EP3084042B1 - Dépôt d'alliages cuivre-étain et cuivre-étain-zinc à partir d'un électrolyte - Google Patents

Dépôt d'alliages cuivre-étain et cuivre-étain-zinc à partir d'un électrolyte Download PDF

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Publication number
EP3084042B1
EP3084042B1 EP14818924.4A EP14818924A EP3084042B1 EP 3084042 B1 EP3084042 B1 EP 3084042B1 EP 14818924 A EP14818924 A EP 14818924A EP 3084042 B1 EP3084042 B1 EP 3084042B1
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EP
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Prior art keywords
copper
electrolyte
tin
acid
zinc
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EP14818924.4A
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German (de)
English (en)
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EP3084042A1 (fr
Inventor
Klaus Bronder
Sascha Berger
Bernd Weyhmueller
Uwe Manz
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Umicore Galvanotechnik GmbH
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Umicore Galvanotechnik GmbH
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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
    • 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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 present invention relates to a cyanide-free electrolyte which contains a phosphate and aliphatic or aromatic thio compounds and also to a process for the electrolytic deposition of an alloy of the elements copper and tin and optionally zinc.
  • the electrolyte and the process are characterized in that stannate ions and copper ions and optionally zinc(II) ions and also aliphatic or aromatic thio compounds are present in the electrolyte used.
  • the solderability of the resulting layer and possibly its mechanical adhesive strength are the critical properties.
  • the appearance of the layers is generally less important than their functionality for use in this field.
  • the decorative effect and also durability of the layer with an appearance which is as unchanged as possible are the important target parameters.
  • EP 2 032 743 B1 describes an electrolyte for producing Cu-Sn-Zn alloy layers for photovoltaic cells.
  • This electrolyte is phosphate-/pyrophosphate-based and uses tin in tetravalent form as stannate, in contrast to all known cyanide-free systems. Matt Cu-Sn-Zn layers can be deposited from this electrolyte in a very narrow current density window.
  • This type of electrolyte in the form described is not suitable for production of decorative bronze layers in drum or rack plating.
  • EP 1 961 840 A1 discloses a nontoxic electrolyte for the deposition of decorative bronze alloy layers, which contains the metals to be deposited in the form of water-soluble salts, with the electrolyte containing one or more phosphonic acid derivatives as complexing agents and being free of cyanides, thiourea derivatives and thio derivatives.
  • the electrolyte contains copper and tin or copper, tin and zinc as metals to be deposited. Tin can be used as divalent or tetravalent tin salt in this case. Stannates are not disclosed.
  • EP 1 961 840 A1 teaches that bronze layers which have been deposited electrochemically from baths with addition of thio compounds have a spotty or matt-veiled appearance and are therefore not suitable for decorative coating of consumer goods.
  • WO 2013/092312 A1 discloses a cyanide-free, pyrophosphate-containing electrolyte and a process for the electrolytic deposition of a ternary alloy of copper, tin and zinc.
  • stannate ions are present in addition to zinc(II) ions and copper(II) ions in the electrolyte. It is not possible to produce uniformly white coatings over a wide current density range when using this electrolyte, so that it is unsuitable for coating decorative articles.
  • WO 2013/092314 A1 discloses a cyanide-free, pyrophosphate-free and phosphonic acid-free electrolyte and a process for the electrolytic deposition of a ternary alloy of copper, tin and zinc.
  • stannate ions are present in addition to zinc (II) ions and copper(II) ions in the electrolyte.
  • the electrolyte disclosed in WO 2013/092312 A1 it is also not possible to produce uniformly white coatings over a wide current density range when using this electrolyte, so that it is unsuitable for coating decorative articles.
  • EP 2 071 057 A2 describes a composition for the electrolytic deposition of white bronzes, which contains tin, copper and zinc ions and also at least one mercaptan selected from the group consisting of mercaptotriazoles and mercaptotetrazoles. Copper can be present in the form of Cu(I) and Cu(II) salts in the composition according to that invention.
  • the tin compounds disclosed are Sn(II) salts.
  • the composition does not contain any phosphates, pyrophosphates or phosphonates. In all examples, bronzes are deposited at pH values of ⁇ 3.
  • EP 1 001 054 A2 discloses electrochemical baths for the deposition of tin-copper alloys.
  • the baths comprise a water-soluble tin(II) or tin(IV) salt, a water-soluble copper(I) or copper(II) salt, an organic or inorganic acid or a water-soluble salt thereof and also at least one compound selected from the group consisting of thioamide and thio compounds.
  • thioamide and thio compounds When sodium stannate(IV) is used, Cu(I) cyanide is also used at the same time - the electrolytes are thus not cyanide-free.
  • the thio compounds serve as bath stabilizers or complexing agents.
  • the inorganic acid or the salt thereof can be phosphoric acid, condensed phosphoric acid, viz. pyrophosphoric acid, and phosphonic acid.
  • the electrochemical baths according to EP 1 001 054 A2 do not contain any zinc compounds.
  • the electrochemical baths according to EP 1 001 054 A2 allow the deposition of tin-copper alloys whose appearance can vary as a function of the copper content, the presence or absence of brighteners and the selected water-soluble metal salts from white to grayish white and from bright to matt.
  • WO 2010/003621 A1 discloses electrolyte baths for the deposition of decorative bronzes, which baths contain copper, tin and optionally zinc and also one or more phosphonic acid derivatives, a disulfide and a carbonate or hydrogencarbonate.
  • the tin is present as tin(II) salt in this case.
  • the electrolyte should have a very simple make-up. Furthermore, the process and the electrolytes of the invention should be superior to the processes and electrolytes known from the prior art from ecological and economic points of view.
  • an aqueous, cyanide-free electrolyte for the electrolytic deposition of an alloy of copper, tin and optionally zinc which comprises at least one salt from the group consisting of phosphates, phosphonates, polyphosphates, diphosphates and mixtures thereof, wherein the sum of the molar amounts of the phosphates, phosphonates, polyphosphates and diphosphates is greater than the sum of the molar amounts of the copper and tin ions, and at least one compound selected from the group consisting of aliphatic and aromatic thio compounds, wherein the thio compound is selected from the list according to claim 1, wherein the metals copper and optionally zinc to be deposited are present in dissolved form and tin is present as dissolved Sn(IV) salt and wherein the pH of the aqueous, cyanide-free electrolyte
  • advantageous copper-tin and copper-tin-zinc alloy compositions can be obtained from the electrolyte described here when at least one salt from the group consisting of phosphates, phosphonates, polyphosphates, diphosphates and mixtures thereof is present in the electrolyte in an excess over the copper and tin ions, when a particular ratio of copper to tin ions is set at the same time and when tin is present at the same time as dissolved Sn(IV) salt. If the electrolyte additionally contains zinc in order to be able to deposit a ternary alloy, both zinc and copper are present in dissolved form.
  • the electrolyte additionally contains an aliphatic or aromatic thio compound, selected from the list according to claim 1, which complexes dissolved Cu salts.
  • the pH of the aqueous electrolyte of the invention is greater than or equal to 9 and thus alkaline.
  • the use of aliphatic and aromatic thio compounds in phosphate- and Sn(IV)-based Cu-Sn alloy electrolytes, which optionally additionally contain Zn, makes it possible to complex copper and at the same time promote the codeposition of tin and optionally zinc in current density ranges from 0.1 to 100 A/dm 2 , advantageously from 0.3 to 1.0 A/dm 2 .
  • the usable current density window is thereby considerably widened compared to known electrolytes.
  • uniformly white coatings of copper-tin and copper-tin-zinc bronzes are deposited over a wide working range.
  • “Uniformly” here means that the coatings have a homogeneous appearance, i.e. same color and same layer properties in respect of gloss, hardness and corrosion resistance.
  • Uniformly white coatings of copper-tin bronzes and copper-tin-zinc bronzes can be deposited with the aid of the electrolyte composition of the invention.
  • the color white can be defined more precisely by means of an L*a*b* color measurement.
  • Electrolytes which use stannate as tin source are known for the deposition of copper-tin and copper-tin-zinc alloys in the prior art, for example EP 1 001 054 A2 as mentioned at the outset.
  • stannates are always used in combination with copper cyanides there.
  • Cu is essentially present as Cu(I) cyanide, i.e. as [Cu(CN) 2 ] - .
  • the deposition of Cu-Sn layers from electrolytes containing stannate and Cu(I) cyanide was carried out in EP 1 001 054 A2 at pH values in the range from 12 to 13 and led to bronze layers whose structure and color was nonuniform. In addition, the bronze layers displayed burnt deposits.
  • the alkaline baths comprising stannate and Cu(I) cyanide also had a poor bath stability.
  • Phosphates and pyrophosphates are used in the prior art for stabilizing Cu-Sn and Cu-Sn-Zn electrolytes, for example in the documents WO 2013/092312 A1 and WO 2013/092314 A1 cited at the outset.
  • the alloy composition is very dependent on the current density employed.
  • aqueous electrolytes of the invention and the process for the deposition of Cu-Sn and Cu-Sn-Zn alloys are explained below, with the invention encompassing all the embodiments indicated below, both individually and in combination with one another.
  • Copper can be added to the electrolyte in the form of monovalent or divalent copper salts or mixtures thereof. Any zinc optionally used is present in the form of divalent ions in the electrolyte. Under the reaction conditions according to the invention, copper and optionally zinc are deposited from their water-soluble compounds. Suitable water-soluble compounds of copper and zinc are selected from the group consisting of pyrophosphates, carbonates, hydrogencarbonates, sulfites, sulfates, phosphates, nitrites, nitrates, halides, hydroxides, oxide-hydroxides, oxides and combinations thereof. Halides can be fluorides, chlorides, bromides or iodides.
  • water-soluble refers to salts of copper and zinc whose solubility in water is at least 0.1 g/l at 25°C.
  • copper is added to the electrolyte in the form of a Cu(I) salt.
  • copper is added to the electrolyte in the form of a Cu(II) salt.
  • Tin is added to the electrolyte of the invention as Sn(IV) salt, i.e. in tetravalent form.
  • Suitable Sn(IV) salts are SnO 2 , Sn(OH) 4 , SnCl 4 , SnBr 4 , SnI 4 , Sn(SO 4 ) 2 , Sn(NO 3 ) 4 , SnS 2 , Na 2 SnO 3 , K 2 SnO 3 , K 2 SnO 7 C 2 .
  • the Sn(IV) salt is a stannate.
  • the stannate is advantageously sodium stannate Na 2 SnO 3 or potassium stannate K 2 SnO 3 .
  • the Sn(IV) salt is sodium stannate.
  • the Sn(IV) salt is potassium stannate.
  • the electrolyte of the invention further comprises at least one salt from the group consisting of phosphates, phosphonates, polyphosphates, diphosphates and mixtures of these salts.
  • Suitable phosphates are, for example, disodium hydrogenphosphate and dipotassium hydrogenphosphate.
  • a person skilled in the art will know that the tribasic phosphoric acid dissociates over three stages and that both dihydrogenphosphates and hydrogenphosphates are ampholytes.
  • the ratio of phosphate (PO 4 3- ) , hydrogenphosphate (HPO 4 2- ) and dihydrogenphosphate (H 2 PO 4- ) ions in a solution is known to depend on the pH of the solution.
  • phosphate, hydrogenphosphate and dihydrogenphosphate ions will therefore be referred to summarily as "phosphate ions".
  • the tribasic phosphonic acid also dissociates over three stages, and both dihydrogenphosphonates and hydrogenphosphonates are ampholytes.
  • the salts of phosphonic acid are referred to summarily as "phosphonates".
  • diphosphoric acid and polyphosphoric acids are also polybasic and the ratio of the corresponding anions of these acids which are present depends, as in the case of phosphoric and phosphonic acids, on the pH of the solution.
  • the compounds from the group consisting of phosphates, phosphonates, polyphosphates and diphosphates which are used in the electrolyte of the invention are salts of phosphoric acid, phosphonic acid, polyphosphoric acid and diphosphoric acid.
  • the salts here are advantageously ammonium, lithium, sodium or potassium salts of these acids.
  • these cations can be identical or different.
  • "Mixtures" of phosphates, phosphonates, polyphosphates and diphosphates can be mixtures of at least two phosphates, at least two phosphonates, at least two polyphosphates or at least two diphosphates.
  • these mixtures can be mixtures of at least two compounds from different groups of salts containing phosphorus and oxygen, i.e., for example, a phosphate and a phosphonate or two phosphates and one diphosphate Phosphates, phosphonates, polyphosphates and diphosphates are the four groups of salts containing phosphorus and oxygen which are used for the purposes of the present invention.
  • the phosphates, phosphonates, polyphosphates and diphosphates are present in excess over the copper and tin ions in the electrolyte.
  • "excess” means that the sum of the molar amounts of the phosphates, phosphonates, polyphosphates and diphosphates is greater than the sum of the molar amounts of the copper and tin ions.
  • the total concentration of the at least one salt from the group consisting of phosphates, phosphonates, polyphosphates, diphosphates and mixtures thereof in the electrolyte is from 0.05 mol/l to 5.0 mol/l.
  • the at least one salt from the group consisting of phosphates, phosphonates, polyphosphates and diphosphates in the aqueous, cyanide-free electrolyte of the invention is a hydrogenphosphate.
  • Particularly suitable hydrogenphosphates are sodium hydrogenphosphate and dipotassium hydrogenphosphate.
  • the electrolyte contains from 20 to 150 g/l of dipotassium hydrogenphosphate.
  • the electrolyte contains from 20 to 150 g/l of disodium hydrogenphosphate.
  • Suitable pyrophosphates are, for example, sodium pyrophosphate and potassium pyrophosphate or mixtures thereof.
  • the electrolyte contains from 5 to 40 g/l of potassium pyrophosphate. In a further advantageous embodiment, the electrolyte contains from 5 to 40 g/l of sodium pyrophosphate.
  • the electrolyte contains from 20 to 150 g/l of hydrogenphosphate, preferably 90 g/l of hydrogenphosphate, in the form of disodium and/or dipotassium hydrogenphosphate, and from 5 to 40 g/l of pyrophosphate, in the form of sodium and/or potassium pyrophosphate.
  • the electrolyte of the invention additionally contains at least one compound selected from the group consisting of aliphatic and aromatic thio compounds.
  • at least one compound from the group consisting of aliphatic and aromatic thio compounds is present in a concentration of from 0.02 to 10 g/l in the electrolyte.
  • at least one compound from the group consisting of aliphatic and aromatic thio compounds means that the electrolyte of the invention comprises
  • the thio compound is selected from among 2-mercaptopropionic acid, mercaptosuccinic acid, 2-thiopropanedicarboxylic acid, Na 3-mercapto-1-propanesulfonate, 2-mercaptonicotinic acid, 2-thiouracil, 4,6-dihydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 2-thiocytosine, 6-mercaptopyrimidine-4-carboxylic acid, 2-mercaptopyrimidin-4-ol, 2-thiohydantoin, 5-sulfosalicylic acid. It is particularly advantageous to use mercaptosuccinic acid and 4,6-dihydroxy-2-mercaptopyrimidine.
  • the thio compound is selected from among from 1 to 10 ml of 2-mercaptopropionic acid, from 0.5 to 10 g of thiopropanedicarboxylic acid, from 0.05 to 5 g of Na 3-mercapto-propanesulfonate, from 0.05 to 5 g of 2-mercaptonicotinic acid, from 0.02 to 5 g of 2-thiouracil and from 0.5 to 10 g of 4,6-dihydroxy-2-mercaptopyrimidine, in each case per liter of electrolyte.
  • the pH of the aqueous electrolyte of the invention is greater than or equal to 9.
  • the electrolyte has a pH of greater than or equal to 11.
  • the electrolyte of the invention additionally contains at least one aliphatic saturated or unsaturated dicarboxylic or tricarboxylic acid, an aromatic carboxylic acid, salts and mixtures thereof.
  • “At least one carboxylic acid, salts and mixtures thereof” means that carboxylic acids and salts thereof mentioned below can be used either individually or in any combination.
  • the aliphatic saturated dicarboxylic acid is advantageously selected from among oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, malic acid.
  • the aliphatic unsaturated dicarboxylic acid is advantageously selected from among maleic acid and fumaric acid.
  • a suitable tricarboxylic acid is citric acid.
  • Suitable aromatic carboxylic acids are, for example, benzoic acid, benzene-1,3,5-tricarboxylic acid and salicylic acid.
  • the salts of the carboxylic acids mentioned are advantageously the ammonium, lithium, sodium or potassium salts.
  • the hydrogen atoms of one or more or all carboxyl groups can be replaced by ammonium, lithium, sodium or potassium ions. If in the case of polybasic carboxylic acids at least two carboxyl hydrogens have been replaced by ammonium, lithium, sodium or potassium ions, these ions can be identical or different.
  • the total concentration of the carboxylic acids or salts thereof is advantageously from 5 to 100 g/l of electrolyte.
  • the carboxylic acid is selected from among oxalic acid, tartaric acid and citric acid or the carboxylic acid salt is selected from among oxalates, tartrates and citrates.
  • the carboxylic acid or salt thereof is oxalic acid or an oxalate.
  • the use of dipotassium oxalate K 2 C 2 O 4 is very particularly advantageous.
  • tartaric acid or a salt thereof for example potassium sodium tartrate, is used.
  • citric acid or a citrate for example potassium citrate, is used.
  • the electrolyte of the invention contains at least one further salt.
  • the anions of these salts are selected from the group consisting of sulfates, fluorides, chlorides, bromides, iodides, carbonates, formates, acetates, propionates, butyrates, valerates, nitrates, nitrites, sulfonates, alkylsulfonates, in particular methanesulfonates, amidosulfonates, sulfamates, anions of aminocarboxylic acids and N-heterocyclic carboxylic acids.
  • the cations of these salts are selected from among ammonium, lithium, sodium and potassium ions.
  • one or all hydrogen atoms can have been replaced by the cations mentioned. If more than one hydrogen atom has been replaced by one of the abovementioned cations, these cations can be identical or different.
  • the at least one further salt will hereinafter also be referred to as "conducting salt”.
  • the electrolyte of the invention additionally comprises at least one brightener.
  • Additions of brighteners to electrolytes for the deposition of bronzes are known to those skilled in the art and can be employed without going outside the scope of protection of the claims.
  • the brightener is advantageously selected from among bis(3-sulfopropyl) disulfide disodium salt, 3-sulfopropyl O-ethyldithiocarbonate potassium salt, 1-(3-sulfopropyl)-pyridinium betaine, 1-(2-hydroxy-3-sulfopropyl)-pyridinium betaine, 3-(2-benzothiazole-2-mercapto)propanesulfonic acid sodium salt, S-isothiouronium 3-propanesulfonate, 3-(sulfopropyl) N,N-dimethyldithiocarbamate sodium salt, 1-benzyl-3-sodiocarboxypyridinium chloride, 3-formyl-1-(3-sulfopropyl)pyridinium betaine, N-(3-sulfopropyl)saccharin sodium salt, saccharin sodium salt, carboxethylisothiuronium betaine, cocoamido
  • the electrolyte of the invention additionally comprises at least one wetting agent.
  • Wetting agent additions to the electrolytes for the deposition of bronzes are known to those skilled in the art and can be employed without going outside the scope of protection of the claims.
  • the wetting agent is advantageously selected from among
  • electrolytes having the abovementioned general compositions 1 to 4 additionally contain at least one brightener, at least one wetting agent or at least one brightener and at least one wetting agent are particularly advantageous.
  • All particularly advantageous embodiments of the electrolyte of the present invention are aqueous, cyanide-free and have a pH of greater than or equal to 9.
  • the metals copper and optionally zinc are present in ionically dissolved form in the electrolyte and tin is present as stannate or another Sn(IV) salt.
  • the ion concentration of copper is advantageously from 0.05 to 10 g/l
  • the ion concentration of tin as stannate is advantageously from 0.5 to 40 g/l
  • the ion concentration of zinc is advantageously from 0.1 to 10 g/l. It is particularly advantageous for the ion concentration of copper to be from 0.5 to 2.0 g/l of electrolyte, that of tin as stannate to be from 10 to 20 g/l of electrolyte and that of zinc to be from 2.0 to 4.0 g/l.
  • the indicated advantageous ion concentrations of copper, tin and optionally zinc apply to all abovementioned advantageous embodiments.
  • the present invention likewise provides a process for the electrolytic deposition of Cu-Sn and Cu-Sn-Zn alloy layers, in which the substrate to be coated is dipped as cathode into an electrolyte according to the invention and current flow is established between the anode and the cathode. It goes without saying that the embodiments named as preferred for the electrolyte are likewise preferred for the process.
  • the proportion of copper in the ternary alloy deposited is in the range from 20 to 80% by weight, the proportion of tin to be in the range from 10 to 60% by weight and the proportion of zinc to be in the range from 1 to 30% by weight.
  • the sum of the proportions of all participating metals in the alloy is in each case 100% by weight.
  • the proportion of copper is in the range from 30 to 90% by weight and the proportion of tin is in the range from 10 to 70% by weight.
  • the sum of the proportions of all participating metals in the alloy is in each case 100% by weight.
  • the ternary alloy deposited is a white layer having a proportion of copper of from 50 to 60% by weight, a proportion of tin of 35-45% by weight and a proportion of zinc of 5-15% by weight, where the sum of the proportions of all participating metals in the alloy is in each case 100% by weight.
  • the deposited alloy can in all embodiments described here have a thickness of 0.4-5 ⁇ m, preferably 0.5-3 ⁇ m and very particularly preferably 1-2 ⁇ m.
  • the alloy composition can likewise change with the temperature prevailing in the electrolysis.
  • the electrolysis is therefore carried out in the range from 20 to 90°C, preferably from 30 to 60°C and very preferably at about 45°C.
  • the composition of the binary alloy of copper and tin or the ternary alloy of copper, tin and zinc can change with the current density set in the electrolysis. It is advantageous to set a current density in the range from 0.1 to 100 ampere per square decimeter.
  • the current density is preferably from 0.2 to 5.0 ampere per square decimeter, very preferably from 0.3 to 1 ampere per square decimeter.
  • insoluble anodes e.g. platinated titanium anodes or mixed metal oxide anodes.
  • soluble anodes composed of a material selected from the group consisting of electrolytic copper, phosphorus-containing copper, tin, tin-copper alloy, zinc-copper alloy and zinc-tin-copper alloy or combinations of these anodes can likewise be used.
  • the electrolyte of the invention and the process of the invention can be used for the electrolytic deposition of alloys of copper, tin and optionally zinc on consumer goods and decorative goods.
  • Example 1 Electrolyte without addition of a thio compound (comparative)
  • Example 4 Electrolyte with thiopropanedicarboxylic acid

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Claims (15)

  1. Électrolyte aqueux sans cyanure pour le dépôt électrolytique d'un alliage de cuivre, d'étain et éventuellement de zinc, qui comprend
    au moins un sel du groupe constitué de phosphates, phosphonates, polyphosphates, diphosphates et des mélanges de ceux-ci, dans lequel la somme des quantités molaires des phosphates, phosphonates, polyphosphates et diphosphates est supérieure à la somme des quantités molaires des ions cuivre et étain,
    et
    au moins un composé choisi dans le groupe constitué de composés thio aliphatiques et aromatiques, dans lequel le composé thio est choisi parmi l'acide 2-mercaptopropionique, l'acide mercaptosuccinique, l'acide 2-thiopropanedicarboxylique, le 3-mercapto-1-propanesulfonate de Na, l'acide 2-mercaptonicotinique, le 2-thio-uracile, la 4,6-dihydroxy-2-mercaptopyrimidine, la 2-mercaptopyrimidine, la 2-thiocytosine, l'acide 6-mercaptopyrimidine-4-carboxylique, le 2-mercaptopyrimidin-4-ol, la 2-thiohydantoïne, l'acide 5-sulfosalicylique,
    dans lequel les métaux cuivre et éventuellement zinc à déposer sont présents sous forme dissoute et l'étain est présent en tant que sel de Sn(IV) dissous
    et dans lequel le pH de l'électrolyte aqueux sans cyanure est supérieur ou égal à 9.
  2. Électrolyte selon la revendication 1,
    caractérisé en ce que
    il comprend en outre au moins un acide dicarboxylique ou tricarboxylique aliphatique saturé ou insaturé, un acide carboxylique aromatique, des sels et des mélanges de ceux-ci.
  3. Électrolyte selon la revendication 1 ou la revendication 2,
    caractérisé en ce que
    il contient en outre au moins un autre sel, dans lequel l'anion est choisi dans le groupe constitué de sulfates, fluorures, chlorures, bromures, iodures, carbonates, acétates, formiates, propionates, butyrates, valérates, benzoates, nitrates, nitrites, sulfonates, alkylsulfonates, amidosulfonates, sulfamates, anions d'acides aminocarboxyliques et acides carboxyliques N-hétérocycliques,
    dans lequel le cation est choisi parmi les ions ammonium, lithium, sodium et potassium.
  4. Électrolyte selon l'une quelconque des revendications 1 à 3,
    caractérisé en ce que
    il contient en outre au moins un azurant choisi dans le groupe constitué de sel disodique de bis(3-sulfopropyl)disulfure, sel de potassium de O-éthyldithiocarbonate de 3-sulfopropyle, 1-(3-sulfopropyl)pyridinium bétaïne, 1-(2-hydroxy-3-sulfopropyl)pyridinium bétaïne, sel de sodium d'acide 3-(2-benzothiazole-2-mercapto)propanesulfonique, 3-propanesulfonate de S-isothiouronium, sel de sodium de N,N-diméthyldithiocarbamate de 3-(sulfopropyle), chlorure de 1-benzyl-3-sodiocarboxypyridinium, 3-formyl-1-(3-sulfopropyl)pyridinium bétaïne, sel de sodium de N-(3-sulfopropyl) saccharine, sel de sodium de saccharine, carboxyéthylisothiuronium bétaïne, cocoamidopropyldiméthylammonium 2-hydroxypropanesulfo-bétaïne, N-(3-cocoamidopropyl-N,N-diméthyl)-N-(3-sulfopropyl)ammonium bétaïne, acide 6-carboxy-2,4-dihydroxypyrimidine, 2-buténoïque.
  5. Électrolyte selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce que
    il contient en outre au moins un agent mouillant choisi parmi
    o un polymère amine cationique ayant des groupes urée,
    o un polymère cationique qui est constitué des monomères morpholine, épichlorhydrine et imidazole et a la formule générale (C4F9NO)x*(C3H5ClO)y*(C3H4N2)z,
    o un polymère cationique qui est constitué des monomères épichlorhydrine et imidazole et a la formule générale (C3H5ClO)x*(C3H4N2)y,
    o des acides N-alkyl-N-(1-oxoalkyl)aminés et des dérivés et sels de ceux-ci et
    o des mélanges de ces agents mouillants.
  6. Électrolyte selon l'une quelconque des revendications 1 à 5,
    caractérisé en ce que
    les métaux cuivre et éventuellement zinc à déposer sont présents sous forme ioniquement dissoute et l'étain est présent en tant que sel de Sn(IV), dans lequel la concentration en ions de cuivre est dans la plage allant de 0,05 à 10 g/L d'électrolyte, la concentration en ions d'étain est dans la plage allant de 0,5 à 40 g/L d'électrolyte et la concentration en ions de zinc est dans la plage allant de 0,1 à 10 g/L d'électrolyte.
  7. Électrolyte selon l'une quelconque des revendications 1 à 6,
    caractérisé en ce que
    les composés des métaux cuivre et éventuellement zinc à déposer qui sont hydrosolubles dans les conditions données sont choisis dans le groupe constitué de pyrophosphates, carbonates, bicarbonates, sulfites, sulfates, phosphates, nitrites, nitrates, halogénures, hydroxydes, oxydes-hydroxydes, oxydes et des combinaisons de ceux-ci.
  8. Électrolyte selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le sel de Sn(IV) dissous est un stannate.
  9. Procédé pour le dépôt électrolytique d'un alliage des éléments cuivre et étain et éventuellement zinc, dans lequel le substrat à revêtir est immergé en tant que cathode dans un électrolyte selon l'une ou plusieurs des revendications 1 à 8 et une circulation électrique est établie entre l'anode et la cathode.
  10. Procédé selon la revendication 9,
    caractérisé en ce que
    la proportion de cuivre dans l'alliage est dans la plage allant de 20 à 80 % en poids, la proportion d'étain est dans la plage allant de 10 à 60 % en poids et la proportion de zinc est dans la plage allant de 1 à 30 % en poids, où la somme des proportions de tous les métaux participants dans l'alliage est dans chaque cas 100 % en poids.
  11. Procédé selon la revendication 9, caractérisé en ce que la proportion de cuivre dans l'alliage va de 50 à 60 % en poids, la proportion d'étain va de 35 à 45 % en poids et la proportion de zinc va de 5 à 15 % en poids, où la somme des proportions de tous les métaux participants dans l'alliage est dans chaque cas 100 % en poids.
  12. Procédé selon la revendication 9, caractérisé en ce que la proportion de cuivre dans l'alliage est dans la plage allant de 30 à 90 % en poids et la proportion d'étain est dans la plage allant de 10 à 70 % en poids, où la somme des proportions de tous les métaux participants dans l'alliage est dans chaque cas 100 % en poids.
  13. Procédé selon l'une quelconque des revendications 9 à 12, caractérisé en ce que
    l'électrolyte est maintenu dans la plage allant de 20 à 90 °C.
  14. Procédé selon l'une quelconque des revendications 9 à 13, caractérisé en ce que
    une densité de courant dans la plage allant de 0,1 à 100 ampères par décimètre carré est définie.
  15. Procédé selon l'une quelconque des revendications 9 à 13, caractérisé en ce que des anodes insolubles (par exemple, des anodes de titane platinées ou des anodes d'oxyde métallique mixte) ou des anodes solubles composées d'un matériau choisi dans le groupe constitué de cuivre électrolytique, cuivre contenant du phosphore, étain, alliage étain-cuivre, alliage zinc-cuivre et alliage zinc-étain-cuivre ou des combinaisons de ces anodes sont utilisées.
EP14818924.4A 2013-12-17 2014-12-11 Dépôt d'alliages cuivre-étain et cuivre-étain-zinc à partir d'un électrolyte Active EP3084042B1 (fr)

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DE102013226297.3A DE102013226297B3 (de) 2013-12-17 2013-12-17 Wässriger, cyanidfreier Elektrolyt für die Abscheidung von Kupfer-Zinn- und Kupfer-Zinn-Zink-Legierungen aus einem Elektrolyten und Verfahren zur elektrolytischen Abscheidung dieser Legierungen
PCT/EP2014/077372 WO2015091201A1 (fr) 2013-12-17 2014-12-11 Dépôt d'alliages cuivre-étain et cuivre-étain-zinc à partir d'un électrolyte

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EP3084042B1 true EP3084042B1 (fr) 2018-11-07

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KR102639867B1 (ko) * 2016-12-28 2024-02-22 아토테크 도이칠란트 게엠베하 운트 콤파니 카게 주석 도금조 및 기판 표면에 주석 또는 주석 합금을 침착시키는 방법
CN109778262A (zh) * 2017-11-10 2019-05-21 丹阳市金地生态园林发展有限公司 一种含环氧氯丙烷的金属合金增白电镀液
CN108063219B (zh) * 2017-11-23 2020-01-10 浙江大学 一种高效液态碱金属合金电极及其制备方法和应用
CN113891958A (zh) 2019-05-28 2022-01-04 德国艾托特克公司 锡电镀浴及于衬底表面上沉积锡或锡合金的方法
EP3770298A1 (fr) 2019-07-24 2021-01-27 ATOTECH Deutschland GmbH Bain de placage d'étain et procédé de dépôt d'étain ou d'alliage d'étain sur une surface d'un substrat
CN110592626A (zh) * 2019-10-21 2019-12-20 广州三孚新材料科技股份有限公司 一种无氰电镀黄铜液及其使用方法
WO2022158896A1 (fr) * 2021-01-21 2022-07-28 김미연 Composition d'additif pour solution de placage
JP7436071B1 (ja) 2022-11-25 2024-02-21 株式会社シミズ 非シアン真鍮めっき浴およびめっき方法

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CN105829583A (zh) 2016-08-03
US20160348259A1 (en) 2016-12-01
CN105829583B (zh) 2019-02-05
WO2015091201A1 (fr) 2015-06-25
DE102013226297B3 (de) 2015-03-26
KR20160100364A (ko) 2016-08-23
EP3084042A1 (fr) 2016-10-26

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