JP2017196702A - Full hard vanadium-based composite coated tool - Google Patents

Full hard vanadium-based composite coated tool Download PDF

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JP2017196702A
JP2017196702A JP2016089992A JP2016089992A JP2017196702A JP 2017196702 A JP2017196702 A JP 2017196702A JP 2016089992 A JP2016089992 A JP 2016089992A JP 2016089992 A JP2016089992 A JP 2016089992A JP 2017196702 A JP2017196702 A JP 2017196702A
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JP6478331B2 (en
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邦夫 斉藤
Kunio Saito
邦夫 斉藤
淳雄 川名
Atsuo Kawana
淳雄 川名
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Japan Coating Center Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a full hard vanadium-based composite coated tool excellent in durability, and capable of elongating a limit life.SOLUTION: A first layer of a VN film, a second layer of a VCN film, a third layer of a VC film, and a coating of a fourth layer are formed successively on a base metal surface by a PVD method. When the atomic composition ratio of the second layer is expressed as Va(CbN(1-a-b)), 0.5≤a≤0.7, 0.1≤b≤0.3 are satisfied, and the atomic composition ratio Y of element C in the third layer satisfies 0.2≤Y≤0.4, and the atomic composition ratio X of element C in the fourth layer satisfies 0.4≤X≤0.6.SELECTED DRAWING: Figure 1

Description

本発明は硬質バナジウム系複合被覆治工具に係り、特に、冷間加工で使用される金型、ウェット環境で使用される切削工具などに好適な治工具に関する。 The present invention relates to a hard vanadium-based composite coated jig / tool, and more particularly to a jig / tool suitable for a die used in cold working, a cutting tool used in a wet environment, and the like.

成形金型や切削工具といった治工具類は高い耐摩耗性が要求され、その表面改質技術として、浸炭、窒化処理や、熱反応析出拡散法(TRD法:Thermal Reactive Deposition and Diffusion)、化学的気相蒸着法(CVD法:Chemical Vapour Deposion)、物理的気相蒸着法(PVD法:Physical Vapour Deposion)などが採用されている。これによって、母材表面の高硬度化によって、耐摩耗性が改善され、治工具類の寿命延長が可能になった。 Jigs and tools such as molding dies and cutting tools are required to have high wear resistance. As surface modification technologies, carburizing, nitriding, thermal reactive deposition and diffusion (TRD method), chemical reaction A vapor deposition method (CVD method: Chemical Vapor Deposition), a physical vapor deposition method (PVD method: Physical Vapor Deposition), or the like is employed. As a result, the hardness of the base metal surface has been improved, so that the wear resistance has been improved and the tool life has been extended.

冷間加工用金型は、冷間工具鋼、熱間工具鋼、高速度鋼、超硬合金などで製作されるが、熱間加工に比較して高い寸法精度が求められるため、TRD法、CVD法のような1000°C近い高温処理は好ましくない。そして、現在、冷間加工に対する寸法精度の要求はますます厳しくなりつつある。 Cold working molds are made of cold tool steel, hot tool steel, high speed steel, cemented carbide, etc., but since high dimensional accuracy is required compared to hot working, the TRD method, A high temperature treatment close to 1000 ° C. such as a CVD method is not preferable. At present, the demand for dimensional accuracy for cold working is becoming stricter.

一方、500°C程度の低温処理が可能なPVD法は寸法精度の点で有利であり、特に、その中のイオンプレーティング法は、密着性を確保しつつ硬質被膜を母材表面に生成し得るので、現在、主流となっている。 On the other hand, the PVD method, which can be processed at a low temperature of about 500 ° C, is advantageous in terms of dimensional accuracy, and in particular, the ion plating method therein produces a hard coating on the base material surface while ensuring adhesion. It has now become mainstream.

イオンプレーティング法で生成される硬質被膜としては、窒化チタン(TiN)、窒化クロム(CrN)、または、これらをベースとして更に添加元素を加えた窒化物、炭窒化物系被膜が一般的であるが、TRD法で使われるバナジウム炭化物もPVD法によって成膜されるようになった。 As the hard coating produced by the ion plating method, titanium nitride (TiN), chromium nitride (CrN), or a nitride or carbonitride-based coating obtained by adding an additional element based on these is common. However, vanadium carbide used in the TRD method is also formed by the PVD method.

特許文献1のバナジウム系被膜の成膜方法では、バナジウムを蒸発源として、窒素ガス、炭化水素ガスを注入するイオンプレーティング法によって、基材(母材)側から、被膜最外表層に向かって窒化バナジウム(VN)、炭窒化バナジウム(VCN)、炭化バナジウム(VC)を順に積層し、各層の膜種によって注入ガス量、ガス圧を調節している。
しかし、この成膜方法によって生成された積層構造は、被膜硬度を高めたときに、VC膜の特徴である低摩擦係数が維持されず、摩擦係数が高まり、成形金型や切削工具において被加工材の凝着やかじりが生じることがあった。
そして、発明者の検討の結果、VN膜、VCN膜、VC膜の積層複合被膜では、金型における充分な成形性能、切削工具における充分な切削性能を発現できないことがあきらかとなった。
すなわち、特許文献1のバナジウム系被膜の成膜方法では、耐久性を充分高めることができなかった。
In the vanadium-based film forming method disclosed in Patent Document 1, from the base material (base material) side toward the outermost surface layer of the film by an ion plating method in which nitrogen gas and hydrocarbon gas are injected using vanadium as an evaporation source. Vanadium nitride (VN), vanadium carbonitride (VCN), and vanadium carbide (VC) are sequentially stacked, and the amount of injected gas and the gas pressure are adjusted depending on the film type of each layer.
However, the laminated structure produced by this film forming method does not maintain the low coefficient of friction that is characteristic of the VC film when the film hardness is increased, and the coefficient of friction increases, so that the work is performed in a molding die or a cutting tool. Adhesion and galling of the material sometimes occurred.
As a result of the inventors' investigation, it has become apparent that the laminated composite coating of the VN film, the VCN film, and the VC film cannot exhibit sufficient molding performance in the mold and sufficient cutting performance in the cutting tool.
That is, the vanadium-based film forming method disclosed in Patent Document 1 cannot sufficiently enhance the durability.

特許3909658号Japanese Patent No. 3909658

本発明はこのような従来の問題を解消すべく創案されたもので、イオンプレーティング法によって耐久性に優れたバナジウム系複合被膜を形成し、硬質バナジウム系複合被覆治工具の限界寿命を延長することを目的とする。   The present invention was devised to solve such a conventional problem. By forming a vanadium-based composite coating excellent in durability by an ion plating method, the critical life of a hard vanadium-based composite coated jig is extended. For the purpose.

前記目的を達成するために、
請求項1記載の硬質バナジウム系複合被覆治工具は、母材表面上に、PVD法により形成された、窒化バナジウム膜の第1層と、前記第1層上に、PVD法により形成された、炭窒化バナジウム膜の第2層であって、元素V、C、Nによる組成を、

Figure 2017196702
とするとき、a、bの原子比が
Figure 2017196702
Figure 2017196702
である第1層と、前記第2層上に、PVD法により形成された、炭化バナジウム膜の第3層であって、元素Cの原子組成比をYとするとき、
Figure 2017196702
である第3層と、前記第3層上に、PVD法により形成された、炭化バナジウム膜の第4層であって、元素Cの原子組成比をXとするとき、
Figure 2017196702
である第4層とを備えた硬質バナジウム系複合被膜が被覆される。 To achieve the above purpose,
The hard vanadium-based composite coated jig according to claim 1 is formed on a base material surface by a PVD method, and on the first layer of a vanadium nitride film and on the first layer by a PVD method. The second layer of the vanadium carbonitride film, the composition of the elements V, C, N,
Figure 2017196702
When the atomic ratio of a and b is
Figure 2017196702
Figure 2017196702
And the third layer of the vanadium carbide film formed by the PVD method on the first layer and the second layer, where the atomic composition ratio of element C is Y,
Figure 2017196702
And the fourth layer of the vanadium carbide film formed by the PVD method on the third layer, and when the atomic composition ratio of the element C is X,
Figure 2017196702
And a hard vanadium-based composite coating provided with a fourth layer.

請求項2記載の硬質バナジウム系複合被覆治工具は、前記第1層のナノインデンター硬さによるビッカース換算値が1500〜2000、前記第2層のナノインデンター硬さによるビッカース換算値が2500〜3000、前記第3層及び第4層のナノインデンター硬さによるビッカース換算値が1900〜2400であり、かつ第2層よりも低硬度である。   The hard vanadium-based composite coated jig according to claim 2 has a Vickers equivalent value of 1500 to 2000 based on the nanoindenter hardness of the first layer, and a Vickers equivalent value of 2500 to 2000 based on the nanoindenter hardness of the second layer. 3000, the Vickers conversion value by the nanoindenter hardness of the said 3rd layer and the 4th layer is 1900-2400, and it is lower hardness than a 2nd layer.

請求項3記載の硬質バナジウム系複合被覆治工具は、前記第2層は、

Figure 2017196702
または
Figure 2017196702
の少なくとも一方に起因する六方晶に配向し、前記第3層は、
Figure 2017196702
に起因する六方晶に配向している。 The hard vanadium-based composite coated jig according to claim 3, wherein the second layer is
Figure 2017196702
Or
Figure 2017196702
Oriented in a hexagonal crystal resulting from at least one of the following:
Figure 2017196702
Oriented to hexagonal crystals due to

本発明によれば、バナジウム系複合被膜を治工具類に施すことで治工具の限界寿命の延長を図ることが可能になる。 According to the present invention, it is possible to extend the limit life of a jig / tool by applying the vanadium-based composite coating to the jig / tool.

本発明に係る硬質バナジウム系複合被覆治工具の実施例における硬質バナジウム系複合被膜の構成を示す表1である。It is Table 1 which shows the structure of the hard vanadium type composite coating in the Example of the hard vanadium type composite coating jig / tool which concerns on this invention. 表1の硬質バナジウム系複合被膜における第1層の形成条件を示す表2である。It is Table 2 which shows the formation conditions of the 1st layer in the hard vanadium type composite film of Table 1. 表1の硬質バナジウム系複合被膜における第2層の形成条件を示す表3である。It is Table 3 which shows the formation conditions of the 2nd layer in the hard vanadium type composite film of Table 1. 表1の硬質バナジウム系複合被膜における第3層、第4層の形成条件を示す表4である。5 is a table 4 showing conditions for forming the third layer and the fourth layer in the hard vanadium-based composite coating of Table 1. 表1の硬質バナジウム系複合被膜の構成を決定するための表5である。It is Table 5 for determining the structure of the hard vanadium type composite film of Table 1. 表1の実施例と、比較例による冷間圧延鋼板の深絞り加工を行った試験結果を示すグラフである。It is a graph which shows the test result which performed the deep drawing process of the cold rolled steel plate by the Example of Table 1, and a comparative example. 表1の実施例と、比較例によるSUS304の深絞り加工を行った試験結果を示すグラフである。It is a graph which shows the test result which performed the deep drawing process of the SUS304 by the Example of Table 1, and a comparative example. 表1の実施例と、比較例によるドリル切削試験を行った結果を示す表6およびグラフである。It is Table 6 and the graph which show the result of having done the drill cutting test by the Example of Table 1, and a comparative example. 図6、図7の深絞り加工の試験のための装置を示す正面図である。It is a front view which shows the apparatus for the test of the deep drawing process of FIG. 6, FIG. 図9の装置に使用したダイスを示す平面図である。It is a top view which shows the dice | dies used for the apparatus of FIG. 図10のダイスを示す縦断面図である。It is a longitudinal cross-sectional view which shows the dice | dies of FIG. 図11の部分拡大図である。It is the elements on larger scale of FIG.

次に本発明に係る硬質バナジウム系複合被覆治工具の好適な実施例を、図面を参照しつつ説明する。   Next, a preferred embodiment of the hard vanadium composite coated jig according to the present invention will be described with reference to the drawings.

硬質バナジウム系複合被覆治工具は母材表面に硬質バナジウム系複合被膜をPVD法により形成したもので、バナジウム系複合被膜は、母材表面から最外表層に向かって、第1層のVN(窒化バナジウム)膜、第2層のVCN(炭窒化バナジウム)膜、第3層および第4層のVC(炭化バナジウム)膜からなり、各層の仕様は図1の表1のとおりである。 The hard vanadium-based composite coated jig / tool is obtained by forming a hard vanadium-based composite coating on the surface of the base material by the PVD method, and the vanadium-based composite coating is formed by VN (nitridation) from the base material surface toward the outermost surface layer. A vanadium) film, a second-layer VCN (vanadium carbonitride) film, a third-layer and a fourth-layer VC (vanadium carbide) film, and the specifications of each layer are as shown in Table 1 of FIG.

表1には、各層の原子組成比、結晶性、ナノインデータ硬さのビッカース換算値(以下、単に「硬度」という。)を示す。
硬質バナジウム系複合被膜の第1層(VN膜)は、ナノインデータ硬さのビッカース換算値が1500〜2000である。
第2層(VCN膜)は原子組成比が、V:0.5〜0.7、C:0.1〜0.3、N:残部、結晶性が六方晶であり、硬度2500〜3000である。
第3層(VC膜)は原子組成比が、C:0.2〜0.4、N:残部、結晶性が六方晶であり、硬度1900〜2400である。
第3層(VC膜)は原子組成比が、C:0.4〜0.6、N:残部、結晶性が六方晶であり、硬度1900〜2400である。
Table 1 shows the Vickers conversion values (hereinafter simply referred to as “hardness”) of the atomic composition ratio, crystallinity, and nanoindata hardness of each layer.
The first layer (VN film) of the hard vanadium-based composite coating has a Vickers conversion value of the nanoindata hardness of 1500 to 2000.
The second layer (VCN film) has an atomic composition ratio of V: 0.5 to 0.7, C: 0.1 to 0.3, N: balance, crystallinity is hexagonal, and has a hardness of 2500 to 3000. is there.
The third layer (VC film) has an atomic composition ratio of C: 0.2 to 0.4, N: balance, crystallinity of hexagonal crystal, and hardness of 1900 to 2400.
The third layer (VC film) has an atomic composition ratio of C: 0.4 to 0.6, N: balance, crystallinity of hexagonal crystal, and hardness of 1900 to 2400.

第1層〜第4層およびその比較例は、溶融蒸発型イオンプレーティング装置を用いてPVD法により超硬合金製テストピースに成膜した。そして、その硬度、密着性(硬度試験の際に生じるクラックを評価して判定する。)を、ロックウェル硬度計を用いた密着性と被膜のナノインデンター硬さによるビッカース換算値を評価した結果である。このナノインデンター硬さは、ナノインデンテーション法により測定される。具体的には、測定装置としてCSM Instrument社(スイス)製の製品名ナノハードネステスターを用い、測定条件を荷重5mNに調整して測定した。 The first to fourth layers and comparative examples thereof were formed on a cemented carbide test piece by the PVD method using a melt evaporation type ion plating apparatus. And the result which evaluated the Vickers conversion value by the nanoindenter hardness of the adhesiveness and film which used the Rockwell hardness meter for the hardness and adhesiveness (it evaluates and evaluates the crack which arises in the case of a hardness test). It is. This nanoindenter hardness is measured by the nanoindentation method. Specifically, a product name Nano Hard Tester manufactured by CSM Instrument (Switzerland) was used as a measuring apparatus, and the measurement conditions were adjusted to a load of 5 mN.

硬質バナジウム系複合被膜の第1層を形成する条件を決定するための試験結果の代表的データを図2の表2に示す。表2には、試験されたVN膜VN−1〜VN−5について、PVD法のバイアス電圧、密着性、硬度を示す。
VN膜は、バイアス電圧の上昇に従って硬度が上昇し、VN−1〜VN−5に対してバイアス電圧を15V、30V、50V、70V、150Vと上昇させると、硬度は1233、1558、1759、1996、2522と増大し、VN−1〜VN−3はクラックが生じなかったが、VN−4で僅かなクラックが生じ、VN−5でクラックが発生した。以上のデータおよび、その他の試験結果を加味して評価した結果、表1の硬度範囲が設定された。
硬度増大にともなって、母材に対する密着性、靭性が低下し、硬度が2000を超えると密着性、靭性の低下により、クラックが生じることが判明した。また、直上に位置する第2層(VCN膜)との硬度ギャップが大きいと層間剥離を生じる可能性が高いため、硬度1233のVN−1も排除すべきである。
以上から、バイアス電圧は30〜70Vが好ましく、特に50Vが望ましいと判断できる。
第1層は、複合被膜において密着性、耐久性を大きく左右する層であり、その密着性、耐久性は、その硬度に依存する。
Table 2 in FIG. 2 shows representative data of test results for determining the conditions for forming the first layer of the hard vanadium-based composite coating. Table 2 shows the bias voltage, adhesion, and hardness of the PVD method for the tested VN films VN-1 to VN-5.
The hardness of the VN film increases as the bias voltage increases. When the bias voltage is increased to 15V, 30V, 50V, 70V, and 150V with respect to VN-1 to VN-5, the hardness is 1233, 1558, 1759, 1996. , 2522, and VN-1 to VN-3 did not crack, but a slight crack occurred in VN-4 and a crack occurred in VN-5. As a result of evaluating the above data and other test results, the hardness range shown in Table 1 was set.
It has been found that, as the hardness increases, the adhesion and toughness with respect to the base material decrease, and when the hardness exceeds 2000, cracks occur due to the decrease in adhesion and toughness. Also, if the hardness gap with the second layer (VCN film) located immediately above is large, there is a high possibility of delamination, so VN-1 with a hardness of 1233 should be excluded.
From the above, it can be determined that the bias voltage is preferably 30 to 70 V, and particularly 50 V is desirable.
A 1st layer is a layer which influences adhesiveness and durability largely in a composite film, and the adhesiveness and durability depend on the hardness.

図3の表3は、第1層と同様のイオンプレーティング装置によって、第1層上に積層せずに、第2層と同一組成のVCN膜単層膜を形成して試験した結果を示す。表3には、試験されたVCN膜VCN−1〜VCN−8について、PVD法のバイアス電圧、原子組成比、結晶性、密着性、硬度を示す。
なお、結晶性については、EPMA(電子線プローブマイクロアナライザー)による被膜組成評価、XRD(X線回折)による評価を行った。硬度については、ナノハードネステスターによる評価を実施し、密着性については、ロックウェル硬度計によって評価した。
Table 3 in FIG. 3 shows the results of testing by forming a VCN single-layer film having the same composition as the second layer without being stacked on the first layer by an ion plating apparatus similar to the first layer. . Table 3 shows the bias voltage, atomic composition ratio, crystallinity, adhesion, and hardness of the PVD method for the tested VCN films VCN-1 to VCN-8.
In addition, about crystallinity, the film composition evaluation by EPMA (electron probe microanalyzer) and the evaluation by XRD (X-ray diffraction) were performed. The hardness was evaluated with a nanohard tester, and the adhesion was evaluated with a Rockwell hardness meter.

第2層でクラックが生じなかったVCN−3〜VCN−5は、原子組成比がV:0.60〜0.64、C:0.12〜0.25であり、その他の試験結果を加味して評価した結果、V:0.5〜0.7、C:0.1〜0.3が許容範囲となる。このとき、バイアス電圧は80V〜120Vであり、対応する硬度は、2864、2649、2915であった。すなわち、バイアス電圧100のときに、硬度が最低となり、密着性、靭性が高くなる。そして、他の試験結果を加味して評価した結果、硬度の許容範囲は、2500〜3000となる。VCN−3〜VCN−5の結晶性をEPMA、XRDで評価したところ、

Figure 2017196702
および
Figure 2017196702
に起因した六結晶に配向していることが判明した。一方、VCN−1は
Figure 2017196702
に起因した立方晶、VCN−2は
Figure 2017196702
のみに起因した六方晶、
VCN−7、VCN−8はVNに起因した立方晶に配向している。VCN−7、VCN−8は、バイアス電圧100に対して、組成比をV>0.7、V<0.5に変化させたとき、硬度上昇によるクラックが生じた例である。 VCN-3 to VCN-5 in which no cracks occurred in the second layer had atomic composition ratios of V: 0.60 to 0.64 and C: 0.12 to 0.25, and other test results were taken into account. As a result of evaluation, V: 0.5 to 0.7 and C: 0.1 to 0.3 are acceptable. At this time, the bias voltage was 80 V to 120 V, and the corresponding hardness was 2864, 2649, 2915. That is, when the bias voltage is 100, the hardness is minimum and the adhesion and toughness are increased. And as a result of evaluating by considering other test results, the allowable range of hardness is 2500 to 3000. When the crystallinity of VCN-3 to VCN-5 was evaluated by EPMA and XRD,
Figure 2017196702
and
Figure 2017196702
It was found that the crystals were oriented to six crystals due to the above. On the other hand, VCN-1
Figure 2017196702
The cubic crystal, VCN-2, due to
Figure 2017196702
Hexagonal crystals, caused only by
VCN-7 and VCN-8 are oriented in a cubic crystal due to VN. VCN-7 and VCN-8 are examples in which cracks due to an increase in hardness occurred when the composition ratio was changed to V> 0.7 and V <0.5 with respect to the bias voltage 100.

以上の結果から、VCN膜は、元素V、C、Nによる組成を、

Figure 2017196702
とするとき、a、bの原子比が
Figure 2017196702
Figure 2017196702
のとき、
Figure 2017196702
または
Figure 2017196702
の少なくとも一方に起因した六方晶に配向し、バイアス電圧100Vのときに、最低硬度の最適条件となる。 From the above results, the VCN film has the composition of the elements V, C, and N,
Figure 2017196702
When the atomic ratio of a and b is
Figure 2017196702
Figure 2017196702
When,
Figure 2017196702
Or
Figure 2017196702
When the bias voltage is 100 V, the optimum condition for the minimum hardness is obtained.

図4の表4のVC3−1〜VC3−7は、第1層、第2層と同様のイオンプレーティング装置によって、第2層上に積層せずに、第3層と同一組成のVC膜単層膜を形成して試験した結果を示す。第2層と同様、形成されたVC膜単層膜について、EPMAによる被膜組成評価、XRDによる結晶性評価、ナノハードネステスターによる硬度評価、ロックウェル硬度計による密着性評価を実施した。 VC 3-1 to VC 3-7 in Table 4 of FIG. 4 are VC films having the same composition as the third layer without being stacked on the second layer by the same ion plating apparatus as the first layer and the second layer. The result of forming and testing a single layer film is shown. Similarly to the second layer, the formed VC film monolayer film was subjected to coating composition evaluation by EPMA, crystallinity evaluation by XRD, hardness evaluation by nanohard tester, and adhesion evaluation by Rockwell hardness meter.

第3層でクラックが生じなかったVC3−2〜VC3−4は、原子組成比がC:0.25〜0.40であり、その他の試験結果を加味して評価した結果、C:0.2〜0.4が許容範囲となる。このときバイアス電圧は80V〜120Vであり、対応する硬度は、1905、1995、2319であり、他の試験結果を加味して評価した結果、硬度1900〜2400が許容範囲となる。
VC3−2〜VC3−4の結晶性をEPMA、CRDで評価したところ、

Figure 2017196702
に起因した六方晶に配向していることが判明した。一方、VC3−1は、VCに起因した立方晶、VC3−5〜VC3−7は、VCに起因した立方晶に配向している。VC3−5は、バイアス電圧150Vで硬度が2664と高く、VC3−6、VC3−7は、バイアス電圧100Vでありながら組成をC:0.82、0.58と変化させ、硬度が2890、2371に増大したものである。VC3−5、VC3−6、VC3−7はVCに起因した立方晶に配向している。 VC3-2 to VC3-4 in which cracks did not occur in the third layer had an atomic composition ratio of C: 0.25 to 0.40, and were evaluated in consideration of other test results. 2 to 0.4 is an allowable range. At this time, the bias voltage is 80 V to 120 V, and the corresponding hardness is 1905, 1995, 2319. As a result of evaluation with other test results taken into account, the hardness of 1900 to 2400 is within the allowable range.
When the crystallinity of VC3-2 to VC3-4 was evaluated by EPMA and CRD,
Figure 2017196702
It was found that the film was oriented in a hexagonal crystal due to. On the other hand, VC3-1 is oriented to a cubic crystal due to VC, and VC3-5 to VC3-7 are oriented to a cubic crystal due to VC. VC3-5 has a high hardness of 2664 at a bias voltage of 150 V, and VC3-6 and VC3-7 have a bias voltage of 100 V, but the composition is changed to C: 0.82, 0.58, and the hardness is 2890, 2371. It has been increased. VC3-5, VC3-6, and VC3-7 are oriented in a cubic crystal due to VC.

このように、

Figure 2017196702
または
Figure 2017196702
に起因した六方晶に配向した炭窒化バナジウムの第2層の上に、
Figure 2017196702
に起因した六方晶に配向している第3層の炭化バナジウム膜を介在させることによって、外部からの負荷を緩衝することができ、硬質バナジウム系複合被膜の耐久性を向上させる。 in this way,
Figure 2017196702
Or
Figure 2017196702
On the second layer of vanadium carbonitride oriented hexagonal due to
Figure 2017196702
By interposing a third-layer vanadium carbide film oriented in a hexagonal crystal resulting from the above, an external load can be buffered, and the durability of the hard vanadium-based composite coating is improved.

図4の表4のVC4−1〜VC4−7は、第1層、第2層と同様のイオンプレーティング装置によって、第3層上に積層せずに、第4層と同一組成のVC膜単層膜を形成して試験した結果を示す。第2層と同様、形成されたVC膜単層膜について、EPMAによる被膜組成評価、XRDによる結晶性評価、ナノハードネステスターによる硬度評価、ロックウェル硬度計による密着性評価を実施した。 VC4-1 to VC4-7 in Table 4 of FIG. 4 are VC films having the same composition as the fourth layer without being stacked on the third layer by the same ion plating apparatus as the first layer and the second layer. The result of forming and testing a single layer film is shown. Similarly to the second layer, the formed VC film monolayer film was subjected to coating composition evaluation by EPMA, crystallinity evaluation by XRD, hardness evaluation by nanohard tester, and adhesion evaluation by Rockwell hardness meter.

第4層でクラックが生じなかったVC4−2〜VC4−4は、原子組成比がC:0.43〜0.59であり、その他の試験結果を加味して評価した結果、C:0.4〜0.6が許容範囲となる。このときバイアス電圧は30V〜70Vであり、対応する硬度は、2133、2319、2391であり、他の試験結果を加味して評価した結果、硬度1900〜2400が許容範囲となる。
VC3−2からVC3−4の結晶性をEPMA、CRDで評価したところ、VCに起因した立方晶に配向していることが判明した。
一方、VC4−1は低バイアス電圧15V時、C:0.62、硬度1890、VC4−5は、高バイアス電圧150V時、C:0.39、硬度2751となり、クラックを生じた。適正バイアス電圧の中央値50Vにおいて、組成を変化させたVC−6,VC−7は、VC−6で、C:0.39、硬度2751、VC4−6でC:0.29、硬度2413となり、大きなクラックを生じた。
VC4-2 to VC4-4 in which cracks did not occur in the fourth layer had an atomic composition ratio of C: 0.43 to 0.59, and were evaluated with consideration of other test results. 4 to 0.6 is an allowable range. At this time, the bias voltage is 30 V to 70 V, and the corresponding hardness is 2133, 2319, 2391. As a result of evaluation with consideration of other test results, the hardness of 1900 to 2400 is within the allowable range.
When the crystallinity of VC3-2 to VC3-4 was evaluated by EPMA and CRD, it was found that the crystals were oriented to cubic crystals due to VC.
On the other hand, VC4-1 has a low bias voltage of 15 V, C: 0.62, hardness 1890, and VC4-5 has a high bias voltage of 150 V, C: 0.39, hardness 2751, and cracks occurred. VC-6 and VC-7 whose composition was changed at a median value of 50 V of the appropriate bias voltage are VC-6, C: 0.39, hardness 2751, VC4-6, C: 0.29, hardness 2413 , Caused a big crack.

各層の被膜組成比及び成膜条件であるバイアス電圧は、第1層のVN膜については30〜70V、第2層のVCN膜については80〜120V、第3層のVC膜については80〜120V、第4層のVC膜については30〜70Vとしたときに、最適な成膜が行われた。
また、第3層のVC膜は、

Figure 2017196702
Figure 2017196702
第4層のVC膜は、
Figure 2017196702
Figure 2017196702
以上の適正な成膜条件で形成された第1層〜第4層よりなる硬質バナジウム系複合被覆は、耐久性に優れるばかりでなく、摩擦係数も低く抑えられる。
特に、硬質バナジウム系複合被膜を、溶融蒸発型イオンプレーティング装置で形成したときは、ドロップレットが生成されず、極めて滑らかに仕上がるため、第4層VC膜の低摩擦係数を効果的に機能させて潤滑性を付与することが可能となる。
同じPVD法であっても、アークイオンプレーティング装置を使用すると、未蒸発、未反応の金属ドロップレットが生成され表面が粗くなりやすい。 The film composition ratio of each layer and the bias voltage, which is the film formation condition, are 30 to 70 V for the first VN film, 80 to 120 V for the second VCN film, and 80 to 120 V for the third VC film. The fourth layer of the VC film was optimally formed when the voltage was 30 to 70V.
The VC film of the third layer is
Figure 2017196702
Figure 2017196702
The fourth layer VC film is
Figure 2017196702
Figure 2017196702
The hard vanadium-based composite coating composed of the first layer to the fourth layer formed under the above appropriate film forming conditions not only has excellent durability, but also has a low coefficient of friction.
In particular, when a hard vanadium-based composite coating is formed with a melt evaporation type ion plating apparatus, droplets are not generated and the finish is extremely smooth, so that the low friction coefficient of the fourth layer VC film is effectively functioned. Thus, lubricity can be imparted.
Even in the same PVD method, when an arc ion plating apparatus is used, unvaporized and unreacted metal droplets are generated and the surface tends to become rough.

溶融蒸発型イオンプレーティング装置を用いて先述の成膜方法で超硬合金製テストピース、冷間工具鋼SKD11製絞りダイス、高速度鋼(SKH51)製の直径6mmストレートドリルに硬質バナジウム系複合被膜を成膜し、それぞれボールオンディスク試験による摩擦係数を、深絞り性能、切削性能を評価した結果を図5の表5、図6、図7に示す。 Hard vanadium based composite coating on cemented carbide test piece, cold tool steel SKD11 drawing die, high speed steel (SKH51) diameter 6mm straight drill using the melt evaporation type ion plating apparatus by the film formation method described above. Table 5 in FIG. 5, FIG. 6, and FIG. 7 show the results of evaluating the friction coefficient, deep drawing performance, and cutting performance in the ball-on-disk test, respectively.

ボールオンディスク試験は、具体的には、測定装置として、CSM Instrument社(スイス)製の「トライボメーター」を用い、SUJ2製ボールを用いて荷重5N、回転速度10cm/sec、回転半径3mm、走行距離1000m、ドライ環境で評価した。 Specifically, the ball-on-disk test uses a “tribometer” manufactured by CSM Instrument (Switzerland) as a measuring device, a load of 5 N, a rotation speed of 10 cm / sec, a rotation radius of 3 mm using a SUJ2 ball, traveling Evaluation was performed at a distance of 1000 m in a dry environment.

図5の表5は、硬質バナジウム系複合被覆の各層を(VN−3、VCN−4、VC3−3、VC4−3)、(VN−2、VCN−3、VC3−3、VC4−3)、(VN−3、VCN−5、VC3−2、VC4−4)、(VN−2、VCN−4、VC3−4、VC4−2)の各組み合わせとした実施例(以上を発明例1、2、3、4と呼ぶ。)と、4層各層を(VN−1、VCN−4、VC3−3、VC4−3)、(VN−3、VCN−2、VC3−3、VC4−3)、(VN−3、VCN−4、VC3−6、VC4−3)、(VN−3、VCN−4、VC3−3、VC4−6)とした比較例1〜4、3層各層を(VN−3、VC3−3、VC4−3)、(VN−3、VCN−4、VC4−3)とした比較例5、6、2層各層を(VC3−3、VC4−3)とした比較例7とを、摩擦係数、耐久性(限界寿命)について比較している。   Table 5 in FIG. 5 shows each layer of the hard vanadium-based composite coating (VN-3, VCN-4, VC3-3, VC4-3), (VN-2, VCN-3, VC3-3, VC4-3). , (VN-3, VCN-5, VC3-2, VC4-4), (VN-2, VCN-4, VC3-4, VC4-2) (Examples of the invention, 2, 4, 4) and 4 layers (VN-1, VCN-4, VC3-3, VC4-3), (VN-3, VCN-2, VC3-3, VC4-3) , (VN-3, VCN-4, VC3-6, VC4-3), (VN-3, VCN-4, VC3-3, VC4-6) Comparative Examples 1 to 4 and 3 layers as (VN -3, VC3-3, VC4-3), (VN-3, VCN-4, VC4-3) Comparative Examples 5, 6, and 2 layers, each layer being (VC3-3 And Comparative Example 7 in which the VC4-3), friction coefficient, are compared for durability (limit life).

摩擦係数は、発明例1〜4では0.28〜0.34であり、比較例1〜7では0.44〜0.68であった。すなわち、発明例1〜4は比較例1〜7に比較して摩擦が軽減され、安定している。比較例1、3、4は走行初期に層間で被膜が剥がれ落ち、摩擦係数が高くなった。このため、比較例1、3、4は著しく耐久性に欠けると判断し、深絞り性能、切削性能の評価を中止した。比較例2は層間の被膜剥がれは生じなかったが、摩擦係数は0.5を超えた。比較例5、7は摩擦係数は比較的低かった。比較例6は初期からかじるような摩擦挙動を示したが、剥がれることなく1000m走行した。   The friction coefficients were 0.28 to 0.34 in Invention Examples 1 to 4, and 0.44 to 0.68 in Comparative Examples 1 to 7. That is, the inventive examples 1 to 4 are stable with less friction compared to the comparative examples 1 to 7. In Comparative Examples 1, 3, and 4, the coating film peeled off between the layers at the beginning of running, and the friction coefficient increased. For this reason, it was judged that Comparative Examples 1, 3, and 4 were extremely lacking in durability, and evaluation of deep drawing performance and cutting performance was stopped. In Comparative Example 2, the film peeling between the layers did not occur, but the friction coefficient exceeded 0.5. In Comparative Examples 5 and 7, the friction coefficient was relatively low. Comparative Example 6 showed frictional behavior that gnawed from the beginning, but traveled 1000 m without peeling.

比較例1はVN−1が非常に硬いため、負荷を緩衝することができず、剥がれを誘発した。比較例3はVC3−6がその直上、直下の層の結晶性に倣わないため、VC3−6を起点に層間で剥がれが生じた。発明例4は、VC4−6が3000を越える高硬度のため、せん断応力が大きくなり、摩擦係数が高まり、剥がれが生じた。   In Comparative Example 1, VN-1 was very hard, so the load could not be buffered, and peeling was induced. In Comparative Example 3, since VC3-6 did not follow the crystallinity of the layer immediately above and below it, peeling occurred between the layers starting from VC3-6. Inventive Example 4 had a high hardness of VC4-6 exceeding 3000, so that the shear stress increased, the friction coefficient increased, and peeling occurred.

比較例5、7の摩擦係数が低いのは、VC3−3、VC4−3が効果的に機能した結果であり、比較例6は第3層(VC膜)が介在しない構成のため、第4層のVC4−3が磨滅したときに、第2層(VCN膜)が露出して、結果的に摩擦係数が増大した。   The low coefficient of friction in Comparative Examples 5 and 7 is the result of the effective operation of VC3-3 and VC4-3, and Comparative Example 6 has a configuration in which the third layer (VC film) is not interposed. When the layer VC4-3 was worn away, the second layer (VCN film) was exposed, resulting in an increased coefficient of friction.

以上の結果から、本実施例の積層複合被膜は、最外表層のVC4−2、VC4−3、VC4−4が低摩擦性能を発揮するためには、第1層のVN−2、VN−3、第2層のVCN−3、VCN−4、VCNー5、第3層のVC3−2、VC3−3、VC3−4が介在することが必須であることが確認された。   From the above results, in the laminated composite coating of this example, the outermost layers VC4-2, VC4-3, and VC4-4 exhibit the low friction performance. 3. It was confirmed that VCN-3, VCN-4, and VCN-5 in the second layer and VC3-2, VC3-3, and VC3-4 in the third layer are essential.

以下に図9〜図12の深絞りプレス試験の評価事例を挙げる。 Examples of evaluation of the deep drawing press test shown in FIGS.

溶融蒸発型イオンプレーティング装置を用いた成膜方法で冷間工具鋼SKD11製絞りダイスに硬質バナジウム系複合被膜を成膜した冷間圧延鋼板(SPCC)及びステンレス鋼(SUS304)のブランク材140を、完全脱脂状態での深絞り試験を行った。なお、図中、100はパンチ、120はブランクホルダ、160はダイスホルダ、162はダイス、C4はダイスのR部であり、dはダイス内径の勾配である。 A cold rolled steel plate (SPCC) and stainless steel (SUS304) blank 140 having a hard vanadium-based composite film formed on a drawing die made of cold tool steel SKD11 by a film forming method using a melt evaporation type ion plating apparatus. Then, a deep drawing test was performed in a completely degreased state. In the figure, 100 is a punch, 120 is a blank holder, 160 is a die holder, 162 is a die, C4 is an R portion of the die, and d is a gradient of the inner diameter of the die.

それぞれの材料に対して100ショット定数加工したときのパンチ100に掛かる加工力の挙動から絞り性を評価した。評価したのは表5における発明例1〜4のほか、比較例2、5、6、7の5種類で、加工力の平均値は表5に、加工力の挙動は図6、7に示す。 The drawability was evaluated from the behavior of the processing force applied to the punch 100 when processing 100 shot constants for each material. In addition to Invention Examples 1 to 4 in Table 5, five types of Comparative Examples 2, 5, 6, and 7 were evaluated. The average value of the processing force is shown in Table 5, and the behavior of the processing force is shown in FIGS. .

図6、7から、発明例1は加工力が低く安定している。早期にダイス162のR部C4に冷間圧延鋼板が摩擦凝着したために比較例6は3ショット、比較例2は21ショットで試験を中断せざるを得なかった。比較例7に関しては定数加工100ショットまで加工できたものの、加工力が上下に大きく変動しており、凝着と凝着物の外れが繰り返し生じていることがわかる。比較例1は比較的低い加工力を示しているが、ところどころで凝着物の影響が挙動に現れている。 6 and 7, Invention Example 1 has a low processing force and is stable. Since the cold rolled steel sheet frictionally adhered to the R part C4 of the die 162 at an early stage, the test was forced to be interrupted with 3 shots in Comparative Example 6 and 21 shots in Comparative Example 2. In Comparative Example 7, although constant machining could be performed up to 100 shots, the machining force greatly fluctuated up and down, and it can be seen that adhesion and detachment of the adherend occurred repeatedly. Comparative Example 1 shows a relatively low processing force, but in some places, the influence of the adherent appears in the behavior.

図6、7から本発明は加工力が極めて低いことがわかる。一方、ダイスのR部C4にステンレス鋼が早期に摩擦凝着したために比較例2、比較例6はそれぞれ6ショットで試験を中断せざるを得なかった。比較例5、比較例7は100ショットまで加工できたものの、全体的に加工力が高く、加工力が上下に暴れていることが確認された。 6 and 7 that the present invention has a very low processing force. On the other hand, because the stainless steel was friction-adhered to the R part C4 of the die at an early stage, Comparative Example 2 and Comparative Example 6 had to be interrupted with 6 shots each. Although Comparative Example 5 and Comparative Example 7 were able to process up to 100 shots, it was confirmed that the overall processing force was high and the processing force was up and down.

以上の結果から、本発明であるバナジウム系複合被膜はSPCC、SUS304、いずれの材料に対して、低い加工力で絞ることが可能であり、結果的に被加工材が凝着しにくいことが推測できる。 From the above results, it can be inferred that the vanadium-based composite coating according to the present invention can be narrowed down with a low processing force with respect to any material of SPCC and SUS304, and as a result, the work material is less likely to adhere. it can.

溶融蒸発型イオンプレーティング装置を用いて先述の成膜方法で高速度鋼(SKH51)製直径6mmストレートドリルにバナジウム系複合被膜を成膜し、穴明け加工ができなくなったときの限界寿命で切削性能を評価した結果を、図8のグラフおよび同図の表6に示す。 A vanadium-based composite coating is formed on a 6 mm diameter straight drill made of high-speed steel (SKH51) using the melt evaporation type ion plating apparatus as described above, and cutting is performed at the limit life when drilling cannot be performed. The results of evaluating the performance are shown in the graph of FIG. 8 and Table 6 of FIG.

ドリル切削条件は被削材SCM440C(硬さ28HRC)、周速40.7m/min、送り速度:200m/min、送り0.09mm/rev、止まり穴15mmを水溶性切削液を用いた環境で穴明け加工した。 Drill cutting conditions are: work material SCM440C (hardness 28HRC), peripheral speed 40.7m / min, feed rate: 200m / min, feed 0.09mm / rev, blind hole 15mm in an environment using water-soluble cutting fluid After dawn processing.

図8から本発明は加工初期の異音がなく、最も穴明け加工数を伸ばすことができた。比較例2は早期に焼き付き15穴で加工が終了となった。比較例5、比較例6、比較例7は加工初期化から削るときの音が大きく、早期に加工不能となった。 From FIG. 8, the present invention had no abnormal noise at the initial stage of machining, and was able to increase the number of drilling processes most. In Comparative Example 2, the processing was completed with 15 holes seized early. In Comparative Example 5, Comparative Example 6, and Comparative Example 7, the noise when cutting from the processing initialization was loud, and processing was impossible at an early stage.

比較例2は極めて高硬度なVCN―1が介在することでVN−3との硬さギャップが大きく、結果的に切削加工時の負荷を緩衝できず、層間剥離を発生して早期に寿命を迎えた。比較例2はVC3−3が介在しないため、VCN−3とVC3−3との界面層間剥がれが発生した。比較例3はVN−3、VCN−3といった強固な下地層が設けられていないため、VC3−3、VC4−3の低摩擦係数を示す被膜の特徴を充分に発揮することができなかった。 Comparative Example 2 has a very high hardness gap with VN-3 due to the presence of extremely high hardness VCN-1, and as a result, the load during cutting cannot be buffered, resulting in delamination and an early life. Greeted. Since VC3-3 was not interposed in Comparative Example 2, interfacial delamination between VCN-3 and VC3-3 occurred. Since the comparative example 3 was not provided with a strong underlayer such as VN-3 and VCN-3, the characteristics of the coating film showing the low friction coefficient of VC3-3 and VC4-3 could not be sufficiently exhibited.

以上の結果から、本発明の硬質バナジウム系複合被膜は最適化が図られたVN−3やVCN−3といった被膜の介在が切削性能に好影響を与えることが確認された。 From the above results, it was confirmed that the hard vanadium-based composite coating of the present invention has a favorable influence on the cutting performance due to the intervention of coatings such as VN-3 and VCN-3 which are optimized.

以上の実施例では、治工具について硬質バナジウム系複合被膜を形成したが、本発明に係る硬質バナジウム系複合被膜を、耐摩耗性が要求される機械部品、例えば、軸受その他の摺動機械部品に適用し得ることはいうまでもない。   In the above embodiment, the hard vanadium composite coating is formed on the tool, but the hard vanadium composite coating according to the present invention is applied to machine parts that require wear resistance, such as bearings and other sliding machine parts. Needless to say, it can be applied.

100 パンチ
120 ブランクホルダ
140 ブランク材
160 ダイスホルダ
162 ダイス
C4 ダイスのR部
d ダイス内径の勾配
100 Punch 120 Blank holder 140 Blank material 160 Die holder 162 Die C4 R part of the die d Gradient of the inside diameter of the die

Claims (3)

母材表面上に、PVD法により形成された、窒化バナジウム膜の第1層と、
前記第1層上に、PVD法により形成された、炭窒化バナジウム膜の第2層であって、元素VC、Nの原子組成比を
Figure 2017196702
とするとき、a、bの原子比が
Figure 2017196702
Figure 2017196702
である第2層と、
前記第2層上に、PVD法により形成された、炭化バナジウム膜の第3層であって、元素Cの原子組成比をYとするとき、
Figure 2017196702
である第3層と、
前記第3層上に、PVD法により形成された、炭化バナジウム膜の第4層であって、元素Cの原子組成比をXとするとき、
Figure 2017196702
である第4層と、
を備えた硬質バナジウム系複合被膜が被覆されたことを特徴とする硬質バナジウム系複合被覆治工具。
A first layer of a vanadium nitride film formed on the surface of the base material by a PVD method;
A second layer of a vanadium carbonitride film formed on the first layer by a PVD method, wherein the atomic composition ratio of the elements VC and N is
Figure 2017196702
When the atomic ratio of a and b is
Figure 2017196702
Figure 2017196702
A second layer,
When the third layer of the vanadium carbide film formed on the second layer by the PVD method and the atomic composition ratio of the element C is Y,
Figure 2017196702
A third layer,
When the fourth layer of the vanadium carbide film formed on the third layer by the PVD method and the atomic composition ratio of the element C is X,
Figure 2017196702
A fourth layer,
A hard vanadium-based composite coating tool characterized by being coated with a hard vanadium-based composite coating.
前記第1層のナノインデンター硬さによるビッカース換算値が1500〜2000、前記第2層のナノインデンター硬さによるビッカース換算値が2500〜3000、前記第3層及び第4層のナノインデンター硬さによるビッカース換算値が1900〜2400であり、かつ第2層よりも低硬度であることを特徴とする請求項1記載の硬質バナジウム系複合被覆治工具。   The Vickers conversion value by the nano indenter hardness of the first layer is 1500 to 2000, the Vickers conversion value by the nano indenter hardness of the second layer is 2500 to 3000, the nano indenters of the third layer and the fourth layer The hard vanadium-based composite coated jig according to claim 1, wherein a Vickers equivalent value by hardness is 1900 to 2400 and has a lower hardness than the second layer. 前記第2層は、
Figure 2017196702
または
Figure 2017196702
の少なくとも一方に起因する六方晶に配向し、前記第3層は、
Figure 2017196702
に起因する六方晶に配向していることを特徴とする硬質バナジウム系複合被覆治工具。
The second layer is
Figure 2017196702
Or
Figure 2017196702
Oriented in a hexagonal crystal resulting from at least one of the following:
Figure 2017196702
A hard vanadium-based composite coated jig characterized by being oriented in hexagonal crystals caused by
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020082190A (en) * 2018-11-19 2020-06-04 Jfeスチール株式会社 Galling resistance evaluation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10237628A (en) * 1997-02-20 1998-09-08 Sumitomo Electric Ind Ltd Coated tool and its production
JP2002371352A (en) * 2001-06-15 2002-12-26 Yuken Industry Co Ltd Method for forming vanadium-based film
JP2005046975A (en) * 2003-07-31 2005-02-24 Nachi Fujikoshi Corp Vanadium-based film coated tool
JP2010202948A (en) * 2009-03-05 2010-09-16 Nachi Fujikoshi Corp Vanadium-containing film, and vanadium-containing film-coated die and tool

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10237628A (en) * 1997-02-20 1998-09-08 Sumitomo Electric Ind Ltd Coated tool and its production
JP2002371352A (en) * 2001-06-15 2002-12-26 Yuken Industry Co Ltd Method for forming vanadium-based film
JP2005046975A (en) * 2003-07-31 2005-02-24 Nachi Fujikoshi Corp Vanadium-based film coated tool
JP2010202948A (en) * 2009-03-05 2010-09-16 Nachi Fujikoshi Corp Vanadium-containing film, and vanadium-containing film-coated die and tool

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020082190A (en) * 2018-11-19 2020-06-04 Jfeスチール株式会社 Galling resistance evaluation method

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