JPH0233798B2 - - Google Patents
Info
- Publication number
- JPH0233798B2 JPH0233798B2 JP62144410A JP14441087A JPH0233798B2 JP H0233798 B2 JPH0233798 B2 JP H0233798B2 JP 62144410 A JP62144410 A JP 62144410A JP 14441087 A JP14441087 A JP 14441087A JP H0233798 B2 JPH0233798 B2 JP H0233798B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- titanium
- plating layer
- ruthenium
- metal plating
- 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
- 238000007747 plating Methods 0.000 claims description 93
- 239000010970 precious metal Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 229910000510 noble metal Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- OVKMDTVKFLNYRN-UHFFFAOYSA-N [Cd].[Cu].[Au] Chemical compound [Cd].[Cu].[Au] OVKMDTVKFLNYRN-UHFFFAOYSA-N 0.000 description 1
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はチタン系素材への貴金属メツキ方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for plating titanium-based materials with precious metals.
チタン系素材は軽量で耐食性に優れるため従来
より各種の分野で用いられているが、近年、金属
製の眼鏡フレームや腕時計外装部品等の材料とし
ての利用が高まるにつれて、より美麗な外観の製
品とするために、チタン系素材の表面に貴金属メ
ツキを施すための種々の試みが行われている。
Titanium-based materials have traditionally been used in a variety of fields due to their light weight and excellent corrosion resistance, but in recent years, as their use as materials for metal eyeglass frames and wristwatch exterior parts has increased, titanium-based materials have become increasingly popular for products with a more beautiful appearance. To this end, various attempts have been made to plate the surface of titanium-based materials with precious metals.
しかしながらチタン系素材上に直接貴金属メツ
キを施した場合、貴金属メツキ層のチタン系素材
への密着性が悪く、美麗な外観光沢を損なうこと
なく良好な貴金属メツキを施すことはきわめて困
難であつた。このため従来はチタン系素材の表面
に貴金属メツキが可能なニツケル張りを行つた
後、貴金属メツキを施したり、ニツケルメツキを
施した後、貴金属メツキを施す方法（例えば、特
開昭59−162296号等）等が採用されているがニツ
ケルは薬品に侵され易い欠点があるため、耐食性
に優れた製品とするためには貴金属メツキ層の厚
さをかなり厚くする必要があり、この結果製品が
非常に高価なものとなるという問題があつた。ま
たこのような方法により貴金属メツキを施した製
品の場合、使用中に貴金属メツキ層の一部が摩耗
したり傷付いたりして貴金属メツキ層下層のニツ
ケルメツキ層が露出すると、ニツケルメツキ層が
汗等により腐食されて貴金属メツキが剥落すると
いう大きな欠点があつた。 However, when noble metal plating is applied directly onto a titanium-based material, the adhesion of the noble metal plating layer to the titanium-based material is poor, and it is extremely difficult to apply good noble metal plating without impairing the beautiful appearance and gloss. For this reason, conventional methods have been to apply nickel plating, which can be plated with precious metals, to the surface of titanium-based materials, and then apply precious metal plating, or to apply nickel plating and then plating with precious metals (for example, JP-A No. 59-162296, etc.). ) etc., but nickel has the disadvantage of being easily attacked by chemicals, so in order to make a product with excellent corrosion resistance, it is necessary to make the precious metal plating layer considerably thicker, and as a result, the product becomes very There was a problem that it was expensive. In addition, in the case of products plated with precious metals using this method, if a part of the precious metal plating layer is worn or scratched during use and the nickel plating layer below the precious metal plating layer is exposed, the nickel plating layer may be damaged by sweat, etc. A major drawback was that the precious metal plating would peel off due to corrosion.
上記の点に鑑み鋭意研究した結果、従来技術の
欠点を解決できる方法としてロジウムストライク
メツキを施した後、貴金属メツキを施す方法（特
願昭60−202456号特開昭62−63699号）、パラジウ
ムストライクメツキを施した後、貴金属メツキを
施す方法（特願昭60−258372号（特開昭62−
120493号））を提案した。 As a result of intensive research in view of the above points, we found a method that can solve the drawbacks of the conventional technology: rhodium strike plating and then noble metal plating (Japanese Patent Application No. 60-202456 and 62-63699), palladium A method of applying precious metal plating after applying strike plating (Japanese Patent Application No. 1983-258372
No. 120493)) was proposed.
これらの方法によればチタン系素材の上に密着
性、耐食性に優れた貴金属メツキ層を施すことが
できるが、メツキ処理後、素材の形状不良等の理
由により、メツキ層を溶解剥離し、再生したい場
合、ロジウムストライクメツキでは溶解剥離がで
きず不良品の再生を行なうことができず、またパ
ラジウムストライクメツキの場合も素材の一部に
銀ロー材が使用されていると硝酸による溶解剥離
ができず、不良品の再生が行なえないという問題
があつた。更にロジウム、パラジウムは高価であ
り、再生不能の不良品の発生は経済的な面でも問
題であつた。 According to these methods, it is possible to apply a noble metal plating layer with excellent adhesion and corrosion resistance on titanium-based materials, but after the plating treatment, due to reasons such as poor shape of the material, the plating layer is dissolved and peeled off and recycled. If you want to do this, rhodium strike plating cannot be removed by dissolving and peeling, and defective products cannot be recycled, and palladium strike plating cannot be removed by dissolving with nitric acid if silver brazing material is used as part of the material. First, there was a problem that defective products could not be recycled. Furthermore, rhodium and palladium are expensive, and the occurrence of defective products that cannot be recycled is an economic problem.
本発明者は更に鋭意研究した結果、ルテニウム
ストライクメツキを施した後、貴金属メツキを施
すことにより、これらの問題を解決できることを
見出し本発明を完成するに至つた。 As a result of further intensive research, the present inventor discovered that these problems could be solved by applying noble metal plating after ruthenium strike plating, and completed the present invention.
即ち本発明はチタン系素材を弗化物を含有する
処理液で処理した後、ルテニウムストライトメツ
キを施し、次いでこの上に更に貴金属メツキを施
すことを特徴とするチタン系素材への貴金属メツ
キ方法を要旨とする。
That is, the present invention provides a method for plating a titanium-based material with a precious metal, which comprises treating the titanium-based material with a treatment solution containing fluoride, applying ruthenium strite plating, and then further applying precious metal plating thereon. This is the summary.
本発明においてチタン系素材としてはチタン及
びチタン合金が用いられ、チタン合金としては例
えばTi−3Al−5Cr、Ti−5Al−2Cr−2Mo、Ti−
7Al−5Cr、Ti−2.5Al−16V、Ti−15Mo−5Zr−
3Al、Ti−4Al−4Mn等が挙げられる。 In the present invention, titanium and titanium alloys are used as titanium-based materials, and examples of titanium alloys include Ti-3Al-5Cr, Ti-5Al-2Cr-2Mo, Ti-
7Al−5Cr, Ti−2.5Al−16V, Ti−15Mo−5Zr−
Examples include 3Al, Ti-4Al-4Mn, and the like.
本発明においてはチタン系素材をまず弗化物を
含有する処理液にて処理するが、通常この処理に
先だつてチタン系素材をアルカリ等により脱脂洗
浄する。弗化物を含有する処理液としては弗化物
を0.1〜20wt％含有するPH6.0以下の溶液が好まし
い。上記弗化物としては例えば酸性弗化アンモニ
ウム、ケイ弗酸、ホウ弗酸、弗化カルシウム、弗
化カリウム、弗化ナトリウム、ケイ弗化カリウ
ム、酸性弗化カリウム、酸性弗化ナトリウム、弗
化水素酸等が挙げられる。弗化物を含有する処理
液による処理は、チタン系素材を該処理液に浸漬
することにより行われるが、処理液の温度１〜60
℃、浸漬時間10〜300秒程度の条件で処理するこ
とが好ましい。 In the present invention, the titanium-based material is first treated with a treatment liquid containing fluoride, but usually prior to this treatment, the titanium-based material is degreased and cleaned with an alkali or the like. As the treatment liquid containing fluoride, a solution containing 0.1 to 20 wt% of fluoride and having a pH of 6.0 or less is preferable. Examples of the above fluorides include acidic ammonium fluoride, fluorosilicic acid, boric fluoride, calcium fluoride, potassium fluoride, sodium fluoride, potassium silicofluoride, acidic potassium fluoride, acidic sodium fluoride, and hydrofluoric acid. etc. Treatment with a treatment solution containing fluoride is performed by immersing the titanium-based material in the treatment solution, but the temperature of the treatment solution is 1 to 60°C.
It is preferable to perform the treatment under conditions such as temperature and immersion time of about 10 to 300 seconds.
弗化物含有処理液で処理を行つたチタン系素材
には次いでルテニウムストライクメツキが施され
る。ルテニウムストライクメツキ工程に用いられ
るメツキ液としては通常のルテニウムメツキに用
いられると同様のメツキ液が使用される。ストラ
イクメツキは、溶融温度20〜80℃、電流密度0.1
〜5A／ｄm2、メツキ時間10〜300秒程度の条件で
行い、厚さ0.1〜1μ程度に形成することが好まし
い。 The titanium-based material that has been treated with a fluoride-containing treatment liquid is then subjected to ruthenium strike plating. The plating liquid used in the ruthenium strike plating process is the same as that used in normal ruthenium plating. Strike metal has a melting temperature of 20 to 80℃ and a current density of 0.1
It is preferable to perform the plating under conditions of ~5 A/dm 2 and a plating time of about 10 to 300 seconds, and form the plate to a thickness of about 0.1 to 1 μm.
なお、本発明における、ルテニウムストライク
メツキはルテニウム−ロジウム、ルテニウム−パ
ラジウム等の合金でもルテニウムストライクメツ
キと変わらない効果を有することが確認されてい
る。さらにルテニウムメツキ厚さは0.1μ以上あれ
ば効果があり、1.0μ以上でも品質面では異常ない
が経済性で好ましくない。 It has been confirmed that the ruthenium strike plating of the present invention has the same effect as the ruthenium strike plating even with alloys such as ruthenium-rhodium and ruthenium-palladium. Furthermore, if the thickness of the ruthenium plating is 0.1μ or more, it is effective, and if it is 1.0μ or more, there is no abnormality in terms of quality, but it is not desirable from an economic point of view.
本発明においてはルテニウムストライクメツキ
を施した後、この上に更に貴金属メツキを施す。
この貴金属メツキ工程に用いられるメツキ液は単
一の貴金属を含有するものでも異なる２種以上の
貴金属を含有するものでもよい。貴金属メツキ液
としては通常の貴金属メツキに用いられると同様
のメツキ液が使用される。上記貴金属メツキは溶
液温度40〜60℃、電流密度0.2〜1.0A／ｄm2で１
〜10分の条件で行うことにより0.2〜5μの貴金属
メツキ層を形成することができる。 In the present invention, after ruthenium strike plating is applied, noble metal plating is further applied thereon.
The plating solution used in this noble metal plating step may contain a single noble metal or two or more different noble metals. As the noble metal plating solution, a plating solution similar to that used for ordinary noble metal plating is used. The above precious metal plating is performed at a solution temperature of 40 to 60℃ and a current density of 0.2 to 1.0A/ dm2 .
A noble metal plating layer of 0.2 to 5μ can be formed by performing the process for ~10 minutes.
以下、実施例を挙げて本発明を更に詳細に説明
する。
Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
チタン合金製眼鏡フレームをアルカリ脱脂した
後、該フレームを酸性弗化アンモニウム20ｇ／
、スルフアミン酸150ｇ／、界面活性剤（フ
ルオロアルキルカルボン酸ナトリウム）0.1ｇ／
を含有するPH0.8の15℃の水溶液中に30秒間浸
漬して処理した後水洗した。次いで金属換算量で
５ｇ／となる硫酸ルテニウム及びスルフアミン
酸100ｇ、硫酸10ｇ／を含有しNaOHでPHを1.0
に調整した70℃の溶液中で白金電極を陽極とし、
電流密度5A／ｄm2で60秒間ルテニウムメツキを
施し、乾燥処理した。次ぎにアルカリ脱脂洗浄後
ただちに水洗した。次いで金属換算量で５ｇ／
となる亜硫酸金ナトリウム、金属換算量で３ｇ／
となるエチレンジアミンパラジウム、金属換算
量で0.01ｇ／となるエチレンジアミン銅、
EDTA・２ナトリウム塩80ｇ／、添加剤（亜
ヒ酸ナトリウム）0.02ｇ／を含有するPH10.5の
50℃のメツキ液中で白金電極を陽極として電流密
度0.6A／ｄm2で３分間メツキを行つたところ、
0.9μ厚の金−パラジウムメツキ層を有する外観美
麗な光沢のある眼鏡フレームが得られた。このフ
レームを200℃にて乾燥後、90度折り曲げ試験及
びキヤス試験10サイクルを行つたが、貴金属メツ
キ層が剥離する等の異常は全く確認されず、良好
な貴金属メツキが施されていることが確認され
た。Example 1 After degreasing a titanium alloy eyeglass frame with alkali, the frame was treated with 20g/20g of acidic ammonium fluoride.
, sulfamic acid 150g/, surfactant (sodium fluoroalkylcarboxylate) 0.1g/
The sample was treated by immersing it in an aqueous solution of pH 0.8 at 15°C for 30 seconds, followed by washing with water. Next, contain ruthenium sulfate and 100 g of sulfamic acid, 10 g of sulfuric acid, and reduce the pH to 1.0 with NaOH, which is 5 g/metal equivalent.
A platinum electrode is used as an anode in a 70℃ solution adjusted to
Ruthenium plating was applied at a current density of 5 A/dm 2 for 60 seconds, followed by drying. Next, after alkaline degreasing and cleaning, it was immediately washed with water. Next, 5g/metal equivalent amount
Sodium gold sulfite, metal equivalent amount: 3g/
Ethylenediamine palladium, which is 0.01g/metal equivalent, ethylenediamine copper,
Contains 80g of EDTA disodium salt and 0.02g of additive (sodium arsenite) with a pH of 10.5.
When plating was performed for 3 minutes in a plating solution at 50°C with a platinum electrode as an anode at a current density of 0.6A/ dm2 ,
A glossy eyeglass frame with a beautiful appearance and a gold-palladium plating layer with a thickness of 0.9 μm was obtained. After drying this frame at 200℃, we conducted 10 cycles of a 90-degree bending test and a casing test, but no abnormalities such as peeling of the precious metal plating layer were observed, indicating that the precious metal plating was in good condition. confirmed.
比較例 １
実施例１と同様の眼鏡フレームを、硫酸ニツケ
ル150ｇ／、塩化ニツケル150ｇ／、ホウ酸40
ｇ／含有し、リン酸でPH0.5に調整した55℃の
メツキ液中でニツケル電極を陽極として電流密度
5A／ｄm2にて60秒間ニツケルメツキを行つた。
次いでニツケルメツキ層の上に実施例１と同様の
条件で金−パラジウムメツキを施し、0.9μ厚の金
−パラジウムメツキ層を形成した。この眼鏡フレ
ームが外観美麗な光沢を有し、90度折り曲げ試験
においても異常は認められなかつたが、キヤス試
験５サイクルでは下層のニツケルメツキ層がキヤ
ス試験液により腐食され、表面の貴金属メツキ層
が剥落する異常が発生した。Comparative Example 1 Eyeglass frames similar to those in Example 1 were prepared using nickel sulfate 150g/nickel chloride 150g/boric acid 40g/
g/containing current density using a nickel electrode as an anode in a plating solution at 55°C adjusted to pH 0.5 with phosphoric acid.
Nickel plating was performed at 5 A/dm 2 for 60 seconds.
Next, gold-palladium plating was applied on the nickel plating layer under the same conditions as in Example 1 to form a gold-palladium plating layer with a thickness of 0.9 μm. This eyeglass frame had a beautiful gloss appearance and no abnormality was observed in the 90 degree bending test, but in 5 cycles of the cast test, the lower nickel plating layer was corroded by the cast test liquid, and the precious metal plating layer on the surface peeled off. An abnormality has occurred.
比較例 ２
弗化物を含有する処理液による処理が行わなか
つた他は実施例１と同様の方法でメツキ処理し、
金−パラジウムメツキ層を形成したが、金−パラ
ジウムメツキ層の密着性がきわめて悪く、90度折
り曲げ試験により表面の貴金属メツキ層が簡単に
剥落した。Comparative Example 2 Plating treatment was performed in the same manner as in Example 1, except that the treatment with a treatment solution containing fluoride was not performed.
Although a gold-palladium plating layer was formed, the adhesion of the gold-palladium plating layer was extremely poor, and the noble metal plating layer on the surface easily peeled off during a 90 degree bending test.
比較例 ３
ニテニウムストライクメツキ工程を行わなかつ
た他は実施例１と同様の方法でメツキ処理し、金
−パラジウムメツキ層を形成したが、金−パラジ
ウムメツキ層の密着性がきわめて悪く、90度折り
曲げ試験により表面の貴金属メツキ層が簡単に剥
落した。Comparative Example 3 A gold-palladium plating layer was formed by plating in the same manner as in Example 1 except that the nitenium strike plating step was not performed, but the adhesion of the gold-palladium plating layer was extremely poor, and the 90° During the bending test, the precious metal plating layer on the surface easily peeled off.
実施例 ２
実施例１と同様にして弗化物を含有する処理液
で処理した後、ルテニウムストライクメツキを施
した眼鏡フレームに白金電極を陽極としてパラジ
ウム−ニツケル合金メツキ（メツキ液温度35℃、
電流密度2A／ｄm2）、金−ニツケル合金メツキ
（メツキ液温度60℃、電流密度1.5A／ｄm2）、金
−銅−カドミウム合金メツキ（メツキ液温度55
℃、電流密度2A／ｄm2）、純金メツキ（メツキ液
温度50℃、電流密度1.0A／ｄm2）、ロジウムメツ
キ（メツキ液温度43℃、電流密度2A／ｄm2）を
各々0.3μ、1.0μ、2.0μ厚に形成したところ、いず
れも90度折り曲げ試験、キヤス試験10サイクルに
よる異常が認められず、貴金属メツキ層が密着性
に優れるとともに、貴金属メツキ層の厚さに関係
なく耐食性に優れていることが認められた。Example 2 After treatment with a treatment solution containing fluoride in the same manner as in Example 1, a ruthenium strike plated eyeglass frame was plated with palladium-nickel alloy using a platinum electrode as an anode (plating solution temperature: 35°C,
Current density 2A/ dm2 ), gold-nickel alloy plating (plating liquid temperature 60℃, current density 1.5A/ dm2 ), gold-copper-cadmium alloy plating (plating liquid temperature 55
℃, current density 2A/dm 2 ), pure gold plating (plating liquid temperature 50℃, current density 1.0A/dm 2 ), rhodium plating (plating liquid temperature 43℃, current density 2A/dm 2 ) 0.3 μ and 1.0, respectively. When formed to a thickness of μ and 2.0 μm, no abnormality was observed in either the 90 degree bending test or 10 cycles of the scraping test, indicating that the precious metal plating layer has excellent adhesion and excellent corrosion resistance regardless of the thickness of the precious metal plating layer. It was recognized that
以上説明したように、本発明はチタン系素材を
弗化物を含有する処理液で処理した後、ルテニウ
ムストライクメツキを施し、次いでこの上に更に
貴金属メツキを施す方法を採用したことにより、
貴金属メツキを施す前にニツケルメツキを施さず
とも、密着性に優れた美麗な光沢の貴金属メツキ
層を確実に形成することができる。しかも本発明
方法は貴金属メツキの下層にニツケルメツキ層を
形成しないため、本発明方法により貴金属メツキ
を施した製品は、貴金属メツキ層の厚さに関係な
く優れた耐食性を有し、従来の方法のように貴金
属メツキ層を必要以上に厚く形成する必要がな
い。しかも本発明方法により貴金属メツキを行つ
た製品は、たとえ貴金属メツキ層の一部に傷が付
いたりしても、従来の方法によりメツキされた製
品のように傷の付いた個所から腐食が進んで貴金
属メツキ層が剥落するという虞れがなく、美麗な
外観を長期間に亘つて保持することができる。
As explained above, the present invention employs a method in which a titanium-based material is treated with a treatment solution containing fluoride, then ruthenium strike plating is applied, and then precious metal plating is applied on top of this.
A noble metal plating layer with excellent adhesion and beautiful luster can be reliably formed without applying nickel plating before applying noble metal plating. Moreover, since the method of the present invention does not form a nickel plating layer under the precious metal plating, products plated with precious metals by the method of the present invention have excellent corrosion resistance regardless of the thickness of the precious metal plating layer, and unlike the conventional method, There is no need to form the precious metal plating layer thicker than necessary. Furthermore, even if a part of the precious metal plating layer is scratched on a product plated with precious metals using the method of the present invention, corrosion will not proceed from the scratched area unlike on products plated using the conventional method. There is no risk that the precious metal plating layer will peel off, and a beautiful appearance can be maintained for a long period of time.
而して本発明によればチタン系素材の耐食性、
軽量性を損なうことなく密着性に優れた貫金属光
沢を有する外観美麗な製品を安価に提供し得る。 According to the present invention, the corrosion resistance of titanium-based materials,
A product with a beautiful appearance and excellent adhesion and a metallic luster can be provided at a low cost without impairing lightness.
更にルテニウムストライクメツキを施したチタ
ン系素材は水酸化カリウム、水酸化ナトリウム等
のアルカリ水溶液中で陽極電解することにより素
地をいためることなくルテニウムを容易に溶解剥
離して再生することができ、加工工程中で発生し
た不良品の再生が容易であるとともに、ルテニウ
ムはロジウム、パラジウムに比べて安価であり、
経済性にも優れコスト低減化を図れる等の種々の
効果を有する。 Furthermore, titanium materials coated with ruthenium strike plating can be recycled by anodic electrolysis in an alkaline aqueous solution such as potassium hydroxide or sodium hydroxide, by easily dissolving and peeling off the ruthenium without damaging the base material. Not only is it easy to recycle defective products that occur during production, but ruthenium is also cheaper than rhodium and palladium.
It has various effects such as excellent economic efficiency and cost reduction.
Claims (1)
理した後、ルテニウムストライクメツキを施し、
次いでこの上に更に貴金属メツキを施すことを特
徴とするチタン系素材への貴金属メツキ方法。1 After treating the titanium-based material with a treatment solution containing fluoride, apply ruthenium strike plating,
A method for plating a titanium-based material with a precious metal, which is then further coated with a precious metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14441087A JPS63310993A (en) | 1987-06-10 | 1987-06-10 | Plating method of noble metal on titanium-base stock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14441087A JPS63310993A (en) | 1987-06-10 | 1987-06-10 | Plating method of noble metal on titanium-base stock |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63310993A JPS63310993A (en) | 1988-12-19 |
| JPH0233798B2 true JPH0233798B2 (en) | 1990-07-30 |
Family
ID=15361522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14441087A Granted JPS63310993A (en) | 1987-06-10 | 1987-06-10 | Plating method of noble metal on titanium-base stock |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63310993A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866585B (en) * | 2017-05-08 | 2021-01-05 | 永保科技(深圳)有限公司 | Refractory metal or stainless steel with electroplated layer on surface and electroplating process for surface of refractory metal or stainless steel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6263699A (en) * | 1985-09-12 | 1987-03-20 | Bikutoria:Kk | Method for plating titanium-base material with noble metal |
| JPS62120493A (en) * | 1985-11-18 | 1987-06-01 | Bikutoria:Kk | Plating method of noble metal to titanium stock |
-
1987
- 1987-06-10 JP JP14441087A patent/JPS63310993A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6263699A (en) * | 1985-09-12 | 1987-03-20 | Bikutoria:Kk | Method for plating titanium-base material with noble metal |
| JPS62120493A (en) * | 1985-11-18 | 1987-06-01 | Bikutoria:Kk | Plating method of noble metal to titanium stock |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63310993A (en) | 1988-12-19 |
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