US2679475A - Metal blackening composition and method - Google Patents
Metal blackening composition and method Download PDFInfo
- Publication number
- US2679475A US2679475A US267509A US26750952A US2679475A US 2679475 A US2679475 A US 2679475A US 267509 A US267509 A US 267509A US 26750952 A US26750952 A US 26750952A US 2679475 A US2679475 A US 2679475A
- Authority
- US
- United States
- Prior art keywords
- blackening
- chloride
- composition
- metal
- metals
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 28
- 239000002184 metal Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 title description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 229910001369 Brass Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010951 brass Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 150000002739 metals Chemical class 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 235000018660 ammonium molybdate Nutrition 0.000 description 8
- 239000011609 ammonium molybdate Substances 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 8
- 229940010552 ammonium molybdate Drugs 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- STECJAGHUSJQJN-USLFZFAMSA-N LSM-4015 Chemical compound C1([C@@H](CO)C(=O)OC2C[C@@H]3N([C@H](C2)[C@@H]2[C@H]3O2)C)=CC=CC=C1 STECJAGHUSJQJN-USLFZFAMSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Definitions
- This invention relates to metal blackening and especially to compositions and methods for use in blackening metals bydipping or plating processes.
- the general object of the present invention is to provide a novel metal blackening composition which is characterized by its ability to produce a desirable black finish upon metals with the finish being permanently bonded to the base metal.
- Another object of the invention is to provide a basic composition which can be varied slightly to make it adaptable for use in blackening certain special metals by dipping or plating operations.
- Another object of the invention is to provide a metal blackening composition for treating substantially any metal to give it a permanent black surface.
- Yet another object of the invention is to provide a relatively inexpensive composition and method for use in blackening metals.
- the present invention broadly relates to a new composition for use in blackening substantially any and all metals, such as brass, copper, nickel, stainless steel, aluminum, zinc or cadmium, or alloys of such metals, by a dipping or plating process, and this composition basically comprises relatively large amounts of nickel and ammonium chlorides and small amounts of Rochelle salt and zinc chloride.
- Example I One specific composition that has been particularly suitable for blackening stainless steel is one which includes the following materials in the quantities (dry weight) indicated:
- ammonium molybdate seems to be vital to the composition for blackening cadmium by dipping, but a small amount of ammonium molybdate aids in securing the action desired in blackening other metals by an electroplating action. In general, the molybdate appears to speed up the blackening action and give a deep black color on the finished product.
- sodium chloride is present in the composition primarily as an electrical conductor but it also aids in obtaining the action desired.
- Example II Another illustration of my composition with the limits of variation in the quantities of materials (dry weight) used for blackening metals such as stainless steel, brass, copper, steel, aluminum and cadmium, or their alloys, would be as follows:
- Nickel chloride About 6 to 12 oz. Ammonium chloride About 3 to 6 oz. Rochelle salt About to 1 oz. Zinc chloride About to 1 oz. Sodium chloride About 1 to 3 oz. Ammonium molybdate About A; oz. Water 1 gallon
- the foregoing composition has given excellent results in providing a desirable blackening action on most metals and their alloys. The composition even is satisfactory for use in treating stainless steel. Variations in the compositions within the limits stated vary the speed of the action slightly but do not materially alter the action secured.
- Zinc articles can be coated by use of my novel composition by either dipping the zinc articles in baskets or by an electroplating process, and cadmium articles can be similarly processed.
- the articles are the cathodes and the anodes are made from stainless steel or, preferably, nickel.
- Example I The specific composition set forth in Example I has given particularly good results on metal articles made from the metals indicated, or with a finish surface of such metals. A very black, tightly bonded coat is obtained in only a few minutes by practice of the invention.
- a composition for blackening metals of the class consisting of brass, copper, nickel, steel, aluminum, zinc, stainless steel, and cadmium by an electroplating process which composition consists essentially of by dry weight, about 8 parts nickel chloride, about 4 parts of ammonium chloride, about 1 part of Rochelle salt, about part of zinc chloride, about 2 parts of sodium chloride, about part of ammonium molybdate, and water.
- a composition for blackening cadmium by a what I dipping process which composition consists essentially of by dry weight, about 8 parts nickel chloride, about 4 parts of ammonium chloride, about 1 part of Rochelle salt, about parts of zinc chloride, about 2 parts of sodium chloride and a small amount of ammonium molybdate, and water.
- a composition for use in blackening metals which composition consists essentially of by dry weight about 6 to 12 parts nickel chloride, about 3 to 6 parts ammonium chloride, about to 1 /2 parts of Rochelle salt, about to 1 part zinc chloride, about 1 to 3 parts sodium chloride, at small quantity of ammonium molybdate, and water.
- a process of blackening a metal surface from the class consisting of steel, brass, copper, aluminum, nickel and cadmium comprising immersing the metal surface in a water bath consisting essentially of per gallon of water about 8 oz. nickel chloride; about 4 oz. of ammonium chloride; about 1 oz. of Rochelle salt; about oz. of zinc chloride; about 2 oz. of sodium chloride; and about oz. of ammonium molybdate, and passing a low voltage electrical current therethrough with the metal as the cathode.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Description
Patented May 25, 1954 OFFICE METAL BLACKENING COMPOSITION AND METHOD Joseph C. Singler, Cleveland, Ohio N 0 Drawing.
This invention relates to metal blackening and especially to compositions and methods for use in blackening metals bydipping or plating processes.
Heretofore there have been some efforts made to provide blackened finishes on metals for some uses, but mostly such black finishes would. not have sufiicient adherence to the base metal as to be satisfactory. Furthermore, not all metals could be blackened. Thus previous compositions and methods for blackening metals have, insofar as I am aware, not been completely satisfactory for one or more reasons.
The general object of the present invention is to provide a novel metal blackening composition which is characterized by its ability to produce a desirable black finish upon metals with the finish being permanently bonded to the base metal.
Another object of the invention is to provide a basic composition which can be varied slightly to make it adaptable for use in blackening certain special metals by dipping or plating operations.
Another object of the invention is to provide a metal blackening composition for treating substantially any metal to give it a permanent black surface.
Yet another object of the invention is to provide a relatively inexpensive composition and method for use in blackening metals.
The foregoing and other objects and advantages of the invention will be made more apparent as the specification proceeds.
The present invention broadly relates to a new composition for use in blackening substantially any and all metals, such as brass, copper, nickel, stainless steel, aluminum, zinc or cadmium, or alloys of such metals, by a dipping or plating process, and this composition basically comprises relatively large amounts of nickel and ammonium chlorides and small amounts of Rochelle salt and zinc chloride.
Example I One specific composition that has been particularly suitable for blackening stainless steel is one which includes the following materials in the quantities (dry weight) indicated:
About 4 oz. of ammonium chloride;
About 8 02. of nickel chloride;
About 1 oz. of Rochelle salt;
About oz. of zinc chloride;
About 2 oz. of sodium chloride;
About oz. of ammonium molybdate; and About 1 gal. of water.
Application January 21, 1952, Serial No. 267,509
4 Claims. (01. 204-43) Of the materials listed, the ammonium molybdate seems to be vital to the composition for blackening cadmium by dipping, but a small amount of ammonium molybdate aids in securing the action desired in blackening other metals by an electroplating action. In general, the molybdate appears to speed up the blackening action and give a deep black color on the finished product.
It appears that a small amount of sodium chloride is present in the composition primarily as an electrical conductor but it also aids in obtaining the action desired.
Example II Another illustration of my composition with the limits of variation in the quantities of materials (dry weight) used for blackening metals such as stainless steel, brass, copper, steel, aluminum and cadmium, or their alloys, would be as follows:
Nickel chloride About 6 to 12 oz. Ammonium chloride About 3 to 6 oz. Rochelle salt About to 1 oz. Zinc chloride About to 1 oz. Sodium chloride About 1 to 3 oz. Ammonium molybdate About A; oz. Water 1 gallon The foregoing composition has given excellent results in providing a desirable blackening action on most metals and their alloys. The composition even is satisfactory for use in treating stainless steel. Variations in the compositions within the limits stated vary the speed of the action slightly but do not materially alter the action secured.
Zinc articles can be coated by use of my novel composition by either dipping the zinc articles in baskets or by an electroplating process, and cadmium articles can be similarly processed.
Of course, any desired quantity of solution could be made as long as the proportions stated are maintained.
When blackening steel, stainless steel, brass, copper, aluminum or nickel articles, or alloys of such metal, and also for cadmium plated or finished articles, it is very desirable that an electroplating process be used to obtain the desired black finish. Thus, in barrel plating, I might use between 6 and 9 volts with amperes of electrical energy flowing through the plating solution. In still plating, only about 4 to 6 volts would be required with about the same amperage of current flow.
It will be appreciated that before articles are blackened by my improved process, these articles 3 should be cleaned by dipping them in conventional cleaning solutions maintained at about 140 F. The articles next would be washed thoroughly in water before being blackened.
When blackening articles by electroplating in accordance with the invention, the articles are the cathodes and the anodes are made from stainless steel or, preferably, nickel.
The specific composition set forth in Example I has given particularly good results on metal articles made from the metals indicated, or with a finish surface of such metals. A very black, tightly bonded coat is obtained in only a few minutes by practice of the invention.
While two complete embodiments of the invention have been disclosed herein, it will be appreciated that modifications of these particular embodiments of the invention may be resorted to without departing from the scop of the invention as defined by the appended claims.
Having thus described my invention, claim is:
1. A composition for blackening metals of the class consisting of brass, copper, nickel, steel, aluminum, zinc, stainless steel, and cadmium by an electroplating process, which composition consists essentially of by dry weight, about 8 parts nickel chloride, about 4 parts of ammonium chloride, about 1 part of Rochelle salt, about part of zinc chloride, about 2 parts of sodium chloride, about part of ammonium molybdate, and water.
2. A composition for blackening cadmium by a what I dipping process, which composition consists essentially of by dry weight, about 8 parts nickel chloride, about 4 parts of ammonium chloride, about 1 part of Rochelle salt, about parts of zinc chloride, about 2 parts of sodium chloride and a small amount of ammonium molybdate, and water.
3. A composition for use in blackening metals, which composition consists essentially of by dry weight about 6 to 12 parts nickel chloride, about 3 to 6 parts ammonium chloride, about to 1 /2 parts of Rochelle salt, about to 1 part zinc chloride, about 1 to 3 parts sodium chloride, at small quantity of ammonium molybdate, and water.
4. A process of blackening a metal surface from the class consisting of steel, brass, copper, aluminum, nickel and cadmium comprising immersing the metal surface in a water bath consisting essentially of per gallon of water about 8 oz. nickel chloride; about 4 oz. of ammonium chloride; about 1 oz. of Rochelle salt; about oz. of zinc chloride; about 2 oz. of sodium chloride; and about oz. of ammonium molybdate, and passing a low voltage electrical current therethrough with the metal as the cathode.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,080,520 Westbrook May 18, 1937 2,228,99 Freed Jan. 14, 1941 2,415,651 Nechamkin Feb. 11, 1947
Claims (1)
- 4. A PROCESS OF BLACKENING A METAL SURFACE FROM THE CLASS CONSISTING OF STEEL, BRASS, COPPER, ALUMINUM, NICKEL AND CADMIUM COMPRISING IMMERSING THE METAL SURFACE IN A WATER BATH CONSISTING ESSENTIALLY OF PER GALLON OF WATER ABOUT 8 OZ. NICKEL CHLORIDE; ABOUT 4 OZ. AMMONIUM CHLORIDE; ABOUT 1 OZ. OF ROCHELLE SALT; ABOUT 3/4 OZ. OF ZINC CHLORIDE; ABOUT 2 OZ. OF SODIUM CHLORIDE; AND ABOUT 1/4 OZ. OF AMMONIUM, MOLYBDATE, AND PASSING A LOW VOLTAGE ELECTRICAL CURRENT THERETHROUGH WITH THE METAL AS THE CATHODE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US267509A US2679475A (en) | 1952-01-21 | 1952-01-21 | Metal blackening composition and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US267509A US2679475A (en) | 1952-01-21 | 1952-01-21 | Metal blackening composition and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2679475A true US2679475A (en) | 1954-05-25 |
Family
ID=23019084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US267509A Expired - Lifetime US2679475A (en) | 1952-01-21 | 1952-01-21 | Metal blackening composition and method |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2679475A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2844530A (en) * | 1957-02-15 | 1958-07-22 | Int Nickel Co | Black nickel plating |
| US2933422A (en) * | 1957-05-31 | 1960-04-19 | Walter A Mason | Product and method for coating metals with copper-tellurium compound |
| US3066055A (en) * | 1958-11-10 | 1962-11-27 | Purex Corp Ltd | Process and composition for producing aluminum surface conversion coatings |
| US3097117A (en) * | 1961-06-14 | 1963-07-09 | Macdermid Inc | Method of and composition for producing electroless black nickel coatings |
| US3127279A (en) * | 1964-03-31 | Aqueous black coating composition con- | ||
| US3314811A (en) * | 1964-01-02 | 1967-04-18 | Mitchell Bradford Chemical Co | Metal treating compositions and processes |
| US3505184A (en) * | 1966-02-07 | 1970-04-07 | Enthone | Acid zinc electrodepositing |
| US3899367A (en) * | 1974-10-24 | 1975-08-12 | Mitchell Bradford Chemical Co | Compositions and methods for blackening hardened steel |
| US4569731A (en) * | 1984-04-25 | 1986-02-11 | Kawasaki Steel Corporation | Production of Zn-Ni alloy plated steel strips |
| US5141778A (en) * | 1989-10-12 | 1992-08-25 | Enthone, Incorporated | Method of preparing aluminum memory disks having a smooth metal plated finish |
| US20060213389A1 (en) * | 2003-06-05 | 2006-09-28 | Pearce Michelle R | Compositions and methods for darkening and imparting corrosion-resistant properties to zinc or other active metals |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080520A (en) * | 1935-04-04 | 1937-05-18 | Du Pont | Zinc plating |
| US2228991A (en) * | 1936-01-20 | 1941-01-14 | Seymour Mfg Co | Production of bright nickel deposit |
| US2415651A (en) * | 1944-02-26 | 1947-02-11 | Hazeltine Research Inc | Process for black finishing metals |
-
1952
- 1952-01-21 US US267509A patent/US2679475A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080520A (en) * | 1935-04-04 | 1937-05-18 | Du Pont | Zinc plating |
| US2228991A (en) * | 1936-01-20 | 1941-01-14 | Seymour Mfg Co | Production of bright nickel deposit |
| US2415651A (en) * | 1944-02-26 | 1947-02-11 | Hazeltine Research Inc | Process for black finishing metals |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3127279A (en) * | 1964-03-31 | Aqueous black coating composition con- | ||
| US2844530A (en) * | 1957-02-15 | 1958-07-22 | Int Nickel Co | Black nickel plating |
| US2933422A (en) * | 1957-05-31 | 1960-04-19 | Walter A Mason | Product and method for coating metals with copper-tellurium compound |
| US3066055A (en) * | 1958-11-10 | 1962-11-27 | Purex Corp Ltd | Process and composition for producing aluminum surface conversion coatings |
| US3097117A (en) * | 1961-06-14 | 1963-07-09 | Macdermid Inc | Method of and composition for producing electroless black nickel coatings |
| US3314811A (en) * | 1964-01-02 | 1967-04-18 | Mitchell Bradford Chemical Co | Metal treating compositions and processes |
| US3505184A (en) * | 1966-02-07 | 1970-04-07 | Enthone | Acid zinc electrodepositing |
| US3899367A (en) * | 1974-10-24 | 1975-08-12 | Mitchell Bradford Chemical Co | Compositions and methods for blackening hardened steel |
| US4569731A (en) * | 1984-04-25 | 1986-02-11 | Kawasaki Steel Corporation | Production of Zn-Ni alloy plated steel strips |
| US5141778A (en) * | 1989-10-12 | 1992-08-25 | Enthone, Incorporated | Method of preparing aluminum memory disks having a smooth metal plated finish |
| US20060213389A1 (en) * | 2003-06-05 | 2006-09-28 | Pearce Michelle R | Compositions and methods for darkening and imparting corrosion-resistant properties to zinc or other active metals |
| US7641743B2 (en) * | 2003-06-05 | 2010-01-05 | Metal Coatings International Inc. | Compositions and methods for darkening and imparting corrosion-resistant properties to zinc or other active metals |
| US20100297354A1 (en) * | 2003-06-05 | 2010-11-25 | Metal Coatings International Inc. | Compositions and methods for darkening and imparting corrosion-resistant properties to zinc or other active metals |
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