JPH0288742A - Surface heat treated sintered alloy and production thereof and coated surface heat treated sintered alloy coating this alloy with hard film - Google Patents
Surface heat treated sintered alloy and production thereof and coated surface heat treated sintered alloy coating this alloy with hard filmInfo
- Publication number
- JPH0288742A JPH0288742A JP63241268A JP24126888A JPH0288742A JP H0288742 A JPH0288742 A JP H0288742A JP 63241268 A JP63241268 A JP 63241268A JP 24126888 A JP24126888 A JP 24126888A JP H0288742 A JPH0288742 A JP H0288742A
- Authority
- JP
- Japan
- Prior art keywords
- sintered alloy
- alloy
- binder phase
- treated
- temp
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 98
- 239000000956 alloy Substances 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011248 coating agent Substances 0.000 title description 5
- 238000000576 coating method Methods 0.000 title description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000010953 base metal Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 29
- 238000005520 cutting process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000005498 polishing Methods 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
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency 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
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005211 surface analysis Methods 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Ｔｉ
Ｃ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。このことがらＮ含有の゛［ｉＣ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、工具部材を低価
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 Ti whose basic composition is TiC-TiN-Ni
C-based sintered alloys tend to have better strength and plastic deformation resistance than N-free TiC-based sintered alloys whose basic composition is TiC-Ni. For this reason, N-containing iC-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, in order to reduce the cost of tool members, the surface of the sintered alloy is sometimes used without polishing or grinding, and in the state of the surface after sintering, that is, the so-called hardened surface state.
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いる場合に比べ
て欠損又はチッピングが生じゃずいという問題がある。When a N-containing TiC-based sintered alloy is used as a burnt surface, there is a problem that chipping or chipping is more likely to occur than when it is used as a polished or ground surface.
このよりな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
５４−１０１７０４号公報がある。A representative example of an attempt to solve the problem of the surface layer in a TiC-based sintered alloy containing more N is JP-A-54-101704.
（発明が解法しようとする問題点）
特開昭５４−１０１７０４号公報は、Ｎ及び／又はＯ含
有のＴｉＣ基焼結合金における焼結合金の表面から０．
００５〜０．２ｍｍまでの硬度が表面から１．Ｏｍｍの
硬度の１．０２（９以下にした焼結合金である。この特
開昭５４−１０１７０４号公報は、焼結合金の全焼結過
程のうち冷却過程のＣｏガス分圧を胃温および焼結過程
のＣｏガス分圧より高くし、表面部における酸素量を内
部における酸素量より多くすることにより、金属結合相
の浸み出しを抑え、表面部と内部における硬さを均一に
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、焼結合金中の酸素の濃度勾配を利用するため、酸
素を必須成分としなければならないこと及びそのために
強度及び耐欠損性に対して未だ不充分であるという問題
がある。(Problems to be Solved by the Invention) JP-A-54-101704 discloses that in a TiC-based sintered alloy containing N and/or O, 0.0% from the surface of the sintered alloy.
The hardness from the surface to 0.005 to 0.2 mm is 1. This is a sintered alloy with a hardness of 1.02 (9 or less) of 0 mm.This Japanese Patent Application Laid-open No. 54-101704 describes the Co gas partial pressure in the cooling process of the entire sintering process of the sintered alloy, based on the gastric temperature and sintering temperature. By increasing the partial pressure of Co gas during the solidification process and making the amount of oxygen at the surface greater than the amount of oxygen inside, the seepage of the metal bonding phase is suppressed, and the hardness at the surface and inside is made uniform. Although this solution solved the problem of hard embrittlement on the surface, oxygen must be an essential component in order to utilize the oxygen concentration gradient in the sintered alloy, and as a result, there are still problems with strength and fracture resistance. There is a question of sufficiency.
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ＴｉＣ基焼結合金の表面部と内部におけ
る結合相の平均含有量を、特開昭５４１０１７０４号公
報による方法とは、全く異なる方法により均一にするこ
と、表面部と内部における硬さを均一にすることまたは
、表面部と内部における結合相の含有量と硬さの両方を
均一・にすることにより、強度及び耐欠損性にすぐれた
焼肌面を有するＮ含有のＴｉＣ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 average content of the binder phase in the surface and inside of the N-containing TiC-based sintered alloy is determined by the method described in Japanese Patent Application Laid-Open No. 54101704. By making the hardness uniform on the surface and inside, or by making both the content and hardness of the binder phase uniform on the surface and inside, the strength can be improved by using a completely different method. The object of the present invention is to provide an N-containing TiC-based sintered alloy having a hardened surface with excellent fracture resistance, a method for producing the same, and a coated surface tempered alloy obtained by coating the sintered alloy with a hard film. be.
（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ＴｉＣ基焼結合金
に比べて強度及び耐欠損性に劣るという原因を検討して
いた所、特開昭５４−１０１７０４号公報に記載されて
いるように、確かに表面に結合相が浸み出しその直下に
内部よりも硬質な層が存在するが、その硬質相の厚さは
０．５ｍｍ前後にも及ぶのに対し、結合相の浸み出しに
よる結合相富化層は高々ＩＯμｍ程度であることを見出
した、ずなわち表面部の硬質相の生成は、結合相の浸み
出しが主因ではなく、昇温及び焼結過程における脱窒素
現象が主因であり、この知見に基いて焼結合金の表面部
と内部の結合相量を均一にすることまたは表面部と内部
の硬さを均一にすることにより焼結合金の強度及び耐欠
損性が向上すること、また焼結合金の表面部と内部の結
合相量の均一化と共に硬さを均一化すると、更に強度及
び耐欠損性が向上するという知見を得た。この知見に基
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 discovered that an N-containing TiC-based sintered alloy having a hardened surface has a higher strength than an N-containing TiC-based sintered alloy having a polished surface or a ground surface. While investigating the cause of the poor fracture resistance, we discovered that, as described in JP-A No. 54-101704, a binder phase had oozed out onto the surface and a layer harder than the inside was directly below it. However, it was found that the hard phase has a thickness of around 0.5 mm, whereas the binder phase-enriched layer due to binder phase leaching is at most about IO μm. The main cause of the formation of a hard phase is not the leaching of the binder phase, but the denitrification phenomenon during the heating and sintering process.Based on this knowledge, the amount of binder phase on the surface and inside of the sintered alloy is The strength and fracture resistance of the sintered alloy can be improved by making the surface and internal hardness uniform, and by making the amount of binder phase uniform on the surface and internal of the sintered alloy. It was found that uniform hardness further improves strength and fracture 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有し、他にＺｒ、
ｌｌｆ、 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０．０５ｍｍ内部ま
での表面層における結合相の平均含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 also contains Zr,
llf, 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 content of the binder phase in the surface layer is 0.7 to 1.2 times the average content of the binder phase inside the sintered alloy.
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ＴｉＣ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
どすべてが対象になり得るものであるが酸素は必須成分
とはしない。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ＴｉＣ，ＴｉＮ、 Ｔｉ（Ｃ，Ｎｌ
、 （Ｔｉ、Ｍ）Ｃ，（Ｔｉ、ＭＡＮ。The sintered alloy in the surface-treated sintered alloy of the present invention is applicable to all the component compositions of conventional N-containing TiC-based sintered alloys, such as the component composition described in the above-mentioned JP-A-54-101704. However, oxygen is not an essential component. The hard phase that makes up the self-burning alloy is
Specifically, for example, TiC, TiN, Ti(C,Nl
, (Ti,M)C, (Ti,MAN.
（Ｔｉ、Ｍｌ （ＣＮ） （但し、Ｍは Ｚｒ、 Ｈ
ｆ、 Ｖ、 Ｎｂ、 Ｔａ。(Ti, Ml (CN) (However, M is Zr, H
f, V, Nb, Ta.
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、Ｃｏ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、
Ａｌ１． Ｍｎなどの含有したものである。At least one of Cr, Mo, and W is shown. ), and the other binder phase constituting the sintered alloy contains at least 50% by volume of Co and/or Ni, and in addition, for example, hard Metal elements and Fe in the compound forming the phase,
Al1. 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付着物を取り除いた
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 the surface condition is a surface condition in which deposits on the burnt surface are removed 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内部までの表面層における結合相の平均含有
量を内部における結合相の平均含有量に近づけたもので
、このことにより焼結合金の強度及び耐欠損性を向上さ
せたものである。この表面層と内部における結合相の含
有量の他に、さらに表面層における平均硬さを内部にお
ける平均硬さの０．９５〜１．１０倍に制御することに
よって一層焼結合金の強度及び耐欠損性を向上させるこ
とができる。The surface-treated sintered alloy of the present invention has a temperature of 0.
．． The average content of the binder phase in the surface layer up to the inside of 0.05 mm is made close to the average content of the binder phase in the interior, thereby improving the strength and fracture resistance of the sintered alloy. In addition to the binder phase content in the surface layer and the interior, the strength and durability of the sintered alloy can be further improved by controlling the average hardness in the surface layer to 0.95 to 1.10 times the average hardness in the interior. Deficiency can be improved.
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、Ｃｏ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ＴｉとＣとＮとを必須成分
とし、他にＺｒ、 Ｈｆ、 Ｖ、 Ｎｂ、 Ｔａ。The method for producing the surface-tempered sintered alloy of the present invention is based on periodic table 4a
, 5a, 6a group metal carbides, nitrides, and mutual solid solutions thereof; and Co and/or powder.
Alternatively, using a mixed powder consisting of a powder mainly composed of Ni, using a conventional powder metallurgy method, Ti, C, and N are essential components, and Zr, Hf, V, Nb, and Ta are also added.
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、粉末冶金法での各製
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
領域における窒素圧力を高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 temperature range below 0°C, use a vacuum or inert gas atmosphere, and in the second temperature range above 1300°C,
A nitrogen gas atmosphere of 20 torr is used, and the nitrogen pressure in the second temperature range is increased as the temperature increases.
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有炭素量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
の結合相の含有量及び硬さの調整が可能となる。また前
述のように１表面部硬質相の生成は昇温及び焼結過程に
おける脱Ｎ現象に起因しているので、焼結合金を脱Ｎし
難い低炭素合金とすることも有効である。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 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 content of the binder phase in the surface layer of the sintered alloy can be increased. Hardness can be adjusted. Furthermore, as mentioned above, the formation of a hard phase on one surface is caused by the de-N phenomenon during the temperature rise and sintering process, so it is also effective to make the sintered alloy a low-carbon alloy that is difficult to de-N.
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（ＰＶＤ法
）や化学蒸着法ｔＣＶＤ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互固溶体並びに窒
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、立方晶窒化ホウ素、ダイ
ヤモンドの中の少なくとも１種の単層又は多重層でなる
硬質膜を被覆することによ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。特に、被覆表面調質焼結
合金は、前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後、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。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０．１〜ｌＯμｍ厚さが
実用的で好ましいものである。The surface of the surface-tempered sintered alloy obtained in this way is coated with, for example, conventional physical vapor deposition (PVD) or chemical vapor deposition (CVD). Hard films with high hardness, specifically, carbides, nitrides, carbonates, nitrides of metals in groups 4a, 5a, and 6a of the periodic table, and their mutual solid solutions, as well as silicon nitride, silicon carbide, and oxides. It is also preferable to form a coated surface-tempered sintered alloy by coating with a hard film consisting of a single layer or multiple layers of at least one of aluminum, aluminum nitride, aluminum oxynitride, cubic boron nitride, and diamond. be. In particular, after sintering of the coated surface-tempered sintered alloy is completed in the second temperature range in the method for manufacturing the surface-tempered sintered alloy described above, the coated surface-tempered sintered alloy is further held for a certain period of time in an atmosphere of high nitrogen pressure to form a nitride film. It is preferable to obtain a hard film formed on the surface of a surface-treated sintered alloy because the process can be simplified and there is no need to add additional equipment. 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 0.1 to 10 μm for the human body 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結合相の平均含有量を従来の
焼結合金に比べて多くしたことにより、焼結合金の強度
及び耐欠損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 increasing the average content of the binder phase in the surface layer up to the interior compared to conventional sintered alloys, it has the effect of increasing the strength and fracture resistance of the sintered alloy.
また、本発明の表面調質焼結合金の製造方法は、焼結」
−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
界に従って窒素圧力を漸増することにより、硬質相の粒
成長抑制と共に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。Furthermore, the method for producing the surface-treated sintered alloy of the present invention includes sintering.
- By switching from the atmosphere in the first temperature range to the atmosphere in the second temperature range in the process and gradually increasing the nitrogen pressure according to the upper temperature limit in the second temperature range, grain growth of the hard phase is suppressed and sintered bonding is achieved. This has the effect of suppressing denitrification in the gold surface layer.
実施例１ 平均粒度１〜２μｍ内にある市販のＴｉＣ。Example 1 Commercially available TiC with average particle size within 1-2 μm.
ＴｉＮ、 ＭＯ２Ｃ，Ｎｉの各粉末を用いて４０ｗＬ％
ＴｉＣ−３０ｗＬ％ＴｉＮ −１５ｗｔ％Ｍｏ、Ｃ−１
５ｗＬ％Ｎｉ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、Ｓ
ＮＭＮＩ２０４０８（ＪＩＳ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１２００℃〜１４５０℃までを第１表に示す雰囲気中
、３℃／ｍｉｎで昇温し、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。40wL% using each powder of TiN, MO2C, and Ni
TiC-30wL%TiN-15wt%Mo, C-1
This blended powder, acetone, and balls were placed in a mixing container and subjected to wet mixing and pulverization for 72 hours. After adding a small amount of paraffin to the mixed powder thus obtained, S
Press molding was performed to obtain NMNI20408 (shape according to JIS standard). After heating and removing paraffin from the compacted powder obtained by this press molding, the temperature was raised from room temperature to 1200°C in 4 hours in a vacuum of 0.05 Lorr, and then the temperature was increased from 1200°C to 1450°C in the atmosphere shown in Table 1. During the process, the temperature was raised at 3° C./min, and the temperature was further held at 1450° C. for 1 hour for sintering. 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.
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ライザ（ＥＩ’ＭＡ）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).
The results are shown in Table 2.
第 ２ 表
なお、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２［１１ｔＶ。In Table 2, the amount of binder phase is calculated by polishing the sintered alloy to an angle of 10°.
This polished surface was accelerated using EPMA at an acceleration voltage of 2 [11 tV.
２ＱＸ ３０μｍ２の面分析条件で５点の平均値により
求めたものである。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。It was determined from the average value of 5 points under the surface analysis conditions of 2QX 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［Ａ）及び＋８）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, cutting tests were conducted using the products 1 to 4 of the present invention and comparative products 1 to 4 under the conditions [A) and +8) below, and the results are shown in Table 3.
ｔＡ） 耐摩耗性切削条件
被削材 ５４８Ｃ（Ｈ，２５０） ２５０ ｍｍφ
チップ形状 ＳＮＭＮ４３２
（０，ｌＸ−３０度直線ホーニング）
切削速度 １６０ｍ／ｍｉｎ
切込みｆｉｌ １．５ｍｍ
送り量０．３ ｍｍ／ｒｅｖ
切削時間 ２０ ｍ１ｎ
（Ｂ） 耐欠損性切削条件
被削材 ３４８Ｃ（ＩＩ８２３０） １２０ｍｍ
φチップ形状
切削速度
切込み量
送り量
評 価
４本スロットと付
ＳＮＭＮ４３２
（０，ｌＸ−３０度直線ホーニング）
１００ ｍ／ｍ１ｎ
１．５ｍｍ
０．３ ｍｍ／ｒｅｖ
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ＴｉＣ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。tA) Wear-resistant cutting conditions Work material 548C (H, 250) 250 mmφ
Chip shape SNMN432 (0,lX-30 degree linear honing) Cutting speed 160m/min Depth of cut fil 1.5mm Feed rate 0.3 mm/rev Cutting time 20 m1n (B) Fracture resistant cutting conditions Work material 348C (II8230) 120mm
φChip shape Cutting speed Depth of cut Feed amount Evaluation With 4 slots SNMN432 (0,l Margin below evaluation based on percentage of defects within 10 minutes (Effect of the invention) The surface-treated sintered alloy of the present invention has almost the same wear resistance as the conventional N-containing TiC-based sintered alloy. Because it has excellent strength, it is about 2 to 3 times more effective in terms of fracture 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. Based on these facts, the sintered alloy of the present invention is superior to the conventional N
An industrially useful material that has a wide range of uses, from the TiC-based sintered alloy containing it to those that require impact resistance and fracture resistance, and is highly stable, and its manufacturing method. It is.
特許出願人 東芝タンガロイ株式会社Patent applicant: Toshiba Tungaloy Corporation
Claims (7)
含有し、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〜
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結合相の平均含有量が焼結合金の
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表面調質焼結合金。(1) Contains Ti, C (carbon), and N (nitrogen) as essential components, and also contains Zr, Hf, V, Nb, Ta, Cr, Mo
, a hard phase 75 containing at least one of W
In a sintered alloy having a burnt surface consisting of 95% by weight, a binder phase mainly composed of Co and/or Ni, and unavoidable impurities, the surface of the sintered alloy up to 0.05 mm inside from the burnt surface of the sintered alloy. A surface-treated sintered alloy characterized in that the average content of the binder phase in the layer is 0.7 to 1.2 times the average content of the binder phase inside the sintered alloy.
焼結合金の表面に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。(2) A hard film having higher hardness than the surface-treated sintered alloy is provided on the surface of the surface-treated sintered alloy according to claim 1 of the claims. A coated surface tempered sintered alloy characterized by being coated.
含有し、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〜
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平均硬さが焼結合金の内部におけ
る平均硬さの０．９５〜１．１０倍であることを特徴と
する表面調質焼結合金。(3) Contains Ti, C (carbon) and N (nitrogen) as essential components, and also contains Zr, Hf, V, Nb, Ta, Cr, Mo
, a hard phase 75 containing at least one of W
In a sintered alloy having a burnt surface consisting of 95% by weight, a binder phase mainly composed of Co and/or Ni, and unavoidable impurities, the surface of the sintered alloy up to 0.05 mm inside from the burnt surface of the sintered alloy. A surface-treated sintered alloy characterized in that the average hardness in the layer is 0.95 to 1.10 times the average hardness in the interior of the sintered alloy.
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。(4) The surface of the surface-treated sintered alloy according to claim 3 is coated with a hard film having a higher hardness than the surface-treated sintered alloy. Coated surface tempered sintered alloy.
含有し、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〜
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結合相の平均含有量が焼結合金の
内部における結合相の平均含有量の０．７〜１．２倍で
あり、かつ該表面層における平均硬さが焼結合金の内部
における平均硬さの０．９５〜１．１０倍であることを
特徴とする表面調質焼結合金。(5) Contains Ti, C (carbon), and N (nitrogen) as essential components, and also contains Zr, Hf, V, Nb, Ta, Cr, Mo
, a hard phase containing at least one type of W 75~
In a sintered alloy having a burnt surface consisting of 95% by weight, a binder phase mainly composed of Co and/or Ni, and unavoidable impurities, the surface of the sintered alloy up to 0.05 mm inside from the burnt surface of the sintered alloy. The average content of the binder phase in the layer is 0.7 to 1.2 times the average content of the binder phase inside the sintered alloy, and the average hardness in the surface layer is higher than the average hardness inside the sintered alloy. A surface-treated sintered alloy characterized by having a diameter of 0.95 to 1.10 times.
焼結合金の表面に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。(6) A hard film having higher hardness than the surface-treated sintered alloy is provided on the surface of the surface-treated sintered alloy according to claim 5 of the claims. A coated surface tempered sintered alloy characterized by being coated.
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。(7) 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 into 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.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63241268A JP2814452B2 (en) | 1988-09-27 | 1988-09-27 | Surface-finished sintered alloy, method for producing the same, and coated surface-finished 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 |
| 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 |
| 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. |
| 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 |
|---|---|---|---|
| JP63241268A JP2814452B2 (en) | 1988-09-27 | 1988-09-27 | Surface-finished sintered alloy, method for producing the same, and coated surface-finished sintered alloy obtained by coating the alloy with a hard film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0288742A true JPH0288742A (en) | 1990-03-28 |
| JP2814452B2 JP2814452B2 (en) | 1998-10-22 |
Family
ID=17071729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63241268A Expired - Lifetime JP2814452B2 (en) | 1988-05-13 | 1988-09-27 | Surface-finished sintered alloy, method for producing the same, and coated surface-finished sintered alloy obtained by coating the alloy with a hard film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2814452B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6057046A (en) * | 1994-05-19 | 2000-05-02 | Sumitomo Electric Industries, Ltd. | Nitrogen-containing sintered alloy containing a hard phase |
| CN109648077A (en) * | 2019-01-28 | 2019-04-19 | 自贡兆强密封制品实业有限公司 | It is a kind of to use (Ti, Cr, Nb) (Cx,N1-x) solid solution production cermet and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6034618A (en) * | 1979-01-12 | 1985-02-22 | アクゾ・エヌ・ヴエー | Silicate fiber, production thereof and friction lining containing said fiber |
-
1988
- 1988-09-27 JP JP63241268A patent/JP2814452B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6034618A (en) * | 1979-01-12 | 1985-02-22 | アクゾ・エヌ・ヴエー | Silicate fiber, production thereof and friction lining containing said fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6057046A (en) * | 1994-05-19 | 2000-05-02 | Sumitomo Electric Industries, Ltd. | Nitrogen-containing sintered alloy containing a hard phase |
| CN109648077A (en) * | 2019-01-28 | 2019-04-19 | 自贡兆强密封制品实业有限公司 | It is a kind of to use (Ti, Cr, Nb) (Cx,N1-x) solid solution production cermet and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2814452B2 (en) | 1998-10-22 |
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