DE19634732A1 - Zinc phosphating containing ruthenium - Google Patents

Abstract

The invention concerns an acidic aqueous phosphate treatment solution containing between 0.2 and 3 g/l zinc ions and between 3 and 50 g/l phosphate ions calculated as PO4. The solution additionally contains between 0.002 and 0.2 g/l ruthenium ions, preferably manganese ions and one or a plurality of accelerators, in particular hydroxylamine.

Description

The invention relates to processes for phosphating metal surfaces aqueous, acid phosphating solutions, the zinc and phosphate ions as well Contain ruthenium ions, and their use as a pretreatment of the metal surfaces for subsequent painting, especially a Electro dip painting or powder painting. The procedure is applicable for the treatment of surfaces made of steel, galvanized or alloy galvanized Steel, aluminum, aluminized or alloy-aluminized steel.

The phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers, which are already the Improve corrosion resistance and in conjunction with paints and others organic coatings to significantly increase paint adhesion and contribute to resistance to infiltration when exposed to corrosion. Such phosphating processes have long been known. For pre-treatment before painting, especially electrocoating, are suitable especially the low-zinc phosphating processes, in which the phosphating sol solutions comparatively low levels of zinc ions of z. B. 0.5 to 2 g / l exhibit. An essential parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the Range is <8 and can take values up to 30.

It has been shown that by using other polyvalent cations in the zinc phosphating baths phosphate layers with significantly improved Corrosion protection and paint adhesion properties can be trained. For example, find low-zinc processes with the addition of z. B. 0.5 to 1.5 g / l Manganese ions and e.g. B. 0.3 to 2.0 g / l of nickel ions as a so-called trication ver drive to prepare metal surfaces for painting  for example for the cathodic electrocoating of car bodies, wide Application.

The high content of nickel ions in the phosphating solutions of the Trication-Ver drive and of nickel and nickel compounds in the formed Phos However, phat layers have disadvantages in that nickel and nickel compounds from the perspective of environmental protection and workplace hygiene as critical get ranked. Recently, low-zinc phos have been increasing phating process described without the use of nickel high-quality phosphate layers similar to the nickel-containing processes to lead. Against the accelerators nitrite and nitrate are possible because of Formation of nitrous gases increasingly raised concerns.

For example, DE-A-39 20 296 describes a phosphating process based on Nickel is dispensed with and magnesium ions are used in addition to zinc and manganese ions. The phosphating baths described here contain 0.2 to 10 g / l nitrate ions further oxidizing agents acting as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.

EP-A-60 716 discloses low-zinc phosphating baths which act as essential cations Contain zinc and manganese and which contain nickel as an optional component can. The necessary accelerator is preferably selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.

Also in EP-A-228 151 phosphating baths are described as being contain essential cations zinc and manganese. The phosphating accelerator will selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzenesulfonate, m- Nitrobenzoate or p-nitrophenol. The nitrate content is in dependent claims to 5 to about 15 g / l and an optional nickel content between 0.4 and 4 g / l certified. The exemplary embodiments for this all contain both nickel and Nitrate.

EP-A-321 059 teaches zinc phosphating baths which, in addition to 0.1 to 2.0 g / l zinc and an accelerator also 0.01 to 20 g / l tungsten in the form of a soluble Tungsten compound, preferably alkali metal or ammonium tungstate or -silicotungstate, alkaline earth metal silicotungstate or boro- or silicotungstic acid. The accelerator is selected from nitrite, m-nitrobenzenesulfonate or  Hydrogen peroxide. Optional components include nickel in Amounts of 0.1-4 g / l and nitrate in amounts of 0.1-15 g / l are given.

DE-C-27 39 006 describes a phosphating process for surfaces made of zinc or zinc alloys that are free of nitrate and ammonium ions. Besides one essential zinc content in amounts between 0.1 and 5 g / l is 1 to 10 Parts by weight of nickel and / or cobalt are required per part by weight of zinc. As Hydrogen peroxide is used as accelerator. From the perspective of the Ar In workplace hygiene and environmental protection, cobalt is no alternative to nickel represents.

DE-A-40 13 483 discloses phosphating processes with which similarly good ones Corrosion protection properties as achieved with the trication process can. These processes do without nickel and use copper instead in low concentrations, 0.001 to 0.03 g / l. For the oxidation of the Pickling reaction of steel surfaces formed bivalent iron in the three valuable stage serve oxygen and / or other oxidizing agents having the same effect. As such, nitrite, chlorate, bromate, peroxy compounds and organic Nitro compounds such as nitrobenzenesulfonate. WO93 / 20259 modifies this process in that as a modifying agent for the Morphology of the phosphate crystals formed hydroxylamine, its salts or Complexes are added in an amount of 0.5 to 5 g / l hydroxylamine.

The use of hydroxylamine and / or its compounds for the leg The shape of the phosphate crystals is from a series of Offenle publication known. EP-A-315 059 gives the as a special effect Use of hydroxylamine in phosphating baths indicates the fact that Then steel the phosphate crystals in a desired column or bulbous form arise when the zinc concentration in the phosphating bath exceeds the usual range for low-zinc processes. This makes it possible the phosphating baths with zinc concentrations up to 2 g / l and with Ge weight ratios of phosphate to zinc down to 3.7. over no advantageous cation combinations of these phosphating baths more detailed statements are made, however, in the patent examples in all cases Nickel used.  

The use of lithium ions in phosphating baths has been isolated in the Literature described. In a monograph from 1950 (W. Machu: "Die Phosphating "Verlag Chemie Weinheim 1950, p. 146) mentions that the Addition of LiNO₃ to phosphate baths lowers the free acid. From the Gas evolution is concluded that Li is the rate of the (pickling) reaction elevated. German patent application 195 00 927.4 describes the use of Lithium in nickel-free zinc phosphating baths.

The object of the invention is to provide phosphating baths, who are free of that for environmental and workplace hygiene reasons questionable nickel or the similar questionable cobalt, but one of the Trication-phosphating processes have comparable corrosion protection effects.

This object is achieved by an acidic, aqueous phosphating solution containing
0.2 to 3 g / l zinc (II) and
3 to 50 g / l phosphate, calculated as PO₄ ^3-
characterized in that the solution additionally
Contains 0.002 to 0.2 g / l ruthenium ions.

Ruthenium is preferred as an acid-soluble salt, especially as a hydroxide, Chloride, carbonate, nitrate or sulfate are used. Since it is in phosphating baths all metals, including those below, are optional listed as ions before. Ru is preferably trivalent and is preferably used in amounts of 0.005 to 0.1 g / l.

The phosphating baths according to the invention can contain further divalent metal ions, the positive effect of which on the corrosion protection of zinc phosphate layers is known in the prior art. It is therefore preferred that the phosphating solution according to the invention additionally contains one or more of the following cations:
0.1 to 4 g / l manganese (II),
0.2 to 2.5 g / l magnesium (II),
0.2 to 2.5 g / l calcium (II),
0.2 to 1.5 g / l lithium (I)
0.01 to 0.5 g / l iron (II)
0.002 to 0.05 g / l copper (II).

The presence of manganese is particularly preferred. The possibility of The presence of divalent iron depends on that described below Accelerator system. The presence of iron (II) in the above Concentration range requires an accelerator that is opposite to this Ion does not have an oxidizing effect. Hydroxylamine is an example of this call.

The phosphating baths are preferably, but not necessarily, free of Nickel and cobalt. This means that these elements or ions the Phosphating baths are not deliberately added. However, it is in practice not to be ruled out that such components over the material to be treated get in traces in the phosphating baths. In particular, it is not out conclude that when phosphating be with zinc-nickel alloys layered steel, nickel ions are introduced into the phosphating solution. However, the expectation is placed on the phosphating baths according to the invention that that under technical conditions the nickel concentration in the baths below 0.01 g / l, in particular below 0.0001 g / l.

For phosphating baths that should be suitable for different substrates it has become common to use free and / or complex bound fluoride in amounts up to 2.5 g / l total fluoride, of which up to 800 mg / l free fluoride should be added. The Such amounts of fluoride are also present for the Phos according to the invention phatizing baths an advantage. In the absence of fluoride, the aluminum content should of the bath do not exceed 3 mg / l. In the presence of fluoride will result the complex formation tolerates higher Al contents, provided that the concentration of the complexed Al does not exceed 3 mg / l. The use of fluoride baths is therefore advantageous if the surfaces to be phosphated are at least partially consist of aluminum or contain aluminum. In these cases it is convenient not complex-bound, only free fluoride, preferably in Concentrations in the range of 0.5 to 1.0 g / l.

It is not absolutely necessary for the phosphating of zinc surfaces that the phosphating baths contain so-called accelerators. For the  Phosphating of steel surfaces, however, requires that the Phosphating solution contains one or more accelerators. Such acceleration ger are in the prior art as components of zinc phosphating baths common. This is understood to mean substances that are caused by the pickling attack This chemically creates hydrogen on the acid on the metal surface bind that they themselves are reduced. Have oxidizing accelerators continues to have the effect of the pickling attack released on steel surfaces Oxidize iron (II) ions to the trivalent stage, so that they as iron (III) - Phosphate can precipitate.

The phosphating baths according to the invention can contain one or more of the following components as accelerators:
0.3 to 4 g / l chlorate ions
0.01 to 0.2 g / l nitrite ions,
0.05 to 2 g / l m-nitrobenzenesulfonate ions,
0.05 to 2 g / l m-nitrobenzoate ions,
0.05 to 2 g / l p-nitrophenol,
0.005 to 0.15 g / l hydrogen peroxide in free or bound form,
0.1 to 10 g / l hydroxylamine in free or bound form,
0.1 to 10 g / l of a reducing sugar.

Additional nitrate ions in amounts of up to 10 g / l can be used as co-accelerators be present, which is particularly true in the phosphating of steel surfaces areas can have a favorable impact. When phosphating galvanized steel however, it is preferable that the phosphating solution contain as little nitrate as possible. Nitrate concentrations of 0.5 g / l should preferably not be exceeded, because at higher nitrate concentrations there is a risk of a so-called "Speck formation" exists. This means there are white, crater-like defects in the Phosphate layer meant.

The use of nitrite as an accelerator leads in particular to steel surfaces for technically satisfactory results. For the sake of Ar occupational safety (danger of developing nitrous gases), however, it is em Recommended to avoid nitrite as an accelerator. For phosphating galvanized surfaces, this is advisable for technical reasons as well  Nitrite can form nitrate, which, as explained above, is a problem of Specks can result.

For reasons of environmental friendliness, hydrogen peroxide, from the tech niche reasons of the simplified formulation options for Nachdo Sierlösungen hydroxylamine is particularly preferred as an accelerator. The however, sharing these two accelerators is not advisable because Hydroxylamine is decomposed by hydrogen peroxide. If you put hydrogen peroxide in free or bound form as accelerators, concentrations of 0.005 to 0.02 g / l hydrogen peroxide is particularly preferred. It can Hydrogen peroxide can be added to the phosphating solution as such. It is however, it is also possible to use hydrogen peroxide in bound form as compounds use the hydrogen peroxide in the phosphating bath by hydrolysis reactions deliver. Examples of such compounds are persalts such as perborates, Perphosphates, percarbonates, peroxosulfates or peroxodisulfates. As another Sources of hydrogen peroxide come from ionic peroxides such as Alkali metal peroxides into consideration.

Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of Hy droxylammonium salts are used. If you add free hydroxylamine Phosphating bath or a phosphating bath concentrate too, it is due to the acidic character of these solutions largely as a hydroxylammonium cation available. When used as a hydroxylammonium salt, the sulfates and the phosphates are particularly suitable. In the case of the phosphates are due preferred the acidic salts for better solubility. Hydroxylamine or its Compounds are added to the phosphating bath in such amounts that the calculated concentration of free hydroxylamine between 0.1 and 10 g / l, preferably between 0.2 and 6 g / l and in particular between 0.3 and 2 g / l lies. Aldoximes or come as bound hydroxylamine Ketoximes into consideration, which can split off hydroxylamine in acidic solution.

It is preferred that the phosphating baths as the only accelerator Hydroxylamine, if necessary together with a maximum of 0.5 g / l nitrate. Therefore in a preferred embodiment, phosphating baths are used which none of the other known accelerators such as nitrite, Contain oxo anions of halogens, peroxides or nitrobenzenesulfonate. As positive side effect reduce hydroxylamine concentrations above about  1.5 g / l the risk of rust formation in insufficiently flooded areas of the phosphating components.

In practice it has been shown that the accelerator hydroxylamine even then can be slowly inactivated if none in the phosphating bath phosphating metal parts are introduced. It has been surprising shown that the inactivation of the hydroxylamine are significantly slowed down can if you add one or more aliphatic to the phosphating bath Hydroxy or amino carboxylic acids with 2 to 6 carbon atoms in a total amount of 0.01 to 1.5 g / l added. The carboxylic acids are preferred selected from glycine, lactic acid, gluconic acid, tartronic acid, malic acid, Tartaric acid and citric acid, being citric acid, lactic acid and glycine are particularly preferred.

The use of reducing sugar as an accelerator is from US-A-5,378 292 known. They can be used in quantities within the scope of the present invention between about 0.01 and about 10 g / l, preferably in amounts between about 0.5 and about 2.5 g / l can be used. Examples of such sugars are galactose, Mannose and especially glucose (dextrose).

Particularly good corrosion protection results are achieved with phosphating baths obtained which contain manganese (II) in addition to zinc and ruthenium. The manganese content the phosphating bath should be between 0.1 and 4 g / l, since less Manganese the positive influence on the corrosion behavior of the Phos phat layers no longer exist and none at higher manganese levels further positive effect occurs. Contents between 0.3 and 2 g / l and especially between 0.5 and 1.5 g / l are preferred. The zinc content of the phosphating bath is preferably set to values between 0.45 and 1.5 g / l. As a result of However, it is pickling removal when phosphating zinc-containing surfaces possible that the current zinc content of the working bath up to 3 g / l increases. The form in which the zinc and manganese ions enter the phosphating baths is basically irrelevant. It is particularly useful as Zinc and / or manganese source to use the oxides and / or the carbonates.  

When the phosphating process is used on steel surfaces, iron goes in Form of iron (II) ions in solution. If the invention Phosphating baths contain no substances that are strong compared to iron (II) have an oxidizing effect, the divalent iron mainly goes off in succession Air oxidation into the trivalent state, so that it is called ferric phosphate can fail. Therefore, iron (II) contents can be found in the phosphating baths build up the baths containing oxidizing agents, which are clearly above the contents contain. In this sense, iron (II) concentrations up to 50 ppm are normal, with short-term values of up to 500 ppm occurring in the production process can. For the phosphating process according to the invention, such iron (II) Concentrations not harmful.

Similar to that described in EP-A-321 059 also brings in the invention According to phosphating baths, the presence of soluble compounds of the sixth valuable tungsten advantages in terms of corrosion resistance and paint adhesion. In the phosphating processes according to the invention can use phosphating solutions Find the additional 20 to 800 mg / l, preferably 50 to 600 mg / l Tungsten in the form of water-soluble tungsten, silicon tungstate and / or Contain borotungstates. The anions mentioned can be in the form of their Acids and / or their water-soluble salts, preferably ammonium salts be used.

The weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred. For the calculation of the concentration of the phosphate ions, the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO₄ ^3- . Accordingly, the known fact that the pH values of the phosphating baths, which are usually in the range from about 3 to about 3.6, only a very small part of the phosphate is actually in the form of the triple negative charged anions. At these pH values, it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogenphosphate anion, together with smaller amounts of non-associated phosphoric acid and double negatively charged hydrogenphosphate anions.

Those skilled in the art are further parameters for controlling phosphating baths the free acid and total acid contents are known. The one in this writing The method of determination used for these parameters is specified in the example section. Free acid values between 0 and 1.5 points for partial phosphating, at Band phosphating up to 2.5 points and total acidity between about 15 and about 30 points are in the usual technical range and are in the frame this invention.

Phosphating baths are usually sold in the form of aqueous concentrates which are adjusted to the application concentrations on site by adding water. For reasons of stability, these concentrates can contain an excess of free phosphoric acid, so that when diluted to a bath concentration, the value of the free acid is initially too high or the pH is too low. By adding alkalis such as ammonia or sodium or potassium hydroxide or carbonate, the value of the free acid is reduced to the desired range. Furthermore, it is known that the free acid content during use of the phosphating baths can increase over time due to the consumption of the layer-forming cations and, if appropriate, through decomposition reactions of the accelerator. In these cases it is necessary to readjust the value of the free acid to the desired range from time to time by adding alkalis. This means that the contents of the alkali metal or ammonium ions in the phosphating baths can vary within wide limits and tend to increase over the course of the service life of the phosphating baths due to the dulling of the free acid. The weight ratio of alkali metal and / or ammonium ions to zinc ions, for example, can therefore be very low in freshly prepared phosphating baths, for example <0.5 and in extreme cases even 0, while it usually increases over time due to bath maintenance measures, so that the ratio < 1 and can take values up to 10 and larger. Low zinc phosphate animal baths generally require additions of alkali metal or ammonium ions in order to be able to adjust the free acid to the desired value range at the desired weight ratio PO₄ ^3- : Zn <8. Analogous considerations can also be made regarding the proportions of alkali metal and / or ammonium ions to other bath components, for example phosphate ions.

Phosphating baths according to the invention are suitable for phosphating Surfaces made of steel, galvanized or alloy galvanized steel, aluminum,  aluminized or alloy aluminized steel. The term "aluminum" closes the technically usual aluminum alloys such as AIMg0.5Si1.4 with a. The materials mentioned can - as in Automotive engineering is becoming increasingly common - also coexisting.

Accordingly, the invention also includes a process for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel and / or Made of aluminum, in which the metal surfaces are sprayed or dipped for a time between 3 seconds and 8 minutes with a phosphating solution according to one or more of claims 1 to 9 in contact. The The process is for use in immersion, spray or spray / immersion processes suitable. It can be used particularly in automotive engineering where Treatment times between 1 and 8 minutes, especially 2 to 5 minutes are common. The use in band phosphating in the steel mill, whereby the Be action times are between 3 and 12 seconds, but is also possible. When used in tape phosphating processes, it is recommended that Bath concentrations in each case in the upper half of the preferred according to the invention Areas. For example, the zinc content can range from 1.5 to 2.5 g / l, the ruthenium content in the range from 0.05 to 0.2 g / l, the manganese content in the Range from 1.5 to 3 g / l and the free acid content in the range from 1.5 to 2.5 Points. It is particularly suitable as a substrate for tape phosphating galvanized steel, in particular electrolytically galvanized steel.

As is also common with other phosphating baths of the prior art, The suitable bath temperatures are independent of the area of application between 30 and 70 ° C, the temperature range between 45 and 60 ° C is preferred.

The phosphating process according to the invention is particularly suitable for the treatment of mentioned metal surfaces before painting, for example before a cathodic electrodeposition coating, as is common in automotive engineering. It is also suitable as a pre-treatment before a powder coating like this is used for example for household appliances. The phosphating process is to be seen as a sub-step of the technically usual pretreatment chain. In this Chain are the steps of cleaning / degreasing the phosphating, Intermediate rinsing and activation upstream, the activation usually with activating agents containing titanium phosphate. The invention  After an intermediate rinse, phosphating can optionally be carried out Follow passivating aftercare. For such a passivating Treatment baths containing chromic acid are widespread. Out For reasons of work and environmental protection as well as for disposal reasons however, the tendency to pass these chrome-containing passivating baths through chrome-free ones To replace treatment baths. Purely inorganic bath solutions are in particular based on zirconium compounds, or also organically reactive Bath solutions, for example based on poly (vinylphenols), are known. Between this post-passivation and the usually subsequent one Painting is usually an intermediate rinse with deionized water carried out.

From the German patent application with the file number 195 11 573.2 known, certain phosphating processes with a passivating rinse an aqueous solution with a pH in the range from about 3 to about 7 to succeed the 0.001 to 10 g / l of one or more of the following Cations contain: lithium ions, copper ions and / or silver ions. Such Rinsing is also suitable for improving the corrosion protection of the phosphating process according to the invention. Preferably one is used for this an aqueous solution containing 0.002 to 1 g / l copper ions. The copper preferably used as acetate. Such is particularly preferred Rinse solution that has a pH in the range of 3.4 to 6 and a temperature in the range of 20 to 50 ° C.

Embodiments 1 to 16 - Comparative Examples 1 to 3

The phosphating processes according to the invention and comparative processes were on steel sheets (St 1405, CRS), on hot-dip galvanized (HDG) and on steel sheets galvanized on both sides (ZE), as used in automobile construction Find use, checked. The following was in body production Common process carried out in the immersion process:

• 1.Clean with an alkaline cleaner (Ridoline® 1501, Henkel KGaA), Batch 2% in city water, 85 ° C, 4 minutes.
• 2. Rinse with deionized water, room temperature, 1 minute.
• 3. Activation with an activating agent containing titanium phosphate (Fixodine® 950, Henkel KGaA), approach 0.2% in deionized water, room temperature, 2 Minutes.
• 4. Phosphating with phosphating baths (bath temperature 50-55 ° C) according to Ta belle 1. In addition to the cations mentioned, the phosphating baths contained Sodium ions to adjust the free acid and Fe (II) in the range of 100 ppm and 0.5 g / l nitrate ions. Hydroxylamine was used as the sulfate. For all Deionized water was used in the baths. The pH of the baths was included 3.0 to 3.1, the free acid content at 2.5 points, the content of Total acidity at 23 points.
• Under the free acid score, consumption in ml becomes 0.1 normal Sodium hydroxide solution understood to make 10 ml bath solution up to a pH of 3.6 to titrate. Similarly, the total acid score gives the consumption in ml up to a pH of 8.2.
• 5. Rinse with deionized water, room temperature, 1 minute.
• 6. Blow dry with compressed air

The mass per unit area ("layer weight") was by detachment in 5% Chromic acid solution determined according to DIN 50942.  

The phosphated test panels were coated with a cathodic dip BASF coated (FT 85-7042). For example 8, a full structure (VW Candy white) applied. The corrosion protection was with a VDA Alternating climate test (1008 hours) checked. Table 2 contains the Paint infiltration at the Ritz (half the width of the Ritz) and information on Layer weight and size of the phosphate crystals that made up Scanning electron microscope photographs were taken. Elemental analytical ruthenium was detected in the phosphate layers.

Table 2

Layer weights, crystal size and paint infiltration (U / 2 = half scratch width)

Claims (12)

1. Containing acidic, aqueous phosphating solution
0.2 to 3 g / l zinc ions
3 to 50 g / l phosphate ions, calculated as PO₄,
characterized in that the solution additionally
Contains 0.002 to 0.2 g / l ruthenium ions. 2. Phosphating solution according to claim 1, characterized in that it additionally contains one or more of the following cations:
0.1 to 4 g / l manganese (II),
0.2 to 2.5 g / l magnesium (II),
0.2 to 2.5 g / l calcium (II),
0.2 to 1.5 g / l lithium (I),
0.01 to 0.5 g / l iron (II),
0.002 to 0.05 g / l copper (II). 3. phosphating solution according to one or both of claims 1 and 2, characterized in that it contains one or more accelerators selected from
0.3 to 4 g / l chlorate ions,
0.01 to 0.2 g / l nitrite ions,
0.05 to 2 g / l m-nitrobenzenesulfonate ions,
0.05 to 2 g / l m-nitrobenzoate ions,
0.05 to 2 g / l p-nitrophenol,
0.005 to 0.15 g / l hydrogen peroxide in free or bound form,
0.1 to 10 g / l hydroxylamine in free or bound form
0.1 to 10 g / l of a reducing sugar.
contains. 4. phosphating solution according to claim 3, characterized in that it is not contains more than 0.5 g / l nitrate ions. 5. phosphating solution according to one or more of claims 1 to 4, characterized characterized in that they additionally contain fluoride in amounts of up to 2.5 g / l Total fluoride, of which up to 1 g / l free fluoride, each calculated as F, contains. 6. phosphating solution according to one or more of claims 1 to 5, characterized characterized in that they act as accelerators 5 to 150 mg / l hydrogen peroxide in contains free or bound form. 7. phosphating solution according to one or more of claims 1 to 5, characterized characterized in that they act as accelerators 0.1 to 10 g / l hydroxylamine in free or bound form. 8. phosphating solution according to one or more of claims 1 to 7, characterized characterized in that they additionally have a total of 0.5 to 1.5 g / l of one or more contains aliphatic hydroxycarboxylic acids with 3 to 6 carbon atoms. 9. phosphating solution according to one or more of claims 1 to 8, characterized characterized that they additionally 20 to 800 mg / l tungsten in the form of water-soluble tungstates, silicon tungstates and / or boron tungstates contains in the form of their acids and / or in the form of their water-soluble salts. 10. Process for phosphating metal surfaces made of steel, galvanized or galvanized steel and / or aluminum, where the Metal surfaces by spraying or dipping for a time between 3  Seconds and 8 minutes with a phosphating solution according to one or brings several of claims 1 to 9 into contact. 11. The method according to claim 10, characterized in that according to the Treatment of the metal surfaces with the phosphating solution and before Painting with a passivating rinse with an aqueous solution a pH in the range of 3 to 7, the total 0.001 to 10 g / l contains one or more of the following cations: lithium ions, copper ions and / or silver ions. 12. Use of the phosphating solution according to one or more of the claims 1 to 9 for the pretreatment of metal surfaces made of steel, galvanized or alloy galvanized steel and / or aluminum before painting.