JP2002038205A - Coated cemented carbide having hard composite layer and its production method - Google Patents
Coated cemented carbide having hard composite layer and its production methodInfo
- Publication number
- JP2002038205A JP2002038205A JP2000226253A JP2000226253A JP2002038205A JP 2002038205 A JP2002038205 A JP 2002038205A JP 2000226253 A JP2000226253 A JP 2000226253A JP 2000226253 A JP2000226253 A JP 2000226253A JP 2002038205 A JP2002038205 A JP 2002038205A
- Authority
- JP
- Japan
- Prior art keywords
- hard
- composite layer
- cemented carbide
- hard composite
- carbide
- 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.)
- Withdrawn
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- Drilling Tools (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Powder Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、チップ，ドリル，
エンドミルに代表される切削工具や各種の耐摩耗工具・
部品に使用される被覆超硬合金とその製造方法に関し、
具体的には、超硬合金表面に結合相が含有されていない
硬質複合層を形成させることにより、耐摩耗性，耐塑性
変形性，膜の密着性を改善して工具寿命を向上させた硬
質複合層を有する被覆超硬合金に関し、また、超硬合金
表面から均一に結合相を除去した後に硬質膜被覆処理を
施することにより、硬質複合層を形成させながら硬質膜
を連続被覆した硬質複合層を有する被覆超硬合金の製造
方法に関するものである。TECHNICAL FIELD The present invention relates to a tip, a drill,
Cutting tools such as end mills and various wear-resistant tools
Regarding coated cemented carbide used for parts and its manufacturing method,
Specifically, by forming a hard composite layer containing no binder phase on the surface of a cemented carbide, the wear resistance, the plastic deformation resistance, and the adhesion of the film are improved to improve the tool life. Regarding coated cemented carbide having a composite layer, and by applying a hard film coating process after uniformly removing the binder phase from the surface of the cemented carbide, a hard composite in which a hard film is continuously coated while forming a hard composite layer The present invention relates to a method for producing a coated cemented carbide having a layer.
【０００２】[0002]
【従来の技術】超硬合金母材にＴｉＣ，ＴｉＣＮ，Ｔｉ
Ｎ，Ａｌ2Ｏ3などの硬質膜を被覆してなる被覆超硬合金
は、母材の強度，靱性と硬質膜の耐摩耗性を兼備してい
るため、切削工具や耐摩耗工具，部品として多用されて
いる。しかし、母材の耐塑性変形性や膜との密着性が劣
ると、使用時の刃先変形や膜剥離によって急激に摩耗し
て寿命が低下する。塑性変形に関しては、一般に母材の
結合相Ｃｏの低減、ＷＣの粗粒化などの方法による改善
が採られているが、強度や靱性が低下して欠損やチッピ
ングを起こし易くなると言う問題がある。一方、密着性
に関しては、母材表面の調整処理，下地層の膜質選定，
下地層のコーティング条件最適化などの方法が試みられ
ているが、母材成分と硬質膜成分が異なるために母材／
硬質膜界面での脆化層の生成、母材と膜との熱膨張差に
よる応力発生などの問題があるために根本的な改善に至
ってない。そこで、母材表面近傍を改質して耐塑性変形
性の改善を試みた先行技術には、特開平２−２２４５３
号公報，特開昭６３−２２９０３号公報などが、表面処
理による密着性改善には、特開昭６３−６０２８０号公
報，特表平１１−５１０８５８号公報などがある。2. Description of the Related Art TiC, TiCN, Ti
Coated cemented carbide made by coating a hard film such as N, Al 2 O 3 has both the strength and toughness of the base material and the wear resistance of the hard film. It is heavily used. However, when the plastic deformation resistance of the base material and the adhesion to the film are poor, the edge is deformed during use or the film is peeled off, and the life is shortened due to rapid wear. With respect to plastic deformation, improvements are generally made by methods such as reduction of the binder phase Co of the base material and coarsening of WC, but there is a problem that the strength and toughness are reduced, so that chipping and chipping are likely to occur. . On the other hand, regarding adhesion, adjustment processing of base material surface, selection of film quality of underlayer,
Attempts have been made to optimize the coating conditions of the underlayer, but the base material component and the hard film component are different,
Fundamental improvements have not been achieved due to problems such as formation of an embrittled layer at the interface of the hard film and generation of stress due to a difference in thermal expansion between the base material and the film. Therefore, prior arts that have attempted to improve the plastic deformation resistance by modifying the vicinity of the base material surface include Japanese Patent Application Laid-Open No. H2-222453.
Japanese Patent Application Laid-Open No. 63-22093 and Japanese Patent Application Laid-Open No. Sho 63-22903, and Japanese Patent Application Laid-Open No. Sho 63-510858 and Japanese Patent Application Laid-Open No. H11-510858 disclose improvements in adhesion by surface treatment.
【０００３】[0003]
【発明が解決しようとする課題】先行技術である母材表
面近傍の改質に関し、特開平２−２２４５３号公報に
は、表面部に、内部から表面に向かってＣｏ量が連続的
に減少、硬さが連続的に増加する表面硬質層を形成した
ＷＣ基超硬合金基体の表面に、Ｔｉ，Ｚｒ，Ｈｆの炭化
物，窒化物などや酸化アルミニウムを０．５〜２０μｍ
の平均層厚で被覆した切削工具用表面被覆炭化タングス
テン基超硬合金が開示されている。この公報に開示され
ている被覆超硬合金母材は、表面近傍が硬化されている
ために切削時の耐塑性変形性は向上するものの、母材と
被覆膜との密着性は変わらず、熱応力の発生はむしろ大
きくなると言う問題がある。With respect to the prior art modification of the vicinity of the base material surface, Japanese Patent Application Laid-Open No. 22453/1990 discloses that the amount of Co continuously decreases from the inside toward the surface. On a surface of a WC-based cemented carbide substrate on which a surface hard layer having a continuously increasing hardness is formed, a carbide, a nitride, or the like of Ti, Zr, Hf, or aluminum oxide is applied in an amount of 0.5 to 20 μm.
Surface-coated tungsten carbide-based cemented carbide for cutting tools coated with an average layer thickness of The coated cemented carbide base material disclosed in this publication improves the plastic deformation resistance during cutting because the surface vicinity is hardened, but the adhesion between the base material and the coating film does not change, There is a problem that the generation of thermal stress is rather large.
【０００４】また、特開昭６３−２２９０３号公報に
は、内部組成がＷＣとＣｏとＴｉおよびＷを主成分とす
る複合金属炭窒化物とからなり、表面部には該複合金属
炭窒化物を含有しない５〜２０μｍのＣｏ富化層を介し
て、平均層厚が０．０１〜５μｍの該複合金属炭窒化物
のみからなる硬質表面層を存在させた超硬合金表面に、
炭化チタン，窒化チタン，炭窒化チタン，酸化アルミニ
ウムなどを順次被覆した表面被覆超硬合金製切削工具が
開示されている。この公報に開示されている被覆超硬合
金母材は、表面近傍が複合金属炭窒化物により硬化され
て耐塑性変形性を向上させ、また複合金属炭窒化物の介
在により母材と被覆膜との密着性も改善される。しか
し、複合金属炭窒化物は硬脆く、また熱膨張係数が大き
くて母材との間に高い残留応力を生じるために、切削時
の熱および機械的衝撃によって逆に膜剥離を起こし易く
なると言う問題がある。Japanese Patent Application Laid-Open No. 63-22903 discloses that a composite metal carbonitride having an internal composition of WC, Co, Ti and W as main components is provided on the surface thereof. Through a Co-enriched layer of 5-20 μm containing no, on the surface of a cemented carbide having a hard surface layer consisting of only the composite metal carbonitride having an average layer thickness of 0.01-5 μm,
A cutting tool made of a surface-coated cemented carbide, which is sequentially coated with titanium carbide, titanium nitride, titanium carbonitride, aluminum oxide, etc., is disclosed. In the coated cemented carbide base material disclosed in this publication, the vicinity of the surface is hardened by the composite metal carbonitride to improve the plastic deformation resistance, and the base metal and the coating film are interposed by the composite metal carbonitride. Is also improved. However, it is said that composite metal carbonitrides are hard and brittle, and have a large thermal expansion coefficient and a high residual stress between them and the base material. There's a problem.
【０００５】一方、先行技術の内、表面処理による密着
性改善に関し、特開昭６３−６０２８０号公報には、予
め超硬合金基体の表面を酸にてエッチングして表面部の
結合相を除去した後、硬質被覆層を化学蒸着法にて形成
する表面被覆炭化タングステン基超硬合金の製造方法が
開示されている。この公報に開示された方法は、約１０
００℃の高温で行われる化学蒸着中での反応ガスによる
表面清浄化が不十分なために、前処理として酸洗浄を行
って超硬合金表面の結合相をエッチング除去することに
より、硬質被覆層との付着強度を高めたものである。し
かし、結合相の除去過多による巣孔発生や最表面のＷＣ
層（結合相無し）と硬質被覆層との熱膨張差による熱応
力発生の問題がある。On the other hand, of the prior art, concerning the improvement of adhesion by surface treatment, Japanese Patent Application Laid-Open No. 63-60280 discloses that the surface of a cemented carbide substrate is etched in advance with an acid to remove a binder phase on the surface. After that, a method for producing a surface-coated tungsten carbide-based cemented carbide in which a hard coating layer is formed by a chemical vapor deposition method is disclosed. The method disclosed in this publication is about 10
Due to insufficient cleaning of the surface by the reaction gas during the chemical vapor deposition performed at a high temperature of 00 ° C., the hard coating layer was formed by performing acid cleaning as a pretreatment to remove the binder phase on the cemented carbide surface by etching. The adhesive strength of the adhesive is increased. However, the formation of pits due to excessive removal of the binder phase and the WC on the outermost surface
There is a problem of thermal stress generation due to a difference in thermal expansion between the layer (without a binding phase) and the hard coating layer.
【０００６】また、特表平１１−５１０８５８号公報に
は、表面を電解処理により最大１０μｍまでの深さに亘
ってバインダー相が除去されたカーバイド支持体にダイ
ヤモンド膜を被覆する超硬合金支持体の処理方法が開示
されている。この公報に開示された方法は、支持体表面
でのバインダー相（Ｃｏ，Ｎｉ）の存在による非ダイヤ
モンド構造の炭素生成を抑制してダイヤモンド膜との密
着性を向上させるもので、上記公報と同様の問題があ
る。Further, Japanese Patent Application Laid-Open No. 11-510858 discloses a cemented carbide support in which a diamond film is coated on a carbide support from which the binder phase has been removed over a depth of up to 10 μm by electrolytic treatment. Is disclosed. The method disclosed in this publication suppresses the generation of carbon having a non-diamond structure due to the presence of a binder phase (Co, Ni) on the surface of a support to improve the adhesion to a diamond film. There is a problem.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、表面被覆
超硬合金について長年に亘り、母材表面近傍の塑性変形
性を向上させると共に、膜との密着性を大幅に改善させ
る方法について検討していた所、超硬合金母材表面に結
合相が無くて硬質相粒子と硬質膜粒子とからなる複合硬
質複合層を設けた後に硬質膜を被覆すると、硬質複合層
が母材の塑性変形を抑制すると同時に、硬質膜との密着
性や耐摩耗性をも向上させること、また、母材表面から
均一に結合相を除去した後に硬質膜を被覆すれば、結合
相と硬質膜成分が置換された硬質複合層が形成され、結
合相が除去されてできた微細な連続巣孔に硬質膜成分を
注入するには、比較的低温でのＣＶＤ法が最適であると
言う知見を得て、本発明を完成するに至ったものであ
る。SUMMARY OF THE INVENTION The present inventors have, for many years, studied a method of improving the plastic deformation near the surface of a base material and significantly improving the adhesion to a film of a surface-coated cemented carbide. When the hard film was coated after providing a composite hard composite layer consisting of hard phase particles and hard film particles without a binder phase on the surface of the cemented carbide base material, the hard composite layer showed plasticity of the base material. At the same time as suppressing deformation, it is also necessary to improve the adhesion and wear resistance with the hard film, and if the hard film is coated after uniformly removing the binder phase from the base material surface, the binder phase and the hard film components will be In order to inject the hard film component into the fine continuous cavities formed by forming the substituted hard composite layer and removing the binder phase, it was found that the CVD method at a relatively low temperature was optimal. Thus, the present invention has been completed.
【０００８】本発明の硬質複合層を有する被覆超硬合金
は、炭化タングステン、あるいは炭化タングステンと周
期律表の４ａ，５ａ，６ａ族金属の炭化物，窒化物，炭
窒化物およびこれらの相互固溶体の中の１種以上からな
る立方晶化合物とを硬質相粒子、鉄族金属を結合相とす
る超硬合金を母材とし、該母材表面に周期律表の４ａ，
５ａ，６ａ族元素，アルミニウム，シリコンの炭化物，
窒化物，酸化物、およびこれらの相互固溶体の中から選
ばれた１種以上の化合物でなる単層または２層以上の積
層でなる０．５〜２０μｍの硬質膜を被覆してなる被覆
超硬合金において、該母材表面から内部に向かって３〜
２０μｍの深さに亘って、該結合相量が０．５重量％以
下で、かつ母材の該硬質相粒子と該硬質膜成分粒子とか
ら構成された均一な硬質複合層が存在することを特徴と
するものである。The coated cemented carbide having a hard composite layer according to the present invention is made of tungsten carbide or carbides, nitrides, carbonitrides of tungsten carbide and metals of groups 4a, 5a and 6a of the periodic table, and a mutual solid solution thereof. And a cubic compound composed of at least one of the above as a hard phase particle, and a cemented carbide having iron group metal as a binder phase.
5a, 6a group element, aluminum, silicon carbide,
Coated carbide formed by coating a single layer of at least one compound selected from nitrides, oxides, and mutual solid solutions thereof, or a hard film having a thickness of 0.5 to 20 μm and a laminate of two or more layers. In the alloy, 3 to 3
It is required that, over a depth of 20 μm, the amount of the binder phase is 0.5% by weight or less and a uniform hard composite layer composed of the hard phase particles of the base material and the hard film component particles is present. It is a feature.
【０００９】本発明の硬質複合層を有する被覆超硬合金
における母材は、具体的には、硬質相粒子が炭化タング
ステンのみからなるＷＣ−Ｃｏ系，ＷＣ−（ＮｉＣｒ）
系合金や、炭化タングステンと立方晶系化合物とからな
るＷＣ−ＴａＣ−Ｃｏ系，ＷＣ−（ＷＴｉＴａ）Ｃ−Ｃ
ｏ系，ＷＣ−（ＷＴｉＴａＮｂ）（ＣＮ）−Ｃｏ系合金
で、鉄族金属の結合相量として３〜３０体積％程度のも
のを挙げることができる。ここで、窒素あるいは酸素が
添加されているＷＣ−（ＷＴｉＴａ）（ＣＮ）−Ｃｏ
系，ＷＣ−（ＷＴｉＴａ）（ＣＯ）−Ｃｏ系合金などで
は、表面に立方晶系化合物がなくてＣｏ量が増加した５
〜３０μｍの強靱表面層が形成されている。The base material of the coated cemented carbide having a hard composite layer according to the present invention is, specifically, a WC-Co-based or WC- (NiCr) alloy in which the hard phase particles are composed only of tungsten carbide.
-Based alloy, WC-TaC-Co based on tungsten carbide and cubic compound, WC- (WTiTa) CC
An o-based, WC- (WTiTaNb) (CN) -Co-based alloy having a bonding phase amount of about 3 to 30% by volume of the iron group metal can be used. Here, WC- (WTiTa) (CN) -Co to which nitrogen or oxygen is added
, A WC- (WTiTa) (CO) -Co-based alloy, etc., has no cubic compound on its surface and the amount of Co increases.
A tough surface layer of ３０30 μm is formed.
【００１０】また硬質膜は、具体的には、化学蒸着法あ
るいは物理蒸着法で作製される０．５〜２０μｍの厚み
でなるＴｉＣ，ＴｉＣＮ，ＴｉＮ，（ＴｉＺｒ）Ｎ，
（ＴｉＡｌ）Ｎ，ＣｒＮなどの単層膜や、母材側からＴ
ｉＣ／ＴｉＮ／ＴｉＣＮ／ＴｉＮ，ＴｉＮ／ＴｉＣ／Ａ
ｌ2Ｏ3，ＴｉＮ／ＴｉＣＮ／ＴｉＣ／Ａｌ2Ｏ3／Ｔｉ
Ｎ，ＴｉＮ／（ＴｉＡｌ）Ｎ／ＴｉＮ，ＴｉＮ／Ｓｉ3
Ｎ4，ＣｒＮ／ＶＮなどの積層膜を挙げることができ
る。ここで、硬質膜の厚みは、０．５μｍ未満では硬質
複合膜の効果のみで、耐摩耗性が不十分であり、２０μ
ｍを超えて厚くなると強度低下が著しくて耐欠損性，耐
チッピング性に劣る。[0010] The hard film is specifically made of TiC, TiCN, TiN, (TiZr) N, having a thickness of 0.5 to 20 µm, which is produced by a chemical vapor deposition method or a physical vapor deposition method.
(TiAl) N, CrN or other single-layer film, or T
iC / TiN / TiCN / TiN, TiN / TiC / A
l 2 O 3 , TiN / TiCN / TiC / Al 2 O 3 / Ti
N, TiN / (TiAl) N / TiN, TiN / Si 3
A laminated film of N 4 , CrN / VN, or the like can be given. Here, if the thickness of the hard film is less than 0.5 μm, only the effect of the hard composite film is obtained, and the wear resistance is insufficient.
When the thickness exceeds m, the strength is remarkably reduced and the chipping resistance and chipping resistance are poor.
【００１１】本発明の硬質複合層を有する被覆超硬合金
における硬質複合層は、ＷＣおよびＴａＣ，（ＷＴｉＴ
ａ）Ｃ，（ＷＴｉＴａＮｂ）（ＣＮ）などの超硬合金中
の硬質相粒子とＴｉＣ，ＴｉＣＮ，ＴｉＮ，ＺｒＮ，Ａ
ｌ2Ｏ3，ＡｌＮ，ＳｉＣ，Ｓｉ3Ｎ4など化学蒸着法によ
って得られる硬質膜成分粒子との混合物で、具体的に
は、ＷＣとＴｉＮ，ＷＣとＡｌ2Ｏ3，ＷＣと（ＷＴｉＴ
ａ）ＣとＴｉＣＮなどの混合物であり、硬質相粒子は超
硬合金中と同一組成、同一粒径で存在し、硬質膜成分粒
子は超硬合金中では結合相であった部分に存在するもの
である。ここで、硬質複合膜の厚みは、３μｍ未満では
耐塑性変形と耐摩耗性の改善効果が低く、また２０μｍ
を超えて厚くなると、製作が困難で、かつ耐欠損性，耐
チッピング性が低下する。また、硬質複合層中での結合
相量は、２．０重量％を超えて多くなると、耐塑性変形
と耐摩耗性が低下する。The hard composite layer of the coated cemented carbide having the hard composite layer of the present invention is made of WC and TaC, (WTit
a) Hard phase particles in a cemented carbide such as C, (WTiTaNb) (CN) and TiC, TiCN, TiN, ZrN, A
A mixture of hard film component particles obtained by a chemical vapor deposition method such as l 2 O 3 , AlN, SiC, Si 3 N 4 , specifically, WC and TiN, WC and Al 2 O 3 , WC and (WTit
a) A mixture of C and TiCN, etc., in which the hard phase particles are of the same composition and the same particle size as in the cemented carbide, and the hard film component particles are present in the portion which was the binder phase in the cemented carbide. It is. Here, when the thickness of the hard composite film is less than 3 μm, the effect of improving plastic deformation and wear resistance is low, and 20 μm
If the thickness exceeds the limit, it is difficult to manufacture, and the chipping resistance and chipping resistance decrease. If the amount of the binder phase in the hard composite layer exceeds 2.0% by weight, the plastic deformation resistance and the wear resistance decrease.
【００１２】本発明の硬質複合層を有する被覆超硬合金
における硬質複合層は、硬質膜成分粒子が異なる複数層
からなると、硬質複合層に耐摩耗性、耐溶着性、耐塑性
変形性、強度など異なる性質を付加して性能が向上する
ので好ましい。具体的には、第１層（母材内部側から）
が２μｍの硬質膜成分粒子：ＴｉＮ、第２層が２μｍの
硬質膜成分粒子：Ａｌ2Ｏ3、第３層が１μｍの硬質膜成
分粒子：ＴｉＣを挙げることができる。また、硬質複合
層の硬質膜成分粒子がチタンの炭化物，窒化物，炭窒化
物および酸化アルミニウムの中の１種以上であると、硬
質複合層の製作が容易なこと、硬質膜との密着性が良好
なこと、切削性能のバランスが良いことなどのために好
ましい。When the hard composite layer of the coated cemented carbide having the hard composite layer according to the present invention is composed of a plurality of layers having different hard film component particles, the hard composite layer has abrasion resistance, welding resistance, plastic deformation resistance, and strength. It is preferable because different properties are added to improve the performance. Specifically, the first layer (from inside the base material)
Are 2 μm hard film component particles: TiN, the second layer is 2 μm hard film component particles: Al 2 O 3 , and the third layer is 1 μm hard film component particles: TiC. When the hard film component particles of the hard composite layer are one or more of titanium carbide, nitride, carbonitride, and aluminum oxide, the hard composite layer can be easily manufactured, and the adhesion to the hard film can be improved. Is preferable because of good balance of cutting performance.
【００１３】本発明の硬質複合層を有する被覆超硬合金
における母材は、硬質複合層から内部に向かって３〜２
０μｍの深さに亘って、結合相量が母材のさらに内部
（約１００μｍ）より多くなっている結合相富化層およ
び／又は立方晶化合物量が少ない立方晶化合物貧化層が
存在すると、耐塑性変形性を損なうことなく耐欠損性，
耐チッピング性が向上するので好ましい。すなわち、硬
質複合層中が厚くなった場合の欠点をカバーすることが
できる。The base material of the coated cemented carbide having the hard composite layer of the present invention is 3 to 2 inward from the hard composite layer.
When a binder phase-enriched layer and / or a cubic compound-poor layer with a small amount of cubic compound are present over a depth of 0 μm, the amount of the binder phase is greater than the inside of the base material (about 100 μm). Fracture resistance without impairing plastic deformation resistance,
It is preferable because chipping resistance is improved. That is, it is possible to cover the disadvantages when the thickness of the hard composite layer is increased.
【００１４】本発明の硬質複合層を有する被覆超硬合金
の製造方法は、炭化タングステン、あるいは炭化タング
ステンと周期律表の４ａ，５ａ，６ａ族金属の炭化物，
窒化物，炭窒化物およびこれらの相互固溶体の中の１種
以上からなる立方晶化合物とを硬質相粒子、鉄族金属を
結合相とする超硬合金において、該超硬合金の表面から
２〜２５μｍの深さに亘って該結合相を均一に除去して
連続空孔とした後、周期律表の４ａ，５ａ，６ａ族元
素，アルミニウム，シリコンの炭化物，窒化物，酸化
物、およびこれらの相互固溶体の中から選ばれた１種以
上の化合物で該連続空孔を封止することにより３〜２０
μｍの硬質複合層を形成させ、続けて該化合物の単層ま
たは２層以上の積層でなる０．５〜２０μｍの硬質膜を
被覆することを特徴とする製造方法である。The method for producing a coated cemented carbide having a hard composite layer according to the present invention comprises the steps of: providing tungsten carbide or a carbide of tungsten carbide and a group 4a, 5a or 6a metal of the periodic table;
In a cemented carbide having hard phase particles and a cubic compound comprising at least one of nitrides, carbonitrides and mutual solid solutions thereof, and a binder phase composed of an iron group metal, two to three After uniformly removing the binder phase over a depth of 25 μm to form continuous pores, elements 4a, 5a and 6a of the periodic table, aluminum, silicon carbides, nitrides, oxides, and the like By sealing the continuous pores with one or more compounds selected from mutual solid solutions, 3 to 20
A production method characterized by forming a hard composite layer having a thickness of μm, and subsequently coating a hard film having a thickness of 0.5 to 20 μm, which is a single layer or a laminate of two or more layers of the compound.
【００１５】本発明の硬質複合層を有する被覆超硬合金
の製造方法における超硬合金母材表面からの結合相の除
去方法は、具体的には、塩酸，硝酸，硫酸，りん酸など
無機酸による通常の浸漬処理を挙げることができるが、
ギ酸，酢酸，シュウ酸などの有機酸を用いた弱酸性水溶
液中での電解処理であると、超硬合金中の硬質粒子成分
の変質，溶解なしに、結合相だけを完全かつ表面から均
一に除去できるので好ましい。ここで、結合相が除去さ
れた超硬合金母材表面は、硬質粒子のみのスケルトンか
ら構成され、除去された結合相部が表面から連続した空
孔（通気孔）を形成しているものである。結合相の除去
深さは、硬質複合層の形成厚みに関係するが、形成時の
結合相移動を考慮すると、２〜２５μｍの範囲となる。The method for removing a binder phase from the surface of a cemented carbide base material in the method for producing a coated cemented carbide having a hard composite layer according to the present invention is carried out by specifically using an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid. Can be mentioned, but
Electrolytic treatment in a weakly acidic aqueous solution using an organic acid such as formic acid, acetic acid, or oxalic acid allows the binder phase to be completely and uniformly removed from the surface without altering or dissolving the hard particle components in the cemented carbide. It is preferable because it can be removed. Here, the surface of the cemented carbide base material from which the binder phase has been removed is composed of a skeleton of only hard particles, and the removed binder phase forms pores (vents) continuous from the surface. is there. The removal depth of the binder phase is related to the formation thickness of the hard composite layer, but is in the range of 2 to 25 μm in consideration of the binder phase movement during the formation.
【００１６】本発明の硬質複合層を有する被覆超硬合金
の製造方法における硬質複合層の形成方法は、具体的に
は、表面に連続空孔を有する超硬合金母材をＣＶＤ法で
もって該連続空孔を封止するものである。ＣＶＤ法は微
細孔中にも反応ガスが浸入して硬質物質を析出させるこ
とができるので、結合相が除去された超硬合金母材表面
に硬質粒子のスケルトンとＣＶＤにより析出した硬質物
質とからなる硬質複合層を形成させることができる。こ
こで、ＣＶＤ方法が有機金属化合物を使用したＭＯＣＶ
Ｄ，低温あるいは中温ＣＶＤ，プラズマＣＶＤなどであ
ると、硬質複合層中への結合相移動が無いこと、超硬合
金中の硬質粒子とＣＶＤ析出した硬質物質との反応が少
ないこと、緻密で微細粒子の硬質物質となるなどのため
に、硬さと靱性に優れた硬質複合膜が得られるので好ま
しい。The method for forming a hard composite layer in the method for producing a coated cemented carbide having a hard composite layer according to the present invention is, specifically, a method in which a cemented carbide base material having continuous pores on its surface is formed by CVD. This seals the continuous holes. In the CVD method, the reaction gas can penetrate into the fine pores to precipitate a hard substance. Therefore, the skeleton of the hard particles and the hard substance deposited by the CVD on the surface of the cemented carbide base material from which the binder phase has been removed. A hard composite layer can be formed. Here, the MOCV using the organometallic compound is used for the CVD method.
D, low-temperature or medium-temperature CVD, plasma CVD, etc., no binding phase transfer into the hard composite layer, little reaction between hard particles in the cemented carbide and the hard substance deposited by CVD, dense and fine It is preferable because a hard composite film having excellent hardness and toughness can be obtained because it becomes a hard substance of particles.
【００１７】[0017]
【作用】本発明の硬質複合層を有する被覆超硬合金は、
母材表面近傍に結合相が無くて硬質相粒子と硬質膜粒子
とからなる硬質複合層を有し、形成させた硬質複合層が
母材の耐塑性変形性，被覆膜との密着性，耐摩耗性など
を向上させて工具寿命を延長させる作用をし、その製造
方法は、母材表面から均一に結合相を除去した後に被覆
処理する硬質膜成分が生成した連続空孔に浸入して超硬
合金母材中の硬質層粒子を再結合して硬質複合層を形成
するする作用をしているものである。The coated cemented carbide having the hard composite layer of the present invention is
There is no binder phase in the vicinity of the base material surface and there is a hard composite layer composed of hard phase particles and hard film particles, and the formed hard composite layer has plastic deformation resistance of the base material, adhesion to the coating film, It works to extend tool life by improving wear resistance and the like, and its manufacturing method is to remove the binder phase uniformly from the base material surface and then penetrate into the continuous pores where the hard film components to be coated are generated. It functions to combine the hard layer particles in the cemented carbide base material to form a hard composite layer.
【００１８】[0018]
【実施例１】市販されている平均粒子径が３．０μｍの
ＷＣ（ＷＣ（Ｌ）と記す）と１．５μｍのＷＣ（ＷＣ
（Ｓ）と記す），１．５μｍの（ＷＴｉＴａ）Ｃ（重量
比でＷＣ／ＴｉＣ／ＴａＣ＝５０／２０／３０の複合炭
化物），１．３μｍのＴｉＣＮ（重量比でＴｉＣ／Ｔｉ
Ｎ＝５０／５０），１．０μｍのＴａＣ，１．２μｍの
Ｃｏの各粉末を用いて、表１に示す配合組成に秤量し、
ステンレス製ポットにアセトン溶媒と超硬合金製ボール
と共に挿入し、４８時間混合粉砕後、加熱・乾燥しなが
ら２重量％のパラフィンワックスを添加してＷ〜Ｚの混
合粉末を得た。Ｗ，Ｘ，Ｙの粉末をＩＳＯ規格でＳＮＭ
Ｎ１２０４０８（ブレーカ付き）の形状用金型に、Ｚの
粉末はＳＮＧＮ１２０４０８の形状用金型に充填し、２
ｔｏｎ／ｃｍ2の圧力でもってプレス成形した後、アル
ミナとカーボン繊維からなるシート上に設置し、雰囲気
圧力１０Ｐａの真空中で、１６７３Ｋに１時間加熱保持
して、それぞれの切削用チップ素材を得た。得られたチ
ップの各１個のコーナ部付近を切断した後、１０００＃
のダイヤモンドホィールでの研削と１μｍダイヤモンド
ペーストでのラップ仕上により断面観察試料を作製し、
光学顕微鏡により表面付近の組織を観察して、（ＷＴｉ
Ｔａ）Ｃ粒子の存在しない層の表面からの厚さ（脱β層
厚み）を測定した。その結果を表１に併記した。Example 1 A commercially available WC having an average particle diameter of 3.0 μm (hereinafter referred to as WC (L)) and a WC having an average particle diameter of 1.5 μm (WC
(S)), 1.5 μm of (WTiTa) C (composite carbide of WC / TiC / TaC = 50/20/30 by weight ratio), 1.3 μm of TiCN (TiC / Ti by weight ratio)
N = 50/50), 1.0 μm of TaC and 1.2 μm of Co powder were weighed to the composition shown in Table 1,
Acetone solvent and a cemented carbide ball were inserted into a stainless steel pot, mixed and pulverized for 48 hours, and 2% by weight of paraffin wax was added while heating and drying to obtain a mixed powder of W to Z. Powder of W, X, Y is SNM according to ISO standard
N120408 (with a breaker) in a shape mold, Z powder is filled in a SNGN120408 shape mold, and
After press-molding at a pressure of ton / cm 2 , it was placed on a sheet made of alumina and carbon fiber, and heated and maintained at 1673K for 1 hour in a vacuum at an atmospheric pressure of 10 Pa to obtain each cutting chip material. Was. After cutting the vicinity of each one corner of each obtained chip, 1000 #
A cross-sectional observation sample was prepared by grinding with a diamond wheel and lapping with 1 μm diamond paste.
Observing the structure near the surface with an optical microscope, (WTi
Ta) The thickness from the surface of the layer where no C particles existed (thickness of the β-removed layer) was measured. The results are shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】そして、Ｗ，Ｘ，Ｙのチップ素材を用い、
ボス面を２７０＃のダイヤモンド砥石で研削加工した
後、刃先部を３２０＃の炭化けい素砥粒を含有したナイ
ロン製ブラシで半径０．０４ｍｍのホーニング加工し、
また、Ｚのチップ素材を用い、上下面と外周面を２７０
＃のダイヤモンド砥石で研削加工した後、刃先部に４０
０＃ダイヤモンド砥石で−２５°×０．１０ｍｍのホー
ニング加工して、被覆超硬合金用の母材チップを得た。
次いで、表２に示した方法と条件で表面処理を行いアセ
トン中で超音波洗浄した後、ＣＶＤコーティング装置を
用いて表３に記載したガス成分，温度，時間でＣＶＤ被
覆処理を順次行って、本発明品１〜１１と比較品１〜７
の被覆超硬工具チップを得た。尚、表面処理によって形
成される結合相除去層の厚みを確認するため、処理後
（ＣＶＤ被覆処理前）のチップの断面組織を観察し、そ
の結果を表２に併記した。ここで、各チップへの被覆処
理には統一性があり、硬質膜の構成を同一にしてある。
本発明品１〜８と比較品１〜５での最内層を除く硬質膜
は、最外層から内層側に向かって、０．３μｍのＴｉ
Ｎ，２．０μｍのＡｌ2Ｏ3，０．２μｍのＴｉＣＯ，
８．０μｍのＴｉＣＮの順に計８．５μｍ、本発明品９
〜１１と比較品６，７では、最外層から内層側に向かっ
て０．２μｍのＴｉＮ，１．０μｍのＡｌ2Ｏ3，０．２
μｍのＴｉＮ，３．０μｍのＴｉＣＮの順に計４．４μ
ｍとなるように調整されている。Then, using W, X, and Y chip materials,
After grinding the boss surface with a 270 # diamond grindstone, the cutting edge is honed with a radius of 0.04 mm with a nylon brush containing 320 # silicon carbide abrasive grains,
Also, using a Z chip material, the upper and lower surfaces and the outer peripheral surface are 270
# After grinding with a diamond grindstone, 40
Honing was performed at -25 ° × 0.10 mm with a 0 # diamond grindstone to obtain a base metal chip for a coated cemented carbide.
Next, after performing a surface treatment under the method and conditions shown in Table 2 and performing ultrasonic cleaning in acetone, a CVD coating treatment was sequentially performed using a CVD coating apparatus at the gas components, temperature, and time described in Table 3, Inventive products 1 to 11 and comparative products 1 to 7
A coated carbide tool tip was obtained. In order to confirm the thickness of the binder phase removal layer formed by the surface treatment, the cross-sectional structure of the chip after the treatment (before the CVD coating treatment) was observed, and the results are shown in Table 2. Here, the coating process on each chip has uniformity, and the configuration of the hard film is the same.
The hard films of the present invention products 1 to 8 and the comparative products 1 to 5 except for the innermost layer have a thickness of 0.3 μm from the outermost layer toward the inner layer side.
N, 2.0 μm Al 2 O 3 , 0.2 μm TiCO,
A total of 8.5 μm in the order of 8.0 μm TiCN;
11 and the comparative products 6 and 7, 0.2 μm TiN, 1.0 μm Al 2 O 3 , 0.2 μm from the outermost layer toward the inner layer side.
μm TiN, 3.0 μm TiCN in order of 4.4 μm.
m.
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【表３】 *ガス組成 Ａ：Ｈ2＋ＴｉＣｌ4＋Ｎ2 Ｂ：Ｈ2＋ＴｉＣｌ4＋ＮＨ3 Ｃ：Ｈ2＋ＴｉＣｌ4＋ＣＨ4 Ｄ：Ｈ2＋ＴｉＣｌ4＋ＣＨ4＋ＣＯ Ｅ：Ｈ2＋ＴｉＣｌ4＋Ｎ2＋ＣＨ4 Ｆ：Ｈ2＋ＴｉＣｌ4＋ＣＨ3ＣＮ Ｇ：Ｈ2＋ＡＣｌ3＋ＣＯ2 Ｈ：Ａｒ＋ＭｅＣｌ2ＴｉＡｌ−ＯＥｔ2(メチルアルミニウムクロライド-ジ エチルエチレート) [Table 3] * Gas composition A: H 2 + TiCl 4 + N 2 B: H 2 + TiCl 4 + NH 3 C: H 2 + TiCl 4 + CH 4 D: H 2 + TiCl 4 + CH 4 + CO E: H 2 + TiCl 4 + N 2 + CH 4 F: H 2 + TiCl 4 + CH 3 CN G: H 2 + ACl 3 + CO 2 H: Ar + MeCl 2 TiAl-OEt 2 (methyl aluminum chloride-diethyl ethylate)
【００２３】表３の続き Continuation of Table 3
【００２４】こうして得た被覆処理チップのそれぞれ１
個について、コーナ部付近の切断面をラップ研磨した試
料ついて、走査電子顕微鏡を用いて超硬合金母材と硬質
膜との界面付近を観察し、組成分析も行った。刃先ホー
ニング部から０．１ｍｍの位置のすくい面において、形
成された硬質複合層の厚みと成分組成、硬質膜の最内層
での厚みと成分組成、硬質複合層下の脱β層での厚みと
成分組成、などの測定結果を表４に示す。Each of the coated chips thus obtained was
With respect to the sample, the cut surface near the corner was lapped and polished, and the vicinity of the interface between the cemented carbide base material and the hard film was observed using a scanning electron microscope, and the composition was analyzed. On the rake face at a position of 0.1 mm from the cutting edge honing part, the thickness and component composition of the formed hard composite layer, the thickness and component composition of the innermost layer of the hard film, and the thickness of the β-removed layer under the hard composite layer Table 4 shows the measurement results such as the composition of the components.
【００２５】[0025]
【表４】 * 本発明品４，８，１１の硬質複合層は２層となって
おり、母材側から順に記載。 ** βは（ＷＴｉＴａ）（ＣＮ）を意味する。 *** 巣孔は０．１〜１μｍで比較的均一に分布。[Table 4] * The hard composite layers of the products 4, 8, and 11 of the present invention are two layers, and are described in order from the base material side. ** β means (WTiTa) (CN). *** Burrows are relatively evenly distributed at 0.1-1 μm.
【００２６】[0026]
【実施例２】実施例１で得られた本発明品１〜８と比較
品１〜５の工具チップを用いた切削試験（１）として、
被削材：Ｓ４５Ｃの２本溝入り，切削速度：３００ｍ／
ｍｉｎ，切込み：２．０ｍｍ，送り：０．２０ｍｍ／ｒ
ｅｖ，乾式の条件で外周断続旋削試験を行った。刃先が
摩滅あるいは欠損するまでの切削寿命時間と損傷理由を
表５に示す。また、切削試験（２）として、被削材：Ｆ
Ｃ３５０，切削速度：５００ｍ／ｍｉｎ，切込み：３．
０ｍｍ，送り：０．５０ｍｍ／ｒｅｖ，乾式の条件で外
周旋削試験を行った。刃先の逃げ面摩耗が０．４ｍｍに
達するまでの切削時間を表５に併記した。Example 2 As a cutting test (1) using the tool tips of the products 1 to 8 of the present invention obtained in Example 1 and the comparative products 1 to 5,
Work material: S45C with two grooves, cutting speed: 300m /
min, depth of cut: 2.0 mm, feed: 0.20 mm / r
ev, an outer peripheral intermittent turning test was performed under dry conditions. Table 5 shows the cutting life time until the cutting edge is worn or chipped and the reason for the damage. As a cutting test (2), the work material: F
C350, cutting speed: 500 m / min, cutting depth: 3.
The outer periphery turning test was performed under the conditions of 0 mm, feed: 0.50 mm / rev, and dry type. Table 5 also shows the cutting time until the flank wear of the cutting edge reaches 0.4 mm.
【００２７】[0027]
【表５】 [Table 5]
【００２８】[0028]
【実施例３】次に、実施例１で得られた本発明品９〜１
１と比較品６，７の工具チップを用いて、被削材：ＳＣ
Ｍ４４０（加工面形状：５０Ｗ×２００Ｌ），切削速
度：１３５ｍ／ｍｉｎ，切込み：２．０ｍｍ，送り：
０．３６ｍｍ／刃，乾式の条件でフライス削り試験を行
った。４０ｐａｓｓ加工した時点で工具刃先部を観察
し、すくい面に発生した熱クラックの本数，クレータ部
での膜剥離面積，逃げ面の平均摩耗量，刃先部の微小チ
ッピングなどを評価した。これらの結果を表６に示す。EXAMPLE 3 Next, the products 9-1 of the present invention obtained in Example 1
Work material: SC using tool tips of 1 and comparative products 6 and 7
M440 (machined surface shape: 50W x 200L), cutting speed: 135m / min, depth of cut: 2.0mm, feed:
A milling test was performed under conditions of 0.36 mm / blade and dry type. At the time of 40-pass machining, the tool edge was observed, and the number of thermal cracks generated on the rake face, the area of film peeling at the crater, the average wear amount of the flank, and the micro chipping of the edge were evaluated. Table 6 shows the results.
【００２９】[0029]
【表６】 [Table 6]
【００３０】[0030]
【実施例４】市販されている超硬合金製ソリッドドリル
（φ６ｍｍ）を表７に示した表面処理を施した後、ＣＶ
Ｄコーティング装置を用いて、表７に併記した条件で被
覆処理して本発明品１２と比較品８の表面被覆超ドリル
を得た。各ドリルの外周切れ刃部分を実施例１と同様の
方法で調査した結果、本発明品１２では厚み：５μｍ，
成分組成：８５ＷＣ−１５ＴｉＮ（ｖｏｌ％）の硬質複
合層と厚み：２μｍのＴｉＣ膜が、比較品８には厚み：
２μｍのＴｉＣ膜のみが確認された。これらのドリルを
用いて、被削材：プリハードン鋼（ＨＲＣ＝４０），切
削速度：３０ｍ／ｍｉｎ，切込み：１０ｍｍ，テーブル
送り：６４ｍｍ，刃当り送り：０．０２ｍｍ／刃，湿式
の条件で溝加工試験を行い、切削長さが５０ｍの時点で
切れ刃の逃げ面摩耗幅を測定した。その結果、本発明品
１２が０．０５ｍｍであるのに対し、比較品８は０．１
０ｍｍであった。Example 4 A commercially available cemented carbide solid drill (φ6 mm) was subjected to the surface treatment shown in Table 7 and then CV
Using a D coating apparatus, coating treatment was carried out under the conditions described in Table 7 to obtain surface-coated super drills of product 12 of the present invention and comparative product 8. As a result of investigating the outer peripheral cutting edge portion of each drill in the same manner as in Example 1, the product 12 of the present invention had a thickness of 5 μm,
Component composition: 85WC-15TiN (vol%) hard composite layer and 2 μm thick TiC film;
Only a 2 μm TiC film was confirmed. Using these drills, work material: pre-hardened steel (HRC = 40), cutting speed: 30 m / min, depth of cut: 10 mm, table feed: 64 mm, feed per blade: 0.02 mm / tooth, groove under wet conditions A processing test was performed, and the flank wear width of the cutting edge was measured when the cutting length was 50 m. As a result, the product 12 of the present invention was 0.05 mm, while the product 8 of the comparative example 8 was 0.1 mm.
It was 0 mm.
【００３１】[0031]
【表７】 [Table 7]
【００３２】[0032]
【実施例４】市販されている約１０φｍｍ×６０ｍｍの
耐摩耗工具用超硬合金素材（ＪＩＳでＶ３０相当）を用
い、全面を１４０＃と８００＃のダイヤモンド砥石で粗
研削と仕上げ研削加工して打抜き加工用のパンチを作製
した後、表８に示した表面処理した後、ＣＶＤコーティ
ング装置を用いて、表８に併記した条件で被覆処理して
本発明品１３と比較品９の表面被覆超硬パンチを得た。
各パンチの外周切れ刃部分を実施例１と同様の方法で調
査した結果、本発明品１３では厚み：９μｍ，成分組
成：８２ＷＣ−１８ＴｉＮ（ｖｏｌ％）の硬質複合層と
厚み：２μｍのＴｉＣＮ膜が、比較品９には厚み：３μ
ｍのＴｉＣＮ膜のみが確認された。これらを用いて、厚
み：０．６ｍｍの亜鉛鋼板を打ち抜き加工し、バリによ
り不良品が発生するまでのショット数を測定した。その
結果、本発明品１３が約１３０万ショットであるのに対
し、比較品１０は約４３万ショットであった。Embodiment 4 Using a commercially available cemented carbide material for wear-resistant tools (approximately V30 according to JIS) of about 10 mm × 60 mm, the entire surface is rough- and finish-ground with 140 # and 800 # diamond grindstones. After producing a punch for punching, the surface treatment shown in Table 8 was carried out, and then the coating treatment was carried out using a CVD coating apparatus under the conditions shown in Table 8, and the surface coating of the product 13 of the present invention and the comparative product 9 was superimposed. I got a hard punch.
The outer peripheral cutting edge of each punch was examined in the same manner as in Example 1. As a result, in the case of the product 13 of the present invention, a hard composite layer having a thickness of 9 μm and a component composition of 82WC-18TiN (vol%) and a TiCN film having a thickness of 2 μm were obtained. However, the thickness of the comparative product 9 is 3 μm.
Only m TiCN film was confirmed. Using these, a zinc steel plate having a thickness of 0.6 mm was punched out, and the number of shots until a defective product was generated due to burrs was measured. As a result, the product 13 of the present invention had about 1.3 million shots, while the comparative product 10 had about 430,000 shots.
【００３３】[0033]
【表８】 [Table 8]
【効果】 化学蒸着法による表面被覆超硬合金におい
て、超硬合金母材と硬質被覆膜との間に母材の硬質粒子
と被覆膜粒子とからなる硬質複合層を設けることによ
り、刃先の塑性変形と硬質膜との密着性や耐摩耗性が大
幅に改善されるために、切削工具用チップ，ドリルや耐
摩耗工具に使用すると、従来の表面被覆超硬合金に比べ
て安定した長寿命が得られる。[Effect] In a surface-coated cemented carbide by a chemical vapor deposition method, a cutting edge is provided by providing a hard composite layer composed of hard particles of a base material and coating film particles between a hard metal base material and a hard coating film. When used for cutting tool inserts, drills and wear-resistant tools, the plastic deformation of the steel and the adhesion and wear resistance of the hard film are greatly improved. Life is obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２２Ｃ 1/05 Ｃ２２Ｃ 1/05 Ｇ 29/02 29/02 Ｅ 29/08 29/08 Ｃ２３Ｃ 16/30 Ｃ２３Ｃ 16/30 16/32 16/32 16/34 16/34 16/40 16/40 Ｆターム(参考） 3C037 CC01 CC02 CC04 CC09 3C046 FF03 FF10 FF11 FF13 FF18 FF22 FF25 4K018 AD03 AD06 FA24 4K030 AA03 AA09 AA10 AA11 AA13 AA14 AA17 AA18 BA35 BA36 BA37 BA38 BA40 BA42 BA43 BA44 BA53 BA56 BA57 BB12 BB13 CA03 DA02 FA01 FA10 JA01 LA22 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C22C 1/05 C22C 1/05 G 29/02 29/02 E 29/08 29/08 C23C 16/30 C23C 16/30 16/32 16/32 16/34 16/34 16/40 16/40 F term (reference) 3C037 CC01 CC02 CC04 CC09 3C046 FF03 FF10 FF11 FF13 FF18 FF22 FF25 4K018 AD03 AD06 FA24 4K030 AA03 AA09 AA10 AA11 AA13 AA14 AA17 AA18 BA35 BA36 BA37 BA38 BA40 BA42 BA43 BA44 BA53 BA56 BA57 BB12 BB13 CA03 DA02 FA01 FA10 JA01 LA22
Claims (7)
ステンと周期律表の４ａ，５ａ，６ａ族金属の炭化物，
窒化物，炭窒化物およびこれらの相互固溶体の中の１種
以上からなる立方晶化合物とを硬質相粒子、鉄族金属を
結合相とする超硬合金を母材とし、該母材表面に周期律
表の４ａ，５ａ，６ａ族元素，アルミニウム，シリコン
の炭化物，窒化物，酸化物、およびこれらの相互固溶体
の中から選ばれた１種以上の化合物でなる単層または２
層以上の積層でなる０．５〜２０μｍの硬質膜を被覆し
てなる被覆超硬合金において、 該母材表面から内部に向かって３〜２０μｍの深さに亘
って、該結合相量が２．０重量％以下で、かつ母材の該
硬質相粒子と該硬質膜成分粒子とから構成された均一な
硬質複合層が存在することを特徴とする硬質複合層を有
する被覆超硬合金。1. Tungsten carbide, or a carbide of tungsten carbide and a metal of a group 4a, 5a, or 6a of the periodic table;
A cubic compound comprising at least one of nitrides, carbonitrides and mutual solid solutions thereof is used as a hard phase particle, and a cemented carbide having a binder phase of an iron group metal is used as a base material. A single layer or a single layer of at least one compound selected from the group consisting of elements of groups 4a, 5a and 6a of the table, aluminum, silicon carbides, nitrides, oxides, and mutual solid solutions thereof;
In a coated cemented carbide coated with a hard film having a thickness of 0.5 to 20 μm, the amount of the binder phase is 2 from the surface of the base material to a depth of 3 to 20 μm inward. A coated cemented carbide having a hard composite layer of not more than 0.0% by weight and having a uniform hard composite layer composed of the hard phase particles of the base material and the hard film component particles.
が異なる複数層からなることを特徴とする請求項１記載
の硬質複合層を有する被覆超硬合金。2. The coated hard metal having a hard composite layer according to claim 1, wherein the hard composite layer comprises a plurality of layers in which the hard film component particles are different.
タンの炭化物，窒化物，炭窒化物および酸化アルミニウ
ムの中の１種以上であることを特徴とする請求項１又は
２記載の硬質複合層を有する被覆超硬合金。3. The hard film according to claim 1, wherein the hard film component particles of the hard composite layer are at least one of titanium carbide, nitride, carbonitride and aluminum oxide. Coated cemented carbide with composite layer.
向かって３〜２０μｍの深さに亘って、上記結合相量が
母材のさらに内部より多い結合相富化層および／又は上
記立方晶化合物量が少ない立方晶化合物貧化層が存在す
ることを特徴とする請求項１，２又は３記載の硬質複合
層を有する被覆超硬合金。4. The binder phase-enriched layer having a larger amount of the binder phase than the inside of the base material and / or the cubic shape from a depth of 3 to 20 μm further from the hard composite layer toward the inside of the base material. 4. The coated cemented carbide having a hard composite layer according to claim 1, wherein a cubic compound-poor layer having a small amount of a crystalline compound is present.
ステンと周期律表の４ａ，５ａ，６ａ族金属の炭化物，
窒化物，炭窒化物およびこれらの相互固溶体の中の１種
以上からなる立方晶化合物とを硬質相粒子、鉄族金属を
結合相とする超硬合金において、該超硬合金の表面から
２〜２５μｍの深さに亘って該結合相を均一に除去して
連続空孔とした後、周期律表の４ａ，５ａ，６ａ族元
素，アルミニウム，シリコンの炭化物，窒化物，酸化
物、およびこれらの相互固溶体の中から選ばれた１種以
上の化合物で該連続空孔を封止することにより３〜２０
μｍの硬質複合層を形成させ、続けて該化合物の単層ま
たは２層以上の積層でなる０．５〜２０μｍの硬質膜を
被覆することを特徴とする硬質複合層を有する被覆超硬
合金の製造方法。5. Tungsten carbide or a carbide of tungsten carbide and a metal of Groups 4a, 5a and 6a of the periodic table;
In a cemented carbide having hard phase particles and a cubic compound comprising at least one of nitrides, carbonitrides and mutual solid solutions thereof, and a binder phase composed of an iron group metal, two to three After uniformly removing the binder phase over a depth of 25 μm to form continuous pores, elements 4a, 5a and 6a of the periodic table, aluminum, silicon carbides, nitrides, oxides, and the like By sealing the continuous pores with one or more compounds selected from mutual solid solutions, 3 to 20
μm of a hard composite layer having a hard composite layer, characterized in that a hard composite layer having a thickness of 0.5 to 20 μm is formed by continuously forming a hard composite layer having a thickness of 0.5 μm to 20 μm. Production method.
方法が、有機酸の弱酸性水溶液を使用した電解処理であ
ることを特徴とする請求項５記載の硬質複合層を有する
被覆超硬合金の製造方法。6. The coated super-compound having a hard composite layer according to claim 5, wherein the method of removing the binder phase from the surface of the cemented carbide base material is an electrolytic treatment using a weakly acidic aqueous solution of an organic acid. Manufacturing method of hard alloy.
化合物を使用したＭＯＣＶＤ，低温あるいは中温ＣＶ
Ｄ，プラズマＣＶＤであることを特徴とする請求項５記
載の硬質複合層を有する被覆超硬合金の製造方法。7. The method for forming the hard composite layer includes MOCVD using an organometallic compound, low-temperature or medium-temperature CV.
D. The method for producing a coated cemented carbide having a hard composite layer according to claim 5, wherein the method is plasma CVD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000226253A JP2002038205A (en) | 2000-07-27 | 2000-07-27 | Coated cemented carbide having hard composite layer and its production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000226253A JP2002038205A (en) | 2000-07-27 | 2000-07-27 | Coated cemented carbide having hard composite layer and its production method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002038205A true JP2002038205A (en) | 2002-02-06 |
Family
ID=18719899
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000226253A Withdrawn JP2002038205A (en) | 2000-07-27 | 2000-07-27 | Coated cemented carbide having hard composite layer and its production method |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006328529A (en) * | 2005-04-20 | 2006-12-07 | Sandvik Intellectual Property Ab | Coated cemented carbide with binder phase enriched surface zone |
| WO2008059896A1 (en) * | 2006-11-17 | 2008-05-22 | Mitsubishi Heavy Industries, Ltd. | Abrasion-resistant film and tool provided with the same |
| JP2010024519A (en) * | 2008-07-23 | 2010-02-04 | Ibiden Engineering Kk | Method for manufacturing wear-resistant metal body |
| US8211358B2 (en) | 2003-10-23 | 2012-07-03 | Sandvik Intellectual Property Ab | Cemented carbide and method of making the same |
-
2000
- 2000-07-27 JP JP2000226253A patent/JP2002038205A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8211358B2 (en) | 2003-10-23 | 2012-07-03 | Sandvik Intellectual Property Ab | Cemented carbide and method of making the same |
| JP2006328529A (en) * | 2005-04-20 | 2006-12-07 | Sandvik Intellectual Property Ab | Coated cemented carbide with binder phase enriched surface zone |
| US7939013B2 (en) | 2005-04-20 | 2011-05-10 | Sandvik Intellectual Property Ab | Coated cemented carbide with binder phase enriched surface zone |
| WO2008059896A1 (en) * | 2006-11-17 | 2008-05-22 | Mitsubishi Heavy Industries, Ltd. | Abrasion-resistant film and tool provided with the same |
| JP2008126334A (en) * | 2006-11-17 | 2008-06-05 | Mitsubishi Heavy Ind Ltd | Wear resistant film and tool having the same |
| JP2010024519A (en) * | 2008-07-23 | 2010-02-04 | Ibiden Engineering Kk | Method for manufacturing wear-resistant metal body |
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