JPH0447020B2 - - Google Patents
Info
- Publication number
- JPH0447020B2 JPH0447020B2 JP57086234A JP8623482A JPH0447020B2 JP H0447020 B2 JPH0447020 B2 JP H0447020B2 JP 57086234 A JP57086234 A JP 57086234A JP 8623482 A JP8623482 A JP 8623482A JP H0447020 B2 JPH0447020 B2 JP H0447020B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered
- decorative
- sintered alloy
- color tone
- sintering
- 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.)
- Expired - Lifetime
Links
Description
本発明は、時計用外装部品、ネクタイピン、ブ
ローチ、釣り具部品等の装飾品用部材に適した装
飾性を兼ね備えた装飾用焼結合金に関する。
従来、装飾品用部材には、耐食性及び耐スクラ
ツチ性が要求されることから硬質合金であるWC
基、TaC基及びTiC基焼結合金が実用化されてい
る。この内、WC基及びTaC基焼結合金は、高価
である上に比重が高く携帯用装飾品用部材として
は不向きであり、WC基及びTiC基焼結合金は、
黒灰色の単調な色彩であるため装飾効果に対する
要求を完全に満していないと云う欠点がある。こ
れらの欠点を補うものとして、TiNおよび／ま
たはTiCを銅及び焼結合金に被覆した被覆合金が
装飾品用部材として使用されている。しかし被覆
合金は、被覆層の表面と内部の色調が異なつた
り、被覆層の剥離が生じたり、製造工程から生じ
る被覆層の膜質及び膜厚の変化により被覆合金表
面に色調むらが起り装飾品としての価値がなくな
ると云う欠点がある。更に有色系焼結合金とし
て、TiN系を主体とした焼結合金が装飾品用部
材として多数提案されているが焼結性が非常に悪
く、焼結性の悪い合金を鏡面光沢の表面状態にし
て使用する場合、鏡面にある欠陥が目立つために
装飾品用部材には適さないという問題がある。
本発明の装飾用焼結合金は、上述したような欠
点及び問題点を解決したものである。
本発明は、化学量論組成近傍のTiNを主原料
としたものとFe族とから成る圧粉体を焼結する
過程で、TiNがFe族に固溶してFe族固溶体を形
成する際、Fe族中にTiとＮは等モルで固溶でき
ず約95％の窒素はN2ガスとして圧粉体外に排出
されるため液相出現以後は、このN2ガスが残留
して焼結性の促進を阻害する現象が起り、この現
象に基づいて脱窒防止に対するる検討を行つた結
果得られた装飾用焼結合金である。
本発明の装飾用焼結合金は、
（Tia，Mb）（Nw，Cx，Oy）Ｚで表わされる
硬質相（但し、ＭはZr，Hf，Ｖ，Nb，Ta，Cr
の中の１種以上、ａはTiの原子比、ｂはＭに相
当する金属の原子比を示し、ａ＋ｂ＝１，１≧ａ
≧0.4，0.6≧ｂ≧０、Ｎは窒素、Ｃは炭素、Ｏは
酸素、Ｗ、Ｘ、Ｙは窒素、炭素、酸素それぞれの
原子比、Ｚは金属に対する非金属構成元素の比を
示し、
Ｗ＋Ｘ＋Ｙ＝１，Ｘ＋Ｙ＞０，１＞Ｗ≧0.4、
0.19≧Ｘ≧０，0.6≧Ｙ≧０，0.93≧Ｚ≧0.6）が
70〜98重量％とFe、Ni、Co、Cr、Mo、Ｗの中
から選ばれた１種以上の結合相が２〜30重量％と
不可避不純物とから成る焼結合金である。このよ
うな本発明の焼結合金は、TiNを主体とする圧
粉体を焼結する過程で生じる脱窒が非化学量論組
成であるTiNz（0.95≧Ｚ≧0.6）粉末を出発原料
とするために系外に排出されていたN2ガスが
TiNz粉末を逆窒化する現象が生じ、このために
脱窒が防止される。又Ti（Nw、Cx、Oy）ｚの如
くTiNzに炭素および／または酸素が加わること
によつて脱窒防止の効果が強くなり、このために
焼結性が促進されて緻密な焼結合金が得られると
共に焼結体の硬さが高く耐摩耗性、耐スクラツチ
性の優れた焼結合金となる。
本発明の装飾用焼結合金は、TiNzを主体にし
た硬質相によつて黄金色系統の色調を保持させる
ものであるがＺの値が化学量論組成よりも少なく
なる程黄金色系から淡黄金色系に変化し、この色
調変化を更に黄金色を呈するTiO、ZrN、HfN、
VN、NbN、TaN、CrN、Cr2N、TaC、NbCを
加えることにより深みのある淡黄金色から鮮明な
黄金色までの色調コントロールが一層容易にな
る。
本発明の装飾用焼結合金は、真空又は非酸化性
雰囲気中で普通焼結方法により充分緻密な焼結合
金が得れられるが熱間静水圧焼結方法（HIP）に
よつて処理することにより更に緻密で強度の高い
焼結合金が得られる。
次に本発明の装飾用焼結合金に於て数値限定し
た理由について述べる。
硬質相である（Tia，Mb）（Nw，Cx，Oy）
Ｚに於て、Ti以外の金属Ｍは、硬質層の粒子成
長を抑制する効果と共に硬質層の強度及び硬さを
高める効果も有る。特に、金属ＭをＭの化合物と
して、黄金色を呈するZrN、HfN、VN、NbN、
TaN、CrN、Cr2Nの中から選ばれた１種以上を
添加する場合には、Tiの原子比ａとＭの原子比
ｂとの混合比を合金的に広く選ぶことが可能でこ
れを制限する本質的な理由は無いが携帯用として
の軽量化と耐スクラツチ性を考慮する必要が有
り、又、ZrC、HfC、VC、Cr2C2等の炭化物を添
加する場合には、色調も考慮する必要が有るため
に１≧ａ≧0.4，0.6≧ｂ≧０と定めた。非金属元
素であるＮ、Ｃ、Ｏは、黄金色系統の焼結合金を
目的にするためにＮを主体にし、Ｃ又はＯは、焼
結性の促進と耐スクラツチ性の向上のためにどち
らか一方又は両方含有している必要が有り、その
含有量が多過ぎると焼結性が低下すると共に焼結
体の硬さも低下するので１＞Ｗ≧0.4、0.19≧Ｘ
≧０，0.6≧Ｙ≧０と定めた。尚炭素Ｃは、金属
炭化物としての炭素よりも遊離炭素として添加す
る方が焼結性促進に対する効果が強い傾向にあ
る。金属元素に対する非金属元素の比を表わすＺ
は、脱ガス防止と焼結体の硬さ向上を目的とする
ために化学量論組成よりも少なくする必要が有
り、逆に少な過ぎると化合物が不安定になると共
に焼結体の寸法精度が低下するので0.93≧Ｚ≧
0.6と定めた。
硬質相量と結合相量の関係は、硬質相量が98重
量％を越えて多くなると相対的に結合相量が２重
量％未満となり、焼結性及び緻密性が低下する。
又、硬質相量が70重量％未満になると相対的に結
合相量が30重量％を越えて多くなり、焼結体の硬
さ低下となつて耐スクラツチ性が悪くなる。以上
のことから硬質相量は70〜98重量％、結合相量は
２〜30重量％と定めた。
以下に本発明の装飾用焼結合金を実施例に従つ
て具体的に説明する。
実施例 １
TiNz、TiC、TiO、Ti（Nw，Cx）ｚ、
Ti（Nw，Oy）ｚ、Ti（Nw，Cx，Oy）ｚ及び各
種結合相金属粉末を所定の割合に配合し、２％の
パラフインを潤滑剤として添加した後、アセトン
溶媒のボールミルにて粉砕混合した。乾燥後、混
合粉末を2t／cm2の加圧力で成形し、10−3〜10−4
mmHgの真空中1400℃〜1600℃の温度で焼結した。
焼結体は、ダイヤモンド砥石により鏡面研摩し、
機械的性質、色調及び耐食性を検討した。機械的
性質は、硬度、抗折力を測定し、耐食性試験は、
50℃の人工海水及び人工汗に７日間各試料を浸漬
した後試料鏡面部を観察することにより行つた。
各試料の配合組成、焼結条件、を表１に、焼結後
の各試料の硬質相の構造、結合相、抗折力、硬
さ、色調及び人工海水、人工汗による耐食性を調
査し、その結果を表２に示した。
The present invention relates to a decorative sintered alloy having decorative properties suitable for decorative parts such as watch exterior parts, tie pins, brooches, and fishing gear parts. Conventionally, materials for decorative items require corrosion resistance and scratch resistance, so WC, which is a hard alloy, has been used.
TaC-based, TaC-based, and TiC-based sintered alloys have been put into practical use. Among these, WC-based and TaC-based sintered alloys are expensive and have a high specific gravity, making them unsuitable for use as components for portable accessories;
The drawback is that the monotonous black-gray color does not fully meet the requirements for decorative effects. To compensate for these drawbacks, coated alloys in which copper and sintered alloys are coated with TiN and/or TiC are used as members for decorative articles. However, coating alloys can be used for decorations because the color tone between the surface and inside of the coating layer may differ, the coating layer may peel off, and color tone unevenness may occur on the coating alloy surface due to changes in the quality and thickness of the coating layer that occur during the manufacturing process. The disadvantage is that it loses its value. Furthermore, many TiN-based sintered alloys have been proposed as colored sintered alloys for decorative parts, but they have very poor sinterability, and it is difficult to make alloys with poor sintering properties into a mirror-glossy surface. When used as a decorative member, there is a problem that defects in the mirror surface are noticeable, making it unsuitable for use as a member for decorative items. The decorative sintered alloy of the present invention solves the above-mentioned drawbacks and problems. In the present invention, in the process of sintering a compact consisting of TiN as a main raw material with a near stoichiometric composition and Fe group, when TiN dissolves in Fe group to form an Fe group solid solution, Ti and N cannot form a solid solution in equimolar amounts in the Fe group, and approximately 95% of nitrogen is discharged from the compact as N 2 gas. After the liquid phase appears, this N 2 gas remains and causes sintering. This decorative sintered alloy was obtained as a result of a study to prevent denitrification based on this phenomenon. The decorative sintered alloy of the present invention has a hard phase represented by (Tia, Mb) (Nw, Cx, Oy) Z (where M is Zr, Hf, V, Nb, Ta, Cr).
one or more of the following, a represents the atomic ratio of Ti, b represents the atomic ratio of the metal corresponding to M, a+b=1, 1≧a
≧0.4, 0.6≧b≧0, N is nitrogen, C is carbon, O is oxygen, W, X, Y are the atomic ratios of nitrogen, carbon, and oxygen, Z is the ratio of nonmetal constituent elements to metal, W+X+Y=1, X+Y>0, 1>W≧0.4,
0.19≧X≧0, 0.6≧Y≧0, 0.93≧Z≧0.6)
It is a sintered alloy consisting of 70 to 98% by weight, one or more binder phases selected from Fe, Ni, Co, Cr, Mo, and W, 2 to 30% by weight, and unavoidable impurities. Such a sintered alloy of the present invention uses TiNz (0.95≧Z≧0.6) powder as a starting material in which denitrification that occurs during the process of sintering a green compact mainly composed of TiN has a non-stoichiometric composition. The N2 gas that was being discharged outside the system due to
A phenomenon of reverse nitriding of TiNz powder occurs, thereby preventing denitrification. Furthermore, the addition of carbon and/or oxygen to TiNz, such as Ti(Nw, Cx, Oy)z, strengthens the denitrification prevention effect, promoting sinterability and forming a dense sintered alloy. As a result, a sintered alloy with high hardness and excellent wear resistance and scratch resistance can be obtained. The decorative sintered alloy of the present invention maintains a golden yellow color tone due to the hard phase mainly composed of TiNz, but as the Z value becomes lower than the stoichiometric composition, the color tone changes from golden yellow to pale. TiO, ZrN, HfN, which changes to a golden color, and this color change becomes even more golden
By adding VN, NbN, TaN, CrN, Cr 2 N, TaC, and NbC, color tone control from deep pale golden yellow to clear golden yellow becomes even easier. The decorative sintered alloy of the present invention can be processed by hot isostatic pressure sintering (HIP), although a sufficiently dense sintered alloy can be obtained by ordinary sintering in vacuum or in a non-oxidizing atmosphere. As a result, a denser and stronger sintered alloy can be obtained. Next, the reason for the numerical limitations in the decorative sintered alloy of the present invention will be described. Hard phase (Tia, Mb) (Nw, Cx, Oy)
In Z, the metal M other than Ti has the effect of suppressing particle growth in the hard layer and also has the effect of increasing the strength and hardness of the hard layer. In particular, when the metal M is used as a compound of M, ZrN, HfN, VN, NbN, which exhibits a golden color,
When adding one or more selected from TaN, CrN, and Cr 2 N, it is possible to select a wide range of mixing ratios between the atomic ratio a of Ti and the atomic ratio b of M. There is no essential reason to limit it, but it is necessary to consider lightweight for portable use and scratch resistance, and when adding carbides such as ZrC, HfC, VC, Cr 2 C 2 , etc., the color tone may also be affected. Since it is necessary to take this into consideration, it is set as 1≧a≧0.4 and 0.6≧b≧0. The nonmetallic elements N, C, and O are mainly composed of N in order to obtain a golden-colored sintered alloy, and either C or O is used to promote sinterability and improve scratch resistance. It is necessary to contain one or both of them, and if the content is too large, the sinterability will decrease and the hardness of the sintered body will also decrease, so 1>W≧0.4, 0.19≧X
It was set as ≧0, 0.6≧Y≧0. Note that carbon C tends to have a stronger effect on promoting sinterability when added as free carbon than as carbon as a metal carbide. Z represents the ratio of non-metallic elements to metallic elements
must be less than the stoichiometric composition for the purpose of preventing degassing and improving the hardness of the sintered body; conversely, if it is too small, the compound will become unstable and the dimensional accuracy of the sintered body will deteriorate. Since it decreases, 0.93≧Z≧
It was set as 0.6. Regarding the relationship between the amount of hard phase and the amount of binder phase, when the amount of hard phase exceeds 98% by weight, the amount of binder phase becomes relatively less than 2% by weight, and sinterability and compactness decrease.
Furthermore, when the amount of hard phase is less than 70% by weight, the amount of binder phase becomes relatively large, exceeding 30% by weight, resulting in a decrease in the hardness of the sintered body and poor scratch resistance. Based on the above, the amount of hard phase was determined to be 70 to 98% by weight, and the amount of binder phase was determined to be 2 to 30% by weight. The decorative sintered alloy of the present invention will be specifically described below based on examples. Example 1 TiNz, TiC, TiO, Ti(Nw, Cx)z, Ti(Nw, Oy)z, Ti(Nw, Cx, Oy)z and various binder phase metal powders were blended in predetermined proportions, and 2% After adding paraffin as a lubricant, the mixture was ground and mixed in a ball mill using an acetone solvent. After drying, the mixed powder is molded with a pressure of 2t/cm 2 to give a shape of 10−3 to 10−4 .
Sintered at a temperature of 1400°C to 1600°C in a vacuum of mmHg.
The sintered body is mirror-polished using a diamond grindstone,
Mechanical properties, color tone and corrosion resistance were investigated. Mechanical properties measure hardness and transverse rupture strength, and corrosion resistance tests
This was done by immersing each sample in artificial seawater and artificial sweat at 50°C for 7 days and then observing the mirror surface of the sample.
The compound composition and sintering conditions of each sample are shown in Table 1, and the structure of the hard phase, binder phase, transverse rupture strength, hardness, color tone, and corrosion resistance due to artificial seawater and artificial sweat of each sample after sintering were investigated. The results are shown in Table 2.
【表】【table】
【表】【table】
【表】
実施例 ２
ZrN、TaN、TaC、NbC、ZrC、VC、HfN、
CrN、（Tia，Mb）Nz、（Tia，Mb）（Nw，Cx）
ｚ、（Tia，Mb）（Nw，Oy）ｚ、（Tia，Mb）
（Nw，Cx，Oy）ｚ及び実施例１で使用した各原
料粉末によつて所定の割合に配合し、実施例１と
同様な製造方法で焼結体とし、焼結した各試料の
機械的性質：色調及び耐食性試験を行つた。各試
料の配合組成及び焼結条件を表３に、焼結後の各
試料の硬質相の構造、結合相、抗折力、硬さ、色
調及び人工海水、人工汗による耐食性を調査し、
その結果を表４に示した。[Table] Example 2 ZrN, TaN, TaC, NbC, ZrC, VC, HfN,
CrN, (Tia, Mb) Nz, (Tia, Mb) (Nw, Cx)
z, (Tia, Mb) (Nw, Oy) z, (Tia, Mb)
(Nw, Cx, Oy) z and each raw material powder used in Example 1 were mixed in a predetermined ratio and made into a sintered body using the same manufacturing method as in Example 1, and the mechanical properties of each sintered sample were Properties: Color tone and corrosion resistance tests were conducted. The composition and sintering conditions of each sample are shown in Table 3, and the structure of the hard phase, binder phase, transverse rupture strength, hardness, color tone, and corrosion resistance due to artificial seawater and artificial sweat of each sample after sintering were investigated.
The results are shown in Table 4.
【表】【table】
【表】【table】
【表】
実施例 ３
実施例１で焼結した試料No.１，５，８と実施例
２で焼結した試料No.15，19，23の各試料を
1500bar−1350℃の条件でHIP処理した後機械的
性質、色調及び耐食性試験を行つた。これらの試
験結果を表５に示した。[Table] Example 3 Samples Nos. 1, 5, and 8 sintered in Example 1 and Samples No. 15, 19, and 23 sintered in Example 2 were
After HIP treatment at 1500bar-1350℃, mechanical properties, color tone and corrosion resistance tests were conducted. The test results are shown in Table 5.
Claims (1)
と、 （Tia，Mb）（Nw，Cx，Oy）Ｚ…(A) 但し、Ｍ：Zr，Hf，Ｖ，Nb，Ta，Crの中の
１種以上 ａ＋ｂ＝１，１≧ａ≧0.4，0.6≧ｂ≧０ Ｗ＋Ｘ＋Ｙ＝１，Ｘ＋Ｙ＞０，１＞Ｗ≧0.4 0.19≧Ｘ≧０，0.6≧Ｙ≧０，0.93≧Ｚ≧0.6 Fe，Ni，Co，Cr，Mo，Ｗの中から選ばれた１
種以上の結合相が２〜30重量％と不可避不純物と
から成ることを特徴とする装飾用焼結合金。[Claims] The hard phase represented by the primary formula (A) is 70 to 98% by weight.
(Tia, Mb) (Nw, Cx, Oy) Z...(A) However, M: one or more of Zr, Hf, V, Nb, Ta, Cr a+b=1, 1≧a≧0.4, 0.6≧b≧0 W+X+Y=1, 1
1. A decorative sintered alloy comprising 2 to 30% by weight of at least one binder phase and unavoidable impurities.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8623482A JPS58204149A (en) | 1982-05-21 | 1982-05-21 | Sintered alloy for decoration |
| US06/474,813 US4702769A (en) | 1982-05-21 | 1983-03-10 | Sintered alloy for decoration |
| CH2755/83A CH656146A5 (en) | 1982-05-21 | 1983-05-19 | SINDERED ALLOY FOR DECORATIONAL PURPOSES. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8623482A JPS58204149A (en) | 1982-05-21 | 1982-05-21 | Sintered alloy for decoration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58204149A JPS58204149A (en) | 1983-11-28 |
| JPH0447020B2 true JPH0447020B2 (en) | 1992-07-31 |
Family
ID=13881100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8623482A Granted JPS58204149A (en) | 1982-05-21 | 1982-05-21 | Sintered alloy for decoration |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58204149A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012121023A1 (en) | 2011-03-07 | 2012-09-13 | 住友電工ハードメタル株式会社 | Material for decorative part |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0169054A3 (en) * | 1984-07-18 | 1987-12-16 | The University Of Newcastle Upon Tyne | Composite materials and products |
| JP5342740B2 (en) * | 2005-09-27 | 2013-11-13 | 京セラ株式会社 | Ceramics for decorative parts and decorative parts for watches using the same |
| JP5342742B2 (en) * | 2006-09-27 | 2013-11-13 | 京セラ株式会社 | Ceramics for decorative parts and decorative parts for watches using the same |
| JP5091945B2 (en) * | 2007-03-13 | 2012-12-05 | 京セラ株式会社 | Ceramics for decorative parts, decorative parts for watches, decorative parts for mobile devices and mobile devices |
| JP5094875B2 (en) | 2007-11-28 | 2012-12-12 | 京セラ株式会社 | Ceramics for decorative parts and decorative parts using the same |
| JP5328784B2 (en) | 2008-05-28 | 2013-10-30 | 京セラ株式会社 | Ceramics for decorative parts and decorative parts using the same |
| CN102405299A (en) | 2009-04-24 | 2012-04-04 | 京瓷株式会社 | Ceramics for decorative component and decorative component using same |
| WO2010137652A1 (en) * | 2009-05-27 | 2010-12-02 | 京セラ株式会社 | Ceramic for decorative parts, and decorative parts |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442341B2 (en) * | 1973-08-08 | 1979-12-13 | ||
| JPS5337113A (en) * | 1976-09-18 | 1978-04-06 | Nippon Shinkinzoku Kk | Titaniummnitrideebased highhstrength sintered alloy |
| JPS5949297B2 (en) * | 1979-07-04 | 1984-12-01 | 三菱マテリアル株式会社 | Hard sintered alloy for decorative parts |
| JPS5658944A (en) * | 1979-10-15 | 1981-05-22 | Seiko Instr & Electronics Ltd | Wrist watch case |
| JPS58133342A (en) * | 1982-01-30 | 1983-08-09 | Toshiba Tungaloy Co Ltd | Decorative sintered alloy |
-
1982
- 1982-05-21 JP JP8623482A patent/JPS58204149A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012121023A1 (en) | 2011-03-07 | 2012-09-13 | 住友電工ハードメタル株式会社 | Material for decorative part |
| US8992657B2 (en) | 2011-03-07 | 2015-03-31 | Sumitomo Electric Hardmetal Corp. | Material for decorative parts |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58204149A (en) | 1983-11-28 |
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