WO2006113473A1 - Method for electrodeposition of bronzes - Google Patents

Method for electrodeposition of bronzes Download PDF

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Publication number
WO2006113473A1
WO2006113473A1 PCT/US2006/014141 US2006014141W WO2006113473A1 WO 2006113473 A1 WO2006113473 A1 WO 2006113473A1 US 2006014141 W US2006014141 W US 2006014141W WO 2006113473 A1 WO2006113473 A1 WO 2006113473A1
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WIPO (PCT)
Prior art keywords
thioether
concentration
electrolytic composition
thiobis
substituted
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PCT/US2006/014141
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French (fr)
Inventor
Katrin Zschintzsch
Joachim Heyer
Marlies Kleinfeld
Stefan Schafer
Ortrud Steinius
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MacDermid Enthone Inc
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Enthone Inc
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Priority to JP2008506756A priority Critical patent/JP2008537017A/en
Priority to KR1020077026291A priority patent/KR101361431B1/en
Priority to EP06750231.0A priority patent/EP1874982B1/en
Priority to CN2006800208357A priority patent/CN101194049B/en
Publication of WO2006113473A1 publication Critical patent/WO2006113473A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • This invention concerns a method for electrodeposition of bronzes, with which the substrate to be coated is plated in an acid electrolyte that contains at least tin and copper ions, an alkylsulfonic acid and a wetting agent, and the preparation of such an electrolyte.
  • acid electrolytes and methods for deposition of qualitatively high grade tin or tin alloys with a higher deposition rate are known from EP 1 111 097 A2 and US 6,176,996 Bl. These are electrolytes that contain at least two divalent metal salts of an organic sulfonic acid and from which are deposited solderable and corrosion resistant coatings that can be used, for example, as substitutes for lead-containing solderable coatings in electronics for manufacture of circuit boards, etc.
  • bronze coatings are used in the jewelry industry as a substitute for expensive silver or allergy-triggering nickel.
  • methods for electrodeposition of bronzes are also gaining importance in some technical fields, for example in electronics for coating electronic components or in mechanical engineering and/or in process technology for coating bearing overlays and friction layers.
  • chiefly white bronzes or the so-called "false bronzes,” whose copper content can be kept quite low due to process conditions, are deposited as nickel substitutes.
  • the invention is based on the task of providing a method for deposition of bronzes that, in contrast to the methods known from the prior art, enables uniform deposition of at least tin and copper side by side from an acid electrolyte at considerably higher deposition rates. Moreover, with this method firmly bonding and pore- free bronze coatings with high copper contents as well as various decorative and mechanical properties are said to be deposited.
  • an acid electrolyte that can have a high content of divalent copper ions, is stable with respect to oxidation-caused sludge formation, and is both economical and environmentally friendly when used over a long period of time, is to be made available.
  • the task is solved in accordance with the invention by a method of the kind mentioned at the start, which is characterized by the fact that an aromatic, nonionic wetting agent is added to the electrolyte.
  • a method for electrodeposition of bronzes is made available, where an anode of a copper-tin alloy and a cathode are connected to the substrate that is to be coated by means of an electrolyte, and coating takes place by passing a direct current through them.
  • an electrolyte that is usable in particular for this method and the coatings that are obtainable by this method are made available .
  • the disadvantages known in the prior art are remedied with the offering of a new electrolyte composition and in this way considerably better deposition results are achieved.
  • the conduct of the method is made to be simpler and more economical. This, too, is chiefly based on the advantageous composition of the electrolyte.
  • the method is carried out at room temperature, or between 17 and 25°C, and the substrate to be coated is plated in a highly acid environment at a pH ⁇ 1.
  • the electrolyte is particularly stable in this temperature range.
  • there are no longer any costs for heating the electrolyte and the plated substrates also do not have to be cooled very much, with large expenditures of time and money.
  • deposition rates of 0.25 microns/min at a current density of 1 A/dm 2 are achieved due to, among other things, the pH value and the advantageous addition of at least one aromatic non-ionic wetting agent. By increasing the metal content this rate can be raised up to 7 A/dm 2 in rack operation and even up to 120 A/dm 2 for continuous plants.
  • usable current densities in a range from 0.1-120 A/dm 2 are reached in each case according to plant type .
  • the wetting of the surfaces to be plated is considerably improved in particular through the addition of at least one nonionic wetting agent to the electrolyte.
  • nonionic wetting agent that is used is that because of the advantageous wetting properties the electrolyte and/or the substrate in the electrolyte need to be agitated only a little or even not at all, in order to achieve the desired deposition results, so that additional devices for agitation of the electrolyte can be omitted.
  • aromatic nonionic wetting agent because of the advantageous use of the aromatic nonionic wetting agent, electrolyte residues drain from the plated substrate better when it is removed from the electrolyte, which leads to reduced entrainment losses and thus to lower process costs .
  • the proposed method is therefore advantageously economical and environmentally friendly compared to the cyanide processes .
  • anionic and/or aliphatic nonionic wetting agent that is known from the prior art is also optionally possible, provided these wetting agents support or even enhance the advantageous effects of the aromatic nonionic wetting agent.
  • polyethylene glycols and/or anionic surfactants are preferably added to the electrolyte as anionic and/or aliphatic nonionic wetting agents .
  • Additional exemplary aliphatic nonionic wetting agents include aliphatic fatty alcohol ethoxylates, with compounds having from 13 to 15 carbon atoms (C-13 to C-15) being especially preferred.
  • the fatty alcohol ethoxylate is incorporated in a concentration of, for example, about 0.1 to 10 g/L; preferably about 0.5 to about 5 g/L.
  • concentration of, for example, about 0.1 to 10 g/L; preferably about 0.5 to about 5 g/L.
  • substituted dithioglycols act advantageously as wetting agents and brighteners . These compounds provide a source of sulphur which has a positive effect on copper plating. Therefore, certain embodiments of the invention include substituted dithioglycols, such as, for example, those selected from the group consisting of:
  • Dithiobis (hentetracontaethyleneglycol) represented by H- (OCH 2 CH 2 ) 4 1 -S-S- (CH 2 CH 2 O) 4X -H,
  • Dithiobis (icosaethyleneglycolpentapropyleneglycol) represented by H- (OC 3 H 6 ) 5 - r (OC 2 H 4 ) 20 -S-S- (OC 2 H 4 ) 20 - (OC 3 H 6 ) 5 -H,
  • (22) 1, 4-Buthanedithiolbis (pentadecaglycerol) thioether represented by H- (OCH 2 CH (OH) CH 2 ) I5 -S-C 4 H 8 -S- (CH 2 CH (OH) CH 2 O) 15 -H,
  • Triacontaethyleneglycolmono (4 -cyanobenzyl) thioether represented by NC-Ph-CH 2 -S-(CH 2 CH 2 O) 30 -H,
  • Tricosaethyleneglycolmono (4 -formylphenetyl) thioether represented by OHC-Ph-CH 2 CH 2 -S-(CH 2 CH 2 O) 2S -H,
  • Pentadecaethyleneglycolmono ⁇ (acetylmethyl) thioethyl ⁇ thioether represented by CH 3 COCH 2 -S-CH 2 CH 2 -S-(CH 2 CH 2 O) 15 -H,
  • Pentatriacontaethyleneglycolmono (2-n- butyldithioethyl) dithioether represented by C 4 H 9 -S-S-CH 2 CH 2 -S-S- (CH 2 CH 2 O) 35 -H,
  • Tridecaethyleneglycolmonomethylthioether represented by CH 3 -S- (CH 2 CH 2 O) I0 -H,
  • Ph represents a phenyl group.
  • the substituted dithioglycol in incorporated in a concentration of about 5 to about 100 mg/L; preferably about 10 to about 50 mg/L.
  • the method in accordance with the invention is characterized in particular by the special composition of the electrolyte. It contains essentially tin and copper ions, an alkylsulfonic acid and an aromatic nonionic wetting agent.
  • stabilizers and/or complexing agents, anionic and/or nonionic, aliphatic and/or substituted dithioglycol wetting agents, oxidation inhibitors, brighteners, and other metal salts can optionally be contained in the electrolyte.
  • the metals that are primarily added to the electrolyte for deposition of bronzes in accordance with the invention - tin and copper - can first and foremost be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates, or as salts of mineral acids, preferably as sulfates.
  • Tin methanesulfonate is especially preferably used as tin salt in the electrolyte preferably in an amount of 5-195 g/L of electrolyte, preferably 11-175 g/L of electrolyte. This corresponds to a use of 2-75 g/L, preferably 4-57 g/L divalent tin ions.
  • Copper methanesulfonate is especially preferably used in the electrolyte as the copper salt, which is advantageously added to the electrolyte in an amount of 8-280 g/L of electrolyte, preferably 16-260 g/L of electrolyte. This corresponds to the use of 2-70 g/L, preferably 4-65 g/L divalent copper ions.
  • an acid preferably a mineral and/or an alkylsulfonic acid
  • an acid is added to the electrolyte in amounts of 140-382 g/L of electrolyte, preferably 175-245 g/L of electrolyte.
  • methanesulfonic acid turned out to be especially advantageous, since for one thing this produces advantageous solubility of metal salts and for another, because of its acid strength, it produces or facilitates the adjustment of the pH needed for the process.
  • methanesulfonic acid has the advantageous property of contributing considerably to the stability of the bath.
  • At least one additional metal and/or chloride is added to the electrolyte.
  • the metals are in the form of their soluble salts.
  • the addition of zinc and/or bismuth has a considerable effect on the properties of the deposited coatings.
  • the metals zinc and/or bismuth added to the electrolyte can namely be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates or as salts of mineral acids, preferably as sulfates.
  • Zinc sulfate is especially preferably uses in the electrolytes as zinc salt, and is advantageously added in an amount of 0-25 g/L of electrolyte, preferably 15-20 g/L of electrolyte.
  • Bismuth methane sulfate is especially preferably used in the electrolyte as bismuth salt and is advantageously added to the electrolyte in an amount of 0-5 g/L of electrolyte, preferably 0.05-0.2 g/L of electrolyte.
  • additives for example stabilizers and/or complexing agents, oxidation inhibitors and brighteners, that are usually used in acid electrolytes for deposition of tin alloys can be added to the electrolyte.
  • Gluconates are advantageously added to the electrolyte and stabilizers and/or complexing agents.
  • the concentration of the stabilizers and/or complexing agents is 0-50 g/L of electrolyte, preferably 20-30 g/L of electrolyte.
  • Compounds from the class of the dihydroxybenzenes, for example mono- or polyhydroxyphenyl compounds like pyrocatechol or phenolsulfonic acid are preferably used as oxidation inhibitors.
  • the concentration of oxidation inhibitors is 0-5 g/L of electrolyte.
  • Sodium hypophosphite is optionally used as an additional oxidation inhibitor.
  • the electrolyte contains hydroquinone as oxidation inhibitor.
  • the conduct of the method in accordance with the invention enables the deposition of bronzes onto various substrates.
  • all of the usual methods for making electronic components can be used.
  • especially hard and wear-resistant bronze coatings can be deposited on materials like bearings, etc., to the method in accordance with the invention.
  • the method in accordance with the invention is advantageously also used in the fields of decorative coating of, for example, fixtures and jewelry, etc., where the deposition of multi-component alloys that contain tin, copper, zinc and bismuth is particularly advantageous in these areas .
  • a really special advantage is that the so-called "true" bronzes that have a copper content >60% can be deposited with the method in accordance with the invention, where the copper content can be up to 95 wt% in each according to the desired properties.
  • the ratio of the amount of copper to the amount of tin in the electrolyte has a considerable effect of properties like hardness and color of the bronze coatings. For instance, at a tin/copper ratio of 40/60 silver-colored coatings, the so-called white bronzes, which are relatively soft, are deposited.
  • the invention is effective for forming white bronze deposits having a tin/copper weight ratio of about 40/60 or less, yellow bronze deposits having a tin/copper weight ratio of about 20/80 or less, and even red bronze deposits having a tin/copper weight ratio of about 10/90 or less.
  • the electrolyte contains brighteners from the class of the aromatic carbonyl compounds and/or a,a- unsaturated carbonyl compounds .
  • the concentration of brighteners is 0-5 g/L of electrolyte.
  • Electrolyte composition :
  • the base electrolyte of the highly acid electrolyte in accordance with the invention contains essentially (per liter of electrolyte)
  • electrolyte per liter of electrolyte: 0-10 g of an anionic and/or aliphatic nonionic wetting agent,
  • the electrolyte is prepared by varying the individual components, as given below as a matter of example Additional information about the corresponding process conditions as well as other properties of the individual coatings can be seen in Table 1.
  • Example 1 (red bronze) 4 g/L Sn 2+ 18 g/L Cu 2+ 286 g/L methanesulfonic acid
  • Example 2b (yellow bronze) 4 g/L Sn 2+ 18 g/L Cu 2+
  • Example 4_ (matte white bronze) 18 g/L Sn 2+
  • Example j5 (high ductility) 4 g/L Sn 2+ 18 g/L Cu 2+
  • Example 1_ (yellow bronze) 14.5 g/L Sn 2+ 65.5 g/L Cu 2+
  • Example B_ (yellow bronze) 2 g/L Sn 2+ 8 g/L Cu 2+
  • Example 9_ (white bronze) 4 g/L Sn 2+ 8 g/L Cu 2+
  • Electrolytic coating was performed on a copper plated brass substrate at 25 C and a current density of 1.2 A/dm 2 with soluble bronze (60Cu/40Sn) anodes for 8 minutes to a thickness of 3 microns. Ductility was acceptable; uniformity was good; hardness was 350 HV25; gloss was very good. The specimens passed a thio acetimide tarnish resistance test (storage 4 hours at 180 C) .

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Abstract

A method for electrodeposition of bronzes, with which the substrate to be coated is plated in an acid electrolyte that contains at least tin and copper ions, an alkylsulfonic acid and a wetting agent, and the preparation of such an electrolyte.

Description

METHOD FOR ELECTRODEPOSITION OF BRONZES
FIELD OF THE INVENTION
This invention concerns a method for electrodeposition of bronzes, with which the substrate to be coated is plated in an acid electrolyte that contains at least tin and copper ions, an alkylsulfonic acid and a wetting agent, and the preparation of such an electrolyte.
BACKGROUND OF THE INVENTION
Methods for deposition of tin and tin alloys on the basis of various types of electrolytes are known from the prior art and are already widely used in practice. Methods for deposition of tin and/or tin alloys from cyanide electrolytes are very common. Such electrolytes, however, are highly toxic, which makes their use problematic from the environmental standpoint, so that for some years there has been a push to develop cyanide-free electrolytes, for example electrolytes based on pyrophosphates or oxalates, which operate in a pH region of 5-9. However, such methods have both economic and technical disadvantages, of which the relatively slow deposition rates may be mentioned here.
For these reasons development is currently going mostly in the direction of making available methods for deposition of tin and/or tin alloys from acid electrolytes, since, for one thing, divalent tin can be very easily reduced to metallic tin in acid electrolytes, which leads to better deposition rates while having qualitatively equivalent coatings, and for another the disadvantageous effect of alkaline electrolytes on substrates, for example ceramic structural elements, is prevented by this.
Thus, acid electrolytes and methods for deposition of qualitatively high grade tin or tin alloys with a higher deposition rate are known from EP 1 111 097 A2 and US 6,176,996 Bl. These are electrolytes that contain at least two divalent metal salts of an organic sulfonic acid and from which are deposited solderable and corrosion resistant coatings that can be used, for example, as substitutes for lead-containing solderable coatings in electronics for manufacture of circuit boards, etc.
However, such methods have their limits in the deposition of tin-copper alloys with high copper contents, such as the so-called "true" bronzes, which have a copper content of at least 10%. For example, due to the high difference of potential between tin and copper higher rates of oxidation of the divalent tin can occur, due to which it very easily becomes oxidized to tetravalent tin in acid electrolytes. However, in this form tin can no longer be electrolytically deposited in an acid and thus is withdrawn from the process, which leads to uneven deposition of the two metals and to a decrease of the deposition rate. In addition, oxidation to tetravalent tin leads to increased sludge formation, which can prevent stable operation and long lifetime of the acid electrolyte. Moreover, because of such contaminated of a firmly bonding and pore-free coating is no longer guaranteed.
Because of such technical process disadvantages, there is currently no large area of use for electrolytically deposited bronze coatings. Occasionally bronze coatings are used in the jewelry industry as a substitute for expensive silver or allergy-triggering nickel. In the same way methods for electrodeposition of bronzes are also gaining importance in some technical fields, for example in electronics for coating electronic components or in mechanical engineering and/or in process technology for coating bearing overlays and friction layers. However, in this case chiefly white bronzes or the so-called "false bronzes," whose copper content can be kept quite low due to process conditions, are deposited as nickel substitutes.
SUMMARY OF THE INVENTION
Therefore, the invention is based on the task of providing a method for deposition of bronzes that, in contrast to the methods known from the prior art, enables uniform deposition of at least tin and copper side by side from an acid electrolyte at considerably higher deposition rates. Moreover, with this method firmly bonding and pore- free bronze coatings with high copper contents as well as various decorative and mechanical properties are said to be deposited.
In addition, an acid electrolyte that can have a high content of divalent copper ions, is stable with respect to oxidation-caused sludge formation, and is both economical and environmentally friendly when used over a long period of time, is to be made available.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The task is solved in accordance with the invention by a method of the kind mentioned at the start, which is characterized by the fact that an aromatic, nonionic wetting agent is added to the electrolyte.
With this invention a method for electrodeposition of bronzes is made available, where an anode of a copper-tin alloy and a cathode are connected to the substrate that is to be coated by means of an electrolyte, and coating takes place by passing a direct current through them. In addition, with the invention an electrolyte that is usable in particular for this method and the coatings that are obtainable by this method are made available . Through the method in accordance with the invention the disadvantages known in the prior art are remedied with the offering of a new electrolyte composition and in this way considerably better deposition results are achieved. Moreover, the conduct of the method is made to be simpler and more economical. This, too, is chiefly based on the advantageous composition of the electrolyte. For example, the method is carried out at room temperature, or between 17 and 25°C, and the substrate to be coated is plated in a highly acid environment at a pH <1. The electrolyte is particularly stable in this temperature range. In addition, there are no longer any costs for heating the electrolyte and the plated substrates also do not have to be cooled very much, with large expenditures of time and money. Moreover, deposition rates of 0.25 microns/min at a current density of 1 A/dm2 are achieved due to, among other things, the pH value and the advantageous addition of at least one aromatic non-ionic wetting agent. By increasing the metal content this rate can be raised up to 7 A/dm2 in rack operation and even up to 120 A/dm2 for continuous plants. Thus, usable current densities in a range from 0.1-120 A/dm2 are reached in each case according to plant type .
Surprisingly, the wetting of the surfaces to be plated, above all those of more complex substrates, is considerably improved in particular through the addition of at least one nonionic wetting agent to the electrolyte. This advantageously has the result that not only are the considerably higher deposition rates achieved through the use of the method in accordance with the invention, but moreover the coatings produced by the method are uniform and qualitatively high grade, have very good adhesion and are generally pore-free. Another advantage of the nonionic wetting agent that is used is that because of the advantageous wetting properties the electrolyte and/or the substrate in the electrolyte need to be agitated only a little or even not at all, in order to achieve the desired deposition results, so that additional devices for agitation of the electrolyte can be omitted. In addition, because of the advantageous use of the aromatic nonionic wetting agent, electrolyte residues drain from the plated substrate better when it is removed from the electrolyte, which leads to reduced entrainment losses and thus to lower process costs .
The addition of 2-40 g/L of one or more aromatic nonionic wetting agents is especially advantageous, with beta-naphthol ethoxylate and/or nonylphenol ethoxylate are especially preferred. Also preferred is sulfopropylated polyalkoxylated naphthol, potassium salt.
The proposed method is therefore advantageously economical and environmentally friendly compared to the cyanide processes .
The additional or alternative use of one or more anionic and/or aliphatic nonionic wetting agent that is known from the prior art is also optionally possible, provided these wetting agents support or even enhance the advantageous effects of the aromatic nonionic wetting agent. In this regard polyethylene glycols and/or anionic surfactants are preferably added to the electrolyte as anionic and/or aliphatic nonionic wetting agents . Additional exemplary aliphatic nonionic wetting agents include aliphatic fatty alcohol ethoxylates, with compounds having from 13 to 15 carbon atoms (C-13 to C-15) being especially preferred. In one embodiment, the fatty alcohol ethoxylate is incorporated in a concentration of, for example, about 0.1 to 10 g/L; preferably about 0.5 to about 5 g/L. These compounds work as emulsifiers for the degradation products of the nonionic wetting agent, and improve uniformity and brightness in combination with the wetting agent and brightener system.
It has also been discovered that substituted dithioglycols act advantageously as wetting agents and brighteners . These compounds provide a source of sulphur which has a positive effect on copper plating. Therefore, certain embodiments of the invention include substituted dithioglycols, such as, for example, those selected from the group consisting of:
(1) Thiobis (diethyleneglycol) represented by H- (OCH2CH2) 2-S- (CH2CH2O)2-H,
(2) Thiobis (hexaethylene glycol),
(3) Thiobis (pentadecaglycelol) represented by H- (OCH2CH(OH)CH2)I5-S- (CH2CH (OH) CH2O) 15-H,
(4) Thiobis (icosaethyleneglycol) represented by H- (OCH2CH2) 20-S- (CH2CH2O) 20-H,
(5) Thiobis (pentacontaethyleneglycol) ,
(6) 4,10-dioxa-7-thiatridecane-2, 12-diol represented by HO-CH (CH3) CH2-OCH2CH2-SCH2CH2-OCH2CH (CH3) -OH,
(7) Thiodiglycerin represented by HOCH2CH (OH) CH2-S-CH2CH (OH) CH2OH,
(8) Thiobis (triglycerin) represented by H- (OCH2CH (OH) CH2) 3-S- (CH2CH(OH)CH2O) -H,
(9) 2,2' -thiodibutanolbis (octaethyleneglycolpentaglycerol) ether represented by H- (OCH2CH(OH) CH2) 5- (OCH2CH2) 8-OC4H8-SC4H8-O- (CH2CH2O)8- (CH2CH(OH)CH2O) -H,
(10) Thiobis (octaethyleneglycol)bis (2-chloroethyl) ether represented by Cl-CH2CH2CH2- (OCH2CH2) 8-S- (CH2CH2O)8-CH2CH2CH2-CI,
(11) Thiobis (decaethyleneglycol) bis (carboxymethyl) ether,
(12) Thiobis (dodecaethyleneglycol)bis (2-nitroethyl) ether,
(13) Thiodiglycolbis (carboxymethyl) ether represented by HOOCCH2OCH2CH2-S-CH2CH2OCH2COOH,
(14) Dithiodiglycolbis (carboxymethyl) ether represented by HOOCCH2OCH2CH2-S-S-CH2CH2OCH2COOH, (15) Thiobis (dodecaethyleneglycol) represented by H- (OCH2CH2) 12-S- (CH2CH2O) I2-H,
(16) Dithiobis (hentetracontaethyleneglycol) represented by H- (OCH2CH2) 41-S-S- (CH2CH2O) 4X-H,
(17) Dithiobis (icosaethyleneglycolpentapropyleneglycol) represented by H- (OC3H6) 5-r(OC2H4) 20-S-S- (OC2H4) 20- (OC3H6) 5-H,
(18) Dithiobis (triglycerol) represented by H- (OCH2CH (OH) CH2) 3-S-S- (CH2CH(OH)CH2O)3-H,
(19) Dithiobis (decaglycelol) ,
( 20 ) 3 , 6 -Dithiaoctane- l , 8 -diol represented by HOCH2CH2S - CH2CH2 - SCH2CH2OH ( also 2 , 2 ' -
(Ethylenedithio) diethanol) ,
(21) 1, 3-Propanedithiolbis (decaethyleneglycol) thioether represented by H-(OC2H4)IO-S-C3H6-S-(OC2H4)Io-H,
(22) 1, 4-Buthanedithiolbis (pentadecaglycerol) thioether represented by H- (OCH2CH (OH) CH2) I5-S-C4H8-S- (CH2CH (OH) CH2O) 15-H,
(23) 1, 3-Dithioglycerolbis (pentaethyleneglycol) thioether represented by H-(OCH2CH2)5-SCH2CH(OH)CH2S-(CH2CH2O)5-H,
(24) 1,2-Ethanedithiolbis (penta(l- ethyl) ethyleneglycol) thioether represented by H-(OCH(C2H5)CH2)S-SC2H4S-(CH2CH(C2H5)O)5-H,
(25) 1,3-Dithioglycerolbis(di(l- ethyl) ethyleneglycol) thioether represented by H- (OCH (CH3) CH2) 2-SCH2CH (OH) CH2S- (CH2CH(CH3)O)2-H,
(26) 2-Mercaptoethylsulfide bis (hexatriacontaethylene-glycol) represented by H- (OC2H4) I8-SC2H4-SC2H4-S- (C2H4O) I8-H,
(27) 2-Mercaptoethylsulfidebis (icosaethyleneglycol) di- methylether represented by
CH3- (OC2H4)Xo-SC2H4-SC2H4-S- (C2H4O) I0-CH3 ,
(28) 2-Mercaptoethyletherbis (diethyleneglycol) represented by H- (OC2H4) 2-S-CH2CH2OCH2CH2-S- (C2H4O)2-H,
(29) Thiodiglyceroltetra (decaethyleneglycol) ether represented by the above formula (6) ,
(30) Diethyleneglycolmonomethylthioether represented by CH3-S- (CH2CH2O)2-H, (31) Decaglycerolmono (6-methylthiohexyl) thioether represented by CH3-S-C6H12-S- (CH2CH (OH) CH2O) I0-H,
(32) 2-Mercaptoethylsulfide-ω-{ (2- bromoethyl) icosaethyleneglycol} thioethe r-ω1 -{ (2- bromoethyl) hectaethyleneglycol} thioether represented by BrCH2CH2- (OCH2CH2) 20~ (S-CH2CH2) 3- (OCH2CH2) 100-OCH2CH2Br,
(33) l,4-Butanediol-ω-{ (2 -benzyloxy-1-methyl) ethyl} thioether- ω' - (de capropyleneglycoloctacontaethyleneglycol) thioether represented by
PhCH2OCH2CH(CH3) -S-C4H8-S- (CH2CH2O)80- (CH2CH(CH3)O)10-H,
(34) Dithiobis (icosaethyleneglycol) bis (2-methyl- thioethyl) ether represented by
CH3-S-CH2CH2- (OCH2CH2) 20-S-S- (CH2CH2O) 20-CH2CH2-S-CH3 ,
(35) 1, 2-Ethanediol-ω- (4-methoxybenzyl) thioether-ω' - (pentacontaethy leneglycol) thioether represented by CH3O-Ph-CH2S-CH2CH2- (CH2CH2O) 50-H,
(36) Triacontaethyleneglycolmono (4 -cyanobenzyl) thioether represented by NC-Ph-CH2-S-(CH2CH2O)30-H,
(37) Thiobis (pentadecaethyleneglycol) bisallylether represented by CH2=CHCH2- (OCH2CH2) 15-S- (CH2CH2O) 15-CH2CH=CH2,
(38) Tricosaethyleneglycolmono (4 -formylphenetyl) thioether represented by OHC-Ph-CH2CH2-S-(CH2CH2O)2S-H,
(39)
Pentadecaethyleneglycolmono{ (acetylmethyl) thioethyl} thioether represented by CH3COCH2-S-CH2CH2-S-(CH2CH2O)15-H,
(40) 1,2-Ethanediol-ω- (glycidyl) thioether-ω' - icosaethyleneglycolthioether represented by
Figure imgf000009_0001
(41) Octadecaethyleneglycolbis (2 -methylthioethyl) ether represented by CH3-S-CH2CH2CO-(CH2CH2O)18-CH2CH2S-CH3, (42) Hexadecaethyleneglycolmono(2-methylthioethyl) thioether represented by CH3-S-CH2CH2-S-(CH2CH2O)I6-H,
(43) Icosaethyleneglycolmonomethylthioether represented by CH3-S-(CH2CH2O)20-H,
(44) Undecaethyleneglycoldi (n-propyl) thioether represented by C3H7-S- (CH2CH2O) 10-CH2CH2S-C3H7,
(45) Dodecaethyleneglycolbis (2-hydroxyethyl) thioether represented by HOCH2CH2-S-(CH2CH2O)II-CH2CH2-S-CH2CH2OH,
(46) Undecaethyleneglycoldimethylthioether,
(47) Pentatriacontaethyleneglycolmono (2-n- butyldithioethyl) dithioether represented by C4H9-S-S-CH2CH2-S-S- (CH2CH2O) 35-H,
(48) 4,8, 12-trithiapentadecane-l, 2, 6, 10, 14, 15-hexaol represented by
HOCH2CH (OH) CH2-S-CH2CH (OH) CH2-S-CH2CH (OH) CH2-S-CH2CH (OH) CH2OH,
(49) Icosaglycerolmono (2-ethylthioethyl) thioether represented by C2H5-S-CH2CH2-S- (CH2CH(OH)CH2O)20-H,
(50) Triacontaethyleneglycolmono (2-methylthioethyl) thioether represented by CH3-S-CH2CH2-S-(C2H4O)30-H,
(51) Dithiobis (icosaethyleneglycol) dibenzylether represented by Ph-CH2- (OC2H4) 20-S-S- (C2H4O)20-CH2-Ph, (52)
Tridecaethyleneglycolmonomethylthioether represented by CH3-S- (CH2CH2O)I0-H,
(53) Hexadecaethyleneglycol dimethylthioether represented by CH3-S- (CH2CH2O) 15-CH2CH2-S-CH3,
(54) 1, 2-Ethanedithiolbis (icosaethyleneglycol) thioether represented by H-(OCH2CHa)20-S-CH2CH2-S-(CH2CH2O)20-H,
(55) Dithiobis (pentadecaethyleneglycol) represented by H-(O CH2CH2) is-S-S- (CH2CH2O)15-H, and
(56) 3, 3 ' -thiodipropanol represented by
HO-CH2CH2CH2-S-CH2CH2CH2-OH. In the above- listed structural formulae, Ph represents a phenyl group.
In one embodiment, the substituted dithioglycol in incorporated in a concentration of about 5 to about 100 mg/L; preferably about 10 to about 50 mg/L. As already mentioned above, the method in accordance with the invention is characterized in particular by the special composition of the electrolyte. It contains essentially tin and copper ions, an alkylsulfonic acid and an aromatic nonionic wetting agent. In addition, stabilizers and/or complexing agents, anionic and/or nonionic, aliphatic and/or substituted dithioglycol wetting agents, oxidation inhibitors, brighteners, and other metal salts can optionally be contained in the electrolyte.
The metals that are primarily added to the electrolyte for deposition of bronzes in accordance with the invention - tin and copper - can first and foremost be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates, or as salts of mineral acids, preferably as sulfates. Tin methanesulfonate is especially preferably used as tin salt in the electrolyte preferably in an amount of 5-195 g/L of electrolyte, preferably 11-175 g/L of electrolyte. This corresponds to a use of 2-75 g/L, preferably 4-57 g/L divalent tin ions. Copper methanesulfonate is especially preferably used in the electrolyte as the copper salt, which is advantageously added to the electrolyte in an amount of 8-280 g/L of electrolyte, preferably 16-260 g/L of electrolyte. This corresponds to the use of 2-70 g/L, preferably 4-65 g/L divalent copper ions.
Since the deposition is clearly higher in an acid environment, an acid, preferably a mineral and/or an alkylsulfonic acid, is added to the electrolyte in amounts of 140-382 g/L of electrolyte, preferably 175-245 g/L of electrolyte. The use of methanesulfonic acid turned out to be especially advantageous, since for one thing this produces advantageous solubility of metal salts and for another, because of its acid strength, it produces or facilitates the adjustment of the pH needed for the process. In addition, methanesulfonic acid has the advantageous property of contributing considerably to the stability of the bath.
In accordance with an additional characteristic of the invention at least one additional metal and/or chloride is added to the electrolyte. Advantageously, the metals are in the form of their soluble salts. In particular, the addition of zinc and/or bismuth has a considerable effect on the properties of the deposited coatings. The metals zinc and/or bismuth added to the electrolyte can namely be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates or as salts of mineral acids, preferably as sulfates. Zinc sulfate is especially preferably uses in the electrolytes as zinc salt, and is advantageously added in an amount of 0-25 g/L of electrolyte, preferably 15-20 g/L of electrolyte. Bismuth methane sulfate is especially preferably used in the electrolyte as bismuth salt and is advantageously added to the electrolyte in an amount of 0-5 g/L of electrolyte, preferably 0.05-0.2 g/L of electrolyte.
In addition, various additives, for example stabilizers and/or complexing agents, oxidation inhibitors and brighteners, that are usually used in acid electrolytes for deposition of tin alloys can be added to the electrolyte.
In particular, the use of suitable compounds for stabilizing the electrolyte is an important condition for rapid as well as qualitative high grade deposition of bronzes. Gluconates are advantageously added to the electrolyte and stabilizers and/or complexing agents. Here in the method in accordance with the invention the preferred use of sodium gluconate turned out to be especially advantageous. The concentration of the stabilizers and/or complexing agents is 0-50 g/L of electrolyte, preferably 20-30 g/L of electrolyte. Compounds from the class of the dihydroxybenzenes, for example mono- or polyhydroxyphenyl compounds like pyrocatechol or phenolsulfonic acid are preferably used as oxidation inhibitors. The concentration of oxidation inhibitors is 0-5 g/L of electrolyte. Sodium hypophosphite is optionally used as an additional oxidation inhibitor. In one embodiment, the electrolyte contains hydroquinone as oxidation inhibitor.
The conduct of the method in accordance with the invention enables the deposition of bronzes onto various substrates. For example, all of the usual methods for making electronic components can be used. In the same way especially hard and wear-resistant bronze coatings can be deposited on materials like bearings, etc., to the method in accordance with the invention. The method in accordance with the invention is advantageously also used in the fields of decorative coating of, for example, fixtures and jewelry, etc., where the deposition of multi-component alloys that contain tin, copper, zinc and bismuth is particularly advantageous in these areas .
A really special advantage is that the so-called "true" bronzes that have a copper content >60% can be deposited with the method in accordance with the invention, where the copper content can be up to 95 wt% in each according to the desired properties. In addition, the ratio of the amount of copper to the amount of tin in the electrolyte has a considerable effect of properties like hardness and color of the bronze coatings. For instance, at a tin/copper ratio of 40/60 silver-colored coatings, the so-called white bronzes, which are relatively soft, are deposited. At a tin/copper ratio of 20/80 yellow gold colored coatings result, the so-called yellow bronzes, and at a tin/copper ratio of 10/90 red gold colored coatings are formed, the so-called red bronzes. As illustrated in the examples below, the invention is effective for forming white bronze deposits having a tin/copper weight ratio of about 40/60 or less, yellow bronze deposits having a tin/copper weight ratio of about 20/80 or less, and even red bronze deposits having a tin/copper weight ratio of about 10/90 or less.
Moreover, the deposition of high-tin white bronzes with a copper content = 10% is also possible.
In each case according to the desired appearance of the bronze coatings additives such as brighteners are added to the electrolyte, in addition to it having a varying copper content. Advantageously, the electrolyte contains brighteners from the class of the aromatic carbonyl compounds and/or a,a- unsaturated carbonyl compounds . The concentration of brighteners is 0-5 g/L of electrolyte.
Some preferred embodiments are presented below for illustration of the invention in more detail, but the invention is not limited to these embodiments .
Electrolyte composition:
The base electrolyte of the highly acid electrolyte in accordance with the invention contains essentially (per liter of electrolyte)
2-75 g divalent tin,
2-70 g divalent copper,
2-40 g of an aromatic nonionic wetting agent, and
140-382 g of a mineral and/or alkylsulfonic acid.
Optionally, other components can be added to the electrolyte (per liter of electrolyte) : 0-10 g of an anionic and/or aliphatic nonionic wetting agent,
0-50 g of a stabilizer and/or complexing agent,
0-5 g of an oxidation inhibitor,
0-5 g of a brightener 0-5 trivalent bismuth
0-25 g divalent zinc.
In order to achieve a specific color of the deposited bronze coatings the electrolyte is prepared by varying the individual components, as given below as a matter of example Additional information about the corresponding process conditions as well as other properties of the individual coatings can be seen in Table 1.
Example 1 (red bronze) 4 g/L Sn2+ 18 g/L Cu2+ 286 g/L methanesulfonic acid
3 g/L aromatic nonionic wetting agent 0.4 g/1 aliphatic nonionic wetting agent 2 g/L oxidation inhibitor
20 mg/L complexing agent
Example 2a (yellow bronze)
4 g/L Sn2+ 18 g/L Cu2+
240 g/L methanesulfonic acid
32.2 g/L aromatic nonionic wetting agent 2 g/L oxidation inhibitor
25 mg/L stabilizer/complexing agent
Example 2b (yellow bronze) 4 g/L Sn2+ 18 g/L Cu2+
286 g/L methanesulfonic acid 32.2 g/L aromatic nonionic wetting agent 6 mg/Lbrightener 2 g/L oxidation inhibitor 50 mg/L stabilizer/coraplexing agent Example 3^ (white bronze)
5 g/L Sn2+ 10 g/L Cu2+
240 g/L methanesulfonic acid
32.2 g/L aromatic nonionic wetting agent
6 mg/Lbrightener
2 g/L oxidation inhibitor
25 mg/L stabilizer/complexing agent
Example 4_ (matte white bronze) 18 g/L Sn2+
2 g/L Cu2+
258 g/L methanesulfonic acid
9 g/L aromatic nonionic wetting agent
To improve the hardness and/or ductility of the deposited bronze coatings the contents of zinc and/or bismuth indicated below as examples are added to the electrolyte. Additional data on the corresponding process conditions and other properties of the individual coatings can be seen in Table 1.
Example j5 (high ductility) 4 g/L Sn2+ 18 g/L Cu2+
238 g/L methanesulfonic acid 32.2 g/L aromatic nonionic wetting agent
3 mg/Lbrightener
2 g/L oxidation inhibitor
25 mg/L stabilizer/complexing agent
20 g/L ZnSO4 Example §_ (hardness) 4 g/L Sn2+ 18 g/L Cu2+
238 g/L methanesulfonic acid 32.2 g/L aromatic nonionic wetting agent 2 g/L oxidation inhibitor 25 mg/L stabilizer/complexing agent 0.1 g/L Bi3+
Example 1_ (yellow bronze) 14.5 g/L Sn2+ 65.5 g/L Cu2+
382 g/L methanesulfonic acid 32.2 g/L aromatic nonionic wetting agent 4 g/L oxidation inhibitor 25 mg/L stabilizer/complexing agent 20 g/L ZnSO4
Example B_ (yellow bronze) 2 g/L Sn2+ 8 g/L Cu2+
400 g/L methanesulfonic acid 2.5 g/L aromatic nonionic wetting agent 1 g/L aliphatic fatty alcohol ethoxylate 4 g/L oxidation inhibitor
Example 9_ (white bronze) 4 g/L Sn2+ 8 g/L Cu2+
400 g/L methanesulfonic acid 1 g/L aromatic nonionic wetting agent 40 mg/L substituted dithioglycol 4 g/L oxidation inhibitor With these exemplary electrolyte compositions coatings with specific properties were deposited under the process conditions listed in the following table.
Figure imgf000018_0001
Example 10 (white bronze)
3 g/L Sn2+ 6 g/L Cu2+
300 - 400 g/L methanesulfonic acid 2 g/L aromatic nonionic wetting agent 15-30 mg/L substituted dithioglycol
4 g/L oxidation inhibitor
Electrolytic coating was performed on a copper plated brass substrate at 25 C and a current density of 1.2 A/dm2 with soluble bronze (60Cu/40Sn) anodes for 8 minutes to a thickness of 3 microns. Ductility was acceptable; uniformity was good; hardness was 350 HV25; gloss was very good. The specimens passed a thio acetimide tarnish resistance test (storage 4 hours at 180 C) .
When introducing elements of the present invention or the preferred embodiment (s) thereof, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements .
In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
As various changes could be made in the above methods and products without departing from the scope of the invention, it is intended that all matter contained in the above description and shown in any accompanying drawings shall be interpreted as illustrative and not in a limiting sense.

Claims

WHAT IS CLAIMED IS:
1. A method for electrolytic deposition of bronze onto a substrate, the method comprising: immersing a substrate in an aqueous acidic electrolytic composition containing a source of tin ions, a source of copper ions, an alkylsulfonic acid, and a compound selected from the groups consisting of aliphatic fatty alcohol ethoxylates, substituted dithioglycols, and combinations thereof and electrolytically depositing tin and copper from the electrolyte to form bronze on the substrate.
2. The method of claim 1 wherein the electrolytic composition further contains an aromatic nonionic wetting agent .
3. The method of claim 1 or claim 2 wherein the electrolytic composition contains said aliphatic fatty alcohol ethoxylate compound.
4. The method of claim 1 or claim 2 wherein the electrolytic composition contains said aliphatic fatty alcohol ethoxylate compound and said aliphatic fatty alcohol ethoxylate compound has from 13 to 15 carbon atoms .
5. The method of any one of claims 1 through 4 wherein the electrolytic composition contains said substituted dithioglycol .
6. The method of any one of claims 1 through 4 wherein the electrolytic composition contains said substituted dithioglycol and said substituted dithioglycol is selected from the group consisting of Thiobis (diethyleneglycol) , Thiobis (hexaethylene glycol), Thiobis (pentadecaglycelol) , Thiobis (icosaethyleneglycol) ,
Thiobis (pentacontaethyleneglycol) , 4, 10-dioxa-7-thiatridecane- 2,12-diol, Thiodiglycerin, Thiobis (triglycerin) , 2,2'- thiodibutanolbis (octaethyleneglycolpentaglycerol) ether, Thiobis (octaethyleneglycol)bis (2-chloroethyl) ether, Thiobis (decaethyleneglycol)bis (carboxymethyl) ether, Thiobis (dodecaethyleneglycol) bis (2-nitroethyl) ether, Thiodiglycolbis (carboxymethyl) ether, Dithiodiglycolbis (carboxymethyl) ether, Thiobis (dodecaethyleneglycol) , Dithiobis (hentetracontaethyleneglycol) , Dithiobis (icosaethyleneglycolpentapropyleneglycol) , Dithiobis (triglycerol) , Dithiobis (decaglycelol) , 3, 6-Dithiaoctane-l, 8-diol, 2,2'- (Ethylenedithio) diethanol) , 1, 3-Propanedithiolbis (decaethyleneglycol) thioether, 1,4-Buthanedithiolbis (pentadecaglycerol) thioether, 1, 3-Dithioglycerolbis (pentaethyleneglycol) thioether, 1, 2-Ethanedithiolbis (penta (1-ethyl) ethyleneglycol) thioether, 1, 3-Dithioglycerolbis (di (1-ethyl) ethyleneglycol) thioether, 2-Mercaptoethylsulfide bis (hexatriacontaethylene-glycol) , 2-Mercaptoethylsulfidebis (icosaethyleneglycol) di-methylether, 2-Mercaptoethyletherbis (diethyleneglycol) , Thiodiglyceroltetra (decaethyleneglycol) ether, Diethyleneglycolmohomethylthioether, Decaglycerolmono (6-methylthiohexyl) thioether, 2-Mercaptoethylsulfide-ω- { (2-bromoethyl) icosaethyleneglycol }thioether-ω' -{ (2-bromoethyl) hectaethyleneglycol } thioether,
1,4-Butanediol-ω- { ( 2 -benzyloxy-1-methyl) ethyl }thioether-ω' - (de capropyleneglycoloctacontaethyleneglycol) thioether, Dithiobis (icosaethyleneglycol) bis (2-methyl-thioethyl) ether, 1, 2-Ethanediol-ω- (4-methoxybenzyl) thioether-ω' - (pentacontaethy leneglycol) thioether, Triacontaethyleneglycolmono (4-cyanobenzyl) thioether, Thiobis (pentadecaethyleneglycol) bisallylether, Tricosaethyleneglycolmono (4-formylphenetyl) thioether, Pentadecaethyleneglycolmono{ (acetylmethyl) thioethyl} thioether
1, 2-Ethanediol-ω- (glycidyl) thioether-ω' - icosaethyleneglycolthioether, Octadecaethyleneglycolbis (2- methy1thioethyl) ether, Hexadecaethyleneglycolmono (2- methylthioethyl) thioether, Icosaethyleneglycolmonomethylthioether, Undecaethyleneglycoldi (n-propyl) thioether, Dodecaethyleneglycolbis (2-hydroxyethyl) thioether, Undecaethyleneglycoldimethylthioether, Pentatriacontaethyleneglycolraono (2 -n- butyldithioethyl) dithioether,
4,8, 12-trithiapentadecane-l, 2, 6, 10, 14, 15-hexaol, Icosaglycerolmono (2-ethylthioethyl) thioether, Triacontaethyleneglycolmono (2 -methylthioethyl) thioether, Dithiobis (icosaethyleneglycol) dibenzylether, Tridecaethyleneglycolmonomethylthioether, Hexadecaethyleneglycol dimethylthioether, 1, 2-Ethanedithiolbis (icosaethyleneglycol) thioether, Dithiobis (pentadecaethyleneglycol) , 3 , 3 ' -thiodipropanol, and combinations thereof.
7. The method of any one of claims 1 through 5 wherein the electrolytic composition contains said substituted dithioglycol and said substituted dithioglycol is 2,2'- (Ethylenedithio) diethanol .
8. The method of any one of claims 1 through 7 wherein the electrolytic composition contains said substituted dithioglycol and said aliphatic fatty alcohol ethoxylate compound.
9. The method of any one of claims 1 through 7 wherein the electrolytic composition contains said substituted dithioglycol and said aliphatic fatty alcohol ethoxylate compound, and said aliphatic fatty alcohol ethoxylate has from 13 to 15 carbon atoms .
10. The method of any one of claims 1 through 9 wherein the electrolytic composition contains the tin ions and the' copper ions in a concentration which yields a bronze deposit having a tin/copper weight ratio of about 40/60 or less.
11. The method of any one of claims 1 through 9 wherein the electrolytic composition contains the tin ions and the copper ions in a concentration which yields a bronze deposit having a tin/copper weight ratio of about 20/80 or less.
12. The method of any one of claims 1 through 9 wherein the electrolytic composition contains the tin ions and the copper ions in a concentration which yields a bronze deposit having a tin/copper weight ratio of about 10/90 or less.
13. The method of any one of claims 1 through 12 wherein the alkylsulfonic acid is methanesulfonic acid in a concentration from 140 to 382 g/L of electrolytic composition.
14. The method of any one of claims 1 through 13 wherein the source of tin ions is tin methanesulfonate in a concentration from 5 to 195 g/L and the source of copper ions is copper methanesulfonate in a concentration from 8 to 280 g/L.
15. The method of any one of claims 1 through 14 wherein the electrolytic composition contains tin ions in a concentration from 2 to 75 g/L and copper ions in a concentration from 2 to 70 g/L.
16. The method of any one of claims 1 through 15 wherein the alkylsulfonic acid comprises methanesulfonic acid in a concentration of at least about 290 g/L.
17. The method of claim 1 wherein the electrolytic composition comprises : tin methane sulfonate in a concentration from 5 to 195 g/L as the source of tin ions; copper methanesulfonate in a concentration from 8 to 280 g/L as the source of copper ions,- and methanesulfonic acid in a concentration from 140 to 382 g/L as the alkylsulfonic acid; wherein the composition further comprises: an aromatic nonionic wetting agent in a concentration from 2 to 40 g/L; an oxidation inhibitor; and a substituted dithioglycol compound as said compound selected from the groups consisting of aliphatic fatty alcohol ethoxylates, substituted dithioglycols, and combinations thereof.
18. The method of claim 1 wherein the electrolytic composition comprises: tin methane sulfonate in a concentration from 5 to 195 g/L as the source of tin ions; copper methanesulfonate in a concentration from 8 to 280 g/L as the source of copper ions,- and methanesulfonic acid in a concentration from 140 to 382 g/L as the alkylsulfonic acid; wherein the composition further comprises : an aromatic nonionic wetting agent in a concentration from 2 to 40 g/L; an oxidation inhibitor; and a fatty alcohol ethoxylate compound as said compound selected from the groups consisting of aliphatic fatty alcohol ethoxylates, substituted dithioglycols, and combinations thereof .
19. An aqueous acidic electrolytic composition for deposition of bronze comprising: a) tin ions; b) copper ions; c) an alkylsulfonic acid; d) an aromatic nonionic wetting agent; and e) a compound selected from the groups consisting of aliphatic fatty alcohol ethoxylates, substituted dithioglycols, and combinations thereof.
20. The electrolytic composition of claim 19 wherein the electrolytic composition contains said aliphatic fatty alcohol ethoxylate compound.
21. The electrolytic composition of claim 19 wherein the electrolytic composition contains said aliphatic fatty alcohol ethoxylate compound and said aliphatic fatty alcohol ethoxylate compound has from 13 to 15 carbon atoms .
22. The electrolytic composition of any one of claims 19 through 21 wherein the electrolytic composition contains said substituted dithioglycol .
23. The electrolytic composition of any one of claims 19 through 21 wherein the electrolytic composition contains said substituted dithioglycol and said substituted dithioglycol is selected from the group consisting of
Thiobis (diethyleneglycol) , Thiobis (hexaethylene glycol), Thiobis (pentadecaglycelol) , Thiobis (icosaethyleneglycol) , Thiobis (pentacontaethyleneglycol) , 4 , 10-dioxa-7-thiatridecane- 2,12-diol, Thiodiglycerin, Thiobis (triglycerin) , 2,2'- thiodibutanolbis (octaethyleneglycolpentaglycerol) ether, Thiobis (octaethyleneglycol)bis (2-chloroethyl) ether, Thiobis (decaethyleneglycol) bis (carboxymethyl) ether, Thiobis (dodecaethyleneglycol)bis (2-nitroethyl) ether, Thiodiglycolbis (carboxymethyl) ether, Dithiodiglycolbis (carboxymethyl) ether, Thiobis (dodecaethyleneglycol) , Dithiobis (hentetracontaethyleneglycol) , Dithiobis (icosaethyleneglycolpentapropyleneglycol) , Dithiobis (triglycerol) , Dithiobis (decaglycelol) , 3,6-Dithiaoctane-l, 8-diol, 2,2'- (Ethylenedithio) diethanol) , 1, 3-Propanedithiolbis (decaethyleneglycol) thioether, 1,4-Buthanedithiolbis (pentadecaglycerol) thioether, 1, 3-Dithioglycerolbis (pentaethyleneglycol) thioether, 1,2-Ethanedithiolbis (penta(l-ethyl) ethyleneglycol) thioether, 1, 3-Dithioglycerolbis (di (1-ethyl) ethyleneglycol) thioether, 2-Mercaptoethylsulfide bis (hexatriacontaethylene-glycol) , 2-Mercaptoethylsulfidebis (icosaethyleneglycol) di-methylether, 2-Mercaptoethyletherbis (diethyleneglycol) , Thiodiglyceroltetra (decaethyleneglycol) ether, Diethyleneglycolmonomethylthioether, Decaglycerolmono (6-methylthiohexyl) thioether, 2-Mercaptoethylsulfide-ω- { (2-bromoethyl) icosaethyleneglycol} thioether-ω' -{ (2-bromoethyl) hectaethyleneglycol } thioether, l,4-Butanediol-ω-{ (2-benzyloxy-1-methyl) ethyl} thioether-ω' - (de capropyleneglycoloctacontaethyleneglycol) thioether, Dithiobis ( icosaethyleneglycol) bis (2-methyl-thioethyl) ether, 1, 2-Ethanediol-ω- (4-methoxybenzyl) thioether-ω' - (pentacontaethy leneglycol) thioether, Triacontaethyleneglycolmono (4 -cyanobenzyl) thioether, Thiobis (pentadecaethyleneglycol) bisallylether, Tricosaethyleneglycolmono (4-formylphenetyl) thioether, Pentadecaethyleneglycolmono{ (acetylmethyl) thioethyl} thioether, 1, 2-Ethanediol-ω- (glycidyl) thioether-ω ' - icosaethyleneglycolthioether, Octadecaethyleneglycolbis (2- methylthioethyl) ether, Hexadecaethyleneglycolmono (2 - methylthioethyl) thioether, Icosaethyleneglycolmonomethylthioether, Undecaethyleneglycoldi (n-propyl) thioether, Dodecaethyleneglycolbis (2-hydroxyethyl) thioether, Undecaethyleneglycoldimethylthioether, Pentatriacontaethyleneglycolmono (2 -n- butyldithioethyl) dithioether,
4,8, 12-trithiapentadecane-l, 2, 6, 10, 14 , 15-hexaol, Icosaglycerolmono (2 -ethylthioethyl) thioether, Triacontaethyleneglycolmono (2-methylthioethyl) thioether, Dithiobis (icosaethyleneglycol) dibenzylether,
Tridecaethyleneglycolmonomethylthioether,
Hexadecaethyleneglycol dimethylthioether,
1, 2-Ethanedithiolbis (icosaethyleneglycol) thioether,
Dithiobis (pentadecaethyleneglycol) , 3,3'-thiodipropanol , and combinations thereof .
24. The electrolytic composition of any one of claims 19 through 23 wherein the electrolytic composition contains said substituted dithioglycol and said substituted dithioglycol is 2,2'- (Ethylenedithio) diethanol .
25. The electrolytic composition of any one of claims 19 through 24 wherein the electrolytic composition contains said substituted dithioglycol and said aliphatic fatty alcohol ethoxylate compound.
26. The electrolytic composition of any one of claims 19 through 24 wherein the electrolytic composition contains said substituted dithioglycol and said aliphatic fatty alcohol ethoxylate compound, and said aliphatic fatty alcohol ethoxylate has from 13 to 15 carbon atoms .
27. The electrolytic composition of any one of claims 19 through 26 wherein the alkylsulfonic acid is methanesulfonic acid in a concentration from 140 to 382 g/L of electrolyte.
28. The electrolytic composition of any one of claims 19 through 27 wherein the source of tin ions is tin methanesulfonate in a concentration from 5 to 195 g/L and the source of copper ions is copper methanesulfonate in a concentration from 8 to 280 g/L.
29. The electrolytic composition of any one of claims 19 through 28 wherein the electrolytic composition contains tin ions in a concentration from 2 to 75 g/L and copper ions in a concentration from 2 to 70 g/L.
30. The electrolytic composition of claim 19 comprising: tin methane sulfonate in a concentration from 5 to 195 g/L as the source of tin ions; copper methanesulfonate in a concentration from 8 to 280 g/L as the source of copper ions; and methanesulfonic acid in a concentration from 140 to 382 g/L as the alkylsulfonic acid; wherein the composition further comprises : an aromatic nonionic wetting agent in a concentration from 2 to 40 g/L; an oxidation inhibitor; and a substituted dithioglycol compound as said compound selected from the groups consisting of aliphatic fatty alcohol ethoxylates, substituted dithioglycols, and combinations thereof .
31. The electrolytic composition of claim 19 comprising: tin methane sulfonate in a concentration from 5 to 195 g/L as the source of tin ions; copper methanesulfonate in a concentration from 8 to 280 g/L as the source of copper ions,- and methanesulfonic acid in a concentration from 140 to 382 g/L as the alkylsulfonic acid; wherein the composition further comprises: an aromatic nonionic wetting agent in a concentration from 2 to 40 g/L; an oxidation inhibitor; and a fatty alcohol ethoxylate compound as said compound selected from the groups consisting of aliphatic fatty alcohol ethoxylates, substituted dithioglycols, and combinations thereof .
PCT/US2006/014141 2005-04-14 2006-04-14 Method for electrodeposition of bronzes Ceased WO2006113473A1 (en)

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EP06750231.0A EP1874982B1 (en) 2005-04-14 2006-04-14 Method for electrodeposition of bronzes
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TW200702498A (en) 2007-01-16
JP2008537017A (en) 2008-09-11
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TWI391534B (en) 2013-04-01
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