US3914162A - Compositions and process for the electrodeposition of metals - Google Patents
Compositions and process for the electrodeposition of metals Download PDFInfo
- Publication number
- US3914162A US3914162A US373051A US37305173A US3914162A US 3914162 A US3914162 A US 3914162A US 373051 A US373051 A US 373051A US 37305173 A US37305173 A US 37305173A US 3914162 A US3914162 A US 3914162A
- Authority
- US
- United States
- Prior art keywords
- metal
- copper
- electroplating
- cap
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
Definitions
- Position of metals comprises an aqueous wlutlo of (a) a metal ion, (b) a carboxy alkylene amino di(- methylene phosphonic acid) and optionally, (c) 1- hydroxy alkylidene-1,l-diph0sphonic acid.
- the present invention relates to the electrodeposition or electroplating of metals. More particularly, the present invention relates to the composition of the electroplating bath from which the metal is deposited.
- the electrodeposition of metals from aqueous solutions of metal ions is an old art.
- the typical electroplating system consists of an electroplating bath and two or more electrodes.
- the cathode of the electrode system is the object to be plated.
- the anode may be carbon or a solid piece of the metal to be plated upon the cathode.
- a solid metal anode is consumed in the electroplating process and provides a constant source of metal ions to the plating bath.
- Metal ions are maintained in solution in the electroplating bath by forming salts or metal complexes.
- Some of the most popular plating compositions utilize inorganic metal cyanides, and cadmium, brass, copper, silver and zinc can all be plated from cyanide baths.
- Electroplatingbaths comprising aqueous alkaline solution of metal cyanides have several disadvantages. Such baths often tend to produce relatively dull and uneven coatings of the plated metal.
- the use of metal cyanide solutions can also be hazardous since if the pH of the electroplating medium should drop to neutral or below there is a danger of poisonous hydrogen cyanide gas being produced.
- the use of metal cyanides presents a disposal problem due to their toxicity, and removing cyanides from waste baths prior to disposal is an expensive undertaking.
- aqueous solution comprising (a) a divalent or polyvalent metal ion; (b)
- a carboxy alkylene amino di(methylene phosphonic acid) having the structure CH (OM) MOOC (CH N pound having the structure I M O P C PO M wherein M is as above defined and R is an alkyl radical having from 1 to II and preferably from l to 5 carbon atoms.
- Such electroplating bath compositions are particularly useful in plating divalent metal ions at a pH of about 6.0 to 10.0.
- carboxy amino phosphonate or CAP is preferably a divalent transitional metal such as copper.
- iron, nickel, zinc, cadmium or alloys 5 such as brass.
- Monoand trivalent metals are preferably a divalent transitional metal such as copper.
- iron, nickel, zinc, cadmium or alloys 5 such as brass.
- Monoand trivalent metals are preferably a divalent transitional metal such as copper.
- the electroplating bath composition of the present invention is an aqueous solution comprising the metal to be plated, the carboxy amino phosphonate, pH adjusters and optionally one or more additives including brighteners, buffering agents, levelers, and the hydroxy alkylidene diphosphonic acid compound (HAD?) 5 which are intended to improve the performance or life of the bath or the quality of the metal deposit, or to impart other beneficial effect.
- HID hydroxy alkylidene diphosphonic acid compound
- the bath is prepared according to conventional techniques by simply dissolving the desired ingredients into a quantity of water.
- the water is preferably low in mineral content and may be deionized.
- the metal to be plated is often added in the form of a water soluble salt such as a metal sulfate, chloride, phosphate, citrate, carbonate or acetate. Carbonate and acetate salts are often preferred because the anions of these salts may be thermally decomposed and thereby removed from the bath when the metal ion is released.
- the carboxy amino phosphonate may be added directly to the bath in either the acid or a salt form as defined above.
- the acid form is generally preferred simply because it does not introduce extraneous metal or ammonium ions into the bath, but the introduction of such anions is usually not detrimental to the electroplating system.
- the alkylene radical of the CAP compound may have from 3 to about 1 1 carbon atoms as defined above, the preferred compounds are those having alkylene radicals of from about 3 to 6 carbon atoms.
- N-(S-carboxypentyl) amino di(methylene phosphonic acid) is one particularly preferred CAP compound.
- CAP compounds useful in the practice of this invention may be prepared by the method of copending patent application Ser. No. 361,383, filed May 17, 1973, which is commonly assigned with the instant application and is incorporated herein by reference.
- the optimum concentration of metal salt and CAP in the electroplating bath will be largely determined by the identity of the metal and metal salt, and by the characteristics of the individual electroplating system. As a rule, the concentrations are limited primarily by the solubilities of the compounds. Generally speaking, there is usually employed sufficient metal salt and CAP to provide from about 1 percent to about 5 percent by weight of metal in solution and to provide a mole ratio of CAP to metal of from about 1:1 to about 5:1.
- the optimum ratio will again depend to some extent on the metal being plated and the conditions and composition of the electroplating bath but as a general rule at least a slight molar excess of CAP is desirable and it is generally preferred that the mole ratio of CAP to metal ion be within the range of from about 1.2:1 to 2: 1. In most instances, the concentration of complex formed between the metal ion and the CAP should not exceed its solubility at the temperature and pH employed in the electroplating operation.
- the electroplating bath is generally operated within a pH range of from about 6 to 12.
- the optimum pH will depend to a great extent upon the identity of the metal being plated, the presence of extraneous anions within the system and the composition and physical nature of the cathode being plated. Since pH is easily adjusted by the addition of alkaline materials such as alkali metal hydroxides, or acid materials such as mineral acids, it is a relatively simple matter to adjust the pH in either direction until optimum plating characteristics are achieved. As a general rule it is often found that lower pH values, that is within the range of from about 6 to 8, give better results in the practice of this invention than higher pH levels although exceptions to this rule may be found.
- HADP compounds useful in the practice of the present invention may be prepared according to the method of U.S. Pat. No. 3,551,480.
- a particularly preferred HADP compound is l-hydroxy ethylidene-1,l-diphosphonic acid (HEDP).
- HEDP l-hydroxy ethylidene-1,l-diphosphonic acid
- a combination of CAP and HADP is particularly effective to produce bright, uniform, and tightly adhering deposits of copper on brass and steel by electroplating at a pH of about 8.0.
- the concentration of HADP used in the composition of this invention is sufficient to provide a mole ratio of HADP to metal of from about 0.5:1 to about 5:], although from about 1:1 to about 2:1 is preferred.
- present invention further provides a process for the electrodeposition ofa divalent or trivalent metal which comprises the steps of electrolyzing an aqueous solution of a metal complex consisting of any of the metal ions hereinbefore described, a CAP compound, and any of the optional additives hereinbefore described.
- metals such as copper, iron, nickel, zinc and cadmium may be electrically deposited upon a cathode such as steel, aluminum, brass, zinc and the like.
- the electroplating bath is maintained at a temperature within the range of the freezing point to boiling point of the bath, generally within a range of from about 30C. to about C. For reasons of current efficiencies it has been found preferable to maintain the temperature of the electroplating bath within the range from about 50C. to about 80C.
- the amount of current employed in the electrodeposition may vary widely, depending upon the particular metal being plated, the temperature of the bath and whether or not the bath is agitated during the electroplating process. In general, the amount of current employed will be sufficient to provide a current density of from about 1 to 300 amperes per square foot of electrode surface. Ordinarily when the electroplating bath is quiescent or unagitated, the current density will be in the range of from about 5 to amperes per square foot, while when the electroplating bath is agitated current densities up to about 300 amperes per square foot may be utilized. The optimum or preferred current density for any particular electroplating situation will depend upon the individual characteristics of the operation and is readily determined by employing conventional electroplating techniques.
- the time required to electroplate or to electrically deposit the metal will vary with the kind of metal, the current density, and bath composition and concentration, as well as upon the thickness of the plate or deposit desired. Generally, the greater the current density, the shorter will be the time required to produce a metal deposit or plate of a given thickness.
- copper is electrically deposited upon a wide variety of base metals or substrates such as zinc, iron, brass, steel, aluminum and the like.
- This preferred process comprises passing an electric current, at a density in the range of from about 5 to about 150 amperes per square foot of cathode surface, through an aqueous solution containing divalent copper ions and CAP or CAP HADP and having a pH in the range of from about 6.0 to about 10.0 and preferably 6.0 to 8.0.
- the concentration of copper in the electroplating bath composition is preferably from about 1% to about 5 percent by weight, based on the weight of the solution.
- the temperature of the solution is preferably maintained within the range of from about 50C. to about 70C. during the electroplating operation.
- the electroplating solutions of the present invention can contain known brighteners, buffers, and leveling agents and other additives commonly used in electroplating operations.
- Boric acid and its salts are compatible buffers for many formulas of the invention, and selenites and arsenites are useful brighteners for copper plating baths while aldehydes and ketones are useful for zinc plating.
- Other additives which may be employed in the electroplating solutions of the present invention include those disclosed in the 39th Annual Edition of Metal Finishing Guidebook Directory, 1973, published by Metals and Plastics Publications, Inc., 99 Kinderkamack Road, Westwook, NJ.
- the plating solutions identified as Test Nos. 1-9 in Table I were individually prepared in deionized water by dissolving measured amounts of CAP and/or HEDP and copper sulfate to provide 2 percent copper and the molar ratio of CAP/HEDP/Cu indicated in Table I.
- the pH of each solution was adjusted to the desired value of 6.0, 8.0, or 10.0 by the addition of potassium hydroxide.
- the solution was heated up to 80C. and stirred vigorously for an additional minutes.
- the solutions were cooled, if necessary, to the plating temperature of 70C. and transferred to a Hull Cell".
- the particular additive utilized, the additive of copper mole ratio and the percent copper in solution are all shown in Table I.
- the Hull Cell is constructed substantially as the electrolysis cell described in US. Pat. No. 2,149,344. This type of Hull Cell is standard equipment for the evaluation of electroplating solutions by the subjective determination of brightness rating" as based on the width of the brightness range, uniformity of brightness, and the presence or absence of smudges, stains and discoloration. In addition, the effectiveness of the bath is also evaluated on the basis of adhesion of plated metal to the cathode.
- the particular cathodes utilized in this test were brass or steel as indicated in Table l and were each 5 X 3 /4 inches in size. The anode utilized in these tests was made of copper and was 2% X 2% inches in size.
- the Hull Cell utilized in this test had a capacity of 1,000 milliliters.
- Test No. 5 accordingly represents a particularly preferred embodiment of the present invention.
- Tests Nos. 7-9 are controls illustrating the results obtained with HEDP alone under similar electroplating conditions. It is observed that HEDP performs best at the higher pH of 10.0, but the quality of the plate is still inferior to that obtained with the combination of CAP and HEDP.
- a process for the electrodeposition of divalent and polyvalent metal ions which comprises the steps of electrolyzing an aqueous solution comprising a. a divalent or polyvalent metal ion,
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US373051A US3914162A (en) | 1973-06-25 | 1973-06-25 | Compositions and process for the electrodeposition of metals |
AR254353A AR207452A1 (es) | 1973-06-25 | 1974-01-01 | Un procedimiento para la electrodeposicion de iones metalicos divalentes y polivalentes y una composicion de bano glavanoplastico para la ejecucion de dicho procedimiento |
CA203,082A CA1038325A (fr) | 1973-06-25 | 1974-06-21 | Composes et procede d'electrodeposition sur metaux |
SE7408241A SE7408241L (fr) | 1973-06-25 | 1974-06-24 | |
IT24337/74A IT1015337B (it) | 1973-06-25 | 1974-06-24 | Composizione e procedimento per la deposizione elettrolitica di metal li |
JP49071438A JPS5036322A (fr) | 1973-06-25 | 1974-06-24 | |
FR7421880A FR2234388B1 (fr) | 1973-06-25 | 1974-06-24 | |
BR5129/74A BR7405129D0 (pt) | 1973-06-25 | 1974-06-24 | Processo e composicao para a eletrodeposicao de metais |
DE2430250A DE2430250A1 (de) | 1973-06-25 | 1974-06-24 | Verfahren zum galvanischen abscheiden von metallen und elektrolytbad zur durchfuehrung des verfahrens |
GB2793974A GB1438080A (fr) | 1973-06-25 | 1974-06-24 | |
BE145834A BE816806A (fr) | 1973-06-25 | 1974-06-25 | Compositions a base d'acide phosphonique et procede pour le depot electrolytique de metaux |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US373051A US3914162A (en) | 1973-06-25 | 1973-06-25 | Compositions and process for the electrodeposition of metals |
Publications (2)
Publication Number | Publication Date |
---|---|
USB373051I5 USB373051I5 (fr) | 1975-01-28 |
US3914162A true US3914162A (en) | 1975-10-21 |
Family
ID=23470708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US373051A Expired - Lifetime US3914162A (en) | 1973-06-25 | 1973-06-25 | Compositions and process for the electrodeposition of metals |
Country Status (11)
Country | Link |
---|---|
US (1) | US3914162A (fr) |
JP (1) | JPS5036322A (fr) |
AR (1) | AR207452A1 (fr) |
BE (1) | BE816806A (fr) |
BR (1) | BR7405129D0 (fr) |
CA (1) | CA1038325A (fr) |
DE (1) | DE2430250A1 (fr) |
FR (1) | FR2234388B1 (fr) |
GB (1) | GB1438080A (fr) |
IT (1) | IT1015337B (fr) |
SE (1) | SE7408241L (fr) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2461024A1 (fr) * | 1979-07-13 | 1981-01-30 | Oxy Metal Industries Corp | Procedes et compositions de depot electrolytique d'argent, utilisant des composes d'argent, des electrolytes sans cyanure et des composes de phosphonate organique |
US4307038A (en) * | 1977-07-20 | 1981-12-22 | Benckiser-Knapsack Gmbh | N-Carboxy alkyl amino alkane polyphosphonic acids |
US4469569A (en) * | 1983-01-03 | 1984-09-04 | Omi International Corporation | Cyanide-free copper plating process |
US4979987A (en) * | 1988-07-19 | 1990-12-25 | First Miss Gold, Inc. | Precious metals recovery from refractory carbonate ores |
US5021324A (en) * | 1990-10-05 | 1991-06-04 | Polychrome Corporation | Printing plate protectant |
US5266212A (en) * | 1992-10-13 | 1993-11-30 | Enthone-Omi, Inc. | Purification of cyanide-free copper plating baths |
US5607570A (en) * | 1994-10-31 | 1997-03-04 | Rohbani; Elias | Electroplating solution |
US7604783B2 (en) | 2004-12-22 | 2009-10-20 | Placer Dome Technical Services Limited | Reduction of lime consumption when treating refractor gold ores or concentrates |
US8061888B2 (en) | 2006-03-17 | 2011-11-22 | Barrick Gold Corporation | Autoclave with underflow dividers |
US8252254B2 (en) | 2006-06-15 | 2012-08-28 | Barrick Gold Corporation | Process for reduced alkali consumption in the recovery of silver |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52106331A (en) * | 1976-03-05 | 1977-09-06 | Kosaku Kk | Plating bath |
USH325H (en) | 1980-07-30 | 1987-09-01 | Richardson Chemical Company | Electroless deposition of transition metals |
DE3347593A1 (de) * | 1983-01-03 | 1984-07-05 | Omi International Corp., Warren, Mich. | Waessriger alkalischer cyanidfreier kupferelektrolyt und verfahren zur galvanischen abscheidung einer kornverfeinerten duktilen und haftfesten kupferschicht auf einem leitfaehigen substrat |
WO2018181190A1 (fr) * | 2017-03-31 | 2018-10-04 | メタローテクノロジーズジャパン株式会社 | Solution de dépôt d'argent électrolytique |
CN114892225B (zh) * | 2021-09-30 | 2023-03-14 | 深圳市联合蓝海黄金材料科技股份有限公司 | 用于在镍镀层上电镀金的镀液和在镍镀层上电镀金的方法和镀金件与应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2673214A (en) * | 1952-06-11 | 1954-03-23 | Bersworth | Polyhydroxyamino acid compounds |
US2961311A (en) * | 1955-12-13 | 1960-11-22 | Dow Chemical Co | Metal ion control |
US3293176A (en) * | 1964-04-01 | 1966-12-20 | Le Roy A White | Method of chelating with an ethergroup-containing sequestering agent |
US3394172A (en) * | 1965-02-25 | 1968-07-23 | Henkel & Cie Gmbh | Perhydrates of nitrogen-containing phosphonic acids and process for their manufacture |
US3475293A (en) * | 1964-09-22 | 1969-10-28 | Monsanto Co | Electrodeposition of metals |
US3617343A (en) * | 1967-12-09 | 1971-11-02 | Knapsack Ag | Process for the chemical nickel-plating of nonmetallic articles |
US3706635A (en) * | 1971-11-15 | 1972-12-19 | Monsanto Co | Electrochemical compositions and processes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1392242A (en) * | 1971-07-26 | 1975-04-30 | Technic | Process for producing by electrodeposition bright deposits of gold and its alloys |
-
1973
- 1973-06-25 US US373051A patent/US3914162A/en not_active Expired - Lifetime
-
1974
- 1974-01-01 AR AR254353A patent/AR207452A1/es active
- 1974-06-21 CA CA203,082A patent/CA1038325A/fr not_active Expired
- 1974-06-24 GB GB2793974A patent/GB1438080A/en not_active Expired
- 1974-06-24 JP JP49071438A patent/JPS5036322A/ja active Pending
- 1974-06-24 FR FR7421880A patent/FR2234388B1/fr not_active Expired
- 1974-06-24 DE DE2430250A patent/DE2430250A1/de not_active Withdrawn
- 1974-06-24 IT IT24337/74A patent/IT1015337B/it active
- 1974-06-24 BR BR5129/74A patent/BR7405129D0/pt unknown
- 1974-06-24 SE SE7408241A patent/SE7408241L/xx unknown
- 1974-06-25 BE BE145834A patent/BE816806A/fr unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2673214A (en) * | 1952-06-11 | 1954-03-23 | Bersworth | Polyhydroxyamino acid compounds |
US2961311A (en) * | 1955-12-13 | 1960-11-22 | Dow Chemical Co | Metal ion control |
US3293176A (en) * | 1964-04-01 | 1966-12-20 | Le Roy A White | Method of chelating with an ethergroup-containing sequestering agent |
US3475293A (en) * | 1964-09-22 | 1969-10-28 | Monsanto Co | Electrodeposition of metals |
US3394172A (en) * | 1965-02-25 | 1968-07-23 | Henkel & Cie Gmbh | Perhydrates of nitrogen-containing phosphonic acids and process for their manufacture |
US3617343A (en) * | 1967-12-09 | 1971-11-02 | Knapsack Ag | Process for the chemical nickel-plating of nonmetallic articles |
US3706635A (en) * | 1971-11-15 | 1972-12-19 | Monsanto Co | Electrochemical compositions and processes |
Non-Patent Citations (1)
Title |
---|
H Koretzky, IBM Tech. Disclosure Bulletin, Vol. 9, No. 11, p. 1634, April 1967. * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4307038A (en) * | 1977-07-20 | 1981-12-22 | Benckiser-Knapsack Gmbh | N-Carboxy alkyl amino alkane polyphosphonic acids |
US4308147A (en) * | 1977-07-20 | 1981-12-29 | Benckiser-Knapsack Gmbh | Composition and treating aqueous solutions with N-carboxy alkyl amino alkane polyphosphonic acids and their alkali metal salts |
FR2461024A1 (fr) * | 1979-07-13 | 1981-01-30 | Oxy Metal Industries Corp | Procedes et compositions de depot electrolytique d'argent, utilisant des composes d'argent, des electrolytes sans cyanure et des composes de phosphonate organique |
US4265715A (en) * | 1979-07-13 | 1981-05-05 | Oxy Metal Industries Corporation | Silver electrodeposition process |
US4469569A (en) * | 1983-01-03 | 1984-09-04 | Omi International Corporation | Cyanide-free copper plating process |
US4979987A (en) * | 1988-07-19 | 1990-12-25 | First Miss Gold, Inc. | Precious metals recovery from refractory carbonate ores |
US5021324A (en) * | 1990-10-05 | 1991-06-04 | Polychrome Corporation | Printing plate protectant |
US5266212A (en) * | 1992-10-13 | 1993-11-30 | Enthone-Omi, Inc. | Purification of cyanide-free copper plating baths |
US5607570A (en) * | 1994-10-31 | 1997-03-04 | Rohbani; Elias | Electroplating solution |
US7604783B2 (en) | 2004-12-22 | 2009-10-20 | Placer Dome Technical Services Limited | Reduction of lime consumption when treating refractor gold ores or concentrates |
US8029751B2 (en) | 2004-12-22 | 2011-10-04 | Placer Dome Technical Services Limited | Reduction of lime consumption when treating refractory gold ores or concentrates |
US8061888B2 (en) | 2006-03-17 | 2011-11-22 | Barrick Gold Corporation | Autoclave with underflow dividers |
US8252254B2 (en) | 2006-06-15 | 2012-08-28 | Barrick Gold Corporation | Process for reduced alkali consumption in the recovery of silver |
Also Published As
Publication number | Publication date |
---|---|
FR2234388A1 (fr) | 1975-01-17 |
GB1438080A (fr) | 1976-06-03 |
FR2234388B1 (fr) | 1978-02-17 |
BR7405129D0 (pt) | 1975-01-21 |
IT1015337B (it) | 1977-05-10 |
USB373051I5 (fr) | 1975-01-28 |
CA1038325A (fr) | 1978-09-12 |
JPS5036322A (fr) | 1975-04-05 |
BE816806A (fr) | 1974-12-27 |
SE7408241L (fr) | 1974-12-27 |
DE2430250A1 (de) | 1975-01-23 |
AR207452A1 (es) | 1976-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3706634A (en) | Electrochemical compositions and processes | |
US3914162A (en) | Compositions and process for the electrodeposition of metals | |
KR101502804B1 (ko) | Pd 및 Pd-Ni 전해질 욕조 | |
US3785939A (en) | Tin/lead plating bath and method | |
US4098656A (en) | Bright palladium electroplating baths | |
US3749649A (en) | Bright tin-lead alloy plating | |
US4469569A (en) | Cyanide-free copper plating process | |
GB2144769A (en) | Zinc and zinc alloy electroplating | |
US2436316A (en) | Bright alloy plating | |
US3475293A (en) | Electrodeposition of metals | |
US3672969A (en) | Electrodeposition of gold and gold alloys | |
US4066517A (en) | Electrodeposition of palladium | |
US3879270A (en) | Compositions and process for the electrodeposition of metals | |
JP6073450B2 (ja) | 環境に優しい金電気めっき組成物及び方法 | |
CA1103197A (fr) | Electrodeposition sur alliages or et cobalt | |
US4515663A (en) | Acid zinc and zinc alloy electroplating solution and process | |
US3149058A (en) | Bright gold plating process | |
US3902977A (en) | Gold plating solutions and method | |
US4554219A (en) | Synergistic brightener combination for amorphous nickel phosphorus electroplatings | |
US4391679A (en) | Electrolytic bath and process for the deposition of gold alloy coatings | |
US4184929A (en) | Trivalent chromium plating bath composition and process | |
EP0663460A1 (fr) | Bain de dépôt électrolytique d'un alliage étain-zinc et procédé d'électrodéposition utilisant ledit bain | |
US3928147A (en) | Method for electroplating | |
US4478692A (en) | Electrodeposition of palladium-silver alloys | |
US4129482A (en) | Electroplating iron group metal alloys |