WO2015091201A1 - Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte - Google Patents

Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte Download PDF

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Publication number
WO2015091201A1
WO2015091201A1 PCT/EP2014/077372 EP2014077372W WO2015091201A1 WO 2015091201 A1 WO2015091201 A1 WO 2015091201A1 EP 2014077372 W EP2014077372 W EP 2014077372W WO 2015091201 A1 WO2015091201 A1 WO 2015091201A1
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WO
WIPO (PCT)
Prior art keywords
copper
electrolyte
tin
acid
zinc
Prior art date
Application number
PCT/EP2014/077372
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English (en)
French (fr)
Inventor
Klaus Bronder
Sascha Berger
Bernd Weyhmueller
Uwe Manz
Original Assignee
Umicore Galvanotechnik Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Umicore Galvanotechnik Gmbh filed Critical Umicore Galvanotechnik Gmbh
Priority to US15/102,051 priority Critical patent/US20160348259A1/en
Priority to CN201480068447.0A priority patent/CN105829583B/zh
Priority to JP2016537456A priority patent/JP2016540893A/ja
Priority to EP14818924.4A priority patent/EP3084042B1/en
Priority to KR1020167019347A priority patent/KR20160100364A/ko
Publication of WO2015091201A1 publication Critical patent/WO2015091201A1/en

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    • 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 elec ⁇ trolyte 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 ali ⁇ phatic or aromatic thio compounds are present in the electrolyte used.
  • the solderability of the result- ing layer and possibly its mechanical adhesive strength are the critical properties.
  • the appearance of the lay ⁇ ers is generally less important than their functionali ⁇ ty 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 Bl 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 cur ⁇ rent density window.
  • This type of electrolyte in the form described is not suitable for production of deco- rative bronze layers in drum or rack plating.
  • EP 1 961 840 Al discloses a nontoxic electrolyte for the deposition of decorative bronze alloy layers, which contains the metals to be deposited in the form of wa ⁇ ter-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 depos- ited. Tin can be used as divalent or tetravalent tin salt in this case. Stannates are not disclosed.
  • EP 1 961 840 Al teaches that bronze layers which have been deposited electrochemically from baths with addi ⁇ tion of thio compounds have a spotty or matt-veiled appearance and are therefore not suitable for decora ⁇ tive coating of consumer goods.
  • WO 2013/092312 Al discloses a cyanide-free, pyrophos- phate-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 Al discloses a cyanide-free, pyrophos- phate-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 cop ⁇ per (II) ions in the electrolyte.
  • 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 mercap- tan selected from the group consisting of mercaptotria- zoles 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 dis- closed are Sn(II) salts.
  • the composition does not con ⁇ tain any phosphates, pyrophosphates or phosphonates .
  • 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 thi- oamide and thio compounds.
  • thi- oamide 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 com ⁇ pounds serve as bath stabilizers or complexing agents.
  • the inorganic acid or the salt thereof can be phosphor- ic 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 al- loys 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 Al 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 car ⁇ bonate or hydrogencarbonate .
  • the tin is present as tin(II) salt in this case. It is an object of the present invention to provide cyanide-free electrolytes and corresponding processes for the deposition of white copper-tin alloys and white copper-tin-zinc alloys, which are able to deposit coat ⁇ ings of uniform color on decorative articles over a wide current density range.
  • Said deposition should be able to be brought about very optimally with a pre ⁇ ferred stoichiometry .
  • the electrolyte should have a very simple make-up.
  • 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 phos ⁇ phates, phosphonates , polyphosphates, diphosphates and mixtures thereof and at least one compound selected from the group consist ⁇ ing of aliphatic and aromatic thio compounds, wherein the metals copper and optionally zinc to be deposited are present in dissolved form and tin is pre- sent as dissolved Sn(IV) salt and wherein the pH of the aqueous, cyanide-free elec ⁇ trolyte is greater than or equal to 9.
  • the electrolyte additionally contains an aliphatic or aromatic thio compound 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 aro- matic 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 op ⁇ tionally 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” here means that the coatings have a homoge ⁇ neous appearance, i.e. same color and same layer prop- erties in respect of gloss, hardness and corrosion re ⁇ sistance .
  • Uniformly white coatings of copper-tin bronzes and cop ⁇ per-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) cya- nide, 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 Al and WO 2013/092314 Al cited at the outset.
  • the alloy composition is very dependent on the current density employed. In the relatively low current density range, red coatings having a high proportion of Cu and a low proportion of Zn are obtained, while in the high current density range, the proportion of Zn is significantly higher but the coatings are matt gray.
  • aqueous electrolytes of the invention and the pro ⁇ cess 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 there ⁇ of. 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 py ⁇ rophosphates, carbonates, hydrogencarbonates, sulfites, sulfates, phosphates, nitrites, nitrates, halides, hy ⁇ droxides, 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/1 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 Sn0 2 , Sn(OH) 4 , SnCl 4 , SnBr 4 , Snl 4 , Sn(S0 4 ) 2 , Sn(N0 3 ) 4 , SnS 2 , Na 2 Sn0 3 , K 2 Sn0 3 , K 2 Sn0 7 C 2 .
  • the Sn(IV) salt is a stannate.
  • the stannate is advantageously sodium stannate Na 2 Sn0 3 or potassium stannate K 2 Sn0 3 .
  • the Sn(IV) salt is sodium stannate. In a further particularly advantageous embodiment, the Sn(IV) salt is potassium stannate.
  • the salts of copper, tin and optionally zinc present in the electrolyte of the invention will hereinafter be summarized under the term "bronze-forming salts".
  • 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 hy- drogenphosphate 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" ) , hy- drogenphosphate (HPO 4 2" ) and dihydrogenphosphate (3 ⁇ 4 ⁇ 0 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 "phos- phate ions”.
  • the tribasic phos- phonic acid also dissociates over three stages, and both dihydrogenphosphonates and hydrogenphosphonates are ampholytes.
  • the salts of phosphonic acid are re ⁇ ferred to summarily as "phosphonates".
  • diphosphoric acid and poly- phosphoric acids are also polybasic and the ratio of the corresponding anions of these acids which are pre ⁇ sent depends, as in the case of phosphoric and phos ⁇ phonic acids, on the pH of the solution.
  • ammonium, lithium, sodium and potassium salts independently of the number of hydrogen atoms of di ⁇ phosphoric acid or polyphosphoric acids that have been replaced by ammonium, lithium, sodium or potassium cat- ions.
  • the compounds from the group consisting of phos ⁇ phates, phosphonates , polyphosphates and diphosphates which are used in the electrolyte of the invention are salts of phosphoric acid, phosphonic acid, polyphos- phoric acid and diphosphoric acid.
  • the salts here are advantageously ammonium, lithium, sodium or potassium salts of these acids.
  • these cati- ons can be identical or different.
  • "Mixtures" of phosphates, phosphonates, polyphosphates and diphosphates can be mixtures of at least two phos ⁇ phates, at least two phosphonates, at least two poly ⁇ phosphates 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 diphos- phates are the four groups of salts containing phospho ⁇ rus and oxygen which are used for the purposes of the present invention.
  • the phosphates, phosphonates, poly- phosphates and diphosphates are present in excess over the copper and tin ions in the electrolyte.
  • ex ⁇ cess means that the sum of the molar amounts of the phosphates, phosphonates, polyphosphates and diphos ⁇ phates 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/1 to 5.0 mol/1.
  • the at least one salt from the group consisting of phosphates, phosphonates , polyphosphates and diphosphates in the aqueous, cyanide-free electro ⁇ lyte of the invention is a hydrogenphosphate.
  • Particu ⁇ larly suitable hydrogenphosphates are sodium hy ⁇ drogenphosphate and dipotassium hydrogenphosphate.
  • the electrolyte contains from 20 to 150 g/1 of dipotassium hydrogenphosphate.
  • the electrolyte contains from 20 to 150 g/1 of disodium hydrogenphos ⁇ phate .
  • Suitable pyrophosphates are, for example, sodium pyro ⁇ phosphate and potassium pyrophosphate or mixtures thereof.
  • the electrolyte contains from 5 to 40 g/1 of potassium pyrophosphate.
  • the electrolyte contains from 5 to 40 g/1 of sodium pyrophosphate.
  • the electrolyte contains from 20 to 150 g/1 of hydrogenphosphate, pref ⁇ erably 90 g/1 of hydrogenphosphate, in the form of disodium and/or dipotassium hydrogenphosphate, and from 5 to 40 g/1 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 consist ⁇ ing of aliphatic and aromatic thio compounds.
  • at least one compound from the group consisting of aliphatic and aromatic thio com- pounds is present in a concentration of from 0.02 to 10 g/1 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
  • Suitable aliphatic thio compounds are, by way of exam- pie but not exhaustively, aliphatic carboxylic and sul ⁇ fonic acids which contain a thio group.
  • Suitable aro ⁇ matic thio compounds are, by way of example but not exhaustively, pyridine, pyrimidine, pyrazine and hydan- toin derivatives which contain a thio group.
  • the thio compound is selected from among 2-mercaptopropionic acid, mercaptosuccinic acid, 2-thiopropanedicarboxylic acid, Na 3-mercapto-l- propanesulfonate, 2-mercaptonicotinic acid,
  • 2-thiouracil 4, 6-dihydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 2-thiocytosine, 6-mercapto- pyrimidine-4-carboxylic acid, 2-mercaptopyrimidin-4-ol, 2-thiohydantoin, 5-sulfosalicylic acid. It is particu ⁇ larly 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-mercapto ⁇ propionic acid, from 0.5 to 10 g of thiopropane- dicarboxylic 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 electro ⁇ lyte .
  • 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 electro ⁇ lyte of the invention additionally contains at least one aliphatic saturated or unsaturated dicarboxylic or tri ⁇ carboxylic 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 indi- vidually 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 tri ⁇ carboxylic acid is citric acid.
  • Suitable aromatic car ⁇ boxylic 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 hydro ⁇ gen 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/1 of electrolyte.
  • the carboxylic acid is selected from among oxalic acid, tartaric acid and cit ⁇ ric acid or the carboxylic acid salt is selected from among oxalates, tartrates and citrates.
  • the carbox ⁇ ylic acid or salt thereof is oxalic acid or an oxalate.
  • dipotassium oxalate K 2 C 2 O 4 is very particu ⁇ larly advantageous.
  • tar ⁇ taric acid or a salt thereof, for example potassium sodium tartrate is used.
  • cit ⁇ ric 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 , ami- dosulfonates , 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 0- 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, l-benzyl-3- sodiocarboxypyridinium chloride, 3-formyl-1- (3- sulfopropyl ) pyridinium betaine, N- (3- sulfopropyl ) saccharin sodium salt, saccharin sodium salt, carboxethylisothiuron
  • the electrolyte of the invention additionally comprises at least one wetting agent.
  • Wetting agent additions to the electro ⁇ lytes 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 wet ⁇ ting agent is advantageously selected from among
  • a cationic polymer which is made up of the mono ⁇ mers epichlorohydrin and imidazole and has the general formula (C 3 H 5 C10) x * (C 3 H 4 N 2 ) y ,
  • salts of N-alkyl-N- (1-oxoalkyl) amino acids are used, they are advantageously the ammonium, lithium, sodium or potassium salts.
  • Particularly advantageous embodiments of the present invention are electrolytes having the following compo ⁇ sitions :
  • At least one salt from the group consisting of phosphates, phosphonates , polyphosphates, diphos ⁇ phates and mixtures of these salts,
  • embodiments of the present invention in which the electrolytes having the abovementioned gen- eral 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 par ⁇ ticularly 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/1
  • the ion concentra ⁇ tion of tin as stannate is advantageously from 0.5 to 40 g/1
  • the ion concentration of zinc is advanta- geously from 0.1 to 10 g/1.
  • 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 inven- tion and current flow is established between the anode and the cathode. It goes without saying that the embod ⁇ iments named as preferred for the electrolyte are like ⁇ wise 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 cop ⁇ per 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 depos ⁇ ited 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 ym, preferably 0.5-3 ym and very particularly preferably 1-2 ym. It may be remarked that the alloy composition can like ⁇ wise 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 elec ⁇ trolysis. It is advantageous to set a current density in the range from 0.1 to 100 ampere per square decime ⁇ ter.
  • 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 electro ⁇ lytic 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 consum ⁇ er goods and decorative goods. Examples
  • Example 1 Electrolyte without addition of a thio compound
  • Example 8 4 , 6-Dihydroxy-2-mercaptopyrimidine Binary Cu/Sn alloy

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  • Chemical Kinetics & Catalysis (AREA)
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PCT/EP2014/077372 2013-12-17 2014-12-11 Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte WO2015091201A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US15/102,051 US20160348259A1 (en) 2013-12-17 2014-12-11 Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte
CN201480068447.0A CN105829583B (zh) 2013-12-17 2014-12-11 从电解质中沉积铜-锡合金和铜-锡-锌合金
JP2016537456A JP2016540893A (ja) 2013-12-17 2014-12-11 電解質からの銅−スズ及び銅−スズ−亜鉛合金の析出
EP14818924.4A EP3084042B1 (en) 2013-12-17 2014-12-11 Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte
KR1020167019347A KR20160100364A (ko) 2013-12-17 2014-12-11 전해질로부터 구리-주석 및 구리-주석-아연 합금의 전착

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DE102013226297.3 2013-12-17
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

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KR (1) KR20160100364A (zh)
CN (1) CN105829583B (zh)
DE (1) DE102013226297B3 (zh)
WO (1) WO2015091201A1 (zh)

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EP3562974B1 (en) 2016-12-28 2020-10-07 ATOTECH Deutschland GmbH Tin plating bath and a method for depositing tin or tin alloy onto a surface of a substrate
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
TW202106928A (zh) 2019-05-28 2021-02-16 德商德國艾托特克公司 錫電鍍浴及於基板表面上沉積錫或錫合金之方法
EP3770298A1 (en) 2019-07-24 2021-01-27 ATOTECH Deutschland GmbH Tin plating bath and a method for depositing tin or tin alloy onto a surface of a substrate
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 (ko) * 2021-01-21 2022-07-28 김미연 도금액용 첨가제 조성물
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

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1001054A2 (en) 1998-11-05 2000-05-17 C. Uyemura & Co, Ltd Tin-copper alloy electroplating bath and plating process therewith
JP2002080993A (ja) * 2000-06-23 2002-03-22 C Uyemura & Co Ltd 錫−銅合金電気めっき浴及びそれを使用するめっき方法
EP1961840A1 (de) 2007-02-14 2008-08-27 Umicore Galvanotechnik GmbH Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
EP2071057A2 (en) 2007-12-12 2009-06-17 Rohm and Haas Electronic Materials LLC Electroplating Bronze
US20090205714A1 (en) * 2006-05-24 2009-08-20 Kuehnlein Holger Metal Plating Composition and Method for the Deposition of Copper-Zinc-Tin Suitable for Manufacturing Thin Film Solar Cell
WO2010003621A1 (en) 2008-07-10 2010-01-14 Umicore Galvanotechnik Gmbh Improved copper-tin electrolyte and process for the deposition of bronze layers
WO2013092312A1 (en) 2011-12-21 2013-06-27 Umicore Galvanotechnik Gmbh Deposition of copper-tin-zinc alloys from an electrolyte
WO2013092314A1 (en) 2011-12-21 2013-06-27 Umicore Galvanotechnik Gmbh Deposition of copper-tin-zink alloys from an electrolyte

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3871013B2 (ja) * 1998-11-05 2007-01-24 上村工業株式会社 錫−銅合金電気めっき浴及びそれを使用するめっき方法
ATE432729T1 (de) * 1999-01-28 2009-06-15 Salviac Ltd Katheter mit einem expandierbaren endabschnitt
JP3939084B2 (ja) * 2000-09-07 2007-06-27 三洋電機株式会社 飲料供給装置
EP1422320A1 (en) * 2002-11-21 2004-05-26 Shipley Company, L.L.C. Copper electroplating bath
US7901282B2 (en) * 2006-07-14 2011-03-08 Igt Gaming device having competitive/bonus matching game
US8012334B2 (en) * 2007-04-03 2011-09-06 Rohm And Haas Electronic Materials Llc Metal plating compositions and methods
JP5471276B2 (ja) * 2009-10-15 2014-04-16 上村工業株式会社 電気銅めっき浴及び電気銅めっき方法
US8268157B2 (en) * 2010-03-15 2012-09-18 Rohm And Haas Electronic Materials Llc Plating bath and method
AT509459B1 (de) * 2010-04-15 2011-09-15 Miba Gleitlager Gmbh Antifrettingschicht
CN102220610B (zh) * 2011-07-29 2012-12-05 福州大学 一种无氰型铜锡合金电镀液

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1001054A2 (en) 1998-11-05 2000-05-17 C. Uyemura & Co, Ltd Tin-copper alloy electroplating bath and plating process therewith
JP2002080993A (ja) * 2000-06-23 2002-03-22 C Uyemura & Co Ltd 錫−銅合金電気めっき浴及びそれを使用するめっき方法
US20090205714A1 (en) * 2006-05-24 2009-08-20 Kuehnlein Holger Metal Plating Composition and Method for the Deposition of Copper-Zinc-Tin Suitable for Manufacturing Thin Film Solar Cell
EP2032743B1 (en) 2006-05-24 2010-10-27 ATOTECH Deutschland GmbH Metal plating composition and method for the deposition of copper-zinc-tin suitable for manufacturing thin film solar cell
EP1961840A1 (de) 2007-02-14 2008-08-27 Umicore Galvanotechnik GmbH Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
EP2071057A2 (en) 2007-12-12 2009-06-17 Rohm and Haas Electronic Materials LLC Electroplating Bronze
WO2010003621A1 (en) 2008-07-10 2010-01-14 Umicore Galvanotechnik Gmbh Improved copper-tin electrolyte and process for the deposition of bronze layers
WO2013092312A1 (en) 2011-12-21 2013-06-27 Umicore Galvanotechnik Gmbh Deposition of copper-tin-zinc alloys from an electrolyte
WO2013092314A1 (en) 2011-12-21 2013-06-27 Umicore Galvanotechnik Gmbh Deposition of copper-tin-zink alloys from an electrolyte

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