EP0636713A2 - Alcaline cyanide baths for electroplating copper-tin alloys coatings - Google Patents
Alcaline cyanide baths for electroplating copper-tin alloys coatings Download PDFInfo
- Publication number
- EP0636713A2 EP0636713A2 EP94109336A EP94109336A EP0636713A2 EP 0636713 A2 EP0636713 A2 EP 0636713A2 EP 94109336 A EP94109336 A EP 94109336A EP 94109336 A EP94109336 A EP 94109336A EP 0636713 A2 EP0636713 A2 EP 0636713A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- cyanide
- copper
- contain
- baths
- lead
- 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.)
- Withdrawn
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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
-
- 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
Definitions
- the invention relates to alkaline cyanide baths for the electrodeposition of bright to shiny, leveled copper-tin alloy coatings, the 1 to 60 g / l copper in the form of copper (I) cyanide, 1 to 50 g / l tin in the form of alkali tannate , 0 to 10 g / l zinc in the form of zinc cyanide, 0.1 to 200 g / l of one or more complexing agents, 1 to 100 g / l free alkali metal cyanide, 1 to 50 g / l free alkali metal hydroxide, 0 to 50 g / l Contain alkali carbonate, 0.01 to 5 g / l brightener and 0 to 100 mg / l lead as lead (II) acetate or lead (II) sulfonate.
- the former are therefore used in decorative electroplating to replace, for example, silver, nickel, chromium or aluminum. Because of their very good soldering properties, their abrasion resistance, their corrosion resistance and their low electrical contact resistance, copper-tin coatings are also used increasingly in technical fields.
- the latter are mainly used in decorative electroplating as a replacement for brass and as an underlayer before electroplating. Copper-tin alloy layers do not cause any known allergies on human skin.
- Copper-tin alloys are mainly deposited from alkaline, cyanide-containing electrolytes that contain copper as copper (I) cyanide and tin as sodium stannate.
- Other electrolytes contain phosphate and / or polyphosphate as complexing agents and also colloids, such as polypeptides as gloss additives (DE-PS 860 300).
- These well-known baths must be operated at high, constant temperatures (65 o C and higher) in order to obtain uniform layers of constant composition. Working with these baths is therefore difficult and cumbersome.
- the copper-tin baths can also contain zinc salts, which means that a few percent of zinc is also separated.
- Copper-tin alloy baths have recently become known (DE-PS 33 39 541) which, in addition to copper cyanide, alkali tannate, phosphates, free alkali metal cyanide and free alkali metal hydroxide as complexing agents, also include organic substances in the form of fatty acid-imido-alkyl-dialkylamine oxides, fatty acid -amido-alkyl-dialkylamine-betaine and / or ethoxylated naphthols and as brighteners contain polyethylenediamines, benzaldehydes, ethynols and / or benzylpyridine carboxylates. These baths also require monitoring of the free cyanide and hydroxide content.
- Oligosaccharides based on pentose and hexose have proven particularly useful.
- the baths preferably contain 50 to 150 g / l of these oligosaccharides.
- Baths of this composition are not very sensitive to fluctuations in the hydroxide and cyanide content.
- the coatings deposited from such baths are shiny and shiny.
- the current density range of 1 to 3 A / dm2 that can be used to achieve uniform layers is relatively small.
- the baths preferably contain 0.5 to 1.5 g / l of this gloss agent.
- group a) e.g. Allylsufonate, vinyl sulfonate, from group b) propyne sulfonate and butyne sulfonate, from group c) 1- (3-sulfopropyl) -2-vinyl-pyridinium betaine, 4-methyl-1- (3-sulfopropyl) pyridinium betaine, 4-Benzyl-1- (3-sulfopropyl) pyridinium betaine, and from group d) S-isothiuronium-3-propanesulfonate, o-ethyl-dithiocarbonic acid (3-sulfopropyl) -ester potassium salt.
- the baths are less dependent on fluctuations in the bath components.
- the coatings do not trigger any known allergies and can therefore also replace nickel coatings.
- the baths according to the invention can be operated with insoluble anodes, e.g. with graphite anodes.
- the operating temperatures are 40 to 62 o C, the current densities between 0.1 and 5.0 A / dm2 and the pH values between 11 and 13.
- Baths containing 5 to 25 g / l copper in the form of copper (I) cyanide have proven successful. 5 to 40 g / l tin in the form of sodium stannate, 50-150 g / l complexing agent, 20 to 60 g / l free alkali metal cyanide, 2 to 40 g / l free alkali metal hydroxide, 0.2 to 1.5 g / l brightener and possibly contain 1 to 100 mg / l lead as lead (II) acetate.
- the copper-tin baths can additionally contain known complexing agents, such as phosphates, hydroxycarboxylic acids, aminocarboxylic acids or polyoxycarboxylic acids.
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)
Abstract
Zur Herstellung blanker bis glänzender, eingeebneter Kupfer-Zinn-Legierungsüberzüge verwendet man galvanische Bäder, die 1 bis 60 g/l Kupfer als Kupfercyanid, 1 bis 50 g/l Zinn als Alkalistannat, 0 bis 10 g/l Zink als Zinkcyanid, 1 bis 100 g/l freies Alkalizyanid, 1 bis 50 g/l freies Alkalihydroxid und als Komplexbildner 1 bis 200 g/l Oligosaccharide und/oder Polysaccheride enthalten und zusätzlich noch 0,01 bis 4 g/l Alkensulfonat, Alkinsulfonat, Pyridinverbindungen oder schwefelhaltige Propansulfonate als Glanzmittel.Galvanic baths containing 1 to 60 g / l copper as copper cyanide, 1 to 50 g / l tin as alkali tannate, 0 to 10 g / l zinc as zinc cyanide, 1 to Contain 100 g / l free alkali cyanide, 1 to 50 g / l free alkali hydroxide and as complexing agent 1 to 200 g / l oligosaccharides and / or polysaccherides and additionally 0.01 to 4 g / l alkene sulfonate, alkyne sulfonate, pyridine compounds or sulfur-containing propane sulfonates as Brightener.
Description
Die Erfindung betrifft alkalisch-cyanidische Bäder zur galvanischen Abscheidung blanker bis glänzender, eingeebneter Kupfer-Zinn-Legierungsüberzüge, die 1 bis 60 g/l Kupfer in Form von Kupfer(I)-cyanid, 1 bis 50 g/l Zinn in Form von Alkalistannat, 0 bis 10 g/l Zink in Form von Zinkcyanid, 0,1 bis 200 g/l eines oder mehrerer Komplexbildner, 1 bis 100 g/l freies Alkalicyanid, 1 bis 50 g/l freies Alkalihydroxid, 0 bis 50 g/l Alkalicarbonat, 0,01 bis 5 g/l Glanzmittel und 0 bis 100 mg/l Blei als Blei(II)-acetat oder Blei(II)-sulfonat enthalten.The invention relates to alkaline cyanide baths for the electrodeposition of bright to shiny, leveled copper-tin alloy coatings, the 1 to 60 g / l copper in the form of copper (I) cyanide, 1 to 50 g / l tin in the form of alkali tannate , 0 to 10 g / l zinc in the form of zinc cyanide, 0.1 to 200 g / l of one or more complexing agents, 1 to 100 g / l free alkali metal cyanide, 1 to 50 g / l free alkali metal hydroxide, 0 to 50 g / l Contain alkali carbonate, 0.01 to 5 g / l brightener and 0 to 100 mg / l lead as lead (II) acetate or lead (II) sulfonate.
In der dekorativen Oberflächentechnik benötigt man Bäder, die die Oberfläche der Unterlage gleichmäßig und konturengetreu beschichten und eventuelle Unebenheiten des Substrats ausgleichen (Einebnung). Außerdem müssen sie wahlweise einen matten, seidenmatten oder brillanten Glanz erzeugen. Diese Anforderungen werden vor allem von galvanischen Nickelbädern erfüllt, sowohl für die Abscheidung von Nickelschichten als Endauflage als auch als Unterbau vor einer anschließenden Beschichtung mit Edelmetallen. Nachteilig ist allerdings, daß Nickel auf einen beträchtlichen Teil der Bevölkerung allergisierend wirkt.In decorative surface technology, you need baths that coat the surface of the underlay evenly and true to the contours and compensate for any unevenness in the substrate (leveling). In addition, they must either produce a matt, silk matt or brilliant shine. These requirements are primarily met by galvanic nickel baths, both for the deposition of nickel layers as a final layer and as a substructure before a subsequent coating with precious metals. However, it is disadvantageous that nickel has an allergic effect on a considerable part of the population.
Es ist seit vielen Jahren bekannt, Kupfer-Zinn-Überzüge aus galvanischen Bädern abzuscheiden. Insbesondere verwendet man Überzüge, die 45 bis 60 % Kupfer enthalten, da diese einen hellen Silberglanz besitzen und nicht zum Anlaufen neigen, oder auch Überzüge, die 75 bis 85 % Kupfer aufweisen, da diese eine gelbe bis goldgelbe Farbe besitzen.It has been known for many years to deposit copper-tin coatings from galvanic baths. In particular, coatings are used which contain 45 to 60% copper, since these have a light silver luster and do not tend to tarnish, or coatings which have 75 to 85% copper, since they have a yellow to golden yellow color.
Erstere finden daher Verwendung in der dekorativen Galvanotechnik als Ersatz für beispielsweise Silber, Nickel, Chrom oder Aluminium. Wegen ihrer sehr guten Löteigenschaften, ihrer Abriebbeständigkeit, ihres Korrosionswiderstandes und ihres niedrigen elektrischen Übergangswiderstandes finden Kupfer-Zinn-Überzüge aber auch steigende technische Anwendung auf anderen Gebieten.The former are therefore used in decorative electroplating to replace, for example, silver, nickel, chromium or aluminum. Because of their very good soldering properties, their abrasion resistance, their corrosion resistance and their low electrical contact resistance, copper-tin coatings are also used increasingly in technical fields.
Letztere finden vorwiegend in der dekorativen Galvanotechnik Verwendung als Ersatz für Messing und als Unterschicht vor einer galvanischen Vergoldung. Schichten aus Kupfer-Zinn-Legierungen bewirken keine bekannten Allergien auf der menschlichen Haut.The latter are mainly used in decorative electroplating as a replacement for brass and as an underlayer before electroplating. Copper-tin alloy layers do not cause any known allergies on human skin.
Kupfer-Zinn-Legierungen werden überwiegend aus alkalischen, cyanidhaltigen Elektrolyten abgeschieden, die Kupfer als Kupfer(I)-cyanid und Zinn als Natriumstannat enthalten. Andere Elektrolyte enthalten Phosphat und/oder Polyphosphat als Komplexbildner und außerdem Kolloide, wie z.B. Polypeptide als Glanzzusätze (DE-PS 860 300). Diese bekannten Bäder müssen bei hohen, konstanten Temperaturen (65o C und höher) betrieben werden, um gleichmäßige Schichten konstanter Zusammensetzung zu erhalten. Das Arbeiten mit diesen Bädern ist daher schwierig und umständlich.Copper-tin alloys are mainly deposited from alkaline, cyanide-containing electrolytes that contain copper as copper (I) cyanide and tin as sodium stannate. Other electrolytes contain phosphate and / or polyphosphate as complexing agents and also colloids, such as polypeptides as gloss additives (DE-PS 860 300). These well-known baths must be operated at high, constant temperatures (65 o C and higher) in order to obtain uniform layers of constant composition. Working with these baths is therefore difficult and cumbersome.
Die Kupfer-Zinnbäder können auch Zinksalze enthalten, wodurch einige Prozente Zink mit abgeschieden werden.The copper-tin baths can also contain zinc salts, which means that a few percent of zinc is also separated.
Es sind neuerdings Kupfer-Zinn-Legierungsbäder bekanntgeworden (DE-PS 33 39 541), die neben Kupfercyanid, Alkalistannat, Phosphaten, freiem Alkalicyanid und freiem Alkalihydroxid als Komplexbildner noch organische Substanzen in Form von Fettsäure-imido-alkyl-dialkyl-aminoxide, Fettsäure-amido-alkyl-dialkylamin-betaine und/oder äthoxylierte Naphthole und als Glanzbildner Polyäthylendiamine, Benzaldehyde, Äthinole und/oder Benzylpyridincarboxylate enthalten. Auch diese Bäder bedürfen einer Überwachung des freien Cyanid- und Hydroxidgehaltes. Außerdem wirken sie nur schwach einebnend. Das gleiche gilt für Kupfer-Zinn-Legierungsbäder, die als Komplexbildner 3 bis 12 g/l Monosaccharide enthalten (Pat. Abstr. of Japan, C-122 Sept. 2, 1982, Vol. 6/No. 169, Jp 57-82492).Copper-tin alloy baths have recently become known (DE-PS 33 39 541) which, in addition to copper cyanide, alkali tannate, phosphates, free alkali metal cyanide and free alkali metal hydroxide as complexing agents, also include organic substances in the form of fatty acid-imido-alkyl-dialkylamine oxides, fatty acid -amido-alkyl-dialkylamine-betaine and / or ethoxylated naphthols and as brighteners contain polyethylenediamines, benzaldehydes, ethynols and / or benzylpyridine carboxylates. These baths also require monitoring of the free cyanide and hydroxide content. In addition, they have a weak leveling effect. The same applies to copper-tin alloy baths which contain 3 to 12 g / l monosaccharides as complexing agents (Pat. Abstr. Of Japan, C-122 Sept. 2, 1982, Vol. 6 / No. 169, Jp 57-82492 ).
Es war daher Aufgabe der vorliegenden Erfindung, cyanidisch-alkalische Bäder zur galvanischen Abscheidung von Kupfer-Zinn-Legierungsüberzügen gemäß Oberbegriff von Anspruch 1 zu entwickeln, die einebnend wirken und bei denen die Überzugszusammensetzung weniger stark von Schwankungen der Badbestandteile abhängig ist. Außerdem sollten die Schichten glänzend sein.It was therefore an object of the present invention to develop cyanide-alkaline baths for the electrodeposition of copper-tin alloy coatings according to the preamble of claim 1, which have a leveling effect and in which the coating composition is less dependent on fluctuations in the bath components. The layers should also be shiny.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Bäder als Komplexbildner Oligosaccharide und/oder Polysaccharide in Mengen von 1 bis 200 g/l und zusätzlich noch 0,01 bis 5 g/l eines oder mehrere Glanzmittel enthalten, ausgewählt aus einer oder mehrerer der folgenden Gruppen:
- a) Alkensulfonate der allgemeinen Formel
R-CH=CH-(CH₂)n-SO₃Na
und deren Derivate, worin
R=H, CH₃, C₂H₅, C₃H₇, C₂H₃ oder C₆H₅ und n = 0 bis 5 bedeutet. - b) Alkinsulfonate der allgemeinen Formel
R-(CH₂)m-C≡C-(CH₂)n-SO₃Na
und deren Derivate, worin
R=H, CH₃, C₂H₅, C₃H₇ oder C₆H₅,
m = 0 bis 5 und
n = 0 bis 5 bedeutet. - c) Pyridiniumverbindungen der allgemeinen Formel
R=H, CHO, C₂H₃O, CONH₂, C₂H₃ oder C₆H₅-CH₂ und
n = 1 bis 5 bedeutet,
wobei R in ortho-, meta- oder para-Stellung auftreten kann. - d) Schwefelhaltige Propansulfonate der allgemeinen Formel
R-(CH₂)₃-SO₃-
und deren Derivate, worin
R = -OH
-NH-C-(CH₂OH)₃
-S-S-CH₂-O-C₂H₅
-S-S-CH₂-N-(CH₃)₂
- a) Alkene sulfonates of the general formula
R-CH = CH- (CH₂) n -SO₃Na
and their derivatives, wherein
R = H, CH₃, C₂H₅, C₃H₇, C₂H₃ or C₆H₅ and n = 0 to 5. - b) alkynesulfonates of the general formula
R- (CH₂) m -C≡C- (CH₂) n -SO₃N a
and their derivatives, wherein
R = H, CH₃, C₂H₅, C₃H₇ or C₆H₅,
m = 0 to 5 and
n = 0 to 5 means. - c) pyridinium compounds of the general formula
R = H, CHO, C₂H₃O, CONH₂, C₂H₃ or C₆H₅-CH₂ and
n = 1 to 5 means
where R can occur in the ortho, meta or para position. - d) Sulfur-containing propane sulfonates of the general formula
R- (CH₂) ₃-SO₃-
and their derivatives, wherein
R = -OH
-NH-C- (CH₂OH) ₃
-SS-CH₂-O-C₂H₅
-SS-CH₂-N- (CH₃) ₂
Besonders bewährt haben sich Oligosaccharide auf Pentose- und Hexose-Basis.Oligosaccharides based on pentose and hexose have proven particularly useful.
Vorzugsweise enthalten die Bäder 50 bis 150 g/l dieser Oligosaccharide.The baths preferably contain 50 to 150 g / l of these oligosaccharides.
Bäder dieser Zusammensetzung sind wenig empfindlich gegen Schwankungen im Hydroxid- und Cyanidgehalt. Die aus solchen Bädern abgeschiedenen Überzüge sind blank und glänzend. Außerdem ist der zur Erzielung gleichmäßiger Schichten anwendbare Stromdichtebereich mit 1 bis 3 A/dm² relativ gering. Vorzugsweise enthalten die Bäder 0,5 bis 1,5 g/l dieser Glanzmittel.Baths of this composition are not very sensitive to fluctuations in the hydroxide and cyanide content. The coatings deposited from such baths are shiny and shiny. In addition, the current density range of 1 to 3 A / dm² that can be used to achieve uniform layers is relatively small. The baths preferably contain 0.5 to 1.5 g / l of this gloss agent.
Als Glanzmittel haben sich aus der Gruppe a) z.B. Allylsufonat, Vinylsulfonat, aus der Gruppe b) Propinsulfonat und Butinsulfonat, aus der Gruppe c) 1-(3-sulfopropyl)-2-vinyl-Pyridinium-betain, 4-Methyl-1-(3-sulfopropyl)-Pyridinium-betain, 4-Benzyl-1-(3-sulfopropyl)-pyridinium-betain, und aus der Gruppe d) S-Isothiuronium-3-Propansulfonat, o-Ethyl-dithiokohlensäure-(3-sulfopropyl)-ester Kaliumsalz bewährt.From group a), e.g. Allylsufonate, vinyl sulfonate, from group b) propyne sulfonate and butyne sulfonate, from group c) 1- (3-sulfopropyl) -2-vinyl-pyridinium betaine, 4-methyl-1- (3-sulfopropyl) pyridinium betaine, 4-Benzyl-1- (3-sulfopropyl) pyridinium betaine, and from group d) S-isothiuronium-3-propanesulfonate, o-ethyl-dithiocarbonic acid (3-sulfopropyl) -ester potassium salt.
Die Bäder sind weniger abhängig von Schwankungen der Badbestandteile. Die Überzüge lösen keine bekannten Allergien aus und können daher auch Nickelüberzüge ersetzen.The baths are less dependent on fluctuations in the bath components. The coatings do not trigger any known allergies and can therefore also replace nickel coatings.
Die erfindungsgemäßen Bäder können mit unlöslichen Anoden betrieben werden, wie z.B. mit Graphitanoden.The baths according to the invention can be operated with insoluble anodes, e.g. with graphite anodes.
Die Betriebstemperaturen liegen bei 40 bis 62o C, die Stromdichten zwischen 0,1 und 5.0 A/dm² und die pH-Werte zwischen 11 und 13.The operating temperatures are 40 to 62 o C, the current densities between 0.1 and 5.0 A / dm² and the pH values between 11 and 13.
Bewährt haben sich Bäder, die 5 bis 25 g/l Kupfer in Form von Kupfer(I)-cyanid. 5 bis 40 g/l Zinn in Form von Natriumstannat, 50-150 g/l Komplexbildner, 20 bis 60 g/l freies Alkalicyanid, 2 bis 40 g/l freies Alkalihydroxid, 0,2 bis 1,5 g/l Glanzmittel und eventuell 1 bis 100 mg/l Blei als Blei(II)-acetat enthalten.Baths containing 5 to 25 g / l copper in the form of copper (I) cyanide have proven successful. 5 to 40 g / l tin in the form of sodium stannate, 50-150 g / l complexing agent, 20 to 60 g / l free alkali metal cyanide, 2 to 40 g / l free alkali metal hydroxide, 0.2 to 1.5 g / l brightener and possibly contain 1 to 100 mg / l lead as lead (II) acetate.
Neben den erfindungsgemäßen Komplexbildnern können die Kupfer-Zinnbäder zusätzlich noch bekannte Komplexbildner, wie Phosphate, Hydroxicarbonsäuren, Aminocarbonsäuren oder Polyoxicarbonsäuren enthalten.In addition to the complexing agents according to the invention, the copper-tin baths can additionally contain known complexing agents, such as phosphates, hydroxycarboxylic acids, aminocarboxylic acids or polyoxycarboxylic acids.
Folgende Beispiele sollen die erfindungsgemäßen Bäder näher erläutern:
- 1. Aus einem Bad mit 12 g/l Kupfer(I)-cyanid, 50 g/l Natriumstannat, 20 g/l Kaliumnatriumtartrat, 20 g/l Lactose, 50 g/l freies Kaliumcyanid, 5 g/l Kaliumhydroxid, 0,5 g/l Propansulfonsaures Natrium und 18 mg/l Blei(II)-acetat werden bei einer Temperatur von 58o C und einer Stromdichte von 1,5 A/dm² mit >70 % Stromausbeute in 10 Minuten 4 µm starke, weiße, glänzende Überzüge erhalten, die 55 % Kupfer enthalten und nicht anlaufen.
- 2. Aus einem Bad mit 12 g/l Kupfer(I)-cyanid, 100 g/l Natriumstannat, 20 g/l Kaliumnatriumtartrat, 20 g/l Lactose, 50 g/l freies Kaliumcyanid, 30 g/l freies Kaliumhydroxid, 0,5 g/l Propansulfonsaures Natrium und 18 mg/l Blei(II)-acetat werden bei einer Temperatur von 58o C und einer Stromdichte von 0,5 A/dm² mit >70% Stromausbeute in 30 Minuten 4 µm starke, weiße, glänzende Überzüge erhalten, die 55 % Kupfer enthalten und nicht anlaufen.
- 3. Aus einem Bad mit 17,5 g/l Kupfer(I)-cyanid, 36 g/l Natriumstannat, 2 g/l Zinkoxid, 20 g/l Kaliumnatriumtartrat, 20 g/l Lactose, 20 g/l Dextrin, 50 g/l freies Kaliumcyanid, 10 g/l freies Kaliumhydroxid 0,5 g/l Propansulfonsaures Natrium, 0,2 g/l 4-Benzyl-1-(3-sulfopropyl)-pyridinium-betain und 18 mg/l Blei(II)-acetat werden bei einer Temperatur von 55o C und einer Stromdichte von 1 A/dm² mit > 70% Stromausbeute in 10 Minuten 3 µm starke, weiße, hochglänzende Überzüge erhalten, die 55 % Kupfer, 42 % Zinn, 2,9 % Zink und 0,1 % Blei enthalten und nicht anlaufen.
- 4. Aus einem Bad mit 14,1 g/l Kupfer(I)-cyanid, 50 g/l Natriumstannat, 20 g/l Kaliumnatriumtartrat, 20 g/l Lactose, 0,5 g/l lösliche Stärke, 35 g/l freies Kaliumcyanid, 25 g/l freies Kaliumhydroxid und 1 g/l Allylsulfonsaures Natrium werden bei einer Temperatur von 50o C und einer Stromdichte von 3 A/dm² mit >70 % Stromausbeute in 10 Minuten 4 µm starke, gelbe, hochglänzende und eingeebnete Überzüge erhalten, die 80 % Kupfer enthalten.
- 5. Aus einem Bad mit 17,5 g/l Kupfer(I)-cyanid, 36 g/l Natriumstannat, 2 g/l Zinkcyanid, 20 g/l Kaliumnatriumtartrat, 20 g/l Maltose, 1 g/l lösliche Stärke, 35 g/l freies Kaliumcyanid, 5 g/l freies Kaliumhydroxid, 1 g/l Vinylsulfonsaures Natrium, 0,5 g/l 4-Benzyl-1-(3-sulfopropyl)-pyridinium-betain und 30 mg/l Blei(II)-acetat werden bei einer Temperatur von 55o C und einer Stromdichte von 3 A/dm² mit >70 % Stromausbeute in 20 Minuten 12 µm starke, gelbe, hochglänzende und eingeebnete Überzüge erhalten, die 80 % Kupfer, 17 % Zinn, 2,5 % Zink und 0,5 % Blei enthalten.
- 6. Aus einem Bad mit 30 g/l Kupfer(I)-cyanid, 36 g/l Natriumstannat, 2 g/l Zinkcyanid, 20 g/l Kaliumnatriumtartrat, 20 g/l Maltose, 1 g/l lösliche Stärke, 35 g/l freies Kaliumcyanid, 5 g/l freies Kaliumhydroxid, 1 g/l Vinylsulfonsaures Natrium, 0,5 g/l 4-Benzyl-1-(3-sulfopropyl)-pyridinium-betain und 30 gm/l Blei(II)-acetat werden bei einer Temperatur von 55o C und einer Stromdichte von 0,5 A/dm² mit >70 % Stromausbeute in 50 Minuten um starke, gelbe, hochglänzende und eineebnete Überzüge erhalten, die 80 % Kupfer, 17 % Zinn, 2,5 % Zink und 0,5 % Blei enthalten.
- 1. From a bath with 12 g / l copper (I) cyanide, 50 g / l sodium stannate, 20 g / l potassium sodium tartrate, 20 g / l lactose, 50 g / l free potassium cyanide, 5 g / l potassium hydroxide, 0, 5 g / l propane sulfonic acid sodium and 18 mg / l lead (II) acetate are at a temperature of 58 o C and a current density of 1.5 A / dm² with> 70% current efficiency in 10 minutes, 4 µm thick, shiny white Get coatings that contain 55% copper and do not tarnish.
- 2. From a bath with 12 g / l copper (I) cyanide, 100 g / l sodium stannate, 20 g / l potassium sodium tartrate, 20 g / l lactose, 50 g / l free potassium cyanide, 30 g / l free potassium hydroxide, 0 , 5 g / l propane sulfonic acid sodium and 18 mg / l lead (II) acetate are at a temperature of 58 o C and a current density of 0.5 A / dm² with> 70% current efficiency in 30 minutes 4 µm thick, white, receive shiny coatings that contain 55% copper and do not tarnish.
- 3. From a bath with 17.5 g / l copper (I) cyanide, 36 g / l sodium stannate, 2 g / l zinc oxide, 20 g / l potassium sodium tartrate, 20 g / l lactose, 20 g / l dextrin, 50 g / l free potassium cyanide, 10 g / l free potassium hydroxide 0.5 g / l propane sulfonic acid sodium, 0.2 g / l 4-benzyl-1- (3-sulfopropyl) pyridinium betaine and 18 mg / l lead (II ) acetate are at a temperature of 55 o C and a current density of 1 A / dm² with> 70% current efficiency in 3 minutes get 3 µm thick, white, high-gloss coatings that contain 55% copper, 42% tin, 2.9% zinc and 0.1% lead and don't start.
- 4. From a bath with 14.1 g / l copper (I) cyanide, 50 g / l sodium stannate, 20 g / l potassium sodium tartrate, 20 g / l lactose, 0.5 g / l soluble starch, 35 g / l Free potassium cyanide, 25 g / l free potassium hydroxide and 1 g / l allylsulfonic acid sodium are 4 µm thick, yellow, high-gloss and leveled coatings at a temperature of 50 o C and a current density of 3 A / dm² with> 70% current efficiency in 10 minutes obtained that contain 80% copper.
- 5. From a bath with 17.5 g / l copper (I) cyanide, 36 g / l sodium stannate, 2 g / l zinc cyanide, 20 g / l potassium sodium tartrate, 20 g / l maltose, 1 g / l soluble starch, 35 g / l free potassium cyanide, 5 g / l free potassium hydroxide, 1 g / l vinyl sulfonic acid sodium, 0.5 g / l 4-benzyl-1- (3-sulfopropyl) pyridinium betaine and 30 mg / l lead (II ) acetate at a temperature of 55 o C and a current density of 3 A / dm² with> 70% current efficiency in 20 minutes, 12 µm thick, yellow, high-gloss and leveled coatings are obtained, which are 80% copper, 17% tin, 2, Contain 5% zinc and 0.5% lead.
- 6. From a bath with 30 g / l copper (I) cyanide, 36 g / l sodium stannate, 2 g / l zinc cyanide, 20 g / l potassium sodium tartrate, 20 g / l maltose, 1 g / l soluble starch, 35 g / l free potassium cyanide, 5 g / l free potassium hydroxide, 1 g / l vinyl sulfonic acid sodium, 0.5 g / l 4-benzyl-1- (3-sulfopropyl) pyridinium betaine and 30 gm / l lead (II) - Acetate at a temperature of 55 o C and a current density of 0.5 A / dm² with> 70% current efficiency in 50 minutes around strong, yellow, obtained high gloss and leveled coatings containing 80% copper, 17% tin, 2.5% zinc and 0.5% lead.
Claims (4)
dadurch gekennzeichnet,
daß sie als Komplexbildner Oligosaccharide und/oder Polysaccharide in Mengen von 1 bis 200 g/l und zusätzlich 0,01 bis 5 g/l eines oder mehrere Glanzmittel enthalten, ausgewählt aus den folgenden Gruppen
R-CH=CH-(CH₂)n-SO₃Na
und deren Derivate, worin
R=H, CH₃, C₂H₅, C₃H₇, C₂H₃ oder C₆H₅ und n = 0 bis 5 bedeutet.
R-(CH₂)m-C≡C-(CH₂)n-SO₃Na
und deren Derivate, worin
R=H, CH₃, C₂H₅, C₃H₇ oder C₆H₅,
m = 0 bis 5 und
n = 0 bis 5 bedeutet.
und deren Derivate, worin
R=H, CHO, C₂H₃O, CH₃, CONH₂, C₂H₃ oder C₆H₅, CH₂ und
n = 1 bis 5 bedeutet,
wobei R in ortho-, meta- oder para-Stellung auftreten kann.
R-(CH₂)₃-SO₃-
und deren Derivate, worin
R = -OH
-NH-C-(CH₂OH)₃
-S-S-CH₂-O-C₂H₅
-S-S-CH₂-N-(CH₃)₂
characterized by
that they contain oligosaccharides and / or polysaccharides as complexing agents in amounts of 1 to 200 g / l and additionally 0.01 to 5 g / l of one or more brighteners selected from the following groups
R-CH = CH- (CH₂) n -SO₃Na
and their derivatives, wherein
R = H, CH₃, C₂H₅, C₃H₇, C₂H₃ or C₆H₅ and n = 0 to 5.
R- (CH₂) m -C≡C- (CH₂) n -SO₃N a
and their derivatives, wherein
R = H, CH₃, C₂H₅, C₃H₇ or C₆H₅,
m = 0 to 5 and
n = 0 to 5 means.
and their derivatives, wherein
R = H, CHO, C₂H₃O, CH₃, CONH₂, C₂H₃ or C₆H₅, CH₂ and
n = 1 to 5 means
where R can occur in the ortho, meta or para position.
R- (CH₂) ₃-SO₃-
and their derivatives, wherein
R = -OH
-NH-C- (CH₂OH) ₃
-SS-CH₂-O-C₂H₅
-SS-CH₂-N- (CH₃) ₂
dadurch gekennzeichnet,
daß sie Oligosaccharide auf Pentose- und Hexosebasis enthalten.Alkaline cyanide baths according to Claim 1,
characterized by
that they contain oligosaccharides based on pentose and hexose.
dadurch gekennzeichnet,
daß sie 50 bis 150 g/l dieser Oligosaccharide enthalten.Alkaline cyanide baths according to claim 1 or 2,
characterized by
that they contain 50 to 150 g / l of these oligosaccharides.
dadurch gekennzeichnet,
daß sie 0,5 bis 1,5 g/l dieser Glanzmittel enthalten.Alkaline-cyanide baths according to one of Claims 1 to 3,
characterized by
that they contain 0.5 to 1.5 g / l of this gloss agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4324995A DE4324995C2 (en) | 1993-07-26 | 1993-07-26 | Cyanide-alkaline baths for the galvanic deposition of copper-tin alloy coatings |
| DE4324995 | 1993-07-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0636713A2 true EP0636713A2 (en) | 1995-02-01 |
| EP0636713A3 EP0636713A3 (en) | 1995-07-26 |
Family
ID=6493699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94109336A Withdrawn EP0636713A3 (en) | 1993-07-26 | 1994-06-17 | Alcaline cyanide baths for electroplating copper-tin alloys coatings. |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5534129A (en) |
| EP (1) | EP0636713A3 (en) |
| JP (1) | JP3305504B2 (en) |
| BR (1) | BR9402931A (en) |
| DE (1) | DE4324995C2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1961840A1 (en) * | 2007-02-14 | 2008-08-27 | Umicore Galvanotechnik GmbH | Copper-tin electrolyte and method for depositing bronze layers |
| EP2085502A1 (en) * | 2008-01-29 | 2009-08-05 | Enthone, Incorporated | Electrolyte composition and method for the deposition of a tin-zinc alloy |
| EP2116634A1 (en) | 2008-05-08 | 2009-11-11 | Umicore Galvanotechnik GmbH | Modified copper-tin electrolyte and method of depositing bronze layers |
| DE102008032398A1 (en) | 2008-07-10 | 2010-01-14 | Umicore Galvanotechnik Gmbh | Improved copper-tin electrolyte and process for depositing bronze layers |
| DE102008050135A1 (en) | 2008-10-04 | 2010-04-08 | Umicore Galvanotechnik Gmbh | Process for depositing platinum rhodium layers with improved brightness |
| WO2011029507A1 (en) | 2009-09-11 | 2011-03-17 | Umicore Galvanotechnik Gmbh | Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation |
| WO2015000010A1 (en) | 2013-07-05 | 2015-01-08 | Ing. W. Garhöfer Gesellschaft M.B.H. | Electrolyte bath and objects or articles coated with the aid of the bath |
| WO2015039152A1 (en) | 2013-09-18 | 2015-03-26 | Ing.W.Garhöfer Gesellschaft M.B.H. | Deposition of cu, sn, zn-layers on metallic substrates |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3313277B2 (en) * | 1995-09-22 | 2002-08-12 | 古河サーキットフォイル株式会社 | Electrodeposited copper foil for fine pattern and its manufacturing method |
| EP1091023A3 (en) * | 1999-10-08 | 2003-05-14 | Shipley Company LLC | Alloy composition and plating method |
| JP3455712B2 (en) * | 2000-04-14 | 2003-10-14 | 日本ニュークローム株式会社 | Pyrophosphate bath for copper-tin alloy plating |
| PL2620529T3 (en) * | 2012-01-25 | 2014-09-30 | Atotech Deutschland Gmbh | Method for producing matt copper deposits |
| CN103422079B (en) * | 2012-05-22 | 2016-04-13 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid and preparation method thereof |
| JP6093143B2 (en) * | 2012-10-19 | 2017-03-08 | 株式会社シミズ | Non-cyanide copper-tin alloy plating bath |
| JP2018127698A (en) * | 2017-02-10 | 2018-08-16 | 学校法人関東学院 | Electroplating method and electroplating film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL75841C (en) * | 1949-06-11 | |||
| NL217034A (en) * | 1956-06-15 | |||
| US2916423A (en) * | 1957-06-19 | 1959-12-08 | Metal & Thermit Corp | Electrodeposition of copper and copper alloys |
| JPS58133391A (en) * | 1982-02-01 | 1983-08-09 | Oosakashi | Electroplating bath for bright copper-nickel alloy |
| DE3339541C2 (en) * | 1983-11-02 | 1986-08-07 | Degussa Ag, 6000 Frankfurt | Alkaline-cyanide bath for the galvanic deposition of copper-tin alloy coatings |
| GB8822641D0 (en) * | 1988-09-27 | 1988-11-02 | Int Paint Plc | Improvements related to coatings |
-
1993
- 1993-07-26 DE DE4324995A patent/DE4324995C2/en not_active Expired - Fee Related
-
1994
- 1994-06-17 EP EP94109336A patent/EP0636713A3/en not_active Withdrawn
- 1994-07-20 US US08/277,631 patent/US5534129A/en not_active Expired - Lifetime
- 1994-07-25 BR BR9402931A patent/BR9402931A/en not_active IP Right Cessation
- 1994-07-26 JP JP17424894A patent/JP3305504B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1961840A1 (en) * | 2007-02-14 | 2008-08-27 | Umicore Galvanotechnik GmbH | Copper-tin electrolyte and method for depositing bronze layers |
| EP2085502A1 (en) * | 2008-01-29 | 2009-08-05 | Enthone, Incorporated | Electrolyte composition and method for the deposition of a tin-zinc alloy |
| EP2116634A1 (en) | 2008-05-08 | 2009-11-11 | Umicore Galvanotechnik GmbH | Modified copper-tin electrolyte and method of depositing bronze layers |
| DE102008032398A1 (en) | 2008-07-10 | 2010-01-14 | Umicore Galvanotechnik Gmbh | Improved copper-tin electrolyte and process for depositing bronze layers |
| DE102008050135A1 (en) | 2008-10-04 | 2010-04-08 | Umicore Galvanotechnik Gmbh | Process for depositing platinum rhodium layers with improved brightness |
| WO2011029507A1 (en) | 2009-09-11 | 2011-03-17 | Umicore Galvanotechnik Gmbh | Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation |
| DE102009041250A1 (en) | 2009-09-11 | 2011-05-12 | Umicore Galvanotechnik Gmbh | Process for the electrolytic copper plating of zinc die casting with reduced tendency to blister |
| DE102009041250B4 (en) * | 2009-09-11 | 2011-09-01 | Umicore Galvanotechnik Gmbh | Process for the electrolytic copper plating of zinc die casting with reduced tendency to blister |
| WO2015000010A1 (en) | 2013-07-05 | 2015-01-08 | Ing. W. Garhöfer Gesellschaft M.B.H. | Electrolyte bath and objects or articles coated with the aid of the bath |
| WO2015039152A1 (en) | 2013-09-18 | 2015-03-26 | Ing.W.Garhöfer Gesellschaft M.B.H. | Deposition of cu, sn, zn-layers on metallic substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| US5534129A (en) | 1996-07-09 |
| BR9402931A (en) | 1995-04-11 |
| DE4324995C2 (en) | 1995-12-21 |
| JP3305504B2 (en) | 2002-07-22 |
| JPH0754187A (en) | 1995-02-28 |
| EP0636713A3 (en) | 1995-07-26 |
| DE4324995A1 (en) | 1995-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE4324995C2 (en) | Cyanide-alkaline baths for the galvanic deposition of copper-tin alloy coatings | |
| DE69025500T2 (en) | Process for producing a copper-clad laminate | |
| DE2363943B2 (en) | Process for the galvanic production of wear-resistant, lubricating surfaces on metal objects | |
| AT514818B1 (en) | Deposition of Cu, Sn, Zn coatings on metallic substrates | |
| DE1496917A1 (en) | Electrolytic baths and processes for the production of galvanic coatings | |
| DE3012999C2 (en) | Bath and process for the galvanic deposition of high-gloss and ductile gold alloy coatings | |
| DE3628361C2 (en) | ||
| DE3339541C2 (en) | Alkaline-cyanide bath for the galvanic deposition of copper-tin alloy coatings | |
| EP2212447A2 (en) | Gold-containing nickel layer | |
| DE2114119A1 (en) | Process for the electrolytic deposition of ruthenium and electrolysis bath to carry out this process | |
| US3892638A (en) | Electrolyte and method for electrodepositing rhodium-ruthenium alloys | |
| AT514427B1 (en) | Electrolyte bath and thus available objects or articles | |
| EP0126921B1 (en) | Bath for the galvanic deposition of gold alloys | |
| DE2333096C3 (en) | Electroplated multilayer metal coating and process for its manufacture | |
| DE2439656C2 (en) | Aqueous acid bath for the electrodeposition of a tin-nickel alloy | |
| DE2538817C3 (en) | Bath and method for electroless nickel plating of metal and metal alloys, in particular aluminum and aluminum alloys | |
| DE2618638B2 (en) | Electroplating bath and process for the deposition of coatings from tin-containing alloys | |
| DE2743847A1 (en) | METHOD FOR GALVANIC DEPOSITION OF NICKEL AND COBALT ALONE OR AS BINARY OR TERNAIRE ALLOYS | |
| DE102020133188A1 (en) | Silver bismuth electrolyte for the deposition of hard silver layers | |
| DE102020131371A1 (en) | Ruthenium alloy layer and their layer combinations | |
| DE3705949A1 (en) | AQUEOUS ACID BATH AND METHOD FOR GALVANIC DEPOSITION OF ZINC ALLOYS | |
| EP4146848B1 (en) | Silver electrolyte for separating silver dispersion layers | |
| DE1496823C (en) | Process for the galvanic separation of corrosion-resistant, three-layer nickel or nickel-cobalt alloy coatings on metals | |
| DE2429275A1 (en) | ELECTROLYTE FOR THE DEPOSITION OF RHODIUM-RTHENIUM ALLOYS | |
| DE102006025847A1 (en) | Use of phosphinic acid in electroplating |
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: 19940617 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT CH DE FR GB IT LI |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT CH DE FR GB IT LI |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DEGUSSA AKTIENGESELLSCHAFT |
|
| 17Q | First examination report despatched |
Effective date: 19960315 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19970114 |