CA2018631C - Process for a passivating postrinsing of phosphate layers - Google Patents
Process for a passivating postrinsing of phosphate layersInfo
- Publication number
- CA2018631C CA2018631C CA002018631A CA2018631A CA2018631C CA 2018631 C CA2018631 C CA 2018631C CA 002018631 A CA002018631 A CA 002018631A CA 2018631 A CA2018631 A CA 2018631A CA 2018631 C CA2018631 C CA 2018631C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- postrinsing
- passivating
- paint
- metal surfaces
- 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 - Fee Related
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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
Abstract
In a process for a passivating postrinsing of phosphate layers on metals before the application of a paint or adhesive, aqueous solutions are employed which have been adjusted to a pH value of 3 to 5 and which contain an aluminum fluorozirconate in which the Al:Zr:F mole ratio is (0.15 to 0.65):1:(5 to 7), and in which solutions the total concentration of Al + Zr + F is 0.1 to 2.0 g/l, preferably 0.2 to 0.8 g/l. the postrinsing solutions may additionally contain at least one of the anions benzoate, caprylate, ethyl hexoate, salicylate in a total concentration of 0.05 to 0.5 g/l and may preferably be adjusted to the required pH
value with cations of volatile bases, such as ammonium, ethanolammonium and di- and triethanolammonium. The paint is subsequently applied suitably by cathodic electrocoating or powder coating or from a low-solvent high-solids paint.
value with cations of volatile bases, such as ammonium, ethanolammonium and di- and triethanolammonium. The paint is subsequently applied suitably by cathodic electrocoating or powder coating or from a low-solvent high-solids paint.
Description
CA 02018631 1999-01-1~
The present invention relates to a process for a passivating postrinsing of phosphate layers on metals, particularly steel, galvanized steel, zinc alloy-plated steel and aluminum, with a chromium-free aqueous solution before the application of a paint or adhesive.
Phosphating is industrially employed on a large scale for the preparation of metal surfaces for a subsequent application of paint. The phosphate layers thus formed result, inter alia, in an improved adhesion of the paint films on the metals, an increased resistance to corrosion and an inhibition of subsurface corrosion which might be initiated at damaged portions of the paint film.
The protective properties of the phosphate layers may further be improved by a passivating postrinsing with an aqueous fluid.
Desirable properties from the aspect of application technology will result from a passivating postrinsing with fluids which contain hexavalent and/or trivalent chromium. But the toxicity of the trivalent and particularly of the hexavalent chromium compounds is often regarded as a disadvantage.
Whereas US-A-4376000 describes a chromium-free postrinsing agent which contains polyvinylphenol, that agent must be used in a comparatively high concentration so that its use will result in an undesired pollution of the sewage, particularly because a large amount of oxygen is required for the decomposition.
CA 02018631 1999-01-1~
US-A-3695942 discloses the use of soluble zirconium compounds for an aftertreatment of conversion layers. In addition to zirconium, the postrinsing agents contain cations consisting of alkali and ammonium. The reference contains an explicit warning against the use of alkaline earth metal cations. Said postrinsing agents, which are used at a pH value from 3 to 8.5, do not result in the same quality as the chromium-containing agents.
US-A-3895970 describes acid aqueous postrinsing agents for treating phosphate layers. Said agents containing simple or complex fluorides and chromium-zirconium fluoride and zirconium fluoride are mentioned as zirconium compounds. With the exception of chromium-zirconium fluoride, the products mentioned in that patent will meet only medium requirements and chromium-zirconium fluoride has the above-mentioned disadvanta~e that it is toxic.
It is an object of the invention to provide for the passivating postrinsing of phosphate layers on metals before an application of a paint or adhesive a process which is free of the disadvantages of the known processes and distinguishes by providing a high protection against corrosion and a strong adhesion to paint and adhesive and does not pollute or only very slightly pollutes the environment.
That object is accomplished in that a process of the kind described first hereinbefore is carried out in accordance with the invention in such a manner that the phosphated metal surfaces are rinsed with aqueous solutions which have been adjusted to a pH value of 3 to 5 and which contain an aluminum fluorozirconate in which the Al:Zr:F
CA 02018631 1999-01-1~
.
mole ratio is (0.15 to 0.67):1:(5 to 7), and in which solutions the total concentration of Al + Zr + F is 0.1 to 2.0 g/l.
According to a preferred feature of the invention the phosphated metal surfaces are rinsed with aqueous solutions in which the total concentration of Al + Zr + F
is 0.2 to 0.8 g/l.
The process in accordance with the invention is suitable for treating phosphate layers of all types which can be formed on metals, particularly on steel, galvanized steel, steel plated with a zinc alloy, aluminum-plated steel, zinc, zinc alloys, aluminum and aluminum alloys.
Such phosphates include, inter alia, zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, nickel phosphate, cobalt phosphate, zinc-iron phosphate, zinc-manganese phosphate, zinc-calcium phosphate, and layers of other types, which contain two or more divalent cations. The process is particularly suitable for treating those phosphate layers which have been formed by low-zinc phosphating processes with or without an addition of further cations, such as Mn, Ni, Co, Mg.
When the metal surfaces have been phosphated, they are suitably rinsed with water before they are aftertreated, e.g., by dipping, spraying, flooding or rolling by means of the process in accordance with the nventlon.
The postrinsing agents used in the process in accordance with the invention may be chemically classified as ~ ~ 7 ~
aluminum fluorozirconates of low acidity. They may be produced, e.g., in a process in which metallic zirconium or zirconium carbonate is dissolved in aqueous hydrofluoric acid so that a complex fluorozirconic acid is formed. Metallic aluminum or aluminum hydroxide is then added and dissolved. Whereas that production process is preferred, the postrinsing agents may alternatively be produced by other processes.
In another preferred embodiment of the invention the phosphated metal surfaces are rinsed with aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethyl hexoate, salicylate in a total concentration of 0.05 to 0.5 g/l. This will particularly result in a further increase of the bare corrosion protection. The anions may be added as the corresponding acids or salts.
The pH value of the postrinsing solutions is preferably adjusted with cations of volatile bases, which particularly include ammonium, ethanolammonium and di- and tri-ethanolammonium.
The passivating postrinsing fluid may be applied to the phosphated metal surfaces by dipping, flooding, spraying and wetting, e.g., by means of rollers. The treating times are between about 1 second and 2 minutes. The fluid may be applied at a temperature from room temperature to about 80~C.
Temperatures between 20 and 50~C are usually preferred.
Deionized or low-salt water is usually employed to prepare the postrinsing baths. Waters having a high salt content are less suitable for preparing the baths.
In another preferred embodiment of the invention the phosphated metal surfaces are finally rinsed with deionized water.
, CA 02018631 1999-01-1~
The process according to the invention is used to prepare the phosphated metal surfaces for an application of paint or adhesive. The process improves the adhesion of the organic films to the metallic substrate, improves also the resistance of the organic films to a formation of blisters under corrosive conditions, and inhibits the progress of subsurface corrosion from damaged portions of the film. The process has proved to be particularly advantageous in conjunction with paints applied by cathodic electrocoating and powder coating or from low-solvent high-solids paints and paints applied mainly with water as a solvent.
The process in accordance with the invention will be explained more in detail and by way of example with reference to the following Example.
Example Degreased sheets made of steel, electrogalvanized steel and AlMgSi are sprayed in a manganese-modified low-zinc phosphating process at 55~C for 2 minutes. The phosphating solution had the following composition:
0.7 g/l Zn0.04 g/l Fe(III) 1.0 g/l Mn13 g/l P2O5 1.0 g/l Ni2.1 g/l NO3 2.9 g/l Na 0.3 g/l F
0.15 g/l NH40.07 g/l NO2 Finely crystalline, uniformly covering phosphate layers weighing 2.5 to 3 g/m2 were formed on the three metal substrates. Thereafter the sheets were rinsed with water and then subjected to a passivating postrinse. The passivating postrinsing was effected by spraying at 30~C
for 1 minute. Thereafter the sheets were rinsed with deionized water and were coated with a primer applied by cathodic electro-coating, with a filler and with a top coat. Each paint film wasseparately baked. The total thickness of the coating amounted to 90 ~m.
The sheets were subsequently scribed by means of a steel needle as far as to the metal substrate and were then subjected to various tests. The results are compiled in Tables 1 to 3.
To prepare the postrinsing fluid used in the process in accordance with the invention, 1.6 g of an aqueous concentrate containing 0.855% Al + 8.62% Zr + 10.7% F by weight was diluted with deionized water and was subsequently adjusted with ammonia to a pH value of 3.5 to 4Ø This resulted in a postrinsinq fluid containing 0.014 g/l Al + 0,14 g/l Zr 0.17 g/l F + 0.026 g/l NH3.
Control tests were conducted with: A postrinsing solution containing Cr~VI) and Cr(III), specifically 0.2 g/l CrO3 and 0.037 g/l Cr(III), and having a pH value of 3.5 to 4.0; a solution of chromium fluorozirconate containing 0.047 g/l Cr(III), 0.083 g/l Zr and 0.121 g/l F and having a pH
value of 3.5 to 4.0; and a solution containing 0.6 g/l polyvinylphenol and having a pH
value of 3.5 to 4Ø
Each sheet specimen was tested by the salt spray test in accordance with DIN 50021 SS(1008 h), the Filiform Test in accordance with ASTM D 2803 (1008 h) and 20 cycles of the General Motors Test Method TM 54-26 (GM Scab Test). The sub-surface corrosion under the organic coating (rate of creep back) was measured in mm.
, ~
~.' TABLE
Results on Steel Afterrinsing pH- Subsurface corrosion under organic agent value coating (mm) in Salt spray Filiform GM Scab test DIN Test ASTM Test (1008 h) (1008 h) (20 cycles) Cr(VI)- 3.5-Cr(III) 4.0 0 - < 1 0 3.5 Chromium 3.5-Fluorozir- 4.0 0 - c 1 0 - c 1 3.5 conate Polyvinyl- 3.5-phenol 4.0 0 - 1 < 1 4.0 Aluminum fluorozir- 3.5-conate 4.0 0 0 3.5 + NH3 to pH
(invention) -Results on Galvanized Steel Afterrinsing pH- Subsurface corrosion under organic agent value coating (mm) in Salt spray Filiform GM Scab test DIN Test ASTM Test (1008 h) (1008 h) (20 cycles) Cr(VI)- 3,5-Cr(III) 4.0 8.5 0 < 1 - 1 Chromium 3.5-Fluorozir- 4.0 7.0 0 - < 1 < 1 - 1 conate Polyvinyl- 3.5-phenol 4.0 6.5 0 - < 1 Aluminum fluorozir- 3.5-conate 4.0 5.5 0 < 1 -1 + NH3 to pH
(invention) , Results on AlMgSi Afterrinsing pH- Subsurface corrosion under organic agent value coating (mm) in Salt spray Filiform GM Scab test DIN Test ASTM Test (1008 h) (1008 h) (20 cycles) Cr(VI)- 3.5-Cr(III) 4.0 < 1 0 0.5 - 1 Chromium 3.5-Fluorozir- 4.0 0 0 conate Polyvinyl- 3.5-phenol 4.0 0 - <1 0 Aluminum fluorozir- 3.5-conate 4.0 0 0 0.5 - 1 + NH3 to pH
(invention) A comparison of the data compiled in the Tables will reveal that the results produced by the process in accordance with the invention are at least as good in each case as the best of the three controls which were also tested.
The present invention relates to a process for a passivating postrinsing of phosphate layers on metals, particularly steel, galvanized steel, zinc alloy-plated steel and aluminum, with a chromium-free aqueous solution before the application of a paint or adhesive.
Phosphating is industrially employed on a large scale for the preparation of metal surfaces for a subsequent application of paint. The phosphate layers thus formed result, inter alia, in an improved adhesion of the paint films on the metals, an increased resistance to corrosion and an inhibition of subsurface corrosion which might be initiated at damaged portions of the paint film.
The protective properties of the phosphate layers may further be improved by a passivating postrinsing with an aqueous fluid.
Desirable properties from the aspect of application technology will result from a passivating postrinsing with fluids which contain hexavalent and/or trivalent chromium. But the toxicity of the trivalent and particularly of the hexavalent chromium compounds is often regarded as a disadvantage.
Whereas US-A-4376000 describes a chromium-free postrinsing agent which contains polyvinylphenol, that agent must be used in a comparatively high concentration so that its use will result in an undesired pollution of the sewage, particularly because a large amount of oxygen is required for the decomposition.
CA 02018631 1999-01-1~
US-A-3695942 discloses the use of soluble zirconium compounds for an aftertreatment of conversion layers. In addition to zirconium, the postrinsing agents contain cations consisting of alkali and ammonium. The reference contains an explicit warning against the use of alkaline earth metal cations. Said postrinsing agents, which are used at a pH value from 3 to 8.5, do not result in the same quality as the chromium-containing agents.
US-A-3895970 describes acid aqueous postrinsing agents for treating phosphate layers. Said agents containing simple or complex fluorides and chromium-zirconium fluoride and zirconium fluoride are mentioned as zirconium compounds. With the exception of chromium-zirconium fluoride, the products mentioned in that patent will meet only medium requirements and chromium-zirconium fluoride has the above-mentioned disadvanta~e that it is toxic.
It is an object of the invention to provide for the passivating postrinsing of phosphate layers on metals before an application of a paint or adhesive a process which is free of the disadvantages of the known processes and distinguishes by providing a high protection against corrosion and a strong adhesion to paint and adhesive and does not pollute or only very slightly pollutes the environment.
That object is accomplished in that a process of the kind described first hereinbefore is carried out in accordance with the invention in such a manner that the phosphated metal surfaces are rinsed with aqueous solutions which have been adjusted to a pH value of 3 to 5 and which contain an aluminum fluorozirconate in which the Al:Zr:F
CA 02018631 1999-01-1~
.
mole ratio is (0.15 to 0.67):1:(5 to 7), and in which solutions the total concentration of Al + Zr + F is 0.1 to 2.0 g/l.
According to a preferred feature of the invention the phosphated metal surfaces are rinsed with aqueous solutions in which the total concentration of Al + Zr + F
is 0.2 to 0.8 g/l.
The process in accordance with the invention is suitable for treating phosphate layers of all types which can be formed on metals, particularly on steel, galvanized steel, steel plated with a zinc alloy, aluminum-plated steel, zinc, zinc alloys, aluminum and aluminum alloys.
Such phosphates include, inter alia, zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, nickel phosphate, cobalt phosphate, zinc-iron phosphate, zinc-manganese phosphate, zinc-calcium phosphate, and layers of other types, which contain two or more divalent cations. The process is particularly suitable for treating those phosphate layers which have been formed by low-zinc phosphating processes with or without an addition of further cations, such as Mn, Ni, Co, Mg.
When the metal surfaces have been phosphated, they are suitably rinsed with water before they are aftertreated, e.g., by dipping, spraying, flooding or rolling by means of the process in accordance with the nventlon.
The postrinsing agents used in the process in accordance with the invention may be chemically classified as ~ ~ 7 ~
aluminum fluorozirconates of low acidity. They may be produced, e.g., in a process in which metallic zirconium or zirconium carbonate is dissolved in aqueous hydrofluoric acid so that a complex fluorozirconic acid is formed. Metallic aluminum or aluminum hydroxide is then added and dissolved. Whereas that production process is preferred, the postrinsing agents may alternatively be produced by other processes.
In another preferred embodiment of the invention the phosphated metal surfaces are rinsed with aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethyl hexoate, salicylate in a total concentration of 0.05 to 0.5 g/l. This will particularly result in a further increase of the bare corrosion protection. The anions may be added as the corresponding acids or salts.
The pH value of the postrinsing solutions is preferably adjusted with cations of volatile bases, which particularly include ammonium, ethanolammonium and di- and tri-ethanolammonium.
The passivating postrinsing fluid may be applied to the phosphated metal surfaces by dipping, flooding, spraying and wetting, e.g., by means of rollers. The treating times are between about 1 second and 2 minutes. The fluid may be applied at a temperature from room temperature to about 80~C.
Temperatures between 20 and 50~C are usually preferred.
Deionized or low-salt water is usually employed to prepare the postrinsing baths. Waters having a high salt content are less suitable for preparing the baths.
In another preferred embodiment of the invention the phosphated metal surfaces are finally rinsed with deionized water.
, CA 02018631 1999-01-1~
The process according to the invention is used to prepare the phosphated metal surfaces for an application of paint or adhesive. The process improves the adhesion of the organic films to the metallic substrate, improves also the resistance of the organic films to a formation of blisters under corrosive conditions, and inhibits the progress of subsurface corrosion from damaged portions of the film. The process has proved to be particularly advantageous in conjunction with paints applied by cathodic electrocoating and powder coating or from low-solvent high-solids paints and paints applied mainly with water as a solvent.
The process in accordance with the invention will be explained more in detail and by way of example with reference to the following Example.
Example Degreased sheets made of steel, electrogalvanized steel and AlMgSi are sprayed in a manganese-modified low-zinc phosphating process at 55~C for 2 minutes. The phosphating solution had the following composition:
0.7 g/l Zn0.04 g/l Fe(III) 1.0 g/l Mn13 g/l P2O5 1.0 g/l Ni2.1 g/l NO3 2.9 g/l Na 0.3 g/l F
0.15 g/l NH40.07 g/l NO2 Finely crystalline, uniformly covering phosphate layers weighing 2.5 to 3 g/m2 were formed on the three metal substrates. Thereafter the sheets were rinsed with water and then subjected to a passivating postrinse. The passivating postrinsing was effected by spraying at 30~C
for 1 minute. Thereafter the sheets were rinsed with deionized water and were coated with a primer applied by cathodic electro-coating, with a filler and with a top coat. Each paint film wasseparately baked. The total thickness of the coating amounted to 90 ~m.
The sheets were subsequently scribed by means of a steel needle as far as to the metal substrate and were then subjected to various tests. The results are compiled in Tables 1 to 3.
To prepare the postrinsing fluid used in the process in accordance with the invention, 1.6 g of an aqueous concentrate containing 0.855% Al + 8.62% Zr + 10.7% F by weight was diluted with deionized water and was subsequently adjusted with ammonia to a pH value of 3.5 to 4Ø This resulted in a postrinsinq fluid containing 0.014 g/l Al + 0,14 g/l Zr 0.17 g/l F + 0.026 g/l NH3.
Control tests were conducted with: A postrinsing solution containing Cr~VI) and Cr(III), specifically 0.2 g/l CrO3 and 0.037 g/l Cr(III), and having a pH value of 3.5 to 4.0; a solution of chromium fluorozirconate containing 0.047 g/l Cr(III), 0.083 g/l Zr and 0.121 g/l F and having a pH
value of 3.5 to 4.0; and a solution containing 0.6 g/l polyvinylphenol and having a pH
value of 3.5 to 4Ø
Each sheet specimen was tested by the salt spray test in accordance with DIN 50021 SS(1008 h), the Filiform Test in accordance with ASTM D 2803 (1008 h) and 20 cycles of the General Motors Test Method TM 54-26 (GM Scab Test). The sub-surface corrosion under the organic coating (rate of creep back) was measured in mm.
, ~
~.' TABLE
Results on Steel Afterrinsing pH- Subsurface corrosion under organic agent value coating (mm) in Salt spray Filiform GM Scab test DIN Test ASTM Test (1008 h) (1008 h) (20 cycles) Cr(VI)- 3.5-Cr(III) 4.0 0 - < 1 0 3.5 Chromium 3.5-Fluorozir- 4.0 0 - c 1 0 - c 1 3.5 conate Polyvinyl- 3.5-phenol 4.0 0 - 1 < 1 4.0 Aluminum fluorozir- 3.5-conate 4.0 0 0 3.5 + NH3 to pH
(invention) -Results on Galvanized Steel Afterrinsing pH- Subsurface corrosion under organic agent value coating (mm) in Salt spray Filiform GM Scab test DIN Test ASTM Test (1008 h) (1008 h) (20 cycles) Cr(VI)- 3,5-Cr(III) 4.0 8.5 0 < 1 - 1 Chromium 3.5-Fluorozir- 4.0 7.0 0 - < 1 < 1 - 1 conate Polyvinyl- 3.5-phenol 4.0 6.5 0 - < 1 Aluminum fluorozir- 3.5-conate 4.0 5.5 0 < 1 -1 + NH3 to pH
(invention) , Results on AlMgSi Afterrinsing pH- Subsurface corrosion under organic agent value coating (mm) in Salt spray Filiform GM Scab test DIN Test ASTM Test (1008 h) (1008 h) (20 cycles) Cr(VI)- 3.5-Cr(III) 4.0 < 1 0 0.5 - 1 Chromium 3.5-Fluorozir- 4.0 0 0 conate Polyvinyl- 3.5-phenol 4.0 0 - <1 0 Aluminum fluorozir- 3.5-conate 4.0 0 0 0.5 - 1 + NH3 to pH
(invention) A comparison of the data compiled in the Tables will reveal that the results produced by the process in accordance with the invention are at least as good in each case as the best of the three controls which were also tested.
Claims (18)
1. A process for a passivating postrinsing of phosphate layers on metal surfaces, with a chromium-free aqueous solution before the application of a paint or adhesive, characterized in that the phosphated metal surfaces are rinsed with an aqueous solution which have been adjusted to a pH value of 3 to 5 and which contain an aluminum fluorozirconate in which the Al:Zr:F mole ratio is (0.15 to 0.67):1:(5 to 7), and in which solution the total concentration of Al + Zr + F is 0.1 to 2.0 g/l.
2. A process according to claim 1, wherein the metals are selected from the group consisting of steel, galvanized steel, zinc alloy-plated steel and aluminum.
3. A process according to claim 1 or 2, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions in which the total concentration of Al + Zr + F is 0.2 to 0.8 g/l.
4. A process according to claim 1 or 2, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions which contain in addition anions of at least one of benzoate, caprylate, ethylhexoate and salicylate in a total concentration of 0.05 to 0.5 g/l.
5. A process according to claim 1, 2, 3 or 4, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions which have been pH-adjusted with cations of volatile bases.
6. A process according to claim 1, 2, 3 or 4, characterized in that the passivating postrinsing is succeeded by final rinsing with deionized water.
7. A process according to claim 1, 2, 3 or 4, characterized in that a paint is applied by cathodic electrocoating after the passivating postrinsing.
8. A process according to claim 1, 2, 3 or 4, characterized in that a paint is applied by powder coating after the passivating postrinsing.
9. A process according to claim 1, 2, 3 or 4, characterized in that a low-solvent high-solids paint is applied after the passivating postrinsing.
10. A process according to claim 1, 2, 3 or 4, characterized in that a coating composition containing a water based solvent is applied after the passivating postrinsing.
11. A process according to claim 3, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions which contain in addition at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0,05 to 0,5 g/l.
12. A process according to claim 11, characterized in that the phosphated metal surfaces are rinsed with aqueous solutions which have been pH-adjusted with cations of volatile bases.
13. A process according to claim 12, wherein the cations of volatile bases are selected from the group consisting of ammonium, ethanolammonium, di- and triethanolammonium.
14. A process according to claim 11, characterized in that the passivating postrinsing is succeeded by final rinsing with deionized water.
15. A process according to claim 11, characterized in that a paint is applied by cathodic electro-coating after the passivating postrinsing.
16. A process according to claim 11, characterized in that a paint is applied by powder coating after the passivating postrinsing.
17. A process according to claim 11, characterized in that a low-solvent high-solids paint is applied after the passivating postrinsing.
18. A process according to claim 11, characterized in that a coating composition containing a water based solvent is applied after the passivating postrinsing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3924984A DE3924984A1 (en) | 1989-07-28 | 1989-07-28 | METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS |
| DEP3924984.0 | 1989-07-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2018631A1 CA2018631A1 (en) | 1991-01-28 |
| CA2018631C true CA2018631C (en) | 1999-05-11 |
Family
ID=6386020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002018631A Expired - Fee Related CA2018631C (en) | 1989-07-28 | 1990-06-08 | Process for a passivating postrinsing of phosphate layers |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0410497B1 (en) |
| JP (1) | JP2909517B2 (en) |
| AT (1) | ATE81533T1 (en) |
| BR (1) | BR9003594A (en) |
| CA (1) | CA2018631C (en) |
| DD (1) | DD298436A5 (en) |
| DE (2) | DE3924984A1 (en) |
| ES (1) | ES2035699T3 (en) |
| PL (1) | PL164742B1 (en) |
| PT (1) | PT94843B (en) |
| ZA (1) | ZA905922B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4017187A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | METHOD FOR REFILLING CONVERSION LAYERS |
| DE4017186A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | GENERATION OF CONVERSION OVERHEADS ON ZINC OR ZINC ALLOY SURFACES |
| US5209788A (en) * | 1990-11-21 | 1993-05-11 | Ppg Industries, Inc. | Non-chrome final rinse for phosphated metal |
| DE19511573A1 (en) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Process for phosphating with metal-containing rinsing |
| DE19834796A1 (en) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Process for phosphating, rinsing and cathodic electrocoating |
| DE19854091C2 (en) * | 1998-11-24 | 2002-07-18 | Audi Ag | Process for the pre-treatment of bodies before painting |
| DE10010355A1 (en) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution |
| KR20020051991A (en) * | 2000-12-23 | 2002-07-02 | 이구택 | Method of producing corrosion- resistance steel sheet coated with zirconium and silane coupling agent |
| MXPA03006677A (en) | 2001-02-16 | 2003-10-24 | Henkel Kgaa | Process for treating multi-metal articles. |
| EP2405031A1 (en) * | 2010-07-07 | 2012-01-11 | Mattthias Koch | Method for coating shaped bodies and coated shaped body |
| US9528187B2 (en) * | 2010-09-15 | 2016-12-27 | Jfe Steel Corporation | Steel sheet for containers and manufacturing method for same |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
| DE102016206418A1 (en) * | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | SUPPRESSION OF PLANT-SPECIFIC PHOSPHATE EXTRACTION IN A PROCESS FOR DIPPING LACQUER |
| DE102016206417A1 (en) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | PROMOTION TREATMENT FOR SUPPRESSING PLANT-ORIENTED PHOSPHATOR TRANSPORT IN A PROCESS FOR DIVING LACQUER |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3695942A (en) * | 1970-12-02 | 1972-10-03 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
| US3966502A (en) * | 1972-08-17 | 1976-06-29 | Amchem Products, Inc. | Zirconium rinse for phosphate coated metal surfaces |
| US3852123A (en) * | 1972-11-20 | 1974-12-03 | Pennwalt Corp | Sealing rinses for phosphate coatings on metal |
| US3895970A (en) * | 1973-06-11 | 1975-07-22 | Pennwalt Corp | Sealing rinse for phosphate coatings of metal |
| US4496404A (en) * | 1984-05-18 | 1985-01-29 | Parker Chemical Company | Composition and process for treatment of ferrous substrates |
| US4650526A (en) * | 1986-03-18 | 1987-03-17 | Man-Gill Chemical Company | Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes |
-
1989
- 1989-07-28 DE DE3924984A patent/DE3924984A1/en not_active Withdrawn
-
1990
- 1990-06-08 CA CA002018631A patent/CA2018631C/en not_active Expired - Fee Related
- 1990-06-26 ES ES199090201689T patent/ES2035699T3/en not_active Expired - Lifetime
- 1990-06-26 DE DE9090201689T patent/DE59000357D1/en not_active Expired - Lifetime
- 1990-06-26 EP EP90201689A patent/EP0410497B1/en not_active Expired - Lifetime
- 1990-06-26 AT AT90201689T patent/ATE81533T1/en not_active IP Right Cessation
- 1990-07-06 JP JP2179367A patent/JP2909517B2/en not_active Expired - Fee Related
- 1990-07-23 DD DD90343003A patent/DD298436A5/en not_active IP Right Cessation
- 1990-07-25 BR BR909003594A patent/BR9003594A/en unknown
- 1990-07-27 PT PT94843A patent/PT94843B/en not_active IP Right Cessation
- 1990-07-27 ZA ZA905922A patent/ZA905922B/en unknown
- 1990-07-27 PL PL90286243A patent/PL164742B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL286243A1 (en) | 1991-04-22 |
| EP0410497A1 (en) | 1991-01-30 |
| PT94843B (en) | 1997-03-31 |
| ZA905922B (en) | 1992-03-25 |
| JPH0361385A (en) | 1991-03-18 |
| EP0410497B1 (en) | 1992-10-14 |
| JP2909517B2 (en) | 1999-06-23 |
| ATE81533T1 (en) | 1992-10-15 |
| ES2035699T3 (en) | 1993-04-16 |
| DE3924984A1 (en) | 1991-01-31 |
| DE59000357D1 (en) | 1992-11-19 |
| PT94843A (en) | 1991-04-18 |
| PL164742B1 (en) | 1994-10-31 |
| CA2018631A1 (en) | 1991-01-28 |
| DD298436A5 (en) | 1992-02-20 |
| BR9003594A (en) | 1991-08-27 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |