JPH0892674A - Decorative titanium alloy and its ornaments - Google Patents

Decorative titanium alloy and its ornaments

Info

Publication number
JPH0892674A
JPH0892674A JP22678394A JP22678394A JPH0892674A JP H0892674 A JPH0892674 A JP H0892674A JP 22678394 A JP22678394 A JP 22678394A JP 22678394 A JP22678394 A JP 22678394A JP H0892674 A JPH0892674 A JP H0892674A
Authority
JP
Japan
Prior art keywords
powder
titanium
hardness
decorative
titanium alloy
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
Application number
JP22678394A
Other languages
Japanese (ja)
Other versions
JP3471092B2 (en
Inventor
Kazuhiro Nakayashiki
和博 中屋敷
Setsuo Shoji
節夫 東海林
Yutaka Wakabayashi
豊 若林
Teruya Shishido
晃哉 宍戸
Tetsuya Kondo
鉄也 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daido Steel Co Ltd
Seiko Instruments Inc
Original Assignee
Daido Steel Co Ltd
Seiko Instruments Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daido Steel Co Ltd, Seiko Instruments Inc filed Critical Daido Steel Co Ltd
Priority to JP22678394A priority Critical patent/JP3471092B2/en
Publication of JPH0892674A publication Critical patent/JPH0892674A/en
Application granted granted Critical
Publication of JP3471092B2 publication Critical patent/JP3471092B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Adornments (AREA)
  • Powder Metallurgy (AREA)

Abstract

(57)【要約】 【目的】 粉末冶金方式による装飾用チタン及びチタン
合金の製造において、鏡面性と硬度が得られるようにす
る。 【構成】 チタン粉末に鉄,モリブデンを複合添加し、
圧粉成形後に焼結して装飾用チタン及びチタン合金を得
る。
(57) [Summary] [Purpose] To obtain specularity and hardness in the production of decorative titanium and titanium alloys by powder metallurgy. [Composition] Iron powder and molybdenum are added to titanium powder,
After compacting, it is sintered to obtain decorative titanium and titanium alloy.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】この発明は、チタン合金を用いた
装飾品、特に腕時計外装部品に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative article using a titanium alloy, and more particularly to a wristwatch exterior part.

【0002】[0002]

【従来の技術】従来、装飾品、特に腕時計外装部品例え
ば、ベゼル、ケースの材料のほとんどに耐食性と鏡面性
の面からステンレス鋼が使用されている。近年、純チタ
ンがその耐食性及びニッケルによる皮膚アレルギー対応
の材料として用いられている。
2. Description of the Related Art Conventionally, stainless steel has been used for most of decorative materials, particularly wristwatch exterior parts such as bezels and cases, from the viewpoint of corrosion resistance and specularity. In recent years, pure titanium has been used as a material for its corrosion resistance and nickel-induced skin allergy.

【0003】[0003]

【発明が解決しようとする課題】従来使用されているス
テンレス鋼は、比重が重い、硬度が低い、環境条件(特
に、海水)によって錆びる、ニッケルを含むため皮膚ア
レルギーを起こしやすい、等の課題を有していた。一
方、純チタンは、軽さ、耐食性、ニッケルアレルギー対
応の面では、ステンレス鋼より優れているが、鏡面が得
られない、傷つきやすい等の課題を有し、装飾用の材料
としてはデザインが単調となり高級感が得られないとい
う課題を有していた。
Conventionally used stainless steels have the following problems: heavy specific gravity, low hardness, rust due to environmental conditions (especially seawater), and easy skin allergy due to nickel. Had. Pure titanium, on the other hand, is superior to stainless steel in terms of lightness, corrosion resistance, and resistance to nickel allergy, but it has problems such as lack of mirror surface and easy scratching, and its design is monotonous. Therefore, there is a problem that a high-class feeling cannot be obtained.

【0004】そこで、この発明の目的は装飾用チタン及
びチタン合金の鏡面性の向上をはかり、硬度を高めるこ
とである。
Therefore, an object of the present invention is to improve the specularity and the hardness of decorative titanium and titanium alloys.

【0005】[0005]

【課題を解決するための手段】上記課題を解決するため
に、この発明はチタンに硬さを付与する鉄と組織の緻密
化を付与するモリブデンを合金化することにより、硬さ
のアップと鏡面性の改善を図り、β変態温度以上に加熱
急冷することによりさらに鏡面性を向上させるようにし
た。
SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention alloys titanium with iron which imparts hardness and molybdenum which imparts densification of structure, thereby increasing hardness and providing a mirror surface. In order to improve the specularity, the specularity was further improved by heating and quenching to the β transformation temperature or higher.

【0006】[0006]

【作用】上記方法によれば、鉄により硬さが高くなるの
で、傷つきがたく、また、モリブデンにより組成が緻密
化されるので鏡面性に優れた装飾品が得られる。
According to the above method, since the hardness is increased by iron, it is less scratched, and the composition is densified by molybdenum, so that a decorative article excellent in mirror surface property can be obtained.

【0007】[0007]

【実施例】【Example】

(実施例1)粉末粒子の大きさが200μm以下の純チ
タン粉末と10μm以下の鉄粉末及び10μm以下のモ
リブデン粉末を混合し、これらの混合粉に0.5wt%
のステアリン酸を混合し、30kgf/mm2 の圧力で
型成形し成形体を得た。次にこれらの成形体を1350
℃で1時間保持し焼結を行い焼結体を得た。各焼結体の
相対密度は95%以上であり、組織は均一なα単相かα
+βの2相組織となり装飾品で要求される鏡面性が得ら
れる。表1に各焼結体の組成と硬さ・密度・鏡面性を示
す。特に溶製材の純チタンではビッカース硬さHv18
0であるが、鉄、あるいは、モリブデン量が増えるに従
って硬さが増す。試験を行ったチタン合金全ての焼結体
において硬さがHv250以上あり、ステンレス鋼の硬
さHv200以上を約Hv50越えることができ、装飾
部品として使用した場合には傷がつきにくく非常に有効
であった。同時に、鏡面性の向上も認めらる。特に、チ
タン粉末として、平均粒径が20μm以下の場合に密度
の向上が顕著であり、鏡面性もさらに向上する。
(Example 1) Pure titanium powder having a particle size of 200 μm or less, iron powder having a particle size of 10 μm or less, and molybdenum powder having a particle size of 10 μm or less were mixed, and 0.5 wt% was added to these mixed powders.
Of stearic acid were mixed and molded under a pressure of 30 kgf / mm 2 to obtain a molded body. Next, these molded bodies were
Sintering was performed by holding at 1 ° C for 1 hour to obtain a sintered body. The relative density of each sintered body is 95% or more, and the structure is uniform α single phase or α
It becomes a + β two-phase structure and the specularity required for ornaments is obtained. Table 1 shows the composition, hardness, density and specularity of each sintered body. Especially, Vitas hardness Hv18 for pure titanium
Although it is 0, the hardness increases as the amount of iron or molybdenum increases. The hardness of all sintered titanium alloys tested is Hv250 or more, and the hardness of stainless steel Hv200 or more can be exceeded by about Hv50. there were. At the same time, improvement in specularity is also recognized. In particular, as the titanium powder, when the average particle diameter is 20 μm or less, the density is remarkably improved, and the specularity is further improved.

【0008】[0008]

【表1】 (実施例2)粉末粒子の大きさが200μm以下の純チ
タン粉末と10μm以下の鉄粉末及び10μm以下のモ
リブデン粉末を混合し、これらの混合粉に17〜18w
t%のEVA−St−CWAX系(酢酸ビニル共重合体
−ステアリン酸−カルナバワックス系)の有機物を混合
し、射出成形により成形体を得た。次にこれらの成形体
から有機物を除去し、その後1200℃,1250℃,
1300℃,1350℃で1時間保持し焼結を行い焼結
体を得た。各焼結体の相対密度は95%以上であり、組
織は均一なα単層かα+βの2相組織となり装飾品で要
求される鏡面性が得られる表2各焼結体の組成と硬さ・
密度・鏡面性を示す。特に硬度チタンではビッカース硬
さHv100であるが、鉄、あるいは、モリブデン量が
増えるに従って硬さが増す。試験を行ったチタン合金全
ての焼結体において硬さがHv250以上あり、ステン
レス鋼の硬さHv200以上を約Hv50越えることが
でき、装飾部品として使用した場合には傷がつきにくく
非常に有効であった。同時に、鏡面性の向上も認められ
る。特に、チタン粉末として、平均粒径が20μm以下
の場合に密度の向上が顕著であり、鏡面性もさらに向上
する。特に、圧粉成形に比較し2〜3%の密度増が認め
られ、鏡面性がより向上している。
[Table 1] (Example 2) Pure titanium powder having a particle size of 200 μm or less, iron powder having a particle size of 10 μm or less, and molybdenum powder having a particle size of 10 μm or less were mixed, and 17 to 18 w were added to these mixed powders.
A t% EVA-St-CWAX-based (vinyl acetate copolymer-stearic acid-carnauba wax-based) organic material was mixed, and a molded body was obtained by injection molding. Next, organic matter is removed from these molded bodies, and then 1200 ° C, 1250 ° C,
Sintering was performed by holding at 1300 ° C and 1350 ° C for 1 hour to obtain a sintered body. The relative density of each sintered body is 95% or more, and the structure becomes a uniform α single layer or a two-phase structure of α + β and the mirror surface property required for ornaments can be obtained Table 2 Composition and hardness of each sintered body・
Shows density and specularity. In particular, titanium has a Vickers hardness of Hv100, but the hardness increases as the amount of iron or molybdenum increases. The hardness of all the sintered titanium alloys tested is Hv250 or more, and the hardness of stainless steel Hv200 or more can be exceeded by about Hv50. there were. At the same time, an improvement in specularity is also recognized. In particular, as the titanium powder, when the average particle diameter is 20 μm or less, the density is remarkably improved, and the specularity is further improved. In particular, a density increase of 2 to 3% was observed as compared with the powder compacting, and the mirror surface property was further improved.

【0009】[0009]

【表2】 この方法であると、有機物の除去時に生じる酸化、窒化
により硬度が実施例1より約20%高めになる。 (実施例3)各焼結体をβ変態温度以上の950℃で3
0分加熱し、油冷による急冷を行った(β溶体化処
理)。試験を行ったチタン合金(0.1wt%以上の
鉄、および、0.1wt%以上のモリブデンを含む)を
溶体化処理することにより硬度はほぼ変化しないが、組
織が微細化する。溶体化処理後の各焼結体を、バフ研磨
による鏡面仕上げを行った。その結果、鏡面性が著しく
向上した。各焼結体のにおける溶体化処理後の硬さ・鏡
面性を表3に示す。
[Table 2] According to this method, the hardness becomes about 20% higher than that in Example 1 due to the oxidation and nitriding that occur when removing the organic matter. (Example 3) Each sintered body was heated to 3 at 950 ° C, which is higher than the β transformation temperature.
It was heated for 0 minutes and quenched by oil cooling (β solution treatment). By subjecting the tested titanium alloy (containing 0.1 wt% or more of iron and 0.1 wt% or more of molybdenum) to the solution treatment, the hardness is hardly changed, but the structure is refined. Each of the sintered bodies after the solution treatment was subjected to buffing for mirror finish. As a result, the specularity was remarkably improved. Table 3 shows the hardness and specularity of each sintered body after the solution treatment.

【0010】[0010]

【表3】 [Table 3]

【0011】[0011]

【発明の効果】本発明によれば、硬度が高く、鏡面性に
優れたチタン合金が得られると言う効果を有している。
According to the present invention, there is an effect that a titanium alloy having high hardness and excellent mirror surface property can be obtained.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 若林 豊 東京都江東区亀戸6丁目31番1号 セイコ ー電子工業株式会社内 (72)発明者 宍戸 晃哉 東京都江東区亀戸6丁目31番1号 セイコ ー電子工業株式会社内 (72)発明者 近藤 鉄也 愛知県名古屋市中川区戸田四丁目1809番地 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yutaka Wakabayashi 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Co., Ltd. (72) Inventor Akiya Shishido 6-31-1, Kameido, Koto-ku, Tokyo No. Seiko Denshi Kogyo Co., Ltd. (72) Inventor Tetsuya Kondo 4, 1809 Toda, Nakagawa-ku, Nagoya, Aichi

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 重量比で0.1〜1.0%の鉄粉末と
0.1〜4.0%のモリブデン粉末を含み、残りがチタ
ン粉末で構成された混合粉を圧粉成形後に1200〜1
350℃で焼結したことを特徴とする装飾用チタン合
金。
1. A mixed powder containing 0.1 to 1.0% by weight of iron powder and 0.1 to 4.0% by weight of molybdenum powder, and the balance of titanium powder after compacting 1200. ~ 1
A decorative titanium alloy characterized by being sintered at 350 ° C.
【請求項2】 重量比で0.1〜1.0%の鉄粉末と
0.1〜4.0%のモリブデン粉末を含み、残りがチタ
ン粉末で構成された混合粉を有機物と混練し、その混練
物を射出成形し得られた成形体から有機物を除去しその
後に1200〜1350℃で焼結したことを特徴とする
装飾用チタン合金。
2. A mixed powder containing 0.1 to 1.0% by weight of iron powder and 0.1 to 4.0% by weight of molybdenum powder, and the balance of titanium powder being kneaded with an organic substance, A decorative titanium alloy, characterized in that an organic material is removed from a molded body obtained by injection molding the kneaded product, and then sintered at 1200 to 1350 ° C.
【請求項3】 焼結後、そのβ変態点温度以上に加熱後
湯冷以上の速度で冷却した後に、表面研磨し鏡面化する
ことを特徴とする請求項1及び請求項2記載の装飾品。
3. The decorative article according to claim 1 or 2, wherein after sintering, after heating to a β transformation point temperature or higher, and then cooling at a rate of hot water cooling or higher, the surface is polished to be mirror-finished. .
JP22678394A 1994-09-21 1994-09-21 Decorative titanium alloy and its ornaments Expired - Lifetime JP3471092B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22678394A JP3471092B2 (en) 1994-09-21 1994-09-21 Decorative titanium alloy and its ornaments

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22678394A JP3471092B2 (en) 1994-09-21 1994-09-21 Decorative titanium alloy and its ornaments

Publications (2)

Publication Number Publication Date
JPH0892674A true JPH0892674A (en) 1996-04-09
JP3471092B2 JP3471092B2 (en) 2003-11-25

Family

ID=16850549

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22678394A Expired - Lifetime JP3471092B2 (en) 1994-09-21 1994-09-21 Decorative titanium alloy and its ornaments

Country Status (1)

Country Link
JP (1) JP3471092B2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008179860A (en) * 2007-01-25 2008-08-07 Technes Co Ltd Sintered body and manufacturing method thereof
EP3138433A1 (en) 2015-09-07 2017-03-08 Seiko Epson Corporation Titanium sintered body and ornament
EP3456441A1 (en) 2017-08-31 2019-03-20 Seiko Epson Corporation Titanium sintered body, ornament, and timepiece
CN111172424A (en) * 2020-01-17 2020-05-19 西部金属材料股份有限公司 Titanium alloy for daily necessities and preparation method thereof
EP3767001A4 (en) * 2018-03-15 2021-11-17 Citizen Watch Co., Ltd. TITANIUM ELEMENT, MANUFACTURING METHOD FOR TITANIUM ELEMENT AND DECORATIVE ARTICLES WITH TITANIUM ELEMENT

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008179860A (en) * 2007-01-25 2008-08-07 Technes Co Ltd Sintered body and manufacturing method thereof
EP3138433A1 (en) 2015-09-07 2017-03-08 Seiko Epson Corporation Titanium sintered body and ornament
EP3456441A1 (en) 2017-08-31 2019-03-20 Seiko Epson Corporation Titanium sintered body, ornament, and timepiece
JP2019044225A (en) * 2017-08-31 2019-03-22 セイコーエプソン株式会社 Sintered titanium, ornaments and watches
US11857034B2 (en) 2017-08-31 2024-01-02 Seiko Epson Corporation Titanium sintered body, ornament, and timepiece
EP3767001A4 (en) * 2018-03-15 2021-11-17 Citizen Watch Co., Ltd. TITANIUM ELEMENT, MANUFACTURING METHOD FOR TITANIUM ELEMENT AND DECORATIVE ARTICLES WITH TITANIUM ELEMENT
US12031204B2 (en) 2018-03-15 2024-07-09 Citizen Watch Co., Ltd. Titanium member, method for manufacturing titanium member, and decorative article including titanium member
CN111172424A (en) * 2020-01-17 2020-05-19 西部金属材料股份有限公司 Titanium alloy for daily necessities and preparation method thereof

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