CA2362556A1 - Method for phosphatizing zinc or aluminium surfaces - Google Patents
Method for phosphatizing zinc or aluminium surfaces Download PDFInfo
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- CA2362556A1 CA2362556A1 CA002362556A CA2362556A CA2362556A1 CA 2362556 A1 CA2362556 A1 CA 2362556A1 CA 002362556 A CA002362556 A CA 002362556A CA 2362556 A CA2362556 A CA 2362556A CA 2362556 A1 CA2362556 A1 CA 2362556A1
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- Prior art keywords
- zinc
- phosphating
- phosphating solution
- hydroxylamine
- aluminium
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- 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
- C23C22/362—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 zinc cations
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- 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
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
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- 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
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- 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
Abstract
The invention relates to a method for phosphatizing zinc or aluminium surfaces with a phosphatizing solution containing 0.5 to 2.0 g/l Zn2+, 0.3 to 2.0 g/l Ni2+, 0.1 to 0.4 g/l NH2OH, at least 3.0 g/l NO3- and 10.0 to 20.0 g/l phosphate (calculated as P2O5). Said solution is applied to the surfaces by immersion or spraying at 35 to 75 ~C, the immersion time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes.
Description
METHOD FOR PHOSPHATIZING ZINC OR ALUMINIUM SURFACES
This invention relates to a method for phosphating zinc surfaces or aluminium surfaces with a pr~osphating solution which is based on zinc and nickel as cations and hydroxylamine as accelerator and may~ contain in addition fluoride and/or complexed fluoride.
The zinc surfaces are a component of workpieces consisting of zinc or zinc alloys, or they are applied by hot-dip galvanising or they are applied by electrolytic galvanising to iron-containing workpieces, in particular to workpieces made of iron and steel.
The aluminium surfaces are a component of workpieces consisting of aluminium or aluminium alloys. Lacquers, paints, plastics layers or oils can be applied to the phosphated zinc surfaces and aluminium surfaces and, as a result of the phosphating, the surfaces provided with such a coating are considerably better protected from corrosion.
Methods for phosphating metallic materials which utilise a phosphating solution containing hydroxylamine as accelerator have been known for several years. Thus EP-A 0 315 059 discloses a method for phosphating iron surfaces which utilises a phosphating solution containing 0.5 to 50 g/1 hydroxylamine and 0.2 to 2.0 g/1 Zn'+, as well as 3 to 25 g/1 phosphate. The phosphating solution may contain, in addition, iron, manganese, nickel, nitrate, fluoride and/or complex fluorides. The known method is suitable for the phosphating not only of iron surfaces, but also for surfaces of zinc, zinc alloys, aluminium and aluminium alloys. The disadvantage of this method is that it utilises relatively high hydroxylamine concentrations of >_ 0.5 g/l, for hydroxylamine, is relatively costly _Z_ and comparatively unstable.
DE-A 195 38 778 discloses a method for phosphating surfaces made of steel, zinc-plated steel, steel plated with zinc alloy as well as of aluminium, wherein the metal surface is immersed for a period of between 1 and 8 minutes in a phosphating solution which contains 0.5 to 2 g/1 zinc ions, 2 to 25 g/l phosphate ions and 1.2 to 5 g/1 hydroxylamine in free, ionic or complexed form, has a free acid content 'of between 0 and 1.5 points and is at a temperature in the range of 32°C to 93°C. This phosphating solution may contain, in addition, 0.2 to 1.5 g/1 manganese ions, 0.2 to 1.5 g/1 nickel ions as well as, additionally, fluoride in free and/or complexed form and in quantities of up to 2.5 g/1 total fluoride. Finally, the phosphating solution is to contain not more than 0.5 g/1 nitrate ions. This method, too, utilises relatively high hydroxylamine concentrations and limits the nitrate content to less than 0.5 g/l.
DE-A 196 06 018 describes a method for phosphating metal surfaces made of steel, steel plated with zinc or zinc alloy and/or of aluminium, wherein the metal surfaces, are brought by spraying or immersion for a period of between 3 seconds and 8 minutes into contact with a zinc-containing phosphating solution which contains 0.2 to 3 g/1 zinc ions, 3 to 50 g/1 phosphate ions, 1 to 100 mg/1 nickel ions, one or more accelerators, for example, 0.01 to 0.2 g/1 nitrite and 0.1 to 10 g/1 hydroxylamine, the nitrate content of this solution being < 0.5 g/T. The solution may contain in addition 0.1 to 4 g/1 manganese ions as well as up to 2.5 g/1 total fluoride. The Examples given in DE-A
196 06 018 show that the known method utilises comparatively high hydroxylamine concentrations (1.7 g/1 hydroxylammonium sulfate) and avoids a nitrate content.
DE-A 196 21 184 discloses a method for phosphating.
S metal surfaces made of steel, steel plated with zinc or zinc alloy, aluminium and/or of aluminium-magnesium alloys, wherein the metal surfaces are brought by spraying or immersion for a period of between 3 seconds and 8 minutes into contact with a zinc-containing phosphating solution which contains 0.2 to 3 g/1 zinc ions, 3 to 50 g/1 phosphate ions, 0.001 to 4 g/1 manganese ions, 0.001 to 0.5 g/1 of one or more polymers and one or more accelerators, for example, 0.01 to 0.2 g/1 nitrite and 0.1 to 10 g/1 hydroxylamine, the solution possibly containing in addition 1 to 50 mg/1 nickel ions and up to f.5 g/1 total fluoride. The phosphating solution used in this method again has a nitrate content which does not exceed 0.5 g/1.
DE-A 197 05 701 describes a method for phosphating surfaces made of steel, zinc-plated steel and/or aluminium and/or of alloys consisting to an extent of at least 50 wt.% of iron, zinc or aluminium, wherein one uses a zinc-containing acidic phosphating solution which is free from copper ions and contains 0.3 to 3 g/1 zinc ions, 0.001 to 0.1 g/1 nickel ions, 5 to 40 g/1 phosphate ions and at least one accelerator, for example, 0.1 to 10 g/1 hydroxylamine. This solution may contain in addition up to 4 g/1 manganese ions and up to 2.5 g/1 total fluoride. The examples given in DE-A
197 05 701 indicate that the known method utilises relatively high hydroxylamine concentrations (1.8 g/1 hydroxylammonium sulfate), and moreover it is stated in this document that a nitrate concentration of 0.5 g/1 should not be exceeded during the phosphat:ing of zinc-" CA 02362556 2001-08-08 plated steel.
WO 93/03 198 discloses a phosphating solution which is used for phosphating steel, zinc alloys and aluminium and contains 5 to 25 g/1 phosphate ions, 0.5 to 2 g/1 zinc ions, 0.2 to 1.5 g/1 nickel ions, 0.2 to 1.5 g/1 manganese ions and 1 to 2.5 g/l of a hydroxylamine compound, O to 1.5 g/1 fluoride and 0 to 2 g/1 nitrate.
Again, this phosphating solution contains a relatively large quantity of hydroxylamine and limits the nitrate content to 2 g/1.
Finally, DE-A 196 39 596 discloses a method for phosphating steel strip or steel strip plated on one or on both sides with zinc or zinc alloy, by spraying or immersion for a period in the range of 2 to 15 seconds at a temperature of 40°C to 70°C, using a phosphating solution which contains 1 to 4 g/1 zinc ions, 0.8 to 3.5 g/1 manganese ions, 10 to 30 g/1 phosphate ions, 0.1 to 3 g/1 hydroxylamine and not more than 1 g/1 nitrate ions and has a free acid content in the range of 0.4 to 4 points. This phosphating solution may contain, in addition, 0.8 to 3.5 g/1 nickel ions as well as up to 0.8 g/l total fluoride. If the phosphating solution is to be used for the phosphating of zinc-plated steel, its nitrate content should not be more than 0.1 g/1.
The prior art informs the person skilled in the art that the accelerator, hydroxylamine, can also be used alone and is then as a rule particularly effective if it is present in the phosphating solution in a concentration of > 0.5 g/1. The prior art also informs the person skilled in the art that the nitrate concentration of the phosphating solution should, as a rule, be < 1 g/i, indeed, in particular when the ' CA 02362556 2001-08-08 phosphating solution is being used for the phosphating of zinc surfaces, then in this ease the nitrate content should be even < 0.5 g/1; as the person skilled in the art proceeds on the assumption that higher nitrate contents will promote the formation of very disadvantageous, so-called "specks", on zinc-plated surfaces. On the other hand, the person skilled in the art knows that a significant nitrate content in the phosphating solution could even be thoroughly advantageous, because the nitrates of zinc, nickel and manganese are very soluble in water and can be easily obtained and handled without difficulty, and the free acid content can optionally be easily adjusted by means of nitric acid.
Accordingly, the object of the invention is to provide a phosphating method which is suitable for phosphating zinc surfaces and aluminium surfaces, which imparts good corrosion properties to the workpieces to be phosphated, in particular, if after the phosphating, they are to be coated with lacquers, paints, plastics layers or oils, and which uses a phosphating solution which is altogether more economical to use than are the known hydroxylamine-containing phosphating solutions, with there being no lowering of the quality of the resulting phosphate layers, for example, through the formation of specks on the zinc surfaces ar through open layers on aluminium surfaces.
The object of the invention is achieved by the provision of a method for phosphating zinc surfaces and aluminium surfaces by means of a phosphating solution which contains 0.5 to 2.0 g/1 Znz+, 0.3 to 2.0 g/1 Ni'+, 0.1 to 0.4 g/1 NH20H, at least 3.0 g/1 N03- and 10.0 to 20.0 g/1 phosphate (calculated as Pz05) and is applied to the surfaces by immersion or by spraying at 35°G to 75°C, the immersion time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes..
The method according to the invention produces uniform, flawless, finely crystalline, closed phosphate layers having a layer weight of 2 to 5 g/m3. Surprisingly, it has, been found that the zinc surfaces phosphated according to the invention exhibited no disadvantageous specks, although the phosphating solution used according to the invention has a high nitrate content;
exceeding 3 g/1, and that even the phosphate layers produced on aluminium surfaces are completely closed, which is to be attributed in particular to the beneficial effect of the high nitrate content. The phosphate layers produced by the method according to the invention impart a very good protection from corrosion, in particular to workpieces which are coated with lacquers, paints, plastics layers or oils after being phosphated.
The prejudice that the high nitrate content of a phosphating solution is responsible for the disadvantageous formation of specks on phosphated zinc surfaces and that the nitrate content must therefore, as far as possible, be < 1 g/l, preferably < 0.5 g/1, runs as a recurring theme through the relevant prior art (see, for example, DE-A 195 38 778, page 3; lines 43 to 49; DE-A 196 06 018, page 4, l:Lnes 8 to 11;
DE-A 196 21 184, page 4, lines 41 to 44; DE-A 197 05 701, page 4, lines 38 to 43; DE-A 196 39 596, page 3, lines 1 to 7). The merit of the invention is the recognition that zinc-containing phosphating solutions having a hydroxylamine content of only 0.1 to 0.4 g/1 and a nitrate content of > 3 g/1 can be used advantageously for phosphating zinc surfaces and aluminium surfaces because, firstly, the accelerating ' CA 02362556 2001-08-08 _ 7 ._ action of the very low hydroxylamine concentration, owing to the synergistic accelerating action of the nitrate, is completely adequate so that the phosphating solution used in order to carry out the method according to the invention does not contain any other accelerators and, secondly, the comparatively high nitrate concentration does not result in the disadvantageous formation of. specks in the case of zinc surfaces and assists the development of a closed phosphate layer even on aluminium surfaces. From this, it also follows that nitrates and optionally nitric acid can readily be used in the preparation of the concentrates from which the phosphating solutions according to the invention are obtained by dilution.
The invention further provides that the phosphating solution used in order to carry out the method according to the invention contains, in addition, 0.4 to 1.5 g/1 Mn2+. The manganese content improves the positive anticorrosive action of zinc phosphate layers in a known manner.
Whereas the phosphating of zinc surfaces by the method according to the invention is carried out using a phosphating solution which does not necessarily contain fluoride and complexed fluoride, the phosphating of aluminium surfaces is carried out using a phosphating solution which does include fluoride and/ar complexed fluoride, the complexed fluoride being usable, for example, in the form of SiF62- or ~F9-. Indeed, it has been found that SiF6z- is particularly suitable for use as complexed fluoride for carrying out the method according to the invention and that, as regards the content of fluoride and complexed fluoride, a given range should be adhered to. Accordingly, the invention provides that the phosphating solution used for ' CA 02362556 2001-08-08 _8_ carrying out the method according to the invention contains, in addition, 0.2 to 1.5 g/1 F- and/or 0.5 to 2.5 g/1 SiF6z-. The presence of such quantities of simple and or complexed fluoride is advantageous in the phosphating of aluminium surfaces, because the above-mentioned fluorides have a beneficial effect on the quality of the phosphate layers deposited on aluminium surfaces. The simple fluoride F- may be in the form of hydrofluoric acid, HF, or its salts. The zinc content is preferably 0.5 to 1.7 g/1.
In this invention, it has proved particularly advantageous that the phosphating solution used for immersion contains 1 to 2 g/1 Znz+ and the phosphating solution used for spraying contains 0.5 to 1.5 g/1 Znz+.
The method according to the invention produces particularly good working results if the phosphating solution contains 3 to 15 g/1 N03-.
Finally, the method according to the invention is carried out using a phosphating solution which contains, in addition to the components already mentioned, preferably 0.5 to 1.3 g/1 Niz+, 12 to 16 g/1 phosphate (calculated as P205) , 0.5 to 1.3 g/1 Mnz+, as well as 0.2 to 1.0 g/1 F- and/or 0.8 to 2.0 g/1 SiF6z-.
Hydroxylamine can be used as free base, as hydroxylamine complex, or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating solution or to the concentrate of this solution, it is largely present as hydroxylammonium ion, owing to the acidic character of these solutions. In the case where hydroxylammonium salts are used, the sulfates and.phosphates are particularly suitable. The hydroxylamine content is preferably up to 0.3 g/1. The nitrate may be added to ' CA 02362556 2001-08-08 _g_ the phosphating solution in the form of HN03 or as the nitrate of zinc; of manganese and/or of nickel. Zinc, manganese and nickel may also be used in the form of their oxides and/or carbonates for the preparation of the phosphating solution. ThP phosphate is used as phosphoric acid or in the form of soluble phosphates.
SiF62- is used, for example, in the form of HZSiF6 for the preparation of the phosphat_~ng solution. Besides the rations of zinc, of nickel and of manganese, the phosphating solution may contain alkali metal rations and/or ammonium rations in order to adjust the free acid content, which, in the method according to the invention, is in a range of 0.5 to 3.5 points.
The term "free acid" is in common use in the field of phosphating. The number of points of the free acid is the number of ml produced when 10 ml phosphating solution, which has been diluted to 50 inl with deionised water, 'is titrated with 0.1 normal sodium hydroxide solution until a pH value of 4.2 is attained;
if the sample contains complex fluoride, then in order, as far as possible, to prevent dissociation of the latter, KC1 is added to the sample being titrated until saturation is reached.
The subject matter of the invention will now be explained in more detail by means of Examples and Comparative Examples. The Examples were carried out using sheets consisting of electrogalvanised steel and of the alloy AlMgSi (AA6016). The sheets were first of all cleaned by being immersed for 10 minutes at 60°C in an aqueous solution containing 20 g/1 of the alkaline cleaning agent BONDER V 845/5M. The sheets were then rinsed by immersion in tap water. Subsequently, the sheets were activated by treatment with an aqueous solution containing 1.0 g/1 of the activator GARDOLENE
V 6513, which contains titanium phosphate. The activation was effected by immersing the sheets for 30 seconds. Cleaning and activation are widely known and commonly used processing steps in phosphating. BONDER
and GARDOLENE are registered trademarks of Chemetall GmbH, Frankfurt am Main.
The sheets were then treated with phosphating solutions of various compositions by immersion for 2.5 minutes at 55°C, then rinsed by immersion in tap water and subsequently dried with compressed air at room temperature. Table 1 gives the composition of the phosphating solutions used and the results attained with the phosphating. Examples 1 to 4 are comparative examples, whereas Examples 5 and 6 were carried out in conformity with the method according to the invention.
The results of the phosphating indicate the following:-a) Comparative Examples 1 and 3, which - as recommended in prior art - contain a small quantity of nitrate, as was to be anticipated, are free from specks, whereas it is surprising that Example 5 according to the invention is free from specks. In Examples 2, 4 and 6 the problem of speck formation is irrelevant, as specks are not formed on Al surfaces in any case.
b) Comparative Examples 2 and 4 - although they were carried out according to prior art, have an open phosphate layer which is therefore useless, as the layer covers only 20% of the A1 surface;
consequently the layer weight could not be determined either. Example 6 according to the invention has a closed phosphate layer with a favourable layer weight, although the phosphating solution had only a low hydroxylamine content and a high nitrate content.
c) Comparative Example 1 - since it used a high hydroxylamine content and a low nitrate content in known manner - has a closed phosphate layer with a favourable layer weight. However, the phosphate layer exhibits a relatively dark coloration. This is disadvantageous if light-coloured one-coat paints are to be applied to the substrate after the phosphating. It is also disadvantageous that a high hydroxylamine content is used in the case of Comparative Example 1. Comparative Example 3 has a closed phosphate layer but the layer weight is excessively high, although the phosphating solution had both a low hydroxylamine content and a low nitrate content. Furthermore, the phosphate layer has an undesirable dark grey colour. Example 5 according to the iwvention has a closed phosphate layer with a favourable layer weight and exhibits the required light grey colour.
To prepare the phosphating solutions which were used in Examples 5 and 6 according to the invention, in each case 60 g of the concentrates given in Table 2 were made up to 1 1 with deionised water. The free acid content in the phosphating solutions was adjusted by adding dilute sodium hydroxide solution. 1'he nitrates of zinc; of nickel and of manganese were conveniently used for the preparation of the concentrates.
Table 1 Phosphating solution 8xamples g/1 1 2 3 4 5 6 Znz+ 1.5 1.5 1.5 1.5 1.5 1.5 Niz+ 1.0 1.0 1.0 1.0 1.0 1.0 Mnz+ 0.8 0.8 0.8 0.8 0.8 0.8 F- - 0.5 - 0.5 0.5 SiF62- - 1.5 - 1.5 - 1.5 N03- 0.1 0.1 0.1 0.1 6.0 6.0 NHZOH 1.0 1.0 0..2 0.2 0.2 0.2 Free acid . 1.9 1.9 1.9 1.9 2.0 2.0 Substrate Zn A1 Zn A1 Zn A1 Layer weight (g/m2) 3.3 nd 7.0 nd 3.5 4.3 Coverage % 100 20 100 20 100 100 Specks - - - - - -Colour of layer dg nd dg nd lg nd dg = dark grey, lg = light grey, nd = not determinable ~ CA 02362556 2001-08-08 Table 2 Concentrate for Constituent Example 5 (g) Example 6 (g) H3P0q (65% PZ(O5) 358 358 ZnO 8.34 8.34 Ni (N03) 2. 6 H20 82 . 7 82 . 7 Mn (N03) z . 4 H20 60 . 8 60 . 8 Zn (N03 ) z . 4 H20 73 . 2 73 . 2 HZSiF6 (31%) - 80.6 0.75 HzO, deionised 410.36 329.01 NHz OH (50%) 6.6 6.6 Total 1000 1000
This invention relates to a method for phosphating zinc surfaces or aluminium surfaces with a pr~osphating solution which is based on zinc and nickel as cations and hydroxylamine as accelerator and may~ contain in addition fluoride and/or complexed fluoride.
The zinc surfaces are a component of workpieces consisting of zinc or zinc alloys, or they are applied by hot-dip galvanising or they are applied by electrolytic galvanising to iron-containing workpieces, in particular to workpieces made of iron and steel.
The aluminium surfaces are a component of workpieces consisting of aluminium or aluminium alloys. Lacquers, paints, plastics layers or oils can be applied to the phosphated zinc surfaces and aluminium surfaces and, as a result of the phosphating, the surfaces provided with such a coating are considerably better protected from corrosion.
Methods for phosphating metallic materials which utilise a phosphating solution containing hydroxylamine as accelerator have been known for several years. Thus EP-A 0 315 059 discloses a method for phosphating iron surfaces which utilises a phosphating solution containing 0.5 to 50 g/1 hydroxylamine and 0.2 to 2.0 g/1 Zn'+, as well as 3 to 25 g/1 phosphate. The phosphating solution may contain, in addition, iron, manganese, nickel, nitrate, fluoride and/or complex fluorides. The known method is suitable for the phosphating not only of iron surfaces, but also for surfaces of zinc, zinc alloys, aluminium and aluminium alloys. The disadvantage of this method is that it utilises relatively high hydroxylamine concentrations of >_ 0.5 g/l, for hydroxylamine, is relatively costly _Z_ and comparatively unstable.
DE-A 195 38 778 discloses a method for phosphating surfaces made of steel, zinc-plated steel, steel plated with zinc alloy as well as of aluminium, wherein the metal surface is immersed for a period of between 1 and 8 minutes in a phosphating solution which contains 0.5 to 2 g/1 zinc ions, 2 to 25 g/l phosphate ions and 1.2 to 5 g/1 hydroxylamine in free, ionic or complexed form, has a free acid content 'of between 0 and 1.5 points and is at a temperature in the range of 32°C to 93°C. This phosphating solution may contain, in addition, 0.2 to 1.5 g/1 manganese ions, 0.2 to 1.5 g/1 nickel ions as well as, additionally, fluoride in free and/or complexed form and in quantities of up to 2.5 g/1 total fluoride. Finally, the phosphating solution is to contain not more than 0.5 g/1 nitrate ions. This method, too, utilises relatively high hydroxylamine concentrations and limits the nitrate content to less than 0.5 g/l.
DE-A 196 06 018 describes a method for phosphating metal surfaces made of steel, steel plated with zinc or zinc alloy and/or of aluminium, wherein the metal surfaces, are brought by spraying or immersion for a period of between 3 seconds and 8 minutes into contact with a zinc-containing phosphating solution which contains 0.2 to 3 g/1 zinc ions, 3 to 50 g/1 phosphate ions, 1 to 100 mg/1 nickel ions, one or more accelerators, for example, 0.01 to 0.2 g/1 nitrite and 0.1 to 10 g/1 hydroxylamine, the nitrate content of this solution being < 0.5 g/T. The solution may contain in addition 0.1 to 4 g/1 manganese ions as well as up to 2.5 g/1 total fluoride. The Examples given in DE-A
196 06 018 show that the known method utilises comparatively high hydroxylamine concentrations (1.7 g/1 hydroxylammonium sulfate) and avoids a nitrate content.
DE-A 196 21 184 discloses a method for phosphating.
S metal surfaces made of steel, steel plated with zinc or zinc alloy, aluminium and/or of aluminium-magnesium alloys, wherein the metal surfaces are brought by spraying or immersion for a period of between 3 seconds and 8 minutes into contact with a zinc-containing phosphating solution which contains 0.2 to 3 g/1 zinc ions, 3 to 50 g/1 phosphate ions, 0.001 to 4 g/1 manganese ions, 0.001 to 0.5 g/1 of one or more polymers and one or more accelerators, for example, 0.01 to 0.2 g/1 nitrite and 0.1 to 10 g/1 hydroxylamine, the solution possibly containing in addition 1 to 50 mg/1 nickel ions and up to f.5 g/1 total fluoride. The phosphating solution used in this method again has a nitrate content which does not exceed 0.5 g/1.
DE-A 197 05 701 describes a method for phosphating surfaces made of steel, zinc-plated steel and/or aluminium and/or of alloys consisting to an extent of at least 50 wt.% of iron, zinc or aluminium, wherein one uses a zinc-containing acidic phosphating solution which is free from copper ions and contains 0.3 to 3 g/1 zinc ions, 0.001 to 0.1 g/1 nickel ions, 5 to 40 g/1 phosphate ions and at least one accelerator, for example, 0.1 to 10 g/1 hydroxylamine. This solution may contain in addition up to 4 g/1 manganese ions and up to 2.5 g/1 total fluoride. The examples given in DE-A
197 05 701 indicate that the known method utilises relatively high hydroxylamine concentrations (1.8 g/1 hydroxylammonium sulfate), and moreover it is stated in this document that a nitrate concentration of 0.5 g/1 should not be exceeded during the phosphat:ing of zinc-" CA 02362556 2001-08-08 plated steel.
WO 93/03 198 discloses a phosphating solution which is used for phosphating steel, zinc alloys and aluminium and contains 5 to 25 g/1 phosphate ions, 0.5 to 2 g/1 zinc ions, 0.2 to 1.5 g/1 nickel ions, 0.2 to 1.5 g/1 manganese ions and 1 to 2.5 g/l of a hydroxylamine compound, O to 1.5 g/1 fluoride and 0 to 2 g/1 nitrate.
Again, this phosphating solution contains a relatively large quantity of hydroxylamine and limits the nitrate content to 2 g/1.
Finally, DE-A 196 39 596 discloses a method for phosphating steel strip or steel strip plated on one or on both sides with zinc or zinc alloy, by spraying or immersion for a period in the range of 2 to 15 seconds at a temperature of 40°C to 70°C, using a phosphating solution which contains 1 to 4 g/1 zinc ions, 0.8 to 3.5 g/1 manganese ions, 10 to 30 g/1 phosphate ions, 0.1 to 3 g/1 hydroxylamine and not more than 1 g/1 nitrate ions and has a free acid content in the range of 0.4 to 4 points. This phosphating solution may contain, in addition, 0.8 to 3.5 g/1 nickel ions as well as up to 0.8 g/l total fluoride. If the phosphating solution is to be used for the phosphating of zinc-plated steel, its nitrate content should not be more than 0.1 g/1.
The prior art informs the person skilled in the art that the accelerator, hydroxylamine, can also be used alone and is then as a rule particularly effective if it is present in the phosphating solution in a concentration of > 0.5 g/1. The prior art also informs the person skilled in the art that the nitrate concentration of the phosphating solution should, as a rule, be < 1 g/i, indeed, in particular when the ' CA 02362556 2001-08-08 phosphating solution is being used for the phosphating of zinc surfaces, then in this ease the nitrate content should be even < 0.5 g/1; as the person skilled in the art proceeds on the assumption that higher nitrate contents will promote the formation of very disadvantageous, so-called "specks", on zinc-plated surfaces. On the other hand, the person skilled in the art knows that a significant nitrate content in the phosphating solution could even be thoroughly advantageous, because the nitrates of zinc, nickel and manganese are very soluble in water and can be easily obtained and handled without difficulty, and the free acid content can optionally be easily adjusted by means of nitric acid.
Accordingly, the object of the invention is to provide a phosphating method which is suitable for phosphating zinc surfaces and aluminium surfaces, which imparts good corrosion properties to the workpieces to be phosphated, in particular, if after the phosphating, they are to be coated with lacquers, paints, plastics layers or oils, and which uses a phosphating solution which is altogether more economical to use than are the known hydroxylamine-containing phosphating solutions, with there being no lowering of the quality of the resulting phosphate layers, for example, through the formation of specks on the zinc surfaces ar through open layers on aluminium surfaces.
The object of the invention is achieved by the provision of a method for phosphating zinc surfaces and aluminium surfaces by means of a phosphating solution which contains 0.5 to 2.0 g/1 Znz+, 0.3 to 2.0 g/1 Ni'+, 0.1 to 0.4 g/1 NH20H, at least 3.0 g/1 N03- and 10.0 to 20.0 g/1 phosphate (calculated as Pz05) and is applied to the surfaces by immersion or by spraying at 35°G to 75°C, the immersion time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes..
The method according to the invention produces uniform, flawless, finely crystalline, closed phosphate layers having a layer weight of 2 to 5 g/m3. Surprisingly, it has, been found that the zinc surfaces phosphated according to the invention exhibited no disadvantageous specks, although the phosphating solution used according to the invention has a high nitrate content;
exceeding 3 g/1, and that even the phosphate layers produced on aluminium surfaces are completely closed, which is to be attributed in particular to the beneficial effect of the high nitrate content. The phosphate layers produced by the method according to the invention impart a very good protection from corrosion, in particular to workpieces which are coated with lacquers, paints, plastics layers or oils after being phosphated.
The prejudice that the high nitrate content of a phosphating solution is responsible for the disadvantageous formation of specks on phosphated zinc surfaces and that the nitrate content must therefore, as far as possible, be < 1 g/l, preferably < 0.5 g/1, runs as a recurring theme through the relevant prior art (see, for example, DE-A 195 38 778, page 3; lines 43 to 49; DE-A 196 06 018, page 4, l:Lnes 8 to 11;
DE-A 196 21 184, page 4, lines 41 to 44; DE-A 197 05 701, page 4, lines 38 to 43; DE-A 196 39 596, page 3, lines 1 to 7). The merit of the invention is the recognition that zinc-containing phosphating solutions having a hydroxylamine content of only 0.1 to 0.4 g/1 and a nitrate content of > 3 g/1 can be used advantageously for phosphating zinc surfaces and aluminium surfaces because, firstly, the accelerating ' CA 02362556 2001-08-08 _ 7 ._ action of the very low hydroxylamine concentration, owing to the synergistic accelerating action of the nitrate, is completely adequate so that the phosphating solution used in order to carry out the method according to the invention does not contain any other accelerators and, secondly, the comparatively high nitrate concentration does not result in the disadvantageous formation of. specks in the case of zinc surfaces and assists the development of a closed phosphate layer even on aluminium surfaces. From this, it also follows that nitrates and optionally nitric acid can readily be used in the preparation of the concentrates from which the phosphating solutions according to the invention are obtained by dilution.
The invention further provides that the phosphating solution used in order to carry out the method according to the invention contains, in addition, 0.4 to 1.5 g/1 Mn2+. The manganese content improves the positive anticorrosive action of zinc phosphate layers in a known manner.
Whereas the phosphating of zinc surfaces by the method according to the invention is carried out using a phosphating solution which does not necessarily contain fluoride and complexed fluoride, the phosphating of aluminium surfaces is carried out using a phosphating solution which does include fluoride and/ar complexed fluoride, the complexed fluoride being usable, for example, in the form of SiF62- or ~F9-. Indeed, it has been found that SiF6z- is particularly suitable for use as complexed fluoride for carrying out the method according to the invention and that, as regards the content of fluoride and complexed fluoride, a given range should be adhered to. Accordingly, the invention provides that the phosphating solution used for ' CA 02362556 2001-08-08 _8_ carrying out the method according to the invention contains, in addition, 0.2 to 1.5 g/1 F- and/or 0.5 to 2.5 g/1 SiF6z-. The presence of such quantities of simple and or complexed fluoride is advantageous in the phosphating of aluminium surfaces, because the above-mentioned fluorides have a beneficial effect on the quality of the phosphate layers deposited on aluminium surfaces. The simple fluoride F- may be in the form of hydrofluoric acid, HF, or its salts. The zinc content is preferably 0.5 to 1.7 g/1.
In this invention, it has proved particularly advantageous that the phosphating solution used for immersion contains 1 to 2 g/1 Znz+ and the phosphating solution used for spraying contains 0.5 to 1.5 g/1 Znz+.
The method according to the invention produces particularly good working results if the phosphating solution contains 3 to 15 g/1 N03-.
Finally, the method according to the invention is carried out using a phosphating solution which contains, in addition to the components already mentioned, preferably 0.5 to 1.3 g/1 Niz+, 12 to 16 g/1 phosphate (calculated as P205) , 0.5 to 1.3 g/1 Mnz+, as well as 0.2 to 1.0 g/1 F- and/or 0.8 to 2.0 g/1 SiF6z-.
Hydroxylamine can be used as free base, as hydroxylamine complex, or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating solution or to the concentrate of this solution, it is largely present as hydroxylammonium ion, owing to the acidic character of these solutions. In the case where hydroxylammonium salts are used, the sulfates and.phosphates are particularly suitable. The hydroxylamine content is preferably up to 0.3 g/1. The nitrate may be added to ' CA 02362556 2001-08-08 _g_ the phosphating solution in the form of HN03 or as the nitrate of zinc; of manganese and/or of nickel. Zinc, manganese and nickel may also be used in the form of their oxides and/or carbonates for the preparation of the phosphating solution. ThP phosphate is used as phosphoric acid or in the form of soluble phosphates.
SiF62- is used, for example, in the form of HZSiF6 for the preparation of the phosphat_~ng solution. Besides the rations of zinc, of nickel and of manganese, the phosphating solution may contain alkali metal rations and/or ammonium rations in order to adjust the free acid content, which, in the method according to the invention, is in a range of 0.5 to 3.5 points.
The term "free acid" is in common use in the field of phosphating. The number of points of the free acid is the number of ml produced when 10 ml phosphating solution, which has been diluted to 50 inl with deionised water, 'is titrated with 0.1 normal sodium hydroxide solution until a pH value of 4.2 is attained;
if the sample contains complex fluoride, then in order, as far as possible, to prevent dissociation of the latter, KC1 is added to the sample being titrated until saturation is reached.
The subject matter of the invention will now be explained in more detail by means of Examples and Comparative Examples. The Examples were carried out using sheets consisting of electrogalvanised steel and of the alloy AlMgSi (AA6016). The sheets were first of all cleaned by being immersed for 10 minutes at 60°C in an aqueous solution containing 20 g/1 of the alkaline cleaning agent BONDER V 845/5M. The sheets were then rinsed by immersion in tap water. Subsequently, the sheets were activated by treatment with an aqueous solution containing 1.0 g/1 of the activator GARDOLENE
V 6513, which contains titanium phosphate. The activation was effected by immersing the sheets for 30 seconds. Cleaning and activation are widely known and commonly used processing steps in phosphating. BONDER
and GARDOLENE are registered trademarks of Chemetall GmbH, Frankfurt am Main.
The sheets were then treated with phosphating solutions of various compositions by immersion for 2.5 minutes at 55°C, then rinsed by immersion in tap water and subsequently dried with compressed air at room temperature. Table 1 gives the composition of the phosphating solutions used and the results attained with the phosphating. Examples 1 to 4 are comparative examples, whereas Examples 5 and 6 were carried out in conformity with the method according to the invention.
The results of the phosphating indicate the following:-a) Comparative Examples 1 and 3, which - as recommended in prior art - contain a small quantity of nitrate, as was to be anticipated, are free from specks, whereas it is surprising that Example 5 according to the invention is free from specks. In Examples 2, 4 and 6 the problem of speck formation is irrelevant, as specks are not formed on Al surfaces in any case.
b) Comparative Examples 2 and 4 - although they were carried out according to prior art, have an open phosphate layer which is therefore useless, as the layer covers only 20% of the A1 surface;
consequently the layer weight could not be determined either. Example 6 according to the invention has a closed phosphate layer with a favourable layer weight, although the phosphating solution had only a low hydroxylamine content and a high nitrate content.
c) Comparative Example 1 - since it used a high hydroxylamine content and a low nitrate content in known manner - has a closed phosphate layer with a favourable layer weight. However, the phosphate layer exhibits a relatively dark coloration. This is disadvantageous if light-coloured one-coat paints are to be applied to the substrate after the phosphating. It is also disadvantageous that a high hydroxylamine content is used in the case of Comparative Example 1. Comparative Example 3 has a closed phosphate layer but the layer weight is excessively high, although the phosphating solution had both a low hydroxylamine content and a low nitrate content. Furthermore, the phosphate layer has an undesirable dark grey colour. Example 5 according to the iwvention has a closed phosphate layer with a favourable layer weight and exhibits the required light grey colour.
To prepare the phosphating solutions which were used in Examples 5 and 6 according to the invention, in each case 60 g of the concentrates given in Table 2 were made up to 1 1 with deionised water. The free acid content in the phosphating solutions was adjusted by adding dilute sodium hydroxide solution. 1'he nitrates of zinc; of nickel and of manganese were conveniently used for the preparation of the concentrates.
Table 1 Phosphating solution 8xamples g/1 1 2 3 4 5 6 Znz+ 1.5 1.5 1.5 1.5 1.5 1.5 Niz+ 1.0 1.0 1.0 1.0 1.0 1.0 Mnz+ 0.8 0.8 0.8 0.8 0.8 0.8 F- - 0.5 - 0.5 0.5 SiF62- - 1.5 - 1.5 - 1.5 N03- 0.1 0.1 0.1 0.1 6.0 6.0 NHZOH 1.0 1.0 0..2 0.2 0.2 0.2 Free acid . 1.9 1.9 1.9 1.9 2.0 2.0 Substrate Zn A1 Zn A1 Zn A1 Layer weight (g/m2) 3.3 nd 7.0 nd 3.5 4.3 Coverage % 100 20 100 20 100 100 Specks - - - - - -Colour of layer dg nd dg nd lg nd dg = dark grey, lg = light grey, nd = not determinable ~ CA 02362556 2001-08-08 Table 2 Concentrate for Constituent Example 5 (g) Example 6 (g) H3P0q (65% PZ(O5) 358 358 ZnO 8.34 8.34 Ni (N03) 2. 6 H20 82 . 7 82 . 7 Mn (N03) z . 4 H20 60 . 8 60 . 8 Zn (N03 ) z . 4 H20 73 . 2 73 . 2 HZSiF6 (31%) - 80.6 0.75 HzO, deionised 410.36 329.01 NHz OH (50%) 6.6 6.6 Total 1000 1000
Claims (9)
1. Method for phosphating zinc surfaces or aluminium surfaces with a phosphating solution which is based on zinc and nickel as cations and hydroxylamine as accelerator and may contain, in addition, fluoride and/or complexed fluoride, characterised in that the phosphating solution contains 0.5 to 2.0 g/l Zn2+, 0.3 to 2.0 g/l Ni2+, 0.1 to 0.3 g/l NH2OH, at least 3.0 g/l NO3- and 10.0 to 20.0 g/l phosphate (calculated as P2O5) and is applied to the surfaces by immersion or spraying at 35ÀC to 75ÀC, the immersion time being 0.5 to 10 minutes and the spraying time being 3 seconds to 5 minutes.
2. Method according to claim 1, characterised in that the phosphating solution contains, in addition, 0.4 to 1.5 g/1 Mn2+.
3. Method according to claim 1, characterised in that phosphating solution contains in addition 0.2 to 1.5 g/l F- and/or 0.5 to 2.5 g/l SiF6 2-.
4. Method according to claim 1, characterised in that the phosphating solution used for immersion contains 1.0 to 2.0 g/l Zn2+ and the phosphating solution used for spraying contains 0.5 to 1.5 g/l Zr2+.
5. Method according to claim 1, characterised in that the phosphating solution contains 3 to 15 g/l NO3-.
6. Method according to claims 1 to 5, characterised in that the phosphating solution contains 0.5 to 1.3 g/l Ni2+.
7. Method according to claims 1 to 5, characterised in that the phosphating solution contains 12 to 16 g/l phosphate (calculated as P2O5).
8. Method according to claims 1 to 5, characterised in that the phosphating solution contains 0.5 to 1.3 g/l Mn2+.
9. Method according to claims 1 to 5, characterised in that the phosphating solution contains 0.2 to 1.0 g/l F- and/or 0.8 to 2.0 g/l SiF6 2-.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19905479.7 | 1999-02-10 | ||
| DE19905479A DE19905479A1 (en) | 1999-02-10 | 1999-02-10 | Process for the phosphatisation of zinc or aluminum surfaces |
| PCT/EP2000/000865 WO2000047799A1 (en) | 1999-02-10 | 2000-02-03 | Method for phosphatizing zinc or aluminium surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2362556A1 true CA2362556A1 (en) | 2000-08-17 |
Family
ID=7897026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002362556A Abandoned CA2362556A1 (en) | 1999-02-10 | 2000-02-03 | Method for phosphatizing zinc or aluminium surfaces |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1155163B1 (en) |
| AT (1) | ATE253651T1 (en) |
| AU (1) | AU2669400A (en) |
| CA (1) | CA2362556A1 (en) |
| DE (2) | DE19905479A1 (en) |
| WO (1) | WO2000047799A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8435360B2 (en) | 2007-06-14 | 2013-05-07 | Atotech Deutschland Gmbh | Anti-corrosion treatment for conversion layers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104361836B (en) * | 2014-11-20 | 2017-01-11 | 无锡科思电子科技有限公司 | Pickling and phosphating method of light-emitting diode (LED) display screen cast iron box body |
| CN109609940B (en) * | 2019-01-10 | 2021-01-29 | 廊坊师范学院 | Preparation method of metal piece abrasion-resistant silicification liquid and workpiece silicification process |
| CA3131809A1 (en) | 2019-02-28 | 2020-09-03 | Atotech Deutschland Gmbh | Aqueous post treatment composition and method for corrosion protection |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3712339A1 (en) * | 1987-04-11 | 1988-10-20 | Metallgesellschaft Ag | METHOD FOR PHOSPHATIZING BEFORE ELECTROPLATING |
| US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
| US5261973A (en) * | 1991-07-29 | 1993-11-16 | Henkel Corporation | Zinc phosphate conversion coating and process |
| IT1274594B (en) * | 1994-08-05 | 1997-07-18 | Itb Srl | ACID WATER PHOSPHATIC SOLUTION AND METALLIC SURFACE PHOSPHATION PROCESS USING IT |
| DE19538778A1 (en) * | 1995-10-18 | 1997-04-24 | Henkel Kgaa | Layer weight control in hydroxylamine-accelerated phosphating systems |
| DE19606018A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinc phosphating with low levels of nickel and / or cobalt |
| DE19621184A1 (en) * | 1996-05-28 | 1997-12-04 | Henkel Kgaa | Zinc phosphating with integrated post-passivation |
| DE19735314C2 (en) * | 1996-09-13 | 2001-05-23 | Bayerische Motoren Werke Ag | Process for the pretreatment of components |
| DE19639597C2 (en) * | 1996-09-26 | 2000-01-20 | Henkel Kgaa | Process for the phosphating of running strips made of cold or hot rolled steel in high-speed conveyor systems |
| DE19639596A1 (en) * | 1996-09-26 | 1998-04-02 | Henkel Kgaa | Process for phosphating steel strips |
| DE19705701A1 (en) * | 1997-02-14 | 1998-08-20 | Henkel Kgaa | Phosphating metal surfaces for subsequent lacquering |
-
1999
- 1999-02-10 DE DE19905479A patent/DE19905479A1/en not_active Withdrawn
-
2000
- 2000-02-03 CA CA002362556A patent/CA2362556A1/en not_active Abandoned
- 2000-02-03 EP EP00905014A patent/EP1155163B1/en not_active Expired - Lifetime
- 2000-02-03 AT AT00905014T patent/ATE253651T1/en not_active IP Right Cessation
- 2000-02-03 WO PCT/EP2000/000865 patent/WO2000047799A1/en active IP Right Grant
- 2000-02-03 DE DE50004321T patent/DE50004321D1/en not_active Expired - Fee Related
- 2000-02-03 AU AU26694/00A patent/AU2669400A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8435360B2 (en) | 2007-06-14 | 2013-05-07 | Atotech Deutschland Gmbh | Anti-corrosion treatment for conversion layers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19905479A1 (en) | 2000-08-17 |
| WO2000047799A1 (en) | 2000-08-17 |
| EP1155163A1 (en) | 2001-11-21 |
| DE50004321D1 (en) | 2003-12-11 |
| AU2669400A (en) | 2000-08-29 |
| EP1155163B1 (en) | 2003-11-05 |
| ATE253651T1 (en) | 2003-11-15 |
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