting of one kind of single layer or two or more kinds of multilayers among group metal carbides, nitrides and mutual solid solutions thereof interposed. The interface between the layer and the hard film is coated so as to maintain a heteroepitaxial relationship.
【００１２】[0012]
【発明の実施の態様】本発明の高強度被覆部材における
基材は、被膜を被覆するときに加熱する温度に耐えるこ
とができる金属部材，焼結合金またはセラミックス焼結
体でなり、具体的には、例えばステンレス鋼，耐熱合
金，高速度鋼，ダイス鋼，Ｔｉ合金，Ａｌ合金に代表さ
れる金属部材、超硬合金，サ−メット，粉末ハイスの焼
結合金、Ａｌ2Ｏ3系焼結体，Ｓｉ3Ｎ4系焼結体，サイア
ロン系焼結体，ＺｒＯ2系焼結体のセラミックス焼結体
を挙げることができる。これらのうち、切削用工具また
は耐摩耗用工具として用いるときには、超硬合金，窒素
含有ＴｉＣ系サ−メットもしくはセラミックス焼結体の
基材が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The base material in the high-strength coating member of the present invention is a metal member, a sintered alloy or a ceramics sintered body capable of withstanding the temperature of heating when coating the coating film. Are, for example, metal members typified by stainless steel, heat resistant alloys, high speed steels, die steels, Ti alloys, Al alloys, cemented carbides, cermets, powdered high speed sintered alloys, and Al 2 O 3 based sintered materials. Examples of the ceramics sintered body include a sintered body, a Si 3 N 4 system sintered body, a sialon system sintered body, and a ZrO 2 system sintered body. Among these, when used as a cutting tool or a wear resistant tool, a cemented carbide, a nitrogen-containing TiC-based cermet or a ceramics sintered body is preferable.
【００１３】この基材上に直接被覆される中間層は、具
体的には、例えばＴｉＣ，ＺｒＣ，ＨｆＣ，ＴａＣ，Ｎ
ｂＣ，ＶＣ，ＷＣ，Ｍｏ2Ｃ，Ｃｒ3Ｃ2，ＴｉＮ，Ｚｒ
Ｎ，ＨｆＮ，ＴａＮ，ＣｒＮ，Ｔｉ（ＣＮ），（Ｔｉ
Ｗ）Ｃ，（ＴｉＴａ）Ｃ，（ＴｉＴａ）ＣＮ，（ＴｉＴ
ａ）Ｎを挙げることができる。これらの中間層は、１種
の単層または２種以上の多層として形成することができ
る。特に、後述するように、基材界面の結晶構造が調整
し難い場合には、多層の中間層とすること、または中間
層と基材との間に、基材との親和性の高い下地層、例え
ばＴｉ，ＴｉＡｌ，Ｔｉ３Ａｌ，ＴｉＡｌ３，Ｗ，に代
表される金属または合金，ＷＣ，Ｍｏ2Ｃ，Ｃｒ2Ｎ，Ｔ
ａＮ，ＶＢ2，ＮｂＢ2，ＴａＢ2，Ｗ2Ｂ5，ＭｏＢ2，Ｃ
ｒＢ2の六方晶結晶構造でなるセラミックスの中から選
ばれた１種の単層または２種以上の複層でなる下地層を
形成することも好ましいことである。この中間層の膜厚
さは、中間層の表面に被覆される硬質膜がヘテロエピタ
キシャル関係を保ち、付着性を高めることができる膜厚
さであればよく、具体的には、例えば０．０１〜５μｍ
厚さ、特に０．０１〜１μｍ厚さでなることが好まし
い。The intermediate layer directly coated on the base material is, for example, TiC, ZrC, HfC, TaC, N.
bC, VC, WC, Mo 2 C, Cr 3 C 2 , TiN, Zr
N, HfN, TaN, CrN, Ti (CN), (Ti
W) C, (TiTa) C, (TiTa) CN, (TiT
a) N can be mentioned. These intermediate layers can be formed as one kind of single layer or two or more kinds of multilayers. In particular, as will be described later, when it is difficult to adjust the crystal structure of the base material interface, use a multilayer intermediate layer, or between the intermediate layer and the base material, an underlayer having a high affinity with the base material. , A metal or alloy represented by Ti, TiAl, Ti3Al, TiAl3, W, WC, Mo 2 C, Cr 2 N, T
aN, VB 2 , NbB 2 , TaB 2 , W 2 B 5 , MoB 2 , C
It is also preferable to form an underlayer composed of one kind of single layer or two or more kinds of multilayers selected from the ceramics having a hexagonal crystal structure of rB 2 . The thickness of the intermediate layer may be such that the hard film coated on the surface of the intermediate layer can maintain the heteroepitaxial relationship and enhance the adhesion, and specifically, for example, 0.01 ~ 5 μm
The thickness is preferably 0.01 to 1 μm.
【００１４】この中間層の表面に被覆される硬質膜は、
具体的には、例えば（Ｔｉ，Ａｌ）Ｎ、（Ｔｉ，Ａｌ）
ＣＮ、（Ｔｉ，Ａｌ）ＮＯ、（Ｔｉ，Ａｌ）ＣＮＯ、を
挙げることができる。この硬質膜は、０．５〜１０μｍ
でなる膜厚さでなることが好ましく、特に耐衝撃性を重
要視する用途においては０．５〜５μｍでなる膜厚さで
なることが好ましい。The hard film coated on the surface of the intermediate layer is
Specifically, for example, (Ti, Al) N, (Ti, Al)
CN, (Ti, Al) NO, (Ti, Al) CNO can be mentioned. This hard film has a thickness of 0.5 to 10 μm.
It is preferable that the film thickness is 5 .mu.m, and particularly in applications where impact resistance is important, the film thickness is preferably 0.5 to 5 .mu.m.
【００１５】これらの硬質膜は、化学量論組成または非
化学量論組成でなる場合でもよいが、特に、（Ｔｉa、
Ａｌb）ＣyＮ1-y の式［但し、式中のＴｉはチタン、
Ａｌはアルミニウムを示し、ａ、ｂはそれぞれＴｉおよ
びＡｌの原子比を、ｙは炭素の原子比を表す。また、ａ
＋ｂ＝１、０．２５≦ａ≦０．７５、 ０≦ｙ≦０．９
５の関係にある］で表わせる複合窒化物および複合炭窒
化物の中の１種以上でなることが耐剥離性から好まし
い。特に、上述の式中におけるＴｉの原子比を表わすａ
および炭素の原子比を表わすｙがそれぞれ０．４≦ａ≦
０．６および０≦ｙ≦０．２の関係にある硬質膜でなる
場合には、硬質膜の強度，耐摩耗性などの特性が優れて
いることから好ましい。These hard films may be of stoichiometric or non-stoichiometric composition, in particular (Ti a ,
Al b ) C y N 1-y [wherein Ti is titanium,
Al represents aluminum, a and b represent the atomic ratio of Ti and Al, and y represents the atomic ratio of carbon. Also, a
+ B = 1, 0.25 ≦ a ≦ 0.75, 0 ≦ y ≦ 0.9
It is preferable that at least one of the composite nitride and the composite carbonitride represented by [4] is present in view of peeling resistance. In particular, a representing the atomic ratio of Ti in the above formula
And y representing the atomic ratio of carbon are respectively 0.4 ≦ a ≦
A hard film having a relationship of 0.6 and 0 ≦ y ≦ 0.2 is preferable because the hard film has excellent properties such as strength and abrasion resistance.
【００１６】本発明の高強度被覆部材は、基材との界面
側における中間層面および／または硬質膜との界面側に
おける中間層面の結晶が配向されること、および中間層
との界面側における硬質膜面の結晶が配向されることで
ある。また、本発明の高強度被覆部材のさらに好ましい
構成は、上述の結晶配向の構成と伴に、中間層と隣接す
る基材面が結晶配向されていることである。In the high-strength coated member of the present invention, the crystal of the intermediate layer surface on the interface side with the substrate and / or the intermediate layer surface on the interface side with the hard film is oriented, and the hard layer on the interface side with the intermediate layer is oriented. That is, the crystals on the film surface are oriented. Further, a more preferable constitution of the high-strength covering member of the present invention is that the base material surface adjacent to the intermediate layer is crystal-oriented in addition to the above-mentioned constitution of crystal orientation.
【００１７】本発明の高強度被覆部材におけるヘテロエ
ピタキシャル関係は、中間層が窒化チタンおよび／また
は炭窒化チタンからなり、基材と接する中間層面の２０
％以上の（１−１１）結晶面が基材表面を構成する結晶
粒の（０００１）結晶面と平行でなり、かつ中間層の＜
１１０＞結晶方向が基材の＜１１−２０＞結晶方向と平
行であり、中間層が上記硬質膜と接する面の２０％以上
の（１−１１）結晶面が硬質膜を構成する結晶粒の（１
−１１）結晶面と平行でなり、かつ中間層の＜１１０＞
結晶方向が硬質膜の＜１１０＞結晶方向と平行であるこ
とが特に好ましい。The heteroepitaxial relationship in the high-strength coated member of the present invention is such that the intermediate layer is made of titanium nitride and / or titanium carbonitride and the intermediate layer surface in contact with the base material is 20.
% Or more of the (1-11) crystal planes are parallel to the (0001) crystal planes of the crystal grains constituting the substrate surface, and
The 110> crystallographic direction is parallel to the <11-20> crystallographic direction of the substrate, and 20% or more of the (1-11) crystallographic planes of the crystal grains that make up the hard film of the intermediate layer contact the hard film. (1
-11) It is parallel to the crystal plane and <110> of the intermediate layer.
It is particularly preferred that the crystallographic direction is parallel to the <110> crystallographic direction of the hard film.
【００１８】また、さらに好ましい本発明の高強度被覆
部材におけるヘテロエピタキシャル関係は、上述の中間
層面の結晶配向の他に、基材の表面における結晶構造が
主として六方晶で構成され、中間層と接する基材表面の
２０％以上が（０００１）結晶面でなり、基材表面の
（０００１）結晶面が中間層を構成する結晶粒の（１−
１１）結晶面と平行でなり、かつ基材表面の＜１１−２
０＞結晶方向が中間層の＜１１０＞結晶方向と平行にな
ることである。Further, a more preferable heteroepitaxial relationship in the high-strength coating member of the present invention is that, in addition to the above-described crystal orientation of the intermediate layer surface, the crystal structure on the surface of the base material is mainly composed of hexagonal crystals, and contacts with the intermediate layer. 20% or more of the surface of the base material is the (0001) crystal plane, and the (0001) crystal surface of the base material surface is (1-).
11) <11-2 which is parallel to the crystal plane and which is on the surface of the substrate.
The 0> crystal direction is parallel to the <110> crystal direction of the intermediate layer.
【００１９】したがって、本発明の高強度被覆部材にお
ける基材は、六方晶炭化タングステンを主成分として含
有する超硬合金、または前述した金属，合金，セラミッ
クス焼結体の基材の表面に六方晶の薄膜でなる下地層、
具体的には、例えばＷＣ，Ｍｏ2Ｃ，Ｃｒ2Ｎ，ＴａＮ，
ＶＢ2，ＮｂＢ2，ＴａＢ2，Ｗ2Ｂ5，ＭｏＢ2，ＣｒＢ2
の１種以上の下地層を形成して用いることが好ましい。Therefore, the base material in the high-strength coated member of the present invention is a cemented carbide containing hexagonal tungsten carbide as a main component, or a hexagonal crystal on the surface of the base material of the above-mentioned metal, alloy or ceramics sintered body. An underlayer consisting of a thin film of
Specifically, for example, WC, Mo 2 C, Cr 2 N, TaN,
VB 2 , NbB 2 , TaB 2 , W 2 B 5 , MoB 2 , CrB 2
It is preferable to form and use one or more types of underlayers.
【００２０】本発明の高強度被覆部材は、従来から市販
されているステンレス鋼，耐熱合金，高速度鋼，ダイス
鋼，Ｔｉ合金，Ａｌ合金に代表される金属部材、超硬合
金，サ−メット，粉末ハイスの焼結合金、Ａｌ2Ｏ3系焼
結体，Ｓｉ3Ｎ4系焼結体，サイアロン系焼結体，ＺｒＯ
2系焼結体のセラミックス焼結体を基材とし、好ましく
はＪＩＳ規格Ｂ４０５３の超硬合金の使用選択基準の中
で分類されているＰ２０〜Ｐ４０，Ｍ２０〜４０および
Ｋ１０〜Ｋ２０相当の超硬合金材質、特に好ましくはＰ
３０，Ｍ２０，Ｍ３０相当の超硬合金材質でなる基材を
用いればよい。この基材の表面を、必要に応じて研磨
し、超音波，有機溶剤などによる洗浄処理を行った後、
従来から行われている物理蒸着法（ＰＶＤ法），化学蒸
着法（ＣＶＤ法）またはプラズマＣＶＤ法により基材上
に被膜を被覆することにより作製することができる。The high-strength coated member of the present invention is a metal member typified by conventionally commercially available stainless steel, heat-resistant alloy, high-speed steel, die steel, Ti alloy, Al alloy, cemented carbide, and cermet. , Powdered HSS sintered alloy, Al 2 O 3 system sintered body, Si 3 N 4 system sintered body, Sialon system sintered body, ZrO
Based on a ceramic sintered body of a 2 series sintered body as a base material, preferably a cemented carbide equivalent to P20 to P40, M20 to 40 and K10 to K20 which is classified in JIS B4053 cemented carbide use selection criteria. Alloy material, particularly preferably P
A base material made of a cemented carbide material corresponding to 30, M20, M30 may be used. If necessary, the surface of this base material is polished, and after cleaning with ultrasonic waves, organic solvents, etc.,
It can be prepared by coating a film on a substrate by a conventional physical vapor deposition method (PVD method), chemical vapor deposition method (CVD method) or plasma CVD method.
【００２１】基材上に被膜を被覆する場合は、必要に応
じて被覆する下地層を含めて、それぞれの膜質に応じて
ＰＶＤ法，ＣＶＤ法，またはプラズマＣＶＤ法を使い分
けることもできる。これらのうち、製造工程上から全て
の被膜を、イオンプレ−ティング法またはスパッタリン
グ法に代表されるＰＶＤ法で行うことが好ましく、この
中でもイオンプレ−ティング法、特にア−クイオンプレ
−ティング法で被覆処理することが好ましい。When a film is coated on a substrate, a PVD method, a CVD method, or a plasma CVD method can be used properly depending on the film quality, including an underlayer to be coated if necessary. Among these, it is preferable to perform all coatings from the manufacturing process by a PVD method typified by an ion plating method or a sputtering method. Among them, coating treatment is preferably performed by an ion plating method, particularly an arc ion plating method. Is preferred.
【００２２】本発明の高強度被覆部材における被膜をイ
オンプレ−ティング法で作製する場合について、さらに
詳述すると、金属源としては金属チタン、金属アルミニ
ウムの２種類を独立して用いてもよく、またはＴｉ−Ａ
ｌ合金を使用してもよい。金属のイオン化の方法もア−
ク放電の他、グロ−放電または高周波加熱などのいずれ
でもよい。イオンプレ−ティング法で使用するガスは、
窒化物を生成するためのガス、すなわち窒素ガスの他、
窒素を含んだアンモニアなどの化合物ガスを用いてもよ
い。この反応ガスを炉内に導入し、金属源としての金属
または合金をイオン化し、基材に負のバイアスを印加す
ると膜の結晶配向が容易となることから好ましい。The case where the coating film of the high-strength coating member of the present invention is produced by the ion plating method will be described in more detail. As the metal source, two kinds of metal titanium and metal aluminum may be used independently, or Ti-A
1 alloy may also be used. A method for ionizing metals
In addition to black discharge, glow discharge or high frequency heating may be used. The gas used in the ion plating method is
In addition to the gas for producing nitride, namely nitrogen gas,
A compound gas such as ammonia containing nitrogen may be used. It is preferable to introduce this reaction gas into the furnace, ionize the metal or alloy as the metal source, and apply a negative bias to the base material because the crystal orientation of the film becomes easy.
【００２３】[0023]
【作用】本発明の高強度被覆部材は、硬質膜が被膜全体
の破壊靭性値および耐摩耗性を向上させる作用をし、か
つ中間層が基材と被膜との界面近傍に残留する応力を緩
和する作用をし、特に超硬合金でなる基材の場合には付
着性を高める作用をし、これらのヘテロエピタキシャル
関係により被覆部材全体に優れた特性を付与させている
ものである。In the high-strength coated member of the present invention, the hard film acts to improve the fracture toughness value and wear resistance of the entire coating, and the intermediate layer alleviates the stress remaining near the interface between the base material and the coating. In particular, in the case of a base material made of a cemented carbide, it has an effect of increasing the adhesiveness, and imparts excellent properties to the entire covering member due to the heteroepitaxial relationship between them.
【００２４】[0024]
【実施例】市販されている形状ＳＮＧＮ１２０４０８の
超硬合金（ＪＩＳ規格Ｂ４０５３のＰ３０相当材質）を
基材とし、この基材表面を有機溶剤で洗浄した後、アー
ク放電プラズマ法のチャンバー内に設置し、（逃げ面と
すくい面へ同時に被覆できる治具を用いて設置）、チャ
ンバー内を１．０×１０-6〜３．０×１０-6Ｔｏｒｒの
真空とした。次いで基材を約４５０℃、アーク放電電流
を約１００Ａに保持し、Ｎ2−Ｈ2ガス雰囲気中でＴｉ金
属を放電してＴｉＮの中間層を被覆した後、チャンバー
内を表１に示すガス組成およびガス圧に保持し、Ｔｉ−
Ａｌ合金を約３０分間放電させて（ＴｉＡｌ）Ｎおよび
（ＴｉＡｌ）ＣＮの硬質膜を合成した。蒸発源としての
Ｔｉ−Ａｌ合金は、表１に示す組成の異なるターゲット
を用いて本発明品１〜４および比較品１〜３を得た。本
発明品の被覆条件と異なる比較品の被覆条件は、被膜前
に水素処理をしなかったこと、ガス圧およびバイアス電
圧条件を従来から用いられている条件としたこと、並び
に本発明品の基材には（０００１）面の成長した板状晶
ＷＣを多量に含有させた超硬合金を用いたのに対し、比
較品の基材には本発明品と組成成分が同一である従来の
市販の超硬合金を用いたことである。[Example] A commercially available cemented carbide of SNGN120408 (a material equivalent to P30 of JIS standard B4053) is used as a base material, the surface of the base material is washed with an organic solvent, and then placed in a chamber of an arc discharge plasma method. (Installed using a jig capable of simultaneously covering the flank surface and the rake surface), and the inside of the chamber was set to a vacuum of 1.0 × 10 −6 to 3.0 × 10 −6 Torr. Then, the substrate was kept at about 450 ° C. and the arc discharge current was kept at about 100 A, Ti metal was discharged in a N 2 —H 2 gas atmosphere to coat the intermediate layer of TiN, and then the inside of the chamber was filled with the gas shown in Table 1. Maintaining composition and gas pressure, Ti-
The Al alloy was discharged for about 30 minutes to synthesize hard films of (TiAl) N and (TiAl) CN. For Ti-Al alloys as evaporation sources, the present invention products 1 to 4 and comparative products 1 to 3 were obtained by using targets having different compositions shown in Table 1. The coating conditions of the comparative product different from the coating conditions of the product of the present invention were that hydrogen treatment was not performed before the coating, that gas pressure and bias voltage conditions were the conventionally used conditions, and The material used was a cemented carbide containing a large amount of (0001) -face grown plate-like crystals WC, whereas the base material of the comparative product had the same composition as the product of the present invention. That is, the above-mentioned cemented carbide was used.
【００２５】こうして得た本発明品１〜４および比較品
１〜３のそれぞれの被膜は、Ｘ線回折装置、電子顕微鏡
およびＥＤＸ装置により調べて、ＴｉＮの中間層と（Ｔ
ｉ、Ａｌ）化合物の硬質膜でなることを確認した。本発
明品１〜４および比較品１〜３の硬質膜組成成分は、Ｘ
線回折装置およびグロー放電発光分析装置により解析し
て表２に示した。また、それぞれの被膜厚さは走査型電
子顕微鏡で調べて、その結果を表２に併記した。The coating films of the present invention products 1 to 4 and the comparative products 1 to 3 thus obtained were examined by an X-ray diffractometer, an electron microscope and an EDX device, and found to be a TiN intermediate layer and (T
It was confirmed that the film was a hard film of i, Al) compound. The hard film composition components of the present invention products 1 to 4 and the comparative products 1 to 3 are X.
The results are shown in Table 2 after being analyzed by a line diffractometer and a glow discharge emission spectrometer. In addition, each film thickness was examined by a scanning electron microscope, and the results are also shown in Table 2.
【００２６】次いで、本発明品１〜４および比較品１〜
３を用いて、引っ掻き硬さ試験機に相当する装置により
被膜のスクラッチ試験を行い、被膜が剥離する臨界荷重
を求めて、その結果を表２に併記した。また、本発明品
１〜４および比較品１〜３を用いて、被削材：Ｓ４５Ｃ
（ＨＢ１９０）、切削速度３００ｍ／ｍｉｎ、送り：
０．５ｍｍ／ｒｅｖ、切込み：２．０ｍｍ、切削時間：
６０ｍｉｎ、乾式切削試験による切削試験を行い、それ
ぞれの平均逃げ面摩耗幅を測定し、その結果を表２に併
記した。Next, products 1 to 4 of the present invention and comparative products 1 to 1
Scratch test of the coating film was performed by using a device corresponding to a scratch hardness tester using No. 3, and the critical load for peeling the coating film was determined, and the results are also shown in Table 2. Further, using the present invention products 1 to 4 and the comparative products 1 to 3, a work material: S45C
(HB190), cutting speed 300 m / min, feed:
0.5 mm / rev, depth of cut: 2.0 mm, cutting time:
A cutting test by a dry cutting test was performed for 60 minutes, the average flank wear width was measured, and the results are also shown in Table 2.
【００２７】基材と中間層と硬質膜とのヘテロエピタキ
シャル関係については、電子線回折法を用いて確認した
ところ、本発明品１〜４は、基材と接する中間層面の２
０％以上の（１−１１）結晶面が基材表面を構成する結
晶粒の（０００１）結晶面と平行でなり、かつ中間層の
＜１１０＞結晶方向が基材の＜１１−２０＞結晶方向と
平行であり、中間層が硬質膜と接する面の２０％以上の
（１−１１）結晶面が硬質膜を構成する結晶粒の（１−
１１）結晶面と平行でなり、かつ中間層の＜１１０＞結
晶方向が硬質膜の＜１１０＞結晶方向と平行であること
を確認した。これらの確認内容のうち各界面間の結晶配
向性（率）を表３に示した。The heteroepitaxial relationship among the base material, the intermediate layer and the hard film was confirmed by using an electron beam diffraction method.
0% or more of (1-11) crystal planes are parallel to the (0001) crystal planes of the crystal grains constituting the substrate surface, and the <110> crystal direction of the intermediate layer is the <11-20> crystal of the substrate. 20% or more of the plane in which the intermediate layer is in contact with the hard film is parallel to the direction, and (1-11) crystal planes of (1-
11) It was confirmed that the film was parallel to the crystal plane and the <110> crystal direction of the intermediate layer was parallel to the <110> crystal direction of the hard film. Table 3 shows the crystal orientation (ratio) between each interface among these confirmation contents.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【発明の効果】本発明の高強度被覆部材は、従来の（Ｔ
ｉＡｌ）Ｎ被膜を被覆した比較品に対比して、被膜の耐
剥離性が優れており、かつ被膜自体が高硬度，高靭性，
耐摩耗性，耐酸化性，耐熱衝撃性，耐欠損性，耐溶着性
を有していることから、この分野での中速切削領域から
高速切削領域に相当する領域において、長寿命になると
いう効果がある。したがって、本発明の高強度被覆部材
は、従来の被覆部材の領域である低速切削領域から高速
切削領域に至るまで広い領域で長寿命を達成できるとい
う優れた効果があること、特にエンドミルおよびドリル
として長寿命が得られるという効果があること、また高
靭性および高硬度な被膜を被覆した被覆部材であること
から、軽切削領域から重切削領域においても優れた効果
を発揮できるものである。The high-strength covering member of the present invention has the conventional (T
Compared to the comparative product coated with iAl) N coating, the coating has excellent peel resistance, and the coating itself has high hardness and high toughness.
It has wear resistance, oxidation resistance, thermal shock resistance, chipping resistance, and welding resistance, so it is said that it will have a long life in the area corresponding to the medium-speed cutting area to the high-speed cutting area in this field. effective. Therefore, the high-strength covering member of the present invention has an excellent effect that a long life can be achieved in a wide area from a low speed cutting area to a high speed cutting area, which is an area of a conventional covering member, particularly as an end mill and a drill. Since it has an effect of obtaining a long life and is a covering member coated with a film having high toughness and high hardness, it can exhibit an excellent effect also in a light cutting region to a heavy cutting region.
Claims (8)
複合窒化物，複合炭窒化物，複合窒酸化物，複合炭窒酸
化物の中の１種以上の単層または多層でなる硬質膜が被
覆された被覆部材において、該基材と該硬質膜との間に
周期律表の４ａ，５ａ，６ａ族金属の炭化物，窒化物お
よびこれらの相互固溶体の中の１種の単層または２種以
上の多層でなる中間層を介在させて、該基材と該中間層
との界面または／および該中間層と該硬質膜との界面が
ヘテロエピタキシャル関係を保つように被覆されている
ことを特徴とする結晶配向性高強度被覆部材。1. A hard film composed of a single layer or a multilayer of one or more of a composite nitride containing titanium and aluminum, a composite carbonitride, a composite oxynitride, and a composite oxycarbonitride on a substrate. In the coated covering member, between the base material and the hard film, a single layer or two kinds of carbides, nitrides and mutual solid solutions of 4a, 5a and 6a metals in the periodic table. The interface between the base material and the intermediate layer and / or the interface between the intermediate layer and the hard film is coated so as to maintain a heteroepitaxial relationship with the intermediate layer consisting of the above multi-layers interposed. A crystal-oriented high-strength covering member having
わされるチタンとアルミニウムとを含む複合窒化物，複
合炭窒化物の１種以上の単層または多層でなることを特
徴とする請求項１記載の結晶配向性高強度被覆部材。 （Ｔｉa、Ａｌb）ＣyＮ1-y −−−−（Ａ） ［但し、（Ａ）式中のＴｉはチタン、Ａｌはアルミニウ
ムを示し、ａ、ｂはそれぞれＴｉおよびＡｌの原子比
を、ｙは炭素の原子比を表す。また、ａ＋ｂ＝１、０．
２５≦ａ≦０．７５、 ０≦ｙ≦０．９５の関係にあ
る］2. The hard film is formed of a single layer or a multi-layer of one or more of composite nitrides and composite carbonitrides substantially containing titanium and aluminum represented by the following formula (A). The crystal-oriented high-strength covering member according to claim 1. (Ti a , Al b ) C y N 1-y --- (A) [wherein Ti in the formula (A) is titanium, Al is aluminum, and a and b are atomic ratios of Ti and Al, respectively. And y represents the atomic ratio of carbon. Further, a + b = 1, 0.
25 ≦ a ≦ 0.75, 0 ≦ y ≦ 0.95]
中におけるａおよびｙがそれぞれ０．４≦ａ≦０．６お
よび０≦ｙ≦０．２の関係を満足することを特徴とする
請求項２記載の結晶配向性高強度被覆部材。3. The hard film represented by the formula (A) is characterized in that a and y in the formula satisfy the relations 0.4 ≦ a ≦ 0.6 and 0 ≦ y ≦ 0.2, respectively. The crystal-oriented high-strength covering member according to claim 2.
なることを特徴とする請求項１，２または３記載の結晶
配向性高強度被覆部材。4. The crystal-oriented high-strength covering member according to claim 1, wherein the hard film has a film thickness of 1 to 10 μm.
ｍでなることを特徴とする請求項１，２，３，または４
記載の結晶配向性高強度被覆部材。5. The intermediate layer has a thickness of 0.01 to 1 μm.
5. The method according to claim 1, 2, 3, or 4,
A high-strength covering member having crystal orientation described in the above.
は炭窒化チタンからなり、上記基材と接する該中間層面
の２０％以上の（１−１１）結晶面が該基材表面を構成
する結晶粒の（０００１）結晶面と平行でなり、かつ該
中間層の＜１１０＞結晶方向が該基材の＜１１−２０＞
結晶方向と平行であり、該中間層が上記硬質膜と接する
面の２０％以上の（１−１１）結晶面が該硬質膜を構成
する結晶粒の（１−１１）結晶面と平行でなり、かつ該
中間層の＜１１０＞結晶方向が該硬質膜の＜１１０＞結
晶方向と平行であることを特徴とする請求項１．２．
３．４または５記載の結晶配向性高強度被覆部材。6. The crystal, wherein the intermediate layer is made of titanium nitride and / or titanium carbonitride, and 20% or more of (1-11) crystal planes of the intermediate layer surface in contact with the base material constitute the surface of the base material. Grains are parallel to the (0001) crystal plane, and the <110> crystal direction of the intermediate layer is <11-20> of the base material.
20% or more of the plane in which the intermediate layer is in contact with the hard film is parallel to the crystal direction, and the (1-11) crystal plane of the crystal grains constituting the hard film is parallel to the (1-11) crystal plane. And the <110> crystal direction of the intermediate layer is parallel to the <110> crystal direction of the hard film.
3.4. The crystallographically-oriented high-strength covering member according to 4 or 5.
晶で構成され、上記中間層と接する該基材表面の２０％
以上が（０００１）結晶面でなり、該基材表面の（００
０１）結晶面が該中間層を構成する結晶粒の（１−１
１）結晶面と平行でなり、かつ該基材表面の＜１１−２
０＞結晶方向が該中間層の＜１１０＞結晶方向と平行で
あることを特徴とする請求項１，２，３，４，５または
６記載の結晶配向性高強度被覆部材。7. The surface of the base material is mainly composed of hexagonal crystals, and 20% of the surface of the base material is in contact with the intermediate layer.
The above is the (0001) crystal face, and the (00
01) The crystal plane of (1-1) of the crystal grains constituting the intermediate layer.
1) parallel to the crystal plane and <11-2 on the surface of the substrate
The crystallographically-oriented high-strength covering member according to claim 1, 2, 3, 4, 5 or 6, wherein the 0> crystallographic direction is parallel to the <110> crystallographic direction of the intermediate layer.
として含有する超硬合金からなることを特徴とする請求
項１，２，３，４，５，６または７記載の結晶配向性高
強度被覆部材。8. The crystallographically-oriented high strength according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the base material is made of a cemented carbide containing tungsten carbide as a main component. Cover member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34830995A JP3333081B2 (en) | 1995-12-18 | 1995-12-18 | Crystal orientation high strength coated member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34830995A JP3333081B2 (en) | 1995-12-18 | 1995-12-18 | Crystal orientation high strength coated member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09170068A true JPH09170068A (en) | 1997-06-30 |
| JP3333081B2 JP3333081B2 (en) | 2002-10-07 |
Family
ID=18396165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34830995A Expired - Fee Related JP3333081B2 (en) | 1995-12-18 | 1995-12-18 | Crystal orientation high strength coated member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3333081B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002513087A (en) * | 1998-04-29 | 2002-05-08 | ユナキス・トレーディング・アクチェンゲゼルシャフト | Tools or mechanical parts and methods for increasing the wear resistance of such parts |
| WO2003037554A1 (en) * | 2001-10-30 | 2003-05-08 | Mitsubishi Materials Kobe Tools Corporation | Surface coated cemented carbide cutting tool having hard coating layer exhibiting excellent wear resistance in high speed machining |
| JP2005199420A (en) * | 2003-12-18 | 2005-07-28 | Hitachi Tool Engineering Ltd | Hard film coated tool |
| JP2005205592A (en) * | 2003-12-26 | 2005-08-04 | Hitachi Tool Engineering Ltd | Hard coating film coated tool |
| US7094479B2 (en) * | 2002-01-21 | 2006-08-22 | Mitsubishi Materials Kobe Tools Corporation | Surface-coated cutting tool member having hard coating layer exhibiting superior wear resistance during high speed cutting operation and method for forming hard coating layer on surface of cutting tool |
| CN100453221C (en) * | 2001-10-30 | 2009-01-21 | 三菱麻铁里亚尔株式会社 | Surface coated cemented carbide cutting tool |
| JP2012016797A (en) * | 2010-07-09 | 2012-01-26 | Mitsubishi Materials Corp | Surface coated cutting tool with hard coating layer excellent in chipping resistance and peeling resistance |
| WO2022244342A1 (en) * | 2021-05-20 | 2022-11-24 | 住友電工ハードメタル株式会社 | Cutting tool |
-
1995
- 1995-12-18 JP JP34830995A patent/JP3333081B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002513087A (en) * | 1998-04-29 | 2002-05-08 | ユナキス・トレーディング・アクチェンゲゼルシャフト | Tools or mechanical parts and methods for increasing the wear resistance of such parts |
| WO2003037554A1 (en) * | 2001-10-30 | 2003-05-08 | Mitsubishi Materials Kobe Tools Corporation | Surface coated cemented carbide cutting tool having hard coating layer exhibiting excellent wear resistance in high speed machining |
| US7150925B2 (en) | 2001-10-30 | 2006-12-19 | Mitsubishi Materials Kobe Tools Corporation | Surface coated cemented carbide cutting tool having hard coating layer exhibiting excellent wear resistance in high speed machining |
| CN100453221C (en) * | 2001-10-30 | 2009-01-21 | 三菱麻铁里亚尔株式会社 | Surface coated cemented carbide cutting tool |
| US7094479B2 (en) * | 2002-01-21 | 2006-08-22 | Mitsubishi Materials Kobe Tools Corporation | Surface-coated cutting tool member having hard coating layer exhibiting superior wear resistance during high speed cutting operation and method for forming hard coating layer on surface of cutting tool |
| JP2005199420A (en) * | 2003-12-18 | 2005-07-28 | Hitachi Tool Engineering Ltd | Hard film coated tool |
| JP2005205592A (en) * | 2003-12-26 | 2005-08-04 | Hitachi Tool Engineering Ltd | Hard coating film coated tool |
| JP2012016797A (en) * | 2010-07-09 | 2012-01-26 | Mitsubishi Materials Corp | Surface coated cutting tool with hard coating layer excellent in chipping resistance and peeling resistance |
| CN102371378A (en) * | 2010-07-09 | 2012-03-14 | 三菱综合材料株式会社 | Surface wrapping cutting tool having excellent defect resistance and stripping resistance of hard wrapping layer |
| WO2022244342A1 (en) * | 2021-05-20 | 2022-11-24 | 住友電工ハードメタル株式会社 | Cutting tool |
| JPWO2022244342A1 (en) * | 2021-05-20 | 2022-11-24 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3333081B2 (en) | 2002-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3420024B2 (en) | Laminated coating member including crystal oriented hard film | |
| JP3452726B2 (en) | Multi-layer coated hard tool | |
| KR100674773B1 (en) | Hard films, multilayer hard films, and production methods thereof | |
| JP2002543992A (en) | PVD coated cutting tool and method for manufacturing the same | |
| JP2015037834A (en) | Surface coated cutting tool | |
| JP3249277B2 (en) | Wear resistant coating | |
| KR20060046478A (en) | Hard coating and its production method | |
| JP3333081B2 (en) | Crystal orientation high strength coated member | |
| WO2021069492A1 (en) | A coated cutting tool | |
| JPH10317123A (en) | Crystalline oriented hard coated member | |
| JP3333080B2 (en) | High-strength coated members with consistent interfaces | |
| JP3358696B2 (en) | High strength coating | |
| JP3159572B2 (en) | High-strength coated object | |
| JP3130734B2 (en) | Heat resistant coating | |
| JP2002370105A (en) | Aluminum oxide coated-tool | |
| JP3179645B2 (en) | Wear resistant coating | |
| JPH08281502A (en) | Crystal orientating coated tool | |
| JPH0820871A (en) | Wear resistant coating member | |
| JP3460571B2 (en) | Milling tool with excellent wear resistance | |
| JPH0827562A (en) | Oxidation resistant coated member | |
| JP2002273607A (en) | Multilayer coat tool | |
| JP3337884B2 (en) | Multilayer coating member | |
| JP2867605B2 (en) | Surface-coated hard members for cutting tools and wear-resistant tools | |
| JP3347247B2 (en) | High toughness coating | |
| JP3347244B2 (en) | High toughness coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020716 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090726 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100726 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100726 Year of fee payment: 8 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100726 Year of fee payment: 8 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100726 Year of fee payment: 8 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100726 Year of fee payment: 8 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |