JP5157300B2 - Cermet having composite surface layer and method for producing the same - Google Patents
Cermet having composite surface layer and method for producing the same Download PDFInfo
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- 239000002344 surface layer Substances 0.000 title claims description 97
- 239000011195 cermet Substances 0.000 title claims description 47
- 239000002131 composite material Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 37
- 150000004767 nitrides Chemical class 0.000 claims description 33
- 229910052726 zirconium Inorganic materials 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 27
- 229910052735 hafnium Inorganic materials 0.000 claims description 27
- 230000000737 periodic effect Effects 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 239000006104 solid solution Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 150000001247 metal acetylides Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 11
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 238000005121 nitriding Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910008322 ZrN Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 102200082816 rs34868397 Human genes 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Description
本発明は、鋼，鋳物の旋削及びフライス切削など広範囲な切削加工において、耐摩耗性と耐チッピング性の両方を向上させることによって工具寿命の延長を図った複合表面層を有するサーメットに関するものである。 The present invention relates to a cermet having a composite surface layer that extends tool life by improving both wear resistance and chipping resistance in a wide range of cutting operations such as turning of steel and castings and milling. .
ＴｉＣＮ−Ｍｏ−Ｎｉ系に代表されるサーメットは、鋼切削における優れた耐摩耗性と共に仕上げ面が美麗なために多用されている。しかし、未だ耐摩耗性や耐チッピング性が不十分なために、更なる改善が求められている。その改善手段として、表面を傾斜組成化したサーメットや表面に硬質層を形成させたサーメット工具が数多く提案されている。 Cermets represented by the TiCN-Mo-Ni system are frequently used because of the beautiful finish surface as well as excellent wear resistance in steel cutting. However, since the wear resistance and chipping resistance are still insufficient, further improvement is required. As the improvement means, many cermets having a gradient composition on the surface and cermet tools having a hard layer formed on the surface have been proposed.
従来の傾斜組成サーメット工具として、表面近傍の結合相量を漸次減少させたることによって、表面部を内部より高靱性・高硬度にしたＴｉＣＮ基サーメットがある（例えば、特許文献１，２参照。）。これらに記載されているＴｉＣＮ基サーメットは、窒素ガス雰囲気中で昇温し、焼結終了前に真空引きすることにより、表面近傍の結合相量を減少させて表面部を高硬度、高耐摩耗性としたものであるが、耐チッピング、耐欠損性が不十分であると言う問題がある。 As a conventional gradient composition cermet tool, there is a TiCN-based cermet whose surface portion is made tougher and harder than the inside by gradually decreasing the amount of the binder phase near the surface (see, for example, Patent Documents 1 and 2). . TiCN-based cermets described in these materials are heated in a nitrogen gas atmosphere and evacuated before the end of sintering, thereby reducing the amount of binder phase near the surface and making the surface portion highly hard and wear-resistant. However, there is a problem that chipping resistance and chipping resistance are insufficient.
また、硬質層を形成させたサーメット工具として、窒素ガス雰囲気中で窒化焼結することによって、最表面に高窒素含有の複合窒化物のみからなる硬質層を形成させたものがある（例えば、特許文献３参照。）。形成された硬質層が高硬度であるために耐摩耗性を向上させるものの、金属結合相を含まないために耐チッピング性に劣ると言う問題がある。 Further, as a cermet tool having a hard layer formed, there is a cermet tool in which a hard layer made of only a high nitrogen content composite nitride is formed on the outermost surface by nitriding and sintering in a nitrogen gas atmosphere (for example, patents) Reference 3). Although the formed hard layer has a high hardness, the wear resistance is improved, but there is a problem that the chipping resistance is inferior because it does not contain a metal binder phase.
本発明は、上記のような問題点を解決したもので、焼き肌面から内部に向かって硬質相の種類と構成が内部とは異なる二つの表面層を形成することによって、耐摩耗性と耐チッピング性の両立を図った複合表面層を有するサーメットの提供を目的とする。 The present invention solves the above-mentioned problems, and by forming two surface layers in which the type and configuration of the hard phase is different from the inside from the burnt surface to the inside, wear resistance and anti-resistance are formed. An object of the present invention is to provide a cermet having a composite surface layer that achieves both chipping properties.
本発明者は、表面層を有するサーメット工具について、耐チッピング性を低下させることなく、耐摩耗性や耐塑性変形性を向上させるために、表面層中に含有される硬質相粒子の種類と構成について検討したところ、焼き肌面において、周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物の第１硬質相と結合相とからなる第１表面層を形成し、第１表面層より内部には、Ｚｒ，Ｈｆの窒化物，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硬質相と第１硬質相と結合相とからなる第２表面層を形成し、第２表面層より内部は、Ｔｉの炭化物，炭窒化物を芯部とし周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物を周辺部とする有芯構造の第３硬質相と第１硬質相と結合相とを含むようにすると、耐摩耗性と耐チッピング性の両方が向上すること、また、この複合表面層を有するサーメット製造するためには、（ａ）Ｚｒ，Ｈｆの窒化物，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：硬質相形成粉末全体に対して５〜２５重量％と、（ｂ）周期律表５ａ，６ａ族元素の炭化物，窒化物，炭窒化物の中の少なくとも１種：硬質相形成粉末全体に対して１０〜４０重量％と、（ｃ）Ｔｉの炭化物，炭窒化物の少なくとも１種：硬質相形成粉末全体に対して３５〜８５重量％とからなる硬質相形成粉末と、ＣｏおよびＮｉの少なくとも１種からなる結合相形成粉末とを用意して、硬質相形成粉末：７５〜９５重量％と、結合相形成粉末：５〜２５重量％とを混合して混合物を得て、混合物を１１００〜１３００℃の温度にて圧力１０ｋＰａ以上の窒素ガス中で保持すると、第２硬質相が形成されること、さらに混合物を１４００〜１５５０℃の温度にて圧力５ｋＰａ以下の窒素ガス中で焼結すると、第１表面層が形成されるという知見を得て、本発明を完成するに至ったものである。 The present inventor, for a cermet tool having a surface layer, in order to improve wear resistance and plastic deformation resistance without reducing chipping resistance, the type and configuration of hard phase particles contained in the surface layer As a result of the study on the surface of the burnt skin, it is bonded to the first hard phase of the composite carbonitride containing one or more elements in the group 5a, 6a of the periodic table, one or more elements in Zr, Hf, and Ti. A first surface layer composed of a phase, and at least one second hard phase of Zr, Hf nitride, carbonitride, and their mutual solid solution and the first surface layer are formed inside the first surface layer. A second surface layer composed of a hard phase and a binder phase is formed, and the inside of the second surface layer is made of Ti carbide or carbonitride as a core and one or more elements in the periodic table 5a, 6a group elements A composite carbonitride containing at least one of Zr and Hf and Ti is used as a peripheral part. Including a third hard phase, a first hard phase, and a binder phase having a core structure improves both wear resistance and chipping resistance, and for producing a cermet having this composite surface layer. (A) at least one of nitrides, carbonitrides and their mutual solid solutions of Zr and Hf: 5 to 25% by weight with respect to the whole hard phase forming powder, and (b) periodic table 5a, At least one of carbides, nitrides and carbonitrides of group 6a elements: 10 to 40% by weight with respect to the entire hard phase forming powder, and (c) at least one of Ti carbides and carbonitrides: hard A hard phase forming powder consisting of 35 to 85% by weight and a binder phase forming powder consisting of at least one of Co and Ni are prepared with respect to the whole phase forming powder, and the hard phase forming powder: 75 to 95% by weight And binder phase forming powder: 5 to 25% by weight When a mixture is obtained and kept in nitrogen gas at a pressure of 10 kPa or higher at a temperature of 1100 to 1300 ° C., a second hard phase is formed, and the mixture is further heated at a temperature of 1400 to 1550 ° C. The inventors have obtained knowledge that a first surface layer is formed by sintering in nitrogen gas at a pressure of 5 kPa or less, and have completed the present invention.
すなわち、本発明の複合表面層を有するサーメットは、周期律表４ａ，５ａ，６ａ族元素の炭化物，窒化物およびこれらの相互固溶体の中の少なくとも１種の硬質相と、ＣｏおよびＮｉの少なくとも１種を主成分とする結合相とからなるサーメットにおいて、サーメットの焼き肌面から内部に向かって平均厚み２〜２０μｍの第１表面層が形成され、第１表面層と第２表面層との界面から内部に向かって平均厚み５〜５０μｍの第２表面層が形成され、
（１）第１表面層は、周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物の第１硬質相と、結合相とからなり、
（２）第２表面層は、Ｚｒ，Ｈｆの窒化物，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硬質相と、第１硬質相と、結合相とからなり、
（３）第１表面層と第２表面層とを除いたサーメットの内部は、Ｔｉの炭化物，炭窒化物を芯部とし、周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物を周辺部とする有芯構造の第３硬質相と、第１硬質相と、結合相とを含むものである。
That is, the cermet having the composite surface layer of the present invention includes at least one hard phase of carbides, nitrides and their mutual solid solutions of the periodic table 4a, 5a, and 6a elements, and at least one of Co and Ni. In the cermet comprising a binder phase mainly composed of seeds, a first surface layer having an average thickness of 2 to 20 μm is formed from the baked skin surface of the cermet toward the inside, and the interface between the first surface layer and the second surface layer A second surface layer having an average thickness of 5 to 50 μm is formed from the inside toward the inside,
(1) The first surface layer is bonded to a first hard phase of a composite carbonitride containing one or more elements in the periodic table 5a and 6a group elements, one or more elements in Zr and Hf, and Ti. Consist of phases
(2) The second surface layer is composed of at least one second hard phase among the nitride of Zr, Hf, carbonitride, and their mutual solid solution, the first hard phase, and the binder phase.
(3) The inside of the cermet excluding the first surface layer and the second surface layer has Ti carbide and carbonitride as a core, and one or more elements in the periodic table 5a, 6a group elements and Zr, It includes a third hard phase having a core structure having a composite carbonitride containing one or more of Hf and Ti as a peripheral portion, a first hard phase, and a binder phase.
本発明のサーメットにおける結合相は、具体的には２０重量％以下のＴｉ，Ｍｏ，Ｗ，Ｃｒなどを固溶したＣｏおよびＮｉの少なくとも一方の合金を挙げることができる。この結合相量は、合金全体に対して５重量％未満になると靱性の低下により耐欠損性が劣化し、逆に２５重量％を超えて多くなると硬さの低下により耐摩耗性や耐塑性変形性が低下するために、結合相量は５〜２５重量％であると好ましい。 Specific examples of the binder phase in the cermet of the present invention include at least one alloy of Co and Ni in which 20% by weight or less of Ti, Mo, W, Cr and the like are dissolved. When the amount of the binder phase is less than 5% by weight based on the whole alloy, the fracture resistance is deteriorated due to a decrease in toughness, and conversely when it exceeds 25% by weight, the hardness is decreased, resulting in wear resistance and plastic deformation. In order to reduce the property, the amount of the binder phase is preferably 5 to 25% by weight.
本発明のサーメットにおける硬質相は、周期律表４ａ，５ａ，６ａ族元素の炭化物，窒化物およびこれらの相互固溶体の中の少なくとも１種からなる。具体的には、（Ｔｉ，Ｚｒ，Ｍｏ）（Ｃ，Ｎ）、（Ｔｉ，Ｚｒ，Ｗ）（Ｃ，Ｎ）、（Ｔｉ，Ｚｒ，Ｎｂ，Ｗ，Ｍｏ）（Ｃ，Ｎ）、（Ｔｉ，Ｈｆ，Ｔａ，Ｗ，Ｍｏ）（Ｃ，Ｎ）などの複合炭窒化物の固溶体粒子、ＺｒＮ、Ｚｒ（Ｃ，Ｎ）、ＨｆＮ、Ｔｉ（Ｃ，Ｎ）の単独粒子、芯部がＴｉＣで周辺部が（Ｔｉ，Ｎｂ，Ｗ）（Ｃ，Ｎ）、（Ｔｉ，Ｚｒ，Ｔａ，Ｗ，Ｍｏ）（Ｃ，Ｎ）である有芯構造粒子、および、これらの混合粒子を挙げることができる。硬質相の含有量は、７５重量％未満になると相対的に結合相量が増大して耐摩耗性や耐塑性変形性が劣化し、逆に９５重量％を超えて多くなると耐欠損性，耐チッピング性が低下するため、硬質相の含有量は７５〜９５重量％であると好ましい。その中でも、本発明の硬質相は、Ｚｒ，Ｈｆの窒化物，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：硬質相全体に対して５〜２５重量％と、周期律表５ａ，６ａ族元素の炭化物，窒化物，炭窒化物の中の少なくとも１種：硬質相全体に対して１０〜４０重量％と、Ｔｉの炭化物，炭窒化物の少なくとも１種：硬質相全体に対して３５〜８５重量％とからなるとさらに好ましい。その理由は以下に示す。 The hard phase in the cermet of the present invention is composed of at least one of carbides, nitrides, and mutual solid solutions of the periodic table 4a, 5a, and 6a group elements. Specifically, (Ti, Zr, Mo) (C, N), (Ti, Zr, W) (C, N), (Ti, Zr, Nb, W, Mo) (C, N), (Ti , Hf, Ta, W, Mo) (C, N) and other solid carbonitride solid solution particles, ZrN, Zr (C, N), HfN, Ti (C, N) single particles, the core is TiC There may be mentioned cored structure particles whose peripheral part is (Ti, Nb, W) (C, N), (Ti, Zr, Ta, W, Mo) (C, N), and mixed particles thereof. . When the content of the hard phase is less than 75% by weight, the amount of the binder phase is relatively increased and the wear resistance and plastic deformation resistance are deteriorated. Since chipping property is lowered, the content of the hard phase is preferably 75 to 95% by weight. Among them, the hard phase of the present invention contains at least one of Zr, Hf nitrides, carbonitrides and their mutual solid solutions: 5 to 25% by weight with respect to the entire hard phase, periodic table 5a, At least one of the carbides, nitrides and carbonitrides of group 6a elements: 10 to 40% by weight based on the entire hard phase, and at least one of Ti carbides and carbonitrides: based on the entire hard phase More preferably, it is 35 to 85% by weight. The reason is shown below.
本発明のサーメットにおける硬質相として、Ｚｒ，Ｈｆの窒化物，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種を添加すると、複合表面層を形成し、サーメット全体の耐塑性変形性、耐溶着性、耐摩耗性を向上させる。Ｚｒ，Ｈｆの窒化物，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種の添加量は、硬質相全体に対して５重量％未満になるとＺｒおよびＨｆの少なくとも１種の窒化物，炭窒化物粒子を第２表面層中に残存させることが困難であり、逆に硬質相全体に対して２５重量％を超えて多くなると、内部に多量に残存するために焼結性が劣化して硬さや靱性が低下する共に、第１表面層中にも残存することから、硬質相全体に対して５〜２５重量％であると好ましい。 When at least one of nitrides of Zr and Hf, carbonitrides and their mutual solid solutions is added as a hard phase in the cermet of the present invention, a composite surface layer is formed, and the plastic deformation resistance, Improve weldability and wear resistance. When the addition amount of at least one of the nitrides, carbonitrides, and their mutual solid solutions of Zr and Hf is less than 5% by weight based on the entire hard phase, at least one nitride and carbon of Zr and Hf It is difficult to leave the nitride particles in the second surface layer. Conversely, if the amount exceeds 25% by weight with respect to the entire hard phase, a large amount remains in the interior, so that the sinterability deteriorates. While the hardness and toughness are reduced, the hardness and toughness remain in the first surface layer, so that the content is preferably 5 to 25% by weight based on the entire hard phase.
本発明のサーメットにおける硬質相として、周期律表５ａ，６ａ族元素の炭化物，窒化物，炭窒化物の中の少なくとも１種を添加すると、硬さ，強度，靱性などを向上させ、耐摩耗性，耐欠損性，耐チッピング性，耐塑性変形性などを向上させる。周期律表５ａ，６ａ族元素の炭化物，窒化物，炭窒化物の中の少なくとも１種の添加量は、硬質相全体に対して１０重量％未満になると特に靱性を高める効果が少なくて耐チッピング性に劣り、逆に硬質相全体に対して４０重量％を超えて多くなると相対的にＴｉの炭化物，窒化物の含有量が減少して耐摩耗性が低下することから、硬質相全体に対して１０〜４０重量％であると好ましい。 When at least one of the carbides, nitrides, and carbonitrides of Group 5a and 6a elements of the periodic table is added as the hard phase in the cermet of the present invention, the hardness, strength, toughness, etc. are improved and the wear resistance is improved. Improve fracture resistance, chipping resistance, plastic deformation resistance, etc. When the addition amount of at least one of carbides, nitrides, and carbonitrides of group 5a and 6a elements in the periodic table is less than 10% by weight with respect to the entire hard phase, the effect of increasing toughness is particularly small and chipping resistance is reduced. On the contrary, if the content exceeds 40% by weight with respect to the entire hard phase, the content of Ti carbide and nitride is relatively reduced and wear resistance is lowered. 10 to 40% by weight is preferable.
本発明のサーメットにおける硬質相として、Ｔｉの炭化物，炭窒化物の少なくとも１種を添加すると、硬さと耐摩耗性を向上させる。Ｔｉの炭化物，炭窒化物の少なくとも１種の添加量は、硬質相全体に対して３５重量％未満になると耐摩耗性が低下し、逆に硬質相全体に対して８５重量％を超えて多くなると強度、靱性や耐欠損性が低下することから、硬質相全体に対して３５〜８５重量％であると好ましい。 When at least one of Ti carbide and carbonitride is added as the hard phase in the cermet of the present invention, hardness and wear resistance are improved. When the amount of at least one of Ti carbide and carbonitride added is less than 35% by weight with respect to the entire hard phase, the wear resistance decreases, and conversely, it exceeds 85% by weight with respect to the entire hard phase. If it becomes, since intensity | strength, toughness, and fracture resistance will fall, it is preferable in it being 35 to 85 weight% with respect to the whole hard phase.
本発明のサーメットにおける焼き肌面は、焼結後の表面を意味するが、未処理の焼き肌面とともに焼き肌面にブラスト処理、電解処理、研削処理などの表面処理を施した場合も含む。 The baked skin surface in the cermet of the present invention means the surface after sintering, but also includes the case where the baked skin surface is subjected to surface treatment such as blasting, electrolytic treatment, and grinding treatment together with the untreated baked skin surface.
本発明のサーメットにおける第１表面層は、周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物の第１硬質相と、結合相とからなるものである。第１表面層の平均厚みは、２μｍ未満になると表面の靱性向上が不十分なためにチッピングし易く、逆に２０μｍを超えて多くなると耐摩耗性が低下するために、２〜２０μｍと定めた。 The first surface layer in the cermet of the present invention includes a first hard phase of a composite carbonitride containing at least one of elements in the periodic table 5a and 6a group, at least one of Zr and Hf, and Ti. , And a binder phase. When the average thickness of the first surface layer is less than 2 μm, the toughness of the surface is not sufficiently improved, so that chipping is easy. Conversely, when the thickness exceeds 20 μm, the wear resistance decreases, so the average thickness is set to 2 to 20 μm. .
本発明のサーメットにおける第２表面層は、Ｚｒ，Ｈｆの窒化物、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硬質相と、第１硬質相と、結合相とからなるものである。第２表面層の平均厚みは、５μｍ未満になると第２硬質相による耐溶着性の向上効果が低減して耐摩耗性が低下し、逆に５０μｍを超えて多くなると耐チッピング性が低下するために、第２表面層の平均厚みは、５〜５０μｍと定めた。 The second surface layer in the cermet of the present invention comprises at least one second hard phase among the nitrides of Zr and Hf, carbonitrides, and their mutual solid solutions, the first hard phase, and the binder phase. Is. When the average thickness of the second surface layer is less than 5 μm, the effect of improving the welding resistance by the second hard phase is reduced and the wear resistance is lowered. Conversely, when the thickness exceeds 50 μm, the chipping resistance is lowered. In addition, the average thickness of the second surface layer was determined to be 5 to 50 μm.
本発明の第１表面層と第２表面層とを除いたサーメットの内部は、Ｔｉの炭化物，炭窒化物を芯部とし周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物を周辺部とする有芯構造の第３硬質相と、第１硬質相と、結合相とを含む。また、本発明のサーメットの内部は、第１硬質相、第３硬質相および結合相以外に第２硬質相を含んでもよい。 The inside of the cermet excluding the first surface layer and the second surface layer of the present invention is composed of Ti carbide and carbonitride as a core and one or more elements in the periodic table 5a, 6a group elements and Zr, Hf. A third hard phase having a core structure having a composite carbonitride containing at least one of the above and Ti as a peripheral portion, a first hard phase, and a binder phase. Moreover, the inside of the cermet of the present invention may include a second hard phase in addition to the first hard phase, the third hard phase, and the binder phase.
本発明のサーメットは、第１表面層，第２表面層，内部の各位置によって特定元素の含有量が変化すると、複合表面層の優れた効果が顕著に現れるので好ましい。第１表面層に含まれる窒素の含有量をＮS1（重量％）、第２表面層に含まれる窒素の含有量をＮS2（重量％）、内部に含まれる窒素の含有量をＮI（重量％）と表したとき、ＮS1、ＮS2、ＮIが、ＮS2＞ＮI＞ＮS1を満足すると、窒素含有量の最も低い第１表面層中の第１硬質相が粗大となって靱性が向上し、窒素含有量の最も高い第２表面層中の第２硬質相の耐溶着性が増大して耐摩耗性が向上するので好ましい。 The cermet of the present invention is preferable when the content of the specific element changes depending on the positions of the first surface layer, the second surface layer, and the inside, because the excellent effect of the composite surface layer appears remarkably. The content of nitrogen contained in the first surface layer is N S1 (% by weight), the content of nitrogen contained in the second surface layer is N S2 (% by weight), and the content of nitrogen contained inside is N I ( Weight%), when N S1 , N S2 , and N I satisfy N S2 > N I > N S1 , the first hard phase in the first surface layer having the lowest nitrogen content becomes coarse. It is preferable because the toughness is improved and the welding resistance of the second hard phase in the second surface layer having the highest nitrogen content is increased to improve the wear resistance.
次に、第１表面層に含まれる周期律表６ａ族元素量を６ａS1（重量％）、第２表面層に含まれる周期律表６ａ族元素量を６ａS2（重量％）、内部に含まれる周期律表６ａ族元素量を６ａI（重量％）と表したとき、６ａS1、６ａS2、６ａIが、６ａS1＞６ａI＞６ａS2を満足すると、６ａ族元素の含有量の最も高い第１表面層中の第１硬質相が高靱性となって耐チッピング性が向上し、６ａ族元素の含有量の最も低い第２表面層中の第１硬質相が高硬度となって耐摩耗性が向上するので好ましい。 Next, the periodic table 6a group element amount contained in the first surface layer is 6a S1 (wt%), the periodic table 6a group element amount contained in the second surface layer is 6a S2 (wt%), and included therein When the amount of group 6a element in the periodic table is expressed as 6a I (weight%), if 6a S1 , 6a S2 , 6a I satisfy 6a S1 > 6a I > 6a S2 , the content of the group 6a element is the most. The first hard phase in the high first surface layer has high toughness and chipping resistance is improved, and the first hard phase in the second surface layer having the lowest content of the group 6a element has high hardness and resistance. This is preferable because the wear resistance is improved.
さらに、第１表面層に含まれるＣｏおよびＮｉの少なくとも１種の含有量をＢＤS1（重量％）、第２表面層に含まれるＣｏおよびＮｉの少なくとも１種の含有量をＢＤS2（重量％）、内部に含まれるＣｏおよびＮｉの少なくとも１種の含有量をＢＤI（重量％）と表したとき、ＢＤS1、ＢＤS2、ＢＤIが、ＢＤI＞ＢＤS2≧ＢＤS1を満足すると、第１表面層のＣｏおよびＮｉの少なくとも１種の含有量が最も低くなり、最表面が高硬度となって耐摩耗性が向上するので好ましい。 Furthermore, the content of at least one of Co and Ni contained in the first surface layer is BD S1 (wt%), and the content of at least one of Co and Ni contained in the second surface layer is BD S2 (wt%). ), When the content of at least one of Co and Ni contained therein is expressed as BD I (% by weight), when BD S1 , BD S2 , BD I satisfies BD I > BD S2 ≧ BD S1 , It is preferable because the content of at least one of Co and Ni in the first surface layer is the lowest and the outermost surface is high in hardness and wear resistance is improved.
本発明の複合表面層を有するサーメットの製造方法は、（ａ）Ｚｒ，Ｈｆの窒化物，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：硬質相形成粉末全体に対して５〜２５重量％と、（ｂ）周期律表５ａ，６ａ族元素の炭化物，窒化物，炭窒化物の中の少なくとも１種：硬質相形成粉末全体に対して１０〜４０重量％と、（ｃ）Ｔｉの炭化物，炭窒化物の少なくとも１種：硬質相形成粉末全体に対して３５〜８５重量％とからなる硬質相形成粉末と、ＣｏおよびＮｉの少なくとも１種からなる結合相形成粉末とを用意して、硬質相形成粉末：混合物全体に対して７５〜９５重量％と、結合相形成粉末：混合物全体に対して５〜２５重量％とを混合して混合物を得る工程と、混合物を１１００〜１３００℃の温度にて圧力１０ｋＰａ以上の窒素ガス中で保持する工程と、混合物を１４００〜１５５０℃の温度にて圧力５ｋＰａ以下の窒素ガス中で焼結する工程とを含むものである。 The method for producing a cermet having a composite surface layer according to the present invention comprises (a) at least one of nitrides, carbonitrides of Zr and Hf, and their mutual solid solution: 5 to 25 with respect to the entire hard phase forming powder. (B) at least one of carbides, nitrides, and carbonitrides of Group 5a and 6a elements of the periodic table: 10 to 40% by weight based on the entire hard phase forming powder, and (c) Ti At least one of carbides and carbonitrides: a hard phase forming powder comprising 35 to 85% by weight with respect to the entire hard phase forming powder, and a binder phase forming powder comprising at least one of Co and Ni. A mixture of hard phase forming powder: 75 to 95% by weight with respect to the whole mixture and binder phase forming powder: 5 to 25% by weight with respect to the whole mixture to obtain a mixture; Pressure of 10 kPa at a temperature of ° C A step of holding in nitrogen gas above the mixture is intended to include the step of sintering in a pressure 5kPa or less of the nitrogen gas at a temperature of from 1,400 to 1550 ° C..
本発明の製造方法において、Ｚｒ，Ｈｆの窒化物，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種の粉末として、ＺｒＮ，ＨｆＮなどの窒化物を使用すると焼結体中でのＺｒＮやＨｆＮの残存量が多くなり、耐溶着性が向上するので好ましい。また、周期律表５ａ，６ａ族元素の炭化物，窒化物，炭窒化物の中の少なくとも１種の粉末を添加すると有芯構造粒子を生じ易いので好ましい。具体的には、Ｍｏ2Ｃ，ＷＣ，ＴａＣ，ＮｂＮなどを挙げることができる。また、Ｔｉの炭化物，炭窒化物の粉末として、ＴｉＣあるいは窒素量の少ないＴｉ（Ｃ，Ｎ）を使用すると、有芯構造粒子を生じ易いので好ましい。 In the production method of the present invention, when nitrides such as ZrN and HfN are used as at least one kind of powders of nitrides, carbonitrides, and their mutual solid solutions of Zr and Hf, ZrN and This is preferable because the residual amount of HfN is increased and the welding resistance is improved. Further, it is preferable to add at least one powder of carbides, nitrides, and carbonitrides of Group 5a and 6a elements of the periodic table because cored structure particles are easily formed. Specifically, Mo 2 C, WC, TaC, NbN and the like can be mentioned. Further, it is preferable to use TiC or Ti (C, N) having a small amount of nitrogen as the Ti carbide or carbonitride powder because cored structure particles are easily formed.
本発明の製造方法における昇温および焼結時の雰囲気は、窒素ガスの分圧を制御するものである。昇温時では、Ｚｒ，Ｈｆ，Ｔｉの窒化が顕著となる１１００℃から粉末成形体の収縮が顕著となる１３００℃までの温度範囲において、１０ｋＰａ以上の窒素ガス中で保持することによって粉末成形体の表面部に高窒素含有領域を形成する。そして、１４００〜１５５０℃の温度領域における焼結時には、５ｋＰａ以下の窒素ガス雰囲気とすることによって、最表面から脱窒させる。すなわち、最表面に窒素含有量の少ない第１表面層を形成させ、その内部に窒素含有量の多い第２表面層を形成させるものである。 The atmosphere at the time of temperature rise and sintering in the production method of the present invention controls the partial pressure of nitrogen gas. When the temperature is raised, the powder molded body is maintained in a nitrogen gas of 10 kPa or more in a temperature range from 1100 ° C. at which nitridation of Zr, Hf, Ti becomes significant to 1300 ° C. at which the shrinkage of the powder molded body becomes significant. A high nitrogen content region is formed on the surface of the substrate. And at the time of sintering in the temperature range of 1400-1550 degreeC, it is denitrified from the outermost surface by setting it as 5 kPa or less nitrogen gas atmosphere. That is, a first surface layer having a low nitrogen content is formed on the outermost surface, and a second surface layer having a high nitrogen content is formed therein.
本発明のサーメットは、焼結時の脱窒が周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物の第１硬質相を含む第１表面層を形成する作用を奏し、昇温時の窒化処理がＺｒ，Ｈｆの窒化物，炭窒化物の中の少なくとも１種の第２硬質相を含有した第２表面層を形成する作用を奏し、形成された第１表面層が耐チッピング性を向上させる作用を奏し、形成された第２表面層が耐摩耗性，耐塑性変形性を向上させる作用を奏し、結果として第１表面層と第２表面層からなる複合表面層がサーメット全体の耐摩耗性と耐チッピング性の両方を同時に向上させる作用を奏しているものである。 In the cermet of the present invention, the denitrification during sintering is a first hard carbonitride that contains at least one of elements in Group 5a and 6a of the periodic table, at least one of Zr and Hf, and Ti. A second surface layer having an effect of forming a first surface layer including a phase, wherein the nitriding treatment at the time of temperature increase includes at least one second hard phase selected from Zr and Hf nitrides and carbonitrides. The formed first surface layer has an effect of improving chipping resistance, and the formed second surface layer has an effect of improving wear resistance and plastic deformation resistance. The composite surface layer composed of the first surface layer and the second surface layer has the effect of simultaneously improving both the wear resistance and chipping resistance of the entire cermet.
本発明の複合表面層を有するサーメットは、従来のサーメットに比べてチッピングを起こし難いために、約１．７倍の切削寿命を達成できると言う効果を有する。 The cermet having the composite surface layer of the present invention is less likely to cause chipping than the conventional cermet, and therefore has an effect that a cutting life of about 1.7 times can be achieved.
市販されている平均粒径１〜２μｍのＴｉＣ，ＴｉＮ，Ｔｉ（Ｃ0.5Ｎ0.5），ＺｒＮ，ＨｆＮ，ＮｂＣ，ＴａＣ，ＷＣ，Ｍｏ2Ｃ，Ｃｏ，Ｎｉ，Ｃｒ2Ｎの各粉末を用いて、表１に示す配合組成に秤量し、ステンレス製ポットにアセトン溶媒と超硬合金製ボールと共に挿入し、４８時間混合粉砕後、乾燥して混合粉末を得た。 Using commercially available powders of TiC, TiN, Ti (C 0.5 N 0.5 ), ZrN, HfN, NbC, TaC, WC, Mo 2 C, Co, Ni, Cr 2 N with an average particle diameter of 1 to 2 μm The mixture composition shown in Table 1 was weighed, inserted into a stainless steel pot together with an acetone solvent and a cemented carbide ball, mixed and ground for 48 hours, and dried to obtain a mixed powder.
これらの混合粉末をＩＳＯ規格でＳＮＭＧ１２０４０８のブレーカ付きチップ用金型に充填し、２００ＭＰａの圧力でもって圧粉成形体を作製し、カーボンブラック粉末を塗布したカーボン板上に設置した後、焼結炉に挿入して加熱し、焼結して、本発明品１〜８および比較品１〜７のサーメットチップを得た。適用した昇温，窒化処理，焼結，冷却の各工程における雰囲気の詳細を表２に一括して示し、その条件番号および焼結時の温度と時間を表１に併記した。 These mixed powders are filled in a chip die with a breaker of SNMG120408 in accordance with ISO standards, a green compact is produced with a pressure of 200 MPa, and placed on a carbon plate coated with carbon black powder, and then a sintering furnace The cermet chips of the present invention products 1 to 8 and comparative products 1 to 7 were obtained. Details of the atmosphere in each of the applied temperature raising, nitriding treatment, sintering, and cooling steps are collectively shown in Table 2, and the condition number and the temperature and time during sintering are also shown in Table 1.
得られたサーメットチップの各１個を切断した後、逃げ面側の断面を研削と１μｍのダイヤモンドペーストによりラップ加工し、光学顕微鏡と走査型電子顕微鏡により硬質相の組織観察を行い、焼き肌面から内部に形成された第１表面層（硬質相が複合炭窒化物の固溶体粒子のみからなる）の平均厚みと第２表面層（硬質相がＺｒおよびＨｆの１種以上の窒化物，炭窒化物の単独粒子と複合炭窒化物の固溶体粒子とからなる）の平均厚みを測定した。また、別のチップの逃げ面を表面から内部に向けて研削，ラップしながらＸ線回折を行い、第１表面層と第２表面層の中央部および表面から０．１ｍｍ内部の硬質相成分を同定した。これらの結果を表３に示す。尚、比較品において第１表面層および第２表面層が存在しない場合は、表面から５μｍ内部と表面から２０μｍ内部で測定した結果を表中の第１表面層、第２表面層の欄にそれぞれ記載した。 After cutting each one of the obtained cermet chips, the flank cross section was ground and lapped with 1 μm diamond paste, and the structure of the hard phase was observed with an optical microscope and a scanning electron microscope. The average thickness of the first surface layer (the hard phase is composed only of solid carbonitride particles of composite carbonitride) and the second surface layer (the hard phase is one or more nitrides of Zr and Hf, carbonitride) The average thickness of the single particles of the product and the solid solution particles of the composite carbonitride was measured. Also, X-ray diffraction is performed while grinding and lapping the flank face of another chip from the surface to the inside, and the hard phase component inside 0.1 mm from the center and the surface of the first surface layer and the second surface layer. Identified. These results are shown in Table 3. In addition, when the first surface layer and the second surface layer are not present in the comparative product, the results measured in the inside of 5 μm from the surface and the inside of 20 μm from the surface are shown in the columns of the first surface layer and the second surface layer in the table, respectively. Described.
また、上記の逃げ面側の断面を観察した試料について、走査型電子顕微鏡を用いて第１表面層と第２表面層の中央部および表面から０．１ｍｍ内部の組織写真を撮り、画像処理装置により結合相を除く硬質相の中で複合炭窒化物の固溶体粒子（ＳＳと記す）、ＺｒおよびＨｆの少なくとも１種の窒化物，炭窒化物の単独粒子（ＺＨＮ記す）、Ｔｉの炭化物，炭窒化物を芯部とし複合炭窒化物を周辺組織とする有芯構造の粒子（ＣＲＳと記す）、Ｔｉの窒化物，炭窒化物の単独粒子（ＴＮと記す）などの含有体積を求めた。ここで、比較品において第１表面層および第２表面層が存在しない場合は、それぞれ表面から５μｍ内部と２０μｍ内部の位置で代用した。その結果を表４に示す。 In addition, with respect to the sample in which the cross section on the flank side is observed, a tissue photograph of 0.1 mm inside is taken from the center and the surface of the first surface layer and the second surface layer using a scanning electron microscope, and an image processing apparatus In the hard phase excluding the binder phase, composite carbonitride solid solution particles (referred to as SS), at least one nitride of Zr and Hf, carbonitride single particles (referred to as ZHN), Ti carbide, charcoal The content volumes of cored structure particles (referred to as CRS) having nitride as the core and composite carbonitride as the surrounding structure, Ti nitride, carbonitride single particles (referred to as TN), and the like were determined. Here, in the case where the first surface layer and the second surface layer were not present in the comparative product, they were substituted at positions within 5 μm and 20 μm from the surface, respectively. The results are shown in Table 4.
表３，表４の結果から、本発明品はすべて複合表面層を有するが、ＺｒＮ添加量の少ない比較品１、ＺｒＮ添加量の多い比較品２、ＴｉＣ配合量の少ない比較品３，４、窒化処理していない比較品５，６、窒化処理せず窒化焼結した比較品７では、第１表面層は形成されるものの、内部と組織構造の異なる第２表面層は形成されていないことが分かる。 From the results of Tables 3 and 4, all the products of the present invention have a composite surface layer, but Comparative Product 1 with a small amount of ZrN added, Comparative Product 2 with a large amount of ZrN added, Comparative Products 3 and 4 with a small TiC content, In the comparative products 5 and 6 that are not nitrided and the comparative product 7 that is nitrided and sintered without the nitriding treatment, the first surface layer is formed, but the second surface layer having a different structure from the inside is not formed. I understand.
次に、上記の逃げ面側の断面を観察した試料について、第１表面層と第２表面層の中央部および表面から０．１ｍｍ内部の成分を走査型分析電子顕微鏡で分析した。その結果を表５に示す。 Next, about the sample which observed the cross section of said flank side, the component inside 0.1 mm from the center part and surface of the 1st surface layer and the 2nd surface layer was analyzed with the scanning analysis electron microscope. The results are shown in Table 5.
表５の結果から、本発明品には第１表面層と第２表面層が形成されていることが分かる。 From the results of Table 5, it can be seen that the first surface layer and the second surface layer are formed in the product of the present invention.
実施例１で得た本発明品３，４，５，７，８と比較品１，３，４，６，７の各サーメットチップを＃２３０のダイヤモンド砥石にて上下面を研削加工した後、切刃部に０．０５ｍｍの丸ホーニング加工を施した。そして、被削材：４本溝入り炭素鋼Ｓ４５Ｃ，切削速度：１５０ｍ／ｍｉｎ，切込み：２．０ｍｍ，送り：０．２ｍｍ／ｒｅｖの条件で乾式での断続旋削試験を行い、刃先が欠損，チッピングを発生するか、あるいは、逃げ面摩耗量が０．２０ｍｍに達するまで時間を測定した。その結果を表６に示す。 After grinding the upper and lower surfaces of the cermet chips of the present invention products 3, 4, 5, 7, 8 obtained in Example 1 and the comparative products 1, 3, 4, 6, 7 with a # 230 diamond grindstone, The cutting edge was subjected to a round honing process of 0.05 mm. Then, cut material: 4-grooved carbon steel S45C, cutting speed: 150 m / min, depth of cut: 2.0 mm, feed: 0.2 mm / rev. Time was measured until chipping occurred or the flank wear amount reached 0.20 mm. The results are shown in Table 6.
表６の結果を見ると、比較品が塑性変形に伴う急激な摩耗やチッピング、欠損を起こし易いのに対して、本発明品は正常な摩耗や微少なチッピングが進行するために、長寿命となっている。 Looking at the results in Table 6, the comparative product is prone to abrupt wear, chipping and chipping due to plastic deformation, whereas the product of the present invention progresses normal wear and minute chipping. It has become.
Claims (7)
（１）第１表面層は、周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物の第１硬質相と、結合相とからなり、
（２）第２表面層は、Ｚｒ，Ｈｆの窒化物，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硬質相と、第１硬質相と、結合相とからなり、
（３）第１表面層と第２表面層とを除いたサーメットの内部は、Ｔｉの炭化物，炭窒化物を芯部とし周期律表５ａ，６ａ族元素の中の１種以上とＺｒ，Ｈｆの中の１種以上とＴｉとを含む複合炭窒化物を周辺部とする有芯構造の第３硬質相と、第１硬質相と、結合相とを含む、
複合表面層を有するサーメット。 In a cermet composed of at least one hard phase of carbides, nitrides and mutual solid solutions of the elements 4a, 5a and 6a of the periodic table, and a binder phase mainly composed of at least one of Co and Ni A first surface layer having an average thickness of 2 to 20 μm is formed from the baked skin surface of the cermet toward the inside, and a second surface having an average thickness of 5 to 50 μm from the interface between the first surface layer and the second surface layer to the inside. A surface layer is formed,
(1) The first surface layer is bonded to a first hard phase of a composite carbonitride containing one or more elements in the periodic table 5a and 6a group elements, one or more elements in Zr and Hf, and Ti. Consist of phases
(2) The second surface layer is composed of at least one second hard phase among the nitride of Zr, Hf, carbonitride, and their mutual solid solution, the first hard phase, and the binder phase.
(3) The inside of the cermet excluding the first surface layer and the second surface layer is composed of Ti carbide or carbonitride as a core and one or more elements in the periodic table 5a, 6a group elements and Zr, Hf Including a third hard phase having a core structure having a composite carbonitride containing at least one of Ti and Ti as a peripheral portion, a first hard phase, and a binder phase;
Cermet with composite surface layer.
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