CA2320865A1 - Electrolytic phosphate chemical treatment method and a compound film formed on a steel surface - Google Patents
Electrolytic phosphate chemical treatment method and a compound film formed on a steel surface Download PDFInfo
- Publication number
- CA2320865A1 CA2320865A1 CA002320865A CA2320865A CA2320865A1 CA 2320865 A1 CA2320865 A1 CA 2320865A1 CA 002320865 A CA002320865 A CA 002320865A CA 2320865 A CA2320865 A CA 2320865A CA 2320865 A1 CA2320865 A1 CA 2320865A1
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- CA
- Canada
- Prior art keywords
- chemical treatment
- phosphate
- phosphate chemical
- metal
- electrolytic
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
A phosphating process suitable for electrolytic treatment, which uses a phosphating bath comprising a phosphate ion and phosphoric acid, nitric acid, a metal ion capable of forming a complex with phosphate ion in the phosphating bath and a metal ion having an electric potential at which the metal ion dissolved in the phosphating bath is reduced and deposited as metal of a value same as or higher than that of the anode electrolysis reaction of water, the solvent used in the bath, wherein the bath contains a metal ion other than a component of a coating to be formed in an amount of 0 to 400 ppm and is substantially free of solids affecting a coating film-forming reaction.
Claims (40)
1. An electrolytic phosphate chemical treatment method of forming a film containing at least a phosphate and a metal that does not form said phosphate on the surface of an article to be treated having electrical conductivity by performing electrolytic treatment by contacting said article to be treated with a phosphate chemical treatment bath containing at least phosphate ions and phosphoric acid, nitrate ions, metal ions that form a complex with said phosphate ions in said phosphate chemical treatment bath, and metal ions for which the electrical potential at which the ions dissolved in said phosphate chemical treatment bath are reduced and precipitate as metal is equal to or greater than the anodic electrolysis reaction potential of the solvent in the form of water or equal to or greater than -0.83 V
(indicated as the hydrogen standard electrode potential);
characterized in that, said phosphate chemical treatment bath has 0-400 ppm of metal ions other than those which are a component of the film, and is substantially free of solids having an effect on the film formation reaction;
and, said article to be treated is treated by electrolysis in said phosphate chemical treatment bath with a metal material that forms a complex with phosphate ions in said phosphate chemical treatment bath, and a metal material for which the electrical potential at which the ions thereof dissolved in said phosphate chemical treatment bath is reduced and precipitates as metal is equal to or greater than the anodic electrolysis reaction potential of the solvent in the form of water or equal to or greater than -0.83 V (indicated as the hydrogen standard electrode potential).
(indicated as the hydrogen standard electrode potential);
characterized in that, said phosphate chemical treatment bath has 0-400 ppm of metal ions other than those which are a component of the film, and is substantially free of solids having an effect on the film formation reaction;
and, said article to be treated is treated by electrolysis in said phosphate chemical treatment bath with a metal material that forms a complex with phosphate ions in said phosphate chemical treatment bath, and a metal material for which the electrical potential at which the ions thereof dissolved in said phosphate chemical treatment bath is reduced and precipitates as metal is equal to or greater than the anodic electrolysis reaction potential of the solvent in the form of water or equal to or greater than -0.83 V (indicated as the hydrogen standard electrode potential).
2. The electrolytic phosphate chemical treatment method as set forth in claim 1 characterized in that said phosphate chemical treatment bath contains 0-100 ppm of metal ions other than those which are a component of said film which at least contains the phosphate.
3. The electrolytic phosphate chemical treatment method as set forth in claim 1 characterized in that said phosphate chemical treatment bath is composed of said nitrate ions at a concentration of 6-140 g/l, said phosphate ions and phosphoric acid at a concentration of 0.5-60 g/l, metal ions that form a complex with phosphate in said phosphate chemical treatment bath at a concentration of 0.5-70 g/l, and metal ions for which the electrical potential at which the ions dissolved in said phosphate chemical treatment bath are reduced and precipitate as metal is equal to or greater than the anodic electrolysis reaction potential of the solvent in the form of water or equal to or greater than -0.83 V
(indicated as the hydrogen standard electrode potential) at a concentration of 0-40 g/l.
(indicated as the hydrogen standard electrode potential) at a concentration of 0-40 g/l.
4. The electrolytic phosphate chemical treatment method as set forth in claim 3 characterized in that said phosphate chemical treatment bath does not contain an acid having a degree of acid dissociation larger than the degree of acid dissociation of said phosphate ions.
5. The electrolytic phosphate chemical treatment method as set forth in claim 4 characterized in that, in said phosphate chemical treatment bath, the acid having a degree of acid dissociation larger than the degree of acid dissociation of said phosphate ion is composed of nitric acid.
6. The electrolytic phosphate chemical treatment method as set forth in claim 1 characterized in that said metal ions that form a complex with said phosphate ions in said phosphate chemical treatment bath are composed of at least one of metal selected from the group consisting of zinc, iron, manganese and calcium.
7. The electrolytic phosphate chemical treatment method as set forth in claim 1 characterized in that said metal ions for which the electrical potential at which the ions dissolved in said phosphate chemical treatment bath are reduced and precipitate as metal is equal to or greater than the anodic electrolysis reaction potential of the solvent in the form of water or equal to or greater than -0.83 v (indicated as the hydrogen standard electrode potential) is at least one of metal selected from the group consisting of nickel and copper.
8. An electrolytic phosphate chemical treatment method of forming a film containing at least phosphate on the surface of an article to be treated having electrical conductivity by electrolytic treatment by contacting said article to be treated in a phosphate chemical treatment bath containing phosphate ions and phosphoric acid, nitrate ions, and metal ions that form a complex with said phosphate ions in said phosphate chemical treatment bath; characterized in that, said phosphate chemical treatment bath has 0-400 ppm of metal ions other than those which are a component of said film, and is substantially free of solids that have an effect on the film formation reaction; and that said article to be treated is treated by electrolysis with metal materials that form a complex with phosphate ions in said phosphate chemical treatment bath.
9. The electrolytic phosphate chemical treatment method as set forth in claim 8 characterized in that said phosphate chemical treatment bath contains 0-100 ppm of metal ions other than those which form said film which at least contains phosphate.
10. The electrolytic phosphate chemical treatment method as set forth in claim 8 characterized in that said phosphate chemical treatment bath is composed of said nitrate ions at a concentration of 6-140 g/l, said phosphate ions and phosphoric acid at a concentration of 0.5-60 g/l, and metal ions that form a complex with phosphate in said phosphate chemical treatment bath at a concentration of 0.5-70 g/l.
11. The electrolytic phosphate chemical treatment method as set forth in claim 8 characterized in that said phosphate chemical treatment bath does not contain acid having a degree of acid dissociation larger than the degree of acid dissociation of said phosphate ions.
12. The electrolytic phosphate chemical treatment method as set forth in claim 11 wherein, in said phosphate chemical treatment bath, the acid having a degree of acid dissociation larger than the degree of acid dissociation of said phosphate ions is composed of nitric acid.
13. The electrolytic phosphate chemical treatment method as set forth in claim 8 wherein said metal ions that form a complex with said phosphate ion in said phosphate chemical treatment bath are composed of at least one of metal selected from the group consisting of zinc, iron, manganese and calcium.
14. The electrolytic phosphate chemical treatment method as set forth in claim 1 or 8 characterized by performing electrolysis using said article to be treated as the anode.
15. The electrolytic phosphate chemical treatment method as set forth in claim 1 or 8 characterized by performing electrolysis using said article to be treated as the cathode.
16. The electrolytic phosphate chemical treatment method as set forth in claim 1 or 8 characterized by performing electrolysis using said article to be treated as the anode followed by performing electrolysis using said article to be treated as the cathode.
17. The electrolytic phosphate chemical treatment method as set forth in claim 1 or 8 wherein cathodic electrolytic treatment, in which electrolysis of said phosphate chemical treatment method is performed using said article to be treated as the cathode, is composed of at least one of either electrolysis in which a metal material identical to a metal for which ions dissolved in said phosphate chemical treatment bath are reduced and precipitated, and/or an electrically conductive material that is insoluble in said phosphate chemical treatment bath, is used as the anode, and electrolysis in which a metal material that forms a complex in said phosphate chemical treatment bath is used as the anode.
18. The electrolytic phosphate chemical treatment method as set forth in claim 1 wherein a cathodic electrolytic treatment of said phosphate chemical treatment method, in which electrolysis is performed using said article to be treated as the anode, characterized by comprising one cycle consisting of performing electrolysis in which a metal material identical to a metal for which ions dissolved in said phosphate chemical treatment bath are reduced and precipitated, and/or an electrically conductive material that is insoluble in said phosphate chemical treatment bath, is used as the anode, followed by performing electrolysis in which a metal material that forms a complex in said phosphate chemical treatment bath is used as the anode, and this cycle being performed at least once.
19. The electrolytic phosphate chemical treatment method as set forth in claim 1 wherein a cathodic electric treatment of said phosphate chemical treatment method is carried out, in which electrolysis is performed using said article to be treated as the anode, characterized in that an electrolytic treatment is performed by separating it into an electrolysis tank in which electrolysis is performed using an electrically conductive material insoluble in the phosphate chemical treatment bath as the anode, and an electrolysis tank in which electrolysis is performed using a metal material that forms a complex in said phosphate chemical treatment bath as the anode.
20. The electrolytic phosphate chemical treatment method as set forth in any of claims 17 through 19 characterized in that said metal material identical to a metal dissolved in said phosphate chemical treatment bath that is reduced and precipitated is at least one of metal selected from the group consisting of nickel and copper.
21. The electrolytic phosphate chemical treatment method as set forth in any of claims 17 through 19 characterized in that said metal material that forms a complex in said phosphate chemical treatment bath is at least one of metal selected from the group consisting of zinc, iron, manganese and calcium.
22. The electrolytic phosphate chemical treatment method as set forth in claim 1 or 8 characterized in that, in the case that said article to be treated is not in contact with said phosphate chemical treatment bath, the metal material, which is used as the anode in electrolytic treatment in which said article to be treated is used as the cathode, is used as a cathode, a material that is insoluble in said phosphate chemical treatment bath is used as an anode, and a voltage of 5 v or less is applied between said anode and said cathode.
23. The electrolytic phosphate chemical treatment method as set forth in either of claims 1 or 8 characterized in that, in the case that said article to be treated is not in contact with said phosphate chemical treatment bath, the metal material, which is used as the anode in electrolytic treatment in which said article to be treated is used as the cathode, is used as a cathode, a material that is insoluble in said phosphate chemical treatment bath is used as an anode, and voltage is applied, to a degree at which said cathode does not substantially dissolve, between said anode and said cathode.
24. The electrolytic phosphate chemical treatment method as set forth in claim 1 or 8 characterized by removing a portion of said phosphate chemical treatment bath from a tank having said phosphate chemical treatment bath, thermodynamically stabilizing the energy state of the portion as a liquid of said phosphate chemical treatment bath and said portion being later returned to said tank.
25. The electrolytic phosphate chemical treatment method as set forth in claim 24, characterized by removing a portion of said phosphate chemical treatment bath from said tank having said phosphate chemical treatment bath, and removing solids that have precipitated in said phosphate chemical treatment bath during the course of the film formation reaction, and said portion being returned to said tank.
26. The electrolytic phosphate chemical treatment method as set forth in claim 24 characterized in that, when replenishing components of said phosphate chemical treatment bath, a portion of said phosphate chemical treatment bath is removed, and that a replenishing liquid is added to said removed bath that contains treatment bath components having a concentration higher than the concentration of at least one component among the components that compose said phosphate chemical treatment bath.
27. An electrolytic phosphate chemical treatment method in which electrolytic treatment is performed using an article to be treated as the cathode characterized by comprising a reaction in which a metal, for which the electrical potential at which the ions of the metal dissolved in a phosphate chemical treatment bath are reduced and precipitate as a metal is equal to or greater than the anodic electrolysis reaction potential of solvent in the form of water or equal to or greater than -0.83 V (indicated as the hydrogen standard electrode potential), is dissolved in the phosphate chemical treatment bath, is reduced by electrolytic treatment from a cationic state and precipitates on the surface of said article to be treated, and a reaction in which metal ions that complex with phosphate ions in said phosphate chemical treatment bath precipitate as phosphate crystal in said phosphate chemical treatment bath corresponding to dehydrogenation of phosphate ions.
28. The electrolytic phosphate chemical treatment method as set forth in claim 27 characterized in that said metal ions that complex with phosphate ions are at least one of metal selected from the group consisting of Fe, Zn, Mn, Ca and Mg.
29. The electrolytic phosphate chemical treatment method as set forth in claim 27 characterized in that said metal for which the electrical potential at which the ions thereof dissolved in said phosphate chemical treatment bath are reduced and precipitate as a metal is equal to or greater than the anodic electrolysis reaction potential of solvent in the form of water or equal to or greater than -0.83 V (indicated as the hydrogen standard electrode potential) is at least one of metal selected from the group consisting of Ni, Cu, Fe and Zn.
30. The electrolytic phosphate chemical treatment method as set forth in at least one of claims 1, 8 and 27 characterized in that the composition of the treatment bath when electrolytic treatment is performed is such that the ratio of the concentration of metal ions that complex with phosphate ions (g/l) to the concentration of phosphate ions and phosphoric acid (g/l) is 0.1 or more.
31. The electrolytic phosphate chemical treatment method in which electrolytic treatment is performed using said article to be treated as the cathode as set forth in at least one of claims 1, 8 and 27, characterized in that at the start of said electrolytic treatment, the voltage applied between metal materials that form an anode and a cathode is varied.
32. The electrolytic phosphate chemical treatment method as set forth in claim 31 characterized in that said variation in the voltage applied at the start of said electrolytic treatment is in the form of pulses.
33. A compound film on a steel surface characterized by being composed of a metal that does not form a phosphate and a phosphate compound, wherein said metal and phosphate compound that compose the film are dispersed throughout the entire film.
34. A compound film on a steel surface characterized by being composed of a metal that does not form a phosphate and a phosphate compound, wherein a metal is present on the uppermost surface of the film that at least does not form phosphate.
35. A compound film on a steel surface characterized by being composed of a metal that does not form a phosphate and a phosphate compound, wherein said film does not demonstrate peaks other than the inevitable unavoidable peak of phosphate in X-ray diffraction analysis.
36. A compound film on a steel surface characterized by being composed of a metal that does not form a phosphate and a phosphate compound, wherein the number of atoms of the metal that does not form a phosphate is 0.25 or more the number of atoms of phosphorus that composes phosphate crystals.
37. The compound film as set forth in at least one of claims 33 through 36 characterized in that said metal that does not form a phosphate is at least one of metal selected from the group consisting of Ni, Cu, Fe and Zn.
38. The compound film as set forth in at least one of claims 33 through 36 characterized in that a metal that forms a phosphate compound is at least one metal selected from the group consisting of Fe, Zn, Mn, Ca and Mg.
39. The compound film as set forth in at least one of claims 33 through 36 characterized in that said steel contains at least 95% by weight of iron (Fe) when the total amount of steel is taken to be 100% by weight.
40. The compound film as set forth in claim 35 characterized in that said X-ray diffraction analysis is performed by ESCA or EDX analysis.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35925498 | 1998-12-17 | ||
| JP10/359254 | 1998-12-17 | ||
| PCT/JP1999/007124 WO2000036191A1 (en) | 1998-12-17 | 1999-12-17 | Electrolytic phosphating process and composite coating formed on steel surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2320865A1 true CA2320865A1 (en) | 2000-06-22 |
| CA2320865C CA2320865C (en) | 2010-03-16 |
Family
ID=18463558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2320865A Expired - Fee Related CA2320865C (en) | 1998-12-17 | 1999-12-17 | Electrolytic phosphate chemical treatment method and a compound film formed on a steel surface |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1074640A4 (en) |
| KR (1) | KR100400522B1 (en) |
| CN (1) | CN1221687C (en) |
| BR (1) | BR9907916B1 (en) |
| CA (1) | CA2320865C (en) |
| WO (1) | WO2000036191A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006007730A1 (en) * | 2004-07-21 | 2006-01-26 | The University Of British Columbia | Method of electrolytically depositing a pharmaceutical coating onto a conductive osteal implant |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3479609B2 (en) * | 1999-03-02 | 2003-12-15 | 日本パーカライジング株式会社 | Sludge-free zinc phosphate treatment liquid and zinc phosphate treatment method |
| JP4019723B2 (en) | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| DE102005023023B4 (en) * | 2005-05-19 | 2017-02-09 | Chemetall Gmbh | Method of preparing metallic workpieces for cold forming, process coated workpieces and their use |
| EP2186928A1 (en) * | 2008-11-14 | 2010-05-19 | Enthone, Inc. | Method for the post-treatment of metal layers |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4111186A1 (en) * | 1991-04-06 | 1992-10-08 | Henkel Kgaa | METHOD FOR PHOSPHATING METAL SURFACES |
| JPH05306497A (en) * | 1992-04-30 | 1993-11-19 | Nippondenso Co Ltd | Phophatizing chemical conversion treatment |
-
1999
- 1999-12-17 CA CA2320865A patent/CA2320865C/en not_active Expired - Fee Related
- 1999-12-17 CN CNB998041718A patent/CN1221687C/en not_active Expired - Lifetime
- 1999-12-17 WO PCT/JP1999/007124 patent/WO2000036191A1/en active IP Right Grant
- 1999-12-17 KR KR10-2000-7008710A patent/KR100400522B1/en active IP Right Grant
- 1999-12-17 EP EP99959898A patent/EP1074640A4/en not_active Ceased
- 1999-12-17 BR BRPI9907916-0A patent/BR9907916B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006007730A1 (en) * | 2004-07-21 | 2006-01-26 | The University Of British Columbia | Method of electrolytically depositing a pharmaceutical coating onto a conductive osteal implant |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010040816A (en) | 2001-05-15 |
| BR9907916B1 (en) | 2011-07-26 |
| KR100400522B1 (en) | 2003-10-10 |
| CN1221687C (en) | 2005-10-05 |
| CA2320865C (en) | 2010-03-16 |
| EP1074640A1 (en) | 2001-02-07 |
| EP1074640A4 (en) | 2006-06-21 |
| WO2000036191A1 (en) | 2000-06-22 |
| CN1293720A (en) | 2001-05-02 |
| BR9907916A (en) | 2002-04-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20131217 |