US3200004A - Process for the after-treatment of phosphate coatings - Google Patents
Process for the after-treatment of phosphate coatings Download PDFInfo
- Publication number
- US3200004A US3200004A US220047A US22004762A US3200004A US 3200004 A US3200004 A US 3200004A US 220047 A US220047 A US 220047A US 22004762 A US22004762 A US 22004762A US 3200004 A US3200004 A US 3200004A
- Authority
- US
- United States
- Prior art keywords
- treatment
- drying
- phosphonic acid
- water
- solutions
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
United States Patent M 3,200,004 PROCESS FOR THE AFTER-TREATMENT GlF PHUSPHATE COATINGS Willy Herhst, Hofheim, Taunus, Fritz Rochlitz, Bad Soden, Taunus, and Herbert Vileseir, Hofheim, Tauuus, Germany, assignors to Farhwerke Hoechst Alrtiengeseilschaft vormals Meister Lucius & Blurring, Frankfurt am Main, Germany, a corporation of Germany.
No Drawing. Filed Aug. 28, 1962, Ser. No. 220,047 Claims priority, application Germany, Aug. 31, 1061, F 34,821 2 Claims. (Cl. 117-69) The present invention relates to a process for the aftertreatment of phosphatized metal surfaces with solutions of alkene phosphonic acids. The phosphate coatings produced on metal surfaces, especially on iron and steel surfaces, for the purpose of corrosion protection, are porous and only otter sufiicient protection for industrial requirements when followed by an appropriate after-treatment. This after-treatment is generally carried out with solutions containing compounds of hexavalent chromium, especially chromic acid. Proposals for improving such after-treatment solutions have already been made. Thus it has been proposed, for example, to add soluble, complex fluorides or certain metal salts, such as cerium nitrate, to chromic acid solutions.
The known after-treatment processes, however, have the disadvantage that they necessitate a special treatment of the waste water. Owing to the toxicity of hexavalent and trivalent chromium, compounds of these ions must be removed almost quantitatively from the waste water.
Now we have found a process for the after-treatment of phosphatized metal surfaces in which the disadvantages of the processes described above, in particular the formation of toxic waste waters, are avoided. The process is characterized in that the phosphatized metal parts are treated with solutions of on alkene phosphonic acid having two or three carbon atoms per molecule, preferably vinyl phosphonic acid, and subsequently dried. Solutions containing about 0.008 to about 2 percent by weight, preferably 0.02 to 0.5 percent by weight, of alkene phosphonic acid, have proved to be particularly suitable.
As solvents for the alkene phosphonic acids there may be used, in addition to water, aliphatic alcohols having 1 to 4 carbon atoms per molecule, preferably isopropanol, or the mixtures thereof with water. The phosphatized metal parts can be treated with the solutions according to the invention in the usual manner, for example, by immersion, spraying or flooding.
The period during which the alkene phosphonic acid solutions may act upon the phosphatized metal parts to be treated is, in most cases, not limited. It is only necessary that the metal parts are satisfactorily wetted with the solutions. It is advisable, however, not to exceed a period of five minutes in the case of concentrated solutions, especially when the solutions contain more than 1 percent by weight of alkene phosphonic acid.
When drying the metal parts treated with the aforesaid solutions, care has only to be taken that a temperature of 200 C. is not exceeded. The drying temperature depends especially on the solvent used.
The following example serves to illustrate the invention, but it is not intended to limit it thereto:
Example Steel plates (of class St VIII), as characterized by Deutsche Industrie Norm DIN 1623 were coated in a commercially available phosphatizing bath with a well adhering, light-gray layer of zinc-phosphate. Some of these phosphatized plates was immersed at room temperature for seconds into an aqueous solution of 0.5 g. of
3,21%,fifi4 Fatented Aug. 10, 1905 vinyl phosphonic acid per liter and then dried in the drying closet at 140 C. for five minutes. Other of the plates were dried at once after the phosphatizing process with out being subjected to an after-treatment. All these test plates were then varnished and subjected to the various usual corrosion and varnish adhesion tests.
It was found that the test samples after-treated according to the invention have excellent test values. Plates that have at once been varnished after the phosphatizing process without being subjected to an after-treatment, however, only possess an inferior protection against corrosion; their test values are poor.
Good results were also obtained when the plates were subjected to an after-treatment with the following solutions:
(a) 4.5 g. of vinyl phosphonic acid dissolved in l l. of water (treatment time 3 seconds; bath temperature 11 C.; drying temperature 150 C.; drying period 10 minutes);
(b) 0.15 g. of vinyl phosphonic acid dissolved in 1 l. of water (treatment time 1 minute; bath temperature 40 C.; drying temperature 110 C.; drying period 6 minutes);
(c) 0.4 g. of allyl phosphonic acid (propene-2,3- phosphonic-l-acid, CH CHCH PO H dissolved in 1 l. of water (treatment time 10 seconds; bath temperature about 20 C.; drying temperature 150 C.; drying period 5 minutes);
(d) 3.1 g. of propene phosphonic acid (propene-l,2- phosphonic-Lucid, CH CH=CHPO H dissolved in 1 l. of water (treatment time 6 seconds; bath temperature about 20 C.; drying temperature 150 C.; drying period 5 minutes);
(e) 1.1 g. of vinyl phosphonic acid dissolved in a mixture of 500 parts of water and 500 parts of isopropanol (treatment time 30 seconds; bath temperature about 20 C.; drying temperature 110 C.; drying period 5 minutes);
(f) 0.4 g. of vinyl phosphonic acid dissolved in a mixture of 700 parts of water and 300 parts of methanol (treatment time 30 seconds; bath temperature about 20 C.; drying temperature 150 C.; drying time 5 minutes);
(g) 18 g. of vinyl phosphonic acid dissolved in a mixture of 700 parts of water, 100 parts of butanol and 200 parts of isopropanol (treatment time 3 seconds; bath temperature 4 C.; drying temperature 150 C.; drying time 5 minutes);
(h) 0.08 g. of vinyl phosphonic acid dissolved in 1 l. of water (treatment time 2 minutes; bath temperature 40 C.; drying temperature 110 C.; drying time 6 minutes).
We claim:
1. A process for improving the corrosion protection of phosphatized metal surfaces, which process comprises after-treating said phosphatized metal surfaces with a solution containing from about 0.008 percent to about 2 percent by weight of an alkene phosphonic acid having 2 to 3 carbon atoms in at least one solvent selected from the group consisting of water and aliphatic alcohols having 1 to 4 carbon atoms, and then drying the treated surface.
2. A process as in claim 1 wherein said solution contains from 0.02 percent to 0.5 percent by weight of said alkene phosphonic acid.
References @ited by the Examiner UNITED STATES PATENTS 2,885,312 5/59 McDonald 148--6.15 3,012,917 12/61 Riou et al 148--6.15
RICHARD D. NEVIUS, Primary Examiner.
WILLIAM D. MARTIN, Examiner.
Claims (1)
1. A PROCESS FOR IMPROVING THE CORRIOSION PROTECTION OF PHOSPHATIZED METAL SURFACES, WHICH PROCESS COMPRISES AFTER-TREATING SAID PHOSPHATIZED METAL SURFACES WITH A SOLUTION CONTAINING FROM ABOUT 0.08 PERCENT TO ABOUT 2 PERCENT BY WEIGHT OF AN ALKENE PHOSPHONIC ACID HAVING 2 TO 3 CARBON ATOMS IN AT LEAST ONE SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER AND ALIPHATIC ALCOHOLS HAVING 1 TO 4 CARBON ATOMS, AND THEN DRYING THE TREATED SURFACE.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF34821A DE1207760B (en) | 1961-08-31 | 1961-08-31 | Process for post-treatment of phosphate layers |
Publications (1)
Publication Number | Publication Date |
---|---|
US3200004A true US3200004A (en) | 1965-08-10 |
Family
ID=7095730
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US220047A Expired - Lifetime US3200004A (en) | 1961-08-31 | 1962-08-28 | Process for the after-treatment of phosphate coatings |
Country Status (7)
Country | Link |
---|---|
US (1) | US3200004A (en) |
BE (1) | BE621988A (en) |
CH (1) | CH404340A (en) |
DE (1) | DE1207760B (en) |
GB (1) | GB1003705A (en) |
LU (1) | LU42245A1 (en) |
NL (1) | NL282487A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3293088A (en) * | 1959-11-18 | 1966-12-20 | Hoechst Ag | Method for producing adherent coatings on clean metal parts |
US3459600A (en) * | 1966-11-07 | 1969-08-05 | Todco Chem Co Inc | Novel zinc coating composition and method |
US3850700A (en) * | 1971-10-18 | 1974-11-26 | Amchem Prod | Method and materials for coating metal surfaces |
US4000012A (en) * | 1973-10-06 | 1976-12-28 | Ciba-Geigy Corporation | Anticorrosive coating of steel |
US20050268991A1 (en) * | 2004-06-03 | 2005-12-08 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
US20080261025A1 (en) * | 2007-04-18 | 2008-10-23 | Enthone Inc. | Metallic surface enhancement |
US20080314283A1 (en) * | 2007-06-21 | 2008-12-25 | Enthone Inc. | Corrosion protection of bronzes |
US20090121192A1 (en) * | 2007-11-08 | 2009-05-14 | Enthone Inc. | Self assembled molecules on immersion silver coatings |
US20100291303A1 (en) * | 2007-11-21 | 2010-11-18 | Enthone Inc. | Anti-tarnish coatings |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2885312A (en) * | 1956-03-05 | 1959-05-05 | Kelite Corp | Metal coating compositions |
US3012917A (en) * | 1957-03-26 | 1961-12-12 | Pechiney Prod Chimiques Sa | Method of protecting metal surfaces |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1174045A (en) * | 1957-03-26 | 1959-03-05 | Pechiney | Metal protection |
-
0
- NL NL282487D patent/NL282487A/xx unknown
- BE BE621988D patent/BE621988A/xx unknown
-
1961
- 1961-08-31 DE DEF34821A patent/DE1207760B/en active Pending
-
1962
- 1962-08-21 LU LU42245D patent/LU42245A1/xx unknown
- 1962-08-28 US US220047A patent/US3200004A/en not_active Expired - Lifetime
- 1962-08-28 GB GB33052/62A patent/GB1003705A/en not_active Expired
- 1962-08-29 CH CH1027462A patent/CH404340A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2885312A (en) * | 1956-03-05 | 1959-05-05 | Kelite Corp | Metal coating compositions |
US3012917A (en) * | 1957-03-26 | 1961-12-12 | Pechiney Prod Chimiques Sa | Method of protecting metal surfaces |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3293088A (en) * | 1959-11-18 | 1966-12-20 | Hoechst Ag | Method for producing adherent coatings on clean metal parts |
US3459600A (en) * | 1966-11-07 | 1969-08-05 | Todco Chem Co Inc | Novel zinc coating composition and method |
US3850700A (en) * | 1971-10-18 | 1974-11-26 | Amchem Prod | Method and materials for coating metal surfaces |
US4000012A (en) * | 1973-10-06 | 1976-12-28 | Ciba-Geigy Corporation | Anticorrosive coating of steel |
US20050268991A1 (en) * | 2004-06-03 | 2005-12-08 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
WO2005121405A1 (en) * | 2004-06-03 | 2005-12-22 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
CN101001980B (en) * | 2004-06-03 | 2011-06-15 | 恩索恩公司 | Corrosion resistance enhancement of tin surfaces |
US7883738B2 (en) | 2007-04-18 | 2011-02-08 | Enthone Inc. | Metallic surface enhancement |
US20100151263A1 (en) * | 2007-04-18 | 2010-06-17 | Enthone Inc. | Metallic surface enhancement |
US20080261025A1 (en) * | 2007-04-18 | 2008-10-23 | Enthone Inc. | Metallic surface enhancement |
US8741390B2 (en) | 2007-04-18 | 2014-06-03 | Enthone Inc. | Metallic surface enhancement |
US20100319572A1 (en) * | 2007-06-21 | 2010-12-23 | Enthone Inc. | Corrosion protection of bronzes |
US20080314283A1 (en) * | 2007-06-21 | 2008-12-25 | Enthone Inc. | Corrosion protection of bronzes |
US10017863B2 (en) | 2007-06-21 | 2018-07-10 | Joseph A. Abys | Corrosion protection of bronzes |
US20090121192A1 (en) * | 2007-11-08 | 2009-05-14 | Enthone Inc. | Self assembled molecules on immersion silver coatings |
US8216645B2 (en) | 2007-11-08 | 2012-07-10 | Enthone Inc. | Self assembled molecules on immersion silver coatings |
US8323741B2 (en) | 2007-11-08 | 2012-12-04 | Abys Joseph A | Self assembled molecules on immersion silver coatings |
US20100291303A1 (en) * | 2007-11-21 | 2010-11-18 | Enthone Inc. | Anti-tarnish coatings |
US7972655B2 (en) | 2007-11-21 | 2011-07-05 | Enthone Inc. | Anti-tarnish coatings |
Also Published As
Publication number | Publication date |
---|---|
GB1003705A (en) | 1965-09-08 |
LU42245A1 (en) | 1962-10-22 |
CH404340A (en) | 1965-12-15 |
DE1207760B (en) | 1965-12-23 |
BE621988A (en) | |
NL282487A (en) |
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