US3397093A - Treatment of metal surfaces - Google Patents
Treatment of metal surfaces Download PDFInfo
- Publication number
- US3397093A US3397093A US368738A US36873864A US3397093A US 3397093 A US3397093 A US 3397093A US 368738 A US368738 A US 368738A US 36873864 A US36873864 A US 36873864A US 3397093 A US3397093 A US 3397093A
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- US
- United States
- Prior art keywords
- solution
- coating
- phosphate
- zone
- cleaning
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- 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.)
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Classifications
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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
- 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
Definitions
- ABSTRACT OF THE DISCLOSURE A process for treating metal surfaces wherein the surface is contacted with an aqueous acidic phosphate coating solution containing at least one additive selected from the group consisting of nonionic surface active agents and emulsified organic solvents, said contact being sufficient to effect cleaning of the surface, and thereafter, without an intervening water rinse, the thus-cleaned surface is contacted with a second aqueous acidic phosphate coating solution, which solution is substantially free of the aforesaid additives, until a phosphate coating is formed on the surface.
- This invention relates to improvements in treating metal surfaces to produce corrosion resistant coatings thereon and more particularly relates to an improved composition and process for cleaning and coating metal surfaces to prevent corrosion thereof.
- Such a cleaning solution can remove grease deposits from the surface very effectively, but it should not be carried over into the phosphating zone, and therefore the surface is rinsed with water between cleaning and phosphating.
- a cleaning solution can remove grease deposits from the surface very effectively, but it should not be carried over into the phosphating zone, and therefore the surface is rinsed with water between cleaning and phosphating.
- two separate rinsing zones are commonly used, fresh water being used in the second zone.
- Rinsing after the coating has been formed is also usual, and often after this rinsing, coated surfaces are sprayed with a solution containing the chromate ion.
- the conventional spraying plant therefore comprises six zones. In view of the space and capital investment for such processing equipment, it is desirable to reduce the number of stages or zones used.
- an object of the present invention to provide a method of cleaning and coating metal surfaces to provide corrosion protection, which method is ac complished in fewer steps than has heretofore been possible.
- Another object of the present invention is to provide a novel cleaning and coating method which is particularly adapted for use in so-called cold and cool spray phosphating processes.
- a further object of the invention is to provide novel cleaning and coating compositions for use in such processes.
- metal surfaces are cleaned by spraying them with a zinc phosphate coating solution containing an additive selected from the group consisting of nonionic surface-active agents, emulsified organic solvents and mixtures thereof. After this cleaning step, the surfaces are immediately sprayed with a zinc phosphate coating solution. It is found that no intermediate rinsing between cleaning and coating is necessary when the cleaning solution described above is used. Although these zinc phosphate solutions adequately clean grease and other dirt from the metal surfaces, they are generally not suitable for the removal of visible rust or scale from ferrous surfaces.
- a surface bearing such rust or scale is desirably subjected to pickling or otherwise treated for rust or scale removal before it is treated in accordance with this invention.
- the zinc phosphate solutions used in the present invention differ from pickling solutions, the former commonly having a pH of from 2.5 to 4, whereas pickling solutions commonly have a pH below 1.
- pickling solutions commonly have a pH below 1.
- zinc phosphate solutions of this type operate at a pH at or slightly above equilibrium, or in other words, under conditions such that zinc tertiary phosphate is in equilibrium with free phosphoric acid and primary zinc phosphate, or under somewhat less acid conditions when the solution is supersaturated with primary zinc phosphate.
- the formation of the phosphate coating is initiated, at least on the cleaner parts of the surface, in the cleaning zone and the crystals formed act as nuclei on which the coating proper may form in the second spray zone. Whether this is the case or not, it has been found that for best results the composi tion of the cleaning solution, with regard to its coacting ingredients, should be the same as that of the coating solution used after cleaning in the second spray zone.
- This method of operation has the additional advantage that the solution in the cleaning zone can be discarded as it becomes dirty and may be replaced by used solution from the second spray zone, which is itself replaced by fresh solution.
- the solution in the second spray zone may also contain a surface-active agent to insure the removal of any grease which may not have been removed in the first zone. If such an agent is not present, then before the phosphate-coating solution is used to replace the cleaning solution in the first zone, a surface-active agent should be included or an organic solvent should be emulsified in it.
- the non-ionic surface-active agents suitable for use in the present invention are usually those organic compounds having an oxygenated side chain, for example, a polyoxyethylene side chain. Included in these are the essentially straight chain polymerized alkylene oxide condensates having more than five alkylene oxide groups in straight line configuration, e.g., higher fatty acid esters of polyoxyethylene alcohols, ethylene oxide-propylene oxide block copolymers of molecular weight between about 1000 to about 20,000, and so forth. More specifically, these include the ditertiary acetylenic glycols, ethylene oxide nonylphenol, polyethylene glycol tertiarydodecylthiourea ethers, fatty acid esters of higher polyglycols and the like.
- a preferred non-ionic surface active agent for use in the present invention is the condensation product of a rosin alcohol with 20 moles of ethylene oxide, terminated by a benzyl ether group.
- the non-ionic sulrface active agents are present in an amount up to about 5 grams per liter of solution, with amounts from about 0.1 to about 2.0 grams per liter being preferred.
- the emulsified solvents which may be used in the present invention are known in the art. These materials may be classified as petroleum solvent materials, used as such or diluted with relatively inexpensive petroleum distillates, and the lower toxicity chlorinated solvents.
- the former group includes materials such as naphtha, paint thinner, various petroleum fractions, including kerosene, diesel oil and the like.
- the latter group includes materials such as trichloroethylene, perchloroethylene, methyl chloroform, methylene chloride, ethylene dichloride, o-dichlorobenzene, propylene dichloride, and the like.
- solvents such as alcohols, glycols, glycol ethers, phenols, cresylic compounds, pine oil and the like.
- solvents such as alcohols, glycols, glycol ethers, phenols, cresylic compounds, pine oil and the like.
- emulsifiers of the anionic, cationic, and non-ionic type may be used so long as they provide the requisite emulsification of the solvent and do not have an adverse or detrimental effect on the solvent, the other components of the cleaning and/or coating solution or the metal being treated.
- the solvent such as kerosene
- the use of an additional emulsifier, to provide emulsification of the solvent may not be necessary.
- the emulsified solvent such as the preferred kerosene, will be used in amounts up to about 20 grams per liter of solution, with amounts within the range of about 1 to about grams per liter being preferred.
- the method of cleaning and then forming a phosphate coating without an intermediate rinse according to the invention is particularly useful when the phosphate coating is formed in the cold, that is to say at a temperature of 40 to 100 F., though usually not exceeding 70 degrees Fahrenheit.
- strong conventional alkaline cleaners are used instead of the solutions of the present invention, there is often difliculty, apparently because the metal surface is passivated, and the coating solutions do not operate satisfactorily at temperatures of 100 degrees Fahrenheit or less.
- an emulsified solvent e.g., kerosene
- a surface-active agent is preferred over an emulsified solvent.
- the use of emulsified kerosene or other solvent to improve the detergent power is generally less important.
- the phosphate coating and cleaning solutions used in the present invention may be characterized as being acid aqueous solutions incorporating metal phosphates, such as zinc iron or manganese phosphate, dissolved therein.
- the solutions used contain zinc phosphate.
- suitable accelerators such as bromides, nitrates, nitrites or chlorates, may also be incorporated in the solutions.
- the solution used for forming the coating may advantageously contain both zinc and manganese phosphate, the manganese content being up to 50 percent by weight of the zinc content, as described in a copending application Ser. No. 306,332, filed Sept. 3, 1963, now US. Patent 3,338,755. Accordingly, this solution may also be used as the basis for the cleaning solution in the first zone.
- surfaces cleaned and coated in accordance with this invention are generally then passed through two rinsing Zones, the first of which is a water-rinse and the second a rinse with a conventional dilute solution of chromic acid, with or without some phosphoric acid.
- the invention may be used with advantage when the coated surface is painted with a water-thinned paint, in particular, a water-thinned primer.
- a water-thinned primer in particular, a water-thinned primer.
- the second rinsing step after the coating may be effected with water or with an aqueous solution having a pH between 7 and 11 as described in a copending application Ser. No. 178,247, filed Mar. 8, 1962, now US. Patent 3,154,438.
- Particularl good results have been achieved when a water-thinned primer is applied by electrophoresis.
- Example 1 Steel panels were treated in four zones. In the first zone they were sprayed for 1 minute at Fahrenheit with a solution of the following composition:
- Kerosene 5 The surface-active agent was a condensation product of a rosin alcohol with 20 moles of ethylene oxide terminated by a benzyl ether group.
- the total acidity of this solution was 20 points and the free acidity was 0.4 point.
- the total acidity given above is the number of ml. of N/ 10 NaOH (points) needed to neutralize a 10 ml. sample of the solution to a phenol-phthalein end-point whereas the free acidity is the number of ml. of N/10 sodium hydroxide (points) required to neutralize a 10 ml. sample to a bromophenol blue end-point.
- the panels were sprayed for 1 minute at 70 degrees Fahrenheit in a solution of the same composition except that the surface-active agent and the kerosene were omitted.
- the coated panels were sprayed for /2 minute at 70 degrees Fahrenheit with water in order to rinse them, and in the fourth zone they were sprayed for /2 minute at 70 degrees Fahrenheit with a solution containing 0.03 gram per liter CrO and 0.03 gram per liter H PO
- the panels were then oven-dried at 250 degrees Fahrenheit, and excellent uniform crystalline phosphate coatings were obtained with a coating weight of 150 mg./sq. ft.
- Example 2 Steel panels were treated similarly in four zones in what may be called a cool rather than a cold process. The panels were first sprayed for 1 minute at degrees Fahrenheit in a solution of the following composition:
- the surface-active agent was the same as in the first example.
- the total acidity was points and the free acidity 1.2 points.
- the panels were sprayed again at 115 degrees Fahrenheit for 1 minute in a solution of the same composition as in the first zone except that the surface-active agent was omitted.
- the panels were rinsed by spraying with water for /2 minute at 70 degrees Fahrenheit, and in the last zone theye were rinsed at the same temperature for /2 minute by a solution containing 0.03 g./l. CrO and 0.03 g./l. H PO Excellent crystalline coatings were obtained f 170 mg./sq. ft. The quality of the coatings was as good as that of panels coated by a conventional process carried out in six zones.
- Example 3 A zinc phosphate coating solution containing manganese was formulated according to the procedure of the example in Ser. No. 306,332, now US. Patent 3,338,755. To this was added the non-ionic surface active agent used in the previous examples in an amount of about 0.5 gram per liter. The cleaning and coating process of Example 1 is carried out using this composition for both the cleaning solution in the first zone and the coating solution in the second zone. In each instance, the solutions are :at 80 degrees Fahrenheit. Using this procedure, there were obtained on the steel panels treated excellent coatings of 150 milligrams per square foot.
- the coated panels were subjected to a 5 per-cent salt spray test for 384 hours, as described in the American Society for Testing and Materials (ASTM) Standard Method B1l7-61, the standard 100% humidity test for 504 hours, the standard knife blade adhesion test and the standard impact test, both concave and convex. In each instance excellent results were obtained with little or no evidence of coating failure on any of the panels.
- ASTM American Society for Testing and Materials
- Example 4 The procedure of Example 4 was repeated with the exception that the coating solution used in the second zone also contained kerosene in a proportion of about 5 grams per liter. Using this procedure, there was obtained a coating weight of about 165 milligrams per square foot on the treated panels, which coating :gave substantially the same results when subjected to the test of Example 3 as did the coatings of Example 3.
- a process for treating metal surfaces which comprises contacting the metal surface with a first aqueous acidic phosphatin-g solution selected from the group consisting of zinc, iron and manganese phosphating solutions, said solution having a pH of from about 2.5 to 4 and containing at least one additive selected from the group consisting of non-ionic surface active agents and emulsified organic solvents, said additives being present in amounts of 0.1 to 5 grams per liter and amounts of l to 20 "grams per liter, respectively, maintaining said first solution in contact with the metal surface for a period sufficient to effect cleaning thereof, thereafter, without an intervening water rinse, contacting the thus-cleaned surface with a second aqueous acidic phosphating solution having a pH of from about 2.5 to 4, said second phosphating solution having the same composition as said first phosphating solution but being substantially free of the additives selected from the indicated group, and maintaining said solution in contact with the metal surface for a period sufiicient to form a phosphate coating.
- both the first and second phosphating solutions are at a temperature from about 40 to degrees Fahrenheit.
- nonionic surface active agent additive is present in an amount of from about 0.1 to 2 grams per liter and the emulsified organic solvent additive is present in an amount from about 1 to 10 grams per liter.
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- 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
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US368738A US3397093A (en) | 1964-05-19 | 1964-05-19 | Treatment of metal surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US368738A US3397093A (en) | 1964-05-19 | 1964-05-19 | Treatment of metal surfaces |
Publications (1)
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US3397093A true US3397093A (en) | 1968-08-13 |
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US368738A Expired - Lifetime US3397093A (en) | 1964-05-19 | 1964-05-19 | Treatment of metal surfaces |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1949713A (en) * | 1932-04-05 | 1934-03-06 | American Chem Paint Co | Material for preparing metal surfaces for painting and the like |
US2209291A (en) * | 1938-11-23 | 1940-07-23 | Frederick Le Pan | Rust removing composition |
US2470136A (en) * | 1944-09-22 | 1949-05-17 | Harry M Bramberry | Composition for treating metallic wear surfaces |
US2479423A (en) * | 1946-02-07 | 1949-08-16 | American Chem Paint Co | Method of and materials for treating surfaces of iron, zinc, and alloys of each |
US2744555A (en) * | 1950-03-31 | 1956-05-08 | Parker Rust Proof Co | Method of simultaneously phosphating and cleaning metal surfaces and composition therefor |
US2800422A (en) * | 1953-04-20 | 1957-07-23 | Piccinelli Achille | Process for rust-proofing and passivating iron articles |
US2809906A (en) * | 1952-11-25 | 1957-10-15 | Wyandotte Chemicals Corp | Phosphating compositions |
US2857298A (en) * | 1957-09-16 | 1958-10-21 | Chester W Smith | Composition and method for cleaning and phosphating metal |
US3007817A (en) * | 1957-11-29 | 1961-11-07 | Parker Rust Proof Co | Cold cleaning and cold phosphate coating process |
-
1964
- 1964-05-19 US US368738A patent/US3397093A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1949713A (en) * | 1932-04-05 | 1934-03-06 | American Chem Paint Co | Material for preparing metal surfaces for painting and the like |
US2209291A (en) * | 1938-11-23 | 1940-07-23 | Frederick Le Pan | Rust removing composition |
US2470136A (en) * | 1944-09-22 | 1949-05-17 | Harry M Bramberry | Composition for treating metallic wear surfaces |
US2479423A (en) * | 1946-02-07 | 1949-08-16 | American Chem Paint Co | Method of and materials for treating surfaces of iron, zinc, and alloys of each |
US2744555A (en) * | 1950-03-31 | 1956-05-08 | Parker Rust Proof Co | Method of simultaneously phosphating and cleaning metal surfaces and composition therefor |
US2809906A (en) * | 1952-11-25 | 1957-10-15 | Wyandotte Chemicals Corp | Phosphating compositions |
US2800422A (en) * | 1953-04-20 | 1957-07-23 | Piccinelli Achille | Process for rust-proofing and passivating iron articles |
US2857298A (en) * | 1957-09-16 | 1958-10-21 | Chester W Smith | Composition and method for cleaning and phosphating metal |
US3007817A (en) * | 1957-11-29 | 1961-11-07 | Parker Rust Proof Co | Cold cleaning and cold phosphate coating process |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
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: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
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 |