US3679493A - Glycol ether-chromium corrosion resistant coatings for metallic surfaces - Google Patents
Glycol ether-chromium corrosion resistant coatings for metallic surfaces Download PDFInfo
- Publication number
- US3679493A US3679493A US18762A US3679493DA US3679493A US 3679493 A US3679493 A US 3679493A US 18762 A US18762 A US 18762A US 3679493D A US3679493D A US 3679493DA US 3679493 A US3679493 A US 3679493A
- Authority
- US
- United States
- Prior art keywords
- composition
- water
- ether
- chromium
- glycol
- 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
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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
- C23C22/05—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
- C23C22/24—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 hexavalent chromium compounds
-
- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/33—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 hexavalent chromium compounds containing also phosphates
Definitions
- ABSTRACT OF THE DISCLOSURE A process and composition for increasing the resistance to corrosion of a metallic surface, which process comprises contacting said metallic surface with a composition obtained by mixing in the presence of water a water soluble chromium compound such as chromium trioxide, ammonium chromate, chromium chromate, and the like, and an oxygenated organic compound having the following formula:
- the instant invention relates to a composition useful in increasing the corrosion resistance of metallic surfaces and a process for protecting metallic surfaces by the application of such compositions thereto.
- the instant invention is directed to the use of a composition comprising a chromium compound and an oxygenated organic compound ('I) to increase the corrosion resistance of metallic surfaces.
- compositions employed also contained additional ingredients such as polymeric materials, a multiplicity of reducing agents, fillers, and the like.
- the composition of the instant invention is a relatively simple one which includes a solution of the 3,679,493 Patented July 25, 1972 reaction product of a water soluble chromium compound with an oxygenated organic compound as the essential ingredient thereof. While other materials may be added to the instant composition, they are not essential to the effectiveness thereof.
- Another object of the instant invention is to provide for a process of improving the corrosion resistance of metallic surfaces.
- composition of the instant invention is considered particularly useful in protecting ferrous metallic surfaces in general such as iron and steel plate or castings, tin coated and zinc coated (galvanized) iron and steel and other ferrous alloys.
- Other metallic surfaces which may be protected by the composition and product of this invention include non-ferrous substrates such as zinc surfaces, aluminum surfaces, magnesium surfaces, tin surfaces, and non-ferrous alloy surfaces such as brass, bronze and the like.
- one of the essential ingredients of the instant composition is a water-soluble chromium compound.
- the useful chromium compounds include, but are not limited to, chromium trioxide, ammonium chromate, zinc chromate, chromium chromate, chromic acid, potassium dichromate, and mixtures thereof. It is, of course, within the scope of the instant invention to employ other chromium salts similar to the above which are soluble in the reaction medium.
- the useful oxygenated organic compounds generally have the formula:
- R represents an alkyl group having from 1 to 6 carbon atoms
- R and -R represent hydrogen or an alkyl group having from 1 to 6 carbon atoms
- n is an integer of from 1 to 4.
- the wetting agent employed must be one which is compatible with, and stable in the presence of, the chromium compound employed in the instant invention. Therefore, preferably, one employs as the wetting agent a nonionic or anionic surfactant material although other types of surfactants may also be employed if compatible under the conditions of use. Representative of the surfactants which may be employed are the following:
- Alkylaryl sulfonates such as sodium alkylnaphthalene sulfonate.
- Alkyl sulfates such as sodium lauryl sulfate.
- phosphoric acid may be added to the composition of the instant invention to increase, to some degree, the adhesion of the coating composition to the metallic surface.
- composition of the instant invention is prepared by admixing the water-soluble chromium compound delineated above with the oxygenated organic compound also delineated above in the presence of Water. While the exact reaction is unknown, it is though that the oxygenated organic compound forms an oxidized complex and this results in an improved corrosion resistant coating.
- compositions of the instant invention it is preferred to employ from about 0.05 to about 50 percent by weight of the oxygenated organic compound and from about 0.5 to about 10 percent by weight of the water-soluble of the chromium compound.
- phosphoric acid in amounts from about 0.5 percent to about 10 percent have been found to be useful.
- wetting agents or surfactants if employed, amounts from about 0.01 percent to about 1 percent by weight are adequate.
- the compositions of the instant invention include from about 0.5 to about 10 percent of the glycol ether and from about 2 to about 7 percent of the water-soluble chromium compound.
- Solution A This solution, containing 40% glycol ether, was prepared by adding to a wide mouth jar.
- Solution B A 10% solution of chromic acid in water was prepared by adding to a wide mouth jar.
- Solution D This solution, containing 10.0% chromic acid and 1.0% phosphoric acid was prepared by adding to a wide mouth jar Grams Chromic trioxide 10.0 86% phosphoric acid 1.0 Water 89.0
- This mixture was shaken to dissolve at room temperature.
- Solutions containing the other compositions listed in Table 1 were prepared in a similar fashion.
- the wetting agent when used, was added by using the proper volume of a dilute (0.10%) aqueous solution of the wetting agent.
- Carbon steel (1010) panels were used for the rust inhibition test. These panels measured 3" x 8" x 0.051" and were cut from steel which had been cold rolled using rolls that yields a surface finish of 6-12 microinches. The panels had been protected from rusting with a vapor phase inhibitor and were used directly as received.
- the panels were dip-coated in the proper formulation, withdrawn from the solution and allowed to drain dry at room temperature. After standing at room temperature for 24 hours, the panels were placed in the QCT condensing humidity cabinet.
- the cabinet was operated with the water temperature at 131 F. and vapor temperature at F. Rusting was induced by the moisture which condensed continuously on the panels.
- the panels were observed daily for the appearance of rust spots and were rated as follows. A perimeter approximately A" wide was excluded from observation.
- a test surface passed if it contained no more than three dots of rust, no one of which was greater than 1 mm. in diameter.
- a test surface failed if it contained one or more dots of rust larger than 1 mm. in diameter or if it contained four or more dots of any size.
- the number of days protection obtained was a measure of product performance.
- Table 1 shows the number of days of rust protection afforded to panels which had been coated with the rust inhibiting compositions described.
- EXAMPLE 2 Coating formulations containing glycol ether and EIQKMPLE 4 5.0% chromic trioxide were prepared by adding to a wide Aqueous coating solutions were prepared using chrommouth jar lum trioxlde and the triand tetraethylene glycols listed Grams in Table 3. Panels were air dried for 24, 120, or 168 Ethylene glycol monobutyl ether 50 50 hours and were oven cured for 15 min. at 100 C. The
- a corrosion-resistant coating composition consisting TABLE 4.-NUMBER OF DAYS RUST PROTECTION IN'QCT CABINET AT 120 F. VAPOR TEMPERATURE Days rust Protection I e Impacted Area Plane area Monobutyl- Air drie Oven dried ether of Ethoxy- 120 hrs. 100 0., 15 min ethylene Ethoxylated Oven dried glycol, Percent Percent lated alkyl- Percent 70 80 70 '80 Air dried 110-110" 0., Formulation ref. percent CrO; H 04 alcohol 1 phenol I water in.-lb in.-lb. in.-lb. in.-lb. 120 hrs 15 m Cir-1a alcohol plus 70% ethyleneoxide.
- compositions of the instant invention including phosphoric acid and a wetting agent, provided superior rust protection.
- EXAMPLE 7 Coating formulations were prepared as in Example 1 containing 5.0% and 20.0% of the dimethyl ethers of triand tetraethylene glycol with 5.0% chromic acid. Some of the solutions contained phosphoric acid; some of them contained a wetting agent. The composition and performance data are shown in Table 6. Some panels were air dried for 24-120 hours; some were oven dried for 15 min. at 100 C.
- R is an alkyl group having from 1 to 6 carbon atoms
- R and R are selected from the group consisting of hydrogen and an alkyl group having from 1. to 6 carbon atoms
- n is an integer of from 1 to 4
- said chromium compound being present in an amount of from about 0.5 to about 10% by weight and said compound of Formula I being present in an amount of from about 0.5 to about 50% by weight.
- said composition of claim 1 wherein said chromium compound is present in an amount of from about 2 to about 7% by weight.
- composition of claim 1 aqueous solution thereof.
- a corrosion-resistant coating composition according to claim 1 additionally including at least one member selected from the group consisting of phosphoric acid, and compatible anionic and non-ionic surfactants.
- composition of claim 5 wherein the water-soluble chromium compound is chromium trioxide.
- composition of claim 5 wherein the compound having the structure of Formula I is the monobutyl ether of ethylene glycol.
- composition of claim 5 wherein the compound of Formula I is the monoalkyl ether'of ethylene glycol.
- composition of claim 5 wherein the compound having the structure of Formula 6 is the monoalkyl ether of diethylene glycol.
- composition of claim 5 wherein the compound having the structure of Formula I is the monoalkyl ether of propylene glycol.
- compositions of the instant invention provide a surprising and unexpected rust protection for metallic surfaces.
- composition of claim 5 wherein the compound having the structure of Formula I is the monoalkyl ether of triethylene glycol.
- composition of claim wherein the phosphoric acid is present in an amount of from about .05 to about percent.
- composition of claim 5 wherein the compound having the structure of Formula I is monobutyl ether of ethylene glycol.
- a process for improving the corrosion resistance of metallic surfaces which comprise contacting a metallic surface with a composition according to claim 1 whereby there is formed a corrosion-resistant film upon said surface and allowing said film to dry thereon.
- composition is in the form of an aqueous solution thereof.
- composition additionally contains at least one member selected from the group consisting of phosphoric acid and anionic and non-ionic surfactants.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
R1-O-(CH(-R2)-CH(-R2)-O)N-R3
WHEREIN R1 IS AN ALKYL GROUP HAVING FROM 1 TO 6 CARBON ATOMS, R2 IS HYDROGEN OR AN ALKYL GROUP HAVING FROM 1 TO 6 CARBON ATOMS, AND R3 HYDROGEN OR AN ALKYL GROUP HAVING FROM 1 TO 6 CARBON ATOMS, N IS AN INTERGER OF FROM 1 TO 4.
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1876270A | 1970-03-11 | 1970-03-11 |
Publications (1)
Publication Number | Publication Date |
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US3679493A true US3679493A (en) | 1972-07-25 |
Family
ID=21789657
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US18762A Expired - Lifetime US3679493A (en) | 1970-03-11 | 1970-03-11 | Glycol ether-chromium corrosion resistant coatings for metallic surfaces |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50105521A (en) * | 1974-01-28 | 1975-08-20 | ||
US3907608A (en) * | 1971-08-19 | 1975-09-23 | Diamond Shamrock Corp | Coated metal and method |
US4098620A (en) * | 1977-06-20 | 1978-07-04 | Diamond Shamrock Corporation | Composite coating of enhanced resistance to attack |
US4497876A (en) * | 1983-03-16 | 1985-02-05 | Kidon William E | Corrosion resistant metal composite with zinc and chromium coating |
US4548646A (en) * | 1982-11-15 | 1985-10-22 | Sermatech International Incorporated | Thixotropic coating compositions and methods |
US5196055A (en) * | 1991-01-23 | 1993-03-23 | The Sherwin-Williams Company | VOC compliant pretreatment primers |
-
1970
- 1970-03-11 US US18762A patent/US3679493A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3907608A (en) * | 1971-08-19 | 1975-09-23 | Diamond Shamrock Corp | Coated metal and method |
JPS50105521A (en) * | 1974-01-28 | 1975-08-20 | ||
US4059452A (en) * | 1974-01-28 | 1977-11-22 | Oxy Metal Industries Corporation | Metal surface treatment |
JPS5347063B2 (en) * | 1974-01-28 | 1978-12-18 | ||
US4098620A (en) * | 1977-06-20 | 1978-07-04 | Diamond Shamrock Corporation | Composite coating of enhanced resistance to attack |
US4548646A (en) * | 1982-11-15 | 1985-10-22 | Sermatech International Incorporated | Thixotropic coating compositions and methods |
US4497876A (en) * | 1983-03-16 | 1985-02-05 | Kidon William E | Corrosion resistant metal composite with zinc and chromium coating |
US5196055A (en) * | 1991-01-23 | 1993-03-23 | The Sherwin-Williams Company | VOC compliant pretreatment primers |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION Free format text: SECURITY INTEREST;ASSIGNOR:DORSET INC. A CORP OF DELAWARE;REEL/FRAME:005122/0370 Effective date: 19890329 |
|
AS | Assignment |
Owner name: GAF CHEMICALS CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:DORSET INC.;REEL/FRAME:005251/0071 Effective date: 19890411 |
|
AS | Assignment |
Owner name: DORSET INC., A DE CORP. Free format text: CHANGE OF NAME;ASSIGNOR:GAF CORPORATION, A DE CORP.;REEL/FRAME:005250/0940 Effective date: 19890410 |