JP2014077178A - Cermet and coated cermet - Google Patents
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Abstract
Description
本発明は、サーメットおよび被覆サーメットに関するものである。 The present invention relates to a cermet and a coated cermet.
サーメットの従来技術として、サーメット表面部の硬度を高めて耐摩耗性を向上させたサーメットがある（例えば、特許文献１参照。）。 As a conventional cermet technology, there is a cermet in which the hardness of the cermet surface portion is increased to improve the wear resistance (see, for example, Patent Document 1).
しかしながら、上記特許文献１の発明は、耐欠損性が不十分であり、切削工具として用いると工具寿命が短いという問題があった。本発明は、上記問題を解決するためになされたもので、耐欠損性および耐摩耗性が優れ、切削工具として用いると従来よりも切削工具の寿命を長くすることができるサーメットおよび被覆サーメットを提供することを目的とする。 However, the invention of the above-mentioned Patent Document 1 has a problem that the fracture resistance is insufficient and the tool life is short when used as a cutting tool. The present invention has been made to solve the above-mentioned problems, and provides a cermet and a coated cermet that have excellent fracture resistance and wear resistance and can extend the life of the cutting tool when used as a cutting tool. The purpose is to do.
本発明は上記の課題を解決するためになされ、その要旨は次のとおりである。
（１）ＷＣからなる第１硬質相：３０〜６５体積％と、チタン化合物からなる第２硬質相：２５〜４５体積％と、鉄族金属を主成分とする結合相：５〜２５体積％とから構成され、これらの合計が１００体積％であり、第２硬質相は芯部と芯部を取り囲む平均厚さ０．１〜３．０μｍの周辺部とからなる有芯構造であり、芯部はＴｉＮからなり、周辺部はＺｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの中から選ばれた少なくとも１種とＴｉとの複合炭窒化物からなり、サーメット全体に含有される炭素量ＣＴ（質量％）、サーメット全体に含有されるタングステン量ＣＷ（質量％）、サーメット全体に含有される窒素量ＣＮ（質量％）が、
５≦（ＣＮ／（ＣＴ−０．０６５３・ＣＷ））≦７０
を満足するサーメット。
（２）サーメットの表面の少なくとも１部に、サーメットの表面から２〜３０μｍの深さに亘って第１硬質相：６５〜９３体積％と、結合相：７〜３５体積％とから構成され、これらの合計が１００体積％である表面領域が形成された（１）のサーメット。
（３）表面領域のビッカース硬さＨｖは１４００以上１６００未満であり、サーメットの表面を基準として３０μｍの深さから８０μｍの深さまでの間にビッカース硬さＨｖが最も高くなるところがあり、ビッカース硬さＨｖの最高値は１６００以上２０００以下であり、サーメットの表面を基準として５００μｍの深さのビッカース硬さＨｖは１４００以上１８００以下である（２）のサーメット。
（４）第１硬質相の平均粒径が０．５〜３．０μｍであり、第２硬質相の平均粒径が１．０〜５．０μｍである（１）〜（３）のいずれかのサーメット。
（５）サーメット全体に含まれるＣｒ元素量は、サーメットの全質量に対して０．２〜２．５質量％である（１）〜（４）のいずれかのサーメット。
（６）（１）〜（５）のいずれかのサーメットの表面に被覆層が形成された被覆サーメット。
The present invention has been made to solve the above problems, and the gist thereof is as follows.
(1) First hard phase composed of WC: 30 to 65% by volume, second hard phase composed of a titanium compound: 25 to 45% by volume, and binder phase mainly composed of iron group metal: 5 to 25% by volume The total of these is 100% by volume, and the second hard phase is a cored structure comprising a core part and a peripheral part having an average thickness of 0.1 to 3.0 μm surrounding the core part, The part is made of TiN, and the peripheral part is made of a composite carbonitride of at least one selected from Zr, Hf, V, Nb, Ta, Cr, Mo, and W and Ti, and is contained in the entire cermet. Carbon amount C T (mass%), tungsten quantity C W (mass%) contained in the whole cermet, nitrogen quantity C N (mass%) contained in the whole cermet,
5 ≦ (C N / (C T −0.0653 · C W )) ≦ 70
Satisfying cermet.
(2) At least a part of the surface of the cermet is composed of a first hard phase: 65 to 93% by volume and a binder phase: 7 to 35% by volume over a depth of 2 to 30 μm from the surface of the cermet. The cermet of (1) in which a surface region in which the total of these was 100% by volume was formed.
(3) The Vickers hardness Hv of the surface region is 1400 or more and less than 1600, and there is a place where the Vickers hardness Hv is highest between a depth of 30 μm and a depth of 80 μm on the basis of the surface of the cermet. The maximum value of Hv is 1600 or more and 2000 or less, and the Vickers hardness Hv having a depth of 500 μm on the basis of the surface of the cermet is 1400 or more and 1800 or less (2).
(4) The average particle diameter of the first hard phase is 0.5 to 3.0 μm, and the average particle diameter of the second hard phase is 1.0 to 5.0 μm, and any one of (1) to (3) Cermet.
(5) The cermet according to any one of (1) to (4), wherein the amount of Cr element contained in the entire cermet is 0.2 to 2.5 mass% with respect to the total mass of the cermet.
(6) A coated cermet in which a coating layer is formed on the surface of any one of (1) to (5).
本発明のサーメットは、ＷＣからなる第１硬質相：３０〜６５体積％と、チタン化合物からなる第２硬質相：２５〜４５体積％と、鉄族金属を主成分とする結合相：５〜２５体積％とから構成される。本発明のサーメットは、表面から深さ５００μｍ未満までの組成が傾斜する場合があるので、表面を基準として深さ５００μｍ以上の組成が安定した内部で第１硬質相、第２硬質相、結合相の体積％を測定するとよい。 The cermet of the present invention comprises a first hard phase composed of WC: 30 to 65% by volume, a second hard phase composed of a titanium compound: 25 to 45% by volume, and a binder phase mainly composed of an iron group metal: 5 to 5%. 25% by volume. In the cermet of the present invention, since the composition from the surface to a depth of less than 500 μm may be inclined, the first hard phase, the second hard phase, and the binder phase are stable inside the composition having a depth of 500 μm or more with respect to the surface. It is good to measure the volume%.
本発明の結合相は、鉄族金属を主成分とする金属である。本発明において鉄族金属とは、Ｃｏ、Ｎｉ、Ｆｅを意味する。具体的には、Ｃｏ、ＮｉおよびＦｅの少なくとも１種の金属、または、Ｃｏ、ＮｉおよびＦｅの少なくとも１種に、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの少なくとも１種を合計して３０質量％未満固溶させた金属である。その中でも、ＣｏおよびＮｉの１種または２種を主成分とする結合相であると、機械的強度が向上するのでさらに好ましく、その中でもＣｏを主成分とする結合相であると、サーメットと被覆層との密着性が向上するのでさらに好ましい。本発明の結合相が、サーメット全体に対して５体積％未満になると耐欠損性が低下し、サーメット全体に対して２５体積％を超えて多くなると耐摩耗性が低下するので、本発明の結合相を５〜２５体積％とした。 The binder phase of the present invention is a metal mainly composed of an iron group metal. In the present invention, the iron group metal means Co, Ni, and Fe. Specifically, at least one of Co, Ni, and Fe, or at least one of Co, Ni, and Fe is replaced with at least one of Zr, Hf, V, Nb, Ta, Cr, Mo, and W. A total of less than 30% by mass of dissolved metal. Among them, a bonded phase mainly composed of one or two of Co and Ni is more preferable because mechanical strength is improved, and among them, a bonded phase mainly composed of Co is cermet and coating. This is more preferable because adhesion to the layer is improved. When the binder phase of the present invention is less than 5% by volume with respect to the entire cermet, the fracture resistance decreases, and when it exceeds 25% by volume with respect to the entire cermet, the wear resistance decreases. The phase was 5-25% by volume.
本発明の第１硬質相はＷＣからなる。ＷＣは熱伝導率が高く、サーメットにサーマルクラックを生じにくくさせる作用がある。さらにＷＣは室温でも容易に塑性変形するため、ＷＣを含むサーメットは靱性が高くなる。本発明の第１硬質相が、サーメット全体に対して３０体積％未満になると耐サーマルクラック性が低下し、サーメット全体に対して６５体積％を超えて多くなると耐摩耗性が低下するので、本発明の第１硬質相を３０〜６５体積％とした。 The first hard phase of the present invention consists of WC. WC has a high thermal conductivity and has the effect of making it difficult for thermal cracks to occur in the cermet. Furthermore, since WC easily plastically deforms even at room temperature, the cermet containing WC has high toughness. When the first hard phase of the present invention is less than 30% by volume with respect to the entire cermet, the thermal crack resistance decreases, and when it exceeds 65% by volume with respect to the entire cermet, the wear resistance decreases. The 1st hard phase of invention was 30-65 volume%.
本発明のチタン化合物からなる第２硬質相は、ＴｉＮの芯部と、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの中から選ばれた少なくとも１種とＴｉとの複合炭窒化物からなる周辺部とから構成された有芯構造である。具体的には、ＴｉＮの芯部と、芯部を取り囲む（Ｔｉ，Ｗ）ＣＮ、（Ｔｉ，Ｗ，Ｔａ）ＣＮ、（Ｔｉ，Ｗ，Ｎｂ）ＣＮ、（Ｔｉ，Ｗ，Ｔａ，Ｎｂ）ＣＮ、（Ｔｉ，Ｗ，Ｎｂ，Ｍｏ，Ｖ）ＣＮ、（Ｔｉ，Ｗ，Ｃｒ，Ｖ）ＣＮ、（Ｔｉ，ＷＮｂ，Ｃｒ，Ｖ）ＣＮ、（Ｔｉ，Ｗ，Ｔａ，Ｎｂ，Ｃｒ，Ｖ）ＣＮ、(Ｔｉ，Ｗ，Ｎｂ，Ｃｒ，Ｚｒ)ＣＮ、（Ｔｉ，Ｗ，Ｃｒ）ＣＮ、（Ｔｉ，Ｗ，Ｎｂ，Ｃｒ，Ｈｆ）ＣＮ、（Ｔｉ，Ｗ，Ｔａ，Ｃｒ）ＣＮ、（Ｔｉ，Ｗ，Ｔａ，Ｎｂ，Ｃｒ）ＣＮなどの周辺部からなる有芯構造である。第２硬質相の周辺部の平均厚さが、０．１μｍ未満になると耐欠損性が低下し、周辺部の平均厚さが３．０μｍを超えて厚くなると、耐熱衝撃性が低下するので、第２硬質相の周辺部の平均厚さを０．１〜３．０μｍとした。本発明のチタン化合物からなる第２硬質相はサーメット全体に対して２５体積％未満になると耐摩耗性が低下し、第２硬質相は４５体積％を超えて多くなると耐欠損性が低下するので、本発明の第２硬質相を２５〜４５体積％とした。本発明のサーメットの組成を上記体積比率にするためには、原料粉末の配合組成を調節することにより達成することができる。本発明の第２硬質相の周辺部の平均厚さを上記の平均厚さにするためには、圧力３ｋＰａ以上の窒素雰囲気中で焼結することにより達成することができる。 The second hard phase comprising the titanium compound of the present invention is a composite carbonitriding of Ti with a core of TiN and at least one selected from Zr, Hf, V, Nb, Ta, Cr, Mo, W and Ti. It is a cored structure composed of a peripheral part made of an object. Specifically, a TiN core part, (Ti, W) CN, (Ti, W, Ta) CN, (Ti, W, Nb) CN, (Ti, W, Ta, Nb) CN surrounding the core part , (Ti, W, Nb, Mo, V) CN, (Ti, W, Cr, V) CN, (Ti, WNb, Cr, V) CN, (Ti, W, Ta, Nb, Cr, V) CN , (Ti, W, Nb, Cr, Zr) CN, (Ti, W, Cr) CN, (Ti, W, Nb, Cr, Hf) CN, (Ti, W, Ta, Cr) CN, (Ti, W, Ta, Nb, Cr) It is a cored structure consisting of peripheral parts such as CN. When the average thickness of the peripheral portion of the second hard phase is less than 0.1 μm, the chipping resistance decreases, and when the average thickness of the peripheral portion exceeds 3.0 μm, the thermal shock resistance decreases. The average thickness of the peripheral part of the second hard phase was set to 0.1 to 3.0 μm. When the second hard phase composed of the titanium compound of the present invention is less than 25% by volume with respect to the whole cermet, the wear resistance is lowered, and when the second hard phase is more than 45% by volume, the fracture resistance is lowered. The second hard phase of the present invention was 25 to 45% by volume. In order to adjust the composition of the cermet of the present invention to the above volume ratio, it can be achieved by adjusting the composition of the raw material powder. In order to make the average thickness of the peripheral portion of the second hard phase of the present invention the above average thickness, it can be achieved by sintering in a nitrogen atmosphere having a pressure of 3 kPa or more.
本発明のサーメットの第２硬質相に含まれる炭素量と窒素量を直接に測定することは難しいので、サーメット全体に含有される炭素量ＣＴ（質量％）、サーメット全体に含有されるタングステン量ＣＷ（質量％）を測定し、計算式：
ＣＣ＝ＣＴ−０．０６５３・ＣＷ
で求めたＣＣ（質量％）に対する、サーメット全体に含有される窒素量ＣＮ（質量％）の比（ＣＮ／ＣＣ）により、本発明のサーメットの特徴の一つを規定した。ここで、ＣＣは以下に詳述するように、第２硬質相の炭素量とみなされる量であり、０．０６５３はＷＣに含まれる炭素量を求めるための係数である。
Since it is difficult to directly measure the amount of carbon and the amount of nitrogen contained in the second hard phase of the cermet of the present invention, the amount of carbon C T (% by mass) contained in the entire cermet, the amount of tungsten contained in the entire cermet Measure C W (mass%) and calculate:
C C = C T −0.0653 · C W
One of the characteristics of the cermet of the present invention was defined by the ratio (C N / C C ) of the amount of nitrogen C N (mass%) contained in the entire cermet to the C C (mass%) obtained in the above. Here, as described in detail below, CC is an amount that is regarded as the amount of carbon in the second hard phase, and 0.0653 is a coefficient for determining the amount of carbon contained in WC.
このことを詳しく述べると、サーメットの結合相に固溶している炭素量は非常に少なく、サーメット全体に含まれる炭素のほとんどは第１硬質相と第２硬質相に含まれている。サーメット全体に含まれるＷは、第１硬質相と第２硬質相に含まれるが、第１硬質相に含まれるＷ量は多く、第２硬質相に含まれるＷ量は非常に少ない。そこで、（１）サーメット全体に含まれるＷが第１硬質相（ＷＣ）を形成するとみなし、（２）サーメット全体の炭素量からＷＣの炭素量を差し引いた値を第２硬質相の炭素量とみなした。具体的には、（１）ＷＣは原子数１８３．８５のＷ（タングステン）と原子数１２．０１のＣ（炭素）で構成されるため、ＷＣに含まれるＣの質量比は０．０６１３、ＷＣに含まれるＷの質量比は０．９３８７となる。サーメット全体のタングステン量をＣＷ（質量％）とすると、ＷＣに含まれる炭素量は、（０．０６１３／０．９３８７）・ＣＷ、すなわち、（０．０６５３・ＣＷ）により求められる。（２）サーメット全体の炭素量ＣＴ（質量％）からＷＣに含まれる炭素量（０．０６５３・ＣＷ）を差し引くと、結合相と第２硬質相に含まれる炭素量を求めることができる。結合相に固溶している炭素量は第２硬質相に含まれる炭素量に比べて非常に少ないので、第２硬質相の炭素量ＣＣ（質量％）は、（ＣＴ−０．０６５３・ＣＷ）とみなすことができる。 More specifically, the amount of carbon dissolved in the cermet binder phase is very small, and most of the carbon contained in the entire cermet is contained in the first hard phase and the second hard phase. W contained in the entire cermet is contained in the first hard phase and the second hard phase, but the amount of W contained in the first hard phase is large, and the amount of W contained in the second hard phase is very small. Therefore, (1) W included in the entire cermet is considered to form the first hard phase (WC), and (2) the value obtained by subtracting the carbon amount of WC from the carbon amount of the entire cermet is the carbon amount of the second hard phase. I saw it. Specifically, since (1) WC is composed of W (tungsten) having 183.85 atoms and C (carbon) having 12.01 atoms, the mass ratio of C contained in WC is 0.0613, The mass ratio of W contained in WC is 0.9387. When the tungsten amount of the entire cermet is C W (mass%), the carbon amount contained in WC is obtained by (0.0613 / 0.9387) · C W , that is, (0.0653 · C W ). (2) By subtracting the carbon amount (0.0653 · C W ) contained in WC from the carbon amount C T (mass%) of the entire cermet, the carbon amount contained in the binder phase and the second hard phase can be obtained. . Since the amount of carbon dissolved in the binder phase is very small compared to the amount of carbon contained in the second hard phase, the carbon amount C C (mass%) of the second hard phase is (C T −0.0653). -It can be regarded as CW ).
一方、窒素は第１硬質相のＷＣに固溶しない。窒素の結合相への固溶量は第２硬質相に含有される窒素量に比べると非常に少ない。窒素のほとんどが第２硬質相に含まれている。そのため、サーメット全体の窒素量は第２硬質相の窒素量に比例するとみなせる。上述のＣＣ（質量％）とＣＮ（質量％）から（ＣＮ／ＣＣ）比、すなわち、第２硬質相中における窒素量に対する炭素量の比を求めると、本発明のサーメット全体に含有される窒素量ＣＮ（質量％）が、５≦（ＣＮ／ＣＣ）≦７０を満足する。（ＣＮ／ＣＣ）比が５未満となると、サーメットの耐熱衝撃性が低下し（ＣＮ／ＣＣ）比が７０を超えて多くなると、サーメットの焼結性が低下し、耐欠損性が低下するので、本発明の窒素量ＣＮ（質量％）を５≦（ＣＮ／ＣＣ）≦７０の範囲、すなわち、５≦（ＣＮ／（ＣＴ−０．０６５３・ＣＷ））≦７０の範囲とした。上記範囲は、より好ましくは、７≦（ＣＮ／（ＣＴ−０．０６５３・ＣＷ））≦６８であり、更に好ましくは９≦（ＣＮ／（ＣＴ−０．０６５３・ＣＷ））≦６６である。第２硬質相に含有される炭素量ＣＣ（質量％）および窒素量ＣＮ（質量％）が、上記範囲を満足するためには、具体的には、第２硬質相用原料粉末の炭素量（Ｃ）と窒素量（Ｎ）の合計に対する窒素量（Ｎ）の割合（Ｎ／（Ｃ＋Ｎ））が質量比で０．８０以上の第２硬質相用原料粉末を使用することにより達成される。 On the other hand, nitrogen does not dissolve in the WC of the first hard phase. The amount of nitrogen dissolved in the binder phase is very small compared to the amount of nitrogen contained in the second hard phase. Most of the nitrogen is contained in the second hard phase. Therefore, it can be considered that the nitrogen amount of the whole cermet is proportional to the nitrogen amount of the second hard phase. From the above-mentioned C C (mass%) and C N (mass%), the (C N / C C ) ratio, that is, the ratio of the carbon amount to the nitrogen amount in the second hard phase, is obtained. The amount of nitrogen C N (% by mass) contained satisfies 5 ≦ (C N / C C ) ≦ 70. When the (C N / C C ) ratio is less than 5, the thermal shock resistance of the cermet decreases, and when the (C N / C C ) ratio exceeds 70, the cermet sinterability decreases and the fracture resistance Therefore, the nitrogen amount C N (mass%) of the present invention is in the range of 5 ≦ (C N / C C ) ≦ 70, that is, 5 ≦ (C N / (C T −0.0653 · C W ). ) ≦ 70. The above range is more preferably 7 ≦ (C N / (C T −0.0653 · C W )) ≦ 68, and more preferably 9 ≦ (C N / (C T −0.0653 · C W). )) ≦ 66. In order for the carbon content C C (mass%) and the nitrogen content C N (mass%) contained in the second hard phase to satisfy the above ranges, specifically, the carbon of the second hard phase raw material powder. The ratio (N / (C + N)) of the nitrogen amount (N) to the sum of the amount (C) and the nitrogen amount (N) is achieved by using a raw material powder for the second hard phase having a mass ratio of 0.80 or more. The
サーメット全体の炭素量ＣＴ（質量％）は高周波燃焼−赤外線吸収法により測定できる。サーメット全体の窒素量ＣＮ（質量％）を不活性ガス融解−熱伝導度法により測定した。サーメット全体のタングステン量ＣＷ（質量％）は蛍光Ｘ線分析装置により測定できる。 Carbon content of the entire cermet C T (wt%) of high-frequency combustion - can be measured by an infrared absorption method. The nitrogen content C N (mass%) of the entire cermet was measured by an inert gas melting-thermal conductivity method. The amount of tungsten C W (% by mass) of the entire cermet can be measured with a fluorescent X-ray analyzer.
本発明のサーメットの表面の少なくとも１部に、表面から内部に向って２〜３０μｍの厚さがあり、結合相：表面領域全体に対して７〜３５体積％と、第１硬質相：表面領域全体に対して６５〜９３体積％とからなる表面領域が形成されると、サーメットの耐欠損性が向上するので好ましい。表面領域の結合相が表面領域全体に対して７体積％が未満になると、耐欠損性が低下し、表面領域の結合相が表面領域全体に対して３５体積％を超えて多くなると、耐摩耗性が低下するので、表面領域の結合相は、表面領域全体に対して７〜３５体積％であると好ましい。表面領域の第１硬質相が表面領域全体に対して６５体積％未満になると、耐熱衝撃性が低下し、表面領域の第１硬質相が表面領域全体に対して９３体積％を超えて多くなると、耐摩耗性が低下するので、表面領域の第１硬質相は、６５〜９３体積％であると好ましい。 At least a part of the surface of the cermet of the present invention has a thickness of 2 to 30 μm from the surface to the inside, and the binder phase: 7 to 35% by volume with respect to the entire surface region, the first hard phase: the surface region It is preferable to form a surface region composed of 65 to 93% by volume with respect to the whole because the fracture resistance of the cermet is improved. When the binder phase in the surface region is less than 7% by volume with respect to the entire surface region, the fracture resistance decreases, and when the binder phase in the surface region exceeds 35% by volume with respect to the entire surface region, wear resistance is reduced. Therefore, the binder phase in the surface region is preferably 7 to 35% by volume with respect to the entire surface region. When the first hard phase in the surface region is less than 65% by volume with respect to the entire surface region, the thermal shock resistance decreases, and when the first hard phase in the surface region exceeds 93% by volume with respect to the entire surface region. Since the wear resistance is lowered, the first hard phase in the surface region is preferably 65 to 93% by volume.
本発明のサーメットの表面の少なくとも１部に表面領域が形成されていることとは、サーメットの表面の１部またはサーメットの表面全部に表面領域が形成されていることを意味している。本発明のサーメットの表面に表面領域があると耐欠損性がさらに向上する。例えば、本発明のサーメットを切削工具として用いる場合、切削工具の刃先など、高い耐欠損性が要求される箇所に表面領域が設けられると好ましい。 That the surface region is formed on at least a part of the surface of the cermet of the present invention means that the surface region is formed on a part of the surface of the cermet or the entire surface of the cermet. When there is a surface region on the surface of the cermet of the present invention, the fracture resistance is further improved. For example, when the cermet of the present invention is used as a cutting tool, it is preferable that a surface region is provided at a location where high fracture resistance is required, such as a cutting edge of the cutting tool.
本発明の表面領域の厚さが２μｍ未満になると、サーメットの耐欠損性を向上させる効果が十分に得られず、本発明の表面領域の厚さが３０μｍを超えて厚くなるとサーメットの耐摩耗性が低下する傾向が見られるので、本発明の表面領域の厚さを２〜３０μｍの範囲にすると好ましい。本発明のサーメットの表面領域の組成と厚さを上記体積比率と上記厚さにするためには、圧力３ｋＰａ以上の窒素雰囲気中で昇温した後、昇温工程よりも低い圧力の窒素雰囲気中、アルゴン雰囲気中または圧力５０Ｐａ以下の真空中で焼結することにより達成することができる。 If the thickness of the surface region of the present invention is less than 2 μm, the effect of improving the fracture resistance of the cermet is not sufficiently obtained, and if the thickness of the surface region of the present invention exceeds 30 μm, the wear resistance of the cermet Therefore, the thickness of the surface region of the present invention is preferably in the range of 2 to 30 μm. In order to make the composition and thickness of the surface region of the cermet of the present invention the volume ratio and the thickness, the temperature is raised in a nitrogen atmosphere at a pressure of 3 kPa or more, and then in a nitrogen atmosphere at a lower pressure than the temperature raising step. It can be achieved by sintering in an argon atmosphere or in a vacuum of a pressure of 50 Pa or less.
本発明の表面領域におけるビッカース硬さＨｖは、１４００以上１６００未満の範囲からなると好ましい。本発明の表面領域におけるビッカース硬さＨｖが１４００未満になると、サーメットの耐摩耗性が低下する傾向が見られ、本発明の表面領域におけるビッカース硬さＨｖが１６００以上となると、サーメットの耐欠損性が低下する傾向が見られるので、本発明の表面領域におけるビッカース硬さＨｖは１４００以上１６００未満であると好ましい。 The Vickers hardness Hv in the surface region of the present invention is preferably in the range of 1400 or more and less than 1600. When the Vickers hardness Hv in the surface region of the present invention is less than 1400, the wear resistance of the cermet tends to be reduced, and when the Vickers hardness Hv in the surface region of the present invention is 1600 or more, the cermet fracture resistance Therefore, the Vickers hardness Hv in the surface region of the present invention is preferably 1400 or more and less than 1600.
本発明のサーメットの表面を基準として、３０μｍの深さから８０μｍの深さまでの間にビッカース硬さＨｖが最も高くなるところがあり、そのときのビッカース硬さＨｖの最高値は１６００以上２０００以下であると好ましい。本発明のサーメットのビッカース硬さの最高値が１６００未満になると、サーメットの耐摩耗性を高める効果が十分に得られず、本発明のサーメットのビッカース硬さの最高値が２０００を超えて高くなると、耐欠損性が低下する傾向が見られるので、本発明のサーメットのビッカース硬さＨｖの最高値は１６００以上２０００以下が好ましい。 On the basis of the surface of the cermet of the present invention, there is a place where the Vickers hardness Hv is highest between a depth of 30 μm and a depth of 80 μm, and the maximum value of the Vickers hardness Hv at that time is 1600 or more and 2000 or less. And preferred. When the maximum value of Vickers hardness of the cermet of the present invention is less than 1600, the effect of enhancing the wear resistance of the cermet is not sufficiently obtained, and when the maximum value of Vickers hardness of the cermet of the present invention exceeds 2000, Since the tendency to decrease the fracture resistance is observed, the maximum value of the Vickers hardness Hv of the cermet of the present invention is preferably 1600 or more and 2000 or less.
本発明のサーメットのビッカース硬さＨｖが最も高くなるところから内部に向かって本発明のサーメットの表面を基準として５００μｍの深さまでの間に、ビッカース硬さＨｖは徐々に減少した後に一定となり、本発明のサーメットの表面を基準として５００μｍの深さのビッカース硬さＨｖは１４００以上１８００以下となると好ましい。本発明のサーメットの表面を基準として５００μｍの深さにおけるビッカース硬さＨｖが１４００未満となると、サーメットの耐摩耗性が低下する傾向が見られ、１８００を超えて高くなると、サーメットの耐欠損性が低下する傾向が見られるので、本発明のサーメットの表面を基準として５００μｍの深さにおけるビッカース硬さＨｖが１４００以上１８００以下であると好ましい。本発明において、ビッカース硬さＨｖを上記範囲にするためには、圧力３ｋＰａ以上の窒素雰囲気中で昇温した後、昇温工程よりも低い圧力の窒素雰囲気中、アルゴン雰囲気中または圧力５０Ｐａ以下の真空中で焼結することにより達成することができる。 From the point where the Vickers hardness Hv of the cermet of the present invention is the highest to the depth of 500 μm from the surface of the cermet of the present invention toward the inside, the Vickers hardness Hv gradually decreases and becomes constant. The Vickers hardness Hv having a depth of 500 μm based on the surface of the cermet of the invention is preferably 1400 or more and 1800 or less. When the Vickers hardness Hv at a depth of 500 μm based on the surface of the cermet of the present invention is less than 1400, the wear resistance of the cermet tends to decrease, and when it exceeds 1800, the fracture resistance of the cermet increases. Since a tendency to decrease is seen, it is preferable that the Vickers hardness Hv at a depth of 500 μm is 1400 or more and 1800 or less based on the surface of the cermet of the present invention. In the present invention, in order to make the Vickers hardness Hv in the above range, after raising the temperature in a nitrogen atmosphere at a pressure of 3 kPa or more, in a nitrogen atmosphere at a pressure lower than that in the temperature raising step, in an argon atmosphere or at a pressure of 50 Pa or less. This can be achieved by sintering in vacuum.
本発明の第２硬質相の平均粒径が１．０〜５．０μｍであると好ましい。本発明の第２硬質相の平均粒径が１．０μｍ未満になると、サーメット全体の硬さが上昇し、熱伝導率が低下するためサーメットの耐熱衝撃性が低下する傾向が見られ、本発明の第２硬質相の平均粒径が５．０μｍを超えて大きくなると、サーメット全体の硬さが低下し、熱伝導率が上昇するためサーメットの耐熱衝撃性が低下する傾向が見られるので、本発明の第２硬質相の平均粒径を１．０〜５．０μｍの範囲にすると好ましい。本発明において、第１硬質相の平均粒径を上記範囲にするためには、上記範囲内の平均粒径の原料粉末を使用することにより達成することができる。本発明の第２硬質相の平均粒径は、サーメットの断面組織を走査電子顕微鏡（ＳＥＭ）で２０００〜１００００倍に拡大した画像から、フルマンの式（１）を用いて求めることができる。
ｄｍ＝（４／π）・（ＮＬ／ＮＳ） （１）
（式中、ｄｍは平均粒径、πは円周率、ＮＬは断面組織上の任意の直線によってヒットされる単位長さあたりの第２硬質相の数、ＮＳは任意の単位面積内に含まれる第２硬質相の数である。）。
The average particle size of the second hard phase of the present invention is preferably 1.0 to 5.0 μm. When the average particle size of the second hard phase of the present invention is less than 1.0 μm, the hardness of the entire cermet is increased and the thermal conductivity is decreased, so that the thermal shock resistance of the cermet tends to be decreased. When the average particle size of the second hard phase exceeds 5.0 μm, the hardness of the entire cermet decreases and the thermal conductivity increases, so the thermal shock resistance of the cermet tends to decrease. The average particle size of the second hard phase of the invention is preferably in the range of 1.0 to 5.0 μm. In this invention, in order to make the average particle diameter of a 1st hard phase into the said range, it can achieve by using the raw material powder of the average particle diameter in the said range. The average particle diameter of the second hard phase of the present invention can be determined from the image obtained by enlarging the cross-sectional structure of the cermet 2000 to 10000 times with a scanning electron microscope (SEM) using Fullman's formula (1).
dm = (4 / π) · (NL / NS) (1)
(In the formula, dm is the average particle diameter, π is the circumferential ratio, NL is the number of second hard phases per unit length hit by an arbitrary straight line on the cross-sectional structure, and NS is included in an arbitrary unit area. The number of second hard phases to be obtained).
本発明の第１硬質相の平均粒径が０．５〜３．０μｍであると好ましい。本発明の第１硬質相の平均粒径が０．５μｍ未満になると、サーメット全体の硬さが上昇し、サーメットの耐欠損性が低下する傾向が見られ、本発明の第１硬質相の平均粒径が３．０μｍを超えて大きくなると、サーメット全体の硬さが低下し、サーメットの耐摩耗性が低下する傾向が見られるので、本発明の第１硬質相の平均粒径を０．５〜３．０μｍの範囲にすると好ましい。本発明において、第２硬質相の平均粒径を上記範囲にするためには、上記範囲内の平均粒径の原料粉末を使用することにより達成することができる。本発明の第１硬質相の平均粒径は、第２硬質相の平均粒径と同様にフルマンの式（１）を用いて求めることができる。 The average particle size of the first hard phase of the present invention is preferably 0.5 to 3.0 μm. When the average particle size of the first hard phase of the present invention is less than 0.5 μm, the hardness of the entire cermet increases and the fracture resistance of the cermet tends to decrease, and the average of the first hard phase of the present invention When the particle size is larger than 3.0 μm, the hardness of the entire cermet is lowered, and the wear resistance of the cermet tends to be lowered. Therefore, the average particle size of the first hard phase of the present invention is 0.5. It is preferable to be in the range of -3.0 μm. In this invention, in order to make the average particle diameter of a 2nd hard phase into the said range, it can achieve by using the raw material powder of the average particle diameter in the said range. The average particle size of the first hard phase of the present invention can be determined using Fullman's formula (1) in the same manner as the average particle size of the second hard phase.
本発明のサーメット全体に含まれるＣｒ元素量は、サーメットの全質量に対して０．２〜２．５質量％であると好ましい。本発明のサーメット全体に含まれるＣｒ元素量が０．２質量％未満となると、表面部における第１硬質相の粒径が粗大化するため耐摩耗性が低下し、２．５質量％以上となると、サーメット全体にＣｒ有害相が晶出してサーメットの強度が低下するので、Ｃｒ元素量は、サーメットの全質量に対して０．２〜２．５質量％の範囲であると好ましい。本発明において、Ｃｒ量を上記範囲にするためには、原料粉末の配合時に所定量のＣｒ化合物を添加することにより達成することができる。 The amount of Cr element contained in the entire cermet of the present invention is preferably 0.2 to 2.5 mass% with respect to the total mass of the cermet. When the amount of Cr element contained in the entire cermet of the present invention is less than 0.2% by mass, the particle size of the first hard phase in the surface portion is coarsened, so that the wear resistance is reduced and is 2.5% by mass or more. Then, since the Cr harmful phase crystallizes in the whole cermet and the strength of the cermet is lowered, the Cr element amount is preferably in the range of 0.2 to 2.5% by mass with respect to the total mass of the cermet. In the present invention, in order to make the Cr amount within the above range, it can be achieved by adding a predetermined amount of Cr compound when blending the raw material powder.
本発明の被覆層は、被覆工具の被覆層として使用されるものであれば特に限定されないが、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、ＡｌおよびＳｉから選択される少なくとも１種と炭素、窒素、酸素および硼素から選択される非金属元素の少なくとも１種とからなる化合物、硬質炭素からなる群より選ばれた少なくとも１種の単層または積層からなる被覆層を被覆した被覆サーメットは耐摩耗性に優れる。被覆層の具体例としては、ＴｉＮ、ＴｉＣ、ＴｉＣＮ、（Ｔｉ，Ａｌ）Ｎ、（Ｔｉ，Ｓｉ）Ｎ、（Ａｌ，Ｃｒ）Ｎ、Ａｌ２Ｏ３、ダイヤモンド、ダイヤモンドライクカーボン（ＤＬＣ）などを挙げることができる。被覆層は単層または２層以上の積層のいずれでも好ましく、組成が異なる平均層厚５〜５００ｎｍの層を交互に２層以上積層した交互積層構造を有しても好ましい。被覆層全体の総層厚は平均層厚で０．１μｍ以上になると耐摩耗性が向上し、３０μｍを超えて厚くなると耐欠損性が低下するので、被覆層全体の総層厚は平均層厚で、０．１μｍ未満であると耐摩耗性が低下し、３０μｍを超えて厚くなると耐欠損性が低下することから、０．１〜３０μｍが好ましい。被覆層全体の総層厚は平均層厚で、より好ましくは１〜２０μｍであり、さらに好ましくは２．５〜１５μｍである。被覆層の各層の平均層厚は、被覆処理時間を調節することで調節することができる。 The coating layer of the present invention is not particularly limited as long as it is used as a coating layer of a coated tool, but is selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, and Si. A compound comprising at least one kind and at least one nonmetallic element selected from carbon, nitrogen, oxygen and boron, and at least one single layer or laminated layer selected from the group consisting of hard carbon is coated. The coated cermet is excellent in wear resistance. Specific examples of the coating layer include TiN, TiC, TiCN, (Ti, Al) N, (Ti, Si) N, (Al, Cr) N, Al 2 O 3 , diamond, diamond-like carbon (DLC), and the like. Can be mentioned. The coating layer is preferably either a single layer or a laminate of two or more layers, and preferably has an alternate laminate structure in which two or more layers having an average layer thickness of 5 to 500 nm having different compositions are alternately laminated. If the total thickness of the coating layer is 0.1 μm or more in average thickness, the wear resistance is improved. If the thickness exceeds 30 μm, the fracture resistance is reduced. In the case where the thickness is less than 0.1 μm, the wear resistance is lowered. On the other hand, if the thickness exceeds 30 μm, the fracture resistance is lowered. The total layer thickness of the entire coating layer is an average layer thickness, more preferably 1 to 20 μm, still more preferably 2.5 to 15 μm. The average layer thickness of each layer of the coating layer can be adjusted by adjusting the coating processing time.
本発明のサーメットを製造する方法としては、
（Ａ）ＷＣからなる第１硬質相用原料粉末：３０〜６５体積％と、少なくともＴｉＮを含むＴｉ，Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの炭化物、窒化物、炭窒化物およびこれらの相互固溶体の中の少なくとも１種の第２硬質相用原料粉末：２５〜４５体積％と、鉄族金属を主成分とする結合相用原料粉末：１０〜２５体積％とから構成され、これらの合計が１００体積％となる混合物を準備する混合工程と、
（Ｂ）混合物を非酸化雰囲気中で常温から１１８０〜１３３０℃の第１加熱温度まで昇温させる第１昇温工程と、
（Ｃ）混合物を窒素雰囲気中で１１８０〜１３３０℃の第１加熱温度から１３５０〜１６００℃の第２加熱温度まで圧力３ｋＰａ以上の窒素雰囲気中で昇温させる第２昇温工程と、
（Ｄ）混合物を１３５０〜１６００℃の第２加熱温度にて第２昇温工程よりも低い圧力の窒素雰囲気中、アルゴン雰囲気中または圧力５０Ｐａ以下の真空中で保持する保持工程と、
（Ｅ）混合物を１３５０〜１６００℃の第２加熱温度から１０００〜１３００℃の第１冷却温度まで保持工程よりも低い圧力の窒素雰囲気中、アルゴン雰囲気中または圧力５０Ｐａ以下の真空中で冷却する第１冷却工程と、
（Ｆ）混合物を１０００〜１３００℃の第１冷却温度から常温に冷却する第２冷却工程と
を含むサーメットの製造方法により得ることができる。
As a method for producing the cermet of the present invention,
(A) Raw material powder for the first hard phase made of WC: 30 to 65% by volume, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W carbide, nitride, carbonitriding containing at least TiN And at least one second hard phase raw material powder: 25 to 45% by volume, and a binder phase raw material powder containing iron group metal as a main component: 10 to 25% by volume. A mixing step of preparing a mixture in which the total of these is 100% by volume;
(B) a first temperature raising step for raising the temperature of the mixture from normal temperature to a first heating temperature of 1180 to 1330 ° C. in a non-oxidizing atmosphere;
(C) a second heating step in which the mixture is heated in a nitrogen atmosphere at a pressure of 3 kPa or more from a first heating temperature of 1180 to 1330 ° C. to a second heating temperature of 1350 to 1600 ° C. in a nitrogen atmosphere;
(D) a holding step of holding the mixture at a second heating temperature of 1350 to 1600 ° C. in a nitrogen atmosphere at a pressure lower than that of the second heating step, in an argon atmosphere, or in a vacuum at a pressure of 50 Pa or less;
(E) The mixture is cooled from a second heating temperature of 1350 to 1600 ° C. to a first cooling temperature of 1000 to 1300 ° C. in a nitrogen atmosphere having a pressure lower than that in the holding step, in an argon atmosphere, or in a vacuum having a pressure of 50 Pa or less. 1 cooling process;
(F) It can obtain by the manufacturing method of a cermet including the 2nd cooling process which cools a mixture from 1st cooling temperature of 1000-1300 degreeC to normal temperature.
第１昇温工程において、混合物を非酸化雰囲気中で昇温させることにより混合物の酸化を防いでいる。非酸化雰囲気として具体的には、窒素雰囲気、不活性雰囲気、水素雰囲気、圧力５０Ｐａ以下の真空などを挙げることができる。 In the first temperature raising step, the mixture is heated in a non-oxidizing atmosphere to prevent oxidation of the mixture. Specific examples of the non-oxidizing atmosphere include a nitrogen atmosphere, an inert atmosphere, a hydrogen atmosphere, and a vacuum with a pressure of 50 Pa or less.
第２昇温工程における窒素雰囲気の圧力は３ｋＰａ以上であるが、窒素雰囲気の圧力が１００ｋＰａを超えて高くなるとサーメットの焼結性が低下する傾向を示すので、第２昇温工程における窒素雰囲気の圧力は３〜１００ｋＰａであると好ましい。 The pressure of the nitrogen atmosphere in the second temperature raising step is 3 kPa or more. However, when the pressure of the nitrogen atmosphere is higher than 100 kPa, the cermet sinterability tends to decrease. The pressure is preferably 3 to 100 kPa.
サーメットおよび被覆サーメットの用途や形状によっては、機械的研磨や化学的研磨などによりサーメットの表面領域を除去しても良い。 Depending on the use and shape of the cermet and the coated cermet, the surface region of the cermet may be removed by mechanical polishing, chemical polishing, or the like.
本発明のサーメットの製造方法として、具体的には、以下の方法が挙げられる。第２硬質相用原料粉末として、少なくともＴｉＮを含むＴｉ，Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの炭化物、窒化物、炭窒化物およびこれらの相互固溶体の中の少なくとも１種の粉末と、第１硬質相用原料粉末としてＷＣ粉末と、結合相用原料粉末として鉄族金属の粉末を用意する。なお、焼結する過程で、第１硬質相用原料粉末（ＷＣ粉末）の一部は第２硬質相用原料粉末の一部と固溶して第２硬質相の周辺部を形成し、第１硬質相用原料粉末（ＷＣ粉末）の一部と第２硬質相用原料粉末の一部は結合相に固溶する。これらの粉末は、市販のものまたは固溶化高温熱処理により調製されたものでもよく、その平均粒径等は特に制限されないが、例えば、米国材料試験協会（ＡＳＴＭ）規格Ｂ３３０に記載のフィッシャー法（Fisher Sub-Sieve Sizer（FSSS））により測定した平均粒径が０．１〜１０μｍであることが好ましく、さらに好ましくは０．２〜５μｍである。これらの粉末を所定比率に秤量し、溶媒とともに湿式ボールミルにて混合し、混合後に溶媒を蒸発させて混合物を得る。得られた混合物にパラフィン等の成形用ワックスを添加して所定の形状に成形する。なお、所定の形状に成形する方法としては、プレス成形、押出成形、射出成形などを挙げることができる。成形した混合物を焼結炉に入れて、窒素雰囲気中で３５０〜５００℃の所定温度まで昇温してワックスを除去させた後、圧力５０Ｐａ以下の真空中または窒素雰囲気中で３５０〜５００℃の所定温度から１１８０〜１３３０℃の第１加熱温度まで昇温させる。さらに、混合物を１１８０〜１３３０℃の第１加熱温度から１３５０〜１６００℃の第２加熱温度まで圧力３ｋＰａ以上の窒素雰囲気中で昇温させ、１３５０〜１６００℃の第２加熱温度にて、第２加熱温度まで昇温させる昇温工程よりも低い圧力の窒素雰囲気中、アルゴン雰囲気中または圧力５０Ｐａ以下の真空中で１０〜１２０分間保持する。その後、第２加熱温度まで昇温させる工程よりも低い圧力の窒素雰囲気中、アルゴン雰囲気中または圧力５０Ｐａ以下の真空中で１０００〜１３００℃の第１冷却温度まで冷却し、その後、常温まで冷却すると本発明のサーメットを製造することができる。 Specifically as a manufacturing method of the cermet of this invention, the following method is mentioned. At least one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W carbides, nitrides, carbonitrides and their mutual solid solutions containing at least TiN as the second hard phase raw material powder WC powder as the first hard phase raw material powder, and iron group metal powder as the binder phase raw material powder. In the sintering process, a part of the first hard phase raw material powder (WC powder) forms a solid solution with a part of the second hard phase raw material powder to form a peripheral portion of the second hard phase, A part of the raw material powder for 1 hard phase (WC powder) and a part of the raw material powder for second hard phase dissolve in the binder phase. These powders may be commercially available or prepared by solid solution high temperature heat treatment, and the average particle size and the like are not particularly limited. For example, the Fisher method (Fisher method described in American Society for Testing and Materials (ASTM) standard B330) The average particle size measured by Sub-Sieve Sizer (FSSS) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm. These powders are weighed at a predetermined ratio, mixed with a solvent by a wet ball mill, and after mixing, the solvent is evaporated to obtain a mixture. A molding wax such as paraffin is added to the obtained mixture to form a predetermined shape. In addition, as a method of shape | molding in a predetermined shape, press molding, extrusion molding, injection molding, etc. can be mentioned. The molded mixture is put in a sintering furnace and heated to a predetermined temperature of 350 to 500 ° C. in a nitrogen atmosphere to remove the wax, and then the vacuum is set to 350 to 500 ° C. in a vacuum of 50 Pa or less or in a nitrogen atmosphere. The temperature is raised from a predetermined temperature to a first heating temperature of 1180 to 1330 ° C. Further, the mixture was heated in a nitrogen atmosphere having a pressure of 3 kPa or more from a first heating temperature of 1180 to 1330 ° C. to a second heating temperature of 1350 to 1600 ° C., and the second heating temperature was 1350 to 1600 ° C. It hold | maintains for 10 to 120 minutes in the nitrogen atmosphere of the pressure lower than the temperature rising process heated up to heating temperature, argon atmosphere, or the vacuum of the pressure of 50 Pa or less. Thereafter, cooling to a first cooling temperature of 1000 to 1300 ° C. in a nitrogen atmosphere at a pressure lower than the step of raising the temperature to the second heating temperature, in an argon atmosphere or in a vacuum of 50 Pa or less, and then cooling to room temperature. The cermet of the present invention can be produced.
本発明のサーメットの表面に、従来のＣＶＤ法やＰＶＤ法により被覆層を被覆することにより本発明の被覆サーメットを得ることができる。 The coated cermet of the present invention can be obtained by coating the surface of the cermet of the present invention with a coating layer by a conventional CVD method or PVD method.
本発明のサーメットおよび被覆サーメットは耐摩耗性および耐欠損性に優れる。本発明のサーメットおよび被覆サーメットは、切削工具として用いると切削工具の寿命を長くするという効果を奏する。 The cermet and coated cermet of the present invention are excellent in wear resistance and fracture resistance. The cermet and coated cermet of the present invention have an effect of prolonging the life of the cutting tool when used as a cutting tool.
サーメットの原料粉末として、平均粒径１．５μｍのＴｉ（Ｃ０．５Ｎ０．５）粉（Ｔｉ（Ｃ０．５Ｎ０．５）に含有されるＣとＮの割合は原子比でＣ：Ｎ＝５：５）、平均粒径１．４μｍのＴｉＮ粉、平均粒径１．０μｍおよび４．５μｍのＷＣ粉、平均粒径１．５μｍのＴａＣ粉、平均粒径１．１μｍのＮｂＣ粉、平均粒径３．１μｍのＺｒＣ粉、平均粒径６．２μｍのＣｒ２Ｎ粉、平均粒径１．０μｍのＣｏ粉、平均粒径２．０μｍのＮｉ粉を用意した。これらを用いて表１に示す配合組成に秤量した。なお、比較品６は平均粒径４．５μｍのＷＣ粉を用い、発明品１〜８と比較品１〜５、７は平均粒径１．０μｍのＷＣ粉を用いた。 As the raw material powder of cermet, the ratio of C and N contained in Ti (C 0.5 N 0.5 ) powder (Ti (C 0.5 N 0.5 ) powder having an average particle diameter of 1.5 μm is an atomic ratio. C: N = 5: 5), TiN powder with an average particle size of 1.4 μm, WC powder with an average particle size of 1.0 μm and 4.5 μm, TaC powder with an average particle size of 1.5 μm, an average particle size of 1.1 μm NbC powder, ZrC powder having an average particle diameter of 3.1 μm, Cr 2 N powder having an average particle diameter of 6.2 μm, Co powder having an average particle diameter of 1.0 μm, and Ni powder having an average particle diameter of 2.0 μm were prepared. These were weighed to the composition shown in Table 1. Comparative product 6 used WC powder having an average particle size of 4.5 μm, and invention products 1 to 8 and comparative products 1 to 5 and 7 used WC powder having an average particle size of 1.0 μm.
秤量した原料粉末を溶媒とともに湿式ボールミルにより混合した。なお、スラリー状の混合物の総質量に対して１〜２質量％のパラフィンを混合時に入れた。湿式ボールミル後に溶媒を蒸発させた混合物を、焼結後の大きさがＩＳＯ規格ＣＮＭＧ１２０４０８のインサート形状になるようにプレス成形した。 The weighed raw material powder was mixed with a solvent by a wet ball mill. In addition, 1-2 mass% paraffin was put at the time of mixing with respect to the gross mass of a slurry-like mixture. The mixture obtained by evaporating the solvent after the wet ball mill was press-molded so that the size after sintering became an insert shape of ISO standard CNMG120408.
発明品１〜８および比較品１〜５については、プレス成形した混合物を焼結炉に入れて、窒素雰囲気中で常温から５５０℃まで徐々に昇温してパラフィンを蒸発させた後、圧力５０Ｐａ以下の真空中で５５０℃から１２５０℃の第１加熱温度まで昇温させた。さらに、混合物を１２５０℃の第１加熱温度から１４５０℃の第２加熱温度まで圧力１３ｋＰａの窒素雰囲気中にて昇温させ、さらに１４５０℃の第２加熱温度にて圧力６．０ｋＰａのアルゴン雰囲気中で６０分間保持した後、１４５０℃の第２加熱温度から１２００℃の第１冷却温度まで圧力６．０ｋＰａのアルゴン雰囲気中にて冷却させ、さらに１２００℃の第１冷却温度から常温まで圧力２５０ｋＰａのアルゴン雰囲気中にて冷却した。 For the inventive products 1-8 and the comparative products 1-5, the press-molded mixture was put in a sintering furnace and gradually heated from room temperature to 550 ° C. in a nitrogen atmosphere to evaporate paraffin, and then the pressure 50 Pa The temperature was raised from 550 ° C. to a first heating temperature of 1250 ° C. in the following vacuum. Further, the mixture was heated from a first heating temperature of 1250 ° C. to a second heating temperature of 1450 ° C. in a nitrogen atmosphere at a pressure of 13 kPa, and further in an argon atmosphere at a pressure of 6.0 kPa at a second heating temperature of 1450 ° C. For 60 minutes and then cooled in an argon atmosphere at a pressure of 6.0 kPa from a second heating temperature of 1450 ° C. to a first cooling temperature of 1200 ° C., and further at a pressure of 250 kPa from the first cooling temperature of 1200 ° C. to room temperature. Cooled in an argon atmosphere.
比較品６については、プレス成形した混合物を焼結炉に入れて、窒素雰囲気中で常温から４５０℃まで徐々に昇温してパラフィンを蒸発させた後、圧力５０Ｐａ以下の真空中で４５０℃から１３００℃の第１加熱温度まで昇温させた。さらに、混合物を１３００℃の第１加熱温度から１４５０℃の第２加熱温度まで圧力１０ｋＰａのアルゴン雰囲気中で昇温させ、さらに１４５０℃の第２加熱温度にて圧力１０ｋＰａのアルゴン雰囲気中で６０分間保持した。その後、圧力５０Ｐａ以下の真空中で１４５０℃の第２加熱温度から常温まで冷却した。 For the comparative product 6, the press-molded mixture was put in a sintering furnace, and the temperature was gradually raised from room temperature to 450 ° C. in a nitrogen atmosphere to evaporate the paraffin, and then from 450 ° C. in a vacuum of 50 Pa or less. The temperature was raised to a first heating temperature of 1300 ° C. Further, the mixture was heated from a first heating temperature of 1300 ° C. to a second heating temperature of 1450 ° C. in an argon atmosphere at a pressure of 10 kPa, and further in an argon atmosphere at a pressure of 10 kPa at a second heating temperature of 1450 ° C. for 60 minutes. Retained. Then, it cooled from 1450 degreeC 2nd heating temperature to normal temperature in the vacuum of a pressure of 50 Pa or less.
比較品７については、プレス成形した混合物を焼結炉に入れて、窒素雰囲気中で常温から５００℃まで徐々に昇温してパラフィンを蒸発させた後、圧力５０Ｐａ以下の真空中で５００℃から１２００℃の第１加熱温度まで昇温させた。さらに、混合物を１２００℃の第１加熱温度から１５３０℃の第２加熱温度まで圧力０．１ｋＰａの窒素雰囲気中で昇温させ、さらに１５３０℃の第２加熱温度にて圧力０．１ｋＰａの窒素雰囲気中で６０分間保持した後、１５３０℃の第２加熱温度から１２００℃の第１冷却温度まで圧力０．１ｋＰａの窒素雰囲気中にて冷却させ、さらに圧力５０Ｐａ以下の真空中で１２００℃の第１冷却温度から常温まで冷却した。 For comparative product 7, the press-molded mixture was placed in a sintering furnace, and the temperature was gradually raised from room temperature to 500 ° C. in a nitrogen atmosphere to evaporate paraffin, and then from 500 ° C. in a vacuum of 50 Pa or less. The temperature was raised to a first heating temperature of 1200 ° C. Further, the mixture was heated in a nitrogen atmosphere at a pressure of 0.1 kPa from a first heating temperature of 1200 ° C. to a second heating temperature of 1530 ° C., and further a nitrogen atmosphere at a pressure of 0.1 kPa at the second heating temperature of 1530 ° C. In a nitrogen atmosphere at a pressure of 0.1 kPa from a second heating temperature of 1530 ° C. to a first cooling temperature of 1200 ° C., and further in a vacuum of a pressure of 50 Pa or less and a first temperature of 1200 ° C. Cooled from the cooling temperature to room temperature.
得られたサーメットについて、表面領域の断面組織と、硬さが一定になる表面を基準として５００μｍの深さの内部の断面組織を、それぞれＳＥＭにて観察し、ＳＥＭ付属のエネルギー分散型Ｘ線分析装置（ＥＤＳ）を用いて、結合相、第１硬質相、第２硬質相、Ｗ化合物、Ｔｉ化合物の組成およびＣｒ量を測定した。Ｃｒ量は表面領域と内部とで同じ値を示すので、サーメット全体に含まれるＣｒ量とした。また、表面を基準として５００μｍの深さの内部の断面組織をＳＥＭで５０００倍に拡大して第２硬質相とＴｉ化合物の周辺部の平均厚さを測定した。これらの結果は表２、３に示した。なお、結合相に含まれる元素のうち、結合相全体に対して７０質量％を超えて含まれる元素を主成分とし、結合相全体に対して３０質量％未満の元素を微量成分とした。また、結合相に鉄族元素が２種以上含まれていて、それらの鉄族元素の合計が結合相全体に対して７０質量％を超えて多く含まれている場合は、それらの鉄族元素を主成分とした。 About the obtained cermet, the cross-sectional structure of the surface region and the internal cross-sectional structure of a depth of 500 μm on the basis of the surface where the hardness becomes constant are observed by SEM, respectively, and energy dispersive X-ray analysis attached to SEM Using an apparatus (EDS), the composition of the binder phase, the first hard phase, the second hard phase, the W compound, the Ti compound, and the Cr amount were measured. Since the Cr amount shows the same value in the surface region and the inside, the Cr amount included in the entire cermet was used. In addition, the internal cross-sectional structure having a depth of 500 μm with respect to the surface was magnified 5000 times with SEM, and the average thickness of the second hard phase and the peripheral portion of the Ti compound was measured. These results are shown in Tables 2 and 3. In addition, among the elements contained in the binder phase, an element contained in an amount exceeding 70% by mass with respect to the whole binder phase was a main component, and an element with less than 30% by mass with respect to the whole binder phase was a minor component. Moreover, when two or more types of iron group elements are contained in the binder phase, and the total of those iron group elements is more than 70% by mass with respect to the whole binder phase, those iron group elements Was the main component.
得られたサーメットの表面から内部までの硬さを測定する為に、試料を試料表面に対して１０°傾けて研磨し、マイクロビッカース硬さ計を用いて印加荷重４．９Ｎのビッカース硬さを測定した。表面領域におけるビッカース硬さ、ビッカース硬さの最高値、ビッカース硬さが最高値を示すところの深さ、表面を基準として５００μｍの深さの内部におけるビッカース硬さを測定した。これらの結果は表４、５に示した。なお、発明品１〜８、比較品１〜６については、ビッカース硬さが最高値を示すところから表面を基準として５００μｍの深さの内部までの間に、ビッカース硬さは徐々に減少して一定になっていた。一方、表面領域がない比較品７については、ビッカース硬さは表面を基準として５μｍの深さで最高値を示し、ビッカース硬さは最高値を示すところから表面を基準として５００μｍの深さの内部までの間に徐々に減少して一定になっていた。 In order to measure the hardness from the surface to the inside of the obtained cermet, the sample was polished at an angle of 10 ° with respect to the sample surface, and a Vickers hardness with an applied load of 4.9 N was measured using a micro Vickers hardness meter. It was measured. The Vickers hardness in the surface region, the maximum value of the Vickers hardness, the depth at which the Vickers hardness shows the maximum value, and the Vickers hardness inside the depth of 500 μm based on the surface were measured. These results are shown in Tables 4 and 5. In addition, for the inventive products 1 to 8 and the comparative products 1 to 6, the Vickers hardness gradually decreases from the point where the Vickers hardness shows the maximum value to the inside of the depth of 500 μm on the basis of the surface. It was constant. On the other hand, for the comparative product 7 having no surface area, the Vickers hardness shows the highest value at a depth of 5 μm with respect to the surface, and the Vickers hardness shows the highest value from the inside to the depth of 500 μm with reference to the surface. Until then, it gradually decreased and became constant.
表面領域の断面組織をＳＥＭで２０００倍に拡大して表面領域の厚さを測定した。また、表面領域の断面組織をＳＥＭで５０００倍に拡大して、表面領域における第１硬質相、Ｗ化合物の平均粒径をフルマンの式を用いて測定した。表面を基準として５００μｍの深さの内部の断面組織をＳＥＭで５０００倍に拡大して、５００μｍの深さの内部における第１硬質相、第２硬質相、Ｗ化合物、Ｔｉ化合物の平均粒径をフルマンの式を用いて測定した。これらの結果は表４、５に示した。 The cross-sectional structure of the surface region was magnified 2000 times with SEM, and the thickness of the surface region was measured. Further, the cross-sectional structure of the surface region was magnified 5000 times by SEM, and the average particle size of the first hard phase and W compound in the surface region was measured using the Fullman equation. The cross-sectional structure inside 500 μm deep is magnified 5000 times with SEM on the basis of the surface, and the average particle size of the first hard phase, second hard phase, W compound, Ti compound inside 500 μm depth is obtained. Measurements were made using the Fullman equation. These results are shown in Tables 4 and 5.
サーメット全体の窒素量ＣＮ（質量％）は不活性ガス融解−熱伝導度法により測定した。サーメット全体の炭素量ＣＴ（質量％）は高周波燃焼−赤外線吸収法により測定した。サーメット全体のタングステン量ＣＷ（質量％）は蛍光Ｘ線分析装置により測定した。これらの値からＣＮ／（ＣＴ−０．０６５３・ＣＷ）を計算し、その結果を表４、５に併記した。 The nitrogen content C N (mass%) of the entire cermet was measured by an inert gas melting-thermal conductivity method. Carbon content of the entire cermet C T (wt%) of high-frequency combustion - was measured by the infrared absorption method. The amount of tungsten C W (% by mass) of the entire cermet was measured with a fluorescent X-ray analyzer. C N / (C T −0.0653 · C W ) was calculated from these values, and the results are also shown in Tables 4 and 5.
ＩＳＯ規格ＣＮＭＧ１２０４０８インサート形状の発明品１〜８、比較品１〜７のサーメットの拘束面を研削し、刃先にホーニングを施した。さらに平均層厚２．０μｍの（Ｔｉ，Ａｌ）Ｎ層をＰＶＤ法により被覆した。ＰＶＤ被覆して得られた被覆サーメット工具を用いて切削試験１、２を行った。 The cermet restraining surfaces of ISO standard CNMG120408 insert-shaped inventions 1 to 8 and comparative products 1 to 7 were ground, and the blade edge was honed. Further, a (Ti, Al) N layer having an average layer thickness of 2.0 μm was coated by the PVD method. Cutting tests 1 and 2 were performed using a coated cermet tool obtained by PVD coating.
[切削試験１]
加工形態：旋削
工具形状：ＣＮＭＧ１２０４０８
被削材：ＳＵＳ３１６Ｌ（形状：円柱に２本の溝を入れた略円柱状）
切削速度：１５０ｍ／ｍｉｎ
切り込み：２．０ｍｍ
送り量：０．１０ｍｍ／ｒｅｖ
クーラント：有り（湿式切削）
試験回数：３回
寿命の判定基準：欠損するまでの切削時間を寿命とする。
[Cutting test 1]
Machining form: Turning tool shape: CNMG120408
Work material: SUS316L (shape: substantially cylindrical shape with two grooves in a cylinder)
Cutting speed: 150 m / min
Cutting depth: 2.0mm
Feed amount: 0.10mm / rev
Coolant: Available (wet cutting)
Number of tests: 3 times Judgment criteria of life: Cutting time until chipping is regarded as life.
[切削試験２]
加工形態：旋削
工具形状：ＣＮＭＧ１２０４０８
被削材：ＳＵＳ３０４（形状：円柱）
切削速度：１５０ｍ／ｍｉｎ
切り込み：２．０ｍｍ
送り量：０．３０ｍｍ／ｒｅｖ
クーラント：有り（湿式切削）
寿命の判定基準：欠損したとき、または、最大逃げ面摩耗幅ＶＢｍａｘもしくはコーナー摩耗幅ＶＣが０．３ｍｍ以上になったときを寿命とする。
[Cutting test 2]
Machining form: Turning tool shape: CNMG120408
Work material: SUS304 (shape: cylinder)
Cutting speed: 150 m / min
Cutting depth: 2.0mm
Feed amount: 0.30mm / rev
Coolant: Available (wet cutting)
Judgment criteria of life: When the chip is missing or when the maximum flank wear width VB max or corner wear width VC is 0.3 mm or more, the life is defined.
切削試験１、２の結果を点数化した。すなわち、切削試験１の切削時間について、１０分以上を３点、５分以上１０分未満を２点、２分以上５分未満を１点、２分未満を０点とし、１回目から３回目までの結果を平均した。また、切削試験２の切削時間について、２５分以上を３点、１５分以上２５分未満を２点、５分以上１５分未満を１点、５分未満を０点とした。切削試験１の点数の平均値と切削試験２の点数とを合計し、その値を総合評価の結果とした。点数が大きいほど切削性能に優れる。得られた総合評価の結果を表８に示した。 The results of cutting tests 1 and 2 were scored. That is, with respect to the cutting time of the cutting test 1, 3 points for 10 minutes or more, 2 points for 5 minutes or more and less than 10 minutes, 1 point for 2 minutes or more and less than 5 minutes, 0 points for less than 2 minutes, the first to the third time The results were averaged. Moreover, about the cutting time of the cutting test 2, 25 minutes or more were made into 3 points, 15 minutes or more and less than 25 minutes were made into 2 points, 5 minutes or more and less than 15 minutes were made into 1 point, and less than 5 minutes were made into 0 points. The average value of the score of the cutting test 1 and the score of the cutting test 2 were totaled, and the value was used as the result of comprehensive evaluation. The larger the score, the better the cutting performance. The obtained comprehensive evaluation results are shown in Table 8.
発明品の総合評価はすべて５．３点以上となり、総合評価において比較品よりも優れることが分かる。 The overall evaluations of the invention products are all 5.3 points or more, which indicates that the overall evaluation is superior to the comparative products.
原料粉末の配合から焼結までを実施例１の発明品１〜８、比較品１〜７と同様な製造方法で作製したサーメットに対して、サーメットの拘束面を研削し、刃先にホーニングを施した。さらに、被覆層全体の総層厚が平均層厚で１５．０μｍであり、被覆層の構成が、（基材側）ＴｉＣＮ層−Ａｌ２Ｏ３層（表面側）である被覆層をＣＶＤ法により被覆した。なお、発明品１〜８、比較品１〜７のサーメットを基材として使用したＣＶＤ法による被覆サーメット工具を、それぞれ発明品９〜１６、比較品８〜１４とした。これらの被覆サーメットを用いて切削試験３を行った。 From the blending of raw material powders to sintering, the constrained surfaces of the cermets are ground to the cermets produced by the same manufacturing method as the inventive products 1 to 8 and the comparative products 1 to 7 in Example 1, and the cutting edges are subjected to honing. did. Furthermore, the total coating thickness of the entire coating layer is 15.0 μm in average layer thickness, and the coating layer is composed of (substrate side) TiCN layer-Al 2 O 3 layer (surface side) by the CVD method. Coated. In addition, the coated cermet tools by the CVD method using the cermets of the inventive products 1 to 8 and the comparative products 1 to 7 as base materials were designated as inventive products 9 to 16 and comparative products 8 to 14, respectively. Cutting test 3 was performed using these coated cermets.
［切削試験３］
加工形態：旋削
工具形状：ＣＮＭＧ１２０４０８
被削材：ＦＣＤ６００（形状：円盤）
切削速度：１５０ｍ／ｍｉｎ
切り込み：２．０ｍｍ
送り量：０．３０ｍｍ／ｒｅｖ
クーラント：有り（湿式切削）
寿命の判定基準：欠損したとき、または、最大逃げ面摩耗幅ＶＢｍａｘもしくはコーナー摩耗幅ＶＣが０．３ｍｍ以上になったときを寿命とする。
[Cutting test 3]
Machining form: Turning tool shape: CNMG120408
Work material: FCD600 (shape: disk)
Cutting speed: 150 m / min
Cutting depth: 2.0mm
Feed amount: 0.30mm / rev
Coolant: Available (wet cutting)
Judgment criteria of life: When the chip is missing or when the maximum flank wear width VB max or corner wear width VC is 0.3 mm or more, the life is defined.
発明品はいずれも比較品よりも切削時間が長く、工具寿命が長いことがわかる。 It can be seen that the invention products all have a longer cutting time and longer tool life than the comparative products.
焼結後の大きさがＩＳＯ規格ＳＥＥＮ１２０３のインサート形状になるようにプレス成形する以外は、原料粉末の配合から焼結までを実施例１の発明品１〜８、比較品１〜７と同様な製造方法でサーメットを作製した。得られたサーメットの全面を研削し、刃先にホーニングを施して、表面領域がないＩＳＯ規格ＳＥＥＮ１２０３インサート形状のサーメット工具を得た。なお、発明品１〜８、比較品１〜７のサーメットから表面領域を除去したサーメット工具を、それぞれ発明品１７〜２４、比較品１５〜２１とした。得られたサーメット工具を用いて切削試験４を行った。 Except for press-molding so that the size after sintering becomes an insert shape of ISO standard SEEN1203, the process from the blending of the raw material powder to the sintering is the same as that of Invention products 1 to 8 and Comparative products 1 to 7 of Example 1. A cermet was produced by the production method. The entire surface of the obtained cermet was ground and the blade edge was honed to obtain an ISO standard SEEN1203 insert-shaped cermet tool having no surface area. In addition, the cermet tool which removed the surface area | region from the cermet of invention products 1-8 and comparative products 1-7 was made into invention products 17-24 and comparative products 15-21, respectively. Cutting test 4 was performed using the obtained cermet tool.
［切削試験４］
加工形態：転削
工具形状：ＳＥＥＮ１２０３
カッター有効径：φ８０ｍｍ（１枚刃取り付け）
被削材：ＳＣＭ４４０（形状：板材）
切削速度：２００ｍ／ｍｉｎ
切り込み：２．０ｍｍ
送り量：０．２０ｍｍ／Ｔｏｏｔｈ
クーラント：無し（乾式切削）
寿命の判定基準：欠損したとき、または、最大逃げ面摩耗幅ＶＢｍａｘもしくはコーナー摩耗幅ＶＣが０．３ｍｍ以上になったときを寿命とする。
[Cutting test 4]
Machining form: Turning tool shape: SEEN1203
Effective cutter diameter: φ80mm (single blade mounting)
Work material: SCM440 (shape: plate material)
Cutting speed: 200 m / min
Cutting depth: 2.0mm
Feed amount: 0.20mm / Tooth
Coolant: None (dry cutting)
Judgment criteria of life: When the chip is missing or when the maximum flank wear width VB max or corner wear width VC is 0.3 mm or more, the life is defined.
発明品はいずれも比較品よりも加工長が長く、工具寿命が長いことがわかる。
It can be seen that all the inventive products have a longer working length and longer tool life than the comparative products.
Claims (6)
５≦（ＣＮ／（ＣＴ−０．０６５３・ＣＷ））≦７０
を満足するサーメット。 First hard phase composed of WC: 30 to 65% by volume, second hard phase composed of titanium compound: 25 to 45% by volume, and binder phase mainly composed of iron group metal: 5 to 25% by volume The total of these is 100% by volume, and the second hard phase is a cored structure comprising a core part and a peripheral part having an average thickness of 0.1 to 3.0 μm surrounding the core part, and the core part is TiN The peripheral part is composed of a composite carbonitride of Ti and at least one selected from Zr, Hf, V, Nb, Ta, Cr, Mo, W, and the carbon content C contained in the entire cermet T (mass%), tungsten amount C W (mass%) contained in the whole cermet, nitrogen quantity C N (mass%) contained in the whole cermet,
5 ≦ (C N / (C T −0.0653 · C W )) ≦ 70
Satisfying cermet.
The covering cermet in which the coating layer was formed in the surface of the cermet in any one of Claims 1-5.
Priority Applications (1)
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|---|---|---|---|
| JP2012226471A JP2014077178A (en) | 2012-10-12 | 2012-10-12 | Cermet and coated cermet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012226471A JP2014077178A (en) | 2012-10-12 | 2012-10-12 | Cermet and coated cermet |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017035750A (en) * | 2015-08-10 | 2017-02-16 | 三菱マテリアル株式会社 | Ti-BASED CERMET CUTTING TOOL EXCELLENT IN ANTI-PLASTIC DEFORMATION, ABNORMAL DAMAGE RESISTANCE AND WEAR RESISTANCE |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017035750A (en) * | 2015-08-10 | 2017-02-16 | 三菱マテリアル株式会社 | Ti-BASED CERMET CUTTING TOOL EXCELLENT IN ANTI-PLASTIC DEFORMATION, ABNORMAL DAMAGE RESISTANCE AND WEAR RESISTANCE |
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