CA1334371C - Process of applying phosphate coatings on metal surfaces using a phosphating solution containing iron iii-ions - Google Patents
Process of applying phosphate coatings on metal surfaces using a phosphating solution containing iron iii-ionsInfo
- Publication number
- CA1334371C CA1334371C CA000607371A CA607371A CA1334371C CA 1334371 C CA1334371 C CA 1334371C CA 000607371 A CA000607371 A CA 000607371A CA 607371 A CA607371 A CA 607371A CA 1334371 C CA1334371 C CA 1334371C
- Authority
- CA
- Canada
- Prior art keywords
- ions
- phosphating solution
- iron
- iii
- zinc
- 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
- C23C22/05—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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
- C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese cations
- C23C22/365—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 fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
Landscapes
- 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
In a process of applying phosphate coatings to surfaces consisting of aluminum and/or zinc and/or its or their alloys by means of phosphating solutions used in low-zinc technology, the number of points of free acid is maintained constant in that the surface is contacted with a phosphating solution which contains iron-III-ions in a concentration of at least 1 mg/l and to which 50 to 2000 mg iron-III-ions, preferably up to 1000 mg iron-III-ions, are added per square meter of treated surface area. The phosphating solution suitably contains 0.4 to 1,5 g/l zinc;
10 to 26 g/l P2O5 and 0 to 1.3 g/l Ni; 0 to 1.3 g/l Mn; 0 to 1.3 g/l Mg and the weight ratio of Zn to P2O5 is in the range from (0,075 to 0.015) : 1 and - if applicable - the weight ratio of Ni, Mn and/or Mg to Zn is up to 1.5 : 1.
The phosphating solution may additionally contain as an accelerator 2 to 25 g/l NO3; 1 to 6 g/l ClO3; 0.1 to 2 g/l organic nitro compound; 0.05 to 0.5 g/l NO2; 0.02 to 0.1 g/l peroxide (calculated as H2O2) or mixtures thereof. It is used at a temperature in the range from 30 to 70°C.
10 to 26 g/l P2O5 and 0 to 1.3 g/l Ni; 0 to 1.3 g/l Mn; 0 to 1.3 g/l Mg and the weight ratio of Zn to P2O5 is in the range from (0,075 to 0.015) : 1 and - if applicable - the weight ratio of Ni, Mn and/or Mg to Zn is up to 1.5 : 1.
The phosphating solution may additionally contain as an accelerator 2 to 25 g/l NO3; 1 to 6 g/l ClO3; 0.1 to 2 g/l organic nitro compound; 0.05 to 0.5 g/l NO2; 0.02 to 0.1 g/l peroxide (calculated as H2O2) or mixtures thereof. It is used at a temperature in the range from 30 to 70°C.
Description
This invention relates to a process of applying phosphate coatings to surfaces consisting of aluminum and/or zinc and/or its or their alloys by means of phosphating solutions used in low-zinc technology.
Phosphating solutions used in low-zinc technology are, by definition, solutions which predominantly contain zinc in a concentration of about 0.4 to 1.5 g/l as a layer-forming cation and in which the ratio of Zn to PO4 is lessthan about 0,08.
It is known that thin phosphate coatings can be applied to metal surfaces consisting of steel, galvanized steel or aluminum in order to provide a suitable base for a finish to be applied by a subsequent electrophoretic dip coating process. The phosphating solutions used for that process usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and/or ammonium ions, also phosphate ions, accelerating additives, such as nitrite, chlorate, bromate, peroxide, m-nitrobenzene sulfonate, nitrophenol or combinations thereof. For a treatment of aluminium, its alloys and steel which has been galvanized by electrodeposition, the solutions preferably contain in addition simple and/or complex fluorides. Additional anions, such as chloride, nitrate and sulfate, serve to maintain electron neutrality. The phosphating solutions may optionally contain grain-refining additives for improving the layer, such as hydroxycarboxylic acids, aminocarboxylic acids or condensed phosphates.
The metal surfaces consist in a major proportion of steel and in changing proportions of galvanized steel and in a small proportion consist of aluminum materials and are treated by spraying and/or dipping processes.
, If surfaces consisting only of zinc and/or aluminum are contacted with the phosphating solution, it will be found that the free acid points and/or the ratio of free acid to total acid in the phosphating solution being used will increase and the phosphating solution will get out of equilibrium. As a result, the formation of the coating will be deteriorated and will finally be suppressed as the throughput increases. The surplus acid cannot be neutralized with sodium hydroxide, ammonium hydroxide or other alkalies because this would result in a co-precipitation of a part of the bath component zinc.
It is an object of the invention to provide for the application of phosphate coatings to surfaces consisting of zinc and/or aluminum and/or its or their alloys by means of phosphating solutions used in low zinc technology a process in which a rise of the free acid content and/or of the acid ratio is prevented so that the disadvantages of the known processes will be avoided whereas the process can be carried out in a simple manner and is economical.
To accomplish that object the process of the kind described firæt hereinbefore is carried out according to the invention in such a manner that the surface is c~ ~ ~ ~
5 l 334371 contains iron-III in a concentration of at least 1 mg/l and to which 50 to 2000 mg iron-III-ions are added per square meter of treated surface area.
More particularly, the invention provides a process of applying a phosphate coating to a surface consisting of a metal compound selected from the group consisting of aluminum, aluminum alloys, zinc, zinc alloys and alloys of zinc and aluminum, by contacting said surface with a phosphating solution as is used in low-zinc technology, said solution cont~;ning 0.4 to 1.5 g/l zinc, and lo to 26 g/l P2O5 and having a weight ratio of Zn to P205 adjusted to a value in the range of 0.075 : l to 0.015 : 1, characterized in that said phosphating solution with which the surface is contacted, also contains iron-III-ions in a minimum concentration of 1 mg/l, the amount of iron-III-ions that is added to the solution being ranging from 50 to 2000 mg iron-III-ions per s~uare meter of treated area. .~
The iron ions may be introduced into the phosphating solution in the form of FeIII-ions, but also in the form of iron-II-ions together with an oxidizing agent 25 ! oxidizing iron-II to iron-III, e.g. chlorate, nitrite, peroxide. Suitable compounds are, e.g., the nitrates, chlorides and fluorides of di- or trivalent iron as well as iron(III) complexes of hydroxycarboxylic acids, amino-carboxylic acids and the like.
It will be particularly desirable to introduce the iron ions in an aqueous solution into the phosphating solution.
In a preferred embodiment of the invention, the metal surface is contacted with a phosphating solution to ¢
5a 1 334371 which SO to 1000 mg iron-III-ions are added per square meter of treated surface area. In that case, too, addition of iron can be performed as mentioned above.
The process in accordance with the invention can be used with all known phosphating solutions used in low-zinc technology.
In another preferred embodiment of the invention the solution that is used, further contains 0.4 to 1.5 g/l zinc to 26 g/l P205 and O to 1.3 g/l Ni O to 1.3 g/l Mn O to 1.3 g/l Mg.
In such solutions the weight ratio of Zn to P20s should be ,~
and - if applicable - the weight ratio of Ni, Mn and/or Mg to Zn should be adjusted to a value up to 1.5 : 1.
In a further desirable embodiment of the invention, phosphating solutions are used which contain as an accelerator 2 to 25 g/l NO3 1 to 6 g/l C103 0.1 to 2 g/l organic nitro compound 0.05 to 0.5 g/l NO2 0.02 to 0.1 g/l peroxide (calculated as H2O2) or mixtures thereof.
The phosphating solutions may be applied by conventional processes. Particularly desirable modes of application are spraying and/or dipping. A temperature in the range from 30 to 70C is preferred.
During non-processing intervals, iron-III-ions must be added to maintain a concentration of at least 1 mg/l.
The process in accordance with the invention will be particularly suitable for a treatment of pure aluminum and alloys, e.g., of the grades AlMgSi, AlMg and AlMgMn.
As to the formation of coatings on zinc surfaces, materials consisting of solid zinc, particularly of steel which has been galvanized by hot dip or- electrolytic processes, may be treated. Other suitable materials are alloys of zinc with, e.g., Ni, Fe or Al in the form of s X
_ 7 - l 3 3 4 3 7 1 By means of the process in accordance with the invention, phosphate coatings which are entirely uniform and~
continuous can be formed even for a prolonged time. Such coatings will be particularly suitable when an electrophoretic 5 dip coating process is to be performed thereafter.
The invention will be explained by way of example and more in detail in the following Examples.
Example Previously degreased and pickled sheet metal elements 10 of aluminum (70%) of the grades AlMgSi and AlMg3 and of electro-galvanized steel (30%) were treated in a 10-liter phosphating container with a phosphating solution which contains 0.7 g/l Zn 0.7 g/l Ni 1.0 g/l Mn 3.4 g/l Na 11.5 g/l P2O5 3.0 g/l NO3 0.5 g/l F
0.1 g/l NO2 The temperature of the solution amounted to 55 to 60C.
The treatment was performed by spraying for 3 minutes. The number of free acid points of the phosphating solution 25 amounted to 1Ø
X
, By an addition of iron(III) citrate, the phosphating solution had been adjusted to an initial iron-III-concentra-tion of 2 mg/l.
During the processing, 250 mg iron(III) citrate (calc.
as Fe) per m2 of surface area were added to the lo liters of phosphating solution. As is apparent from the following Table, the number of free acid points was virtually constant.
The resulting phosphate covering was uniform and continuous throughout.
Throughput (m2) 0.4 0.8 1.2 1.6 2.4 2.8 3.2 Free acid points l.o 1.1 1.1 1.0 l.o 1.1 l.o 5 Control Example In a control example, sheet metal elements having the same quality were treated in the same manner with the above-mentioned phosphating solution, with the difference that said solution did not contain iron-III-ions and was not replenished lo by an addition of iron-III-ions. As the throughput increased, the number of free acid points increased as stated below.
Whereas high-grade phosphate coatings were initially obtained, the quality deteriorated as the number of points increased.
No coating was formed when the number of free acid points 15 amounted to 1.50 or more.
Throughput (m ) 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2 Free acid points l.o 1.15 1.~5 1.3~ ~ o ~ ~
Phosphating solutions used in low-zinc technology are, by definition, solutions which predominantly contain zinc in a concentration of about 0.4 to 1.5 g/l as a layer-forming cation and in which the ratio of Zn to PO4 is lessthan about 0,08.
It is known that thin phosphate coatings can be applied to metal surfaces consisting of steel, galvanized steel or aluminum in order to provide a suitable base for a finish to be applied by a subsequent electrophoretic dip coating process. The phosphating solutions used for that process usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and/or ammonium ions, also phosphate ions, accelerating additives, such as nitrite, chlorate, bromate, peroxide, m-nitrobenzene sulfonate, nitrophenol or combinations thereof. For a treatment of aluminium, its alloys and steel which has been galvanized by electrodeposition, the solutions preferably contain in addition simple and/or complex fluorides. Additional anions, such as chloride, nitrate and sulfate, serve to maintain electron neutrality. The phosphating solutions may optionally contain grain-refining additives for improving the layer, such as hydroxycarboxylic acids, aminocarboxylic acids or condensed phosphates.
The metal surfaces consist in a major proportion of steel and in changing proportions of galvanized steel and in a small proportion consist of aluminum materials and are treated by spraying and/or dipping processes.
, If surfaces consisting only of zinc and/or aluminum are contacted with the phosphating solution, it will be found that the free acid points and/or the ratio of free acid to total acid in the phosphating solution being used will increase and the phosphating solution will get out of equilibrium. As a result, the formation of the coating will be deteriorated and will finally be suppressed as the throughput increases. The surplus acid cannot be neutralized with sodium hydroxide, ammonium hydroxide or other alkalies because this would result in a co-precipitation of a part of the bath component zinc.
It is an object of the invention to provide for the application of phosphate coatings to surfaces consisting of zinc and/or aluminum and/or its or their alloys by means of phosphating solutions used in low zinc technology a process in which a rise of the free acid content and/or of the acid ratio is prevented so that the disadvantages of the known processes will be avoided whereas the process can be carried out in a simple manner and is economical.
To accomplish that object the process of the kind described firæt hereinbefore is carried out according to the invention in such a manner that the surface is c~ ~ ~ ~
5 l 334371 contains iron-III in a concentration of at least 1 mg/l and to which 50 to 2000 mg iron-III-ions are added per square meter of treated surface area.
More particularly, the invention provides a process of applying a phosphate coating to a surface consisting of a metal compound selected from the group consisting of aluminum, aluminum alloys, zinc, zinc alloys and alloys of zinc and aluminum, by contacting said surface with a phosphating solution as is used in low-zinc technology, said solution cont~;ning 0.4 to 1.5 g/l zinc, and lo to 26 g/l P2O5 and having a weight ratio of Zn to P205 adjusted to a value in the range of 0.075 : l to 0.015 : 1, characterized in that said phosphating solution with which the surface is contacted, also contains iron-III-ions in a minimum concentration of 1 mg/l, the amount of iron-III-ions that is added to the solution being ranging from 50 to 2000 mg iron-III-ions per s~uare meter of treated area. .~
The iron ions may be introduced into the phosphating solution in the form of FeIII-ions, but also in the form of iron-II-ions together with an oxidizing agent 25 ! oxidizing iron-II to iron-III, e.g. chlorate, nitrite, peroxide. Suitable compounds are, e.g., the nitrates, chlorides and fluorides of di- or trivalent iron as well as iron(III) complexes of hydroxycarboxylic acids, amino-carboxylic acids and the like.
It will be particularly desirable to introduce the iron ions in an aqueous solution into the phosphating solution.
In a preferred embodiment of the invention, the metal surface is contacted with a phosphating solution to ¢
5a 1 334371 which SO to 1000 mg iron-III-ions are added per square meter of treated surface area. In that case, too, addition of iron can be performed as mentioned above.
The process in accordance with the invention can be used with all known phosphating solutions used in low-zinc technology.
In another preferred embodiment of the invention the solution that is used, further contains 0.4 to 1.5 g/l zinc to 26 g/l P205 and O to 1.3 g/l Ni O to 1.3 g/l Mn O to 1.3 g/l Mg.
In such solutions the weight ratio of Zn to P20s should be ,~
and - if applicable - the weight ratio of Ni, Mn and/or Mg to Zn should be adjusted to a value up to 1.5 : 1.
In a further desirable embodiment of the invention, phosphating solutions are used which contain as an accelerator 2 to 25 g/l NO3 1 to 6 g/l C103 0.1 to 2 g/l organic nitro compound 0.05 to 0.5 g/l NO2 0.02 to 0.1 g/l peroxide (calculated as H2O2) or mixtures thereof.
The phosphating solutions may be applied by conventional processes. Particularly desirable modes of application are spraying and/or dipping. A temperature in the range from 30 to 70C is preferred.
During non-processing intervals, iron-III-ions must be added to maintain a concentration of at least 1 mg/l.
The process in accordance with the invention will be particularly suitable for a treatment of pure aluminum and alloys, e.g., of the grades AlMgSi, AlMg and AlMgMn.
As to the formation of coatings on zinc surfaces, materials consisting of solid zinc, particularly of steel which has been galvanized by hot dip or- electrolytic processes, may be treated. Other suitable materials are alloys of zinc with, e.g., Ni, Fe or Al in the form of s X
_ 7 - l 3 3 4 3 7 1 By means of the process in accordance with the invention, phosphate coatings which are entirely uniform and~
continuous can be formed even for a prolonged time. Such coatings will be particularly suitable when an electrophoretic 5 dip coating process is to be performed thereafter.
The invention will be explained by way of example and more in detail in the following Examples.
Example Previously degreased and pickled sheet metal elements 10 of aluminum (70%) of the grades AlMgSi and AlMg3 and of electro-galvanized steel (30%) were treated in a 10-liter phosphating container with a phosphating solution which contains 0.7 g/l Zn 0.7 g/l Ni 1.0 g/l Mn 3.4 g/l Na 11.5 g/l P2O5 3.0 g/l NO3 0.5 g/l F
0.1 g/l NO2 The temperature of the solution amounted to 55 to 60C.
The treatment was performed by spraying for 3 minutes. The number of free acid points of the phosphating solution 25 amounted to 1Ø
X
, By an addition of iron(III) citrate, the phosphating solution had been adjusted to an initial iron-III-concentra-tion of 2 mg/l.
During the processing, 250 mg iron(III) citrate (calc.
as Fe) per m2 of surface area were added to the lo liters of phosphating solution. As is apparent from the following Table, the number of free acid points was virtually constant.
The resulting phosphate covering was uniform and continuous throughout.
Throughput (m2) 0.4 0.8 1.2 1.6 2.4 2.8 3.2 Free acid points l.o 1.1 1.1 1.0 l.o 1.1 l.o 5 Control Example In a control example, sheet metal elements having the same quality were treated in the same manner with the above-mentioned phosphating solution, with the difference that said solution did not contain iron-III-ions and was not replenished lo by an addition of iron-III-ions. As the throughput increased, the number of free acid points increased as stated below.
Whereas high-grade phosphate coatings were initially obtained, the quality deteriorated as the number of points increased.
No coating was formed when the number of free acid points 15 amounted to 1.50 or more.
Throughput (m ) 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2 Free acid points l.o 1.15 1.~5 1.3~ ~ o ~ ~
Claims (7)
1. A process a process of applying a phosphate coating to a surface consisting of a metal compound selected from the group consisting of aluminum, aluminum alloys, zinc, zinc alloys and alloys of zinc and aluminum, by contacting said surface with a phosphating solution as is used in low-zinc technology, said solution containing 0.4 to 1.5 g/l zinc, and to 26 g/l P2O5 and having a weight ratio of Zn to P2O5 adjusted to a value in the range of 0.075 : 1 to 0.015 : 1, characterized in that said phosphating solution with which the surface is contacted, also contains iron-III-ions in a minimum concentration of 1 mg/l, the amount of iron-III-ions that is added to the solution being ranging from 50 to 2000 mg iron III-ions per square meter of treated area.
2. A process according to claim 1, characterized in that the amount of iron-III-ions added to the phosphating solution is ranging from 50 to 1000 mg iron-III-ions per square meter of treated area.
3. A process according to claim 1 or 2, characterized in that the phosphating solution with which the surface is contacted, further contains up to 1.3 g/l Ni up to 1.3 g/l Mn up to 1.3 g/l Mg.
4. A process according to claim 3, characterized in that the phosphating solution with which the surface is contacted is selected so that the weight ratio of Ni, Mn and/or Mg to Zn is adjusted to a value up to 1.5 : 1.
5. A process according to claim 1, 2 or 4, characterized in that the phosphating solution with which the surface is contacted additionally contains 2 to 25 g/l NO3 1 to 6 g/l ClO3 0.1 to 2 g/l organic nitro compound 0.05 to 0.5 g/l NO2 0.02 to 0.1 g/l peroxide (calculated as H2O2) or mixtures thereof.
6. A process according to claim 1, 2 or 4, characterized in that the surface is contacted with the phosphating solution at a temperature in the range from 30 to 70°C.
7. A process according to claim 5, characterized in that the surface is contacted with the phosphating solution at a temperature in the range from 30 to 70°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3839802 | 1988-11-25 | ||
| DEP3839802.8 | 1988-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334371C true CA1334371C (en) | 1995-02-14 |
Family
ID=6367867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000607371A Expired - Fee Related CA1334371C (en) | 1988-11-25 | 1989-08-02 | Process of applying phosphate coatings on metal surfaces using a phosphating solution containing iron iii-ions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0370535B1 (en) |
| JP (1) | JP2845246B2 (en) |
| CA (1) | CA1334371C (en) |
| DD (1) | DD299968A5 (en) |
| DE (1) | DE58902702D1 (en) |
| ES (1) | ES2036023T3 (en) |
| GB (1) | GB2226829B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238506A (en) * | 1986-09-26 | 1993-08-24 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
| DE3828676A1 (en) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | PHOSPHATING PROCESS |
| DE3918136A1 (en) * | 1989-06-03 | 1990-12-06 | Henkel Kgaa | METHOD FOR PRODUCING MANAGE-CONTAINING PHOSPHATE COATINGS ON METAL SURFACES |
| JPH0525652A (en) * | 1990-01-26 | 1993-02-02 | Ppg Ind Inc | Method for applying phosphate coating film composition and zinc-nickel-manganese phosphate coating |
| US5261973A (en) * | 1991-07-29 | 1993-11-16 | Henkel Corporation | Zinc phosphate conversion coating and process |
| JPH05306497A (en) | 1992-04-30 | 1993-11-19 | Nippondenso Co Ltd | Phophatizing chemical conversion treatment |
| US5645706A (en) * | 1992-04-30 | 1997-07-08 | Nippondenso Co., Ltd. | Phosphate chemical treatment method |
| DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
| DE4243214A1 (en) * | 1992-12-19 | 1994-06-23 | Metallgesellschaft Ag | Process for the production of phosphate coatings |
| US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
| US5900073A (en) * | 1996-12-04 | 1999-05-04 | Henkel Corporation | Sludge reducing zinc phosphating process and composition |
| JP3366826B2 (en) * | 1997-04-30 | 2003-01-14 | 本田技研工業株式会社 | Zinc phosphate treatment agent for aluminum alloy |
| JP4019723B2 (en) * | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| RU2560891C1 (en) * | 2014-05-05 | 2015-08-20 | Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") | Method of iron-cobalt alloy phosphating |
| EP3280830B1 (en) * | 2015-04-07 | 2021-03-31 | Chemetall GmbH | Method for specifically adjusting the electrical conductivity of conversion coatings |
| RU2624566C1 (en) * | 2016-02-15 | 2017-07-04 | Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") | Method of phosphatory of magnetic-aluminium alloys of type permalloy (versions) |
| US11124880B2 (en) | 2016-04-07 | 2021-09-21 | Chemetall Gmbh | Method for nickel-free phosphating metal surfaces |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2738283A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| DE2738282A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR APPLYING PHOSPHATE |
| DE2738281A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| US4278477A (en) * | 1980-03-19 | 1981-07-14 | Amchem Products, Inc. | Metal treatment |
| US4486241A (en) * | 1981-09-17 | 1984-12-04 | Amchem Products, Inc. | Composition and process for treating steel |
| DE3245411A1 (en) * | 1982-12-08 | 1984-07-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METAL GOODS |
| FR2569203B1 (en) * | 1984-08-16 | 1989-12-22 | Produits Ind Cie Fse | PROCESS FOR THE TREATMENT BY CHEMICAL CONVERSION OF SUBSTRATES IN ZINC OR IN ONE OF ITS ALLOYS, CONCENTRATE AND BATH USED FOR THE IMPLEMENTATION OF THIS PROCESS |
| JPS63100185A (en) * | 1986-10-16 | 1988-05-02 | Nippon Parkerizing Co Ltd | Phosphating method |
-
1989
- 1989-07-22 EP EP89201936A patent/EP0370535B1/en not_active Expired - Lifetime
- 1989-07-22 DE DE8989201936T patent/DE58902702D1/en not_active Expired - Lifetime
- 1989-07-22 ES ES198989201936T patent/ES2036023T3/en not_active Expired - Lifetime
- 1989-08-02 CA CA000607371A patent/CA1334371C/en not_active Expired - Fee Related
- 1989-08-04 GB GB8917936A patent/GB2226829B/en not_active Expired - Fee Related
- 1989-11-21 JP JP1300984A patent/JP2845246B2/en not_active Expired - Lifetime
-
1990
- 1990-04-19 DD DD339887A patent/DD299968A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2226829B (en) | 1993-01-20 |
| DD299968A5 (en) | 1992-05-14 |
| JP2845246B2 (en) | 1999-01-13 |
| GB8917936D0 (en) | 1989-09-20 |
| EP0370535B1 (en) | 1992-11-11 |
| GB2226829A (en) | 1990-07-11 |
| EP0370535A1 (en) | 1990-05-30 |
| JPH02190478A (en) | 1990-07-26 |
| DE58902702D1 (en) | 1992-12-17 |
| ES2036023T3 (en) | 1993-05-01 |
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