JP4247032B2 - Coated carbide end mill - Google Patents
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【０００１】
【発明が属する技術分野】
本発明は、金型、機械部品等の切削加工に使用される超硬エンドミルの表面被覆材として有用な硬質皮膜を被覆することにより、優れた耐摩耗性を発揮する被覆超硬エンドミルに関する。
【０００２】
【従来の技術】
ＡｌＣｒ系皮膜は、耐高温酸化特性に優れた硬質皮膜材として、下記に示す特許文献１から３が開示されている。
【特許文献１】
特許第３０２７５０２号公報（第６頁、図１）
【特許文献２】
特許第３０３９３８１号公報（第４頁、図１）
【特許文献３】
特開平２００２−１６０１２９号公報（第３頁、図１）
【０００３】
切削加工の低コスト化に伴い、高能率切削加工すなわち高速切削加工、高送り切削加工が行なわれ、超硬エンドミル切刃近傍の切削温度は、著しく向上した。このことにより超硬エンドミル表面に被覆される硬質皮膜においても、さらに高温及びもしくは高圧摩耗環境下で優れた耐摩耗性を有することが望まれており、更に皮膜硬度が高く、耐高温酸化特性に優れた硬質皮膜を被覆した被覆超硬エンドミルの開発が望まれていた。特許文献１は金属成分としてＡｌＣｒとＣ、Ｎ、Ｏの１種より選択されるＡｌＣｒ系硬質膜において、高硬度を有する非晶質膜に関する事例が開示されている。しかしこの非晶質膜の硬度は最大でもヌープ硬さ２１ＧＰａ程度であり、超硬エンドミルとして、耐摩耗効果は改善されず、密着性に関しても十分ではない。特許文献２及び特許文献３に開示されている硬質皮膜はＡｌＣｒの窒化物であり、約１０００℃の耐高温酸化特性を有しているが、１０００℃以上の耐酸化特性の検討は行われていない。また硬度はビッカ−ス硬さ２１ＧＰａ程度で硬度の改善が不十分であり耐摩耗性に乏しい。
【０００４】
【発明が解決しようとする課題】
本願発明は、上記の問題点を改善し、（ＡｌＣｒ）Ｎ系皮膜の欠点である硬度を高めることにより耐摩耗性を著しく改善し、その結果優れた工具寿命を発揮する被覆超硬エンドミルを提供することを目的とする。
【０００５】
【課題を解決するために手段】
本発明は、被覆超硬エンドミルにおいて、該被覆はアーク放電式イオンプレーティング法により被覆された硬質皮膜であり、該硬質皮膜は、（ＡｌｘＣｒ１−ｘ−ｙＳｉｙ）（Ｎ１−α−β−γＢαＣβＯγ）、但し、ｘ、ｙ、α、β、γは夫々原子比率を示し、０．４５＜ｘ＜０．８５、０≦ｙ＜０．３５、０．５０≦ｘ＋ｙ＜１．０、０≦α＜０．１５、０≦β＜０．６５、０．０８≦γ＜０．６５、０＜α＋β＋γ≦１．０で示される少なくとも１層以上からなり、θ−２θ法によるＸ線回折において測定される岩塩構造型の（２００）面に回折強度を有し、その回折ピークの半価幅が、０．５度以上、２．０度以下であり、該岩塩構造型の（１１１）面の回折強度をＩ（１１１）、（２００）面の回折強度をＩ（２００）とした時、０．３＜Ｉ（２００）／Ｉ（１１１）＜１２であり、Ｘ線光電子分光分析における５２５ｅＶから５３５ｅＶの範囲に、Ａｌ、Ｃｒ及び／又はＳｉと酸素との結合エネルギーを有し、該被覆超硬エンドミルの基体は、Ｃｏ含有量が重量％で２．０＜Ｃｏ＜１４．０であり、更にＣｒ、Ｔａ、Ｔｉ、Ｚｒから選択される１種以上の金属、炭化物、窒化物、酸化物もしくはその組み合わせから選択される金属及び／又は化合物を１種以上含有し、該被覆超硬エンドミルの基体内のタングステンカーバイドの平均粒径が０．２μｍ以上、０．７μｍ未満であり、ロックウェル硬度がＨＲＡで９３．０以上、９４．５未満であることを特徴とする被覆超硬エンドミルである。上記構成を採用することにより、基体と硬質皮膜との密着性に優れ、高硬度化することが可能となり、その結果、優れた耐摩耗性を発揮する本発明の被覆超硬エンドミルを完成させた。
【０００６】
本発明硬質皮膜は、該硬質皮膜の最表面から深さ方向に５００ｎｍ以内の深さ領域で酸素濃度が最大となる場合、耐高温酸化特性並びに耐摩耗特性改善に極めて有効である。また、本願発明の硬質皮膜は、硬質皮膜表面の凸部を機械的処理により平滑にすると、表面の摩擦係数が低減しこれによって切屑排出性が改善される。
【０００７】
【発明の実施の形態】
本発明の硬質皮膜を構成する金属元素の組成は、（ＡｌｘＣｒ１−ｘ−ｙＳｉｙ）において、ｘが０．４５＜ｘ＜０．８５、ｙが０≦ｙ＜０．３５、０．５０≦ｘ＋ｙ＜１．０を満足する必要がある。ｘの値が０．４５以下、またｘ＋ｙの値が０．５よりも少なくなる場合では皮膜硬度並びに耐高温酸化特性の改善効果が十分ではなく、ｘの値が０．８５以上またはｘ＋ｙの値が１の場合、皮膜硬度の著しい低下を招き耐摩耗性に劣る。またｙの値が０．３５以上では、硬質皮膜内に残留する圧縮応力が過大になり、被覆直後に自己破壊を誘発するなどの基体密着強度を著しく低下させる場合がある。
非金属元素の組成は、（Ｎ１−α−β−γＢαＣβＯγ）において、αは０．１５以上では皮膜が脆化し、好ましいαの上限値は０．０７である。硼素の添加は被加工物との耐溶着性と高温環境下での摩擦係数を低減し、潤滑性を向上させる効果がある。βは０．６５以上で皮膜が著しく脆化する。炭素の含有量の上限値は、炭素を含有する層厚に依存する。炭素を含有する層厚が０．５μｍ未満であれば、βの上限値は０．５である。炭素の添加は硬質皮膜の硬度を高めると同時に、摩擦係数を低減し、潤滑性を向上させる効果がある。γは０．０８以上、０．６５未満にすることが必要である。γが０の場合、耐高温酸化特性並びに皮膜硬度が充分ではなく耐摩耗性に乏しい。０．６５以上でも皮膜硬度が低下する。好ましいγの値は、酸素を含有する層厚に依存するが、０．５μｍ未満であれば、γの上限値は０．３である。酸素の添加は、硬質皮膜内に残留する圧縮応力を低減し、基体と皮膜との密着性を向上させる作用に加え、皮膜が緻密化することによる高硬度化と酸素の拡散経路である基体と垂直方向の結晶粒界を減少させることより、耐高温酸化性の改善に効果的である。
更に、金属元素のＡｌ、Ｃｒ、Ｓｉに対する非金属元素のＮ、Ｂ、Ｃ、Ｏの比は、化学量論的に（Ｎ、Ｂ、Ｃ、Ｏ）／（Ａｌ、Ｃｒ、Ｓｉ）＞１．０がより好ましい。
【０００８】
本発明の硬質皮膜はθ−２θ法によるＸ線回折において測定される岩塩構造型の（２００）面に回折強度を有し、その回折ピークの２の半価幅が、０．５度以上、２．０度以下とした。その理由は、０．５未満の場合は結晶粒が粗大化し、皮膜硬度並びに高温酸化特性が充分ではなく、耐摩耗性に乏しく、２．０を超えると皮膜が脆化し、基体密着強度を著しく劣化させるためである。
【０００９】
硬質皮膜はＸ線光電子分光分析にて、５２５ｅＶから５３５ｅＶの範囲に少なくともＡｌ、Ｃｒ及び／又はＳｉと酸素との結合エネルギーを有することが必要である。これは、これら金属元素が酸素との結合を有することにより、皮膜が緻密化し高硬度化され、さらに酸化雰囲気において酸素の拡散経路となる基体に対して垂直方向の結晶粒界が減少し、酸素の内向拡散を抑制する機能を有することによるものである。本発明皮膜の特徴である、Ｃｒ、Ａｌ及び／又はＳｉと酸素との結合状態を形成するには、最適な被覆条件と一定以上の酸素を硬質皮膜内に含有させることが必要である。
超硬合金基体は、Ｃｏ含有量が重量％で２．０＜Ｃｏ＜１４．０の範囲であり、Ｃｒ、Ｔａ、Ｔｉ、Ｚｒから選択される１種以上の金属、炭化物、窒化物、酸化物もしくはその組み合わせから選択される金属及び／又は化合物を少なくとも１種以上含有することとする。Ｃｏ含有量が２．０重量％以下となる場合は、切刃のチッピングが発生し易くなり、超硬エンドミルとしての特性を充分に発揮できない場合がある。１４．０重量％以上の場合、切刃の塑性変形が大きくなる傾向にあり、異常摩耗が発生し易くなる。好ましくは、３．０以上８．２未満である。これらの構成により、エンドミルによる切削加工の高速化並びに長寿命化を達成することが可能となる。
被覆超硬エンドミルの超硬合金内におけるタングステンカーバイドの平均粒径が０．２μｍ以上０．７μｍ未満、ロックウェル硬度がＨＲＡで９３．０以上９４．５未満である場合、本発明の硬質皮膜との密着強度に特に優れるとともに、高速切削加工で安定した切削寿命を示し、より好ましい被覆超硬エンドミルが得られる。
【００１０】
被覆超硬エンドミルにおいて、該硬質皮膜のθ−２θ法によるＸ線回折で測定される岩塩構造型の（１１１）面の回折強度をＩ（１１１）、（２００）面の回折強度をＩ（２００）とした時、０．３＜Ｉ（２００）／Ｉ（１１１）＜１２とすることが好ましい。皮膜の密着性は残留圧縮応力に強く依存し、この残留圧縮応力は被覆条件であるイオンエネルギーに強く依存している。即ち、イオンエネルギーが低い条件下では皮膜の残留圧縮応力は低い結果となる。逆に、イオンエネルギーが高い条件下では皮膜の残留圧縮応力は高い結果となる。ここで、イオンエネルギーを決定する要素は、具体的には成膜条件であるバイアス電圧、反応ガス圧力であり、これによって制御することができる。本発明は、残留圧縮応力が高い場合、Ｘ線回折において皮膜は（１１１）面に強く配向し、皮膜の硬度も、この高い残留圧縮応力の影響を受けて高硬度とする事が可能となる。一方、皮膜の密着性に着目すると、硬質皮膜内の残留圧縮応力を高くすると、皮膜の高硬度化を達成できるが、基体と皮膜界面近傍においてせん断応力が増大する方向に作用するため、密着性を損なうこととなり、好ましくない。従って、基体と皮膜との密着性及び皮膜硬度とのバランスを最適に制御することが重要となる。本発明では、０．３＜Ｉ（２００）／Ｉ（１１１）＜１２とすることにより、両者のバランスを最適に制御することを可能にした。
【００１１】
更に、該硬質皮膜の最表面から深さ方向に５００ｎｍ以内の深さ領域で酸素濃度が最大となる場合、特に切削寿命に優れ好ましい。切削過程における硬質皮膜の酸化は硬質皮膜最表面からの酸素の拡散が支配的である。従って、硬質皮膜表面を酸素リッチにすることにより、結晶が緻密化し酸素の拡散経路となる基体と垂直方向成分の結晶粒界を減少させることができ、より耐高温酸化特性に優れ切削寿命が向上する。また、硬質皮膜最表面を酸素リッチにすることにより、切り屑流れを助長する効果も確認され、潤滑特性を改善することが可能となり好ましい。
【００１２】
本発明の皮膜を被覆し、被覆基体表面の研磨面や研削面に沿った硬質皮膜表面の凸部や、被覆中に発生したマクロ粒子等の付着により凸部が形成される場合があるため、その凸部を機械的処理により平滑にすることにより、切屑除去効果に更に優れ望ましい。更に、被覆後に切刃エッジに機械的処理を施すことにより、なじみ効果も確認され、耐欠損、耐チッピング特性を改善することができ、より好ましい皮膜超硬エンドミルを得ることができる。
【００１３】
本発明である該硬質皮膜は、アークイオンプレーティング法による被覆により、基体との密着性に特に優れ、緻密で耐高温酸化特性、高硬度を有する極めて長寿命を有する被覆超硬エンドミルが得られる。
【００１４】
該硬質皮膜の結晶粒のアスペクト比について、本発明の皮膜破断面の膜厚Ｔについて、膜厚Ｔの２５％から５０％の厚みであるＴ１に相当する上下膜厚方向の上端位置と下端位置とを求める。この時、上端位置と下端位置は、Ｔ／２に相当する基準位置より上下膜厚方向に略均等となる様に割り振る。各上下端位置における水平方向の上端側粒径Ｋと下端側粒径Ｌを求める。そこで、アスペクト比をＴ１／（（Ｋ＋Ｌ）／２）とすると、柱状結晶構造からなる該硬質皮膜の結晶粒のアスペクト比が、０．２から１２である。アスペクト比が１２を超えて大きくなると、結晶粒が膜厚方向に細長くなり、皮膜の靭性が低下し好ましくない。０．２未満では粒状結晶が増加する傾向となり、皮膜硬度が低下し好ましくない。更に、該硬質皮膜の残留圧縮応力が、０．５ＧＰａ以上、４．０ＧＰａ以下であることが、硬質皮膜に靭性を持たせ、皮膜硬度と基体密着性とのバランスに適した範囲となり、性能の改善に効果的である。
【００１５】
更に、本発明の硬質皮膜において金属成分の１０原子％未満を周期律表の４ａ、５ａ、６ａ族の金属成分の少なくとも１種以上で置き換えた場合、また本発明に関わる硬質皮膜を１層以上含有する複層構造においても、同様な効果が確認され好ましく、本発明の技術的範囲に含まれるものである。以下、実施例に基づき、本発明を具体的に説明する。
【００１６】
【実施例】
（実施例１）
成膜には酸素を３２００ｐｐｍ含有した粉末法により作成した合金ターゲットを用い、基本となる被覆条件は、反応ガスを真空装置内に導入後、全圧を１０Ｐａ、バイアス電圧を−１２０Ｖ、被覆温度を４５０℃、膜厚を約３．５ｍとし、（Ａｌ０．６５Ｃｒ０．３５）（Ｎ０．８０Ｃ０．０８Ｏ０．１０Ｂ０．０２）からなる硬質皮膜を被覆し、本発明例１とした。皮膜組成は、電子プローブＸ線マイクロアナリシス及びオージェ電子分光法により決定した。硬質皮膜の酸素との結合状態を解析するためのＸ線光電子分光分析は、ＰＨＩ社製１６００Ｓ型Ｘ線光電子分光分析装置を用い、Ｘ線源はＭｇＫαを用い４００Ｗとし、分析領域を直径０．４ｍｍの円内部を分析した。十分に脱脂洗浄した後、真空装置内で硬質皮膜表面に付着した汚染物質等を除去するために５分間Ａｒイオンガンを用いて表面をエッチングした後、ワイドスペクトルを測定し、更に３０秒間エッチングした後、ナロースペクトルを測定した。ＡｒイオンガンによるエッチングレートはＳｉＯ２換算で１．９ｎｍ／分であった。本発明例１のＸ線光電子分光分析結果を図１に示す。図１は結合エネルギーが５３０ｅＶ近傍のナロースペクトル示し、Ｃｒ−Ｏ及びＡｌ−Ｏの結合の存在を示す。図２はＣｒ−Ｎ及びＣｒ−Ｏの結合の存在を示す。図３はＡｌ−Ｎ及びＡｌ−Ｏの結合の存在を示す。図４は、本発明例１のθ−２θ法によるＸ線回折結果を示す。
【００１７】
（実施例２）
超硬合金を基体に用い、表１に示す皮膜組成の、本発明例２〜５、比較例６〜１３及び従来例１４を製作した。被覆条件は実施例１に準ずる。表１に皮膜の組成等を示す。
【００１８】
【表１】
表１の試料を用いて、大気中１１００℃の酸化条件で処理した皮膜の酸化層の厚さ、実施例２同様に微小押込み硬さ、薄板の変形量より算出した残留圧縮応力、弾性回復率を測定した。表１より、酸化層厚さは、本発明例２〜５、は、殆ど酸化進行が無く、耐高温酸化特性に優れていることが確認された。従来例１４は酸化進行が著しく、硬質皮膜は殆ど酸化物となり、酸素の内向拡散が激しく、酸化層は基体まで到達していた。押込み硬さも炭素、硼素を含有させることにより、更に高硬度となる。残留圧縮応力は、本発明例２〜５は低い。
【００２０】
次に、表１の本発明例２〜５、比較例６〜１３及び従来例１４を用いて圧痕試験による皮膜剥離状況を併記する。測定はロックウェル硬度計により１４７０Ｎの荷重で圧痕を形成し、光学顕微鏡により圧痕周辺部の剥離状況を観察した。本発明例２〜５は剥離が無く、優れた密着性を示した。これは本発明例が適正なＥ値の範囲内にあるためである。比較例６〜１３、従来例１４は被覆基体の塑性変形に追従することができず、圧痕周辺部に膜剥離が発生した。
【００２１】
（実施例３）
表１に示す本発明例２〜５、比較例６〜１３及び従来例１４の硬質皮膜を外径８ｍｍ、６枚刃、超硬エンドミルに被覆した。被覆条件は実施例１に準ずる。表１に示す本発明例２〜５、比較例６〜１３及び従来例１４の被覆超硬エンドミルを用いて、下記条件の切削試験を行いエンドミルが切削不能に至るまでの時間を表１に併記する。
（切削諸元）
切削方法：側面加工
被削材：ＳＫＤ１１（硬さＨＲＣ６３）
切り込み：Ａｄ８ｍｍ、Ｒｄ０．２ｍｍ
切削速度：２００ｍ／ｍｉｎ
送り：０．０６ｍｍ／刃
切削油：無し（乾式エアーブロー）
【００２２】
表１より、本発明例２〜５の超硬合金を基体とした被覆超硬エンドミルは、従来例１４と比較して切削不能に至るまでの切削時間が長く、耐摩耗性に優れている。本発明例５は硬質皮膜最表面の酸素濃度が高く、硬質皮膜内部が硬質皮膜最表面に比べ、低い場合の発明例を示すが、極めて寿命が長い。比較例６は被覆条件をバイアス電圧−５００Ｖで被覆した硬質皮膜のＸ線回折による最強強度面指数が（２２０）面を示し、Ｉ（２００）／Ｉ（１１１）の値が０．２となり、本発明例に比べて切削寿命が短い。比較例７はターゲットに含有する酸素濃度が１２００ｐｐｍからなるターゲットを使用した場合を示すが、Ｘ線光電子分光分析により酸化物としての結合状態が確認されず、本発明例に比べて切削寿命が短い。比較例８は超硬合金基体中のＣｏ含有量が１５．０重量％の場合の比較例であるが本発明例に比較して、寿命が短い。比較例９は、超硬合金基体中にＷＣ−Ｃｏ以外に添加元素がない場合の比較例であるが寿命が短い。比較例１０はＡｌ含有量が２０原子％の場合であり、弾性回復率が２８よりも低く、切削寿命が短く、耐摩耗性が十分ではないことを示す。比較例１１はＡｌ含有量が９０原子％の場合であり、切削寿命が短く耐摩耗性に劣る。比較例１２は酸素含有量が６８原子％の場合であるが、耐摩耗性が十分ではない。比較例１３はＡｌ含有量が４３原子％の場合であるが耐摩耗性が十分ではない。
【００２３】
【発明の効果】
本願発明の被覆超硬エンドミルを適用することにより、過酷な切削加工に用いても十分な耐摩耗性を有し、基体表面とその直上の硬質皮膜との密着性改善を図り、更に高硬度で耐高温酸化特性に優れた被覆超硬エンドミルを得ることが出来た。
【図面の簡単な説明】
【図１】図１は、本発明例のＣｒ−Ｏ及びＡｌ−Ｏの結合エネルギーを示す。
【図２】図２は、本発明例のＣｒ−Ｎ及びＣｒ−Ｏの結合エネルギーを示す。
【図３】図３は、本発明例のＡｌ−Ｎ及びＡｌ−Ｏの結合エネルギーを示す。
【図４】図４は、本発明例のＸ線回折結果を示す。
【図５】図５は、本発明例と従来例のＡｌ添加量と皮膜硬度の関係を示す。[0001]
[Technical field to which the invention belongs]
The present invention relates to a coated carbide end mill that exhibits excellent wear resistance by coating a hard coating useful as a surface coating material for a carbide end mill used for cutting of molds, machine parts, and the like.
[0002]
[Prior art]
Patent Documents 1 to 3 shown below are disclosed as hard coating materials having excellent high-temperature oxidation resistance for AlCr-based coatings.
[Patent Document 1]
Japanese Patent No. 3027502 (page 6, FIG. 1)
[Patent Document 2]
Japanese Patent No. 3039381 (page 4, FIG. 1)
[Patent Document 3]
Japanese Patent Laid-Open No. 2002-160129 (page 3, FIG. 1)
[0003]
Along with cost reduction of cutting, high-efficiency cutting, that is, high-speed cutting and high-feed cutting, was performed, and the cutting temperature near the carbide end mill cutting edge was remarkably improved. As a result, even hard coatings coated on the surface of carbide end mills are expected to have excellent wear resistance under higher temperature and / or high pressure wear environments, and have higher coating hardness and high temperature oxidation resistance. Development of a coated carbide end mill coated with an excellent hard coating has been desired. Patent Document 1 discloses an example of an amorphous film having high hardness in an AlCr hard film selected from AlCr and one of C, N, and O as a metal component. However, the hardness of this amorphous film is at most about 21 GPa of Knoop hardness, and as a carbide end mill, the wear resistance effect is not improved and the adhesion is not sufficient. The hard coatings disclosed in Patent Document 2 and Patent Document 3 are AlCr nitrides and have high-temperature oxidation resistance of about 1000 ° C., but oxidation resistance characteristics of 1000 ° C. or higher have been studied. Absent. Further, the hardness is about 21 GPa in Vickers hardness, and the improvement of the hardness is insufficient and the wear resistance is poor.
[0004]
[Problems to be solved by the invention]
The present invention provides a coated carbide end mill that improves the above-mentioned problems and significantly improves the wear resistance by increasing the hardness, which is a drawback of (AlCr) N-based coatings, resulting in excellent tool life. The purpose is to do.
[0005]
[Means for solving the problems]
In the coated carbide end mill according to the present invention, the coating is a hard coating coated by an arc discharge ion plating method, and the hard coating is (Al x Cr 1-xy Si y ) (N 1- [alpha]-[beta]-[gamma] B [ alpha] C [ beta] O [ gamma] ), where x, y, [alpha], [beta], and [gamma] each represent an atomic ratio, 0.45 <x <0.85, 0≤y <0.35, 0. .50 ≦ x + y <1.0, 0 ≦ α <0.15, 0 ≦ β <0.65, 0.08 ≦ γ <0.65, 0 <α + β + γ ≦ 1.0 And having a diffraction intensity on the (200) plane of the rock salt structure type measured in the X-ray diffraction by the θ-2θ method, and the half width of the diffraction peak is not less than 0.5 degrees and not more than 2.0 degrees Yes, I (111) diffraction intensity of the該岩salt structure type (111) plane, when the (200) diffraction intensity of the plane I (200), 0 3 <I (200) / I (111) < is 12, the range of 535eV from 525eV in the X-ray photoelectron spectroscopy, Al, has a binding energy between Cr and / or Si and oxygen, the coating superhard The substrate of the end mill has a Co content of 2.0 <Co <14.0 by weight%, and one or more metals selected from Cr, Ta, Ti, Zr, carbide, nitride, oxide or Containing one or more metals and / or compounds selected from the combination, the average particle size of tungsten carbide in the substrate of the coated carbide end mill is 0.2 μm or more and less than 0.7 μm, and the Rockwell hardness is It is a coated carbide end mill characterized by having an HRA of 93.0 or more and less than 94.5. By adopting the above configuration, it is possible to achieve high hardness with excellent adhesion between the substrate and the hard film, and as a result, the coated carbide end mill of the present invention that exhibits excellent wear resistance has been completed. .
[0006]
The hard coating of the present invention is extremely effective for improving the high temperature oxidation resistance and the wear resistance when the oxygen concentration becomes maximum in a depth region within 500 nm in the depth direction from the outermost surface of the hard coating. Moreover, when the hard film of this invention makes the convex part of the hard film surface smooth by mechanical processing, the friction coefficient of a surface will reduce and this will improve chip discharge | emission property.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the composition of the metal element constituting the hard coating of the present invention, in (Al x Cr 1-xy Si y ), x is 0.45 <x <0.85, y is 0 ≦ y <0.35, It is necessary to satisfy 0.50 ≦ x + y <1.0. When the value of x is 0.45 or less and the value of x + y is less than 0.5, the effect of improving the film hardness and the high temperature oxidation resistance is not sufficient, and the value of x is 0.85 or more or x + y Is 1, the film hardness is remarkably lowered and the wear resistance is poor. On the other hand, if the value of y is 0.35 or more, the compressive stress remaining in the hard film becomes excessive, and the substrate adhesion strength such as inducing self-destruction immediately after coating may be significantly reduced.
The composition of the nonmetallic element is (N 1-α-β-γ B α C β O γ ). When α is 0.15 or more, the film becomes brittle, and the preferable upper limit value of α is 0.07. Addition of boron has the effect of improving the lubricity by reducing the welding resistance to the workpiece and the coefficient of friction in a high temperature environment. When β is 0.65 or more, the coating becomes extremely brittle. The upper limit value of the carbon content depends on the layer thickness containing carbon. If the layer thickness containing carbon is less than 0.5 μm, the upper limit of β is 0.5. The addition of carbon has the effect of increasing the hardness of the hard coating and at the same time reducing the coefficient of friction and improving the lubricity. γ needs to be 0.08 or more and less than 0.65. When γ is 0, the high temperature oxidation resistance and the film hardness are not sufficient, and the wear resistance is poor. Even at 0.65 or more, the film hardness decreases. The preferable value of γ depends on the layer thickness containing oxygen, but if it is less than 0.5 μm, the upper limit of γ is 0.3. The addition of oxygen reduces the compressive stress remaining in the hard coating, improves the adhesion between the substrate and the coating, increases the hardness due to the densification of the coating, and the substrate that is the oxygen diffusion path. By reducing the grain boundaries in the vertical direction, it is effective in improving high-temperature oxidation resistance.
Furthermore, the ratio of the non-metallic elements N, B, C, O to the metallic elements Al, Cr, Si is stoichiometrically (N, B, C, O) / (Al, Cr, Si)> 1. 0.0 is more preferable.
[0008]
The hard film of the present invention has a diffraction intensity on the (200) plane of the rock salt structure type measured in the X-ray diffraction by the θ-2θ method, and the half width of 2 of the diffraction peak is 0.5 degrees or more, It was set to 2.0 degrees or less. The reason is that if it is less than 0.5, the crystal grains become coarse, the film hardness and high-temperature oxidation characteristics are not sufficient, and the wear resistance is poor, and if it exceeds 2.0, the film becomes brittle and the adhesion strength of the substrate is remarkably increased. It is for deteriorating.
[0009]
The hard coating is required to have a binding energy of at least Al, Cr and / or Si and oxygen in the range of 525 eV to 535 eV by X-ray photoelectron spectroscopy. This is because these metal elements have a bond with oxygen, the film is densified and hardened, and the grain boundaries in the direction perpendicular to the substrate, which becomes the oxygen diffusion path in an oxidizing atmosphere, are reduced. This is because it has a function of suppressing inward diffusion of the. In order to form a bonded state of Cr, Al and / or Si and oxygen, which is a feature of the coating of the present invention, it is necessary to contain optimum coating conditions and a certain amount of oxygen in the hard coating.
Cemented carbide substrate is in the range of 2.0 <Co <14.0 Co content in weight%, Cr, Ta, Ti, 1 or more metals selected from Zr, carbides, nitrides, oxides And at least one metal and / or compound selected from the above or a combination thereof. When the Co content is 2.0% by weight or less, chipping of the cutting edge is likely to occur, and the characteristics as a carbide end mill may not be sufficiently exhibited. When it is 14.0% by weight or more, the plastic deformation of the cutting edge tends to increase, and abnormal wear tends to occur. Preferably, it is 3.0 or more and less than 8.2. With these configurations, it is possible to achieve high speed cutting and long life of the end mill.
When the average particle size of tungsten carbide in the cemented carbide of the coated carbide end mill is 0.2 μm or more and less than 0.7 μm and the Rockwell hardness is 93.0 or more and less than 94.5 in HRA, In particular, the coated cemented carbide end mill can be obtained with excellent adhesion strength and a stable cutting life by high-speed cutting.
[0010]
In a coated carbide end mill, the diffraction intensity of the (111) plane of the rock salt structure type measured by X-ray diffraction of the hard coating by the θ-2θ method is I (111), and the diffraction intensity of the (200) plane is I (200 ), It is preferable that 0.3 <I (200) / I (111) <12. The adhesion of the film strongly depends on the residual compressive stress, and this residual compressive stress strongly depends on the ion energy which is the coating condition. That is, the residual compressive stress of the film is low under the condition where the ion energy is low. Conversely, the residual compressive stress of the film is high under conditions where ion energy is high. Here, the factors that determine the ion energy are specifically the bias voltage and the reaction gas pressure, which are film formation conditions, and can be controlled by this. In the present invention, when the residual compressive stress is high, the film is strongly oriented in the (111) plane in X-ray diffraction, and the hardness of the film can also be increased by the influence of the high residual compressive stress. . On the other hand, paying attention to the adhesion of the film, if the residual compressive stress in the hard film is increased, the hardness of the film can be increased, but it acts in the direction of increasing the shear stress in the vicinity of the interface between the substrate and the film. This is not preferable. Therefore, it is important to optimally control the balance between the adhesion between the substrate and the film and the film hardness. In the present invention, by setting 0.3 <I (200) / I (111) <12, the balance between the two can be optimally controlled.
[0011]
Furthermore, when the oxygen concentration becomes maximum in a depth region within 500 nm in the depth direction from the outermost surface of the hard coating, it is particularly preferable because of excellent cutting life. The oxidation of the hard coating during the cutting process is dominated by the diffusion of oxygen from the outermost surface of the hard coating. Therefore, by making the hard coating surface oxygen-rich, the crystal becomes denser and the grain boundary of the component perpendicular to the substrate that becomes the oxygen diffusion path can be reduced, and it has better high-temperature oxidation resistance and improved cutting life. To do. Further, by making the outermost surface of the hard coating rich in oxygen, the effect of promoting the chip flow is also confirmed, and it is possible to improve the lubricating characteristics, which is preferable.
[0012]
Since the coating of the present invention is coated, the convex portion of the hard coating surface along the polished surface or ground surface of the coated substrate surface, or the convex portion may be formed by adhesion of macro particles generated during coating, By smoothing the convex portion by mechanical treatment, it is further excellent in chip removal effect and desirable. Furthermore, by applying a mechanical treatment to the cutting edge after coating, a conforming effect can be confirmed, the chipping resistance and chipping resistance can be improved, and a more preferable coated carbide end mill can be obtained.
[0013]
The hard coating according to the present invention is coated with an arc ion plating method, and is particularly excellent in adhesion to a substrate, and can provide a coated carbide end mill having a dense, high temperature oxidation resistance, high hardness and extremely long life. .
[0014]
Regarding the aspect ratio of the crystal grains of the hard film, the upper end position and the lower end position in the vertical film thickness direction corresponding to T1 which is 25% to 50% of the film thickness T with respect to the film thickness T of the film fracture surface of the present invention. And ask. At this time, the upper end position and the lower end position are allocated so as to be substantially equal in the vertical film thickness direction from the reference position corresponding to T / 2. The upper end side particle size K and the lower end side particle size L in the horizontal direction at each upper and lower end position are obtained. Therefore, when the aspect ratio is T1 / ((K + L) / 2), the aspect ratio of the crystal grains of the hard coating having a columnar crystal structure is 0.2 to 12. When the aspect ratio is larger than 12, the crystal grains are elongated in the film thickness direction, and the toughness of the film is lowered, which is not preferable. If it is less than 0.2, the granular crystals tend to increase, and the film hardness decreases, which is not preferable. Furthermore, if the residual compressive stress of the hard coating is 0.5 GPa or more and 4.0 GPa or less, the hard coating has toughness, which is in a range suitable for the balance between the coating hardness and the substrate adhesion. It is effective for improvement.
[0015]
Further, in the hard coating of the present invention, when less than 10 atomic% of the metal component is replaced with at least one metal component of groups 4a, 5a, and 6a of the periodic table, one or more hard coatings related to the present invention are also included. The same effect is also confirmed in the multilayer structure to be contained, and it is included in the technical scope of the present invention. Hereinafter, based on an Example, this invention is demonstrated concretely.
[0016]
【Example】
Example 1
An alloy target prepared by a powder method containing 3200 ppm of oxygen was used for film formation. The basic coating conditions were as follows: after introducing the reaction gas into the vacuum apparatus, the total pressure was 10 Pa, the bias voltage was -120 V, and the coating temperature was A hard film made of (Al 0.65 Cr 0.35 ) (N 0.80 C 0.08 O 0.10 B 0.02 ) was coated at 450 ° C. and a film thickness of about 3.5 m, and the present invention Example 1 was adopted. The film composition was determined by electron probe X-ray microanalysis and Auger electron spectroscopy. The X-ray photoelectron spectroscopic analysis for analyzing the bonding state of the hard film with oxygen uses a PHI 1600S type X-ray photoelectron spectroscopic analyzer, the X-ray source is 400 W using MgKα, and the analysis region has a diameter of 0. The inside of a 4 mm circle was analyzed. After thoroughly degreasing and cleaning, the surface is etched using an Ar ion gun for 5 minutes to remove contaminants attached to the surface of the hard film in a vacuum apparatus, then a wide spectrum is measured, and etching is further performed for 30 seconds. The narrow spectrum was measured. The etching rate by Ar ion gun was 1.9 nm / min in terms of SiO 2 . The X-ray photoelectron spectroscopic analysis result of Example 1 of the present invention is shown in FIG. FIG. 1 shows a narrow spectrum with a binding energy of around 530 eV, indicating the presence of Cr—O and Al—O bonds. FIG. 2 shows the presence of Cr—N and Cr—O bonds. FIG. 3 shows the presence of Al—N and Al—O bonds. FIG. 4 shows an X-ray diffraction result according to the θ-2θ method of Example 1 of the present invention.
[0017]
(Example 2)
Using cemented carbide for the substrate, Invention Examples 2 to 5, Comparative Examples 6 to 13 and Conventional Example 14 having the film compositions shown in Table 1 were produced. The coating conditions are the same as in Example 1. Table 1 shows the composition of the film.
[0018]
[Table 1]
Using the sample of Table 1, the thickness of the oxide layer of the film treated under the oxidizing condition of 1100 ° C. in the atmosphere, the micro-indentation hardness, the residual compressive stress calculated from the amount of deformation of the thin plate, and the elastic recovery rate as in Example 2. Was measured. From Table 1, it was confirmed that the oxide layer thicknesses of Invention Examples 2 to 5 had little oxidation progress and were excellent in high-temperature oxidation resistance. In Conventional Example 14, the oxidation progressed remarkably, the hard coating almost became an oxide, the inward diffusion of oxygen was intense, and the oxide layer reached the substrate. The indentation hardness is further increased by containing carbon and boron. Residual compressive stress is low in inventive examples 2-5.
[0020]
Next, the present examples 2-5, comparative examples 6-13, and conventional example 14 in Table 1 are used to describe the state of film peeling by an indentation test. In the measurement, an indentation was formed with a load of 1470 N using a Rockwell hardness meter, and the peeling state around the indentation was observed using an optical microscope. Invention Examples 2 to 5 showed no adhesion and excellent adhesion. This is because the example of the present invention is within an appropriate E value range. Comparative Examples 6 to 13 and Conventional Example 14 could not follow the plastic deformation of the coated substrate, and film peeling occurred in the periphery of the indentation.
[0021]
(Example 3)
The hard films of Invention Examples 2 to 5, Comparative Examples 6 to 13 and Conventional Example 14 shown in Table 1 were coated on an outer diameter of 8 mm, 6 blades, and a carbide end mill. The coating conditions are the same as in Example 1. Using the coated carbide end mills of Invention Examples 2 to 5, Comparative Examples 6 to 13 and Conventional Example 14 shown in Table 1, the cutting test under the following conditions is performed and the time until the end mill becomes uncuttable is also shown in Table 1. To do.
(Cutting specifications)
Cutting method: Side machining Work material: SKD11 (hardness HRC63)
Cutting depth: Ad8mm, Rd0.2mm
Cutting speed: 200 m / min
Feed: 0.06mm / blade Cutting oil: None (dry air blow)
[0022]
From Table 1, the coated cemented carbide end mill based on the cemented carbides of Examples 2 to 5 of the present invention has a longer cutting time until it becomes incapable of cutting than the conventional example 14, and is excellent in wear resistance. Invention Example 5 shows an invention example where the oxygen concentration on the outermost surface of the hard coating is high and the inside of the hard coating is lower than the outermost surface of the hard coating, but the life is extremely long. Comparative Example 6 shows that the hardest surface index by X-ray diffraction of a hard coating coated with a coating condition at a bias voltage of −500 V is a (220) plane, and the value of I (200) / I (111) is 0.2, The cutting life is shorter than that of the example of the present invention. Comparative Example 7 shows a case where a target having an oxygen concentration of 1200 ppm contained in the target is used, but the bonding state as an oxide is not confirmed by X-ray photoelectron spectroscopy, and the cutting life is shorter than that of the present invention. . Although Comparative Example 8 is a comparative example where Co content in the cemented carbide substrate is a 15.0 wt% compared to the present invention embodiment, a short life. Although the comparative example 9 is a comparative example when there is no additive element other than WC-Co in the cemented carbide substrate , the lifetime is short. Comparative Example 10 is a case where the Al content is 20 atomic%, and shows that the elastic recovery rate is lower than 28, the cutting life is short, and the wear resistance is not sufficient. Comparative Example 11 is a case where the Al content is 90 atomic%, and the cutting life is short and the wear resistance is poor. In Comparative Example 12, the oxygen content is 68 atomic%, but the wear resistance is not sufficient. In Comparative Example 13, the Al content is 43 atomic%, but the wear resistance is not sufficient.
[0023]
【The invention's effect】
By applying the coated carbide end mill of the present invention, it has sufficient wear resistance even when used in severe cutting work, and improves the adhesion between the substrate surface and the hard film directly above it, with higher hardness. A coated carbide end mill with excellent high-temperature oxidation resistance could be obtained.
[Brief description of the drawings]
FIG. 1 shows the binding energy of Cr—O and Al—O of the present invention example.
FIG. 2 shows the binding energy of Cr—N and Cr—O of the present invention example.
FIG. 3 shows the binding energies of Al—N and Al—O of the examples of the present invention.
FIG. 4 shows the X-ray diffraction results of an example of the present invention.
FIG. 5 shows the relationship between the amount of Al added and film hardness in the present invention example and the conventional example.
Claims (3)
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| JP2004306237A (en) * | 2003-04-10 | 2004-11-04 | Hitachi Tool Engineering Ltd | Coated end mill and roughing |
| JP2004337989A (en) * | 2003-05-13 | 2004-12-02 | Hitachi Tool Engineering Ltd | Coated high-speed steel tool |
| JP4459936B2 (en) * | 2006-08-31 | 2010-04-28 | ユニオンツール株式会社 | Hard coating for cutting tools |
| JP2008240079A (en) * | 2007-03-28 | 2008-10-09 | Tungaloy Corp | Coated member |
| JP2012505308A (en) * | 2008-10-10 | 2012-03-01 | エリコン・トレーディング・アクチェンゲゼルシャフト，トリュープバッハ | Non-gamma phase cubic AlCrO |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54116342A (en) * | 1978-03-03 | 1979-09-10 | Mitsubishi Metal Corp | Coated sintered hard alloy member |
| JP2918133B2 (en) * | 1992-05-25 | 1999-07-12 | 三菱マテリアル株式会社 | Surface coated cutting tool |
| JPH0681072A (en) * | 1992-09-01 | 1994-03-22 | Mitsubishi Materials Corp | Tungsten carbide base sintered hard alloy |
| JPH10227360A (en) * | 1992-09-16 | 1998-08-25 | Riken Corp | Sliding material, piston ring, and manufacture of sliding material |
| JP3179645B2 (en) * | 1993-11-19 | 2001-06-25 | 東芝タンガロイ株式会社 | Wear resistant coating |
| JP2901043B2 (en) * | 1993-12-03 | 1999-06-02 | 神鋼コベルコツール株式会社 | Abrasion and welding resistant hard film coated tool and its manufacturing method |
| JPH0827562A (en) * | 1994-07-15 | 1996-01-30 | Toshiba Tungaloy Co Ltd | Oxidation resistant coated member |
| JPH08281502A (en) * | 1995-04-14 | 1996-10-29 | Toshiba Tungaloy Co Ltd | Crystal orientating coated tool |
| JPH09184042A (en) * | 1995-12-28 | 1997-07-15 | Hitachi Tool Eng Ltd | Superfine-grained cemented carbide |
| JPH1158105A (en) * | 1997-08-12 | 1999-03-02 | Hitachi Tool Eng Co Ltd | Covered cemented carbide tool for high speed-high feed |
| JP3001849B2 (en) * | 1998-03-16 | 2000-01-24 | 日立ツール株式会社 | Coated hard tool |
| JP2000087217A (en) * | 1998-09-08 | 2000-03-28 | Kobe Steel Ltd | Titanium nitride coated sliding member excellent in wear resistance |
| JP4393650B2 (en) * | 2000-01-14 | 2010-01-06 | 日立ツール株式会社 | Wear-resistant coated tool |
| JP3877124B2 (en) * | 2000-03-09 | 2007-02-07 | 日立ツール株式会社 | Hard coating coated member |
| JP2001277251A (en) * | 2000-03-29 | 2001-10-09 | Bridgestone Corp | Thin film for molding mold, and mold |
| JP4112836B2 (en) * | 2001-06-19 | 2008-07-02 | 株式会社神戸製鋼所 | Target for forming hard coatings for cutting tools |
| JP3598074B2 (en) * | 2001-05-11 | 2004-12-08 | 日立ツール株式会社 | Hard coating tool |
| JP2002346811A (en) * | 2001-05-23 | 2002-12-04 | Toshiba Tungaloy Co Ltd | Coated sintered tool |
| JP2004249394A (en) * | 2003-02-20 | 2004-09-09 | Hitachi Tool Engineering Ltd | Coated drill |
| JP2004249433A (en) * | 2003-02-21 | 2004-09-09 | Hitachi Tool Engineering Ltd | Coated broach |
| JP2004314182A (en) * | 2003-02-25 | 2004-11-11 | Hitachi Tool Engineering Ltd | Coated drill |
| JP2004255482A (en) * | 2003-02-25 | 2004-09-16 | Hitachi Tool Engineering Ltd | Coated end mill |
| JP2004255553A (en) * | 2003-02-28 | 2004-09-16 | Hitachi Tool Engineering Ltd | Coated broach |
| JP2004298972A (en) * | 2003-03-28 | 2004-10-28 | Hitachi Tool Engineering Ltd | Coated insert |
-
2003
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| JP2004306216A (en) | 2004-11-04 |
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