JPH01287246A - Surface heat-treated sintered alloy, its manufacture and coated surface heat-treated sintered alloy with hard film - Google Patents
Surface heat-treated sintered alloy, its manufacture and coated surface heat-treated sintered alloy with hard filmInfo
- Publication number
- JPH01287246A JPH01287246A JP63116351A JP11635188A JPH01287246A JP H01287246 A JPH01287246 A JP H01287246A JP 63116351 A JP63116351 A JP 63116351A JP 11635188 A JP11635188 A JP 11635188A JP H01287246 A JPH01287246 A JP H01287246A
- Authority
- JP
- Japan
- Prior art keywords
- sintered alloy
- average
- hard phase
- surface layer
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 88
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000011230 binding agent Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 4
- 239000012071 phase Substances 0.000 description 35
- 238000005520 cutting process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002747 voluntary effect Effects 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001063191 Elops affinis Species 0.000 description 1
- 235000002756 Erythrina berteroana Nutrition 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- HKPHPIREJKHECO-UHFFFAOYSA-N butachlor Chemical compound CCCCOCN(C(=O)CCl)C1=C(CC)C=CC=C1CC HKPHPIREJKHECO-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、切削工具用部材、耐摩耗工具用部材、耐衝撃
工具用部材又は装飾用部材を含めた主に構造用材料とし
て適した表面調質焼結合金及びその製造方法並びにその
表面調質焼結合金に硬質膜を被覆してなる被覆表面調質
焼結合金に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a surface material suitable mainly as a structural material, including a cutting tool component, a wear-resistant tool component, an impact-resistant tool component, or a decorative component. The present invention relates to a heat-treated sintered alloy, a method for producing the same, and a coated surface-tempered sintered alloy obtained by coating the surface-tempered sintered alloy with a hard film.
（従来の技術）
ＴｉＣ−ＴｉＮ −Ｎｉを基本組成とする Ｎ含有のＴ
ｉＣ基焼結合金は、ＴｉＣ−Ｎｉを基本組成とするＮ無
含有のＴｉＣ基焼結合金に比べて強度及び耐塑性変形性
にすぐれる傾向がある。このことからＮ含有のＴｉＣ基
焼結合金は、例えば切削工具用部材として用いる場合に
は重切削領域又は高送り領域にまで広い範囲で実用でき
る傾向になる。これらの用途領域では、二［具部材を低
価格にする必要から焼結合金の表面を研摩又は研削など
を施さないで焼結後の表面状態、所謂焼肌面の状態のま
まで用いる場合がある。(Prior art) N-containing T whose basic composition is TiC-TiN-Ni
An iC-based sintered alloy tends to have better strength and plastic deformation resistance than an N-free TiC-based sintered alloy whose basic composition is TiC-Ni. For this reason, N-containing TiC-based sintered alloys tend to be useful in a wide range of applications, including heavy cutting areas and high feed areas, when used as members for cutting tools, for example. In these application areas, there are cases where the surface of the sintered alloy is used in its sintered surface state, the so-called hardened surface state, without polishing or grinding the surface of the sintered alloy due to the need to reduce the cost of the components. be.
Ｎ含有のＴｉＣ基焼結合金は、焼肌面の状態のままで用
いると、研摩又は研削した面の状態で用ｌ／Ｘる場合に
比べて欠損又はチッピングが生じゃすし１という問題が
ある。このようなＮ含有のＴｉＣ基焼結合金における表
面層の問題を解決しようとしたものの代表例としては、
特開昭５４−１１１１７０４号公報がある。When N-containing TiC-based sintered alloys are used with a burnt surface, there is a problem of chipping or chipping compared to when they are used with a polished or ground surface. . A typical example of an attempt to solve the problem of the surface layer in N-containing TiC-based sintered alloys is as follows:
There is Japanese Unexamined Patent Publication No. 54-1111704.
（発明が解決しようとする問題点）
特開昭５４−１０１７０４号公報は、Ｎ及び／又は０含
有のＩ’ ｉ Ｃ基焼結合金における焼結合金の表面か
ら０００５〜Ｇ、Ｚｍｍまでの硬度が表面から１．Ｇｍ
ｍの硬度の１０２倍以下にした焼結合金である。この特
開昭５４−１０１７０４号公報は、焼結合金の表面部と
内部における結合相量を均一にすることにより硬さも均
一にし、その結果表面部の硬脆化を解決したものである
けれども、焼結合金の表面部と内部における硬質層の粒
度の不均一化が解決されていないために強度及び耐塑性
変形性に対して未だ十分満足するに至っていないという
問題がある。(Problems to be Solved by the Invention) Japanese Patent Application Laid-Open No. 101704/1983 discloses that in an I' i C-based sintered alloy containing N and/or 0, the hardness from the surface of the sintered alloy to 0005 to G, Zmm is is 1 from the surface. Gm
This is a sintered alloy with a hardness of 102 times or less than m. Although this Japanese Patent Application Laid-Open No. 54-101704 makes the hardness uniform by making the amount of binder phase uniform on the surface and inside of the sintered alloy, this solves the hard embrittlement of the surface. There is a problem that the strength and plastic deformation resistance are not yet fully satisfied because the non-uniformity of the grain size of the hard layer on the surface and inside of the sintered alloy has not been solved.
本発明は、上記のような問題点を解決したもので、具体
的にはＮ含有の゛ｒｉｃ基焼結合金の表面部と内部にお
ける硬質相の粒度を均一にすること、又は表面部と内部
における硬質相の粒度と結合相の含有量の両方を均一に
することにより、強度及び耐塑性変形性にすぐれた焼肌
面を有する Ｎ含有の’ｒ ｉ Ｃ基焼結合金及びその
製造方法並びにその焼結合金に硬質膜を被覆してなる被
覆表面調質焼結合金の提供を目的とするものである。The present invention solves the above-mentioned problems. Specifically, the present invention aims to make the particle size of the hard phase uniform on the surface and inside of the N-containing tric-based sintered alloy, or to An N-containing 'r i C-based sintered alloy having a hardened surface with excellent strength and plastic deformation resistance by making both the particle size of the hard phase and the content of the binder phase uniform, and a method for producing the same. The object of the present invention is to provide a surface-treated sintered alloy which is obtained by coating the sintered alloy with a hard film.
（問題点を解決するための手段）
本発明者らは、焼肌面を有するＮ含有のＴｉＣ基焼結合
金が研摩面又は研削面でなる Ｎ含有の’ｌ’ｉｃ基焼
結合全焼結合金強度及び耐塑性変形性に劣るという原因
を検討していた所、従来のＮ含有のＴｉＣ基焼結合金の
焼肌面表面部における硬質相の粒度は、内部における硬
質相の粒度に比べて著しく粗粒化していること、これに
対して、焼結合金の焼肌面表面部と内部とにおける硬質
相の粒度を均一にすると強度及び耐塑性変形性がすぐれ
ること、また、焼結合金の焼肌面表面部と内部とにおけ
る硬質相の粒度の均一化と共に結合相の含有量の均一化
を併合させると一層強度及び耐塑性変形性が著しくすぐ
れるという知見を得たものである。この知見に基づいて
、本発明を完成するに至ったものである。(Means for Solving the Problems) The present inventors have proposed an N-containing TiC-based sintered alloy having a burnt surface and a polished surface or a ground surface. When examining the causes of poor strength and plastic deformation resistance, we found that the grain size of the hard phase on the surface of the burnt surface of conventional N-containing TiC-based sintered alloys was significantly larger than the grain size of the hard phase inside. On the other hand, if the grain size of the hard phase on the surface and inside of the burnt surface of the sintered alloy is made uniform, the strength and plastic deformation resistance will be excellent. It has been found that combining uniformity of the particle size of the hard phase on the surface and inside of the burnt surface as well as uniformity of the content of the binder phase significantly improves the strength and plastic deformation resistance. Based on this knowledge, we have completed the present invention.
すなわち、本発明の表面調質焼結合金は、ＴｉとＣ（炭
素）と Ｎ（窒素）を必須成分として含イｊし、他にＺ
ｒ、 Ｈｒ、 Ｖ、 Ｎｂ、 Ｔａ、 Ｃｒ、 Ｍｏ、
Ｗの中の少なくとも１種を含有してなる硬質相７５〜９
５重量％と、残りＣｏ及び／又はＮｉを主成分とする結
合相と不可避不純物とからなる焼肌面を有する焼結合金
であって、該焼結合金の焼肌面からＱ、Ｑ５＋ｎｍ内部
までの表面層における前記硬質相の平均粒度が該表面層
を除いた該焼結合金の内部における前記硬質相の平均粒
度の０８〜１２倍であることを特徴とするものである。That is, the surface-treated sintered alloy of the present invention contains Ti, C (carbon), and N (nitrogen) as essential components, and Z
r, Hr, V, Nb, Ta, Cr, Mo,
Hard phase 75 to 9 containing at least one type of W
5% by weight, the remaining binder phase mainly composed of Co and/or Ni, and unavoidable impurities. The average particle size of the hard phase in the surface layer is 08 to 12 times the average particle size of the hard phase in the interior of the sintered alloy excluding the surface layer.
本発明の表面調質焼結合金における焼結合金は、従来の
Ｎを含有したＴ ｉ Ｃ基焼結合金の成分組成、例えば
前述の特開昭５４−１０１７０４号公報に記載の成分組
成など全てが対象になり得るものであり、その自焼結合
金を構成している硬質相は、具体的には、例えばＹｉｃ
、 ＴｉＮ、 Ｔｉ（ＣＮ）、 （Ｔｉ、Ｍ）Ｃ。The sintered alloy in the surface-treated sintered alloy of the present invention has all the component compositions of conventional N-containing T i C-based sintered alloys, such as the component composition described in the above-mentioned Japanese Patent Application Laid-Open No. 101704/1983. can be a target, and the hard phase constituting the self-burning alloy is specifically, for example, Yic
, TiN, Ti(CN), (Ti,M)C.
（Ｔｉ、ＭＡＮ、 （１’ｉ、Ｍ） （ＣＮ） （
但し、 Ｍは Ｚｒ、 Ｈｆ、 Ｖ。(Ti, MAN, (1'i, M) (CN) (
However, M is Zr, Hf, V.
Ｎｂ、 ｌ’ａ、 Ｃｒ、 Ｍｏ、 Ｗの中の少なくと
も１種を示す。）の中の少なくとも１種からなるもので
あり、焼結合金を構成しているもう一方の結合相は、Ｃ
ｏ及び／又はＮｉが結合相中の少なくとも５０体積％を
占め、他に、例えば硬質相を形成している化合物中の金
属元素やＦｅ、 ／１． Ｍｎなどの含有したもので
ある。At least one of Nb, l'a, Cr, Mo, and W is shown. ), and the other binder phase constituting the sintered alloy is C
o and/or Ni occupy at least 50% by volume in the binder phase, and in addition, for example, metallic elements in the compound forming the hard phase, Fe, /1. It contains Mn and the like.
また、本発明の表面調質焼結合金における焼結合金の焼
肌面とは、焼結後の表面状態、又は焼結後に水や有機溶
媒で洗浄及び乾燥した後の表面状態、もしくは焼結後に
サンドブラスト処理などで焼肌面の（＝Ｊ着物を取り除
いた表面状態を代表的な面として挙げることができる。In addition, the sintered surface of the sintered alloy in the surface-treated sintered alloy of the present invention refers to the surface condition after sintering, or the surface condition after washing and drying with water or an organic solvent after sintering, or the surface condition after sintering. A typical example of this is the surface condition after removing the burnt surface (=J kimono) by sandblasting or the like.
本発明の表面調質焼結合金は、焼結合金の焼肌面から０
．０５ｍｍ内部まての表面層における合金組織を内部の
合金組織に近づけたもので、この合金組織の内、表面層
に存在する硬質相の平均粒度を内部に存在する硬質相の
平均粒度に近づけることにより焼結合金の強度及び耐塑
性変形性を向−１ニさせたものである。この表面層と内
部における硬質相の粒度の他に、さらに表面層に存在す
る結合相の５［ε均含有量が内部に存在する結合相の平
均含有量の０７〜１．２倍に制御することに」：つて−
層焼結合金の強度及びｉ＝１塑性変形性を向上させるこ
とができる。この表面層と内部における硬質相の粒度及
び結合相の平均含有量の他に、表面層における平均硬さ
を内部におＧづる平均硬さの０９５〜１１０倍に制御す
ることにより焼結合金の強度及び耐塑性変形性に対する
安定化が高まるので好ましいことである。The surface-treated sintered alloy of the present invention has a temperature of 0.
．． 05mm The alloy structure in the surface layer of the inner machete is made closer to the inner alloy structure, and within this alloy structure, the average grain size of the hard phase existing in the surface layer is made closer to the average grain size of the hard phase existing inside. This improves the strength and plastic deformation resistance of the sintered alloy. In addition to the particle size of the hard phase in the surface layer and the interior, the average content of the binder phase present in the surface layer is controlled to be 07 to 1.2 times the average content of the binder phase present in the interior. Especially”: tsute-
The strength and i=1 plastic deformability of the layered sintered alloy can be improved. In addition to the particle size of the hard phase and the average content of the binder phase in the surface layer and inside, the average hardness in the surface layer is controlled to 095 to 110 times the average hardness in the inside. This is preferable because it increases the stability of strength and plastic deformation resistance.
本発明の表面調質焼結合金の製造方法は、周期律表４ａ
、５ａ、６ａ族金属の炭化物、窒化物及びこれらの相互
固溶体の中の少なくとも１種の粉末と、Ｃ。The method for producing the surface-tempered sintered alloy of the present invention is based on periodic table 4a
, at least one powder of carbides, nitrides, and mutual solid solutions of group 5a and 6a metals, and C.
及び／又はＮｉを主成分とする粉末とでなる混合粉末を
用いて、従来の粉末冶金法でもって′「！と ＣとＮと
を必須成分とし、他ｉ、ｍ Ｚｒ、 Ｈｆ、 Ｖ、 Ｎ
ｂ、 Ｔａ。and/or a powder whose main component is Ni, using a conventional powder metallurgy method.
b, Ta.
Ｃｒ、 Ｍｏ、 Ｗの中の少なくとも１種を含有してな
る硬質相７５〜９５重量％と、残りＣｏ及び／又はＮｉ
を主成分とする結合相と不可避不純物とからなる焼結合
金を得るための製造方法であって、粉末冶金法ての各製
造工程の内、焼結工程における温度及び雰囲気が１３０
０℃以下の第１ Ａ２度領域では真空又は不活性ガスの
雰囲気とし、１３００℃を超える第２温度領域では０１
〜２ＧＬｏｒｒの窒素ガス雰囲気とし、さらに該第２温
度領域における窒素圧力を品温になるほど高くすること
を特徴とするものである。75 to 95% by weight of a hard phase containing at least one of Cr, Mo, and W, and the remainder being Co and/or Ni.
A manufacturing method for obtaining a sintered alloy consisting of a binder phase mainly composed of
In the first A2 temperature range below 0℃, use a vacuum or inert gas atmosphere, and in the second temperature range above 1300℃
It is characterized by having a nitrogen gas atmosphere of ~2 GLorr, and further increasing the nitrogen pressure in the second temperature region as it approaches the product temperature.
本発明の表面調質焼結合金を製造する場合には、出発物
としての混合粉末中の含イ〕炭素晴及び含有窒素量の調
整が重要であり、さらに製造工程の内の焼結工程におけ
る温度及びそのときの雰囲気を微細に制御することが重
要である。特に、焼結工程における第１温度領域よりも
液相の発生と共に焼結が進行する第２温度領域における
窒素圧力を微細に制御することにより焼結合金の表面層
中の硬質相の粒度及び結合相の含有量の調整が可能とな
る。When producing the surface-treated sintered alloy of the present invention, it is important to adjust the amount of carbon and nitrogen contained in the mixed powder as a starting material. It is important to finely control the temperature and the atmosphere at that time. In particular, by finely controlling the nitrogen pressure in the second temperature region where sintering progresses with the generation of a liquid phase than in the first temperature region in the sintering process, the particle size and bonding of the hard phase in the surface layer of the sintered alloy can be improved. It becomes possible to adjust the phase content.
このようにして得られる表面調質焼結合金の表面に、例
えば従来から行われているような物理蒸着法ｔ Ｐ Ｖ
Ｄ法）や化学蒸着法ＣＣＶＤ法）でもって、この表面
調質焼結合金よりも硬さの高い硬質膜、具体的には、例
えば周期律表の４ａ、 ５ａ、 ６ａ族金属の炭化物、
窒化物、炭酸化物、窒酸化物及びこれらの相ｈ：固溶体
並びに窒化ケイ素、炭化ケイ素、酸化アルミニウム、窒
化アルミニウム、酸窒化アルミニウム、ダｌ方品窒化ホ
ウ素、ダイヤモンドの中の少なくとも１種の１ｊｔ層又
は多重層でなる硬質膜を被覆することにＪ：り被覆表面
調質焼結合金とすることも好ましいことである１、特に
、被覆表面調質焼結合金は、１）ｉｉ述の表面調質焼結
合金の製造方法における第２温度領域で焼結が完了した
温度中、高窒素圧力の雰囲気状態で一定時間さらに保持
して窒化膜でなる硬質膜を表面調質焼結合金の表面に形
成することにより得ると、工程が簡略化できること及び
設備の増設の必要がないことから好ましいことである。The surface of the surface-treated sintered alloy thus obtained is coated with, for example, a conventional physical vapor deposition method.
D method) or chemical vapor deposition method (CCVD method)), a hard film with higher hardness than this surface-tempered sintered alloy, specifically, for example, a carbide of a group 4a, 5a, or 6a metal of the periodic table,
Nitride, carbonate, oxynitride and their phases: solid solutions and layers of at least one of silicon nitride, silicon carbide, aluminum oxide, aluminum nitride, aluminum oxynitride, boron nitride, diamond Alternatively, it is also preferable to use a coated surface-treated sintered alloy to coat a hard film consisting of multiple layers. In the second temperature range in the method for producing a quality sintered alloy, the temperature at which sintering is completed is further held in a high nitrogen pressure atmosphere for a certain period of time to form a hard film made of a nitride film on the surface of the surface-tempered sintered alloy. Obtaining it by forming it is preferable because the process can be simplified and there is no need to add additional equipment.
この被覆表面調質焼結合金における硬質膜の厚さは、硬
質膜の材質、用途及び形状によって選定する必要があり
、人体０１〜１０μｍ厚さが実用的で好ましいものであ
る。The thickness of the hard film in this coated surface-tempered sintered alloy needs to be selected depending on the material, purpose, and shape of the hard film, and a thickness of 01 to 10 μm is practical and preferable.
（作用）
本発明の表面調質焼結合金は、焼肌面から０、０５ｍｍ
内部までの表面層における硬質相の粒度な従来の焼結合
金に比べて微細にしたことにより、表面層中の硬質相へ
の応力が分散され、その結果として焼結合金の強度及び
耐塑性変形性を高める作用をしているものである。(Function) The surface-tempered sintered alloy of the present invention is 0.05 mm from the sintered surface.
By making the grain size of the hard phase in the inner surface layer finer than in conventional sintered alloys, the stress on the hard phase in the surface layer is dispersed, resulting in improved strength and plastic deformation resistance of the sintered alloy. It has the effect of increasing sex.
また、本発明め表面調質焼結合金の製造方法は、焼結工
程における第１温度領域での雰囲気から第２温度領域で
の雰囲気への切換え、並びに第２温度領域での温度上昇
に従って窒素圧力を漸増することにより、焼結合金の表
面層での脱窒が抑制されるという作用をしているもので
ある。In addition, the method for manufacturing the surface-treated sintered alloy of the present invention includes switching from the atmosphere in the first temperature range to the atmosphere in the second temperature range in the sintering process, and nitrogen nitrogen as the temperature rises in the second temperature range. By gradually increasing the pressure, denitrification in the surface layer of the sintered alloy is suppressed.
実施例１ 平均粒度１〜２μｍ内にある市販の１’ ｉ Ｃ。Example 1 Commercially available 1'iC with an average particle size within 1-2 μm.
ＴｉＮ、 Ｍｏ２Ｃ，Ｎｉの各粉末を用いて４０ｗシ％
ＴｉＣ−３０１＋
ｗし％ＴｉＮ −１５ｗＬ％ＭＯ２Ｃ−１５Ｗｌ；％Ｎ
ｉに配合し、この配合粉末とアセトンとボールを混合容
器に入れて７２時間の湿式混合粉砕した。こうして得た
混合粉末にパラフィンを少量添加して後、３８ＭＮｉ２
０４０８（，１１Ｓ規格の形状）が得られるようにプレ
ス成形した。このプレス成形により得た圧粉体からパラ
フィンを加熱除去した後、０．０５Ｌｏｒｒの真空中、
室温から１２００℃までを４時間で昇温、次いで１２０
０℃〜１４５０℃までを第１表に示す雰囲気中、３℃／
ｍｉｎでＦｌ’ ｆＫＡし、さらに１４５０℃で１時間
保持して焼結した。焼結後は、５０℃／ｍｉｎの速度で
冷却して本発明の焼結合金１〜４及び従来の焼結工程に
相当する比較の焼結合金１〜４を得た。40w% using each powder of TiN, Mo2C, and Ni
TiC-301+w%TiN-15wL%MO2C-15Wl;%N
This blended powder, acetone, and balls were placed in a mixing container and wet mixed and pulverized for 72 hours. After adding a small amount of paraffin to the mixed powder thus obtained, 38MNi2
Press molding was performed to obtain 0408 (shape according to the 11S standard). After heating and removing paraffin from the green compact obtained by this press molding, in a vacuum of 0.05 Lorr,
Raise the temperature from room temperature to 1200℃ in 4 hours, then 120℃
3℃/3℃ in the atmosphere shown in Table 1 from 0℃ to 1450℃
Fl' fKA was carried out at min. After sintering, the sintered alloys were cooled at a rate of 50° C./min to obtain sintered alloys 1 to 4 of the present invention and comparative sintered alloys 1 to 4 corresponding to the conventional sintering process.
以下余白
こうして得た本発明品１〜４及び比較品１〜４のそれぞ
れの焼結合金の表面層と内部を走査型電子顕微鏡（ＳＥ
Ｍ）’、電子線マイクロアナリシス（、ＥＰＭＡ）及び
ビッカース硬度計により調査し、その結果を第２表に示
した。The surface layer and interior of the sintered alloys of the invention products 1 to 4 and comparative products 1 to 4 thus obtained were examined using a scanning electron microscope (SE).
M)', electron beam microanalysis (EPMA) and Vickers hardness tester were used to investigate, and the results are shown in Table 2.
以下余白
なお、第２表に示した硬質相の粒度は、ＳＥＭによる５
０００倍の合金組織写真から求めたものである。また、
結合相量は、焼結合金を傾斜角１０°に研摩し、この研
摩面をＥＰＭＡを用いて加速電圧２０ＫＶ、 ２０Ｘ
３０μｍ２の面分析条件て５点の平均値により求めたち
のである。特に、結合相量と硬さは、表面層内での変動
が大きいことから表面から内部へ向っての等間距離によ
る５点の平均値として求めた。In the margin below, the particle size of the hard phase shown in Table 2 is 5.
This was determined from a photograph of the alloy structure at a magnification of 1,000 times. Also,
The amount of binder phase was determined by polishing the sintered alloy to an inclination angle of 10°, and applying an acceleration voltage of 20 KV and 20X to the polished surface using EPMA.
It was determined from the average value of 5 points under the condition of area analysis of 30 μm2. In particular, the amount of binder phase and hardness were determined as average values of five points at equal distances from the surface toward the inside, since there were large fluctuations within the surface layer.
次に、本発明品１〜４及び比較品１〜４を用いて、下記
の（Δ）及び（１１）の条件により切削試験を行い、そ
の結果を第３表に示した。Next, a cutting test was conducted using the products 1 to 4 of the present invention and the comparative products 1 to 4 under the conditions (Δ) and (11) below, and the results are shown in Table 3.
（Ａ） 耐摩耗性切削条件
被削材 ５４８Ｃ（ｌｌ＋、 ２５０１２５０ ｍ
ｍφ゛デツプ形状 ＳＮＭＮ４３２
（０，ｌＸ−３０度直線ホーニング）
切削速度 １６０ ｍ／ｍｉｎ
切込み’；７）１．５ｍｍ
送りｉ７．ｊ ０．３ ｍｍ／ ｒｅｖ切削時
間 ２０ ｍｉｎ
（１３） 耐欠損性切削条件
被削材 ５４８Ｃ（ｌｌｎ ２３０） １２０ｍ
ｍφ４本スロットと付
チップ形状 ＳＮＭＮ４３２
（０，ｌＸ−３０度直線ホーニング）
切削速度 ｔｏｏ ｍ／ｍｉｎ ’切込み量
１．５ｍｍ
送り量 ０．３ ｍｍ／ｒｃｖ
評 価 １０分間の切削を１０回繰返し、うち１０
分以内に欠損した割合
で評価
以下余白
（発明の効果）
本発明の表面調質焼結合金は、従来のＮ含有の’ｒｉＣ
基焼結合金に比較して耐摩耗性においては殆ど同等であ
るが強度及び耐塑性変形性にすぐれていることから切削
試験における耐欠損性で約２〜３倍も高い効果があるも
のである。また、この表面調質焼結合金の表面に硬質膜
を被覆してなる本発明の被覆表面調質焼結合金は、耐摩
耗性が著しくすぐれると共にさらに一層耐欠損性もすぐ
れるという効果がある。これらのことから、本発明の焼
結合金は、従来のＮ含有のＴｉＣ基焼結合金の用途範囲
から、さらに耐衝撃性及び耐欠損性を必要とする用途範
囲までと、広い用途範囲を有し、安定性も高いという産
業上有用な材料及びその製造方法である。(A) Wear-resistant cutting conditions Work material 548C (ll+, 2501250 m
mφ゛Dep shape SNMN432 (0, lX-30 degree linear honing) Cutting speed 160 m/min Depth of cut; 7) 1.5 mm Feed i7. j 0.3 mm/rev Cutting time 20 min (13) Fracture resistant cutting conditions Work material 548C (lln 230) 120m
Insert shape with mφ4 slots SNMN432 (0,lX-30 degree linear honing) Cutting speed too m/min 'Depth of cut 1.5 mm Feed amount 0.3 mm/rcv Evaluation Repeated cutting for 10 minutes 10 times, including 10
The margin below the evaluation based on the percentage of defects within minutes (effect of the invention) The surface-tempered sintered alloy of the present invention is
Compared to base sintered alloys, it has almost the same wear resistance, but it has excellent strength and plastic deformation resistance, so it is about 2 to 3 times more effective in chipping resistance in cutting tests. . In addition, the coated surface-tempered sintered alloy of the present invention, which is obtained by coating the surface of the surface-tempered sintered alloy with a hard film, has the effect of significantly superior wear resistance and even better chipping resistance. be. For these reasons, the sintered alloy of the present invention has a wide range of applications, from the conventional N-containing TiC-based sintered alloy to applications that require higher impact resistance and chipping resistance. It is an industrially useful material that is highly stable, and a method for producing the same.
特許出願人 東芝タンガロイ株式会社
千続補正書（自発）
１．事件の表示
特願昭６３− ］ １６３５１号
２、発明の名称
表面調質焼結合金及びその製造方法並びにその合金に硬
質膜を被覆してなる被覆表面調質焼結合金
３、補正をする者
事件との関係 特許出願人
神奈川県用崎市幸区塚越１丁目７番地
４、補正命令のＨ付 自発
５、補正により増加する請求項の数 なし明細書の発明
の詳細な説明の欄を以下のとおりに補正する。Patent applicant: Toshiba Tungaloy Co., Ltd. Sensugu Amendment (voluntary) 1. Indication of Case Patent Application No. 16351 No. 16351 No. 2, Title of Invention: Surface-tempered sintered alloy and method for producing the same, and coated surface-tempered sintered alloy obtained by coating the alloy with a hard film 3. Person making amendment Relationship to the case Patent applicant 1-7-4 Tsukagoe, Saiwai-ku, Yozaki City, Kanagawa Prefecture, Amendment order with H Voluntary action 5, Number of claims increased by amendment None The detailed description of the invention in the specification is as follows. Correct as shown below.
（１） 明細書の第＋ｏＨ第１６行目に記載の「・・
・完了した温度中、」を１・・・完了した後、その温度
以下て、」と補正する。(1) “...” stated in line 16 of +oH of the specification
・Correct ``at the temperature at which the process is completed'' to 1...at a temperature below that temperature after the process is completed.
（２） 明細書の第１１頁第１６行「１に記・戒の「
することにＪ：す、」の後に、「硬質相の粒成長が抑制
されると共に」を追加補正する、。(2) Page 11, line 16 of the specification, “In 1.
After the phrase ``J:su'', ``the grain growth of the hard phase is suppressed'' is added as a correction.
（３） 明細書の第１４頁第３行目に記載の「・・・
マイクロアナリシス」を「・・・マイクロアナライザ」
と補正する。(3) “...” stated on page 14, line 3 of the specification.
"Micro analysis" is changed to "...Micro analyzer"
and correct it.
以上that's all
Claims (5)
、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの中の少なく
とも１種を含有してなる硬質相７５〜９５重量％と、残
りＣｏ及び／又はＮｉを主成分とする結合相と不可避不
純物とからなる焼肌面を有する焼結合金において、該焼
結合金の焼肌面から０．０５ｍｍ内部までの表面層にお
ける前記硬質相の平均粒度が該表面層を除いた該焼結合
金の内部における前記硬質相の平均粒度の０．８〜１．
２倍であることを特徴とする表面調質焼結合金。(1) Contains Ti, C, and N as essential components, and also contains Zr.
, Hf, V, Nb, Ta, Cr, Mo, and 75 to 95% by weight of a hard phase containing at least one of W, the remainder being a binder phase mainly composed of Co and/or Ni, and unavoidable impurities. In the sintered alloy having a burnt surface consisting of, the average particle size of the hard phase in the surface layer up to 0.05 mm inside from the burnt surface of the sintered alloy is within the inside of the sintered alloy excluding the surface layer. The average particle size of the hard phase in 0.8 to 1.
A surface-tempered sintered alloy characterized by twice the surface temperature.
有量が焼結合金の内部における結合相の平均含有量の０
．７〜１．２倍であることを特徴とする特許請求の範囲
の請求項第１項記載の表面調質焼結合金。(2) The surface layer has an average binder phase content that is 0% of the average binder phase content inside the sintered alloy.
．． The surface-treated sintered alloy according to claim 1, wherein the surface-treated sintered alloy is 7 to 1.2 times as large.
合金の内部における平均硬さの０．９５〜１．１０倍で
あることを特徴とする特許請求の範囲の請求項第１項又
は第２項記載の表面調質焼結合金。(3) The surface layer has an average hardness that is 0.95 to 1.10 times the average hardness inside the sintered alloy. The surface-treated sintered alloy according to item 1 or 2.
物及びこれらの相互固溶体の中の少なくとも１種の粉末
と、Ｃｏ及び／又はＮｉを主成分とする粉末とでなる混
合粉末から焼結工程を経て、ＴｉとＣとＮとを必須成分
とし、他にＺｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、
Ｗの中の少なくとも１種を含有してなる硬質相７５〜９
５重量％と、残りＣｏ及び／又はＮｉを主成分とする結
合相と不可避不純物とからなる焼結合金を得るための製
造方法において、前記焼結工程における温度及び雰囲気
が１３００℃以下の第１温度領域では真空又は不活性ガ
スの雰囲気とし、１３００℃を超える第２温度領域では
０．１〜２０ｔｏｒｒの窒素ガス雰囲気とし、さらに該
第２温度領域での窒素圧力を高温になるほど高くするこ
とを特徴とする表面調質焼結合金の製造方法。(4) A mixed powder consisting of at least one kind of powder among carbides, nitrides, and mutual solid solutions of metals of groups 4a, 5a, and 6a of the periodic table, and a powder mainly composed of Co and/or Ni. Through the sintering process, Ti, C, and N are made essential components, and Zr, Hf, V, Nb, Ta, Cr, Mo,
Hard phase 75 to 9 containing at least one type of W
In the manufacturing method for obtaining a sintered alloy consisting of 5% by weight, a binder phase mainly composed of Co and/or Ni, and unavoidable impurities, the temperature and atmosphere in the sintering step are 1300 ° C. or less. A vacuum or inert gas atmosphere is used in the temperature range, a nitrogen gas atmosphere of 0.1 to 20 torr is used in the second temperature range exceeding 1300 ° C, and the nitrogen pressure in the second temperature range is increased as the temperature increases. A method for producing a characterized surface-treated sintered alloy.
項に記載の表面調質焼結合金の表面に該表面調質焼結合
金よりも硬さの高い硬質膜を被覆してなることを特徴と
する被覆表面調質焼結合金。(5) Claim 1, 2 or 3 of the scope of claims
A coated surface-tempered sintered alloy, characterized in that the surface of the surface-tempered sintered alloy according to item 1 is coated with a hard film having a higher hardness than the surface-tempered sintered alloy.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63116351A JP2511694B2 (en) | 1988-05-13 | 1988-05-13 | Surface-tempered sintered alloy, method for producing the same, and coated surface-tempered sintered alloy obtained by coating the alloy with a hard film |
| US07/320,059 US4990410A (en) | 1988-05-13 | 1989-03-07 | Coated surface refined sintered alloy |
| DE68921246T DE68921246T2 (en) | 1988-05-13 | 1989-03-22 | Sintered, surface-refined alloy with and without hard coating as well as a process for producing the alloy. |
| EP89105118A EP0344421B1 (en) | 1988-05-13 | 1989-03-22 | Burnt surface sintered alloy with and without a rigid surface film coating and process for producing the alloy |
| KR1019890006361A KR0151843B1 (en) | 1988-05-13 | 1989-05-11 | Surface refined sintered alloy and process for producing the same and coated surface refined intered alloy comprising rigid film coated on the alloy |
| US07/424,185 US4963321A (en) | 1988-05-13 | 1989-10-19 | Surface refined sintered alloy and process for producing the same and coated surface refined sintered alloy comprising rigid film coated on the alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63116351A JP2511694B2 (en) | 1988-05-13 | 1988-05-13 | Surface-tempered sintered alloy, method for producing the same, and coated surface-tempered sintered alloy obtained by coating the alloy with a hard film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01287246A true JPH01287246A (en) | 1989-11-17 |
| JP2511694B2 JP2511694B2 (en) | 1996-07-03 |
Family
ID=14684803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63116351A Expired - Lifetime JP2511694B2 (en) | 1988-05-13 | 1988-05-13 | Surface-tempered sintered alloy, method for producing the same, and coated surface-tempered sintered alloy obtained by coating the alloy with a hard film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2511694B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995005497A1 (en) * | 1993-08-16 | 1995-02-23 | Sumitomo Electric Industries, Ltd. | Cemented carbide alloy for cutting tool and coated cemented carbide alloy |
| US6057046A (en) * | 1994-05-19 | 2000-05-02 | Sumitomo Electric Industries, Ltd. | Nitrogen-containing sintered alloy containing a hard phase |
| EP1452621A2 (en) * | 2002-09-04 | 2004-09-01 | Seco Tools Ab | Composite structured wear resistant coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54101704A (en) * | 1978-01-27 | 1979-08-10 | Sumitomo Electric Ind Ltd | Sintered hard alloy and manufacture thereof |
-
1988
- 1988-05-13 JP JP63116351A patent/JP2511694B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54101704A (en) * | 1978-01-27 | 1979-08-10 | Sumitomo Electric Ind Ltd | Sintered hard alloy and manufacture thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995005497A1 (en) * | 1993-08-16 | 1995-02-23 | Sumitomo Electric Industries, Ltd. | Cemented carbide alloy for cutting tool and coated cemented carbide alloy |
| US5624766A (en) * | 1993-08-16 | 1997-04-29 | Sumitomo Electric Industries, Ltd. | Cemented carbide and coated cemented carbide for cutting tool |
| US6057046A (en) * | 1994-05-19 | 2000-05-02 | Sumitomo Electric Industries, Ltd. | Nitrogen-containing sintered alloy containing a hard phase |
| EP1452621A2 (en) * | 2002-09-04 | 2004-09-01 | Seco Tools Ab | Composite structured wear resistant coating |
| EP1452621A3 (en) * | 2002-09-04 | 2004-09-08 | Seco Tools Ab | Composite structured wear resistant coating |
| US7083868B2 (en) | 2002-09-04 | 2006-08-01 | Seco Tools Ab | Composite structured wear resistant coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2511694B2 (en) | 1996-07-03 |
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