JPH0368738A - Hard sintered alloy - Google Patents
Hard sintered alloyInfo
- Publication number
- JPH0368738A JPH0368738A JP1204264A JP20426489A JPH0368738A JP H0368738 A JPH0368738 A JP H0368738A JP 1204264 A JP1204264 A JP 1204264A JP 20426489 A JP20426489 A JP 20426489A JP H0368738 A JPH0368738 A JP H0368738A
- Authority
- JP
- Japan
- Prior art keywords
- sintered alloy
- hard
- sintering
- rare earth
- hard sintered
- 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.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims description 6
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 abstract 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 abstract 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- -1 iron group metals Chemical class 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の利用分野）
本発明は、低温での焼成が可能で、高い強度を有する硬
質焼結合金に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a hard sintered alloy that can be fired at low temperatures and has high strength.
（従来技術）
炭化チタン（ＴｉＣ） 、炭窒化チタン（ＴｉＣＮ）、
窒化チタン（ＴｆＮ）等のＴｉ化合物を主成分とする硬
質焼結合金は、硬度、抗折強度等の機械的特性に優れる
ことから、工具をはじめとする産業機械用部品として、
また、一方では、ＴｉＮは金色、ＴｉＣは銀色の色調を
呈することから、装飾用材料として広い分野で汎用され
ている。(Prior art) Titanium carbide (TiC), titanium carbonitride (TiCN),
Hard sintered alloys mainly composed of Ti compounds such as titanium nitride (TfN) have excellent mechanical properties such as hardness and bending strength, so they are used as parts for industrial machinery such as tools.
On the other hand, since TiN has a golden color and TiC has a silver color, they are widely used as decorative materials in a wide range of fields.
一般に、上記硬質焼結合金は、単体では難焼結性であり
、ホットプレス法等の手法によっても理論密度の９０乃
至９５％の密度しか得られず、焼結温度も１８００乃至
２２００″Ｃと非常に高い温度に設定する必要があり、
焼成炉等の設備が大がかりとなり、コスト的にも実用的
ではない。In general, the above-mentioned hard sintered alloys are difficult to sinter when used alone, and even with methods such as hot pressing, a density of only 90 to 95% of the theoretical density can be obtained, and the sintering temperature is 1800 to 2200''C. Must be set to a very high temperature,
Equipment such as a kiln is large-scale, and it is not practical in terms of cost.
そこで、従来よりこれらの主成分に対し、Ｆｅ、Ｃｏ、
Ｎｉ等の鉄族金属を低融点物質として添加し、さらに
はＷＣ，Ｍｏ□Ｃ等の第６８族炭化物をぬれ性改善の目
的で添加することにより、焼結性を改善しようとする試
みがなされている。Therefore, conventionally, for these main components, Fe, Co,
Attempts have been made to improve sinterability by adding iron group metals such as Ni as low melting point substances and further adding group 68 carbides such as WC and Mo□C for the purpose of improving wettability. ing.
（発明が解決しようとする問題点）
ところが、上記のように鉄族金属を添加することにより
、焼結性は改善され、強度も上昇するという効果はある
ものの、逆に硬度が低下するという欠点を有しており、
さらには焼結合金の金属部分で腐食が進行し易いため、
酸性や塩基性雰囲気での使用が出来ず１１例えば装飾用
材料として用いた場合には汗等により表面に変色が生じ
るという欠点を有していた。(Problems to be Solved by the Invention) However, although the addition of iron group metals as described above has the effect of improving sinterability and increasing strength, it has the disadvantage of decreasing hardness. It has
Furthermore, since corrosion easily progresses in the metal parts of the sintered alloy,
It cannot be used in acidic or basic atmospheres11, and when used, for example, as a decorative material, it has the disadvantage that the surface discolors due to sweat and the like.
よって、本発明の目的は、鉄族金属を添加せずとも低温
焼成が可能であり、且つ硬度を低下させることなく、強
度を向上し得る硬質焼結合金を提供するにある。Therefore, an object of the present invention is to provide a hard sintered alloy that can be fired at low temperatures without adding iron group metals and that can improve strength without reducing hardness.
（問題点を解決するための手段）
本発明者等は、上記問題点に対し研究を重ねた結果、Ｔ
ｉｃ 、 ＴｉＣＮ５ＴｉＮの焼結に際し、Ｙ２Ｏ３あ
るいは希土類元素酸化物を適量添加することによって、
上記目的が達成されることを知見した。(Means for Solving the Problems) As a result of repeated research into the above problems, the inventors found that T.
ic, by adding an appropriate amount of Y2O3 or rare earth element oxide during sintering of TiCN5TiN,
It has been found that the above objectives are achieved.
即ち、本発明は、Ｔｉｃ 、 Ｔ１ＣＮ、 ＴｉＮから
選ばれる少なくとも１種を主成分とする硬質焼結合金に
おいて、Ｔ２０．あるいは希土類元素酸化物から選ばれ
る少なくとも１種を０．０５乃至２０重量％の割合で含
有することを特徴とするものであり、それにより、鉄族
金属を用いたのと同等に低温焼成が可能となるとともに
焼結合金の硬度を低下させることなく、強度の向上を図
ることができる。That is, the present invention provides a hard sintered alloy whose main component is at least one selected from Tic, T1CN, and TiN. Alternatively, it is characterized by containing at least one selected from rare earth element oxides in a proportion of 0.05 to 20% by weight, which allows for low-temperature firing equivalent to that using iron group metals. At the same time, it is possible to improve the strength of the sintered alloy without reducing its hardness.
以下、本発明を詳述する。The present invention will be explained in detail below.
本発明の対象となる焼結合金はＴｉＣ，Ｔ１ＣＮ、 Ｔ
ｉＮのチタン化合物から少なくとも１種を主成分とする
もので、具体的にはこれらが焼結合金中に７０重量％以
上存在するもので、上記のチタン化合物は炭素あるいは
窒素の一部が酸素で置換される場合もある。The sintered alloys targeted by the present invention include TiC, T1CN, and T
The main component is at least one type of iN titanium compound, specifically, it is present in the sintered alloy in an amount of 70% by weight or more. May be replaced.
また、Ｔ１ＣＮでは炭素と窒素の比率がＯ：１００〜１
００：０の任意の値のものでよい。In addition, in T1CN, the ratio of carbon to nitrogen is O:100~1
Any value between 00:0 may be used.
本発明によれば、上記主成分に対し、Ｔ２０．あるいは
Ｃｅ、０．、Ｎｄｚ０３ 、ＳｍｚＯ＝ 、Ｙｂｚ（］
＋ 、ＤｙｚＯ＝等の希土類元素酸化物を添加すること
を特徴とするもので、この添加量が０．０５重量％未満
では、所望の焼結性改善効果が得られず、２０重量％を
越えると、逆に焼結不良となることから、全量中０．０
５乃至２０重量％、特に１乃至１０重量％の割合で配合
することが望ましい。According to the present invention, T20. Or Ce, 0. , Ndz03 , SmzO= , Ybz(]
It is characterized by the addition of rare earth element oxides such as On the other hand, 0.0% of the total amount will result in poor sintering.
It is desirable that the amount is 5 to 20% by weight, particularly 1 to 10% by weight.
本発明の硬質焼結合金の製造に際しては、ＴｉＣ１Ｔｉ
ＣＮＳＴｉＮのＴｉ化合物に対して適量のＹ２Ｏ３ある
いは希土類元素酸化物を添加混合して、公知の成形手段
で底形を行う。When producing the hard sintered alloy of the present invention, TiC1Ti
An appropriate amount of Y2O3 or rare earth element oxide is added to and mixed with the Ti compound of CNSTiN, and a bottom shape is formed using a known molding method.
次に、得られた成形棒を真空焼成の他、ホットプレス、
真空ホットプレスあるいは熱間静水圧焼成法等の焼成方
法によって焼成する。この時の焼成温度は、従来ＴｉＣ
、ＴｌＣＮ％ ＴｔＮの単味での焼成温度が１８００〜
２２００°Ｃであったのに対し、本発明に従いＹｔＯｉ
あるいは希土類元素酸化物を適量添加することにより１
４００〜１８００″Ｃの低温での焼成が可能となる。Next, the obtained formed rod is vacuum fired, hot pressed,
Firing is performed by a firing method such as vacuum hot pressing or hot isostatic pressing. The firing temperature at this time was
, TlCN% The firing temperature for TtN alone is 1800~
2200°C, whereas YtOi according to the present invention
Alternatively, by adding an appropriate amount of rare earth element oxide,
Firing at a low temperature of 400 to 1800''C is possible.
本発明の硬質焼結合金はＴｉｃ 、 Ｔ１ＣＮ、 Ｔｉ
Ｎから選ばれる少なくとも１種とＴ２０．あるいは希土
類元素酸化物の少なくとも１種を必須の要件とするもの
であるが、本発明によれば、前述した効果を維持し得る
範囲内で他の金属化合物を添加することも可能である。The hard sintered alloy of the present invention is Tic, T1CN, Ti
At least one type selected from N and T20. Alternatively, at least one rare earth element oxide is an essential requirement, but according to the present invention, it is also possible to add other metal compounds within a range that can maintain the above-mentioned effects.
具体的には、第１Ｖａ族（Ｚｒ、Ｈｆ）、第Ｖａ族（Ｖ
、Ｎｂ、Ｔａ） 、第ＶＩａ族（Ｃｒ、Ｍｏ、Ｗ）等の
炭化物、窒化物、酸化物を添加することも可能である。Specifically, the first Va group (Zr, Hf), the Va group (V
, Nb, Ta), group VIa (Cr, Mo, W), etc., carbides, nitrides, and oxides can also be added.
以下、本発明を次の例で説明する。The invention will now be explained with the following examples.
（実施例）
平均粒径がおよそ１μ重のＴｔＣ，Ｔ１ＣＮ、ＴｉＮの
各粉末に対し、第１表に示す通りの比率でＴ２０．ある
いは希土類元素酸化物を添加し、樹脂ポットに入れ、ジ
ルコニアボールを用いアセトンとともに４２時間混合粉
砕した。次いでこの混合物を乾燥後、パラフィンを４重
量％加え、１．５ｔｏｎ／ ｃｉで加圧成形し、脱バイ
ンダ後、１６００〜１８００°Ｃ，１０−’ｔｏｒｒの
真空中で１〜５時間焼戒を行った。(Example) T20. Alternatively, a rare earth element oxide was added, placed in a resin pot, and mixed and pulverized for 42 hours with acetone using zirconia balls. Next, after drying this mixture, 4% by weight of paraffin was added, pressure molded at 1.5 ton/ci, and after removing the binder, it was burned in a vacuum of 1600-1800°C and 10-'torr for 1-5 hours. went.
かくして得られた焼成合金の抗折強度、ビッカース硬度
および耐食性試験を実施した。抗折強度はＪＩＳＲ１６
０１に従い３点曲げ法により、耐食性試験については人
工汗および塩水噴霧試験（ＪＩＳＺ２３７１−７６）を
行い、変色が認められたものに○、変色がなかったもの
に×を付した。The sintered alloy thus obtained was tested for flexural strength, Vickers hardness, and corrosion resistance. The bending strength is JISR16
Regarding the corrosion resistance test, artificial sweat and salt water spray tests (JIS Z2371-76) were conducted according to the 3-point bending method according to JIS 01, and those with discoloration were marked with ○, and those with no discoloration were marked with x.
結果は第１表に示す。The results are shown in Table 1.
（以下余白）
第１表の結果によれば、Ｔｉｃ、ＴｉＮ、の単味の焼成
を行ったｋｌ、２では、いずれも焼成温度は２０００〜
２２００°Ｃと高くする必要があり、特性面では硬度は
高いが抗折強度が低いという問題がある。(Margins below) According to the results in Table 1, in kl, 2, where Tic and TiN were fired, the firing temperature was between 2000 and 2000.
It is necessary to raise the temperature to 2200°C, and there is a problem in that the hardness is high but the bending strength is low.
一方、従来のサーメットの技術に従い、Ｎｉ金属を添加
したＮＱ、ｉｌ、１２では焼成温度が低く、抗折強度も
高いが、金属添加による硬度低下が阻１，２と比較して
も顕著であり、耐食性においても変色が観察された。On the other hand, NQ, IL, and 12, in which Ni metal is added according to conventional cermet technology, have a low firing temperature and high bending strength, but the decrease in hardness due to metal addition is significant compared to cermets 1 and 2. , Discoloration was also observed in corrosion resistance.
これに対し、Ｙ２Ｏ，あるいは希土類元素酸化物を添加
した試料のうちＮα３〜９ではいずれも焼成温度を単体
時と比較して２００〜４００°Ｃ低下させるこたができ
るとともに、特性上も１８００ｋｇ／ｍｍ”以上のビッ
カース硬度を維持しながらも６５ｋｇ／ｍｍ”以上に抗
折強度を向上することができた。しかも耐食性において
も何ら変色は見られなかった。On the other hand, among the samples to which Y2O or rare earth element oxides have been added, for Nα3 to 9, the firing temperature can be lowered by 200 to 400°C compared to when the element is alone, and in terms of characteristics, the firing temperature is 1800 kg/ It was possible to improve the bending strength to 65 kg/mm" or more while maintaining a Vickers hardness of 65 kg/mm" or more. Furthermore, no discoloration was observed in terms of corrosion resistance.
しかし、希土類元素酸化物の添加量が２０重量％を越え
るＮα１０では、抗折強度の改善効果は得られずビッカ
ース硬度は低下した。However, in Nα10 in which the amount of rare earth element oxide added exceeds 20% by weight, the effect of improving the bending strength was not obtained and the Vickers hardness decreased.
（発明の効果）
以上詳述した通り、本発明の硬質焼結合金は従来から用
いられていた鉄族金属を用いることなく低温焼成が可能
となるとともに、ＴｉＣ，ＴｔＣＮ、ＴｉＮの有する高
強度、耐食性を維持しつつ強度を向上させることができ
る。それにより、Ｔｉ化合物系焼結体の産業機械的用材
料としてその利用分野を、酷第でき、特に装飾用として
優れた耐環境性を発揮することができる。(Effects of the Invention) As detailed above, the hard sintered alloy of the present invention can be fired at low temperatures without using conventionally used iron group metals, and also has the high strength of TiC, TtCN, and TiN. Strength can be improved while maintaining corrosion resistance. As a result, the field of use of the Ti compound-based sintered body as an industrial and mechanical material can be expanded, and it can exhibit excellent environmental resistance particularly for decorative purposes.
Claims (1)
ずれかを主成分とする硬質合金において、Ｙ＿２Ｏ＿３
あるいは希土類元素酸化物から選ばれる少なくとも１種
を０．０５乃至２０重量％の割合で含有することを特徴
とする硬質焼結合金。In a hard alloy containing at least one of titanium carbide, titanium carbonitride, and titanium nitride as a main component, Y_2O_3
Alternatively, a hard sintered alloy containing at least one selected from rare earth element oxides in a proportion of 0.05 to 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1204264A JPH0368738A (en) | 1989-08-07 | 1989-08-07 | Hard sintered alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1204264A JPH0368738A (en) | 1989-08-07 | 1989-08-07 | Hard sintered alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0368738A true JPH0368738A (en) | 1991-03-25 |
Family
ID=16487587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1204264A Pending JPH0368738A (en) | 1989-08-07 | 1989-08-07 | Hard sintered alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0368738A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014112314A1 (en) * | 2013-01-16 | 2014-07-24 | 並木精密宝石株式会社 | Decorative member |
| CN110527857A (en) * | 2019-09-27 | 2019-12-03 | 广西科技大学 | A kind of sintering titanium alloy and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59215457A (en) * | 1983-05-19 | 1984-12-05 | Sumitomo Electric Ind Ltd | Sintered hard alloy |
| JPS61272344A (en) * | 1985-05-28 | 1986-12-02 | Sumitomo Electric Ind Ltd | Sintered hard alloy |
-
1989
- 1989-08-07 JP JP1204264A patent/JPH0368738A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59215457A (en) * | 1983-05-19 | 1984-12-05 | Sumitomo Electric Ind Ltd | Sintered hard alloy |
| JPS61272344A (en) * | 1985-05-28 | 1986-12-02 | Sumitomo Electric Ind Ltd | Sintered hard alloy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014112314A1 (en) * | 2013-01-16 | 2014-07-24 | 並木精密宝石株式会社 | Decorative member |
| JPWO2014112314A1 (en) * | 2013-01-16 | 2017-01-19 | 並木精密宝石株式会社 | Decorative material |
| CN110527857A (en) * | 2019-09-27 | 2019-12-03 | 广西科技大学 | A kind of sintering titanium alloy and preparation method thereof |
| CN110527857B (en) * | 2019-09-27 | 2020-12-22 | 广西科技大学 | Sintered titanium alloy and preparation method thereof |
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