EP0698676A1 - Bain d'électrodéposition d'alliages cuivre-étain - Google Patents
Bain d'électrodéposition d'alliages cuivre-étain Download PDFInfo
- Publication number
- EP0698676A1 EP0698676A1 EP95104355A EP95104355A EP0698676A1 EP 0698676 A1 EP0698676 A1 EP 0698676A1 EP 95104355 A EP95104355 A EP 95104355A EP 95104355 A EP95104355 A EP 95104355A EP 0698676 A1 EP0698676 A1 EP 0698676A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- bath
- copper
- cyanide
- potassium
- 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
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- 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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Definitions
- the invention relates to a bath for the electrodeposition of copper-tin alloys, which consists of water, copper cyanide, tin (IV) compound, alkali metal cyanide, alkali metal hydroxide, a complexing agent and optionally an alkali metal phosphate.
- the bath known from DE 33 39 541 C2 for the electrodeposition of copper-tin alloy coatings contains 1-60 g / l copper as copper cyanide, 7-30 g / l tin as alkali metal stannate, 0.1-100 g / l one or more Complexing agents from the group of phosphate, polyphosphate, phosphonate and polyoxycarboxylic acids, 1-50 g / l alkali metal cyanide, 1-50 g / l alkali metal hydroxide, 0-50 g / l alkali metal carbonate and 0.05-5 g / l of one or more additives from the Groups of fatty acid amido alkyl dialkylamine oxides, dialkylamine betaines and ethoxylated naphthols.
- the coatings deposited from this bath are bare. In order to obtain glossy coatings too, brighteners have to be added to the bath.
- DE 33 46 721 A1 describes an alkaline, cyanide-containing bath for the electrodeposition of high-gloss coatings (bronzing) from copper and tin, as well as other alloy metals - namely zinc, molybdenum, cadmium, mercury, lead, zirconium, vanadium, beryllium and / or cobalt - Containing alloys described.
- the other alloy metals are present in the bath in the form of organic complexes or chelates, including at least one aminopolycarboxy complexing agent, and hydroxide complexes.
- tartrates, citrates, acetates, pyrophosphates, glycerophosphates, thione phosphates and / or carbonates may also be present.
- the aim of the invention is to create a bath of the type described in the introduction, from which shiny copper-tin alloy layers can be deposited without the need for additional brighteners.
- the bathroom should be as simple as possible, which means that it does not require any additional additives, and should be easy to monitor and maintain.
- the composition of the deposited copper-tin alloys should be as independent as possible from fluctuations in the current density.
- the bath according to the invention is characterized in that it contains the potassium salt of gluconic acid, glucaric acid and / or glucuronic acid as a complexing agent and has a pH of 8-14.
- the bathroom has proven itself as a preparation from water and 5 - 20 g / l Copper (I) cyanide, 10 - 150 g / l Tin (IV) compound, 50-100 g / l Potassium cyanide, 1 - 80 g / l Potassium hydroxide and 50-150 g / l Potassium salt of gluconic acid, glucaric acid and / or glucuronic acid.
- Copper (I) cyanide 10 - 150 g / l Tin (IV) compound
- 50-100 g / l Potassium cyanide 1 - 80 g / l Potassium hydroxide
- 50-150 g / l Potassium salt of gluconic acid, glucaric acid and / or glucuronic acid 5 - 20 g / l Copper (I) cyanide, 10 - 150 g / l Tin (IV) compound, 50-100 g / l Potassium
- the bath is preferably a preparation of water and 10 - 15 g / l Copper (I) cyanide, 30-100 g / l Tin (IV) compound, 50 - 70 g / l Potassium cyanide, 5 - 50 g / l Potassium hydroxide and 80-120 g / l Potassium salt of gluconic acid, glucaric acid and / or glucuronic acid.
- Alkaline metal stannates especially potassium stannate
- tin (IV) halides especially tin (IV) chloride
- tin (IV) compound Alkaline metal stannates, especially potassium stannate, and tin (IV) halides, especially tin (IV) chloride, are preferred as the tin (IV) compound.
- the potassium salt of gluconic acid has proven particularly useful as a complexing agent.
- an alkali metal phosphate is present in the bath, an amount of 50-100 g / l has proven to be favorable.
- the bath can be operated at temperatures of 20-70 ° C., preferably at 50-70 ° C., and with current densities of 0.1-10 A / dm, preferably 2-6 A / dm.
- the copper-tin alloys separated from the bath are characterized by a high gloss.
- the additional use of gloss agents is not necessary.
- All of the components forming the bath contribute to the good properties which characterize the bath according to the invention.
- the potassium hydroxide and the potassium salt of gluconic acid, glucaric acid and glucuronic acid are of particular importance.
- the bath can be used for electroplating small parts as well as tapes and wires and enables the deposition of copper alloys with a tin content of up to 60% by weight.
- the deposition of alloys with a tin content of 30-60% by weight is preferred.
- the alloys are bronze to silver-colored and are suitable for technical and decorative purposes. They are particularly important as a substitute for nickel, which is a potential allergen.
- a faster deposition of the alloys can be achieved by increasing the current density and the bath temperature without major fluctuations in the composition of the deposited alloys - given the copper and tin content of the bath.
- the bath obtained in this way is turned into a shiny, silver-colored copper-tin alloy of 68% by weight copper and 32% by weight at a bath temperature of 65 ° C. and with current densities of 0.1-5 A / dm (Hull cell). Tin deposited.
- the bathroom is stable; There is no precipitation.
- the bath obtained in this way is turned into a shiny, silver-colored copper-tin alloy of 60% by weight copper and 40% by weight at a bath temperature of 65 ° C. and with current densities of 0.1-5 A / dm (Hull cell). Tin deposited.
- the bathroom is stable; There is no precipitation.
- a shiny, silver-colored copper-tin alloy composed of 51% by weight of tin and 49% by weight of copper is deposited from the bath thus obtained at a bath temperature of 60 ° C. and with current densities of 1-5 A / dm (Hull cell) .
- the bathroom is stable; There is no precipitation.
- a shiny, silver-colored copper-tin alloy composed of 53% by weight of tin and 47% by weight of copper is deposited from the bath thus obtained at a bath temperature of 60 ° C. and with current densities of 1-5 A / dm (Hull cell) .
- the bathroom is stable; There is no precipitation.
- a shiny, silver-colored copper-tin alloy composed of 51% by weight of tin and 49% by weight of copper is deposited from the bath thus obtained at a bath temperature of 60 ° C. and with current densities of 1-5 A / dm (Hull cell) .
- the bathroom is stable; There is no precipitation.
- a shiny, silver-colored copper-tin alloy composed of 30% by weight of tin and 70% by weight of copper is deposited from the bath thus obtained at a bath temperature of 65 ° C. and with current densities of 1-10 A / dm (Hull cell) .
- the bathroom is stable; There is no precipitation.
- the addition of the baths necessary in the course of the separation is carried out in a simple manner by adding the substances used for the preparation of the baths.
- a continuous one It is not necessary to determine the concentration of the potassium salt of gluconic acid, glucaric acid and glucuronic acid; based on the addition of tin (IV) compound, it is added in a ratio of 1: 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4426914 | 1994-07-29 | ||
DE4426914A DE4426914C1 (de) | 1994-07-29 | 1994-07-29 | Bad zum galvanischen Abscheiden von Kupfer-Zinn-Legierungen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0698676A1 true EP0698676A1 (fr) | 1996-02-28 |
EP0698676B1 EP0698676B1 (fr) | 1997-09-24 |
Family
ID=6524448
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95104355A Expired - Lifetime EP0698676B1 (fr) | 1994-07-29 | 1995-03-24 | Bain d'électrodéposition d'alliages cuivre-étain |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0698676B1 (fr) |
DE (2) | DE4426914C1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104962959A (zh) * | 2015-07-21 | 2015-10-07 | 深圳市新富华表面技术有限公司 | 电镀液 |
IT202100008084A1 (it) * | 2021-03-31 | 2022-10-01 | Bluclad S P A | Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3339541A1 (de) * | 1983-11-02 | 1985-05-15 | Degussa Ag, 6000 Frankfurt | Alkalisch-cyanidisches bad zur galvanischen abscheidung von kupfer-zinn-legierungsueberzuegen |
DE3346721A1 (de) * | 1983-12-23 | 1985-06-27 | Fa. Karl-Wilh. Hen, 5820 Gevelsberg | Alkalisches bad zum aufbringen eines hochglaenzenden galvanischen ueberzugs auf einen traeger |
-
1994
- 1994-07-29 DE DE4426914A patent/DE4426914C1/de not_active Expired - Fee Related
-
1995
- 1995-03-24 EP EP95104355A patent/EP0698676B1/fr not_active Expired - Lifetime
- 1995-03-24 DE DE59500711T patent/DE59500711D1/de not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3339541A1 (de) * | 1983-11-02 | 1985-05-15 | Degussa Ag, 6000 Frankfurt | Alkalisch-cyanidisches bad zur galvanischen abscheidung von kupfer-zinn-legierungsueberzuegen |
DE3346721A1 (de) * | 1983-12-23 | 1985-06-27 | Fa. Karl-Wilh. Hen, 5820 Gevelsberg | Alkalisches bad zum aufbringen eines hochglaenzenden galvanischen ueberzugs auf einen traeger |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, Columbus, Ohio, US; * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104962959A (zh) * | 2015-07-21 | 2015-10-07 | 深圳市新富华表面技术有限公司 | 电镀液 |
IT202100008084A1 (it) * | 2021-03-31 | 2022-10-01 | Bluclad S P A | Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno |
Also Published As
Publication number | Publication date |
---|---|
DE4426914C1 (de) | 1995-08-17 |
DE59500711D1 (de) | 1997-10-30 |
EP0698676B1 (fr) | 1997-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69808497T2 (de) | Cyanidfreie, monovalente kupferelektrobeschichtungslösung | |
DE1207177B (de) | Verfahren zur Herstellung glaenzender galvanischer Metallueberzuege | |
DE3821073A1 (de) | Verfahren zum galvanischen beschichten von aus aluminium oder aluminiumlegierungen gefertigten gegenstaenden mit einem vorzugsweise loetbaren metallueberzug | |
DE3317493C2 (fr) | ||
WO2004035875A2 (fr) | Procede de depot galvanique de bronzes | |
DE670403C (de) | Verfahren zur elektrolytischen Herstellung von im wesentlichen aus Zinn bestehenden UEberzuegen | |
EP1190118B1 (fr) | Systeme de bain pour depot de metaux par voie galvanique | |
DE3875227T2 (de) | Verfahren zur herstellung eines bades fuer die elektroplattierung einer binaeren zinn-kobalt-, zinn-nickel- oder zinn-blei- legierung und damit hergestelltes elektroplattierungsbad. | |
DE3628361C2 (fr) | ||
DE2657925A1 (de) | Ammoniakfreies, waessriges bad zur galvanischen abscheidung von palladium bzw. palladiumlegierungen | |
DE3601698A1 (de) | Ein bad und ein verfahren fuer die galvanische abscheidung von palladium und palladiumlegierungen | |
DE860300C (de) | Kupfer- und Zinnsalze enthaltender Elektrolyt zur Erzeugung von Kupfer-Zinn-Legierungsueberzuegen und Verfahren zum Erzeugen dieser UEberzuege | |
US4252618A (en) | Method of electroplating tin and alkaline electroplating bath therefor | |
WO2000079031A1 (fr) | Bain acide pour deposer par voie electrolytique des couches d'or ou d'alliage d'or brillantes, et agent de brillantage prevu a cet effet | |
AT514427B1 (de) | Elektrolytbad sowie damit erhältliche Objekte bzw. Artikel | |
EP3067444B1 (fr) | Deposition de revetements decoratifs en alliage palladium-fer sur des substances metalliques | |
DE1254932B (de) | Bad zum galvanischen Abscheiden von Zinn-Wismut-Legierungen | |
DE3013191A1 (de) | Im wesentlichen cyanidfreies bad zur elektrolytischen abscheidung von silber oder silberlegierung | |
EP0698676B1 (fr) | Bain d'électrodéposition d'alliages cuivre-étain | |
EP0149029A1 (fr) | Bain de palladium | |
DE2459428C2 (de) | Verfahren zur Herstellung eines Glanzbildners für saure galvanische Zinnbäder und dessen Verwendung | |
EP0126921B1 (fr) | Bain de dépôt galvanique d'alliages d'or | |
DE1952218A1 (de) | Verfahren und Mittel zum galvanischen Verzinnen | |
DE1521043B2 (de) | Bad und Verfahren zum galvanischen Abscheiden von Gold-Palladium-Legierungen | |
EP0194432A1 (fr) | Bain de dépôt galvanique de couches d'alliage d'or-étain |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19950403 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR GB IT LI |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17Q | First examination report despatched |
Effective date: 19961017 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR GB IT LI |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 19970924 Ref country code: GB Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19970924 Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19970924 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59500711 Country of ref document: DE Date of ref document: 19971030 |
|
EN | Fr: translation not filed | ||
GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 19970924 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990331 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990331 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20010313 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021001 |