EP0239876A1 - Bath for electroplating silver-palladium alloys - Google Patents
Bath for electroplating silver-palladium alloys Download PDFInfo
- Publication number
- EP0239876A1 EP0239876A1 EP87103932A EP87103932A EP0239876A1 EP 0239876 A1 EP0239876 A1 EP 0239876A1 EP 87103932 A EP87103932 A EP 87103932A EP 87103932 A EP87103932 A EP 87103932A EP 0239876 A1 EP0239876 A1 EP 0239876A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- palladium
- bath
- silver
- bath according
- polyphosphate
- 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
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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
-
- 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
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
Definitions
- the present invention relates to an aqueous bath for the electrolytic deposition of silver-palladium alloys with the features specified in the preamble of claim 1.
- a bath with these features which is used to deposit silver-palladium alloys with up to 5 percent by weight of palladium, is known from DE-OS 27 04 691.
- it contains silver as silver nitrate, palladium as palladiumethylene diamine sulfate and succinimide and sodium hydroxide solution , with which a pH value of 8 is set.
- the known bath composition is unsuitable for the deposition of silver-palladium alloys with a higher palladium content.
- the invention has for its object to provide an aqueous, cyanide-free, alkaline bath for the deposition of silver-palladium alloys with a higher proportion of palladium and with the largest possible composition range.
- potassium hydroxide or sodium hydroxide can additionally be added in a manner known per se. Usable separation conditions are achieved with a pH between 7 and 12; a pH value between 8 and 10 is optimal.
- a buffer substance can be added in a manner known per se; Standard buffers are suitable, for example borates, phosphates and dicarboxylic acids;
- the pH value can be stabilized to values between 8 and 10 using a boric acid / sodium hydroxide solution.
- the bath according to the invention contains the silver in the form of a complex compound with succinimide or its derivatives (e.g. 2-methylsuccinimide, 2-ethylsuccinimide or maleimide) insofar as they are easily soluble in weakly alkaline, aqueous solution.
- succinimide or its derivatives e.g. 2-methylsuccinimide, 2-ethylsuccinimide or maleimide
- the bath according to the invention can contain between 0.5 and 15 g / l silver and between 1 and 25 g / l palladium. It can be used to deposit silver-palladium alloys in which the weight ratio of silver to palladium can be set between 20/80 and 80/20; the setting is made by appropriately setting the silver concentration and palladium concentration in the bath and by choosing the bath temperature.
- the palladium is in the bath according to the invention in the form of palladium diphosphate and / or palladium polyphosphate contain. These compounds can be added directly to the bath; it is also possible to add a palladium nitrite complex compound to the bath and to react it in excess with diphosphoric acid or polyphosphoric acid or its salts, for example with potassium diphosphate. Instead of a palladium nitrite complex compound, it is also possible to start from other palladium compounds, in particular from palladium hydroxide, and to react this in excess with di- or polyphosphoric acid or its salts. The succinimide should expediently also be present in excess. The excess of complexing substances is intended to make it possible for the palladium and the silver, which have been in the bath from the beginning or have been added in the form of a supplemental salt over time, to be bound in a completely complex manner.
- the bath according to the invention expediently contains an additive which acts as a wetting agent and favors the formation of a fine-grained and crack-free silver-palladium alloy.
- Water-soluble, sulfonated, aromatic aldehydes of which anisaldehyde sulfonic acid and benzaldehyde disulfonic acid are particularly noteworthy, have proven to be particularly suitable fine grain additives and wetting agents for the bath according to the invention.
- Other suitable representatives from the group of the sulfonated aromatic aldehydes are sulfonated vanillin, sulfonated salicylaldehyde and sulfonated cinnamaldehyde.
- the sulfonated aldehydes are advantageously added to the bath in an amount of 0.1 to 5 g / l, preferably 1 to 3 g / l.
- Ductile, crack-free coatings made of silver-palladium alloys with a satin-gloss surface can be deposited with baths of the composition according to the invention.
- the bath contains 10 g / l palladium as potassium tetranitritopalladate (II), 2 g / l silver as a silver succinimide complex 30 g / l succinimide 40 g / l potassium diphosphate, 30 g / l boric acid 1 g / l salicylaldehyde sulfonic acid.
- a pH of 9.5 is set in the bath by adding potassium hydroxide and the deposition is carried out at a temperature of 25 ° C. and a current density of 0.5 A / dm2. It is best to use platinum-coated titanium as anodes, which do not dissolve in the bath.
- the deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
- the bath contains: 7 g / l palladium as palladium polyphosphate, made from palladium oxide hydrate and polyphosphate, 1 g / l silver as silver succinimide complex, 25 g / l succinimide, 20 g / l sodium polyphosphate, 30 g / l boric acid 1 g / l benzaldehyde disulfonic acid.
- a pH of 9.5 is set by adding potassium hydroxide and the deposition is carried out at a temperature of 40 ° C. and a current density of 0.5 A. / dm2.
- Platinum-plated titanium is best chosen as the anode material.
- the deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
- the bath contains: 5 g / l palladium as palladium polyphosphate, 0.5 g / l silver as a silver succinimide complex, 20 g / l succinimide, 60 g / l sodium polyphosphate, 15 g / l of a soluble dicarboxylic acid, for example malonic acid or higher homologues, 0.5 g / l benzaldehyde disulfonic acid.
- a pH of 9.5 is set by adding potassium hydroxide and the deposition is carried out at a temperature of 40 ° C. and a current density of 0.5 A. / dm2.
- Platinum-plated titanium is best chosen as the anode material.
- the deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
Abstract
Description
Die vorliegende Erfindung handelt von einem wässrigen Bad zum elektrolytischen Abscheiden von Silber-Palladium-Legierungen mit den im Oberbegriff des Anspruchs 1 angegebenen Merkmalen.The present invention relates to an aqueous bath for the electrolytic deposition of silver-palladium alloys with the features specified in the preamble of claim 1.
Ein Bad mit diesen Merkmalen, welches zum Abscheiden von Silber-Palladium-Legierungen mit bis zu 5 Gewichtsprozent Palladium dient, ist bekannt aus der DE-OS 27 04 691. Es enthält im konkreten Fall Silber als Silbernitrat, Palladium als Palladiumäthylendiaminsulfat und Succinimid sowie Natronlauge, mit welcher ein pH-Wert von 8 eingestellt wird. Für das Abscheiden von Silber-Palladiumlegierungen mit höherem Palladiumgehalt ist die bekannte Badzusammensetzung ungeeignet.A bath with these features, which is used to deposit silver-palladium alloys with up to 5 percent by weight of palladium, is known from DE-OS 27 04 691. In the specific case, it contains silver as silver nitrate, palladium as palladiumethylene diamine sulfate and succinimide and sodium hydroxide solution , with which a pH value of 8 is set. The known bath composition is unsuitable for the deposition of silver-palladium alloys with a higher palladium content.
Der Erfindung liegt die Aufgabe zugrunde, ein wässriges, cyanidfreies, im alkalischen Bereich arbeitendes Bad zum Abscheiden von Silber-Palladium-Legierungen mit höherem Palladiumanteil sowie mit einem möglichst großen Zusammensetzungsbereich anzugeben.The invention has for its object to provide an aqueous, cyanide-free, alkaline bath for the deposition of silver-palladium alloys with a higher proportion of palladium and with the largest possible composition range.
Diese Aufgabe wird gelöst durch ein Bad mit der im Patentanspruch 1 angegebenen Zusammensetzung.This object is achieved by a bath with the composition specified in claim 1.
Wegen seines Gehalts an Diphosphat und/ oder Polyphosphat reagiert dieses Bad bereits schwach basisch. Zur Einstellung des gewünschten pH-Wertes kann ergänzend in an sich bekannter Weise Kaliumhydroxid oder Natriumhydroxid zugesetzt werden. Brauchbare Abscheidebedingungen erreicht man mit einem pH-Wert zwischen 7 und 12; optimal ist ein pH-Wert zwischen 8 und 10.Zum Stabilisieren des pH-Wertes kann man in an sich bekannter Weise eine Puffersubstanz zugeben; geeignet sind Standardpuffer, beispielsweise Borate, Phosphate und Dikarbonsäuren; z.B. läßt sich durch einen Borsäure-Natronlauge-Puffer der pH-Wert auf Werte zwischen 8 und 10 stabilisieren.Because of its diphosphate and / or polyphosphate content this bath already reacts weakly basic. To adjust the desired pH, potassium hydroxide or sodium hydroxide can additionally be added in a manner known per se. Usable separation conditions are achieved with a pH between 7 and 12; a pH value between 8 and 10 is optimal. To stabilize the pH value, a buffer substance can be added in a manner known per se; Standard buffers are suitable, for example borates, phosphates and dicarboxylic acids; For example, the pH value can be stabilized to values between 8 and 10 using a boric acid / sodium hydroxide solution.
Das erfindungsgemäße Bad enthält das Silber in Form einer Komplexverbindung mit Succinimid oder dessen Derivaten (z.B. 2-Methylsuccinimid, 2-Äthylsuccinimid oder Maleimid) soweit sie in schwach alkalischer, wässriger Lösung leicht lösbar sind.The bath according to the invention contains the silver in the form of a complex compound with succinimide or its derivatives (e.g. 2-methylsuccinimide, 2-ethylsuccinimide or maleimide) insofar as they are easily soluble in weakly alkaline, aqueous solution.
Das erfindungsgemäße Bad kann zwischen 0,5 und 15g/l Silber enthalten und zwischen 1 und 25 g/l Palladium. Damit lassen sich Silber-Palladium-Legierungen abscheiden, in denen das Gewichtsverhältnis von Silber zu Palladium zwischen 20/80 und 80/20 einstellbar ist; die Einstellung erfolgt durch entsprechendes Einstellen der Silberkonzentration und Palladiumkonzentration im Bad sowie durch Wahl der Badtemperatur.The bath according to the invention can contain between 0.5 and 15 g / l silver and between 1 and 25 g / l palladium. It can be used to deposit silver-palladium alloys in which the weight ratio of silver to palladium can be set between 20/80 and 80/20; the setting is made by appropriately setting the silver concentration and palladium concentration in the bath and by choosing the bath temperature.
Das Palladium ist in dem erfindungsgemäßen Bad in Form von Palladiumdiphosphat und/oder Palladiumpolyphosphat enthalten. Diese Verbindungen können dem Bad unmittelbar zugegeben werden; es ist auch möglich, dem Bad eine Palladiumnitritkomplexverbindung zuzusetzen und diese mit Diphosphorsäure oder Polyphosphorsäure oder deren Salzen, beispielsweise mit Kaliumdiphosphat, im Überschuß umzusetzen. Anstatt von einer Palladiumnitritkomplexverbindung kann man aber auch von anderen Palladiumverbindungen, insbesondere vom Palladiumhydroxid ausgehen und dieses mit Di- oder Polyphosphorsäure oder deren Salzen im Überschuß umsetzen. Im Überschuß sollte zweckmässigerweise auch das Succinimid vorhanden sein. Durch den Überschluß an komplexbildenden Substanzen soll ermöglicht werden, daß das Palladium und das Silber, welche von Beginn an im Bad sind oder im Laufe der Zeit in Form eines Ergänzungssalzes zugegeben werden, vollständig komplex gebunden werden können.The palladium is in the bath according to the invention in the form of palladium diphosphate and / or palladium polyphosphate contain. These compounds can be added directly to the bath; it is also possible to add a palladium nitrite complex compound to the bath and to react it in excess with diphosphoric acid or polyphosphoric acid or its salts, for example with potassium diphosphate. Instead of a palladium nitrite complex compound, it is also possible to start from other palladium compounds, in particular from palladium hydroxide, and to react this in excess with di- or polyphosphoric acid or its salts. The succinimide should expediently also be present in excess. The excess of complexing substances is intended to make it possible for the palladium and the silver, which have been in the bath from the beginning or have been added in the form of a supplemental salt over time, to be bound in a completely complex manner.
Zweckmässigerweise enthält das erfindungsgemäße Bad einen Zusatz, welcher als Netzmittel wirkt und die Ausbildung einer feinkörnigen und rißfreien Silber-Palladium-Legierung begünstigt. Als besonders geeignete Feinkornzusatz- und Netzmittel für das erfindungsgemäße Bad haben sich wasserlösliche, sulfonierte, aromatische Aldehyde erwiesen, von denen Anisaldehydsulfonsäure und Benzaldehyddisulfonsäure besonders hervorzuheben sind. Andere geeignete Vertreter aus der Gruppe der sulfonierten aromatischen Aldehyde sind sulfoniertes Vanillin, sulfonierter Salicylaldehyd und sulfonierter Zimtaldehyd. Die sulfonierten Aldehyde werden dem Bad zweckmäßigerweise in einer Menge von 0,1 bis 5 g/l, vorzugsweise 1 bis 3 g/l,zugegeben.The bath according to the invention expediently contains an additive which acts as a wetting agent and favors the formation of a fine-grained and crack-free silver-palladium alloy. Water-soluble, sulfonated, aromatic aldehydes, of which anisaldehyde sulfonic acid and benzaldehyde disulfonic acid are particularly noteworthy, have proven to be particularly suitable fine grain additives and wetting agents for the bath according to the invention. Other suitable representatives from the group of the sulfonated aromatic aldehydes are sulfonated vanillin, sulfonated salicylaldehyde and sulfonated cinnamaldehyde. The sulfonated aldehydes are advantageously added to the bath in an amount of 0.1 to 5 g / l, preferably 1 to 3 g / l.
Mit Bädern von erfindungsgemäßer Zusammensetzung lassen sich duktile, rißfreie Überzüge aus Silber-Palladium-Legierungen mit seidenglänzender Oberfläche abscheiden.Ductile, crack-free coatings made of silver-palladium alloys with a satin-gloss surface can be deposited with baths of the composition according to the invention.
Nachfolgend werden noch drei Ausführungsbeispiele angegeben.Three exemplary embodiments are given below.
Das Bad enthält
10 g/l Palladium als Kaliumtetranitritopalladat (II),
2 g/l Silber als Silber-Succinimid-Komplex
30 g/l Succinimid
40 g/l Kaliumdiphosphat,
30 g/l Borsäure
1 g/l Salicylaldehydsulfonsäure.The bath contains
10 g / l palladium as potassium tetranitritopalladate (II),
2 g / l silver as a silver succinimide complex
30 g / l succinimide
40 g / l potassium diphosphate,
30 g / l boric acid
1 g / l salicylaldehyde sulfonic acid.
Zum Abscheiden einer Legierung aus 70 Gew.-% Silber und 30 Gew.-% Palladium stellt man in dem Bad durch Zugabe von Kaliumhydroxid einen pH-Wert von 9,5 ein und führt die Abscheidung bei einer Temperatur von 25°C und einer Stromdichte von 0,5 A/dm² durch. Als Anoden verwendet man am besten solche aus platiniertem Titan, welche sich in dem Bad nicht auflösen.To deposit an alloy of 70% by weight of silver and 30% by weight of palladium, a pH of 9.5 is set in the bath by adding potassium hydroxide and the deposition is carried out at a temperature of 25 ° C. and a current density of 0.5 A / dm². It is best to use platinum-coated titanium as anodes, which do not dissolve in the bath.
Die abgeschiedene Silber-Palladium-Legierung ist duktil und rißfrei und hat eine seidenglänzende Oberfläche.The deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
Das Bad enthält:
7 g/l Palladium als Palladiumpolyphosphat, hergestellt aus Palladiumoxidhydrat und Polyphosphat,
1 g/l Silber als Silber-Succinimid-Komplex,
25 g/l Succinimid,
20 g/l Natriumpolyphosphat,
30 g/l Borsäure
1 g/l Benzaldehyddisulfonsäure.The bath contains:
7 g / l palladium as palladium polyphosphate, made from palladium oxide hydrate and polyphosphate,
1 g / l silver as silver succinimide complex,
25 g / l succinimide,
20 g / l sodium polyphosphate,
30 g / l boric acid
1 g / l benzaldehyde disulfonic acid.
Zum Abscheiden einer Legierung aus 50 Gew.-% Silber und 50 Gew.-% Palladium wird durch Zugeben von Kalumhydroxid ein pH-Wert von 9,5 eingestellt und die Abscheidung bei einer Temperatur von 40°C und einer Stromdichte von 0,5 A/dm² durchgeführt. Als Anodenwerkstoff wählt man am besten wiederum platiniertes Titan.To deposit an alloy of 50% by weight of silver and 50% by weight of palladium, a pH of 9.5 is set by adding potassium hydroxide and the deposition is carried out at a temperature of 40 ° C. and a current density of 0.5 A. / dm². Platinum-plated titanium is best chosen as the anode material.
Die abgeschiedene Silber-Palladium-Legierung ist duktil und rißfrei und hat eine seidenglänzende Oberfläche.The deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
Das Bad enthält:
5 g/l Palladium als Palladiumpolyphosphat,
0,5 g/l Silber als Silber-Succinimid-Komplex,
20 g/l Succinimid,
60 g/l Natriumpolyphosphat,
15 g/l einer löslichen Dikarbonsäure, z.B. Malonsäure oder höhere Homologe,
0,5 g/l Benzaldehyddisulfonsäure.The bath contains:
5 g / l palladium as palladium polyphosphate,
0.5 g / l silver as a silver succinimide complex,
20 g / l succinimide,
60 g / l sodium polyphosphate,
15 g / l of a soluble dicarboxylic acid, for example malonic acid or higher homologues,
0.5 g / l benzaldehyde disulfonic acid.
Zum Abscheiden einer Legierung aus 50 Gew.-% Silber und 50 Gew.-% Palladium wird durch Zugeben von Kalumhydroxid ein pH-Wert von 9,5 eingestellt und die Abscheidung bei einer Temperatur von 40°C und einer Stromdichte von 0,5 A/dm² durchgeführt. Als Anodenwerkstoff wählt man am besten wiederum platiniertes Titan.To deposit an alloy of 50% by weight of silver and 50% by weight of palladium, a pH of 9.5 is set by adding potassium hydroxide and the deposition is carried out at a temperature of 40 ° C. and a current density of 0.5 A. / dm². Platinum-plated titanium is best chosen as the anode material.
Die abgeschiedene Silber-Palladium Legierung ist duktil und rißfrei und hat eine seidenglänzende Oberfläche.The deposited silver-palladium alloy is ductile and crack-free and has a satin surface.
Claims (10)
dadurch gekennzeichnet, daß es das Palladium als Palladiumdiphosphat und/oder als Palladiumpolyphosphat enthält.1. Aqueous, alkaline, cyanide and ammonia-free bath for the electrolytic deposition of silver-palladium alloys from soluble silver-succinimide complex or silver-succinimide derivative complex compounds and from soluble palladium compounds,
characterized in that it contains the palladium as palladium diphosphate and / or as palladium polyphosphate.
dadurch gekennzeichnet, daß es zwischen 0,5 und 15g/l Silber enthält.2. Bath according to claim 1,
characterized in that it contains between 0.5 and 15 g / l of silver.
dadurch gekennzeichnet, daß es zwischen 1 und 25 g/l Palladium enthält.3. Bath according to claim 1,
characterized in that it contains between 1 and 25 g / l palladium.
dadurch gekennzeichnet, daß es das Palladiumdiphosphat bzw. das Palladiumpolyphosphat als Reaktionsprodukt aus einer Palladiumverbindung, z.B. Palladiumhydroxid oder Palladiumnitritverbindung, und Di- bzw. Polyphosphorsäure oder deren Salzen enthält.4. Bath according to claim 1,
characterized in that it contains the palladium diphosphate or the palladium polyphosphate as a reaction product of a palladium compound, for example palladium hydroxide or palladium nitrite compound, and di- or polyphosphoric acid or its salts.
dadurch gekennzeichnet, daß es die Di- bzw. Polyphosphorsäure bzw. deren Salze - verglichen mit der Palladiumnitritverbindung - mindestens im stöchiometrischen Überschuß enthält.5. Bath according to claim 4,
characterized in that it contains the di- or polyphosphoric acid or its salts - compared to the palladium nitrite compound - at least in a stoichiometric excess.
dadurch gekennzeichnet, daß das Bad das Palladium als Reaktionsprodukt aus Kaliumtetranitritopalladat (II) und Kaliumdiphosphat oder Kaliumpolyphosphat enthält.6. Bath according to claim 4,
characterized in that the bath contains the palladium as a reaction product of potassium tetranitritopalladate (II) and potassium diphosphate or potassium polyphosphate.
dadurch gekennzeichnet, daß es bis zu 200 g/l, vorzugsweise 5 bis 50 g/l Succinimid im Überschuß enthält.7. Bath according to claim 1,
characterized in that it contains up to 200 g / l, preferably 5 to 50 g / l, of excess succinimide.
dadurch gekennzeichnet, daß es als Feinkornzusatz- und Netzmittel (Tensid) einen wasserlöslichen, sulfonierten, aromatischen Aldehyd enthält.8. Bath according to claim 1,
characterized in that it contains a water-soluble, sulfonated, aromatic aldehyde as fine grain additive and wetting agent (surfactant).
dadurch gekennzeichnet, daß es als Aldehyd einen oder mehrere Vertreter aus der Gruppe von sulfoniertem Vanillin, Anis-, Salicyl-, Zimt- und Benzaldehyd enthält, wobei Anisaldehydsulfonsäure und Benzaldehyddisulfonsäure besonders bevorzugt sind.9. Bath according to claim 8,
characterized in that it contains as aldehyde one or more representatives from the group of sulfonated vanillin, anis, salicyl, cinnamon and benzaldehyde, anisaldehyde sulfonic acid and benzaldehyde disulfonic acid being particularly preferred.
dadurch gekennzeichnet, daß das Bad den Aldehyd in einer Menge von 0,1 bis 5 g/l, vorzugsweise 1 bis 3 g/l enthält.10. Bath according to claim 8,
characterized in that the bath contains the aldehyde in an amount of 0.1 to 5 g / l, preferably 1 to 3 g / l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3609309 | 1986-03-20 | ||
| DE19863609309 DE3609309A1 (en) | 1986-03-20 | 1986-03-20 | BATH FOR THE ELECTROLYTIC DEPOSITION OF SILVER-PALLADIUM ALLOYS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0239876A1 true EP0239876A1 (en) | 1987-10-07 |
| EP0239876B1 EP0239876B1 (en) | 1990-09-05 |
Family
ID=6296792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87103932A Expired - Lifetime EP0239876B1 (en) | 1986-03-20 | 1987-03-18 | Bath for electroplating silver-palladium alloys |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0239876B1 (en) |
| DE (2) | DE3609309A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4412253A1 (en) * | 1993-04-07 | 1994-10-13 | Atotech Deutschland Gmbh | Electrolytic deposition of palladium or palladium alloys |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02104699A (en) * | 1988-10-11 | 1990-04-17 | C Uyemura & Co Ltd | Electrolytic peeling agent for silver and electrolytically peeling method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2343062A2 (en) * | 1976-03-01 | 1977-09-30 | Technic | ELECTROLYTIC BATH CONTAINING NO CYANIDE FOR THE ELECTROLYTIC DEPOSIT OF SILVER |
| GB2046794A (en) * | 1979-04-04 | 1980-11-19 | Engelhard Min & Chem | Silver and gold/silver alloy plating bath and method |
| FR2496127A1 (en) * | 1980-12-17 | 1982-06-18 | Hooker Chemicals Plastics Corp | BATHS AND ELECTROLYTIC PROCESS FOR THE DEPOSIT OF WHITE PALLADIUM |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4478692A (en) * | 1982-12-22 | 1984-10-23 | Learonal, Inc. | Electrodeposition of palladium-silver alloys |
-
1986
- 1986-03-20 DE DE19863609309 patent/DE3609309A1/en active Granted
-
1987
- 1987-03-18 DE DE8787103932T patent/DE3764685D1/en not_active Expired - Lifetime
- 1987-03-18 EP EP87103932A patent/EP0239876B1/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2343062A2 (en) * | 1976-03-01 | 1977-09-30 | Technic | ELECTROLYTIC BATH CONTAINING NO CYANIDE FOR THE ELECTROLYTIC DEPOSIT OF SILVER |
| GB2046794A (en) * | 1979-04-04 | 1980-11-19 | Engelhard Min & Chem | Silver and gold/silver alloy plating bath and method |
| FR2496127A1 (en) * | 1980-12-17 | 1982-06-18 | Hooker Chemicals Plastics Corp | BATHS AND ELECTROLYTIC PROCESS FOR THE DEPOSIT OF WHITE PALLADIUM |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 97, Nr. 12, September 1982, Seite 570, Zusammenfassung Nr. 100709j, Columbus, Ohio, US; & JP-A-82 76 196 (KUMAMOTO PREFECTURE) 13-05-1982 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4412253A1 (en) * | 1993-04-07 | 1994-10-13 | Atotech Deutschland Gmbh | Electrolytic deposition of palladium or palladium alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0239876B1 (en) | 1990-09-05 |
| DE3609309C2 (en) | 1988-06-01 |
| DE3764685D1 (en) | 1990-10-11 |
| DE3609309A1 (en) | 1987-09-24 |
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