JP2007056354A - Hard film and its manufacturing method - Google Patents
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本願発明は、高硬度化による優れた耐摩耗性を有し、更に耐欠損性、潤滑性の特性も兼ね備えた硬質皮膜及びその製造方法に関する。 The present invention relates to a hard film having excellent wear resistance due to high hardness and also having characteristics of fracture resistance and lubricity, and a method for producing the same.
下記の文献は、耐摩耗性硬質皮膜に関する各種技術を開示している。 The following documents disclose various techniques related to the wear-resistant hard coating.
特許文献１、２は、硬質皮膜に濃度分布を形成させる技術、連続的に組成の変化する組成変化の繰り返し層を持った膜を形成することによって、耐摩耗性を向上させる技術が開示されている。特許文献３は、機械加工用工具に潤滑性を得る目的で二硫化モリブデンを被覆する技術が開示されている。特許文献４は、二硫化モリブデンとＴｉＮとを組み合わせた被膜の例が開示されている。これらは潤滑特性の改善を目的としているが、密着性、硬度が十分ではなく、切削工具の耐摩耗性に課題を残し、硬質皮膜の機械的強度、靭性が不足している。特許文献５、６の多層積層構造は主に超格子（人工格子）積層により、硬質皮膜を高硬度化させる手法ならびに、積層させた特定の層内において硬質膜の組成を意図的に変調させる技術開示である。特許文献７は、多層積層構造を有する硬質皮膜の複合成膜方法について開示されている。特許文献８は、Ｂ４Ｃ、ＢＮ、ＴｉＢ２などといった硬質粒子を含有させる手法で高硬度硬質皮膜を得ており、特に潤滑に関する説明はない。
本願発明の目的は、硬質皮膜の耐欠損性、潤滑性の特性を犠牲にすることが無く、特に高硬度化による優れた耐摩耗性を有する硬質皮膜を提供することとその製造方法を提供することである。
Patent Documents 1 and 2 disclose a technique for forming a concentration distribution in a hard film, and a technique for improving wear resistance by forming a film having a repeated layer of composition change in which the composition continuously changes. Yes. Patent Document 3 discloses a technique of coating molybdenum disulfide for the purpose of obtaining lubricity in a machining tool. Patent Document 4 discloses an example of a film in which molybdenum disulfide and TiN are combined. These are intended to improve the lubrication characteristics, but the adhesion and hardness are not sufficient, leaving problems in the wear resistance of the cutting tool, and the mechanical strength and toughness of the hard coating are insufficient. The multilayer laminated structure of Patent Documents 5 and 6 is a technique for increasing the hardness of a hard film mainly by superlattice (artificial lattice) lamination, and a technique for intentionally modulating the composition of the hard film in a specific layer. Disclosure. Patent Document 7 discloses a composite film forming method of a hard film having a multilayer laminated structure. Patent Document 8 obtains a high-hardness hard film by a method of containing hard particles such as B 4 C, BN, TiB 2 and the like, and there is no description regarding lubrication.
An object of the present invention is to provide a hard film having excellent wear resistance due to high hardness without sacrificing the chipping resistance and lubricity characteristics of the hard film and to provide a method for producing the same. That is.
本願発明の硬質皮膜は、４ａ、５ａ、６ａ族、Ａｌ、Ｂ、Ｓｉから選択される１種以上の金属元素と、Ｓを含みＣ、Ｎ、Ｏから選択される１種以上の非金属元素によって構成され、該硬質皮膜は柱状組織構造を有し、該柱状組織構造の結晶粒はＳ成分に組成差を有する多層構造を有し、少なくとも該多層構造における層間の境界領域で結晶格子縞が連続している領域があり、各層の厚みＴ（ｎｍ）が０．１≦Ｔ≦１００、Ｘ線回折による（２００）面のピーク強度をＩｂ、（１１１）面のピーク強度をＩａとしたとき、そのピーク強度比Ｉｂ／Ｉａは、Ｉｂ／Ｉａ≦１．０であることを特徴とする硬質皮膜である。更に、本願発明の硬質皮膜を物理蒸着法（以下、ＰＶＤ法と記す。）により被覆する際には、アーク放電型イオンプレーティング法（以下、ＡＩＰ法と記す。）とマグネトロンスパッタリング法（以下、ＭＳ法と記す。）を併用し、両者の蒸着源を同一チャンバー内で同時に放電させることにより多層構造を有する硬質皮膜を製造する方法である。本構成を採用することによって、硬質皮膜の耐欠損性、潤滑性の特性を犠牲にすることが無く、特に高硬度化による優れた耐摩耗性を有する硬質皮膜を提供することができる。 The hard coating of the present invention comprises at least one metal element selected from 4a, 5a, 6a group, Al, B, and Si, and at least one nonmetallic element selected from C, N, and O containing S. The hard coating has a columnar structure, the crystal grains of the columnar structure have a multilayer structure having a compositional difference in the S component, and crystal lattice fringes are continuous at least in the boundary region between layers in the multilayer structure. When the thickness T (nm) of each layer is 0.1 ≦ T ≦ 100, the peak intensity of the (200) plane by X-ray diffraction is Ib, and the peak intensity of the (111) plane is Ia, The peak intensity ratio Ib / Ia is a hard film characterized by Ib / Ia ≦ 1.0. Further, when the hard coating of the present invention is coated by a physical vapor deposition method (hereinafter referred to as PVD method), an arc discharge ion plating method (hereinafter referred to as AIP method) and a magnetron sputtering method (hereinafter referred to as “PVD method”). This is a method for producing a hard film having a multilayer structure by simultaneously discharging both vapor deposition sources in the same chamber. By adopting this configuration, it is possible to provide a hard film having excellent wear resistance due to high hardness without sacrificing the chipping resistance and lubricity characteristics of the hard film.
本願発明は、硬質皮膜の耐欠損性、潤滑性の特性を犠牲にすることが無く、特に高硬度化による優れた耐摩耗性を有する硬質皮膜を得ることができた。更に該硬質皮膜の製造方法を提供することができた。本願発明の硬質皮膜を、例えば切削工具等に適用した場合、溶着の激しいダイカスト金型用鋼の乾式高能率切削加工をはじめ、金型加工時の断続切削状況下においても安定性と、長い工具寿命が得られ、切削加工を必要とする産業における生産性の向上に極めて有効である。 The present invention was able to obtain a hard film having excellent wear resistance by increasing the hardness without sacrificing the chipping resistance and lubricity characteristics of the hard film. Furthermore, the manufacturing method of this hard film could be provided. When the hard coating of the present invention is applied to, for example, a cutting tool or the like, a long tool that is stable even under intermittent cutting conditions at the time of die processing, including dry high-efficiency cutting of die casting steel for severe welding It has a long life and is extremely effective in improving productivity in industries that require cutting.
本願発明は、硬質皮膜にＳを含有させることで、潤滑特性を改善することができる。硬質皮膜がＳを含有することによって、例えば切削で発生する切削熱が、大気中２００℃程度の比較的低温環境下であっても硬質皮膜表面に酸化現象を発生する。この酸化現象が、硬質皮膜表面の保護膜として機能し、摩擦係数を低下させ、潤滑特性が向上する。例えば本願発明の硬質皮膜を切削工具に適用した場合を想定すると、大気中における切削温度近傍における硬質皮膜の摩擦係数は、Ｓを含有しない場合と比較して著しく低減する。更に酸化現象による保護膜は、被加工物の溶着を抑制し、切削熱など酸化雰囲気の高温下における被加工物の硬質皮膜中への内向拡散を防ぐことから、耐摩耗性や耐欠損性に優れ、安定した切削加工を可能にする効果がある。
本願発明の硬質皮膜は、柱状組織構造を有し、結晶粒成長方向に対して界面を形成することなく境界領域で結晶粒が連続的に成長した硬質皮膜である。ここで、柱状組織構造とは、膜厚方向に伸びた縦長成長結晶組織である。該硬質皮膜は多結晶材料であるが、結晶粒１つ１つの単位で捉えれば、単結晶材料の成長に類似した形態となっている。しかも、硬質皮膜の柱状組織構造における結晶粒は、結晶粒成長方向に対してＳ成分に組成差を有する多層構造であって、少なくとも該多層構造における層間の境界領域で結晶格子縞が連続している領域がある。硬質皮膜の結晶粒がＳ成分に組成差を有する多層構造であることによって、硬質皮膜全体として靭性を持たせることができる。例えば、Ｓ成分の含有量が多い層では、比較的軟らかい皮膜が形成される。この軟らかい層が、他の比較的硬い層の層間に存在するとクッション効果を示し、硬質皮膜全体として靭性に富むようになる。更に、最適化された硬質皮膜を用いてＳの特徴である高潤滑特性と融合させることによって、強靭性による耐欠損性、且つ高潤滑特性を有する硬質皮膜を得ることができる。しかし、この時の好ましいＳ成分の組成差は、最大でも１０％である。
本願発明における硬質皮膜の各層の厚みＴ（ｎｍ）が０．１≦Ｔ≦１００、となっていることが好ましい。Ｔが１００ｎｍを超えると、各層の境界領域に歪が発生し、結晶粒中の格子縞が不連続となり、硬質皮膜の機械的強度が低下するため不都合である。例えば、本願発明の硬質皮膜を切削工具に適用した場合、切削初期において硬質膜表面に切削衝撃による皮膜の層状破壊が発生し、硬質皮膜の機械的強度に問題が発生することを確認した。各層の境界領域の歪発生を回避することは、硬質皮膜と基体との密着性の改善に有効である。一方、Ｔの下限値を０．１ｎｍとしたのは、現在の層構造を確認する手段にＸ線回折装置や透過型電子顕微鏡が用いた場合、層構造を確認できる最小厚みが０．１ｎｍであるからである。また、被覆を行う際に０．１ｎｍ未満の積層周期で被覆を行うと、皮膜特性のばらつきが発生し、安定品質の製品を供給することが出来ない。そこで、Ｔの下限値を０．１ｎｍに規定した。本願発明の硬質皮膜は、被加工物との激しい衝撃に耐え得る機械的強度を持ち合わせなければならない。そのためには、硬質皮膜の断面組織が柱状組織形態を有するように成膜を行う。
更に、本願発明の硬質皮膜は、Ｘ線回折におけるピーク強度比Ｉｂ／Ｉａ値が、Ｉｂ／Ｉａ≦１．０、である。ＰＶＤ法によって得られるｆｃｃ構造の硬質皮膜は、（１１１）面、（２００）面と（２２０）面に強いピークが現われる。本願発明の硬質皮膜の場合、（１１１）面に強く結晶を配向させるように制御する。これによって、硬質皮膜は高硬度化による優れた耐摩耗性と、潤滑性を有する硬質皮膜となる。これは、（１１１）面に配向した本願発明の硬質皮膜が、より緻密化し、高硬度となるからである。機械的強度が増し耐衝撃特性も向上する。一方、（２００）面に配向させた場合、耐衝撃特性に劣り、また、残留圧縮応力を比較的低くすることが可能であるが、高硬度化に対しての効果が低くなってしまう。そこで、皮膜の高硬度化を改善する目的から、Ｘ線回折におけるピーク強度比Ｉｂ／Ｉａ値を、Ｉｂ／Ｉａ≦１．０に規定した。
配向面を制御するためには、成膜時に印加するバイアス電圧の適正化が有効である。即ち、１００Ｖ以上の電位を与えれば、（１１１）面に配向するようになり、一方、１００Ｖを下回る電位を与えた場合、（２００）面への配向強度が強くなる。近年の硬質皮膜が適用される環境以上の過酷な使用環境下においては、（２００）面に配向させた硬質皮膜を被覆し、密着性を確保した後、（１１１）面に配向する硬質皮膜を成膜すると更に効果的である。ピーク強度の範囲は、好ましくは、０．０＜Ｉｂ／Ｉａ≦１．０である。本願発明の硬質皮膜は単結晶ではないため、必ず複数のピークが出現する。そのため、Ｉｂ／Ｉａ＞０となる。以上の理由から、Ｘ線回折におけるピーク強度比を規定した。
In the present invention, the lubricating properties can be improved by adding S to the hard coating. When the hard coating contains S, for example, the cutting heat generated by cutting causes an oxidation phenomenon on the surface of the hard coating even in a relatively low temperature environment of about 200 ° C. in the atmosphere. This oxidation phenomenon functions as a protective film on the surface of the hard film, lowers the friction coefficient, and improves the lubrication characteristics. For example, assuming that the hard coating of the present invention is applied to a cutting tool, the friction coefficient of the hard coating in the vicinity of the cutting temperature in the atmosphere is significantly reduced as compared with the case where S is not contained. Furthermore, the protective film by oxidation phenomenon suppresses the welding of the work piece and prevents the inward diffusion of the work piece into the hard film under the high temperature of the oxidizing atmosphere such as cutting heat. It has the effect of enabling excellent and stable cutting.
The hard film of the present invention is a hard film having a columnar structure and having crystal grains continuously grown in the boundary region without forming an interface with respect to the crystal grain growth direction. Here, the columnar structure is a vertically grown crystal structure extending in the film thickness direction. The hard coating is a polycrystalline material, but has a form similar to the growth of a single crystal material if it is grasped in units of crystal grains. Moreover, the crystal grains in the columnar structure of the hard coating have a multilayer structure having a compositional difference in the S component with respect to the crystal grain growth direction, and crystal lattice fringes are continuous at least in the boundary region between the layers in the multilayer structure. There is an area. When the hard coating crystal grains have a multilayer structure having a compositional difference in the S component, toughness can be imparted to the entire hard coating. For example, in a layer having a high content of S component, a relatively soft film is formed. If this soft layer is present between other relatively hard layers, a cushioning effect is exhibited, and the entire hard coating becomes tough. Furthermore, by using an optimized hard coating and fusing with the high lubrication characteristics that are characteristic of S, it is possible to obtain a hard coating having fracture resistance due to toughness and high lubrication characteristics. However, the preferable compositional difference of the S component at this time is 10% at the maximum.
The thickness T (nm) of each layer of the hard coating in the present invention is preferably 0.1 ≦ T ≦ 100. If T exceeds 100 nm, distortion occurs in the boundary region between the layers, the lattice fringes in the crystal grains become discontinuous, and the mechanical strength of the hard coating is lowered, which is disadvantageous. For example, when the hard coating of the present invention was applied to a cutting tool, it was confirmed that a layered fracture of the coating due to a cutting impact occurred on the surface of the hard coating at the initial stage of cutting, and a problem occurred in the mechanical strength of the hard coating. Avoiding the occurrence of distortion in the boundary region of each layer is effective in improving the adhesion between the hard film and the substrate. On the other hand, the lower limit value of T is set to 0.1 nm because, when an X-ray diffractometer or a transmission electron microscope is used as a means for confirming the current layer structure, the minimum thickness for confirming the layer structure is 0.1 nm. Because there is. In addition, when coating is performed with a lamination period of less than 0.1 nm when coating is performed, variations in film characteristics occur, and stable quality products cannot be supplied. Therefore, the lower limit value of T is defined as 0.1 nm. The hard coating of the present invention must have mechanical strength that can withstand severe impacts with the workpiece. For this purpose, film formation is performed so that the cross-sectional structure of the hard film has a columnar structure.
Furthermore, the hard film of the present invention has a peak intensity ratio Ib / Ia value in X-ray diffraction of Ib / Ia ≦ 1.0. In the hard film having the fcc structure obtained by the PVD method, strong peaks appear on the (111) plane, the (200) plane, and the (220) plane. In the case of the hard coating of the present invention, control is performed so that crystals are strongly oriented in the (111) plane. As a result, the hard film becomes a hard film having excellent wear resistance and lubricity due to higher hardness. This is because the hard coating of the present invention oriented in the (111) plane becomes denser and has a high hardness. Increases mechanical strength and impact resistance. On the other hand, when oriented in the (200) plane, the impact resistance is inferior and the residual compressive stress can be made relatively low, but the effect of increasing the hardness is reduced. Therefore, for the purpose of improving the hardness of the film, the peak intensity ratio Ib / Ia value in X-ray diffraction is defined as Ib / Ia ≦ 1.0.
In order to control the orientation plane, it is effective to optimize the bias voltage applied during film formation. That is, when a potential of 100 V or higher is applied, the film is oriented in the (111) plane, whereas when a potential lower than 100 V is applied, the orientation strength of the (200) plane is increased. In a severe usage environment over the environment where the recent hard coating is applied, the hard coating oriented on the (200) plane is coated, and after securing the adhesion, the hard coating oriented on the (111) plane is applied. It is more effective to form a film. The range of the peak intensity is preferably 0.0 <Ib / Ia ≦ 1.0. Since the hard film of the present invention is not a single crystal, a plurality of peaks always appear. Therefore, Ib / Ia> 0. For the above reasons, the peak intensity ratio in X-ray diffraction was defined.
本願発明の硬質皮膜は、Ｓ−Ｏ結合を有することが好ましい。Ｓ−Ｏ結合の存在により優れた潤滑特性を発揮し、例えば切削加工初期における激しい溶着を抑制することができる。Ｓ−Ｏ結合は、硬質皮膜のＸＰＳ分析法により１６７〜１７４ｅＶの範囲にピークが存在することにより確認できる。ＸＰＳ分析法の測定条件は、Ｘ線源がＡｌ、Ｋα、分析領域がφ１００μｍ、電子中和銃の使用条件とした。
本願発明硬質皮膜のＳ含有量は原子％で、０．１％以上、１０％以下であることが好ましい。０．１％未満の含有量では、汎用の分析機器を用いた検出が困難であり、量産管理性が乏しくなる。そのため、簡易的に検出可能な０．１％以上とした。一方、Ｓ含有量が１０％を超えると、硬質皮膜の結晶組織が柱状晶形態からアモルファス状の微細組織に変化し、更に多層構造を有する各層の格子縞が不連続になるといった不都合が生じる。その結果、硬質皮膜の機械的強度が低下すること、硬質皮膜の硬度低下や密着性低下に大きく影響を及ぼす残留圧縮応力が増大して、外部からの強い衝撃により硬質皮膜の剥離が発生すること、などの不都合な現象が発生する。これらの理由から、Ｓ含有量は１０％以下であることが好ましい。より好ましくは、０．１％以上、７％以下の範囲に制御することである。
The hard coating of the present invention preferably has an S—O bond. Due to the presence of the S—O bond, excellent lubrication characteristics can be exhibited, and for example, severe welding in the initial stage of cutting can be suppressed. The S—O bond can be confirmed by the presence of a peak in the range of 167 to 174 eV by XPS analysis of the hard film. The measurement conditions of the XPS analysis method were such that the X-ray source was Al and Kα, the analysis region was φ100 μm, and the electron neutralizing gun was used.
The S content of the hard coating of the present invention is atomic%, preferably 0.1% or more and 10% or less. If the content is less than 0.1%, detection using a general-purpose analytical instrument is difficult, and mass production controllability becomes poor. Therefore, it was set to 0.1% or more that can be easily detected. On the other hand, when the S content exceeds 10%, the crystal structure of the hard film changes from a columnar crystal form to an amorphous microstructure, and further, the lattice fringes of each layer having a multilayer structure become discontinuous. As a result, the mechanical strength of the hard coating decreases, the residual compressive stress that greatly affects the hardness reduction and adhesion reduction of the hard coating increases, and the hard coating peels off due to strong external impact. Such an inconvenient phenomenon occurs. For these reasons, the S content is preferably 10% or less. More preferably, it is controlled within a range of 0.1% to 7%.
本願発明の硬質皮膜の被覆方法としてＰＶＤ法を採用し、該ＰＶＤ法はＡＩＰ法とＭＳ法である。更に該ＡＩＰ法と該ＭＳ法とを併用し、両者の蒸着源を同一チャンバー内で同時に放電させることである。この理由は、ＡＩＰ法とＭＳ法とを同時に行うことにより、硬質皮膜の結晶粒成長方向に対して界面を形成させることなく結晶が連続的に成長した硬質皮膜を得ることが可能となるからである。これにより、硬質膜内部の結晶そのものの機械的強度がより強固になる。また、プラズマ密度の異なる成膜方式を同時に使用すると、夫々の放電により発生したプラズマから価数の異なるイオンが同時に基体表面に到達する。プラズマ密度の高いＡＩＰ法の蒸発源近傍では、硬質結晶が主体の第１の層をなし、プラズマ密度の低いＭＳ法の蒸発源近傍では、軟質結晶が主体の第２の層をなす。更に両方の蒸着源からの影響を受ける第３の層が形成され、これらが多層構造を有する。即ち第１の層、第２の層と第３の層とが積層する。第２の層が第１の層間にサンドイッチされた状態で存在すると、第２の層がクッション効果を示し、硬質皮膜全体として靭性に富むようになる。更に、第３の層の存在によって、ＭＳ法の蒸発源から供給される成分が硬質皮膜中で組成変調することに、硬質皮膜の密着性の改善効果を有する。
Ｓの添加方法についての制約はないが、４ａ、５ａ、６ａ族、Ｂ、Ｓｉ、Ａｌから選択される元素が主体のターゲット中に、あらかじめ添加させておくのが好ましい。化学蒸着法で用いられるような硫化水素によっても、硬質皮膜中にＳを添加することは可能であるが、環境上、安全上、好ましくない。
本願発明の硬質皮膜の柱状組織構造からなる結晶粒はＳ成分に組成差を有し、これを最大でも１０％に制御し、更にＴを１００ｎｍ以下に制御し、且つ結晶格子縞が連続して成長し多層構造を有するためには、ＭＳ法の蒸着源の放電出力を６．５ｋＷ以下に設定することが望ましい。例えばＭＳ法による蒸発源に設置される硫化物の放電によって得られる硬質皮膜は、ＡＩＰ法主体で得られる硬質皮膜よりも若干軟らかい。特にＳ含有量が多い領域では、比較的軟らかい硬質皮膜が形成される。このように最適化された硬質皮膜を用いれば被覆部材の耐衝撃特性が向上して、強靭性且つ高潤滑特性を有する硬質皮膜を得ることが可能となる。一方、プラズマ密度が比較的高いＡＩＰ法は、放電時のエネルギーが非常に大きく硬質皮膜にＳを添加させることが比較的難しい。そのため、好ましくはＭＳ蒸発源に取り付けるターゲットにＳを含有させたものを使用するのが良い。更に、環境上の面、また安全性など取り扱いの面から、ＰＶＤ法は有効である。蒸発源に設置される金属ターゲット材にあらかじめＷＳ、ＣｒＳ、ＮｂＳ、ＴｉＳなどＳ添加したものを使用することが出来るからである。しかもＭＳ法は、ＷＳ、ＣｒＳ、ＮｂＳ、ＴｉＳターゲット材単体を用いることができる。ＡＩＰ法では、ＷＳ、ＣｒＳ、ＮｂＳ、ＴｉＳターゲット材単体は放電が非常に困難である理由から、４ａ、５ａ、６ａ族、Ｂ、Ｓｉ、Ａｌから選択される１種以上の金属マトリックス中にＳ添加したターゲット材を用いる必要がある。硬質皮膜にＳ−Ｏ結合を形成させるためには、主体となる反応ガス中にＯを含有させて得ることが好ましい。
ＡＩＰ法とＭＳ法とを同時に行うことにより得られる硬質皮膜は、結晶格子縞が連続した多層構造を有する。更にこれによって得られる硬質皮膜は、結晶格子縞が連続した多層構造を有する。しかし、両者を間欠的に用いた場合、例えばＡＩＰ法とＭＳ法とを交互に放電させることによってＳを添加すると、界面をもつ多層構造が生じ、その界面に発生する歪が影響して、各層の接合が脆弱化するため好ましくない。
本願発明の硬質皮膜を例えば切削工具等、高硬度特性が要求される耐摩耗部材や耐熱部材の表面に適用すると、硬質皮膜の高硬度化により耐摩耗性を改善し、加えて特に、潤滑特性が著しく向上するため、切削加工の高温状態での耐溶着性並びに硬質皮膜への被削材元素の拡散を抑制することができる。更に、切削加工の乾式化、高速化、高送り化に対応する硬質皮膜被覆工具を提供することができる。ここでの高送り加工とは、切削条件における１刃当たりの送り量が０．３ｍｍ／刃を超えるような切削を言う。
The PVD method is adopted as the method for coating the hard film of the present invention, and the PVD method is an AIP method and an MS method. Further, the AIP method and the MS method are used in combination, and both vapor deposition sources are discharged simultaneously in the same chamber. This is because by simultaneously performing the AIP method and the MS method, it is possible to obtain a hard film in which crystals are continuously grown without forming an interface with respect to the crystal growth direction of the hard film. is there. Thereby, the mechanical strength of the crystal itself in the hard film becomes stronger. In addition, when film forming methods having different plasma densities are used at the same time, ions having different valences simultaneously reach the substrate surface from the plasma generated by the respective discharges. In the vicinity of the evaporation source of the AIP method having a high plasma density, a hard crystal forms the first layer mainly, and in the vicinity of the evaporation source of the MS method having a low plasma density, a soft crystal forms the second layer. In addition, a third layer is formed which is influenced by both deposition sources and has a multilayer structure. That is, the first layer, the second layer, and the third layer are stacked. When the second layer is sandwiched between the first layers, the second layer exhibits a cushioning effect, and the entire hard coating is rich in toughness. Furthermore, due to the presence of the third layer, the component supplied from the evaporation source of the MS method undergoes compositional modulation in the hard film, thereby having an effect of improving the adhesion of the hard film.
Although there is no restriction | limiting about the addition method of S, It is preferable to add beforehand in the target mainly composed of the element selected from 4a, 5a, 6a group, B, Si, and Al. Although it is possible to add S to the hard film even by hydrogen sulfide used in the chemical vapor deposition method, it is not preferable in terms of environment and safety.
The crystal grains composed of the columnar structure of the hard coating of the present invention have a compositional difference in the S component, which is controlled to 10% at the maximum, T is controlled to 100 nm or less, and crystal lattice fringes continuously grow. In order to have a multilayer structure, it is desirable to set the discharge output of the MS deposition source to 6.5 kW or less. For example, a hard film obtained by the discharge of a sulfide placed in an evaporation source by the MS method is slightly softer than a hard film obtained mainly by the AIP method. In particular, in a region where the S content is large, a relatively soft hard film is formed. If the hard coating optimized in this way is used, the impact resistance characteristics of the covering member are improved, and a hard coating having toughness and high lubricating characteristics can be obtained. On the other hand, in the AIP method having a relatively high plasma density, it is relatively difficult to add S to the hard coating because the energy during discharge is very large. Therefore, it is preferable to use a target containing S in a target attached to the MS evaporation source. Furthermore, the PVD method is effective from the viewpoint of environment and handling such as safety. This is because it is possible to use a metal target material installed in the evaporation source in which S, such as WS, CrS, NbS, and TiS is added in advance. Moreover, the MS method can use a WS, CrS, NbS, or TiS target material alone. In the AIP method, WS, CrS, NbS, TiS target material alone is very difficult to discharge, so S is contained in one or more kinds of metal matrix selected from 4a, 5a, 6a group, B, Si, Al. It is necessary to use the added target material. In order to form an S—O bond in the hard coating, it is preferable to obtain the main reaction gas by containing O.
A hard film obtained by simultaneously performing the AIP method and the MS method has a multilayer structure in which crystal lattice stripes are continuous. Furthermore, the hard coating obtained thereby has a multilayer structure in which crystal lattice fringes are continuous. However, when both are used intermittently, for example, when S is added by alternately discharging the AIP method and the MS method, a multilayer structure having an interface is generated, and the strain generated at the interface affects each layer. This is not preferable because the bonding of the material becomes weak.
When the hard coating of the present invention is applied to the surface of a wear-resistant member or heat-resistant member that requires high hardness characteristics such as a cutting tool, the wear resistance is improved by increasing the hardness of the hard coating, and in particular, lubrication characteristics Therefore, it is possible to suppress welding resistance at high temperature during cutting and diffusion of the work material element into the hard coating. Furthermore, it is possible to provide a hard film coated tool that can cope with dry cutting, high speed, and high feed of cutting. The high feed processing here refers to cutting in which the feed amount per blade under the cutting conditions exceeds 0.3 mm / tooth.
本発明の硬質皮膜の被覆には、小型真空装置内にＡＩＰ方式の蒸発源と、ＭＳ方式の蒸発源とを併設した装置を用いて。基体は超硬合金製インサートを用い、反応ガスはＮ２ガス、ＣＨ４ガス、Ａｒ／Ｏ２混合ガスから目的の皮膜が得られるものを選択した。反応圧力は、真空装置内で両者の成膜法が同時にプラズマを発生させることが可能な圧力範囲を選定し、２種の蒸発源を同時に放電させるために反応圧力は３．０Ｐａに設定した。基体温度は４００℃、バイアス電圧は−１００Ｖから−１５０Ｖの範囲の電圧を印加した。蒸発源は各種合金製ターゲットが選択可能であり、ＡＩＰ蒸発源には所定組成の合金ターゲット材、ＭＳ蒸発源にはＷＳ２、ＮｂＳ、ＣｒＳ、ＴｉＳなどのターゲット材を用いた。硬質皮膜にＳを効果的に添加するために、ＡＩＰ蒸発源とＭＳ蒸発源とを同時に放電させた。得られた硬質皮膜の評価は、以下に示す切削条件にて切削試験を行った。切削試験で用いた被削材は、ダイカスト金型用鋼種として用いられるＳＫＤ６１、硬さはＨＲＣ４５、を選択した。本鋼種は、切削加工初期に刃先部における溶着現象が発生し、被覆インサート刃先部の硬質皮膜尊損傷が激しくなる。評価方法は、この被削材表面を高能率加工条件にて切削を行う事により、インサートが切削初期に発生する溶着がもたらす摩耗やヒートクラックによって欠損に至るまでの切削可能長を評価した。表１、２に本発明例及び比較例、従来例に関する硬質皮膜の詳細、使用したターゲット材組成及び切削試験の結果を示す。 For the coating of the hard coating of the present invention, a device in which an AIP evaporation source and an MS evaporation source are provided in a small vacuum apparatus is used. The substrate used was a cemented carbide insert, and the reaction gas was selected from N 2 gas, CH 4 gas, and Ar / O 2 mixed gas to obtain the desired film. The reaction pressure was set to a pressure range in which both film forming methods can simultaneously generate plasma in a vacuum apparatus, and the reaction pressure was set to 3.0 Pa in order to discharge two kinds of evaporation sources simultaneously. The substrate temperature was 400 ° C., and the bias voltage was a voltage in the range of −100V to −150V. Various alloy targets can be selected as the evaporation source, and an alloy target material having a predetermined composition is used as the AIP evaporation source, and a target material such as WS 2 , NbS, CrS, or TiS is used as the MS evaporation source. In order to effectively add S to the hard coating, the AIP evaporation source and the MS evaporation source were simultaneously discharged. Evaluation of the obtained hard film performed the cutting test on the cutting conditions shown below. As the work material used in the cutting test, SKD61 used as a steel type for die casting molds and HRC45 as the hardness were selected. In this steel type, a welding phenomenon occurs at the cutting edge portion in the early stage of cutting, and the hard coating is severely damaged at the coated insert cutting edge portion. In the evaluation method, the length of the work material was evaluated by cutting the surface of the work material under high-efficiency machining conditions, so that the insert could be damaged due to wear or heat crack caused by welding generated in the early stage of cutting. Tables 1 and 2 show the details of the hard coating, examples of the composition of the present invention, comparative examples, and conventional examples, the composition of the target material used, and the results of cutting tests.
（切削条件）
工具：正面フライス
インサート形状：ＳＤＥ５３タイプ特殊形状
切削方法：センターカット方式
被削材形状：巾１００ｍｍ×長さ２５０ｍｍ
被削材：ＳＫＤ６１、硬さ、ＨＲＣ４５
切り込み量：１．５ｍｍ
切削速度：１００ｍ／ｍｉｎ
１刃送り量：０．６ｍｍ／刃
切削油：なし
表２は、評価結果であり、本発明例１から１４、比較例１５から２８、従来例２９から３５を示す。表２より、本発明例１から１４は、硬質皮膜が柱状組織構造を有し、結晶粒がＳ成分に組成差を有する多層構造を有し、少なくとも該多層構造における層間の境界領域で結晶格子縞が連続している領域があり、各層の厚みＴ（ｎｍ）が０．１≦Ｔ≦１００、Ｘ線回折におけるＩｂ／Ｉａ≦１．０、を満たすことによって、優れた切削性能を有することを確認した。また、硬質皮膜表面付近のＳ−Ｏ結合の有無や、２種以上の物理蒸発源を用いてＳを硬質皮膜に添加させた時のＳ含有量の範囲が、切削性能に影響を及ぼすことも確認した。本発明例１から１４に示した様に、本発明の硬質皮膜は、従来実現が困難であった切削加工を行うことが可能となった。本発明例９に示したＮｂＳによってＳが添加された硬質皮膜は、今回の評価の中で最も良い結果を示した。本発明例９の硬質皮膜を調査した結果、図１に示す様にＸＰＳ分析において１６７〜１７４ｅＶの範囲にＳ−Ｏ結合が確認された。このＳ−Ｏ結合の存在により、切削加工初期の激しい溶着が抑制されることが確認された。また、Ｘ線回折におけるＩｂ／Ｉａ値が０．５６であった。図２に示す様にＳ−Ｏ結合の他に２００〜２１５ｅＶにおいてＮｂ−Ｏ結合、図１に示す様に１６１〜１６４ｅＶに金属元素との硫化物が存在することを確認した。この様に、本発明例９の硬質皮膜表面付近には、潤滑特性の優れる硫化物の存在、並びに酸化物が形成されるために、溶着が激しく発生する金属の加工において、著しい効果を発揮した。また添加したＳはＮｂＳをＭＳ法蒸着源に設置し、放電出力を６．５ｋＷに設定し、成膜温度を６００℃に設定した。その結果、硬質皮膜を全体的に見た場合、Ｓ含有量は５．４％であり、本発明で規定するＳ含有量の範囲内であった。図３に示す様に、硬質皮膜の破断面組織を倍率１５０００倍で観察した結果、柱状組織構造であった。この結果、高送り加工などの衝撃の激しい切削加工において、耐摩耗性改善による寿命向上だけでなく、せん断方向に対する機械的強度も得られていることを確認した。
図４は、本発明例９の硬質皮膜の破面を透過電子顕微鏡により２万倍で観察した結果であり、硬質皮膜の柱状組織構造を有する結晶粒は多層構造を有していた。図５は、図４に示した結晶粒の１部を更に拡大して２０万倍で観察を行った結果であり、結晶粒はコントラストの異なる黒色層と灰色層とが複数存在している多層構造を有していることを確認した。ここで、１つ１つの結晶粒は同一方向に結晶成長したものであり、電子回折によって確認することができる。ここで、図４の観察で見られたコントラストの縞模様の数と、図５の観察で見られたコントラストの縞模様の数との間には、観察倍率が異なっている点から相関性は無い。また図５に示したコントラストの縞模様から、膜厚方向の層の厚さを得ることができる。測定の結果、各層の層厚は、３から５ｎｍ程度であった。図５の観察状態から更に観察倍率を高くして、結晶格子縞の状態を２００万倍で観察した。この時の観察結果を図６に示す。図６の観察領域は、図５の観察形態を参照しながら進めていった。即ち、図５で見られた黒色層と灰色層とが交互に積層されている領域を確認し、観察倍率を高くした場合でも観察視野には、常に黒色層、灰色層とその境界領域とが含まれるように配慮した。図６に便宜的に示した線は、夫々黒色層と灰色層とに対応する領域を区別するために使用した。更に、図７に図６の概略図を示した。図６より、多層構造における層間の境界領域で結晶格子縞が連続している領域があることを確認した。ここで、格子縞の連続性はすべての境界領域で成立する必要はなく、透過電子顕微鏡により層の境界領域を観察した時に、格子縞の連続性が認められる領域が存在すれば本発明の優れた作用効果を得ることができる。図６には、左側の領域の１部に黒色のコントラストを示す領域が存在しているが、これは図５に示した黒色層、灰色層とは観察倍率が異なっている点から関連はない。更に、図６で観察した領域に配慮しながら、電子回折像を調べた。電子回折像を調べるにあたり、調査領域が、黒色層と灰色層との境界領域となるように配慮した。観察によって得られた電子回折像を図８に示す。図８では、略単一の電子回折像が得られた。この観察結果について考察を行うと、略単一の電子回折像が得られたことは、図９の概略図で示す様に、星印で示した黒色層の電子回折図形と、丸印で示した灰色層の電子回折図形とが一致していることを示し、これよりこの調査領域ではエピタキシャルな関係により格子縞が連続していることを確認した。従って、多層構造を有する結晶粒について層の境界領域の電子回折を行った結果、マクロ的には多結晶構造ではあるが、ミクロ的な観察により単結晶の様な形態をなしていることを見いだしたのである。更に、表３は本発明例９の多層構造の各層における組成分析を行った結果である。
(Cutting conditions)
Tool: Face mill Insert shape: SDE53 type special shape Cutting method: Center cut method Workpiece shape: width 100mm x length 250mm
Work material: SKD61, hardness, HRC45
Cutting depth: 1.5mm
Cutting speed: 100 m / min
1-blade feed amount: 0.6 mm / blade Cutting oil: none Table 2 shows the evaluation results, which show Invention Examples 1 to 14, Comparative Examples 15 to 28, and Conventional Examples 29 to 35. From Table 2, Invention Examples 1 to 14 show that the hard coating has a columnar structure, the crystal grains have a multilayer structure having a compositional difference in the S component, and crystal lattice fringes at least in the boundary region between the layers in the multilayer structure. In which the thickness T (nm) of each layer satisfies 0.1 ≦ T ≦ 100 and Ib / Ia ≦ 1.0 in X-ray diffraction, thereby having excellent cutting performance. confirmed. In addition, the presence or absence of S—O bonds near the surface of the hard coating and the range of the S content when S is added to the hard coating using two or more physical evaporation sources may affect the cutting performance. confirmed. As shown in Examples 1 to 14 of the present invention, the hard coating of the present invention can be subjected to cutting which has been difficult to realize in the past. The hard film to which S was added by NbS shown in Example 9 of the present invention showed the best result in this evaluation. As a result of investigating the hard film of Example 9 of the present invention, as shown in FIG. 1, an S—O bond was confirmed in the range of 167 to 174 eV in the XPS analysis. It was confirmed that vigorous welding at the initial stage of cutting was suppressed by the presence of this S—O bond. Further, the Ib / Ia value in X-ray diffraction was 0.56. As shown in FIG. 2, it was confirmed that in addition to the S—O bond, Nb—O bond was present at 200 to 215 eV, and sulfide with a metal element was present at 161 to 164 eV as shown in FIG. Thus, in the vicinity of the hard coating surface of Example 9 of the present invention, the presence of sulfides with excellent lubrication characteristics and the formation of oxides exhibited a remarkable effect in the processing of metals that generate severe welding. . The added S was NbS installed in the MS deposition source, the discharge output was set to 6.5 kW, and the film formation temperature was set to 600 ° C. As a result, when the hard coating was viewed as a whole, the S content was 5.4%, which was within the range of the S content defined in the present invention. As shown in FIG. 3, the fracture surface structure of the hard coating was observed at a magnification of 15000. As a result, it was a columnar structure. As a result, it was confirmed that, in cutting with high impact such as high feed machining, not only the life was improved by improving the wear resistance but also the mechanical strength in the shear direction was obtained.
FIG. 4 shows the result of observing the fracture surface of the hard film of Example 9 of the present invention at a magnification of 20,000 with a transmission electron microscope, and the crystal grains having the columnar structure of the hard film had a multilayer structure. FIG. 5 is a result of further enlarging a part of the crystal grain shown in FIG. 4 and observing it at 200,000 times. The crystal grain is a multilayer in which a plurality of black layers and gray layers having different contrasts exist. It was confirmed to have a structure. Here, each crystal grain is grown in the same direction, and can be confirmed by electron diffraction. Here, the correlation between the number of contrast stripes seen in the observation of FIG. 4 and the number of contrast stripes seen in the observation of FIG. 5 is different because the observation magnification is different. No. Further, the layer thickness in the film thickness direction can be obtained from the contrast stripe pattern shown in FIG. As a result of the measurement, the layer thickness of each layer was about 3 to 5 nm. The observation magnification was further increased from the observation state of FIG. 5, and the state of crystal lattice fringes was observed at 2 million times. The observation result at this time is shown in FIG. The observation region in FIG. 6 was advanced with reference to the observation form in FIG. That is, the region where the black layer and the gray layer seen in FIG. 5 are alternately stacked is confirmed, and even when the observation magnification is increased, the observation visual field always includes the black layer, the gray layer, and the boundary region. Considered to be included. For convenience, the lines shown in FIG. 6 were used to distinguish the areas corresponding to the black layer and the gray layer, respectively. FIG. 7 is a schematic diagram of FIG. From FIG. 6, it was confirmed that there is a region where crystal lattice fringes are continuous in the boundary region between layers in the multilayer structure. Here, the continuity of the lattice fringes does not have to be established in all the boundary regions, and if the region where the continuity of the lattice fringes is observed when the boundary region of the layer is observed with a transmission electron microscope, the excellent effect of the present invention is obtained. An effect can be obtained. In FIG. 6, there is a black contrast region in a part of the left region, but this is not related to the black layer and gray layer shown in FIG. 5 because the observation magnification is different. . Further, an electron diffraction image was examined while considering the region observed in FIG. In examining the electron diffraction image, consideration was given so that the investigation region was a boundary region between the black layer and the gray layer. An electron diffraction image obtained by the observation is shown in FIG. In FIG. 8, a substantially single electron diffraction image was obtained. Considering this observation result, the fact that a substantially single electron diffraction image was obtained is indicated by a black layer electron diffraction pattern indicated by a star and a circle as shown in the schematic diagram of FIG. It was confirmed that the electron diffraction pattern of the gray layer coincided with this, and from this, it was confirmed that lattice fringes were continuous due to the epitaxial relationship in this investigation region. Therefore, as a result of electron diffraction in the boundary region between the layers of the crystal grains having a multi-layer structure, it was found that although it is a polycrystalline structure macroscopically, it has a single crystal-like form by microscopic observation. It was. Further, Table 3 shows the results of composition analysis in each layer of the multilayer structure of Example 9 of the present invention.
分析は透過電子顕微鏡に付設されるエネルギー分散型Ｘ線分析装置（以下、ＥＤＸと記す。）にて行った。分析した領域は、図６の観察による黒色層と灰色層との領域に配慮した。表３の分析領域を図６の点Ｐ、点Ｑに示す。分析結果から、添加したＳ成分の組成差が確認された。Ｓ含有量が１０％を超えると、結晶組織が微細化するため、組成差は、最大でも１０％以内に制御しなければならない。本発明例９は、放電させるＮｂＳの放電出力を６．５ｋＷに設定したため、Ｓ含有量差を７．６％に制御できた。図１０には、摩擦係数の測定結果を示す。摩擦係数の測定は、ボールオンディスク方式の摩擦摩耗試験機を用い、大気中６００℃の高温下における摩擦係数の測定を行った。その結果、硬質皮膜にＳを添加することにより、潤滑特性が大幅に向上することが確認した。Ｃｒ、Ｔｉなどの硫化物の形も潤滑特性に優れることが確認された。切削が安定し、優れた切削性能を発揮させるために、ターゲット材としてはＮｂＳが適している傾向にあった。また、ＣｒＳ、ＮｂＳ、ＴｉＳを使用した場合でも、耐摩耗性や潤滑特性が向上し切削特性が向上することを確認した。これより、溶着が激しく発生する金属の加工においては、本発明の構成要素を満たす硬質皮膜によって十分に満足の行くが結果が得られた。今回の切削試験価で最も良好な本発明例９は、他の条件として、金型で見られる固定穴等、切削加工においては断続となる部位の加工も行ってみた。その結果、適正な膜厚を有した多層構造を形成していたため、硬質皮膜の靭性が著しく向上し、激しい衝撃に対しても欠損することなく、安定した切削を行うことができた。これは、２種以上のプラズマ密度の異なる成膜方式を同時に使用すると、それぞれの放電により発生したプラズマから価数の異なるイオンが同時に基体表面に到達する。第１の層はＡＩＰ方式の蒸発源近傍で硬質結晶が主体に層をなし、第２の層はＭＳ方式の蒸発源近傍で軟質結晶が主体の層をなして多層構造を有する。第１の層と第２の層とが混在して基体表面で層として堆積する。その際に、第２の層が第１の層の結晶間に存在するとクッション効果を示し、その結果、皮膜全体として靭性に富むようになる。このようにして被覆部材の耐衝撃特性が向上するものであり、本発明の特徴である著しく優れた潤滑特性を有し、かつ耐欠損特性に優れた硬質皮膜を見出すに至った。 The analysis was performed with an energy dispersive X-ray analyzer (hereinafter referred to as EDX) attached to the transmission electron microscope. As the analyzed region, the region of the black layer and the gray layer observed in FIG. 6 was considered. The analysis regions in Table 3 are indicated by points P and Q in FIG. From the analysis result, the compositional difference of the added S component was confirmed. When the S content exceeds 10%, the crystal structure becomes finer, so the compositional difference must be controlled within 10% at the maximum. In Invention Example 9, since the discharge output of NbS to be discharged was set to 6.5 kW, the S content difference could be controlled to 7.6%. FIG. 10 shows the measurement result of the friction coefficient. The coefficient of friction was measured using a ball-on-disk type friction and wear tester at a high temperature of 600 ° C. in the atmosphere. As a result, it was confirmed that by adding S to the hard coating, the lubrication characteristics were greatly improved. It was confirmed that sulfide forms such as Cr and Ti are also excellent in lubrication characteristics. NbS tended to be suitable as a target material in order to stabilize cutting and exhibit excellent cutting performance. In addition, even when CrS, NbS, and TiS were used, it was confirmed that the wear resistance and lubrication characteristics were improved and the cutting characteristics were improved. As a result, in the processing of a metal in which welding is generated violently, a satisfactory result was obtained with a hard film satisfying the constituent elements of the present invention. In Example 9 of the present invention, which is the best in the cutting test price this time, as an additional condition, machining of intermittent parts in cutting, such as a fixing hole found in a mold, was also performed. As a result, since a multilayer structure having an appropriate film thickness was formed, the toughness of the hard coating was remarkably improved, and stable cutting could be performed without loss even with severe impact. When two or more kinds of film forming methods having different plasma densities are used at the same time, ions having different valences simultaneously reach the substrate surface from the plasma generated by each discharge. The first layer is mainly composed of hard crystals in the vicinity of the AIP evaporation source, and the second layer has a multi-layer structure mainly consisting of soft crystals in the vicinity of the MS evaporation source. The first layer and the second layer are mixed and deposited as a layer on the substrate surface. At that time, if the second layer exists between the crystals of the first layer, a cushioning effect is exhibited, and as a result, the entire film becomes rich in toughness. In this way, the impact resistance of the covering member is improved, and a hard film having a remarkably excellent lubricating property and an excellent fracture resistance characteristic of the present invention has been found.
比較例１５、１６、１８から２０、２４から２６、２８はＳ含有量が多く、１０％以上であった。Ｓ含有量が多い場合、Ｘ線回折におけるＩｂ／Ｉａ値は、１．０よりも大きくなる傾向にあった。また、比較例２０はＳ含有量が１７％と多量に添加されていた。この破断面組織を確認した結果、図１１に示す様なアモルファス状の微細組織になっていた。硬質皮膜の硬度も２２ＧＰａ程度と軟質化傾向にあった。たとえＳ−Ｏ結合を有し、多層構造における１層の厚みが本発明の規定範囲内であっても、切削特性に満足の行く結果は得られなかった。従って、Ｓ含有量の適正な制御も大切な項目であり、過酷な使用状況下に耐えるだけの機械的強度が得られなくなる。比較例１７は、Ｓ−Ｏ結合が表面付近に形成されて、硬質皮膜のＳ含有量が、本発明の規定範囲内の９．５％であった。しかも、Ｘ線回折におけるＩｂ／Ｉａ値は０．１２であり、本発明の範囲であったが、ＡＩＰ方式とＭＳ方式とを同時に放電させて得られた硬質皮膜が有する多層構造の１層の厚みが１００ｎｍを超えてしまった。この時、ＭＳ方式の蒸着源の放電出力は６．６ｋＷであった。その結果、多層構造の各層の結晶格子縞に歪が発生し、格子縞が不連続となり硬質皮膜の結晶組織が微細化し早期摩耗に至った。比較例２３は、硬質皮膜のＳ含有量、多層構造の１層の厚みが３０．６ｎｍ、Ｓ−Ｏ結合も形成され、本発明の規定範囲に近い状態にあった。しかし、Ｉｂ／Ｉａ値が６．８７と、今回開示した試料の中でもっとも大きい値を示し、得られた硬質皮膜が（２００）面へ強い配向を示した。その結果、Ｓ添加の効果による切削性能は得られたが、切削初期の耐衝撃性が不足して欠損に至った。比較例２３は、印加したバイアス電圧を７０Ｖに設定したため、（２００）面へ強く配向してしまった。比較例２１、２２は、夫々の成膜で使用したＷＳ２、ＮｂＳを放電させるときの放電出力を１ｋＷに落として被覆した。その結果、多層構造における１層の厚みは夫々確認限界に近い０．２ｎｍ、０．８ｎｍであった。得られたＳ含有量は、ＸＰＳ分析などの分析装置を使用してもＳの検出が不可能なほど少量であった。そのため、切削初期の溶着が激しく発生した。特に比較例２２は火花が発生し、評価を途中で中止した。硬質皮膜へのＳ含有量や結合状態、積層周期となる１層の厚みを制御するが重要であり、また、硬質皮膜のＸ線回折における配向強度比のＩｂ／Ｉａ値の制御も大切なことである。 In Comparative Examples 15, 16, 18 to 20, 24 to 26, and 28, the S content was large and was 10% or more. When the S content was large, the Ib / Ia value in X-ray diffraction tended to be larger than 1.0. In Comparative Example 20, the S content was added in a large amount of 17%. As a result of confirming the fracture surface structure, an amorphous microstructure as shown in FIG. 11 was obtained. The hardness of the hard coating also had a tendency to soften at about 22 GPa. Even if it has an S—O bond and the thickness of one layer in the multilayer structure is within the specified range of the present invention, a satisfactory result in cutting characteristics was not obtained. Therefore, proper control of the S content is also an important item, and mechanical strength sufficient to withstand severe use conditions cannot be obtained. In Comparative Example 17, an S—O bond was formed near the surface, and the S content of the hard film was 9.5% within the specified range of the present invention. Moreover, the Ib / Ia value in X-ray diffraction was 0.12, which was within the scope of the present invention. However, the single layer of the multilayer structure possessed by the hard coating obtained by discharging the AIP method and the MS method simultaneously. The thickness has exceeded 100 nm. At this time, the discharge output of the MS deposition source was 6.6 kW. As a result, distortion occurred in the crystal lattice fringes of each layer of the multilayer structure, the lattice fringes became discontinuous, the crystal structure of the hard coating became finer, and early wear occurred. In Comparative Example 23, the S content of the hard coating, the thickness of one layer of the multilayer structure was 30.6 nm, S—O bonds were also formed, and the state was close to the specified range of the present invention. However, the Ib / Ia value was 6.87, the largest value among the samples disclosed this time, and the obtained hard coating showed a strong orientation to the (200) plane. As a result, cutting performance due to the effect of addition of S was obtained, but the impact resistance at the initial stage of cutting was insufficient, leading to defects. In Comparative Example 23, since the applied bias voltage was set to 70 V, it was strongly oriented to the (200) plane. In Comparative Examples 21 and 22, the discharge output when discharging WS2 and NbS used in the respective film formations was reduced to 1 kW and coated. As a result, the thickness of one layer in the multilayer structure was 0.2 nm and 0.8 nm, which are close to the confirmation limit, respectively. The obtained S content was so small that S could not be detected even using an analyzer such as XPS analysis. Therefore, intense welding occurred at the initial stage of cutting. In particular, in Comparative Example 22, a spark occurred, and the evaluation was stopped midway. It is important to control the S content in the hard film, the bonding state, and the thickness of one layer that is the lamination cycle, and it is also important to control the Ib / Ia value of the orientation strength ratio in the X-ray diffraction of the hard film. It is.
Claims (4)
A hard film coated by a PVD method, wherein the PVD method is an arc discharge ion plating method and a magnetron sputtering method, and the hard film is selected from 4a, 5a, 6a group, Al, B, and Si It is composed of one or more kinds of metal elements and one or more kinds of nonmetallic elements selected from C, N, and O, including S, and the hard coating has a columnar structure, and the crystal grains of the columnar structure are: A method for producing a hard coating, comprising a multilayer structure having a compositional difference in S component, wherein the multilayer structure is formed by simultaneously discharging the PVD deposition source in the same chamber.
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| JP7015978B2 (en) | 2017-12-27 | 2022-02-04 | 三菱マテリアル株式会社 | Surface-coated cutting tools with excellent wear resistance with a hard coating layer |
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