US2658032A - Electrodeposition of bright copper-tin alloy - Google Patents

Electrodeposition of bright copper-tin alloy Download PDF

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Publication number
US2658032A
US2658032A US98642A US9864249A US2658032A US 2658032 A US2658032 A US 2658032A US 98642 A US98642 A US 98642A US 9864249 A US9864249 A US 9864249A US 2658032 A US2658032 A US 2658032A
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Prior art keywords
tin
copper
bath
bright
cyanide
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US98642A
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English (en)
Inventor
Charles L Faust
Wilbur G Hespenheide
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City Auto Stamping Co
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City Auto Stamping Co
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Publication date
Priority to BE496261D priority Critical patent/BE496261A/xx
Priority to NL75841D priority patent/NL75841C/xx
Application filed by City Auto Stamping Co filed Critical City Auto Stamping Co
Priority to US98642A priority patent/US2658032A/en
Priority to DEC1130A priority patent/DE860300C/de
Priority to FR1019841D priority patent/FR1019841A/fr
Priority to GB14318/50A priority patent/GB680937A/en
Priority to CH294029D priority patent/CH294029A/fr
Application granted granted Critical
Publication of US2658032A publication Critical patent/US2658032A/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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper

Definitions

  • This invention is generally described with reference to copper-tin alloy plating.
  • this. invention relates to a bright. copper-tin alloy plate, to a method of plating bright coppertin alloy, to a composition useful in the process of producing a bright copper-tin plate, and to an article having an electroplated bright copper-tin alloy thereon.
  • this invention relates to the. continuous co-electrodeposition of copper and tin as a bright, hard, adherent, speculum metal.
  • Speculum metal the well-known alloy containing 55 to 66 per cent copper and the balance tin, has long been known for its excellent resistance to tarnishing and for its pleasing white color.
  • white metals that are now known, among those of non-noble metal quality, speculum is the closest in approach to the color of pure silver. Although pure silver has the best reflectivity of any of the metals, it soon loses its advantage in that respect because of tarnishme.
  • speculum metal although having almost the same reflectivity as pure silver, retains its initial reflectivity, and after a few hours of exposure, it will have much better reflectivity than silver because speculum metal does not tarnish. This relationship is well known to those skilled in the art.
  • speculum metal is a brittle material, it is difiioult to make shaped parts from the solid metal.
  • it has been the practice to electrodeposit the speculum metal on the surface of articles made from other metals and alloys which were fabricated into the desired shape and form before plating.
  • the copper-tin alloy electrodeposited from the baths of the. prior art is a dull, or at best, only a semi: bright mat finish.
  • the prior art. baths have employed tin in the oxidized or stanniev form in the presence of copper in, the cuuric or cuprous form. In order to produce the pleasing appearance of the speculum metal, the mat. copperetin alloy coatings electrodeposited from the prior art baths must then be buffed and colored.
  • cone te ates e use f a l n e ials as the cathode which will receive speculum plates.
  • sults are ebtained by employing the double anode sy tem at pure tin nd op eh n alloy tqn ai n p ta 1.5.
  • the plate as deposited from this electrolytic bath is a bright alloy of essentially pure coelectrodeposited copper and tin. Very minor amounts of impurities are probably present in the electrodeposited coating and bath of this invention although the precise kind and quantity of impurities are unknown; however, they do not appear to materially affect the resulting bright copper-tin alloy. Whenever, due to a change in the amount of bath constituents or factors or in operating conditions, an increase in the copper content of the alloy plate occurs, there will be a corresponding decrease in the tin content so that there are always essentially only two elements present, i.
  • cuprous copper is added to the bath in the form of cuprous cyanide, or other cuprous salt along with the required amount of potassium cyanide.
  • the copper exists as a soluble alkaline cuprous complex, i. e., a soluble potassium cupro-cyanide complex.
  • a cuprous halide such as the chloride or iodide for example
  • the corresponding alkali salt for example potassium chloride or iodide.
  • a negligible, if any, amount of copper may exist in a pyrophosphate complex.
  • tin salt such as stannous sulfate, chloride, or pyrophosphate. It is believed that the tin exists in the bath as the soluble alkaline stannous complex, i. e., the soluble potassium stannous pyrophosphate complex, regardless of the anion with which it m g be added as a stannous salt. If any stannic tin is present, its concentration is very minor and not critical in the baths of this invention. From about 2 to about 50 g./l. of stannous sulfate provide the desired concentration of the stannous complex in the bath. It is desirable, however, to add from 5 to 15 g./l of stannous sulfate to the bath, where the pyrophosphate is present in an amount of from 40 to g./l., so that this constitutes a preferred range.
  • a tin salt such as stannous sulfate, chloride, or pyrophosphate.
  • Orthophosphate is added to the bath as potassium orthophosphate.
  • the mono-, di-, or tribasic potassium orthophosphates can be used since the adjustment of the bath pH will result in the same end product, i. e., the conversion of these phosphates to the monobasic orthophosphate form.
  • the orthophosphate does not cause precipitation of either stannous or cuprous compounds and with the glue at the specified pH ranges causes bright deposits of copper-tin alloys to be obtained. It is used in the bath in an amount of from about 5 to about g./1. per 8 to 300 g./l. of alkali pyrophosphate, although it has been found desirable to use orthophosphate in the range of from 10 to 30 g./1. when the pyrophosphate compound is present in an amount of about 40 to 90 g./l.
  • a colloid or soluble addition agent such as a polypeptide or more specifically a protein, is, as stated above, also a necessary ingredient of the baths for producing bright copper-tin alloy and speculum metal plates.
  • Amino acids, and their derivatives and mixtures thereof, can likewise be used.
  • Glue and gelatin have been found eminently successful in the baths of this invention, although many other proteins are also applicable.
  • the glue or gelatin is added as a suspension in water. To be immediately effective in the bath, this suspension should be prepared several days in advance. Alternatively, this aging period can be eliminated by partially hydrolyzing the glue or gelatin. This hydrolysis is conducted by refluxing a suspension of glue or gelatin in an acid or alkaline solution.
  • the pH thereof may be adjusted in the range of from '7 to 10 before adding to the bath. From about 0.01 to about 5.0 g./l. of glue per 8 to 300 g./l. of pyrophosphate provides a satisfactory concentration in the bath, although it is preferred to use from 0.5 to 2.0 g./l. of glue.
  • the pH of the bath is adjusted by adding a suitable acid, such as orthophosphoric or pyrophosphoric acid. If stannous sulfate has been used in making up the plating bath, sulfuric acid can also be used when it is necessary to reduce the pH. Where it is necessary to increase the pH in order to adjust or raise it to the desired value, potassium hydroxide can be added to the bath. Two precautions should, however, be observed. If the pH of the bath exceeds about 10.5 for any appreciable period of time stannous hydroxide, which is very diflicultly soluble in the bath, will be precipitated, reducing the concen tration of the stannous pyrophosphate complex.
  • a suitable acid such as orthophosphoric or pyrophosphoric acid.
  • the bath will be thrown out of balance and the composition of the plate will be altered.
  • the pH of the bath is less than about 6.5 for any appreciable time, difiicultly soluble cyanide salts will be precipitated, resulting ina loss of cyanide and changing the concentration of the soluble cuprous cyanide complex. This, too, alters the desired ratio of constituents in the bath and also "the appearance and compositions! the plate.
  • equivalent sodium salts or bases can be used wherever potassium salts or bases are disclosed.
  • equivalent ammonium salts or bases i. e., those containing the ammonium radical,
  • ammonium salts and bases are to be considered as included with the sodium .and potassium salts and basesshown above,
  • the corresponding carbonates can likewise be used in full or partial replacement of the hydroxides when adjusting the pH or to minimize changes due to absorption of carbon dioxide from the atmosphere. If not added they will form, as in the instance of all alkaline baths, by carbon dioxide absorption from the atmosphere. Excessive concentration of carbonate lowers the anode and cathode ef iciencies which, for some plate compositions may be desirable. The carbonate concentration should, however, not exceed 120 g./l.
  • the electrolytic baths used to make the bright speculum or other bright copper-tin alloy plates of this invention can be advantageously prepared by a number of methods. For example, one method is to dissolve the desired quantity of cuprous cyanide in a solution of potassium cyanide. The required amount of stannous sulfate is next dissolved in a solution of potassium pyrophosphate. These solutions are then mixed, followed by the addition thereto of the necessary amounts of potassium orthophosphate and glue. The pH of the resulting electrolytic solution is finally adjusted to the desired value by the addition of acid or alkali.
  • the electrolytic bath can be prepared by dissolving the required amounts of the constituents in water in the following order: potassium pyrophosphate, potassium cyanide, cuprous cyanide, stannous sulfate, potassium crthophosphate and glue.
  • the pI-l of the bath is then adjusted to the desired figure by adding appropriate amounts of acid or alkali.
  • a third method is to mix all of the bath c n i e except the glue, in the dry state by any known means to obtain a homogeneousappearing mixture of dry solids. This mixture is then dissolved in the required amount of water, followed by the addition of the. glue. If neces- 6. sary, the pH can be adjusted to the desired range by appropriate additions of acid or alkali.
  • the bright plating baths disclosed herein are stable at operating temperatures up to the boiling point of the solution; however, the optimum operating temperatures usually do not exceed 190 F.
  • the preferred temperature range is from to F. During the plating process an increase in temperature within this range equal-- izes the anode and cathode current efliciencies so that the proper dissolved metal balance in the bath is maintained during continuous operation.
  • Operatingcathode current densities of up to 90 amps/sq. ft. or more can be used in this process for producing speculum metal plates. It has been found best to employ current densities not in excess of about 50 amps/sq. it. and preferably in the range of from 10 to 40 amps/sq. ft. By varying the current density, the agitation and temperature, the composition of the bright copper-tin alloys can be varied somewhat.
  • the customary methods known to the art for cleaning, degreasing and pickling can be used in preparing a metallic (or non-metallic) surface for receiving the speculum plate or other alloy plate of copper-tin.
  • the surface of the basis material or cathode being now in a cleaned condition can be directly plated with the speculum metal of this invention.
  • the articles to be plated as the cathodes can be made of iron, steel, nickel, copper, brass, zinc, zinc die castings or alloys and aluminum, as well as many other materials normally used and on which it would be desirable to plate speculum metal.
  • the basis material may also be strike-plated with copper, nickel, silver, etc. by electroplating prior to depositing thereon the bright'speculum alloy coating of copper and tin of this invention.
  • continuous operation can also be efiected through the use of insoluble anodes, such as iron, nickel, or other suitable conductor with pure tin and pure copper anodes or copper-tin alloy anodes containing up to 15 per cent tin and the balance copper. Where part of the current is carried by the insoluble anodes, they lower the total efficiency of the copper and tin anodes so that the tin concentration is kept constant.
  • insoluble anodes such as iron, nickel, or other suitable conductor with pure tin and pure copper anodes or copper-tin alloy anodes containing up to 15 per cent tin and the balance copper.
  • Current densities for each anode can range up to 30 amps/sq. ft., although it is preferred to maintain the individual current density of each anode within the range of from 1 to amps./ sq. ft.
  • the ratio of copper and tin dissolution, and also their rate of dissolution can be balanced against the deposition rate and ratio of these two metals on the cathode so that the concentration of copper and tin in the electrolytic bath remains substantially constant. It is also necessary, in order to control the dissolution of the anodes, to have a voltage drop of from 0.5 to 2 volts between the copper and tin (or the copper and copper-tin) anodes. Furthermore, this voltage drop, determined by the geometry of the plating cell, should not appreciably exceed 2 volts to prevent the deposition of copper and/or copper-tin alloy on the tin anode.
  • the copper anode to cathode voltage during bright plating should be in the range of from 2 to 3 volts.
  • the upper limit can vary above 3 volts, of course, depending on the distance between the anodes and cathodes.
  • the upper limit on the tin anode to cathode voltage is determined by the appearing of the undesirable reactions Sn- Sn+ and Sn+ Sn+ because Sn+ does not produce bright or speculum metal plates.
  • the lower limit is set by the requirement that copper should not deposit on the tin anodes by immersion.
  • tin anode to cathode voltage from 0.1 to less than 2 volts 1 where the copper anode to cathode voltage is from 2 to 3 volts.
  • the tin anode to cathode voltage range can, of course, be increased as the copper anode to cathode voltage is increased.
  • the time during which the process is carried on relates only to the thickness of the speculum plate to be deposited on the cathode, as will be obvious to those skilled in the art.
  • EXANCPLEI An electrolyte was prepared containing the following ingredients:
  • KCN Potassium cyanide
  • Cuprous cyanide C112(CN)2 18.8 g./1.
  • Potassium pyrophosphate K4P2O7.3H2O
  • SnSOr Stannous sulfate
  • KH2PO4 Potassium orthophosphate
  • the pH of this bath was about 9.0.
  • the bath was brought to an operating temperature of F. and a stel cathode and insoluble steel anodes inserted therein. A potential of 3.8 volts gave a cathode current density of 30 amperes per square foot. The bath was then operated for ten minutes and resulted in a deposit on the cathode of bright speculum alloy plate, 54 per cent copper and 46 per cent tin.
  • EXAMPLE 7 EXAMPLE 3 praw ep m v p H 9.5, andoathode cur-- ree de si y. 40 ..am
  • the cathode film because of removal of ions by electrodeposition and by simple diffusion, has a composition that is difierent from the body of the electroplating bath. With the proper concentration and combination of dissolved components and of pH in the bath, the cathode film will assume a slightly different pH, at which value some constituent will momentarily precipitate and thereby influence the deposition process to produce a mirror-bright plate. It is believed that the operating pH values are very close to those at which some constituent of the plating bath will precipitate as a compound in the cathode film and at or near the cathode surface.
  • this invention discloses that, in the presence of cuprous and stannous complexes within a pH range of 6.5 to 10.5, the small concentrations of orthophosphate added to the bath or from hydrolysis of the pyrophosphate at this pH, and also glue are essential for setting up the conditions in the cathode film for depositing bright copper-tin alloys.
  • the dense, uniform and bright speculum plate of this invention will be desired for decorative purposes, relying upon its appearance without any further plating or finishing operations.
  • other bright metals such as bright nickel and/or chromium
  • a particularly important attribute of the present process is its ability to bright-plate an alloy of copper and tin directly on zinc die castings without the need for one or more strike plates as is required when using other baths, which, due to their strong alkaline or acidic nature, readily attack the zinc alloy.
  • zinc die castings can be finished to an attractive bright, whitemetal appearance, which is retained indefinitely and which has been found to possess important protective qualities relative to the customary composite plate of copper, nickel, and chromium on zinc die castings.
  • the bath of the present invention has excellent throwing power and attributes for electrodepositing copper-tin alloys in a wide range of compositions, and the process can be practiced for other purposes than merely decorative plating. Thick plates, for example, 0.030 inch have been satisfactorily deposited with mirror-like appearance without noticeable treeing or roughness.
  • this invention teaches that bright, lustrous and speculum metal alloy plates of copper and tin can be readily electrodeposited on a basis material from a mildly alkaline bath containing a cuprous complex, a stannous complex, a cyanide, an orthophosphate, a pyrophosphate, and an addition agent such as a polypeptide.
  • the composition of the bath and the operating conditions and elements can be varied over a wide range to obtain bright and/or speculum metal platesand the bath can be operated continuously to 7 plate copper and tin.
  • the present invention involves the novel feature of combining cuprous copper and stannous tin salts in a relatively stable solution which can be used to produce bright speculum and other copallo slates. nother and feature of n eseat' ar n iq iisth' 6 may ,h tas. all.
  • ns t os hat al mater a d sclo ed is m b nterpreted as. lusira re a n in' a imi ng, sense;
  • electrodepositmg an alloy of copper a d tin, comprising passingan electric current from an anode to a cathode through an electrolyte having a'pH of from; 6.5 to 10.5 and consisting essentially oi a cuprous compound sel ted from the.
  • rqun cons s f upr us cyanide and halide a stannous compound selected from the group consisting of stannous chloride, pyrophosphate, and sul fate, a cyanide selected from the group,consistingotammonium, sodium, and pptass ium cyanide, an excess of alkali pyro- HhQSD hate, a material selected irom the, group consisting of; glue, gelatir' and hydrolysis products, the s'q an lka i lr hon phate- '3',
  • the process of electrodepositing a bright alloy of copper and tin on a basis metal comprising making the basis metal' the cathode, in anelectrolyte having a pH offrom '7 to 9 .5.
  • halide and cuprous cyanide from 22 to grams per liter of, a cyanide selected from the group consisting, 0,15 ammonium, potassium andsodium cyanidea from 5 t l5igramsper liter of a, soluble stannous om pound selected from the group consisting of; stannous chloride, pyroph sphate and. sulfat rom 10 to 3.0.
  • grams per liter of an orthophosphate compound selected from. the group consisting of ammonium, potassium. and sodium mQ o-, im and, triorthophosphates, from 0.5 to ;.0 grams per literv oi a material. selected from the group consisting 'of. gl e, gel t n an yd is prod:
  • cyanide from 22' to.- 120igrams, per liter of a: cyanide compound selected -from thegroup: con sisting of ammonium, potassium, and; sodium cyanides, from 5 to 1 5* grams-perliter of a soluble stannous compoundfselected from the group con,-
  • nd sodium, mono-, di; and triorthopho sphates from 55, 9 ,0 ra Her, it r i; ma e alL e ted; from the group consisting of glue, gelatin, and hydrolysis products thereof, and water, adjusting the pH of the electrolyte to from 7 to 9.5, and passing an electric current from said cathode to copper and tin containing anodes in a manner to create a current density at said cathode of from 10 to 40 amps/sq. ft. and at the anodes of from 1 to 15 amps/sq. ft.
  • the ratio of tin containing anode to cathode voltage from 0.1 to less than 2 volts where the copper anode to cathode voltage is from 2 to 3 volts and the temperature of the bath from to F.
  • the steps consisting of immersing the basis material as a cathode to be alloy coated in an electrolytic bath having a pH of from 6.5 to 10.5 and comprising essentially from 8 to 300 grams per liter of a pyrophosphate compound selected from the group consisting of ammonium, potassium and sodium pyrophosphates, from 2 to 230 grams per liter of a soluble cuprous compound selected from the group consisting of cuprous cyanide and halide, from 2 to 350 grams per liter of a cyanide selected from the group consisting of ammonium, potassium and sodium cyanides, from 2 to 50 grams per liter of a soluble stannous compound selected from the group consisting of a stannous chloride, pyrophosphate and sulfate, from to 120 grams per liter of an orthophosphate compound selected from the group consisting of ammonium, potassium and sodium mono-,
  • a composition of matter consisting essentially of an alkali cyanide, an excess of alkali phyrophosphate, an alkali orthophosphate, a material selected from the group consisting of glue, gelatin, and hydrolysis products thereof, a cuprous compound selected from the group consisting of cuprous cyanide and halide, and a stannous salt selected from the group consisting of stannous sulfate, halide, and pyrophosphate.
  • An aqueous solution having a pH of from 6.5 to 10.5 and consisting essentially of a cuprous compound selected from the grou consisting of cuprous cyanide and halide, a stannous compound selected from the group consisting of stannous chloride, pyrophosphate, and sulfate, an alkali cyanide, a material selected from the group consisting of glue, gelatin, and hydrolysis products thereof, an excess of alkali pyrophosphate, and an alkali orthophosphate.
  • a composition of matter consisting essentially, by weight, of from 8 to 300 parts of a pyrophosphate compound selected from the group consisting of ammonium, potassium, and sodium pyrophosphates, from 2 to 230 parts of a soluble cuprous compound selected from the group consisting of cuprous cyanide and halide, from 2 to 350 parts of a cyanide selected from the group 1 consisting of ammonium, potassium, and sodium cyanides, from 2 to parts of a stannous compound selected from the group consisting of stannous chloride, pyrophosphate, and sulfate, from 5 to 120 parts of an orthophosphate compound selected from the group consisting of ammonium, potassium, and sodium mono-, di-, and triorthophosphates, and from 0.01 to 5.0 parts of a, material selected from the group consisting of glue, gelatin, and hydrolysis products thereof.
  • a composition of matter consisting essentially, by weight, of from 40 to parts of a pyrophosphate selected from the group consisting of ammonium, potassium, and sodium pyrophosphates, from 15 to 80 parts of a soluble cuprous compound selected from the group consisting of cuprous halide and cuprous cyanide, from 22 to parts of a cyanide selected from the group consisting of ammonium, potassium, and sodium cyanides, from 5 to 15 grams per liter of a stannous compound selected from the group consisting of stannous chloride, pyrophosphate, and sulfate, from 10 to 30 parts of an orthophosphate compound selected from the group consisting of ammonium, potassium, and sodium mono-, di-, and triorthophosphates, from 0.5 to 2.0 parts of a material selected from the grou consisting of glue, gelatin, and hydrolysis products thereof.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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US98642A 1949-06-11 1949-06-11 Electrodeposition of bright copper-tin alloy Expired - Lifetime US2658032A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE496261D BE496261A (en)) 1949-06-11
NL75841D NL75841C (en)) 1949-06-11
US98642A US2658032A (en) 1949-06-11 1949-06-11 Electrodeposition of bright copper-tin alloy
DEC1130A DE860300C (de) 1949-06-11 1950-06-03 Kupfer- und Zinnsalze enthaltender Elektrolyt zur Erzeugung von Kupfer-Zinn-Legierungsueberzuegen und Verfahren zum Erzeugen dieser UEberzuege
FR1019841D FR1019841A (fr) 1949-06-11 1950-06-08 Dépôt électrolytique d'un alliage de cuivre et d'étain
GB14318/50A GB680937A (en) 1949-06-11 1950-06-08 Improvements in electroplating
CH294029D CH294029A (fr) 1949-06-11 1950-06-10 Procédé de formation électrolytique sur un métal d'un revêtement en un alliage de cuivre et d'étain.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2854388A (en) * 1955-03-14 1958-09-30 City Auto Stamping Co Electrodeposition of copper-tin alloys
US2885331A (en) * 1956-10-24 1959-05-05 Du Pont Copper plating
US2886500A (en) * 1956-11-01 1959-05-12 Battelle Development Corp Electroplating of copper alloys
US3440151A (en) * 1965-06-02 1969-04-22 Robert Duva Electrodeposition of copper-tin alloys
US4565608A (en) * 1983-11-02 1986-01-21 Degussa Aktiengesellschaft Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings
WO2004011663A2 (de) 2002-07-24 2004-02-05 Schering Aktiengesellschaft Mikrobiologische verfahren zur herstellung von 7alpha-substituierten 11alpha-hydroxysteroiden
US20060068234A1 (en) * 2004-09-24 2006-03-30 Jarden Zinc Products, Inc. Electroplated metals with silvery-white appearance and method of making
WO2006036479A1 (en) * 2004-09-24 2006-04-06 Jarden Zinc Products, Inc. Electroplated metals with silvery-white appearance and method of making
IT202100008084A1 (it) * 2021-03-31 2022-10-01 Bluclad S P A Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno

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Publication number Priority date Publication date Assignee Title
DE4324995C2 (de) * 1993-07-26 1995-12-21 Demetron Gmbh Cyanidisch-alkalische Bäder zur galvanischen Abscheidung von Kupfer-Zinn-Legierungsüberzügen
US5614327A (en) * 1994-09-09 1997-03-25 Sarthoise De Revetements Electrolytiques Process for protecting a silver or silver-coated part
JP6088295B2 (ja) * 2013-03-07 2017-03-01 ローム・アンド・ハース電子材料株式会社 スズ合金めっき液
AT514427B1 (de) * 2013-07-05 2015-01-15 W Garhöfer Ges M B H Ing Elektrolytbad sowie damit erhältliche Objekte bzw. Artikel

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US1970548A (en) * 1931-10-19 1934-08-21 City Auto Stamping Co Metal finish
US1970549A (en) * 1932-10-18 1934-08-21 City Auto Stamping Co Process of electroplating bronze
US2079842A (en) * 1935-11-16 1937-05-11 Cinamon Lionel Electroplating bath composition and method of producing the same
US2216605A (en) * 1938-03-30 1940-10-01 Special Chemicals Corp Electroplating
US2397522A (en) * 1939-10-25 1946-04-02 City Auto Stamping Co Process for the electrodeposition of tin alloys
US2436316A (en) * 1946-04-25 1948-02-17 Westinghouse Electric Corp Bright alloy plating
US2468825A (en) * 1944-12-21 1949-05-03 Westinghouse Electric Corp Plating
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US1536859A (en) * 1924-06-05 1925-05-05 Udylite Process Company Electroplating
US1970548A (en) * 1931-10-19 1934-08-21 City Auto Stamping Co Metal finish
US1970549A (en) * 1932-10-18 1934-08-21 City Auto Stamping Co Process of electroplating bronze
US2079842A (en) * 1935-11-16 1937-05-11 Cinamon Lionel Electroplating bath composition and method of producing the same
US2216605A (en) * 1938-03-30 1940-10-01 Special Chemicals Corp Electroplating
US2511395A (en) * 1939-02-20 1950-06-13 City Auto Stamping Co Process for the electrodeposition of tin alloys
US2397522A (en) * 1939-10-25 1946-04-02 City Auto Stamping Co Process for the electrodeposition of tin alloys
US2468825A (en) * 1944-12-21 1949-05-03 Westinghouse Electric Corp Plating
US2436316A (en) * 1946-04-25 1948-02-17 Westinghouse Electric Corp Bright alloy plating

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2854388A (en) * 1955-03-14 1958-09-30 City Auto Stamping Co Electrodeposition of copper-tin alloys
US2885331A (en) * 1956-10-24 1959-05-05 Du Pont Copper plating
US2886500A (en) * 1956-11-01 1959-05-12 Battelle Development Corp Electroplating of copper alloys
US3440151A (en) * 1965-06-02 1969-04-22 Robert Duva Electrodeposition of copper-tin alloys
US4565608A (en) * 1983-11-02 1986-01-21 Degussa Aktiengesellschaft Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings
US4605474A (en) * 1983-11-02 1986-08-12 Gerd Hoffacker Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings
WO2004011663A2 (de) 2002-07-24 2004-02-05 Schering Aktiengesellschaft Mikrobiologische verfahren zur herstellung von 7alpha-substituierten 11alpha-hydroxysteroiden
US20060068234A1 (en) * 2004-09-24 2006-03-30 Jarden Zinc Products, Inc. Electroplated metals with silvery-white appearance and method of making
US20060068219A1 (en) * 2004-09-24 2006-03-30 Alltrista Zinc Products, L.P. Electroplated metals with silvery-white appearance and method of making
WO2006036479A1 (en) * 2004-09-24 2006-04-06 Jarden Zinc Products, Inc. Electroplated metals with silvery-white appearance and method of making
US7296370B2 (en) * 2004-09-24 2007-11-20 Jarden Zinc Products, Inc. Electroplated metals with silvery-white appearance and method of making
JP2008515050A (ja) * 2004-09-24 2008-05-08 ジャーデン ジンク プロダクツ，インコーポレイテッド 電気めっきされた外観が銀白色の金属とその製造方法
EP1791693A4 (en) * 2004-09-24 2009-02-25 Jarden Zinc Products Inc METALS DEPOSITED BY ELECTRODEPOSITION HAVING A SILVER WHITE APPEARANCE AND PROCESS FOR PRODUCING THE SAME
KR100906008B1 (ko) * 2004-09-24 2009-07-06 자덴 징크 프로덕츠, 인코포레이티드 은백색 외관을 갖는 전기도금된 금속 및 그 제조방법
JP4927742B2 (ja) * 2004-09-24 2012-05-09 ジャーデン ジンク プロダクツ，エルエルシー 電気めっきされた外観が銀白色のコイン
IT202100008084A1 (it) * 2021-03-31 2022-10-01 Bluclad S P A Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno

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BE496261A (en))
CH294029A (fr) 1953-10-31
GB680937A (en) 1952-10-15
DE860300C (de) 1952-12-18
FR1019841A (fr) 1953-01-27
NL75841C (en))

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