JPH0128825B2 - - Google Patents
Info
- Publication number
- JPH0128825B2 JPH0128825B2 JP57186503A JP18650382A JPH0128825B2 JP H0128825 B2 JPH0128825 B2 JP H0128825B2 JP 57186503 A JP57186503 A JP 57186503A JP 18650382 A JP18650382 A JP 18650382A JP H0128825 B2 JPH0128825 B2 JP H0128825B2
- Authority
- JP
- Japan
- Prior art keywords
- decorative
- cemented carbide
- tin
- particles
- particle size
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
Landscapes
- Powder Metallurgy (AREA)
Description
本発明は、従来にない外観をつくり出した付加
価値の高い装飾用超硬合金に関するものである。
一般に、装飾用合金に要求される主な性質とし
ては、表面光沢が良好で長い間、その外観が保た
れ、又使用環境によつて腐食、変色が生じず、さ
らに色調に特徴があり材料自体に装飾価値がある
ことが求められている。
従来使用されている装飾用合金には、WC系や
TaC系の超硬合金、Ni合金、Co合金系の硬質合
金、18K，14K，10K合金等の金合金、さらには
ステンレス鋼や黄銅への各種メツキ品等があり、
これらの合金は、ネツクレス、イヤリング、指
輪、ブレスレツト、ウオツチケース、ライター等
の装身具類に広く用いられている。しかし、装飾
的な要求が多様化するにつれ、可能ならば上記の
材料では出せない新しいイメージを演出できる様
な新しい装飾合金が要求されてきている。
しかし、従来のものでは新しいイメージは出来
たとしても、耐久性という点では欠点を有してい
た。
本発明は、この課題を解決するもので耐久性の
あるバイカラーあるいはトリカラーにした装飾用
超硬合金を提供するものである。
本発明の装飾用超硬合金は、
平均粒径が0.3〜３mmのWC，TaC，TiN，
HfNのうちから選ばれたいずれかの少なくとも
１種の24〜50wt％と、
平均粒径が1.3〜1.8μmのWC，TiC，TiN，
NbC，VCのうちから選ばれたいずれかの少なく
とも１種の40〜56wt％と、
金属バインダーとして、Ni，Co，Crのうちか
ら選ばれたいずれかの少なくとも２種の粉末の10
〜20wt％とを用いて焼結したことを特徴とする。
すなわち、本発明は、炭化物又は窒化物あるい
はそれらを主成分として製造した超硬合金による
約0.3〜３mmφの粒子に、それとは異なる系の炭
化物又は窒化物の微粒子とバインダーとなる金属
成分を混合して焼結して得る。さらに、粒子層と
マトリツクス層となる金属層とのコントラストを
はつきりさせるためにエツチングを行うことによ
り外観の見栄えをあげる。これは装飾用超硬合金
において、色調の異なる粒子を混合し焼結した場
合、通常の研削肌や、ポリツシング上りの鏡面に
おいては色相の違いが明確には出にくく、よりコ
ントラストをつけた方が装飾的効果が増大してく
るためである。このエツチング処理を加えること
により、たとえば銀白色と黄金色が入り混つた新
しい概念の装飾用超硬合金をより容易に形成する
ことができる。
本発明で数値を限定したのは次の理由による。
すなわち、WC，TaC，TiN，HfNの平均粒系
を0.3〜３mmとしたのは、0.3mm未満では、バイカ
ラーまたはトリカラーとするための装飾効果が余
り出ず、また３mmをこえると外観的に余り高級感
を与えず、さらには強度的にも低下が起こるため
であり、その量は24〜50wt％の範囲が装飾的な
効果に最も適しているためである。また50wt％
をこえると強度的にも低下が起こる。
また、金属バインダー中に分散させるための
WC，TiC，TiN，NbC，VCの平均粒径を1.3〜
1.8μmとしたのは、この範囲が最も金属バインダ
ー中に容易に分散でき、また耐摩耗性を上げるの
に都合が良いためである。
さらに、金属バインダーとしては、２種以上の
金属を用いて合金とするのが融点などからよく、
またCo，Cr，Niなどの金属の量を10〜20wt％と
したのは、10wt％未満では機械的な強度が充分
ではなく、20wt％をこえると耐摩耗性及び外観
が余り好ましくないためである。なお、装飾用超
硬合金の表面を梨地状にすればするほど、超硬粒
子又は金属のどの部分が上面に来ても均一な耐摩
耗性が要求されることから、本発明の効果がよく
表われて来る。
ついでに述べるならば本発明の炭化物および窒
化物及び炭化タングステンのうち、銀白色系の化
合物はTiC，VC，WCであり、黄金色系の化合物
はNbC，TaC，TiN，HfN，TaNである。
以下に、本発明による装飾用超硬合金を実施例
により説明する。
実施例 １
原料粉末として、平均粒径0.7mmのTaC粒子を
平均粒径1.3μmのWC粉末と平均粒径3μの、バイ
ンダー金属を第１表に示す最終成分組成を持つよ
うに混合し、真空雰囲気中で1300〜1400℃で１時
間焼結し、さらに1350℃500気圧で熱間静水圧プ
レスを行うことにより本発明の装飾用超硬合金を
製造した。この合金について、ダイヤモンド研削
盤による荒研削及びラツプ盤によるラツプ仕上げ
を行つた。この後、この合金を下記のエツチング
液中に90℃で10分間浸漬したところ、WC部分が
黒色に変色し、TaC粒の部分も梨地化されより
黄金のイメージに近づくため、黒地に金色粒が分
散された超硬合金を形成できた。
エツチング液
K3Fe（CN）6 3g
KOH 10g
H2O 100ml
この様にして作成した合金を、ISO（国際標準
化機構）規格に則した人工汗（PH＝4.7）を腐食
液として使用し、温度40℃±２℃に保持した前記
人工汗中に鏡面研磨した試片の下半分を24時間浸
漬し、前記研磨面にくもりが発生するか否かを観
察する耐食試験を行つたところ特に変色等の問題
は生じなかつた。さらに上記合金を用いてウオツ
チ用の胴を製作し、カバーガラス、裏ぶた等を組
み込んだ後、コンクリート上へ落下した場合に
も、1.0mの高さまで割れ等の問題を生ぜず実用
上の問題はなかつた。本発明の装飾用超硬合金
は、耐食性、耐衝撃性共に問題がなく、さらに硬
度的にもHv＝1300以上を有するため、実用上の
傷等が生じることは全くなかつた。この様に、従
来の超硬合金と同等の各種特性を有していなが
ら、本合金はTaCの黄金色の粒の周囲をWC―Co
―Cr系の銀白色系の超硬合金がとりまく、新し
いイメージの耐摩耗性が均一な装飾用超硬合金を
つくることができた。
The present invention relates to a highly value-added decorative cemented carbide that has an unprecedented appearance. In general, the main properties required for decorative alloys are that they have good surface gloss and maintain their appearance for a long time, that they do not corrode or discolor depending on the environment in which they are used, and that they have a characteristic color tone and the material itself. It is required to have decorative value. Traditionally used decorative alloys include WC series and
We have TaC type cemented carbide, Ni alloy, Co alloy type hard alloy, gold alloy such as 18K, 14K, 10K alloy, and various plated products on stainless steel and brass.
These alloys are widely used in jewelry such as necklaces, earrings, rings, bracelets, watch cases, and lighters. However, as decorative requirements become more diverse, new decorative alloys are required that, if possible, can produce new images that cannot be produced with the above-mentioned materials. However, even if the conventional products created a new image, they had drawbacks in terms of durability. The present invention solves this problem by providing a durable bicolor or tricolor decorative cemented carbide. The decorative cemented carbide of the present invention includes WC, TaC, TiN, and
24-50wt% of at least one selected from HfN, WC, TiC, TiN, with an average particle size of 1.3-1.8μm,
40 to 56 wt% of at least one selected from NbC and VC, and 10 to 56 wt% of at least two powders selected from Ni, Co, and Cr as a metal binder.
It is characterized by being sintered using ~20wt%. That is, in the present invention, particles of about 0.3 to 3 mm diameter made of carbide or nitride or a cemented carbide manufactured using these as main ingredients are mixed with fine particles of carbide or nitride of a different type and a metal component to serve as a binder. obtained by sintering. Furthermore, etching is performed to enhance the contrast between the particle layer and the metal layer that will become the matrix layer, thereby improving the appearance. This is because in decorative cemented carbide, when particles of different tones are mixed and sintered, it is difficult to clearly differentiate the hues on a normally ground surface or a mirror surface after polishing, so it is better to create more contrast. This is because the decorative effect increases. By adding this etching treatment, it is possible to more easily form a new concept of decorative cemented carbide having a mixture of silvery white and golden yellow, for example. The reason why the numerical values are limited in the present invention is as follows. In other words, the reason why the average grain size of WC, TaC, TiN, and HfN is set to 0.3 to 3 mm is that if it is less than 0.3 mm, the decorative effect for bicolor or tricolor will not be obtained much, and if it exceeds 3 mm, the appearance will be poor. This is because it does not give a very luxurious feel and also causes a decrease in strength, and the amount in the range of 24 to 50 wt% is most suitable for decorative effects. Also 50wt%
If it exceeds this, a decrease in strength will occur. Also, for dispersion in metal binder
The average particle size of WC, TiC, TiN, NbC, VC is 1.3~
The reason for setting the diameter to 1.8 μm is that this range is most easily dispersed in the metal binder and is convenient for increasing wear resistance. Furthermore, as a metal binder, it is best to use two or more metals to form an alloy due to their melting points.
In addition, the amount of metals such as Co, Cr, and Ni was set at 10 to 20 wt% because if it is less than 10 wt%, the mechanical strength is not sufficient, and if it exceeds 20 wt%, the wear resistance and appearance are not very desirable. be. Note that the more the surface of the decorative cemented carbide is made into a matte finish, the more uniform wear resistance is required no matter which part of the cemented carbide particles or metal is on the top surface, so the effect of the present invention will be better. It will appear. Incidentally, among the carbides, nitrides, and tungsten carbide of the present invention, silvery white compounds are TiC, VC, and WC, and golden yellow compounds are NbC, TaC, TiN, HfN, and TaN. EXAMPLES Below, the decorative cemented carbide according to the present invention will be explained with reference to Examples. Example 1 As a raw material powder, TaC particles with an average particle size of 0.7 mm were mixed with WC powder with an average particle size of 1.3 μm and a binder metal with an average particle size of 3 μm so as to have the final component composition shown in Table 1, and the mixture was heated under vacuum. The decorative cemented carbide of the present invention was produced by sintering in an atmosphere at 1300 to 1400°C for 1 hour and then hot isostatic pressing at 1350°C and 500 atm. This alloy was subjected to rough grinding using a diamond grinder and lapping finishing using a lapping machine. After this, when this alloy was immersed in the following etching solution at 90℃ for 10 minutes, the WC part turned black and the TaC grain part also became matte, giving it a more golden image. A dispersed cemented carbide could be formed. Etching liquid K 3 Fe (CN) 6 3 g KOH 10 g H 2 O 100 ml The alloy thus prepared was heated using artificial sweat (PH = 4.7) in accordance with ISO (International Organization for Standardization) standards as an etching liquid. A corrosion resistance test was conducted by immersing the lower half of the mirror-polished specimen in the artificial sweat kept at 40°C ± 2°C for 24 hours and observing whether clouding occurred on the polished surface. No problems occurred. Furthermore, even if a watch body was manufactured using the above alloy and a cover glass, case back, etc. were installed, it would not cause any problems such as cracks up to a height of 1.0 m even if it was dropped onto concrete, and there would be no practical problems. Nakatsuta. The decorative cemented carbide of the present invention has no problems in corrosion resistance or impact resistance, and has a hardness of Hv=1300 or more, so no scratches were caused in practical use. In this way, although it has various properties equivalent to conventional cemented carbide, this alloy has WC-Co around the golden grains of TaC.
- We were able to create a decorative cemented carbide with a new image of uniform wear resistance, surrounded by Cr-based silvery-white cemented carbide.
【表】
実施例 ２
原料粉末として、平均粒径0.3〜３mmのTaC粒
子、TiN粒子、HfN粒子を平均粒径1.5μmのTiC
粉末と平均粒径1.8μmのTiN粉末と平均粒径3μm
の金属バインダーを第２表に示す最終組成を持つ
よう混合し、実施例１と同様の工程で焼結し、装
飾用超硬合金を作成した。この合金を実施例１と
同様の条件で研磨を行い、下記の成分のエツチン
グ液中にて、下記の条件で処理を行つた。
エツチング液
ピクリン酸 2g
NaOH 25g
H2O 100ml
エツチング条件
温度 20℃
陽極 試料
陰極 白金
電圧 7V
時間 １分
この超硬合金を実施例１と同様の評価を行つ
た。その結果、耐食性、耐衝撃性、硬度等特に問
題はなく、従来の超硬合金と同等の各種特性を有
しながら、黄金色が微妙に異なるTaC，TiN，
HfN粒子がTiC系の白色超硬合金の中に分散して
いる新しい耐摩耗性が均一な装飾用超硬合金をつ
ることができた。[Table] Example 2 As raw material powders, TaC particles, TiN particles, and HfN particles with an average particle size of 0.3 to 3 mm were mixed with TiC particles with an average particle size of 1.5 μm.
Powder and average particle size 1.8μm TiN powder and average particle size 3μm
The metal binders were mixed to have the final composition shown in Table 2 and sintered in the same process as in Example 1 to produce a decorative cemented carbide. This alloy was polished under the same conditions as in Example 1, and treated in an etching solution with the following components under the following conditions. Etching liquid Picric acid 2g NaOH 25g H 2 O 100ml Etching conditions Temperature 20°C Anode Sample Cathode Platinum Voltage 7V Time 1 minute This cemented carbide was evaluated in the same manner as in Example 1. As a result, TaC, TiN, etc. have no particular problems with corrosion resistance, impact resistance, hardness, etc., and have various properties equivalent to conventional cemented carbide, but with a slightly different golden color.
A new decorative cemented carbide with uniform wear resistance was created in which HfN particles were dispersed in a TiC-based white cemented carbide.
【表】
実施例 ３
原料粉末として、平均粒系1.0mmのWC粒子に平
均粒系1.5μmのTiNとNbCとVCの粉末に、平均
粒系3μmの金属バインダーを第３表に示す最終成
分組成を持つように混合し、実施例１と同様の工
程で焼結と下記の内容のエツチング処理を行うこ
とにより、本発明の装飾用超硬合金を製造した。
これも、実施例１〜２と同様の特性を有し銀白色
のWC粒子を黄金色系のTiN系超硬合金がとり囲
む耐摩耗性が均一装飾用超硬合金をつくることが
できた。
エツチング液
NaCN 10g
H2O 90ml
エツチング条件
温度 25℃
陽極 試料（エツチング用）
陰極 試料（エツチング用）
電圧 6V
時間 ７分[Table] Example 3 As raw material powders, WC particles with an average grain size of 1.0 mm, TiN, NbC, and VC powders with an average grain size of 1.5 μm, and a metal binder with an average grain size of 3 μm were used as the final component composition shown in Table 3. The decorative cemented carbide of the present invention was manufactured by mixing the materials so as to have the same properties and performing sintering and etching treatment as described below in the same steps as in Example 1.
This also made it possible to produce a decorative cemented carbide having the same properties as Examples 1 and 2 and having uniform wear resistance in which silvery white WC particles were surrounded by golden TiN based cemented carbide. Etching solution NaCN 10g H 2 O 90ml Etching condition temperature 25℃ Anode sample (for etching) Cathode sample (for etching) Voltage 6V Time 7 minutes
【表】
以上の通り、本発明によれば、
平均粒径0.3〜３mmのWC，TaC，TiN，HfN
のいずれかの少なくとも１種の所定量を用いると
ともに、
平均粒径が1.3〜1.8μmのWC，TiC，TiN，
NbC，VCのいずれかの１種の所定量を金属バイ
ンダーの所定量に分散させることにより、
バイカラーまたはトリカラーのすぐれた外観が
得られるとともに、大きな粒子間を結合する金属
バインダー中にも超硬微粒子が分散されているの
で、どの部分をとつてもほぼ同様なすぐれた耐摩
耗性を有した装飾用超硬合金を得ることができ
る。[Table] As described above, according to the present invention, WC, TaC, TiN, HfN with an average particle size of 0.3 to 3 mm
Use a predetermined amount of at least one of: WC, TiC, TiN, with an average particle size of 1.3 to 1.8 μm.
By dispersing a predetermined amount of either NbC or VC into a predetermined amount of a metal binder, an excellent bicolor or tricolor appearance can be obtained, and the metal binder that binds large particles can also contain Since the hard particles are dispersed, it is possible to obtain a decorative cemented carbide having excellent wear resistance that is almost the same in all parts.
Claims (1)
HfNのうちから選ばれたいずれかの少なくとも
１種の24〜50wt％と、 平均粒径が1.3〜1.8μmのWC，TiC，TiN，
NbC，VCのうちから選ばれたいずれかの少なく
とも１種の40〜56wt％と、 金属バインダーとして、Ni，Co，Crのうちか
ら選ばれたいずれかの少なくとも２種の粉末の10
〜20wt％とを用いて焼結したことを特徴とする
装飾用超硬合金。[Claims] 1. WC, TaC, TiN, with an average particle size of 0.3 to 3 mm,
24-50wt% of at least one selected from HfN, WC, TiC, TiN, with an average particle size of 1.3-1.8μm,
40 to 56 wt% of at least one selected from NbC and VC, and 10 to 56 wt% of at least two powders selected from Ni, Co, and Cr as a metal binder.
A decorative cemented carbide characterized by being sintered using ~20wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57186503A JPS5976801A (en) | 1982-10-23 | 1982-10-23 | Decorative cemented carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57186503A JPS5976801A (en) | 1982-10-23 | 1982-10-23 | Decorative cemented carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5976801A JPS5976801A (en) | 1984-05-02 |
| JPH0128825B2 true JPH0128825B2 (en) | 1989-06-06 |
Family
ID=16189629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57186503A Granted JPS5976801A (en) | 1982-10-23 | 1982-10-23 | Decorative cemented carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5976801A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6553667B1 (en) | 1997-09-08 | 2003-04-29 | Trent West | Apparatus and method for manufacturing composite articles including wear resistant jewelry and medical and industrial devices and components thereof |
| KR100734014B1 (en) | 2006-03-31 | 2007-07-04 | 김성훈 | Method for manufacturing ring of hard material with precious metal inlaid and ring inlaid with precious metal on outer circumferential surface |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5232608A (en) * | 1975-09-09 | 1977-03-12 | Sony Corp | Signal control circuit |
| JPS569345A (en) * | 1979-07-05 | 1981-01-30 | Hitachi Chem Co Ltd | Carbon sphere dispersed metal or alloy material |
-
1982
- 1982-10-23 JP JP57186503A patent/JPS5976801A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5976801A (en) | 1984-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4589917A (en) | Decorative golden sintered alloy | |
| US4606767A (en) | Decorative silver-colored sintered alloy | |
| JP2766661B2 (en) | Boron treated hard metal | |
| KR100239844B1 (en) | Gold sintered gold | |
| US6171989B1 (en) | Silver-colored sintered product and method of producing the same | |
| JPH0128825B2 (en) | ||
| DE3335414C2 (en) | Process for the production of ceramic articles from titanium nitride and zirconium oxide | |
| JP7819240B2 (en) | Cermet timepiece or jewelry components | |
| US4422874A (en) | Golden sintered alloy for ornamental purpose | |
| JP3255744B2 (en) | Golden sintered body and method for producing the same | |
| JPS5982157A (en) | Production of alloy for decoration | |
| JPS5941444A (en) | Decorative cemented carbide | |
| JP3020663B2 (en) | Seal | |
| KR950007174B1 (en) | Manufacturing method of hard alloy for watch case | |
| JP3231873B2 (en) | Silver sintered alloy and method for producing the same | |
| JPS5916945A (en) | Exterior parts for watches | |
| JPS5913045A (en) | External decorative parts for timepiece | |
| JPS62235440A (en) | Sintered materials for decorative parts | |
| JPH0344138B2 (en) | ||
| JPS597341B2 (en) | Hard sintered alloy with excellent corrosion resistance | |
| JPH05311311A (en) | Gold-colored sintered alloy | |
| JPS5948948B2 (en) | Sintered hard alloy with excellent corrosion resistance | |
| JP2722118B2 (en) | Titanium carbide based silver sintered alloy | |
| DE3426176A1 (en) | Hard-silver ceramic for decorative purposes | |
| JPS5941401A (en) | Manufacture of ornamental alloy |