JP2000212743A - Surface coated sintered alloy excellent in peeling resistance and its production - Google Patents
Surface coated sintered alloy excellent in peeling resistance and its productionInfo
- Publication number
- JP2000212743A JP2000212743A JP11017787A JP1778799A JP2000212743A JP 2000212743 A JP2000212743 A JP 2000212743A JP 11017787 A JP11017787 A JP 11017787A JP 1778799 A JP1778799 A JP 1778799A JP 2000212743 A JP2000212743 A JP 2000212743A
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- JP
- Japan
- Prior art keywords
- base material
- sintered alloy
- coated
- hard film
- hard
- 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.)
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- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、スローアウエイチ
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・部品に使用される表面被覆焼結合金およ
びその製法に関し、具体的には、超硬合金またはサーメ
ットでなる焼結合金の母材表面に残存する機械加工によ
る加工変質層、特に加工変質層としてのクラックを除去
し、加工変質層の除去された母材表面に硬質膜を被覆す
ることにより、硬質膜の耐剥離性を改善して工具寿命を
向上させた表面被覆焼結合金およびその製法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-coated sintered alloy used for cutting tools such as throw-away tips, drills and end mills and various wear-resistant tools and parts, and a method for producing the same. , To remove the cracks as the work-affected layer due to machining remaining on the base material surface of the cemented carbide or sintered alloy made of cermet, especially cracks as the work-affected layer, BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-coated sintered alloy in which the hard film is improved in peeling resistance by coating to improve tool life and a method for producing the same.
【0002】[0002]
【従来の技術】焼結合金のうち、特に超硬合金の母材に
TiC,TiCN,TiN,Al2O3などの硬質膜を化
学蒸着法(以下、[CVD法」という)あるいは物理蒸
着法(以下、「PVD法」という)で被覆した表面被覆
焼結合金は、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、母材と硬質膜との密着性が劣る
と、使用時の硬質膜剥離によって急激に摩耗し、寿命が
低下する。そこで、密着性を確保するため、母材表面の
調整処理,母材と硬質膜との間に下地層を介在させる方
法、その下地層の膜質選定,下地層コーティング条件の
最適化など種々の方法が試みられている。一般に表面被
覆焼結合金の母材は、研削加工などにより用途に応じた
形状を作製しているため、母材表面から1〜5μm深さ
の母材近傍に、研削屑の付着,硬質相粒子内のクラッ
ク,硬質相粒子同士あるいは硬質相粒子と結合相との界
面欠陥,結合相の変態に代表される加工変質層を残存し
ている。2. Description of the Related Art Among sintered alloys, a hard film such as TiC, TiCN, TiN, or Al 2 O 3 is formed on a base material of a cemented carbide by a chemical vapor deposition method (hereinafter referred to as a “CVD method”) or a physical vapor deposition method. Surface-coated sintered alloys (hereinafter referred to as “PVD method”) are often used as cutting tools, wear-resistant tools and parts because they have both the strength and toughness of the base material and the wear resistance of the hard film. ing. However, if the adhesiveness between the base material and the hard film is poor, the hard film is peeled off during use, so that it is rapidly worn and its life is shortened. Therefore, in order to ensure adhesion, various methods such as adjusting the surface of the base material, interposing an underlayer between the base material and the hard film, selecting the film quality of the underlayer, and optimizing the coating conditions of the underlayer. Have been tried. Generally, since the base material of the surface-coated sintered alloy is formed according to the intended use by grinding or the like, grinding dust is attached to the base material at a depth of 1 to 5 μm from the base material surface, and hard phase particles are formed. Cracks in the inside, interface defects between the hard phase particles or between the hard phase particles and the binder phase, and a work-affected layer typified by transformation of the binder phase remains.
【0003】この加工変質層は、母材と硬質膜との密着
強度を低下させる傾向にある。そのために、加工変質層
に対する対策、具体的には、母材表面の粗さ調整,合金
組成の調整、加工変質層の改質などの処理が重要とな
る。この処理法の1種として、硬質膜を被覆する前工程
での酸,アルカリによる洗浄を行うが、加工変質層はほ
とんど除去できない。一方、CVD法による硬質膜の被
覆工程では、被覆工程時の昇温雰囲気や下地層の被覆時
の温度,ガス条件,膜種などによる化学反応と拡散現象
により、ある程度は加工変質層である付着研削屑を除去
することが可能であるが、母材表面近傍に存在する硬質
相粒子内のクラックまでは除去することができない。ま
た、PVD法による硬質膜の被覆工程では、被覆工程前
のボンバード処理により、母材表面から数μm内部まで
の加工変質層を除去できるが、母材の全面に亘って均一
に加工変質層を除去することが困難であること、または
目的とする表面部分の加工変質層を除去することは困難
であるという問題がある。The deteriorated layer tends to lower the adhesion strength between the base material and the hard film. For this purpose, it is important to take measures against the work-affected layer, specifically, treatments such as adjusting the roughness of the base material surface, adjusting the alloy composition, and modifying the work-affected layer. As one type of this treatment method, washing with an acid or alkali is performed in the step before coating the hard film, but the deteriorated layer can hardly be removed. On the other hand, in the process of coating a hard film by the CVD method, due to chemical reactions and diffusion phenomena due to the temperature rising atmosphere during the coating process, the temperature at the time of coating the underlayer, gas conditions, film types, etc. Although it is possible to remove grinding debris, it is not possible to remove cracks in hard phase particles existing near the base material surface. Further, in the hard film coating step by the PVD method, the bombardment treatment before the coating step can remove the work-affected layer from the surface of the base material to within several μm, but the work-affected layer is uniformly formed over the entire surface of the base material. There is a problem that it is difficult to remove, or it is difficult to remove a work-affected layer on a target surface portion.
【0004】これまでに、加工変質層を軽減あるいは除
去して表面被覆超硬合金の剥離強度を改善する手段とし
て、研削条件をコントロールして母材表面粗さを調整す
る方法や母材を再焼結する方法が提案されている。母材
表面粗さの調整方法としては、代表的なものに特開平6
ー108253号公報があり、また再焼結法としては、
代表的なものに特開平5ー123903号公報,および
特開平7ー97603号公報がある。一方、表面被覆焼
結合金の被覆前処理として電解研磨を被覆前に適用した
代表的なものに、特開昭63ー134660号公報,特
開平8ー92741号公報,特開平10ー130092
号公報および特表平10−510877号公報がある。Hitherto, as a means of reducing or removing a work-affected layer and improving the peel strength of a surface-coated cemented carbide, a method of controlling the grinding condition and adjusting the surface roughness of the base material and a method of re-working the base material have been proposed. A method of sintering has been proposed. As a method of adjusting the base material surface roughness, a typical method is disclosed in
-108253, and as a resintering method,
Representative examples are JP-A-5-123903 and JP-A-7-97603. On the other hand, representative examples of applying electropolishing as a pre-coating treatment for a surface-coated sintered alloy before coating are disclosed in JP-A-63-134660, JP-A-8-92741, and JP-A-10-130092.
And Japanese Patent Publication No. 10-510877.
【0005】[0005]
【発明が解決しようとする課題】先行技術である特開平
6ー108253号公報には、超硬合金の母材表面を、
例えばブラシ研磨加工して平均表面粗さRaが0.15
〜0.4μmで、かつランダムな方向に研磨傷が形成さ
れた表面に硬質膜を被覆した被覆超硬合金が開示されて
いる。同公報に開示されている被覆超硬合金は、硬質膜
と母材との付着強度を高めてはいるが、加工変質層の除
去が不十分なため、硬質膜と母材との界面における母材
中の硬質相粒子にクラックが残存し、膜剥離による異常
損傷を起こし易いという問題がある。The prior art, Japanese Patent Application Laid-Open No. Hei 6-108253, discloses that the base material surface of a cemented carbide is
For example, the average surface roughness Ra is 0.15 by brush polishing.
A coated cemented carbide is disclosed in which a hard film is coated on a surface having a polishing scratch formed in a random direction in a thickness of about 0.4 μm. Although the coated cemented carbide disclosed in the publication increases the adhesive strength between the hard film and the base material, the removal of the work-affected layer is insufficient, so that the base material at the interface between the hard film and the base material is insufficient. There is a problem that cracks remain in the hard phase particles in the material and abnormal damage due to film peeling easily occurs.
【0006】また、特開平5ー123903号公報に
は、超硬合金の母材表面を研削加工した後に高圧の不活
性ガス雰囲気中、液相出現温度以上で再焼結し、次いで
母材表面にCVD法にて硬質膜を形成した表面被覆超硬
合金製切削工具部材の製造方法が開示されており、特開
平7ー97603号公報には、超硬合金チップの母材刃
先にR=0.03mmの円弧ホーニング加工を施した
後、1%N2−Arの雰囲気中で再焼結し、母材表面に
窒素含有の凹凸層を形成したダイヤモンド被覆用母材お
よびその製造方法が開示されている。これら両公報に開
示されている再焼結による母材加熱表面では、加工変質
層が除去され、かつ炭化タングステンあるいは立方晶構
造化合物の粒成長による凹凸面が形成されるために、剥
離強度は改善されるが、硬質膜被覆後の膜表面にも凹凸
が残るために使用時に被加工材が凝着し易くなって、逆
に膜剥離が増大し、被加工材の仕上げ面精度も低下する
という問題がある。さらに、再焼結により母材の成分組
成の変動が生じるなどから、母材加熱表面の組成、特に
結合相量および立方晶構造化合物量を制御することが困
難となり、母材と硬質膜との密着強度が安定しないとい
う問題もある。[0006] Japanese Patent Application Laid-Open No. 5-123903 discloses that the surface of a base material of a cemented carbide is ground, then re-sintered in a high-pressure inert gas atmosphere at a temperature not lower than a liquid phase appearance temperature. A method of manufacturing a surface-coated cemented carbide cutting tool member in which a hard film is formed by a CVD method is disclosed in Japanese Patent Application Laid-Open No. 7-97603. Disclosed is a diamond coating base material in which a 0.03 mm arc honing process is performed and then resintering in an atmosphere of 1% N 2 -Ar to form a nitrogen-containing uneven layer on the base material surface and a method for producing the same. ing. In the base material heated surface by re-sintering disclosed in both of these publications, since the work-affected layer is removed and an irregular surface is formed by the grain growth of tungsten carbide or a cubic structure compound, the peel strength is improved. However, since the surface of the film after the coating of the hard film also has irregularities on the surface, the material to be processed is liable to adhere during use, conversely, film peeling increases, and the finished surface accuracy of the material to be processed also decreases. There's a problem. Furthermore, since the resintering causes a change in the component composition of the base material, it becomes difficult to control the composition of the base material heating surface, particularly the amount of the binder phase and the amount of the cubic structure compound, and the base material and the hard film are hardly controlled. There is also a problem that the adhesion strength is not stable.
【0007】一方、電解液に関連する先行技術である特
開昭63ー134660号公報には、炭窒化チタン基サ
ーメットの母材表面を予めアルカリ処理(電解処理も含
む)した後、CVD法で硬質膜を被覆した表面被覆炭窒
化チタン基サーメットの製造方法が開示されている。同
公報に開示されているNaOH,KOHのアルカリ溶液
を用いた電解処理は、母材表面の活性化により硬質膜と
の付着強度を改善したものではあるが、母材中の硬質相
の粒子が炭窒化チタンを主成分とするため、水酸化チタ
ンなどの電解生成物が残留し易くて均一な電解研磨が困
難である。また、電解研磨条件により、母材表面の硬質
相粒子にはクラック(電解腐食による溝)が逆に発生し易
くなるという問題、および結合相が殆ど電解されなく母
材表面に多孔質層が形成され易く、被覆後の界面に巣孔
が発生し易いという問題がある。On the other hand, JP-A-63-134660, which is a prior art relating to an electrolytic solution, discloses that a base material surface of a titanium carbonitride-based cermet is preliminarily treated with an alkali (including an electrolytic treatment) and then subjected to a CVD method. A method for producing a surface-coated titanium carbonitride-based cermet coated with a hard film is disclosed. The electrolysis treatment using an alkaline solution of NaOH and KOH disclosed in the above publication improves the adhesion strength to the hard film by activating the surface of the base material. Since titanium carbonitride is the main component, electrolytic products such as titanium hydroxide are likely to remain and uniform electrolytic polishing is difficult. Also, depending on the electropolishing conditions, cracks (grooves due to electrolytic corrosion) are likely to be generated in the hard phase particles on the surface of the base material, and a porous layer is formed on the surface of the base material because almost no bonding phase is electrolyzed. There is a problem that burrows are easily generated at the interface after coating.
【0008】また、特開平8ー92741号公報には、
超硬合金の母材表面にセラミックス粒子を埋め込んだ
後、鉱酸を電解液とした電解エッチング処理をすること
より、三角錐状の突起からなる凹凸を形成したダイヤモ
ンド堆積用超硬合金の表面処理方法が開示されており、
特開平10ー130092号公報には、焼結合金の母材
表面を強アルカリ溶液で強く電解処理した後、酸処理で
結合相を除去することにより、母材表面に大きな凹凸面
を形成した後、ダイヤモンドおよび/またはダイヤモン
ドライクカーボンの硬質膜を被覆した被覆焼結合金の表
面処理方法が開示されている。これら両公報に開示され
ている電解処理は、ダイヤモンドの硬質膜と母材との密
着性を楔状に機械的保持力によって向上させるために、
電解研磨により母材表面に大きい凹凸面を形成させるも
ので、母材と硬質膜との拡散による接着が困難なダイヤ
モンド膜では有効な方法ではあるが、被覆後の硬質膜表
面も著しく粗くなるという問題がある。[0008] Japanese Patent Application Laid-Open No. 8-92741 discloses that
After embedding ceramic particles in the surface of the cemented carbide base material, the surface treatment of diamond deposited cemented carbide with irregularities consisting of triangular pyramid-shaped projections is performed by electrolytic etching using mineral acid as an electrolyte. A method is disclosed,
Japanese Patent Application Laid-Open No. Hei 10-130992 discloses that after forming a large uneven surface on the surface of a base material of a sintered alloy by subjecting the surface of the base material of the sintered alloy to strong electrolytic treatment with a strong alkaline solution and then removing the binding phase by acid treatment. Surface treatment method for a coated sintered alloy coated with a hard film of diamond, diamond and / or diamond-like carbon. The electrolytic treatment disclosed in both these publications, in order to improve the adhesion between the diamond hard film and the base material by wedge-shaped mechanical holding force,
This method forms a large uneven surface on the base material surface by electrolytic polishing, and is an effective method for a diamond film that is difficult to adhere due to diffusion between the base material and the hard film, but the hard film surface after coating is also extremely rough. There's a problem.
【0009】これらの従来の電解研磨技術は、酸化性の
強酸による腐食と電気化学反応とにより超硬合金製工具
のエッジ部を急速に溶解除去するもので、機械的な研削
除去法に比べて量産性,コスト面などでは優れる。しか
し、処理表面の凹凸が激しく、かつ表面付近の結合相が
優先的に除去されるために、硬質膜を被覆した際に膜直
下には巣孔が多量に発生し、逆に膜が剥離し易くなると
いう問題がある。These conventional electropolishing techniques rapidly dissolve and remove the edge of a cemented carbide tool by corrosion and electrochemical reaction caused by an oxidizing strong acid. It is excellent in terms of mass productivity and cost. However, because the surface of the treated surface is severe and the binder phase near the surface is removed preferentially, a large number of pits are generated immediately below the film when the hard film is coated, and the film peels off. There is a problem that it becomes easier.
【00010】[00010]
【発明が解決しようとする課題】本発明者らは、長年に
亘り、表面被覆焼結合金における膜の剥離強度を大幅に
改善させる方法について検討していた所、研削加工など
の機械的な方法で加工した焼結合金の母材表面には、研
削屑の付着,硬質相粒子内のクラックに代表される加工
変質層が生じていること、研削加工が施されていない母
材焼結肌面には、粗大硬質粒子,結合相の過多あるいは
過少になった表面層が生じていること、これらの母材表
面に硬質膜が被覆されると、硬質膜の剥離強度の低下原
因になること、特に、超硬合金母材と硬質膜との界面に
残存する微細な硬質相の粒子と硬質相の粒子内クラック
とを除去すると剥離強度が大幅に改善されるために実用
性能が飛躍的に向上すること、表面の平滑化と表面組成
の調整も含めたこれら欠陥の完全除去には、周期律表の
1a族元素の水酸化物とフェリシアン塩との混合液,周
期律表の1a族元素の亜硝酸塩,亜硫酸塩,亜燐酸塩,
炭酸塩の中から選ばれた少なくとも1種を必須成分とす
る溶液中で電解研磨することが最適であり、そして電解
処理した母材表面に硬質膜を被覆した被覆超硬合金は、
剥離強度に優れるという知見を得て、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 been studying a method for greatly improving the peel strength of a film on a surface-coated sintered alloy for many years. The surface of the base material of the sintered alloy processed in step 2 shows that the surface of the base material has not been subjected to grinding, and that the surface of the base material has not been ground. In addition, there are surface layers with excessively large or small number of coarse hard particles and binder phase, and when the hard film is coated on the surface of the base material, the peel strength of the hard film is reduced. In particular, the removal of fine hard phase particles and cracks in the hard phase particles remaining at the interface between the cemented carbide base material and the hard film significantly improves the peeling strength and dramatically improves practical performance. And smoothing of the surface and adjustment of the surface composition. The complete removal of Luo defect, a mixture of a hydroxide and ferricyanide salts of Group 1a elements of the periodic table, nitrites, sulfites Group 1a elements of the periodic table, phosphites,
It is most preferable to perform electropolishing in a solution containing at least one selected from carbonates as an essential component, and a coated cemented carbide in which a hard film is coated on the surface of an electrolytically treated base material,
The inventors have found that the present invention has excellent peel strength, and have completed the present invention.
【00011】本発明の耐剥離性に優れた表面被覆焼結合
金は、硬質相と結合相とを含有する超硬合金またはサー
メットでなる焼結合金の母材における、該母材の少なく
とも一部の表面が機械加工されており、該母材表面に、
該母材よりも高硬度な硬質膜を1層または2層以上の積
層に被覆された表面被覆焼結合金であり、該硬質膜の被
覆された該母材表面側の該硬質相の粒子内に該機械加工
によるクラックが存在しないようにしたことを特徴とす
るものである。The surface-coated sintered alloy excellent in peeling resistance according to the present invention comprises at least a part of a base metal of a cemented carbide or a cermet-based sintered alloy containing a hard phase and a binder phase. Is machined, and the surface of the base material is
A surface-coated sintered alloy in which a hard film having a hardness higher than that of the base material is coated in one or two or more layers, and in the hard phase particles on the surface of the base material covered with the hard film. Wherein no cracks due to the machining are present.
【0012】[0012]
【発明の実施の態様】本発明の表面被覆焼結合金におけ
る母材は、具体的には、炭化タングステンのみからなる
硬質相と、Coおよび/またはNiを主成分とする結合
相とからなる、例えばWC−Co系合金,WC−Ni系
合金,WC−(Co,Ni)系合金,WC−(Ni−C
r)系合金,WC−(Co,Cr)系合金,WC−(C
o,Cr,V)系合金でなる超硬合金、また炭化タング
ステンと立方晶構造化合物とからなる硬質相と、Coを
主成分とする結合相とからなる、例えばWC−TaC−
Co系合金,WC−(W,Ti,Ta)C−Co系合
金,WC−(W,Ti,Ta,Nb)(C,N)−Co
系合金でなる超硬合金、さらにTi(C,N),Ti
N,TiCを主成分とする硬質相と、Coおよび/また
はNiを主成分とする結合相とからなる、例えばTi
(C,N)−(Ti,W)Cー(Co,Ni)系合金,
Ti(C,N)−(Ti,W)(C,N)−(Co,N
i)系合金,Ti(C,N)−(Ti,W,Ta)Cー
(Co,Ni)系合金,Ti(C,N)−(Ti,W,
Ta)(C,N)−(Co,Ni)系合金でなるサーメ
ットを挙げることができる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The base material of the surface-coated sintered alloy of the present invention specifically includes a hard phase composed of only tungsten carbide and a binder phase containing Co and / or Ni as a main component. For example, WC-Co alloy, WC-Ni alloy, WC- (Co, Ni) alloy, WC- (Ni-C
r) -based alloy, WC- (Co, Cr) -based alloy, WC- (C
(o, Cr, V) based alloy, or a hard phase composed of tungsten carbide and a cubic structure compound, and a binder phase mainly composed of Co, for example, WC-TaC-
Co-based alloy, WC- (W, Ti, Ta) C-Co-based alloy, WC- (W, Ti, Ta, Nb) (C, N) -Co
Based alloys, Ti (C, N), Ti
A hard phase mainly composed of N and TiC, and a binder phase mainly composed of Co and / or Ni.
(C, N)-(Ti, W) C- (Co, Ni) -based alloy,
Ti (C, N)-(Ti, W) (C, N)-(Co, N
i) alloy, Ti (C, N)-(Ti, W, Ta) C- (Co, Ni) alloy, Ti (C, N)-(Ti, W,
Ta) A cermet made of a (C, N)-(Co, Ni) alloy can be used.
【0013】これらのうち、炭化タングステンと立方晶
構造化合物とからなる硬質相と、Coおよび/またはN
iを主成分とする結合相とからなる超硬合金の場合は、
母材の強度、靱性および硬さなどの特性と、母材と硬質
膜との密着性および両者のバランスに優れていること、
硬質膜の磨滅後の母材の急激な損傷が少ないなどから好
ましいことである。また、これらの合金に含有する結合
相量は、合金の特性および合金の作製し易さなどから、
3〜30体積%からなるものが好ましいものである。Among them, a hard phase composed of tungsten carbide and a cubic structure compound, Co and / or N
In the case of a cemented carbide composed of a binder phase containing i as a main component,
Excellent properties such as strength, toughness and hardness of the base material, adhesion between the base material and the hard film, and excellent balance between both,
This is preferable because abrupt damage to the base material after the hard film is worn is small. Also, the amount of the binder phase contained in these alloys depends on the properties of the alloy and the ease of manufacturing the alloy, and so on.
What consists of 3-30 volume% is preferable.
【0014】これらの母材上に被覆する硬質膜は、ダイ
ヤモンド,ダイヤモンドライクカーボン,硬質窒化ホウ
素,立方晶窒化ホウ素の膜、または周期律表の4a,5
a,6a族元素,Al,Si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種の単層
または2種以上の積層からなる場合を挙げることができ
る。これらの硬質膜のうち、単層の膜としては、例えば
TiC,TiCN,TiN,(Ti,Zr)N,(T
i,Al)N,CrNに代表される少なくとも1種から
なる場合が耐摩耗性および耐溶着性にすぐれることから
好ましく、積層の膜としては、母材側からTiC/Ti
N/TiCN/TiNの順に被覆された膜,TiN/T
iC/Al2O3の順に被覆された膜,TiN/TiCN
/TiC/Al2O3/TiNの順に被覆された膜,Ti
N/(Ti,Al)N/TiN,TiN/Si3N4の順
に被覆された膜,CrN/VNの順に被覆された膜に代
表される組み合わせでなる場合を挙げることができる。The hard film to be coated on these base materials is a film of diamond, diamond-like carbon, hard boron nitride, cubic boron nitride, or 4a, 5a of the periodic table.
Examples thereof include a single layer or a laminate of two or more elements selected from the group consisting of elements a and 6a, carbides, nitrides, oxides of Al and Si, and mutual solid solutions thereof. Among these hard films, single-layer films include, for example, TiC, TiCN, TiN, (Ti, Zr) N, (T
i, Al) N and CrN are preferable because they are excellent in abrasion resistance and welding resistance.
Film coated in the order of N / TiCN / TiN, TiN / T
a film coated in the order of iC / Al 2 O 3 , TiN / TiCN
/ TiC / Al 2 O 3 / TiN coated film in this order, Ti
There may be mentioned a combination represented by a film coated in the order of N / (Ti, Al) N / TiN, TiN / Si 3 N 4 and a film coated in the order of CrN / VN.
【0015】この母材と硬質膜との位置関係の構成は、
母材に直接隣接した状態で硬質膜が被覆される場合、母
材と硬質膜との間に、母材よりも軟質な、例えばTi,
Zr,W,Moの1種以上の金属または合金でなる下地
層を介在させる場合などを代表的な構成として挙げるこ
とができる。これらの硬質膜の厚さは、下地層の有無,
全膜種その組み合わせなどの膜構成,用途および形状な
どにより調整する必要があり、特に、CVD法あるいは
PVD法で作製される場合には1〜20μmの厚みにす
ると耐摩耗性および耐剥離性に優れることから好ましい
ことである。これらの硬質膜は、化学量論組成または非
化学量論組成からなる場合でもよく、特に、上述したT
i含有化合物の単層または積層の場合には非化学量論組
成でなる可能性が高い。The configuration of the positional relationship between the base material and the hard film is as follows.
When the hard film is coated directly adjacent to the base material, a softer material, such as Ti, than the base material, is provided between the base material and the hard film.
A typical example is a case where an underlayer made of one or more metals or alloys of Zr, W, and Mo is interposed. The thickness of these hard films depends on the presence or absence of an underlayer,
It is necessary to adjust according to the film configuration, application, shape, etc. of all film types and their combinations. In particular, when the film is manufactured by the CVD method or the PVD method, when the thickness is 1 to 20 μm, the abrasion resistance and the peeling resistance are reduced. This is preferable because it is excellent. These hard films may be of stoichiometric or non-stoichiometric composition, and in particular, the T
In the case of a single layer or a lamination of the i-containing compound, it is highly possible that the compound has a non-stoichiometric composition.
【0016】硬質膜が被覆された母材表面側における硬
質相粒子内クラックは、具体的には、表面被覆焼結合金
の断面組織での走査型電子顕微鏡観察において、例えば
超硬合金の母材の場合には、WC硬質相粒子および
(W,Ti,Ta)Cなどの立方晶構造化合物の硬質相
粒子の表面から内部に向かって伝播あるいは貫通した微
細なクラックの有無を確認することで判断できる。この
硬質相粒子内クラックは、ダイヤモンド砥石による研削
などの機械的加工により母材表面の直下に生じたもので
ある。The cracks in the hard phase particles on the surface of the base material coated with the hard film are specifically observed by scanning electron microscope observation of the cross-sectional structure of the surface-coated sintered alloy. Is determined by confirming the presence or absence of fine cracks that propagate or penetrate from the surface to the inside of the hard phase particles of the WC hard phase particles and the cubic structure compound such as (W, Ti, Ta) C. it can. The cracks in the hard phase particles are generated immediately below the base material surface by mechanical processing such as grinding with a diamond grindstone.
【0017】これらの被膜構成のうち、、硬質膜が母材
に直接隣接して被覆されている場合には、被覆された母
材表面における硬質相の粒子が0.2μmを越えた大き
さでなると、耐剥離性に優れる傾向にあることから好ま
しく、特に機械加工されてない母材表面も含めた全面に
おいて、0.2μmを越えた硬質相の粒子とすることが
好ましいことである。具体的には、焼結合金の母材表面
の一面もしくは全面に、加工変質層が除去されて粗粒の
硬質相の粒子となって存在するものである。When the hard film is coated directly adjacent to the base material, the hard phase particles on the surface of the coated base material have a size exceeding 0.2 μm. In this case, it is preferable because the resistance to peeling tends to be excellent. In particular, it is preferable to form hard phase particles exceeding 0.2 μm over the entire surface including the surface of the unprocessed base material. Specifically, the work-affected layer is removed on one or the entire surface of the surface of the base material of the sintered alloy to be present as coarse hard phase particles.
【0018】また、硬質膜が周期律表の4a,5a,6
a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
の単層または2種以上の積層でなり、かつ硬質膜が母材
に直接隣接して被覆されている場合には、硬質膜が接着
される母材表面、特に、機械加工されない母材表面も含
めた全界面において、局部的に2.0μm未満の凹凸に
すると、耐剥離性がさらに優れるので好ましい。具体的
には、焼結合金の母材表面の焼結肌面の凹凸や研削傷に
よる凹凸などが平滑化されていることを意味し、例え
ば、走査型電子顕微鏡観察による断面観察において、2
0μmの範囲おける任意界面の平均水準に対して2.0
μm未満の凹凸でなるものである。Further, the hard film is made of 4a, 5a, 6 in the periodic table.
group a element, aluminum, silicon carbide, nitride,
When the hard film is composed of one single layer or a laminate of two or more types selected from oxides and their mutual solid solutions, and the hard film is coated directly adjacent to the base material, the hard film is bonded. It is preferable to locally form irregularities of less than 2.0 μm on the surface of the base material to be formed, particularly on all interfaces including the surface of the base material that is not machined, because the peeling resistance is further excellent. Specifically, it means that unevenness of the sintered skin surface of the base material surface of the sintered alloy or unevenness due to grinding scratches is smoothed.
2.0 relative to the average level of any interface in the range of 0 μm
It has irregularities of less than μm.
【0019】さらに、硬質膜が周期律表の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種の単層または2種以上の積層でなり、かつ硬質膜が
母材に直接隣接して被覆されている場合には、硬質膜が
接着される母材表面、特に硬質膜と機械加工されない母
材表面も含めた全界面において、硬質膜と母材表面の硬
質相粒子との接着界面に対する硬質膜と母材表面の結合
相との接着界面の面積比が、0.4〜0.8であると、
実用的な耐剥離性がさらに優れるので好ましい。この面
積比は、具体的には、界面での結合相量が合金内部より
やや多いことを意味し、界面直下からの剥離防止に効果
を示すものである。この面積比が0.4未満では、耐剥
離性の向上効果が弱くなる傾向となり、逆に0.8を超え
て大きくなると巣孔発生も伴うため、耐剥離性が低下す
る傾向となる。Further, the hard film is made of any one of 4a, 5a,
A hard film directly adjacent to the base material, which is composed of one single layer or a laminate of two or more selected from the group 6a elements, aluminum, silicon carbides, nitrides, oxides and mutual solid solutions thereof; In the case where the hard film is coated with the hard film, the bonding interface between the hard film and the hard phase particles on the surface of the base material, particularly at the entire interface including the hard film and the non-machined base material surface. When the area ratio of the adhesive interface between the hard film and the binder phase on the base material surface is 0.4 to 0.8,
It is preferable because practical peel resistance is further excellent. Specifically, this area ratio means that the amount of the bonding phase at the interface is slightly larger than the inside of the alloy, and is effective in preventing peeling from immediately below the interface. When the area ratio is less than 0.4, the effect of improving the peeling resistance tends to be weak, and when the area ratio is larger than 0.8, burrows are generated, and the peeling resistance tends to decrease.
【0020】その他、母材が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からなる立方晶構造化合物
とでなる硬質相と、Coおよび/またはNiを主成分と
する結合相とからなる超硬合金でなる場合は、硬質膜と
直接接着している母材表面部、特に機械加工されてない
母材表面も含めた全表面において、母材の内部に含有す
る立方晶構造化合物量に対し、母材表面の立方晶構造化
合物量が減少または含有しなくなると、実用的な耐剥離
性がさらに優れるので好ましいことである。具体的に
は、WC−(W,Ti,Ta)C−Co系の超硬合金母
材の焼結肌面や研削面に存在する(W,Ti,Ta)C
粒子を優先的に除去し、WCとCoのみからなる表面を
形成した後に硬質膜を被覆するものである。In addition, a hard phase whose base material is tungsten carbide and a cubic structure compound composed of carbides, nitrides, carbonitrides of metals belonging to groups 4a, 5a and 6a of the periodic table, and a mutual solid solution thereof; And / or a cemented carbide composed of a binder phase containing Ni as a main component, the surface of the base material directly bonded to the hard film, particularly on the entire surface including the unmachined base material surface It is preferable that the amount of the cubic structure compound on the surface of the base material is reduced or no longer contained in the surface of the base material relative to the amount of the cubic structure compound contained in the base material, because practical peel resistance is further excellent. Specifically, the (W, Ti, Ta) C present on the sintered surface or ground surface of the WC- (W, Ti, Ta) C-Co-based cemented carbide base material
Particles are removed preferentially, and a hard film is coated after forming a surface consisting only of WC and Co.
【0021】本発明の表面被覆焼結合金は、従来の粉末
冶金技術および表面処理技術を駆使して作製することが
可能であるが、以下の製造方法で行うと簡易で製造工程
上からも好ましい方法である。すなわち、本発明の表面
被覆焼結合金の製法は、硬質相と結合相とを含有する超
硬合金またはサーメットの焼結合金母材の少なくとも一
部の表面を機械加工する第1工程と、該機械加工後に該
母材表面をアルカリ性の電解液中で電解研磨し、該母材
表面に残存していた該機械加工による加工変質層を除去
する第2工程と、該加工変質層を除去した該母材表面
に、該母材よりも高硬度な硬質膜を1層または2層以上
の積層に被覆する第3工程とを含むことを特徴とする方
法である。The surface-coated sintered alloy of the present invention can be produced by making use of the conventional powder metallurgy technology and surface treatment technology. However, the following production method is simple and preferable in the production process. Is the way. That is, the method for producing a surface-coated sintered alloy of the present invention includes a first step of machining at least a part of the surface of a cemented carbide or a cermet sintered alloy base material containing a hard phase and a binder phase; After machining, the base material surface is electropolished in an alkaline electrolyte to remove a machining-damaged layer remaining on the base material surface due to the machining, and a second step of removing the processing-damaged layer. Covering the surface of the base material with a hard film having a higher hardness than the base material in one or two or more layers.
【0022】この本発明の製法における第1工程で母材
表面を機械加工する方法は、具体的には、従来から行わ
れている砥石加工、ブラシ加工、ラップ加工、ブラスト
加工、バレル加工、砥粒を含有した液体中での超音波加
工に代表される方法により、母材表面を研削加工および
/またはラッピング加工を行うことである。これらのう
ち、バレル加工を除く他の方法の場合には、本発明の製
法後における母材表面が平坦で電解ラッピング状になる
ことから好ましいことである。The method of machining the surface of the base material in the first step of the manufacturing method of the present invention is, for example, a grinding stone, a brush, a lap, a blast, a barrel, a grinding, or the like which has been conventionally performed. Grinding and / or lapping the base material surface by a method represented by ultrasonic processing in a liquid containing grains. Of these, the other method except for the barrel processing is preferable because the surface of the base material after the manufacturing method of the present invention is flat and electrolytically wrapped.
【0023】この本発明の製法における第2工程で使用
する電解液は、具体的には、アルカリ性を示す、例えば
NaOH,KOH,LiOH,NaNO2,KNO2,N
a2S03,Na2HPO3など周期律表の1a族金属の水
酸化物,亜硝酸塩,亜硫酸塩,亜燐酸塩,炭酸塩の中か
ら選ばれた少なくとも1種を必須成分とし、酒石酸ナト
リウム,硝酸カリウム,燐酸ナトリウム,硫酸ナトリウ
ム,硼砂,ロッシェル塩,タングステン酸ナトリウム,
フェリシアン化カリウムなど塩類との水溶液やアミン
類,アルコール類などの有機溶媒液から選択される1種
の溶液を挙げることができる。The electrolytic solution used in the second step of the production method of the present invention is, for example, NaOH, KOH, LiOH, NaNO 2 , KNO 2 , N
a 2 S0 3, Na 2 HPO 3 1a group metal hydroxides of the Periodic Table such as nitrites, sulfites, phosphites, and at least one of the essential components selected from among carbonates, sodium tartrate , Potassium nitrate, sodium phosphate, sodium sulfate, borax, Rochelle salt, sodium tungstate,
Examples thereof include one type of solution selected from aqueous solutions of salts such as potassium ferricyanide and organic solvents such as amines and alcohols.
【0024】これらの電解液がナトリウムおよび/また
はカリウムの亜硝酸塩を主成分とする水溶液からなる場
合には、母材表面は、平滑で結合相のやや富化された電
解研磨面となることから好ましい。また、電解液がナト
リウムおよび/またはカリウムの炭酸塩とフェリシアン
塩とを主成分とする水溶液からなる場合には、母材表面
は、立方晶構造化合物が優先的に除去され、かつ結合相
が富化された表面が得られるので好ましい。さらに、電
解液がナトリウムおよび/またはカリウムの亜硝酸塩,
炭酸塩と塩化物とを主成分とする水溶液からなる場合に
は、その成分比により母材表面の結合相量を制御できる
ので好ましい。When these electrolytic solutions are composed of an aqueous solution containing sodium and / or potassium nitrite as a main component, the surface of the base material becomes an electropolished surface having a smooth and slightly enriched binder phase. preferable. When the electrolytic solution is composed of an aqueous solution containing sodium and / or potassium carbonate and ferricyanate as main components, the cubic structure compound is preferentially removed from the surface of the base material, and the bonding phase is reduced. This is preferred because an enriched surface is obtained. In addition, the electrolyte is sodium and / or potassium nitrite,
It is preferable to use an aqueous solution containing a carbonate and a chloride as main components, since the amount of the binder phase on the surface of the base material can be controlled by the component ratio.
【0025】これらの電解液を使用して電解研磨すると
きの条件として、まず装置は、金属の電解研磨に使用さ
れる装置をほぼそのままの状態で使用可能であり、電解
条件などは、具体的には、例えば、溶液濃度:50〜3
00g/l,電圧:1〜5V,電流値:0.02〜0.
5A/cm2,電解時間:0.2〜5minを挙げるこ
とができる。As conditions for performing electropolishing using these electrolytic solutions, first, the apparatus can be used in almost the same state as the apparatus used for electropolishing of metal. For example, the solution concentration: 50 to 3
00 g / l, voltage: 1 to 5 V, current value: 0.02 to 0.
5 A / cm 2 , electrolysis time: 0.2 to 5 min.
【0026】このようにして作製された母材表面に硬質
膜を被覆させる方法は、従来からの製法であるCVD
法、プラズマCVD法、もしくはイオンプレーテング法
やスパッター法に代表されるPVD法の1種または2種
以上を組み合わせた方法により作製することができる。
この硬質膜の他に、母材と硬質膜との間に下地層を介在
させる場合には、下地層は、上述のCVD法、プラズマ
CVD法、PVD法により作製することも可能である
が、その他、例えばガス処理による浸炭処理や浸窒処理
などの乾式処理法または電解メッキ、無電解メッキ、溶
液中で浸漬加熱による浸炭処理や浸窒処理などの湿式処
理法により作製することも可能である。A method for coating the surface of the base material thus manufactured with a hard film is a conventional method of CVD.
It can be produced by a method, a plasma CVD method, or a method combining one or two or more of PVD methods represented by an ion plating method and a sputtering method.
In addition to this hard film, when an underlayer is interposed between the base material and the hard film, the underlayer can be formed by the above-described CVD method, plasma CVD method, or PVD method. In addition, it can also be produced by a dry treatment method such as carburizing treatment or nitriding treatment by gas treatment or a wet treatment method such as electrolytic plating, electroless plating, carburizing treatment by immersion heating in a solution, or nitriding treatment. .
【0027】[0027]
【作用】本発明の表面被覆焼結合金は、硬質膜が被覆さ
れた母材表面、好ましくは母材の全面に母材中の硬質相
粒子内にクラックが存在しないことが、膜の耐剥離性を
向上させる作用および外部の衝撃により発生したクラッ
クの進展を抑制させる作用をし、場合によっては、母材
と硬質膜との全界面における母材表面に微細な硬質相粒
子が存在しないこと、界面が平滑なこと、界面中の母材
表面における、硬質膜と母材の結合相との接合面積比が
硬質膜と母材の硬質相粒子との接合面積比よりも大きい
こと、界面中の母材表面において、立方晶構造化合物粒
子が存在しないことにより、膜の耐剥離性をさらに向上
させる作用、外部からの衝撃を吸収し、クラックの発生
を抑制する作用および外部の衝撃により発生したクラッ
クの進展を抑制する作用をしているものである。The surface-coated sintered alloy of the present invention is characterized in that no cracks are present in the hard phase particles in the base material on the surface of the base material coated with the hard film, preferably on the entire surface of the base material. Acts to improve the properties and suppress the growth of cracks generated by external impact, in some cases, the absence of fine hard phase particles on the surface of the base material at all interfaces between the base material and the hard film, That the interface is smooth, that the bonding area ratio between the hard film and the bonding phase of the base material on the surface of the base material in the interface is larger than the bonding area ratio between the hard film and the hard phase particles of the base material, The absence of cubic structure compound particles on the surface of the base material further enhances the peeling resistance of the film, absorbs external shocks, suppresses the occurrence of cracks, and cracks generated by external shocks Restrain progress It is one that has the effect.
【0028】また、本発明の表面被覆焼結合金の製法
は、母材表面の少なくとも一面に機械的加工で生じた加
工変質層をアルカリ性の電解液で電解研磨および/また
は電解ラッピングすることにより、母材表面に存在する
硬質相粒子内のクラックや微細な硬質相粒子を除去する
作用をし、さらには、機械的加工されていない焼結肌面
も含めて、表面の平滑化や組成を調整する作用をしてい
るものである。The method for producing a surface-coated sintered alloy according to the present invention is characterized in that at least one surface of the base material surface is subjected to electrolytic polishing and / or electrolytic lapping with an alkaline electrolytic solution on an affected layer formed by mechanical processing. It works to remove cracks and fine hard phase particles in the hard phase particles existing on the base material surface, and furthermore, adjusts the surface smoothness and composition, including the sintered surface that has not been mechanically processed. It has the function of doing.
【0029】[0029]
【実施試験1】配合組成成分が86.0%WC−1.5
%TiC−0.5%TiN−4.0%TaC−8.0%
Co(重量%)相当でなり、形状がISO規格でCNM
G120408のブレーカ付き超硬合金製スローアウエ
イチップを母材とし、ボス面を270#のダイヤモンド
砥石で研削加工し、刃先部を320#の炭化珪素砥粒を
含有したナイロン製ブラシで半径0.04mmのホーニ
ング加工した後、表1に示した電解液,電圧,電流値,
処理時間でもって室温で電解処理を施し、表1に示した
本発明品1〜8および比較品1に使用する表面処理した
母材を作製した。また、同一母材を用いて、電解処理を
施さずに、炭化珪素砥粒含有のブラシ加工処理した比較
品2に使用する表面処理母材と、同じく炭化珪素砥粒含
有のブラシ加工後にラップ加工した比較品3に使用する
表面処理母材と、同じく刃先部を1000#のダイヤモ
ンド砥粒を含有したナイロン製ブラシでホーニング加工
した比較品4に使用する表面処理母材を作製した。[Test 1] The composition was 86.0% WC-1.5.
% TiC-0.5% TiN-4.0% TaC-8.0%
Co (weight%) equivalent, the shape is CNM according to ISO standard
G120408 is a cemented carbide throwaway tip with a breaker as a base material, the boss surface is ground with a 270 # diamond grindstone, and the cutting edge is a 0.04mm radius with a nylon brush containing 320 # silicon carbide abrasive grains. After honing, the electrolyte, voltage, current,
Electrolytic treatment was performed at room temperature for a treatment time, and surface-treated base materials used for inventive products 1 to 8 and comparative product 1 shown in Table 1 were produced. Also, using the same base material, the surface-treated base material used for the comparative product 2 which was subjected to the brushing treatment containing silicon carbide abrasive grains without performing the electrolytic treatment, and the lapping after the brushing treatment also containing the silicon carbide abrasive grains. A surface-treated base material to be used for the comparative product 3 and a surface-treated base material to be used for the comparative product 4 in which the cutting edge was similarly honed with a nylon brush containing 1000 # diamond abrasive grains.
【0030】[0030]
【表1】 [Table 1]
【0031】これらの表面加工済みスローアウエイチッ
プの母材を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、母材側から1.0μmのTi
N,8.0μmの柱状晶TiCN,1.5μmのAl2
O3,0.5μmのTiNとでなる合計膜厚11.0μ
mを被覆し、本発明品1〜8と比較品1〜4の表面被覆
スローアウエイチップを得た。こうして得た表面被覆ス
ローアウエイチップのそれぞれ1個を切断し、切断面を
研削加工と0.3μmのダイヤモンドペーストでラップ
加工した後、電界放射型の走査電子顕微鏡を用いて母材
と硬質膜との界面付近を観察した。観察場所は、刃先の
被加工面とブレーカ内の焼肌面である。観察内容は、硬
質相粒子内のクラックの有無,0.2μm以下の硬質相
微細粒子の有無,2.0μm以上の粗大凹凸の有無,硬
質膜と硬質粒子との接着界面に対する硬質膜と結合相と
の界面における面積比,母材表面における(W,Ti,
Ta)C相の有無について行い、これらの観察結果を表
2に示した。After the base material of the surface-treated throw-away tip is subjected to ultrasonic cleaning in acetone, a 1.0 μm Ti
N, 8.0 μm columnar TiCN, 1.5 μm Al 2
Total film thickness of 11.0 μm consisting of O 3 and 0.5 μm TiN
m to obtain surface-coated throw-away chips of inventive products 1 to 8 and comparative products 1 to 4. One of the surface-coated throw-away chips thus obtained was cut, and the cut surface was ground and wrapped with a 0.3 μm diamond paste. Then, the base material and the hard film were cut using a field emission scanning electron microscope. The vicinity of the interface was observed. The observation places are the work surface of the cutting edge and the burnt surface in the breaker. The observations included the presence or absence of cracks in the hard phase particles, the presence or absence of hard phase fine particles of 0.2 μm or less, the presence or absence of coarse irregularities of 2.0 μm or more, the hard film and the bonding phase with respect to the adhesive interface between the hard film and the hard particles. Ratio at the interface with the substrate, (W, Ti,
Ta) The presence or absence of the C phase was determined, and the results of these observations are shown in Table 2.
【0032】次に、それぞれの表面被覆スローアウエイ
チップ5個を用いて、被削材:S45Cの4本溝入り,
切削速度:150m/min,切込み:2.0mm,送
り:0.30mm/rev,湿式の条件で外周断続旋削
試験を行った。断続切削による衝撃回数が1万回に達す
るまでの刃先欠損、1万回に達したものはその時点での
膜剥離(チッピング)などの結果を表2に併記した。こ
の表2に示した切削試験結果は、それぞれの表面被覆ス
ローアウエイチップ5個のうち、欠損、膜剥離および正
常摩耗を観察して、それぞれの個数として表示した。Next, using each of the five surface-coated throw-away tips, a work material: S45C having four grooves,
An outer peripheral intermittent turning test was performed under the conditions of cutting speed: 150 m / min, depth of cut: 2.0 mm, feed: 0.30 mm / rev, and wet type. Table 2 also shows the results such as chipping of the blade edge until the number of impacts due to intermittent cutting reaches 10,000, and film peeling (chipping) at the time when the number of impacts reached 10,000. The results of the cutting test shown in Table 2 were shown as the number of each of the five surface-coated throw-away tips by observing defects, film peeling, and normal wear.
【0033】[0033]
【表2】 [Table 2]
【0034】[0034]
【実施試験2】配合組成成分が88.0%WC−2.0
%TaC−10.0%Co(重量%)相当でなり、形状
がISO規格でSNGN120408でなる超硬合金製
スローアウエイチップの母材を用い、この母材の上下面
と外周面を270#のダイヤモンド砥石で研削加工し、
刃先部に400#ダイヤモンド砥石で−25°×0.1
0mmのホーニング加工した後、実施試験1の表1に記
載した本発明品1と本発明品3の条件で電解処理を施し
た。これらと電解処理を施していないチップとをアセト
ン中で超音波洗浄した後、CVDコーティング装置を用
いて、母材側から0.5μmのTiN,3.5μmの柱
状晶TiCN,0.5μmのAl2O3,0.5μmのT
iNとでなる合計膜厚5.0μmを被覆し、本発明品
9,10と比較品5の表面被覆スローアウエイチップを
得た。[Experimental test 2] The composition was 88.0% WC-2.0.
% TaC-10.0% Co (% by weight), and the base material of a cemented carbide throwaway chip having a shape of SNGN120408 according to the ISO standard is used. Grinding with a diamond whetstone,
-25 ° × 0.1 with 400 # diamond grindstone on the cutting edge
After a honing process of 0 mm, an electrolytic treatment was performed under the conditions of the product 1 of the present invention and the product 3 of the present invention described in Table 1 of Test 1. After ultrasonic cleaning of these and the chip not subjected to the electrolytic treatment in acetone, using a CVD coating apparatus, 0.5 μm of TiN, 3.5 μm of columnar crystal TiCN, and 0.5 μm of Al were used from the base material side. 2 O 3 , 0.5 μm T
A total thickness of 5.0 μm of iN was coated to obtain surface-coated throw-away chips of products 9 and 10 of the present invention and comparative product 5.
【0035】こうして得た表面被覆スローアウエイチッ
プについて、実施試験1と同様に走査型電子顕微鏡で観
察した結果、本発明品9,10では共に硬質相粒子内の
クラック,0.2μm以下の硬質相粒子が認められず、
硬質膜と結合相との接着界面の面積比が0.50と0.
55であったのに対し、比較品5では硬質相粒子内に無
数のクラックと界面に多数の微細硬質相粒子が認めら
れ、硬質膜と結合相との接着界面の面積比は0.30で
あった。Observation of the thus obtained surface-coated throw-away tip with a scanning electron microscope in the same manner as in Example 1 showed that the products 9 and 10 of the present invention exhibited cracks in the hard phase particles and a hard phase of 0.2 μm or less. No particles are found,
The area ratio of the adhesive interface between the hard film and the binder phase is 0.50 to 0.5.
On the other hand, in Comparative Product 5, innumerable cracks were found in the hard phase particles and a large number of fine hard phase particles were found at the interface, and the area ratio of the adhesive interface between the hard film and the bonding phase was 0.30. there were.
【0036】次に、それぞれの表面被覆スローアウエイ
チップについて、被削材:SCM440(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
件でフライス切削を行った。被削材面の切削回数を40
pass加工した時点で刃先部を観察した結果、すくい
面に発生した熱クラックの本数は本発明品9,10とも
3本であったのに対し、比較品5は5本であった。ま
た、比較品5では、熱クラック周辺にV溝状の摩耗、刃
先部に微小チッピング、すくい面のクレータ部に膜剥離
が認められた。Next, for each of the surface-coated throw-away tips, a work material: SCM440 (working surface shape:
Milling was carried out under the following conditions: 50 W × 200 L), cutting speed: 135 m / min, depth of cut: 2.0 mm, feed: 0.36 mm / tooth, dry type. Number of cuts on the work surface is 40
As a result of observing the cutting edge portion at the time of the pass processing, the number of thermal cracks generated on the rake face was 3 in each of the products 9 and 10 of the present invention, while that of the comparative product 5 was 5. In Comparative product 5, wear in the form of a V-groove around the thermal crack, micro chipping at the cutting edge, and film peeling at the crater on the rake face were observed.
【0037】[0037]
【実施試験3】市販されている超硬合金製ソリッドエン
ドミル(6φmm,2枚刃)を母材とし、この母材表面
を実施試験1の表1に記載した本発明品1の条件で電解
処理を施し(本発明品11用母材)、電解処理してない
母材(比較品6用母材)と一緒にアセトン中で超音波洗
浄した後、アークイオンプレーティング装置に設置し、
約3.0μmの(Ti,Al)N膜を被覆して本発明品
11と比較品6の表面被覆超硬エンドミルを得た。これ
らを用いて、被削材:プリハードン鋼(HRC=4
0),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。このときの
逃げ面摩耗幅は、本発明品11が0.06mmであるの
に対し、比較品6は0.11mmであった。EXAMPLE 3 A commercially available cemented carbide solid end mill (6 mm, 2 flutes) was used as a base material, and the surface of the base material was subjected to electrolytic treatment under the conditions of the product 1 of the present invention described in Table 1 of Example 1. (Base material for product 11 of the present invention), ultrasonic cleaning in acetone together with a base material that has not been subjected to electrolytic treatment (base material for comparative product 6), and then installed in an arc ion plating apparatus,
A (Ti, Al) N film of about 3.0 μm was coated to obtain surface-coated carbide end mills of the present invention 11 and the comparative product 6. Using these, the work material: pre-hardened steel (HRC = 4
0), cutting speed: 30 m / min, depth of cut: 10 mm,
Table feed: 64 mm, feed per blade: 0.02 mm /
Groove processing test is performed under the condition of blade and wet type, cutting length is 50m
At the point of time, the flank wear width of the cutting edge was measured. At this time, the flank wear width of the product 11 of the present invention was 0.06 mm, while that of the comparative product 6 was 0.11 mm.
【0038】[0038]
【実施試験4】市販されている約10φmm×60mm
の耐摩耗工具用超硬合金(JIS規格B4053ー19
96のV30相当)を母材とし、母材全面を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、実施試験1の
表1に記載した本発明品1の条件で電解処理を施し、本
発明品12用母材とした。この本発明品12用母材と電
解処理を施していない比較品7用母材のパンチとをアセ
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、母材側から0.5μmのTiN,3.5μmの
TiCNでなる合計膜厚4.0μmを被覆し、本発明品
12と比較品7の表面被覆超硬パンチを得た。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12が約90万ショットで
あるのに対し、比較品7は約35万ショットであった。[Test 4] Approximately 10φmm × 60mm commercially available
Cemented carbide for wear resistant tools (JIS B4053-19)
96 (equivalent to V30) was used as a base material, and the whole surface of the base material was subjected to rough grinding and finish grinding with 140 # and 800 # diamond grindstones to produce punches for punching. Electrolytic treatment was performed under the conditions of the invention product 1 to obtain a base material for the invention product 12. The base material for the product 12 of the present invention and the punch of the base material for the comparative product 7 not subjected to the electrolytic treatment were subjected to ultrasonic cleaning in acetone, and then 0.5 μm TiN was used from the base material side using a CVD coating apparatus. , 3.5 μm of TiCN to obtain a total film thickness of 4.0 μm, thereby obtaining surface-coated carbide punches of the present invention product 12 and the comparative product 7. 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 12 of the present invention had about 900,000 shots, while the comparative product 7 had about 350,000 shots.
【0039】[0039]
【実施試験5】実施試験2における本発明品10と比較
品5のうち、母材のみを市販されている炭窒化チタン含
有サーメット{配合組成成分:53%Ti(C,N)−
15%WC−10%TaCー5%Mo2Cー1%NbC
−1%ZrC−5%Ni−10%Co(重量%)相当}
とした以外は、ほぼ同条件により作製して本発明品13
および比較品8を得て、実施試験2の方法とはぼ同様に
して比較測定した結果、本発明品13と比較品8との対
比関係は、実施試験2における本発明品12と比較品7
との対比関係に相当した。[Test 5] Of the product 10 of the present invention and the product of comparison 5 in test 2, only the base material is commercially available. Cermet containing titanium carbonitride. Composition: 53% Ti (C, N)-
15% WC-10% TaC-5% Mo2C-1% NbC
-1% ZrC-5% Ni-10% Co (% by weight) equivalent}
The product 13 of the present invention was produced under substantially the same conditions except that
As a result of comparison and measurement in the same manner as in the test 2, the comparative relationship between the product 13 of the present invention and the comparative product 8 is as follows.
This corresponds to a contrast relationship with.
【0040】[0040]
【発明の効果】本発明の表面被覆焼結合金は、従来の表
面被覆焼結合金に比べて、母材表面の硬質相粒子内にク
ラックが存在しないことにより、母材と硬質膜との耐剥
離性が顕著に優れること、この結果切削工具として耐摩
耗性、耐欠損性および耐剥離性などの性能および耐摩耗
工具としての寿命が顕著に向上するという効果がある。
また、本発明の表面被覆焼結合金は、上述の他に母材表
面平滑度の高さ、母材表面の立方晶構造化合物量および
結合相量の調整を行うことにより、上述の効果がより一
層発揮されることになる。さらに、本発明の表面被覆焼
結合金の製法は、従来の機械加工や電解研磨による母材
表面の処理方法に対比して、母材表面の加工変質層が完
全に除去されて、母材表面における硬質相粒子内のクラ
ックの除去から平滑度の向上という電解荒研磨〜電解ラ
ッピング状の処理まで可能とした優れた方法である。As described above, the surface-coated sintered alloy of the present invention has less cracks in the hard phase particles on the surface of the base material than the conventional surface-coated sintered alloy. The peelability is remarkably excellent, and as a result, there is an effect that the performance such as wear resistance, chipping resistance and peel resistance as a cutting tool and the life as a wear-resistant tool are remarkably improved.
In addition, the surface-coated sintered alloy of the present invention, in addition to the above, by adjusting the height of the base material surface smoothness, the amount of the cubic structure compound and the amount of the binder phase on the base material surface, the above-mentioned effect is more enhanced It will be demonstrated even more. Furthermore, the method for producing a surface-coated sintered alloy of the present invention is characterized in that, in comparison with the conventional method of processing the base material surface by machining or electrolytic polishing, the work-affected layer on the base material surface is completely removed, and the base material surface is removed. This is an excellent method that enables from electrolytic rough polishing to electrolytic lapping-like treatment of removing cracks in the hard phase particles and improving smoothness in the above.
───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 3J011 DA02 QA03 SB01 SB02 SB04 SB14 SB19 SD02 SD03 4K029 AA02 AA04 AA21 BA43 BA44 BA46 BA54 BA55 BA56 BA58 BC00 BD05 CA04 DD06 FA01 FA03 4K030 BA02 BA18 BA29 BA36 BA37 BA38 BA40 BA41 BA42 BA43 BA44 BA53 BA56 BA57 BB01 BB13 CA03 CA11 DA02 LA01 LA22 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 3J011 DA02 QA03 SB01 SB02 SB04 SB14 SB19 SD02 SD03 4K029 AA02 AA04 AA21 BA43 BA44 BA46 BA54 BA55 BA56 BA58 BC00 BD05 CA04 DD06 FA01 FA03 4K030 BA02 BA18 BA29 BA36 BA37 BA38 BA40 BA41 BA42 BA BA44 BA53 BA56 BA57 BB01 BB13 CA03 CA11 DA02 LA01 LA22
Claims (12)
はサーメットでなる焼結合金の母材における、該母材の
少なくとも一部の表面が機械加工されており、該母材表
面に、該母材よりも高硬度な硬質膜を1層または2層以
上の積層に被覆された表面被覆焼結合金であり、該硬質
膜の被覆された該母材表面側の該硬質相の粒子内に該機
械加工によるクラックが存在しないようにした耐剥離性
に優れた表面被覆焼結合金。1. A base material of a cemented carbide or a sintered alloy made of cermet containing a hard phase and a binder phase, wherein at least a part of the surface of the base material is machined, and the surface of the base material is A surface-coated sintered alloy in which a hard film having a hardness higher than that of the base material is coated in one layer or two or more layers, and particles of the hard phase on the surface of the base material covered with the hard film. A surface-coated sintered alloy excellent in exfoliation resistance, in which cracks due to the machining are not present.
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種以上の立
方晶構造化合物とからなる硬質相と、鉄族金属を主成分
とする結合相とからなる超硬合金である請求項1に記載
の耐剥離性に優れた表面被覆焼結合金。2. The base material is composed of tungsten carbide as a main component and carbides, nitrides of metals belonging to groups 4a, 5a and 6a of the periodic table.
The cemented carbide according to claim 1, wherein the cemented carbide is a hard phase composed of carbonitride and at least one cubic compound in the mutual solid solution, and a binder phase mainly composed of an iron group metal. Surface coated sintered alloy with excellent peel resistance.
a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
種の単層もしくは2層以上の積層でなる請求項1または
2に記載の耐剥離性に優れた表面被覆焼結合金。3. The hard film is composed of 4a, 5a, 6 of the periodic table.
group a element, aluminum, silicon carbide, nitride,
Oxides and one selected from these mutual solid solutions
The surface-coated sintered alloy excellent in peeling resistance according to claim 1 or 2, wherein the surface-coated sintered alloy is formed of a single layer or a multilayer of two or more layers.
は、該母材の内部に含有する上記立方晶構造化合物に対
比して、該母材表面の該立方晶構造化合物が減少または
含有してないようにした請求項2または3に記載の耐剥
離性に優れた表面被覆焼結合金。4. The surface of the base material coated with the hard film, wherein the cubic structure compound on the surface of the base material is reduced or reduced as compared with the cubic structure compound contained in the base material. The surface-coated sintered alloy excellent in peeling resistance according to claim 2 or 3, which is not contained.
れている請求項1〜3のいずれか1項に記載の耐剥離性
に優れた表面被覆焼結合金。5. The surface-coated sintered alloy according to claim 1, wherein the hard film is coated adjacent to the base material.
において、該母材表面の凹凸が2.0μm未満でなる請
求項5に記載の耐剥離性に優れた表面被覆焼結合金。6. The surface coating with excellent peel resistance according to claim 5, wherein the surface of the base material has irregularities of less than 2.0 μm at an interface between the base material and the hard film. Binding gold.
において、該母材表面に存在する上記硬質相の粒子が
0.2μmを越える大きさでなる請求項5または6に記
載の耐剥離性に優れた表面被覆焼結合金。7. The base material according to claim 5, wherein at the interface between the base material and the hard film, the particles of the hard phase present on the surface of the base material have a size exceeding 0.2 μm. A surface-coated sintered alloy excellent in the described peeling resistance.
該母材中の上記硬質相と該硬質膜との接着界面に対する
該母材中の上記結合相と該硬質膜との接着界面の面積比
が0.4〜0.8である請求項5〜7のいずれか1項に
記載の耐剥離性に優れた表面被覆焼結合金。8. An interface between the base material and the hard film,
The area ratio of the bonding interface between the bonding phase and the hard film in the base material to the bonding interface between the hard phase and the hard film in the base material is 0.4 to 0.8. The surface-coated sintered alloy according to any one of the above items 7, which is excellent in peeling resistance.
はサーメットの焼結合金母材の少なくとも一部の表面を
機械加工する第1工程と、該機械加工後に該母材表面を
アルカリ性の電解液中で電解研磨し、該母材表面に残存
していた該機械加工による加工変質層を除去する第2工
程と、該加工変質層を除去した該母材表面に、該母材よ
りも高硬度な硬質膜を1層または2層以上の積層に被覆
する第3工程とを含む耐剥離性に優れた表面被覆焼結合
金の製法。9. A first step of machining a surface of at least a part of a cemented carbide or cermet sintered alloy base material containing a hard phase and a binder phase, and after the machining, the base material surface is made alkaline. A second step of electropolishing in the electrolytic solution of the above, and removing the machining-damaged layer remaining on the surface of the base material by the mechanical processing; and And a third step of coating a hard film having a high hardness on one or two or more laminated layers.
1種以上含む水酸化物とフェリシアン塩とを含有する溶
液、周期律表の1a族元素を1種以上含む亜硝酸塩,亜
硫酸塩,亜燐酸塩,炭酸塩を含有する溶液から選ばれた
少なくとも1種からなる請求項9に記載の耐剥離性に優
れた表面被覆焼結合金の製法。10. The electrolyte comprises a solution containing a hydroxide containing at least one Group 1a element of the periodic table and a ferricyan salt, a nitrite containing at least one Group 1a element of the Periodic Table, 10. The method for producing a surface-coated sintered alloy having excellent peeling resistance according to claim 9, comprising at least one selected from solutions containing sulfites, phosphites, and carbonates.
研削加工、ラップ加工、ブラスト加工、超音波加工の中
の少なくとも1種からなる請求項9または10に記載の
耐剥離性に優れた表面被覆焼結合金の製法。11. The surface excellent in peeling resistance according to claim 9, wherein said machining comprises at least one of grinding wheel grinding, brush grinding, lapping, blasting, and ultrasonic machining. Manufacturing method of coated sintered alloy.
び物理蒸着法により被覆される請求項9〜11のうちの
いずれか1項に記載の耐剥離性に優れた表面被覆焼結合
金の製法。12. The surface-coated sintered alloy according to claim 9, wherein said hard film is coated by a chemical vapor deposition method and / or a physical vapor deposition method. Manufacturing method.
Priority Applications (1)
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JP11017787A JP2000212743A (en) | 1999-01-27 | 1999-01-27 | Surface coated sintered alloy excellent in peeling resistance and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11017787A JP2000212743A (en) | 1999-01-27 | 1999-01-27 | Surface coated sintered alloy excellent in peeling resistance and its production |
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JP2000212743A true JP2000212743A (en) | 2000-08-02 |
Family
ID=11953441
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JP11017787A Pending JP2000212743A (en) | 1999-01-27 | 1999-01-27 | Surface coated sintered alloy excellent in peeling resistance and its production |
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---|---|---|---|---|
JP2002275571A (en) * | 2001-03-13 | 2002-09-25 | Toshiba Tungaloy Co Ltd | cBN-BASE SINTERED COMPACT, AND COATED TOOL CONSISTING THEREOF |
JP2005271193A (en) * | 2004-02-23 | 2005-10-06 | Hitachi Tool Engineering Ltd | Surface-coated cemented carbide cutting tool |
JP2007031779A (en) * | 2005-07-27 | 2007-02-08 | Tungaloy Corp | Film-coated sintered alloy |
AU2003211875B2 (en) * | 2002-01-25 | 2008-05-08 | Sumitomo Bakelite Co., Ltd. | Transparent composite composition |
JP2011074473A (en) * | 2009-10-01 | 2011-04-14 | Toyota Central R&D Labs Inc | Coated cemented carbide member |
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1999
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002275571A (en) * | 2001-03-13 | 2002-09-25 | Toshiba Tungaloy Co Ltd | cBN-BASE SINTERED COMPACT, AND COATED TOOL CONSISTING THEREOF |
AU2003211875B2 (en) * | 2002-01-25 | 2008-05-08 | Sumitomo Bakelite Co., Ltd. | Transparent composite composition |
JP2005271193A (en) * | 2004-02-23 | 2005-10-06 | Hitachi Tool Engineering Ltd | Surface-coated cemented carbide cutting tool |
JP2007031779A (en) * | 2005-07-27 | 2007-02-08 | Tungaloy Corp | Film-coated sintered alloy |
JP2011074473A (en) * | 2009-10-01 | 2011-04-14 | Toyota Central R&D Labs Inc | Coated cemented carbide member |
WO2012153437A1 (en) | 2011-05-10 | 2012-11-15 | 住友電工ハードメタル株式会社 | Surface coated cutting tool |
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US8945707B2 (en) | 2011-05-10 | 2015-02-03 | Sumitomo Electric Hardmetal Corp. | Surface-coated cutting tool |
JP2019147162A (en) * | 2018-02-26 | 2019-09-05 | 株式会社エンビジョンAescジャパン | Tool for ultrasonic jointing and method of manufacturing the same |
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