US2434525A - Coating on metals - Google Patents

Coating on metals Download PDF

Info

Publication number
US2434525A
US2434525A US499710A US49971043A US2434525A US 2434525 A US2434525 A US 2434525A US 499710 A US499710 A US 499710A US 49971043 A US49971043 A US 49971043A US 2434525 A US2434525 A US 2434525A
Authority
US
United States
Prior art keywords
coating
metal
zinc
metals
acid
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
Application number
US499710A
Inventor
Robert M Thomas
Charles W Ostrander
Walter H Kaelin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rheem Manufacturing Co
Original Assignee
Rheem Manufacturing Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rheem Manufacturing Co filed Critical Rheem Manufacturing Co
Priority to US499710A priority Critical patent/US2434525A/en
Application granted granted Critical
Publication of US2434525A publication Critical patent/US2434525A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/30Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also trivalent chromium

Definitions

  • This invention relates to the treatment of zinc and cadmium and castings thereof and particularly galvanized metal, but may be used in the treatment of copper or brass and other copper alloys, including bronzes.
  • the primary object of the invention is to form on the metal surface an insoluble, integral, corrosion-resistant coating which is visible and may be produced in a variety of shades.
  • dip compositions employing chromium for coating metals are known and commercially available.
  • the present invention is an improvement in such dips and possesses the characteristics of reliability and simplicity, and may be carried out at commercially acceptable costs.
  • soluble chromium compounds alone do not produce a desirable coating, a very effective coating is produced when certain anions are added to the solution.
  • soluble compounds containing the following anions Br-, SON, S203- 103*.
  • chromic acid, or dichromates such as sodium or potassium dichromate, together with such soluble salts as potassium or sodium iodate, bromide, thiocyanate, and thiosulfate.
  • the specific anions mentioned above have the special virtue of promoting the oxidation-reduction reactions that occur between the metal surface to be treated and the chromium compound. More specifically, they also permit the formation of a chromium compound with the base metal which is formed as an integral part of the metal surface and thus resists rubbing off or flaking and chipping. This formation of an integral surface compound goes beyond the ordinary meaning of adhesion, which implies the gluing or sticking together of two dissimilar ma terials by attractive forces inherent in one or both materials.
  • the composition of the formed coating may be controlled within limits to produce a variety of colors, ranging from a golden yellow through orange, to greens and black, colors which reflect the greater or lesser extent to which the chromium compounds have been reduced from a valence of 6 to a lower valence.
  • Precise shades of color are considered to be determined by a mixture of chrome ions of several valences, in combination with the base metal, and to the presence of compounds of chromium, such as chromic dichromate, either alone or in combination with other ions.
  • the clip composition reacts with the metal surface and for purposes of illustration, in the case of galvanized metal, either hot dipped or elec-. troplated, forms the coating on the surface of the relatively thin surface layer of spelter metal or the pure zinc plated layer to produce the visible corrosion-resistant coating.
  • the period of immersion of the metal to be coated is between about 5 to 120 seconds at a temperature of about 60 F. to 212 F., whereby a dark-to-light bronze coating is produced.
  • the immersion time is the same as described above, and the temperature is preferably maintained at about 180 F. to 212 F. for obtaining a bronze coating.
  • the coating may be accomplished by subjecting the surface to be coated, to suitable spraying with the solution.
  • the articles are rinsed in hot water and suitably dried as in an oven or by blowing hot or cold air over the same, whereupon they are immediately ready for use.
  • zinc or cadmium we intend to include pure zinc and pure cadmium, as well as mixtures thereof, articles coated with zinc or cadmium, or mixtures thereof, so-called.
  • copper we intend to include copper and its alloys, of which brass is the most prominent example, as well as bronze alloys.
  • the method of" producing an integral corrosion-resistant coating on zinc, cadmium or copper comprising subjecting the same to an aqueous dip essentially consisting of water, a water soluble chromium compound selected from the group consisting of chromic. acid and salts thereof and. an alkali metal ⁇ - thiosulfatein smaller amount than said chromium compound.
  • aqueous dip essentially consisting of water, a water soluble chromium compound selected from the group consisting of chromic. acid and salts thereof and. an alkali metal ⁇ - thiosulfatein smaller amount than said chromium compound.

Landscapes

  • 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)
  • Chemical Treatment Of Metals (AREA)

Description

Patented Jan. 13, 1948 COATING ON METALS Robert M. Thomas, Charles W. Ostrander, and Walter H. Kaelin, Baltimore, Md., assignors, by mesne assignments, to Rheem Manufacturing cisco, Calif., a corporation Company, San Fran of California No Drawing. Application August 23, 1943,
- Serial No. 499,710
1 Claim.
This invention relates to the treatment of zinc and cadmium and castings thereof and particularly galvanized metal, but may be used in the treatment of copper or brass and other copper alloys, including bronzes.
The primary object of the invention is to form on the metal surface an insoluble, integral, corrosion-resistant coating which is visible and may be produced in a variety of shades.
Many dip compositions employing chromium for coating metals are known and commercially available. The present invention is an improvement in such dips and possesses the characteristics of reliability and simplicity, and may be carried out at commercially acceptable costs.
We have discovered that Whereas soluble chromium compounds alone do not produce a desirable coating, a very effective coating is produced when certain anions are added to the solution. Among these are soluble compounds containing the following anions: Br-, SON, S203- 103*. We use chromic acid, or dichromates, such as sodium or potassium dichromate, together with such soluble salts as potassium or sodium iodate, bromide, thiocyanate, and thiosulfate.
The specific anions mentioned above, such as iodate, bromide, thiocyanate, and thiosulfate, have the special virtue of promoting the oxidation-reduction reactions that occur between the metal surface to be treated and the chromium compound. More specifically, they also permit the formation of a chromium compound with the base metal which is formed as an integral part of the metal surface and thus resists rubbing off or flaking and chipping. This formation of an integral surface compound goes beyond the ordinary meaning of adhesion, which implies the gluing or sticking together of two dissimilar ma terials by attractive forces inherent in one or both materials. It is to promote the formation of this integral surface compound of the base metal and the chromium compounds that necessitates the use of anions of the order of those mentioned above, in preference to other anions which conceivably may result in the formation of a reduced chromium compound with some tendency to adhere to the base metal but which can be rubbed off to a greater or less extent,
By varying the concentration of the ingredients of the bath or dip solution, and also the temperature of the solution and period of treatment, the composition of the formed coating, may be controlled within limits to produce a variety of colors, ranging from a golden yellow through orange, to greens and black, colors which reflect the greater or lesser extent to which the chromium compounds have been reduced from a valence of 6 to a lower valence. Precise shades of color .are considered to be determined by a mixture of chrome ions of several valences, in combination with the base metal, and to the presence of compounds of chromium, such as chromic dichromate, either alone or in combination with other ions.
The clip composition reacts with the metal surface and for purposes of illustration, in the case of galvanized metal, either hot dipped or elec-. troplated, forms the coating on the surface of the relatively thin surface layer of spelter metal or the pure zinc plated layer to produce the visible corrosion-resistant coating.
In order that the invention may be more clearly understood, we will describe several satisfactory examples or aqueous dips.
gms./liter 1. Sodium bichromate 13o Potassium bromide 27 Sunamlc arm 25 2. Sodium bicnromate 83 Chrome acid 33 Potassium bromide 27 3. Chromlc acid Potassium bromide 27 4. Chromic acid 20 Potassium iooate 10 5. Cnromic acid 100 'lnlocyanate (sodium or potassium) 27 6. Cnrormc acid 500mm thiosulfate l5 Hydrobromic acid, and ammonium, sodium, and zinc bromides may be substituted in th foregoing formulations for the bromide constituent.
In the case of formulations 1, 2, and 3, the period of immersion of the metal to be coated is between about 5 to 120 seconds at a temperature of about 60 F. to 212 F., whereby a dark-to-light bronze coating is produced.
In the case of formulation No. 4, the immersion time is the same as described above, and the temperature is preferably maintained at about 180 F. to 212 F. for obtaining a bronze coating.
In the case of formulations 5 and 6, the time I periods are as recited above for producing a bronze coating in the case of Examples 1, 2, and 3, and this is likewise true of the temperature ranges.
Instead of an immersion treatment, the coating may be accomplished by subjecting the surface to be coated, to suitable spraying with the solution.
After th coating has been accomplished, the articles are rinsed in hot water and suitably dried as in an oven or by blowing hot or cold air over the same, whereupon they are immediately ready for use.
By treatment of the metal surface with solutions as above set forth, the rapid and destruc tive formation of zinc salts, such as oxides and hydroxides that form in the presence of moisture or moist air, are prevented;
The treatments just above described are used equally well for treating copper, brass and other copper alloys, including bronzes.
In referring in the claim to zinc or cadmium, we intend to include pure zinc and pure cadmium, as well as mixtures thereof, articles coated with zinc or cadmium, or mixtures thereof, so-called.
zinc and cadmium castings and, of course, electroplated and hot dipped galvanized metal.
In referring in the claim to copper, we intend to include copper and its alloys, of which brass is the most prominent example, as well as bronze alloys.
We claim:
The method of" producing an integral corrosion-resistant coating on zinc, cadmium or copper comprising subjecting the same to an aqueous dip essentially consisting of water, a water soluble chromium compound selected from the group consisting of chromic. acid and salts thereof and. an alkali metal}- thiosulfatein smaller amount than said chromium compound. ROBERT M. THOMAS. CHARLES W. OSTRANDER. WALTER H. KAELIN.
REFERENCES CITED The-following references are of record in the file of this patent:
US499710A 1943-08-23 1943-08-23 Coating on metals Expired - Lifetime US2434525A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US499710A US2434525A (en) 1943-08-23 1943-08-23 Coating on metals

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US499710A US2434525A (en) 1943-08-23 1943-08-23 Coating on metals

Publications (1)

Publication Number Publication Date
US2434525A true US2434525A (en) 1948-01-13

Family

ID=23986376

Family Applications (1)

Application Number Title Priority Date Filing Date
US499710A Expired - Lifetime US2434525A (en) 1943-08-23 1943-08-23 Coating on metals

Country Status (1)

Country Link
US (1) US2434525A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768104A (en) * 1952-03-25 1956-10-23 Heintz Mfg Co Method for coating iron
US2777785A (en) * 1953-07-30 1957-01-15 Heintz Mfg Co Composition for and method of treating metals as well as the treated product
US2844496A (en) * 1957-02-25 1958-07-22 Newell Isaac Laird Formation of corrosion resistant films on aluminum
DE1180217B (en) * 1959-02-04 1964-10-22 Philips Nv Process for the passivation of metal objects
US3352669A (en) * 1964-01-31 1967-11-14 Xerox Corp Photoconductive member and processes of preparing and using same
US3457124A (en) * 1966-09-07 1969-07-22 Cowles Chem Co Chromate conversion coatings
US3942989A (en) * 1970-10-22 1976-03-09 Mayhew John T White rust prevention for zinc coated surfaces

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1911726A (en) * 1931-07-07 1933-05-30 Metal Finishing Res Corp Production of phosphate coatings on metals
US1967715A (en) * 1933-06-02 1934-07-24 Carter Carburetor Corp Surface treatment for zinc base alloys
US2016904A (en) * 1930-10-08 1935-10-08 Gen Electric Electric discharge device
US2035380A (en) * 1933-05-13 1936-03-24 New Jersey Zinc Co Method of coating zinc or cadmium base metals
US2080348A (en) * 1936-12-10 1937-05-11 Edward S Truitt Metal etching mordant
US2114151A (en) * 1935-07-09 1938-04-12 American Chem Paint Co Art of finishing ferrous metal
US2169584A (en) * 1938-09-09 1939-08-15 Surface Combustion Corp Prevention of corrosion
US2276353A (en) * 1935-09-28 1942-03-17 Parker Rust Proof Co Process of coating
US2313925A (en) * 1937-04-16 1943-03-16 Parker Rust Proof Co Coating metals by the aid of acid sulphites

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016904A (en) * 1930-10-08 1935-10-08 Gen Electric Electric discharge device
US1911726A (en) * 1931-07-07 1933-05-30 Metal Finishing Res Corp Production of phosphate coatings on metals
US2035380A (en) * 1933-05-13 1936-03-24 New Jersey Zinc Co Method of coating zinc or cadmium base metals
US1967715A (en) * 1933-06-02 1934-07-24 Carter Carburetor Corp Surface treatment for zinc base alloys
US2114151A (en) * 1935-07-09 1938-04-12 American Chem Paint Co Art of finishing ferrous metal
US2276353A (en) * 1935-09-28 1942-03-17 Parker Rust Proof Co Process of coating
US2080348A (en) * 1936-12-10 1937-05-11 Edward S Truitt Metal etching mordant
US2313925A (en) * 1937-04-16 1943-03-16 Parker Rust Proof Co Coating metals by the aid of acid sulphites
US2169584A (en) * 1938-09-09 1939-08-15 Surface Combustion Corp Prevention of corrosion

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768104A (en) * 1952-03-25 1956-10-23 Heintz Mfg Co Method for coating iron
US2777785A (en) * 1953-07-30 1957-01-15 Heintz Mfg Co Composition for and method of treating metals as well as the treated product
US2844496A (en) * 1957-02-25 1958-07-22 Newell Isaac Laird Formation of corrosion resistant films on aluminum
DE1180217B (en) * 1959-02-04 1964-10-22 Philips Nv Process for the passivation of metal objects
US3352669A (en) * 1964-01-31 1967-11-14 Xerox Corp Photoconductive member and processes of preparing and using same
US3457124A (en) * 1966-09-07 1969-07-22 Cowles Chem Co Chromate conversion coatings
US3942989A (en) * 1970-10-22 1976-03-09 Mayhew John T White rust prevention for zinc coated surfaces

Similar Documents

Publication Publication Date Title
US4419199A (en) Process for phosphatizing metals
US2393663A (en) Coating for cadmium and zinc
GB2059445A (en) Chromium-free or low-chromium metal surface passivation
US2868679A (en) Process and compositions for producing aluminum surface conversion coatings
US2121574A (en) Art of coating zinc
US3539403A (en) Solutions for the deposition of protective layers on zinc surfaces and process therefor
US2434525A (en) Coating on metals
US4444601A (en) Metal article passivated by a bath having an organic activator and a film-forming element
US3076734A (en) Protective coatings on metals
US3404046A (en) Chromating of zinc and aluminum and composition therefor
US2933422A (en) Product and method for coating metals with copper-tellurium compound
US2393665A (en) Corrosion resistant metal
EP0087288A1 (en) Bath and method for black chromate plating of zinc and cadmium surfaces
US2927874A (en) Process for producing aluminum surface coatings
US2393943A (en) Coating
US2499231A (en) Method of producing surface conversion coatings on zinc
JPH06306632A (en) Bright bluing method for hot dip-aluminum alloy plated steel sheet
JPS60190588A (en) Method for blackening zinc or zinc alloy plated steel sheet
US2522474A (en) Treatment of zinc surfaces
US2431728A (en) Treatment of ferrous metals to improve resistance to rusting
US3090710A (en) Method and solution for producing chromate coatings on zinc and zinc alloys
US2798830A (en) Method of improving the corrosion resistance of certain coated aluminum surfaces
CN104250842A (en) Technology for pretreating aluminum alloy surface before plating
JPH0949086A (en) Production of electrogalvanized steel sheet having high whiteness and excellent in coating suitability
US3397090A (en) Metal-coating composition and process