JPS634630B2 - - Google Patents
Info
- Publication number
- JPS634630B2 JPS634630B2 JP58058918A JP5891883A JPS634630B2 JP S634630 B2 JPS634630 B2 JP S634630B2 JP 58058918 A JP58058918 A JP 58058918A JP 5891883 A JP5891883 A JP 5891883A JP S634630 B2 JPS634630 B2 JP S634630B2
- Authority
- JP
- Japan
- Prior art keywords
- gold alloy
- coating layer
- base member
- hard
- sputtering
- 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
- 229910001020 Au alloy Inorganic materials 0.000 claims description 33
- 239000003353 gold alloy Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- -1 cyanide compound Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Description
この発明は、例えば時計ケースや時計バンド、
さらにネツクレスやブレスレツトなどの基体部材
の表面に硬質金合金被覆層を形成する方法に関す
るものである。
通常、上記のような各種の装飾品においては、
ステンレス鋼や真ちゆうなどの基体部材の表面に
湿式電気メツキ法などを用いて金合金をメツキす
ることが行なわれている。
しかし、このような金合金メツキ法において
は、
(a) 金合金メツキ層自体が純金に近く、軟質であ
るため、傷がつき易く、摩耗し易い。
(b) 金合金メツキ層はピンホールが多く、耐食性
に劣るものであるため、下地としてNiメツキ
などを行なう必要がある。
(c) メツキ液として、シアン化合物を使用するた
め、廃水処理用プラントを必要とし、コスト高
の原因となる。
などの問題点を有するものである。
そこで、本発明者等は、上述のような観点か
ら、装飾品などの基体部材の表面に、硬質にして
耐食性のすぐれた金合金被覆層を形成すべく研究
を行なつた結果、
ターゲツトとして、
(a) Au：41.6〜91.6％、AgおよびCuのうちの１
種または２種、並びに不可避不純物：残りから
なる組成（以上重量％、以下％は重量％を示
す）を有する金合金。
(b) Au：41.6〜91.6％、Ni，Co，FeおよびPdの
うちの１種または２種以上：0.5〜10％、Agお
よびCuのうちの１種または２種、並びに不可
避不純物：残りからなる組成を有する金合金。
(c) Au：41.6〜91.6％、Al：0.5〜５％、Agおよ
びCuのうちの１種または２種、並びに不可避
不純物：残りからなる組成を有する金合金。
(d) Au：41.6〜91.6％、Zn：0.5〜５％、Agおよ
びCuのうちの１種または２種、並びに不可避
不純物：残りからなる組成を有する金合金。
以上(a)〜(d)のうちのいずれかの金合金と、
Ti，Zr、およびCr、並びにこれらの合金のう
ちの１種または２種以上からなる硬化金属とを用
い、
N2およびNH3のうちの１種または２種を含有
するArガス雰囲気中でスパツタリングを行なう
と、ステンレス鋼や真ちゆうなどの基体部材の表
面に、上記(a)〜(d)のうちのいずれかの金合金中
に、上記硬化金属が主として窒化物の形で分散含
有した組織を有する金合金被覆層が蒸着形成され
るようになり、この結果の金合金被覆層は、きわ
めて硬質で、ビツカース硬さで400〜700Kg／mm2の
著しく高い硬さをもち、かつピンホールなどの形
成もないので、金合金自体のもつ耐食性によつて
すぐれた耐食性をもつという知見を得たのであ
る。
この発明は、上記知見にもとづいてなされたも
のであつて、ターゲツトとして、上記組成の金合
金と、上記硬化金属とを用い、N2およびNH3の
いずれか、または両方を１〜80容量％含有し、残
りがArからなる混合ガス雰囲気中で、スパツタ
リングを行なうことにより、基体部材の表面に、
上記金合金中に、上記硬化金属が主として窒化物
の形で0.5〜５％含有した硬質金合金被覆層を形
成する方法に特徴を有するものである。
なお、この発明の方法において、混合ガス雰囲
気中のN2およびNH3の含有量を１〜80容量％と
限定したのは、１容量％未満の含有では、金合金
被覆層に所望の高硬度を付与することができず、
一方80容量％を越えた含有になると、スパツター
速度が低下し、実用的でなくなるという理由によ
るものであり、また、金合金被覆層における硬化
金属の含有量が0.5％未満では所望の高硬度を確
保することができず、一方その含有量が５％を越
えると窒化物の量が多くなりすぎ、この窒化物に
よつて金合金自体のもつ色調が損なわれるように
なることから、その含有量を0.5〜５％と定めた。
さらに、この発明の方法は、直流または高周波
電流を用いる通常のスパツタリング法によつて実
施することができるが、望ましくは蒸着速度の速
いマグネトロンスパツタリング法を用いるのがよ
く、しかもこれによつて光沢の良好な蒸着表面が
得られるようになる。
つぎに、この発明の方法を実施例により具体的
に説明する。
実施例
それぞれ第１表に示される材質の基体部材、金
合金ターゲツト、および硬化金属ターゲツトを用
意し、これら各部材を同じく第１表に示される組
合せで通常のスパツタリング装置内に装着し、さ
らに同じく第１表に示されるスパツタリング条件
にてスパツタリングを行なうことによつて本発明
法１〜18をそれぞれ実施した。
ついで、この結果形成された金合金被覆層につ
いて、その組成をＸ線マイクロアナライザーにて
定量すると共に、硬さ、平均層厚、および色調を
測定し、観察した。これらの結果を第２表に示し
た。第２表には比較の目的で金合金ターゲツトの
硬さも示した。
第２表に示される結果から、本発明法１〜18に
よつて形成された金合金被覆層は、いずれも高い
硬さを有し、かつ金合金ターゲツトのもつ色調と
ほぼ同じ色をもつものであつた。
上述のように、この発明の方法によれば、ピン
ホールなどの欠陥のない硬質の金合金被覆層をコ
This invention can be applied to watch cases, watch bands, etc.
The invention further relates to a method for forming a hard gold alloy coating layer on the surface of a base member such as a necklace or bracelet. Usually, in the various ornaments mentioned above,
Gold alloy is plated on the surface of a base member such as stainless steel or brass using a wet electroplating method or the like. However, in such a gold alloy plating method, (a) the gold alloy plating layer itself is close to pure gold and is soft, so it is easily scratched and abraded. (b) The gold alloy plating layer has many pinholes and has poor corrosion resistance, so it is necessary to use Ni plating as a base layer. (c) Since a cyanide compound is used as the plating liquid, a wastewater treatment plant is required, which causes high costs. This method has the following problems. Therefore, from the above-mentioned viewpoint, the present inventors conducted research to form a hard gold alloy coating layer with excellent corrosion resistance on the surface of a base member such as an ornament, and as a result, as a target: (a) Au: 41.6-91.6%, one of Ag and Cu
A gold alloy having a composition consisting of one or two species, and unavoidable impurities: the remainder (the above weight percent, the below weight percent). (b) Au: 41.6 to 91.6%, one or more of Ni, Co, Fe, and Pd: 0.5 to 10%, one or two of Ag and Cu, and unavoidable impurities: the remainder A gold alloy with the following composition. (c) A gold alloy having a composition consisting of Au: 41.6 to 91.6%, Al: 0.5 to 5%, one or two of Ag and Cu, and unavoidable impurities: the remainder. (d) A gold alloy having a composition consisting of Au: 41.6 to 91.6%, Zn: 0.5 to 5%, one or two of Ag and Cu, and unavoidable impurities: the remainder. Using any of the gold alloys (a) to (d) above, Ti, Zr, and Cr, and a hardened metal consisting of one or more of these alloys, N 2 and NH When sputtering is performed in an Ar gas atmosphere containing one or two of the above three , any of the above (a) to (d) may occur on the surface of a base member such as stainless steel or brass. A gold alloy coating layer having a structure in which the hardened metal is mainly dispersed in the form of nitride is formed by vapor deposition in the gold alloy, and the resulting gold alloy coating layer is extremely hard and has a Vickers hardness. The gold alloy has extremely high hardness of 400 to 700 kg/mm 2 and does not form pinholes, so it was found that it has excellent corrosion resistance due to the corrosion resistance of the gold alloy itself. This invention was made based on the above findings, and uses a gold alloy having the above composition and the above hardened metal as a target, and injects 1 to 80% by volume of either N 2 or NH 3 or both. By performing sputtering in a mixed gas atmosphere containing Ar, and the remainder being Ar, on the surface of the base member,
The method is characterized by forming a hard gold alloy coating layer containing 0.5 to 5% of the hardened metal mainly in the form of nitride in the gold alloy. In addition, in the method of this invention, the content of N 2 and NH 3 in the mixed gas atmosphere is limited to 1 to 80% by volume, because if the content is less than 1% by volume, the gold alloy coating layer will not have the desired high hardness. cannot be granted,
On the other hand, if the content exceeds 80% by volume, the sputtering speed will decrease, making it impractical.If the content of hardened metal in the gold alloy coating layer is less than 0.5%, it will be difficult to achieve the desired high hardness. On the other hand, if the content exceeds 5%, the amount of nitrides will be too large, and the color tone of the gold alloy itself will be impaired by these nitrides. was set at 0.5% to 5%. Furthermore, although the method of the present invention can be carried out by a conventional sputtering method using direct current or high-frequency current, it is preferable to use a magnetron sputtering method which has a high deposition rate. A deposited surface with good gloss can be obtained. Next, the method of the present invention will be specifically explained using examples. Example A base member, a gold alloy target, and a hardened metal target each made of the materials shown in Table 1 are prepared, and these members are mounted in a normal sputtering device in the combinations also shown in Table 1, and then the same Methods 1 to 18 of the present invention were carried out by sputtering under the sputtering conditions shown in Table 1. Next, the composition of the gold alloy coating layer thus formed was determined using an X-ray microanalyzer, and the hardness, average layer thickness, and color tone were measured and observed. These results are shown in Table 2. Table 2 also shows the hardness of gold alloy targets for comparison purposes. From the results shown in Table 2, the gold alloy coating layers formed by methods 1 to 18 of the present invention all have high hardness and have almost the same color tone as the gold alloy target. It was hot. As described above, according to the method of the present invention, a hard gold alloy coating layer free from defects such as pinholes is coated.
【表】【table】
【表】【table】
【表】
スト安く形成することができ、しかもこれを装飾
品などに適用した場合には、傷がつきにくく、か
つ摩耗し難いので、金合金自体のもつ美麗な黄金
色を、すぐれた光沢を保持した状態で著しく長期
に旦つて確保できるようになるのである。[Table] It can be formed at a low cost, and when applied to decorative items, it is hard to scratch and wear, so it can maintain the beautiful golden color of the gold alloy itself with excellent luster. This means that it can be secured for an extremely long period of time.
Claims (1)
よびCr、並びにこれらの合金のうち１種または
２種以上からなる硬化金属とを用い、 N2およびNH3のうちの１種または２種：１〜
80容量％、Ar：残りからなる混合ガス雰囲気中
で、スパツタリングを行なうことにより、基体部
材表面に、上記金合金中に上記硬化金属が主とし
て窒化物の形で0.5〜５重量％含有した組成を有
する硬質金合金を蒸着させることを特徴とする硬
質金合金被覆層の形成方法。[Claims] 1. A gold alloy, Ti, Zr, and Cr, and a hardened metal consisting of one or more of these alloys are used as targets, and one of N 2 and NH 3 is used as a target. Species or 2 types: 1~
By performing sputtering in a mixed gas atmosphere consisting of 80% by volume, Ar: and the rest, a composition containing 0.5 to 5% by weight of the above-mentioned hardening metal mainly in the form of nitride in the above-mentioned gold alloy is formed on the surface of the base member. 1. A method for forming a hard gold alloy coating layer, comprising depositing a hard gold alloy comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5891883A JPS59185774A (en) | 1983-04-04 | 1983-04-04 | Formation of coated hard gold alloy layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5891883A JPS59185774A (en) | 1983-04-04 | 1983-04-04 | Formation of coated hard gold alloy layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59185774A JPS59185774A (en) | 1984-10-22 |
| JPS634630B2 true JPS634630B2 (en) | 1988-01-29 |
Family
ID=13098198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5891883A Granted JPS59185774A (en) | 1983-04-04 | 1983-04-04 | Formation of coated hard gold alloy layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59185774A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6067654A (en) * | 1983-09-22 | 1985-04-18 | Seiko Instr & Electronics Ltd | Preparation of hard gold alloy plating |
| FR2589484A1 (en) * | 1985-11-04 | 1987-05-07 | Asulab Sa | OBJECT WITH PRECIOUS METAL COATING RESISTANT TO WEAR |
| JPH0520683U (en) * | 1991-09-03 | 1993-03-19 | 積水化学工業株式会社 | Washbasin unit |
| CN106756842B (en) * | 2016-12-16 | 2019-03-15 | 安徽宝恒新材料科技有限公司 | A kind of processing method improving stainless steel machinery performance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS542942A (en) * | 1977-06-10 | 1979-01-10 | Tsuneo Nishida | Golddcolorrtrimmed members |
-
1983
- 1983-04-04 JP JP5891883A patent/JPS59185774A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS542942A (en) * | 1977-06-10 | 1979-01-10 | Tsuneo Nishida | Golddcolorrtrimmed members |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59185774A (en) | 1984-10-22 |
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