US3620822A - Process of copper plating super-refined steel - Google Patents
Process of copper plating super-refined steel Download PDFInfo
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- US3620822A US3620822A US778117A US3620822DA US3620822A US 3620822 A US3620822 A US 3620822A US 778117 A US778117 A US 778117A US 3620822D A US3620822D A US 3620822DA US 3620822 A US3620822 A US 3620822A
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- copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
Definitions
- PROCESS OF COPPER PLATING SUPER-REFINED STEEL This invention relates to a process for the currentless copper plating of ferrous metal, and more particularly it relates to a method for the currentless copper plating of superrefined steel through cementation by treatment with an aqueous, acidic copper solution.
- organic inhibitors which will suppress the dissolution of iron in the coating bath.
- These inhibitors are added to a copper plating solution which contains fluoride, bromide, or chloride ions, in addition to hydrogen ions, and include various coal-tar bases, bases extracted from distillation products, aldehyde-amine reaction products, aldehyde-ketone reaction products, various amino-acids, alkaloids, such as quinine, quinoidine, sulfated derivatives of these, and the like.
- polyhydroxy thiols are proposed as inhibitors while another process proposes the use of ethoxylated long chain aliphatic amines as modifying materials.
- adipic alcohols condensation products of adipic alcohols, adipic acids, tall oil, alkyl phenolene, adipic amines, ethylene oxide substituted thio-uric acids; long chain organic amines; reducing sugars; decomposition products of sugar; quaternary ammonium salts, such as, laurylpyredinium sulfate; aryl sulfides and sulfoxides.
- acridine and various acridine derivatives as inhibitors or modifying agents for a currentless copper plating bath which is an aqueous acidic solution containing copper ions and chloride ions.
- a further object of the present invention is to provide an improved currentless copper plating process, which process is capable of forming a satisfactory copper coating on superrefined steel surfaces.
- the drawing is a phase diagram illustrating the concentration ranges for various bath components at several temperatures.
- the present invention includes a process for producing a copper plating on ferrous metal, without the use of current, which process comprises contacting the ferrous metal surface with an aqueous acidic solution containing copper ions, hydrogen ions, and fluoride ions, which solution is free of inhibitors, and maintaining the solution in contact with the ferrous surface until the desired copper coating is obtained, wherein the concentration of the fluoride ions is maintained within the limits denoted by the following coordinates depending upon the solution temperature:
- the ferrous metal surface to be plated is brought into contact with an aqueous acidic solution which consists essentially of copper ions, hydrogen ions, and fluoride ions and is free of inhibitors and which contain the hydrogen ions and fluoride ions within the limits set forth hcreinabove, which limits are a function of the temperature of the coating solution.
- an aqueous acidic solution which consists essentially of copper ions, hydrogen ions, and fluoride ions and is free of inhibitors and which contain the hydrogen ions and fluoride ions within the limits set forth hcreinabove, which limits are a function of the temperature of the coating solution.
- the concentration of both the hydrogen ion and fluoride ions in the coating baths of the present invention are important and should be within the limits which have been indicated, the effect of the copper ion concentration on the bath performance has not been found to be as great. Accordingly, any copper ion concentration in the bath which will produce the desired copper plating on the metal surfaces treated may be used although, preferably, the copper ion concentration will be from about 5 to 60 grams per liter, calculated as CuSO,-5H,O.
- the plating baths of the present invention desirably also contain nitrate and/or sulfate and/or chloride ions. Generally, it is preferred that these ions be introduced into the coating bath as the anions of compounds containing the copper or hydrogen cation.
- the coating baths of the present invention may be formulated by using copper sulfate or copper nitrate as the source of copper ions, nitrate ions and/or sulfate ions, and sulfuric acid, hydrochloric acid, or nitric acid, as the source of hydrogen ions, chloride ions, sulfate ions, or nitrate ions.
- the fluoride ions are desirably introduced into the solution as hydrogen fluoride, thus providing a source of both hydrogen ions and fluoride ions.
- other compounds containing these ions may also be used in formulating the plating solutions of the present invention, provided such compounds are water soluble and do not contain anions or cations which are detrimental to the coating bath or have an adverse effect on the copper plating obtained.
- Typical of such compounds which may be used are the alkali metal compounds, such as sodium fluoride, sodium sulfate, sodium nitrate and the like.
- the specific compounds used in formulating the plating baths will be chosen so that the resulting bath contains the hydrogen ions and fluoride ions in the indicated amounts for the particular bath temperature which is to be used.
- super-refined steel in referring to super-refined steel, it is intended to include those rust and acid resistant super alloys which contain at least about 13 percent of chromium and/or nickel. Such alloys have a low carbon content, typically less than about 0.1 percent, and may also contain other elements, such as molybdenum, titanium, and the like. While the present process and coating solutions may be used to form satisfactory copper coatings on various ferrous metal surfaces, the advantages of the present invention become particularly apparent when it is used in the treatment of the super-refined steels, which steels have not, heretofore, been capable of being coated with the currentless copper plating solutions of the prior art.
- the fluoride concentration, given in moles per liter is the ordinate while the hydrogen ion concentration, given in moles per liter, is the abscissa for temperatures of C., 35 C., 50 C., and 55 C. It is found that those copper coating compositions in which the concentration of hydrogen and fluoride ions are within the areas bordered by the heavy lines will produce light colored, satisfactory platings.
- the lower treatment temperatures are, generally, more desirable, with treatment temperatures at about room temperature being particularly suitable.
- the concentration ranges for the bath components are not as narrow as is the case when higher treatment temperatures are used.
- the lower treating temperatures there is a wider range of component concentrations which will produce satisfactory results so that a less stringent control on the bath concentration is necessary than when operating at the higher temperatures.
- the hydrogen and fluoride ion concentrations must be maintained between such narrow limits that it becomes very difficult to obtain satisfactory copper plating with the operating control conditions which prevail in many commercial plating operations.
- the copper plating bath is formulated so as to contain the desired components in the amounts which have been indicated hereinabove.
- This aqueous acidic copper coating bath is then brought into contact with the ferrous metal surface, such as a surface of super refined steel, for a period sufficient to effect the formation of the desired copper coating on the metal surface.
- the ferrous metal surface such as a surface of super refined steel
- immersion contacting techniques are generally preferred.
- the workpiece is subjected to suitable pretreating operations, such as degreasing, pickling and the like. Thereafter, the copper plating bath is brought into contact with the workpiece and maintained until the desired copper coating is obtained.
- the contact times will be from about 15 to 60 minutes, although other suitable contact times may also be used which will produce a satisfactory coating.
- a copper deposit typically having a coating weight of from about 5 to 30 grams per square meter, will be produced on the metal surface treated.
- variations in the thickness of the coating may be obtained by shortening or lengthening the duration of the treatment.
- EXAMPLE 2 Super-refined steel wires of the quality given in the preceding example were treated in the same copper plating solution, using a treatment temperature of 20 C. and immersion time of 20 minutes. After removing the wires from the treating solution, rinsing them with cold water and drying, the wires were found to have a light-colored uniform copper coating of excellent hardness with a coating weight of 5 grams per square meter.
- EXAMPLE 3 Super-refined steel wires of the quality set forth in example 1 were pretreated as in that example and then immersed for 20 minutes at a temperature of 20 C. in a copper plating bath having the following composition:
- a process for producing a copper plating on ferrous metal without the use of current which comprises contacting a super-refined steel surface to be coated with an aqueous acidic solution consisting essentially of copper ions, hydrogen ions and fluoride ions, which solution is free of inhibitors, and maintaining the solution in contact with the surface until the desired copper coating is obtained, wherein the concentration of the fluoride ions is maintained within the limits given in the figure of the drawing as a function of temperature and delineated by the following coordinates:
- the coating solution also contains at least one additional ion selected from nitrate, sulfate and chloride ions.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
Abstract
Description
Claims (4)
- 2. The process as claimed in claim 1 wherein the coating solution contains from about 5 to 60 grams per liter of copper calculated as CuS04.5H20.
- 3. The process as claimed in claim 2 wherein the coating solution also contains at least one additional ion selected from nitrate, sulfate and chloride ions.
- 4. The process as claimed in claim 3 wherein the treatment of the surface is carried out at a temperature within the range of 20 to 70 degrees C.
- 5. The process as claimed in claim 4 wherein the treatment of the surface is carried out at a temperature of about 20 degrees C.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US77811768A | 1968-11-22 | 1968-11-22 |
Publications (1)
Publication Number | Publication Date |
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US3620822A true US3620822A (en) | 1971-11-16 |
Family
ID=25112352
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US778117A Expired - Lifetime US3620822A (en) | 1968-11-22 | 1968-11-22 | Process of copper plating super-refined steel |
Country Status (1)
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US (1) | US3620822A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3751289A (en) * | 1971-08-20 | 1973-08-07 | M & T Chemicals Inc | Method of preparing surfaces for electroplating |
US4199623A (en) * | 1974-11-01 | 1980-04-22 | Kollmorgen Technologies Corporation | Process for sensitizing articles for metallization and resulting articles |
US4450190A (en) * | 1977-05-13 | 1984-05-22 | Kollmorgen Technologies Corporation | Process for sensitizing articles for metallization and resulting articles |
US5776231A (en) * | 1994-11-11 | 1998-07-07 | Metallgesellschaft Aktiengesellschaft | Concentrate for the electroless deposition of copper coatings on iron and iron alloy surfaces |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2111199A (en) * | 1935-12-12 | 1938-03-15 | Du Pont | Flash copper coating |
US2217921A (en) * | 1938-03-23 | 1940-10-15 | American Chem Paint Co | Art of drawing ferrous metal |
US2410844A (en) * | 1942-01-14 | 1946-11-12 | Du Pont | Metal plating process |
US2445372A (en) * | 1945-04-26 | 1948-07-20 | American Steel & Wire Co | Process of copper coating stainless steel |
US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
US2814589A (en) * | 1955-08-02 | 1957-11-26 | Bell Telephone Labor Inc | Method of plating silicon |
US2825682A (en) * | 1953-08-31 | 1958-03-04 | Menasco Mfg Company | Process and composition for coating titanium surfaces |
US3280038A (en) * | 1964-03-20 | 1966-10-18 | Dow Chemical Co | Method for cleaning stainless steel |
-
1968
- 1968-11-22 US US778117A patent/US3620822A/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2111199A (en) * | 1935-12-12 | 1938-03-15 | Du Pont | Flash copper coating |
US2217921A (en) * | 1938-03-23 | 1940-10-15 | American Chem Paint Co | Art of drawing ferrous metal |
US2410844A (en) * | 1942-01-14 | 1946-11-12 | Du Pont | Metal plating process |
US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
US2445372A (en) * | 1945-04-26 | 1948-07-20 | American Steel & Wire Co | Process of copper coating stainless steel |
US2825682A (en) * | 1953-08-31 | 1958-03-04 | Menasco Mfg Company | Process and composition for coating titanium surfaces |
US2814589A (en) * | 1955-08-02 | 1957-11-26 | Bell Telephone Labor Inc | Method of plating silicon |
US3280038A (en) * | 1964-03-20 | 1966-10-18 | Dow Chemical Co | Method for cleaning stainless steel |
Non-Patent Citations (1)
Title |
---|
Metals Handbook, Ohio, American Society of Metals, 1948, p. 557. 156 18 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3751289A (en) * | 1971-08-20 | 1973-08-07 | M & T Chemicals Inc | Method of preparing surfaces for electroplating |
US4199623A (en) * | 1974-11-01 | 1980-04-22 | Kollmorgen Technologies Corporation | Process for sensitizing articles for metallization and resulting articles |
US4450190A (en) * | 1977-05-13 | 1984-05-22 | Kollmorgen Technologies Corporation | Process for sensitizing articles for metallization and resulting articles |
US5776231A (en) * | 1994-11-11 | 1998-07-07 | Metallgesellschaft Aktiengesellschaft | Concentrate for the electroless deposition of copper coatings on iron and iron alloy surfaces |
US6261644B1 (en) | 1994-11-11 | 2001-07-17 | Metallgesellschaft Aktiengesellschaft | Process for the electroless deposition of copper coatings on iron and iron alloy surfaces |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP 32100 STEPHENSON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003942/0016 Effective date: 19810317 |
|
AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
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AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
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AS | Assignment |
Owner name: PARKER CHEMICAL COMPANY, 32100 STEPHENSON HWY., MA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004194/0047 Effective date: 19830928 |