US3370992A - Pretreatment of a metal surface for conversion coating - Google Patents
Pretreatment of a metal surface for conversion coating Download PDFInfo
- Publication number
- US3370992A US3370992A US316182A US31618263A US3370992A US 3370992 A US3370992 A US 3370992A US 316182 A US316182 A US 316182A US 31618263 A US31618263 A US 31618263A US 3370992 A US3370992 A US 3370992A
- Authority
- US
- United States
- Prior art keywords
- metal
- solution
- coating
- bath
- phosphate
- 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
- 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
- C23C22/00—Chemical 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
- C23C22/73—Chemical 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 characterised by the process
-
- 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
- C23C22/00—Chemical 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
- C23C22/05—Chemical 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
- C23C22/06—Chemical 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
- C23C22/07—Chemical 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 phosphates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
Definitions
- phosphate coats or chromic acid in combination with any of the other activator ingredients such as chlorides, sulfates, fluorides, phosphates, complex fluorides, borates, etc. to form a protective coating on the surface.
- activator ingredients such as chlorides, sulfates, fluorides, phosphates, complex fluorides, borates, etc.
- They generally are applied in the following manner: the sheet metal or strip is first thoroughly cleaned in an alkaline solution, the adherent solution then being removed by a water rinse. The clean metal is next either immersed in a hot bath or sprayed with a solution containing the bonding coat material until a coating of desired thickness or weight is formed.
- the weight of the bond coating is in the range of about 30 to 200 or more milligrams per square foot, preferably about 50 to 150 milligrams per square foot.
- a water rinse follows to remove all coating solution and nonadherent sludge. Some of these processes produce colorless coatings while others produce gray-colored coatings, but all are considered to contain a metallic phosphate or chromate or their combination as one of the coating components.
- the bonding coat is dried at any convenient temperature as by air drying, since there is nothing required beyond the removal of the moisture from the bonded surface.
- a solution containing a phosphorus-containing compound and an oxidizing agent such as a chlorate has been previously proposed for the treatment of metal surfaces.
- an oxidizing agent such as a chlorate
- the use of such phosphoruscontaining solutions has been for the purpose of produc ing a passivating phosphorus-containing coating on the metal surface.
- the phosphorus-containing compound is added to the solution in the form of either an alkali metal phosphate or a Group II metal phosphate to form a substantially insoluble rust and corrosionqe sistan't phosphate coating on such surfaces.
- conventional phosphate coatings are formed by a process using a single bath which contains phosphates, an oxidizing agent and sometimes other ingredients.
- the metallic article to be coated is placed in such bath and the required reactive conditions are established and maintained until the desire-d coating is formed.
- the present invention utilizes a novel solution for, and a process of, preparing or conditioning metal surfaces to receive a bonding coat.
- the properly cleaned metallic articles to be treated are immersed in or sprayed with an oxidizing bath containing about 0.5 to '10 percent, preferably about 1 to 3 percent, phosphoric acid by weight and 1 to 10 .grams, preferably 1 to 5 grams, of chlorate ion per liter of bath solution and the balance water while maintaining the acidity of the bath at a pH level within the range of from 0.5 to 2.7, preferably 1 to 2.2 at a bath temperature of between about 50 to 212 F., preferably to 180 F.
- the time of reaction during which the articles to be treated are subjected to the action of the solution depends on the composition of the metal, the nature of the surface, and the purpose for which the treated working piece is intended to serve. As a general rule, the articles need only be immersed in or sprayed with the solution for a short time, for the reaction taking place at the surface of the metal to be completed. Generally, it is sufficient when operating at temperatures of between 50 and 212 F. to treat the surface for a period of time up to about 3 minutes but generally varying from about 5 seconds to 5 minutes and preferably about 15 seconds to 2 minutes.
- an increase of the temperature does not require a substantial alteration of the treatment period, but it has been found that by increasing the temperature, the time during which the article to be treated is subjected to the action of the solution may be decreased.
- phosphoric acid is intended to include meta-phosphoric, ortho-phosphoric, pyro-phosphoric, trip0ly-phosphoric, tetra-poly-phosphoric acid and other polyphosphoric acids.
- the chlorate ions may be conveniently introduced into the bath solution in the form of a metallic salt and preferably as the sodium salt. However, other metal salts such as potassium, barium, or magnesium chlorates may also be used.
- the aqueous solution shows a certain depletion of its ingredients since they have been consumed in the treating of the metal surface. For this reason, the ingredients of the solution are replenished at a rate corresponding to their consumption, by introducing solutions containing the desired ingredients to the original solution to maintain the pH level within a range of about 0.5 to 2.7. Also, to avoid the undesirable formation of sludge in the treating bath, and to allow continual operation, it has been found advantageous to add about 1 to grams per liter of solution, preferably 1 to 5 grams per liter of solution, nitric acid.
- the metal surfaces may be after-treated by thoroughly rinsing them with water in order to remove adhering ingredients of the bath, and thereafter Without permitting the article to be dried immersing the pretreated metal article into the coating bath described hereinbelow.
- the siccative paint-bonding coat which may be applied to the pretreated metallic surface can include any of the bond coatings commercially used.
- Table I contains various formulations of chromate-phosphate solutions which may be used in forming the siccative paint-bonding coating.
- Ammonium bichromate may be substituted for the chromic acid.
- Calcium oxide may be substituted in equivalent amounts for the calcium carbonate.
- Aluminum hydroxide, magnesium oxide or magnesium carbonate may be substituted in equivalent amounts for the zlnc oxide.
- alkyl aryl polyether alcohol made by condensing one mol of p-(n-octyl)phenol with three mols of ethylene oxide.
- the bond-coating solution may be applied to the pretreated metal surface either by spraying or by dipping the article into the soltuion.
- the metal carrying film of coating solution may be heated to a temperature of from about 100 F. to about 400 F., at which temperature the oxidants and reducing agents are substantially completely destroyed in the coating film with reduction of hexavalent chromium and formation of a highly adherent, oxidation-resisting, chemically inert, bonding coat consisting chiefly of compounds of chromium and phosphorus, probably chromic phosphate.
- the bonding coat which forms on the pretreated metal surface is continuous, thin, highly adherent, hard, smooth, and lustrous, and without nonadherent material. These features permit repeated flexing of the coated metal through 360 degrees, deep-drawing of the metal up to the point where the metal itself tears, and similar fabricating operations involving deforming techniques, without destruction of the coating.
- organic finishes when applied to siccative paint-bonding coatings on metal surfaces which have been pretreated according to the present invention do not decompose at the interface and are very diificult if not impossible to remove from the pretreated metal surface containing the bonding coat, short of destruction of the metal surface itself.
- metal surfaces pretreated according to the method of the present invention may receive organic finishes having an end use as: automobile finishes, can coatings, appliance coatings, precoatings of strip metals, coatings on metal building panels (house siding, gutters, downspouts, etc.), mobile home exteriors, exterior trim, metal cabinets and tables, and the like.
- epoxy resins e.g. reaction product of epichlorohydrin and polyhydric phenols, oxidation of olefins with peracetic acid or phenol-formaldehyde condensate esterfied with epichilorohydrin vinyl resins (homopolymers and copolymers), e.g. polyvinyl chloride, polyvinyl fluoride, polyvinyl acetate,
- Organic finishes may be applied to the bonding coating up to a thickness of about 100 to 200 mils when used in corrosion type coatings; but, generally, they are applied in the range of about 0.2 to 20 mils.
- the coated article is heated for a suificient period of time to achieve essentially a dry organic finish. Temperatures in the range of about 70 to 600 F. are generally used for a period of time from a few minutes up to about 48 hours, usually from about 1 hour to about 24 hours.
- Metal surfaces which may be treated according to the practice of the present invention include the ferrous metals, zinc, aluminum, and their alloys.
- Seven steel panels (4" x 12") are cleaned with an aqueous solution containing g./l. NaOH and 10 g./l. KMnO Into each of the above-identified pretreatment bath solutions is dipped one of the six previously cleaned steel panels for 45 seconds at a temperature of 140 F. The steel panels are then removed from the bath solutions and rinsed with water. The water-rinsed pretreated steel panels are then dipped into a 10% bond-coating solution consisting of:
- the painted steel panels are subjected to a bend test conducted in accordance with the standard method of ASTM B-522-41, which generally involves bending a lengthwise portion of the panel through 180 around a conical mandrel (Gardener Laboratories Conical Mandrel), having a small diameter of A inch, the diameter four inches from the small end being one inch, and a length of 8 inches.
- the results of the bending test are reported in terms of flaking or fracture (craze) of the paint system. Flaking indicates separation of the coating from the panel surface.
- Scotch adhesion test using Scotch filament tape #880. The results of the bend and adhesion tests are given in Table III.
- Example 2 Three 4" X 12" steel panels (Samples H to L) are cleaned with an aqueous solution containing 20 g./l. r NaOH and g./l. KMnO Each of these steel panels are then dipped into an aqueous pretreatment bath solution for 1 minute at a temperature of 140 F.
- the pretreatment bath contains 10 cc./l. of H PO (85%) and 3 grams/l. NaClO and has a pH of 1.8.
- the pretreated steel panels are removed from the pretreatment bath solution and rinsed with water. Each panel is then dipped in a bond-coating solution, removed and heated for 3 minutes at 350 F.
- the bond-coating solutions are identified in Table IV below.
- the three steel panels are then painted with an acrylic paint system and baked at 385 F. for 20 minutes.
- the painted steel panels are then subjected to the bend and adhesion tests described in Example 1. These results are also reported in Table IV.
- Example 3 Samples M to R, (tour 4" X 12" panels of each) are prepared using various treating and bond coating compositions. Samples P to R are commercially prepared metal panels containing zinc phosphate as the bond coating. TWO panels of each sample are painted with an epoxy paint system and the remaining two panels of each sample are painted. With an acrylic paint system. The treatment of the metal panels are described in Table V, below.
- One panel of each sample, painted With the epoxy paint system; and one panel of each sample, painted with the acrylic paint system, are subject to an appliance detergent test which comprises immersing the painted samples in a 1% detergent solution, maintained at a temperature of 165 Hi3.
- the detergent solution contains:
- a surface active agent-sodium alkyl aryl sulfonate is provided.
- the remaining painted panels are subjected to the Gravelometer test which indicates adhesion of the paint system to the metal surface and comprises shooting 20 pounds of steel shot with 60 pounds of air pressure against the painted surfaces.
- the results of the appliance detergent test and the Gravelometer test are also reported in Table V.
- Samples M and N pretreated with the composition for conditioning metal surfaces, are equivalent to commercially prepared coated metal surfaces, Samples 0 to R.
- I.V. 4 cleaned galvanized steel panels are treated the same as .do Do.
- Sample R (Galvanized Steel) 1. Previously prepared zinc phoshpate bond coating on a particud0 Dc.
- a method for conditioning the surface of a metal selected from the group consisting of ferrous metal, Zinc, aluminum, and alloys thereof to receive a bonding coating selected from the group consisting of chromate, phosphate and chromate-phosphate bonding coats which method comprises the steps of applying to said surface an aqueous solution maintained at a pH level less than 2.7, said solution consisting essentially of phosphoric acid and a metal chlorate as an oxidizing agent, said phosphoric acid being present in said solution from 0.5 to 10 percent by weight, and from 1 to 10 grams of chlorate ion per liter of solution.
- metal chlorate is selected from the group consisting of sodium, potassium, barium and magnesium chlorate.
- metal chlorate is sodium chlorate and the chlorate ion is present in the aqueous solution in an amount from 1 to 5 grams per liter of solution.
- a method of conditioning the surface of a metal selected from a group consisting of ferrous metal, zinc, aluminum, and alloys thereof, to receive a bonding coating selected from the group consisting of chromate, phosphate and chromate-phosphate bonding coats which method comprises the steps of applying to said surface an aqueous solution maintained at a pH from 0.5 to 2.7 in a temperature range from 50 to 212 F., and the contact time is from 10 seconds to 5 minutes, said solution consisting essentially of 1 to 10 percent by weight of phosphoric acid and from 1 to 5 grams per liter of solution of chlorate ion, said chlorate ion being supplied to said solution by sodium chlorate.
- a method for producing an adherent bonding coat selected from the group consisting of chromate, phosphate and chromate-phosphate bonding coats on a metal base selected from the group consisting of ferrous metal, zinc, aluminum and alloys thereof which method comprises the steps of applying to said base an aqueous solution maintained at a pH level less than 2.7, at a temperature within the range of 50 to 212 F.
- said solution consisting essentially of phosphoric acid and a metal chlorate as an oxidizing agent, said phosphoric acid being present in said solution from 0.5 to 10 percent by weight, and from 1 to 10 grams of chlorate ion per liter of solution; removing the treated metal base from said solution, rinsing said treated metal base with water, applying to said treated metal base a bonding coat selected from the group consisting of chromate, phosphate and chromate-phosphate bonding coats having a bonding coat weight of 30 to 200 milligrams per square foot and heating said applied bonding coat to a temperature suificient to substantially destroy the oxidants and reducing agents in said bonding coat.
- a method of producing an adherent organic finish on a metal base selected from a group consisting of ferrous metal, zinc, aluminum and alloys thereof and having a bonding coating thereon selected from the group consisting of chromate, phosphate and chromate-phosphate bonding coats which method comprises the steps of applying to said base an aqueous solution maintained at a pH level less than 2.7, at a temperature within the range of 50 to 212 F.
- said solution consisting essentially of phosphoric acid and a metal chlorate as an oxidizing agent, said phosphoric acid being present in said solution from 0.5 to 10 percent by weight, and from 1 to 10 grams of chlorate ion per liter of solution; removing the treated metal base from said solution, rinsing said treated metal base with water, applying to said treated metal base a bonding coat selected from the group consisting of chromate, phosphate and chromate-phosphate bonding coats having a bonding coat weight of 30 to 200 milligrams per square foot, heating said applied bonding coat to a temperature suflicient to substantially destroy the oxidants and reducing agents in said bonding coat, and applying to said bonding coat an organic finish.
Description
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US316182A US3370992A (en) | 1963-10-14 | 1963-10-14 | Pretreatment of a metal surface for conversion coating |
NL6411887A NL6411887A (en) | 1963-10-14 | 1964-10-13 | |
BE654310D BE654310A (en) | 1963-10-14 | 1964-10-13 | |
FR991199A FR1411432A (en) | 1963-10-14 | 1964-10-13 | Method and compositions for the treatment of metal surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US316182A US3370992A (en) | 1963-10-14 | 1963-10-14 | Pretreatment of a metal surface for conversion coating |
Publications (1)
Publication Number | Publication Date |
---|---|
US3370992A true US3370992A (en) | 1968-02-27 |
Family
ID=23227879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US316182A Expired - Lifetime US3370992A (en) | 1963-10-14 | 1963-10-14 | Pretreatment of a metal surface for conversion coating |
Country Status (3)
Country | Link |
---|---|
US (1) | US3370992A (en) |
BE (1) | BE654310A (en) |
NL (1) | NL6411887A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3532611A (en) * | 1965-05-25 | 1970-10-06 | Nippon Kokan Kk | Process for the manufacture of surface-treated metallic sheets or the like,with superior coating and anti-corrosive performance |
US4165242A (en) * | 1977-11-21 | 1979-08-21 | R. O. Hull & Company, Inc. | Treatment of metal parts to provide rust-inhibiting coatings by phosphating and electrophoretically depositing a siccative organic coating |
ES2338204A1 (en) * | 2009-08-06 | 2010-05-04 | Automat Industrial S.L | Continuous wire galvanizing method and corresponding galvanizing machine |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2318656A (en) * | 1941-04-25 | 1943-05-11 | Parker Rust Proof Co | Coated metal article and method of making same |
US2813815A (en) * | 1955-07-26 | 1957-11-19 | American Chem Paint Co | Method of treating phosphate coatings on metal surfaces |
US3144361A (en) * | 1955-11-10 | 1964-08-11 | Klinghoffer Stefan | Pretreating iron or steel |
-
1963
- 1963-10-14 US US316182A patent/US3370992A/en not_active Expired - Lifetime
-
1964
- 1964-10-13 NL NL6411887A patent/NL6411887A/xx unknown
- 1964-10-13 BE BE654310D patent/BE654310A/xx unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2318656A (en) * | 1941-04-25 | 1943-05-11 | Parker Rust Proof Co | Coated metal article and method of making same |
US2813815A (en) * | 1955-07-26 | 1957-11-19 | American Chem Paint Co | Method of treating phosphate coatings on metal surfaces |
US3144361A (en) * | 1955-11-10 | 1964-08-11 | Klinghoffer Stefan | Pretreating iron or steel |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3532611A (en) * | 1965-05-25 | 1970-10-06 | Nippon Kokan Kk | Process for the manufacture of surface-treated metallic sheets or the like,with superior coating and anti-corrosive performance |
US4165242A (en) * | 1977-11-21 | 1979-08-21 | R. O. Hull & Company, Inc. | Treatment of metal parts to provide rust-inhibiting coatings by phosphating and electrophoretically depositing a siccative organic coating |
ES2338204A1 (en) * | 2009-08-06 | 2010-05-04 | Automat Industrial S.L | Continuous wire galvanizing method and corresponding galvanizing machine |
Also Published As
Publication number | Publication date |
---|---|
NL6411887A (en) | 1965-04-15 |
BE654310A (en) | 1965-04-13 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: DIAMOND SHAMROCK CHEMICALS COMPANY Free format text: CHANGE OF NAME;ASSIGNOR:DIAMOND SHAMROCK CORPORATION CHANGED TO DIAMOND CHEMICALS COMPANY;REEL/FRAME:004197/0130 |
|
AS | Assignment |
Owner name: METAL COATINGS INTERNATIONAL INC. A DE CORP. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DIAMOND SHAMROCK CHEMICALS COMPANY;REEL/FRAME:004326/0164 Effective date: 19840831 |
|
AS | Assignment |
Owner name: NATIONAL CITY BANK AS AGENT FOR BANKS Free format text: SECURITY INTEREST;ASSIGNOR:METAL COATINGS INTERNATONAL INC. A DE CORP;REEL/FRAME:004352/0906 Effective date: 19840831 |
|
AS | Assignment |
Owner name: METAL COATINGS INTERNATIONAL INC., A CORP. OF DE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NATIONAL CITY BANK, AS AGENT;REEL/FRAME:004969/0537 Effective date: 19880916 Owner name: METAL COATINGS INTERNATIONAL INC., STATELESS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. SEE RECORD FOR DETAILS;ASSIGNOR:NATIONAL CITY BANK, AS AGENT;REEL/FRAME:004969/0537 Effective date: 19880916 |