JPS5816089A - Bath for electrically depositing palladium/nickel alloy - Google Patents
Bath for electrically depositing palladium/nickel alloyInfo
- Publication number
- JPS5816089A JPS5816089A JP57032483A JP3248382A JPS5816089A JP S5816089 A JPS5816089 A JP S5816089A JP 57032483 A JP57032483 A JP 57032483A JP 3248382 A JP3248382 A JP 3248382A JP S5816089 A JPS5816089 A JP S5816089A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- nickel
- bath
- sodium
- nickel 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は、浴が、５ないし３０ ｆ／ｌの範囲の）ζラ
ジウム含有量および同様に５ないし３０ ｆ／ｌの範囲
のニッケル含有量、およびスルホン酸塩の添加物を含む
パラジウムおよびニッケルアミンの水溶液から成り、こ
の水溶液において、電気的に析出される合金が３０ない
し９０重量％のノぐラジウム含有量を有するように、ノ
くラジウムとニッケルの比が設定されている、装飾的お
よび工業的な被伽のためパラジウム／ニッケル合金を電
気的に析出する浴に関する。このような浴によって作ら
れる被覆は金の代用として使われる。DETAILED DESCRIPTION OF THE INVENTION The present invention provides that the bath contains a an aqueous solution of palladium and nickel amine containing nickel, in which the ratio of radium to nickel is set such that the alloy to be electro-deposited has a radium content of 30 to 90% by weight. Baths for electrolytic deposition of palladium/nickel alloys for decorative and industrial applications. The coating produced by such baths is used as a gold substitute.
公知の浴（英国特許第１１４３１７８号明細書）におい
て、スルホン酸および／またはその塩の添加物が光沢を
形成するために使われる。詳細に述べれば、ナフタリン
−１，５−ジスルホン酸のナトリウム塩、ナフタリン−
１，３，６−）リスルホ／酸のナトリウム塩、およびサ
ッカリン（０−スルホ安息香酸イミド）およびＰ−）ル
オスルホンアミドのような、ナフタリンスルホン酸およ
び芳香族スルホンアミドの塩が挙げられる。しかし実線
にはくのような浴により作られる被〜は、機械り
的に考ヅして要求には相応せず、かつ光沢すら多くの装
飾のために不十分であるとわかった。本発明の基礎とす
る知識によればこれら欠点は、不完全な易溶体形成によ
る。In the known bath (GB 1 143 178), additives of sulfonic acid and/or its salts are used to create the gloss. Specifically, the sodium salt of naphthalene-1,5-disulfonic acid, naphthalene-1,5-disulfonic acid,
Included are the sodium salts of 1,3,6-) lysulfo/acids, and the salts of naphthalene sulfonic acids and aromatic sulfonamides, such as saccharin (0-sulfobenzoic acid imide) and P-)luosulfonamide. However, it has been found that the coatings produced by baths such as those shown in solid line do not meet the requirements from a mechanical point of view, and even the luster is insufficient for many decorations. According to the knowledge on which the invention is based, these disadvantages are due to incomplete formation of readily soluble materials.
本発明の課題は、支障ない易溶体形成が行われるように
初めに述べたような浴を構成することにある。The object of the invention is to construct a bath of the type mentioned at the beginning in such a way that an easily soluble formation takes place without any problems.
この課題を解決するため、本発明は次のことを示してい
る。すなわち易溶体形成を改善するため添加物が、ナト
リウムアリルスルホナート、ナトリウムアリルスルホナ
ート、ナトリウムグロビンスルホナート、ナトリウムメ
タリルスルホナート、Ｎ−ピリジニウムプロピルスルホ
ベタイン、Ｎ−ピリジニウムメチルスルホベタイン、Ｎ
−ベアジルピリジニウム−２−エチルスルホン酸、ナト
リウム塩のうち１つの物質またはこれら物質の混合物か
ら成る。本発明の教示に従って添加物を選択すれ゛ば、
電気的析出によって浴からパラジウム／ニッケル被覆が
得られ、これら被覆は、非常に細かくかつ均一な微結晶
および支障ない易溶体形成の点で優れている。それによ
り光沢、伸度および種々の腐食作用に対する耐腐食性が
高められる。In order to solve this problem, the present invention shows the following. That is, in order to improve the formation of easily dissolved substances, additives include sodium allylsulfonate, sodium allylsulfonate, sodium globinsulfonate, sodium methallylsulfonate, N-pyridiniumpropylsulfobetaine, N-pyridiniummethylsulfobetaine, N-pyridiniummethylsulfobetaine,
- beazylpyridinium-2-ethylsulfonic acid, sodium salt or a mixture of these substances. If additives are selected according to the teachings of the present invention,
Palladium/nickel coatings are obtained from the bath by electro-deposition, and these coatings are distinguished by very fine and uniform crystallites and by easy formation of easily dissolved materials. The gloss, elongation and corrosion resistance against various corrosive effects are thereby increased.
さらに平坦度も改善されている。Furthermore, flatness has also been improved.
次に本発明および得られた効果を典形的な実施例によっ
て説明する。Next, the present invention and the effects obtained will be explained using typical examples.
例１（脂肪族スルホン酸塩の添加） 次のような電解質が作られた。Example 1 (addition of aliphatic sulfonate) The following electrolytes were made:
（Ｐｄ（ＮＨａ）４）Ｃｌ３として２０２のパラジウム
、（Ｎｉ （ＮＨ３）６）ＳＯ４として１０ ｆのニッ
ケル、電＃負に十分な導電度を設定するため（ＮＨ４）
２ｓｏ４またはＮＨ４Ｃｌとして５０２の支持電解質（
Ｌｅｉｔｓａｌｚ）、
ｐＨ！を８．５＄ ａ定’ｔ ルｆ、：メＮＨ４ＯＨ。202 palladium as (Pd(NHa)4)Cl3, 10 f nickel as (Ni(NH3)6)SO4, to set sufficient conductivity to the negative voltage (NH4)
Supporting electrolyte of 502 as 2so4 or NH4Cl (
Leitsalz), pH! 8.5$ a constant: NH4OH.
Ｉｔの浴にするため水、
２．５２のナトリウムアリルスルホナート、電気的析出
の際の浴温度３０℃、わずかな物−品の動き、陰極電流
密度Ｉ Ａ／ｄｎ？、露出時間１０分。water to make a bath of It, 2.52 sodium allylsulfonate, bath temperature during electrodeposition 30°C, slight movement of the articles, cathode current density I A/dn? , exposure time 10 minutes.
ブラシをかけたしんちゅう板上に、明白な平坦度なしに
かつ阻害現象なしに光沢のあるパラジウム・ニッケル層
が得られた。A bright palladium-nickel layer was obtained on the brushed brass plate without any obvious flatness and without any inhibition phenomena.
耐腐食性を試験するため、このようにして得られたテス
ト片は、室温で６０秒秒間的られた硝酸に浸され、この
硝酸は、等部の濃槽酸と水から作らｔた。腐食作用は見
られなかった。To test the corrosion resistance, the test specimens thus obtained were immersed for 60 seconds at room temperature in nitric acid, which was made from equal parts concentrated acid and water. No corrosive effects were observed.
しかし初めに述べた英国特許第１１４３１７８号明細書
に従って、ナトリウムアリルスルホナートの代りに１０
２のナトリウムナフタリン−１，３，６−ドリスルホナ
ートを電解質に加えると、ノくラジウム・ニッケル層は
得られるが、この層は、前記の硝酸試験においてかなり
腐食した。この原因は、不完全な易溶体形成にある。Ｘ
線検査によれば、遊離したニッケルが検出され、これが
腐食の原因をなしている。However, according to GB 1 143 178 mentioned at the outset, 10
Addition of sodium naphthalene-1,3,6-dolisulfonate of 2 to the electrolyte results in a radium-nickel layer, which corrodes considerably in the nitric acid test described above. The cause of this is incomplete formation of easily soluble material. X
Line inspection revealed free nickel, which is responsible for the corrosion.
例２（脂肪族スルホン酸塩組合せの添加）次のような電
解質が作られた。Example 2 (Addition of aliphatic sulfonate combination) The following electrolyte was made.
（Ｐｄ（Ｎｌ（３ン４）Ｃｌ３として９Ｑ ｆのパラジ
ウム、（Ｎｉ （ＮＨ３）６ ）ＳＯ４としてｉｏ ｙ
のニッケル、亀＃賀に十分な導電度を設定するため（Ｎ
Ｈ４ｈｓｏ４またはＮＨ４Ｃｌとして５０りの支持電解
質（Ｌｅｊｔｓａｌｚ）、
ｐＨｆｆ１を８．５に設定するためＮＨ４ＯＨ。(Pd(Nl(3-4)Cl3 as 9Q f palladium, (Ni(NH3)6)SO4 as io y
In order to set sufficient conductivity to nickel, turtle (N
50 ml of supporting electrolyte (Lejtsalz) as H4hso4 or NH4Cl, NH4OH to set pHff1 to 8.5.
ｌｔの浴にするため水、
２．５２のナトリウムアリルスルホナート、０．２５
Ｆのナトリウムグロビンスルホナート、電気的析出の際
の浴温度３０℃、わずかな物品の動き、陰極電流密度Ｉ
Ｍｄｔｒ？、に出時間１０分。water to make a lt bath, 2.52 sodium allylsulfonate, 0.25
Sodium globin sulfonate of F, bath temperature 30 °C during electrodeposition, slight article movement, cathodic current density I
Mdtr? , it takes 10 minutes.
ブラシをかげたしんちゅう板上に、著しい平坦度なしに
かつ阻害現象なしに例１と比較して一層光沢のあるパラ
ジウム・ニッケル層が得られた。A more shiny palladium-nickel layer than in Example 1 was obtained on the brushed brass plate without significant flatness and without any interference phenomena.
例１による硝ｔ１１試験に同様に良好に耐えた。It also withstood the Nit11 test according to Example 1 well.
例３（脂肪族および異裡壌状のスルホ／酸塩を組合せて
添加）
次のよ５な′＃ａ、ａ負が作られた。Example 3 (Combined addition of aliphatic and heterogeneous sulfo/acid acids) The following 5'#a,a negative were made.
（Ｐｄ （ＮＨ３）４）８０４として２０２のパラジウ
ム、（Ｎｉ （ＮＨ３）６）Ｃ６２として１０ ｆのニ
ッケル、電解質に十分な導電度を設定するため（ＮＨ４
）２ｓｏ４またはＮＨ４Ｃｌとして５０’ｆの支持電解
質、ｐＨ値を８．５に設定するためＮＨ４０Ｈ１１ｔの
浴にするため水、
２．５ｇのナトリウムアリルスルホナート、０．１２の
Ｎ−ピリジニウムプロピルスルホベタイン、
電気酌析出の際の浴温度３０℃、わずかな物品の動き、
陰極電流密度１１ｙ’ｄｔｒ？、露出時間１０分。202 palladium as (Pd (NH3)4)804, 10 f nickel as (Ni (NH3)6)C62, (NH4
) 50'f supporting electrolyte as 2so4 or NH4Cl, water to make a bath of NH40H11t to set the pH value to 8.5, 2.5 g sodium allylsulfonate, 0.12 N-pyridinium propylsulfobetaine, Bath temperature 30℃ during electrodrunk deposition, slight movement of the article,
Cathode current density 11y'dtr? , exposure time 10 minutes.
ブラシをかけたしんちゅう板上に、明白な平坦度なしに
かつ阻害現象なしに光沢のあるパラジウム・ニッケル層
が得られた。硝酸試験に良好に耐えた。A bright palladium-nickel layer was obtained on the brushed brass plate without any obvious flatness and without any inhibition phenomena. Withstood the nitric acid test well.
特許出願人 ラングバインープファンハウゼル・ウエル
ケ・アクチェ／ ゲゼルシャフト代理人弁理士 田代蒸
治Patent applicant: Langbeinoop van Hausel Welke Akce / Gesellschaft representative patent attorney: Tsugeji Tashiro
Claims (1)
量および同様［５ないし３０ ｆ／ｌの範囲のニッケル
含有量、およびスルホン酸塩の添加物を含むパラジウム
およびニッケルアミンの水溶液から成り、この水溶液に
おいて、電気的に析出される合金が３０ないし９０重量
％のパラジウム含有量を有するように、パラジウムとニ
ッケルの比が設定されている、装飾的および工業的な被
覆のためパラジウム／ニッケル合金を電気的に析出する
浴において、易溶体形成を改善するため添加物が、ナト
リウムビニルスルホナート、ナトリウムアリルスルホナ
ート、ナトリウムプロピンスルホナート、ナトリウムメ
タリルスルホナート、Ｎ−ピリジニウムメチルスルホベ
タイン、Ｎ−ピリジニウムメチルスルホベタイン、Ｎ−
ベンジルピリジニウム−２−エチルスルホン酸、ナトリ
ウム塩の５ち１つの物質またはこれら物質の混合物から
成ることを特徴とする、パラジウム／ニッケル合金を電
気的゛に析出する浴。The bath is prepared from an aqueous solution of palladium and nickel amines containing a palladium content in the range of 5 to 30 f/l and a similar nickel content in the range of 5 to 30 f/l, and an additive of sulfonate. palladium/nickel for decorative and industrial coatings, in which the ratio of palladium to nickel is set such that the electro-deposited alloy has a palladium content of 30 to 90% by weight. In baths for electrolytic deposition of nickel alloys, additives such as sodium vinylsulfonate, sodium allylsulfonate, sodium propynesulfonate, sodium methallylsulfonate, N-pyridinium methylsulfobetaine are used to improve the formation of easily dissolved substances. , N-pyridinium methylsulfobetaine, N-
A bath for electrolytic deposition of palladium/nickel alloys, characterized in that it consists of one substance or a mixture of these substances: benzylpyridinium-2-ethylsulfonic acid, sodium salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3108508A DE3108508C2 (en) | 1981-03-06 | 1981-03-06 | Bath for the electrodeposition of a palladium / nickel alloy |
| DE3108508.3 | 1981-03-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5816089A true JPS5816089A (en) | 1983-01-29 |
| JPS6112038B2 JPS6112038B2 (en) | 1986-04-05 |
Family
ID=6126504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57032483A Granted JPS5816089A (en) | 1981-03-06 | 1982-03-03 | Bath for electrically depositing palladium/nickel alloy |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5816089A (en) |
| AT (1) | AT377013B (en) |
| AU (1) | AU535531B2 (en) |
| BE (1) | BE892344A (en) |
| BR (1) | BR8201157A (en) |
| CA (1) | CA1176204A (en) |
| CH (1) | CH649318A5 (en) |
| DE (1) | DE3108508C2 (en) |
| FR (1) | FR2501243B1 (en) |
| GB (1) | GB2094836B (en) |
| IT (1) | IT1150627B (en) |
| NL (1) | NL8200908A (en) |
| SE (1) | SE8201299L (en) |
| ZA (1) | ZA821367B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3443420A1 (en) * | 1984-11-26 | 1986-05-28 | Siemens AG, 1000 Berlin und 8000 München | Electroplating bath for the rapid deposition of palladium alloys |
| US4628165A (en) * | 1985-09-11 | 1986-12-09 | Learonal, Inc. | Electrical contacts and methods of making contacts by electrodeposition |
| DE3809139A1 (en) * | 1988-03-18 | 1989-09-28 | Lpw Chemie Gmbh | USE OF A PALLADIUM / NICKEL ALLOY LAYER AS AN INTERMEDIATE LAYER BETWEEN A NON-CORROSION-RESISTANT OR LESS-CORROSION-RESISTANT METAL BASE MATERIAL AND A COATING APPLIED BY THE PVD PROCESS |
| GB2242200B (en) * | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| US5415685A (en) * | 1993-08-16 | 1995-05-16 | Enthone-Omi Inc. | Electroplating bath and process for white palladium |
| EP0916747B1 (en) * | 1997-11-15 | 2002-10-16 | AMI Doduco GmbH | Electrolytic bath for the deposition of palladium and palladium alloys |
| CN113699565B (en) * | 2021-09-28 | 2023-07-04 | 万明电镀智能科技(东莞)有限公司 | High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2328243A (en) * | 1941-04-28 | 1943-08-31 | Posture Res Corp | Chair |
| US2800442A (en) * | 1955-10-04 | 1957-07-23 | Udylite Res Corp | Electrodeposition of nickel |
| JPS4733176B1 (en) * | 1967-01-11 | 1972-08-23 | ||
| US3730854A (en) * | 1971-10-29 | 1973-05-01 | Basf Ag | Stabilized aqueous solutions of unsaturated aliphatic sulfonic acids or salts thereof |
| CH572989A5 (en) * | 1973-04-27 | 1976-02-27 | Oxy Metal Industries Corp | |
| GB1553503A (en) * | 1976-05-14 | 1979-09-26 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| FR2364980A1 (en) * | 1976-09-17 | 1978-04-14 | Parker Ste Continentale | Electrodeposition of palladium alloys for jewellery - or protective coatings, using bath contg. organic cpds. and brighteners |
| DE2825966A1 (en) * | 1978-06-14 | 1980-01-03 | Basf Ag | ACID GALVANIC NICKEL BATH, WHICH CONTAINS SULFOBETAINE AS A GLOSSY AND LEVELING AGENT |
-
1981
- 1981-03-06 DE DE3108508A patent/DE3108508C2/en not_active Expired
-
1982
- 1982-02-18 GB GB8204857A patent/GB2094836B/en not_active Expired
- 1982-02-26 CH CH1184/82A patent/CH649318A5/en not_active IP Right Cessation
- 1982-03-02 ZA ZA821367A patent/ZA821367B/en unknown
- 1982-03-02 AU AU81049/82A patent/AU535531B2/en not_active Ceased
- 1982-03-03 BE BE2/59611A patent/BE892344A/en not_active IP Right Cessation
- 1982-03-03 AT AT0082182A patent/AT377013B/en not_active IP Right Cessation
- 1982-03-03 JP JP57032483A patent/JPS5816089A/en active Granted
- 1982-03-03 SE SE8201299A patent/SE8201299L/en not_active Application Discontinuation
- 1982-03-04 FR FR8203613A patent/FR2501243B1/en not_active Expired
- 1982-03-05 BR BR8201157A patent/BR8201157A/en unknown
- 1982-03-05 NL NL8200908A patent/NL8200908A/en not_active Application Discontinuation
- 1982-03-05 IT IT19992/82A patent/IT1150627B/en active
- 1982-03-05 CA CA000397678A patent/CA1176204A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2501243A1 (en) | 1982-09-10 |
| ATA82182A (en) | 1984-06-15 |
| IT8219992A0 (en) | 1982-03-05 |
| DE3108508C2 (en) | 1983-06-30 |
| AT377013B (en) | 1985-01-25 |
| CH649318A5 (en) | 1985-05-15 |
| FR2501243B1 (en) | 1988-05-27 |
| BE892344A (en) | 1982-07-01 |
| JPS6112038B2 (en) | 1986-04-05 |
| GB2094836A (en) | 1982-09-22 |
| SE8201299L (en) | 1982-09-07 |
| IT1150627B (en) | 1986-12-17 |
| GB2094836B (en) | 1984-12-05 |
| ZA821367B (en) | 1983-01-26 |
| BR8201157A (en) | 1982-11-23 |
| DE3108508A1 (en) | 1982-09-16 |
| AU8104982A (en) | 1982-09-09 |
| AU535531B2 (en) | 1984-03-29 |
| CA1176204A (en) | 1984-10-16 |
| NL8200908A (en) | 1982-10-01 |
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