MXPA05006897A - Process for providing a thin corrosion inhibiting coating on a metallic surface. - Google Patents

Abstract

The invention relates to a process for coating metallic surfaces with a phosphating coating by contacting metallic surfaces at a temperature not above 45 ¦C and at a pH value less than 3.5 with an aqueous acidic alkali metal phosphating solution or dispersion containing: At least one compound of at least one phosphorus containing acid and/or at least one of their derivatives like esters and salts in a total content of all kinds of acids and all their derivatives like esters and salts together of less than 20 g/L calculated on mole base as orthophosphate, whereby the content of such phosphorus containing compounds/ions is at least 50 % by weight in comparison to all such compounds/ions and at least one ion selected from the group consisting of at least one alkali metal ion and ammonium ion, whereby the phosphating coating has a coating composition with a phosphorus content of not more than 8 atomic% as measured by Secondary Neutral Mass Spectroscopy (SNMS) and whereby the phosphating coating has a coating weight in the range from 0.01 to 0.5 g/m2.

Description

PROCESS TO PROVIDE A SLID CORROSION INHIBITOR COATING ON A METALLIC SURFACE FIELD OF THE INVENTION This invention relates to a process for coating the surface of a metal coil, part of a wire with an aqueous acidic phosphating solution containing predominantly alkali metal ions and / or ammonium ions as well as in many cases phosphate ions. . It also refers to a phosphating solution to be used in this process, to generate excellent corrosion inhibiting coatings on metal surfaces. In some cases, said coating can be used for cold forming the metal part. These solutions are called alkaline metal phosphating solutions or, if they are used on iron-rich surfaces, iron phosphating solutions. The invention relates particularly to a coating or conversion coating in aluminum, aluminum alloy, iron alloy such as steel and stainless steel, magnesium alloy, zinc or zinc alloy, as well as to a process, a concentrate and a solution for the formation of a phosphate coating on surfaces of these metallic materials.

Said coating solution is especially suitable for the generation of pretreatment coatings on substrate surfaces which will be coated in a second stage with at least one organic film, especially at least one film such as a layer of electro-thin coating lacquer. , a paint layer, a silane-rich layer and / or an adhesive layer. Alternatively, the coating can be used for a treatment such as a passivation without being covered with an additional coating such as a paint layer. BACKGROUND OF THE INVENTION Processes for the production of alkali metal phosphating coatings especially before lacquering, in relatively few cases are described in comparison with zinc phosphating or manganese phosphating of which there are a large number of publications. Fresh solutions for alkaline metal phosphating that have not yet been used, typically show only a very low or even virtually zero aluminum, iron and zinc content. Fresh aqueous acidic alkali metal phosphating solutions contain ions of at least one type of alkali metal ions and / or ammonium ions as well as phosphate ions. Due to the pickling effect of such acidic solutions on metal surfaces, the ions of dissolved metals such as aluminum, iron and zinc, as well as traces of other alloying constituents of the metallic pickling materials will be enriched during the ongoing phosphating process in the phosphating solution. Typically, the main phases of the alkali metal phosphating coatings are the corresponding phosphates oxides and / or hydroxides of the metal constituents of the metal base material (s). The solutions respectively phosphating alkali metal coatings are referred to as iron phosphating coatings respectively if they are used on iron alloy surfaces such as steel. The same applies to aluminum and aluminum alloys where said solutions or coatings are respectively described as solutions for aluminum phosphating. Often surfaces of very different metallic materials can be coated in the same alkaline metal phosphating bath at the same time or one after the other, whereby the ions of the different metals / alloys of the basic materials will be collected in the bath. These coatings are-you found coatings of the so-called zinc phosphate, phosphated zinc-manganese or manganese primordial or totally amorphous or extraordinarily fine grain. The alkali metal phosphates are described by Werner ausch: The Phosphating of Metals, ASM International, Finishing Publications Ltd., Teddington, England 1990 (especially pages 94-100, 120-130) in detail and are referred to as "uncoated phosphating" or in other publications "amorphous phosphating". The term "uncoated phosphating" is misleading, since there will be coatings generated although such coatings will be significantly thinner than those created during for example zinc phosphating or zinc-manganese phosphating. The very thin alkaline phosphated metal coatings are not, are poorly or-if they are colored or gray-well visible; the coatings can only be visible by colors caused by physical effects, by their type of gray appearance and / or by their matt appearance. The alkali metal phosphating solution always contains a certain content of at least one alkali metal such as sodium, potassium and / or ammonium. Alkali metal phosphating coatings are typically -in contrast to thick crystalline coatings of so-called "phosphates forming coatings" - more or less amorphous and show under the scanning electron microscope, typically nothing of crystalline grain shapes. Alkali metal phosphating coatings are primarily deficient, almost free or completely free of manganese and zinc, if there are no surfaces rich in manganese and / or zinc to pretreat or treat. Typically they are deficient, almost free or completely free of chromium, cobalt, copper, nickel, tin and / or other heavy metals. The phases primarily generated and / or precipitated during iron phosphating, which is carried out by contacting iron-rich metallic surfaces with an alkaline metal phosphating solution, are iron phosphates, iron oxides and iron hydroxides such as for example viyanite and / or magnetite. The contents of the dissolved ions of the metal surface and then transported in the alkali metal phosphating solution, especially aluminum, chromium, copper, iron, manganese, tin, titanium, respectively zinc are relatively low since said compounds respectively cations do not normally they are added to the bath, but only or almost only are present due to the pickling effect of the aqueous acidic alkali metal phosphating solution on the metal surfaces of the parts, sheets, strips or wires to be coated. Said contents will precipitate and generate the coating that primarily contains phosphates, oxides and / or hydroxides of the content of the metals in the solution additionally, there may be traces or even low contents of said ions caused by impurities by pickling of the bath containers and tubes of connection as well as by dragging the previous stages of the process sequence. A significant difference of the alkali metal phosphating process compared to the phosphating process of the "phosphate coating former" is also that the cation (s) necessary for the formation of coating during the alkali metal phosphating are always present in a small percentage, primordially or completely dissolved from the surface of the metallic base substrates, where for example during zinc phosphating, zinc-manganese, zinc-nickel or zinc-manganese-nickel there will be a relatively high addition for example of zinc, so that the zinc is contained primarily in a content greater than 0.3 g / L respectively, often greater than 1 g / L in the phosphating solution. This high zinc content is often caused by the addition of zinc compounds of at least 40 percent, primarily more than 60 percent, often even more than 80 percent of the total bath content, while only the remaining content is primarily it is generated by the pickling effect on surfaces with zinc. The coating generated by the phosphating of zinc, zinc-manganese, zinc-nickel or zinc-manganese-nickel typically shows the phases containing predominantly zinc and / or manganese hurealite, phosphophyllite, scolecite and / or hopeite, in significant crystalline fo The alkali metal phosphating coatings exhibit other significant properties such as zinc rich phosphates: they have a coating thickness in the range of 0.1 to 0.8 μt respectively, only a coating weight in the range of 0.2 to 1.3 g / m2. . Unlike most zinc-rich phosphate coatings that appear in brownish gray, the thinner alkali metal phosphates are primarily transparent or exhibit iridescent colors related to their extremely thin thickness. Then they show the colors of "superior orders" and can be for example almost transparent, yellowish, golden, reddish, a little violet, greenish or often bluish, partially iridescent. Only in the case that the alkali metal phosphating coatings have a higher coating weight, especially greater than 0.7 and probably up to about 1.3 g / m2, can they show a more dull gray appearance. In particular, alkaline-metal phosphates rich in aluminum can occur as silver or silver-iridescent. Alkali metal phosphating coatings can be prepared without any subsequent generation for example from at least one layer of paint and / or another layer of organic paint. Then this coating process can be referred to as treatment. If the phosphating coatings are to be used for protection against corrosion for a limited time, then the coatings may be referred to as a passivation. However, at least one paint layer and / or another organic paint-like layer, such as a primer, a lacquer, a silane layer, a base coat and / or a top coat and / or respectively together with an adhesive can be used and can then be used. called a pre-treatment. In general, alkali metal phosphating coatings are produced prior to painting by contacting the aqueous acidic phosphating solution which typically contains at least one mono- and / or orthophosphate and subsequently by electro-coating the phosphated metal surfaces and / or often by powder painting for example of metal construction parts that are well accessible from the outside as radiators and automotive bodies. Typically, the current alkali metal phosphate processes are carried out with solutions containing alkali metal and / or ammonium and at least one type of phosphate, primarily orthophosphate, as well as always at least one accelerator, thus showing a value of pH during operation in the range of 4 to 6. These aqueous acidic solutions are contacted with the metal surfaces typically at temperatures in the range of 48 to 72 degrees C. Their typical coating weights are in the range of 0.3 to 1 g / m2 . Current coatings are rich in at least one phosphorus compound, they primarily show bluish or light gray coatings and often a coating weight in the range of 0.5 to 1.5 g / m2. DE-A1-100 06 338 describes a typical process for iron phosphating wherein a small amount of copper ions has been added to solutions of a pH value in the range of 3.5 to 6.5 at a temperature in the range of 30 to 70 degrees C and especially at a pH value of about 4.8 to about 55 degrees C. DE-A1-1 942 156 shows the alkaline metal phosphating process by using a high pressure spray method to contact the metal surfaces with solutions with a temperature of 60 degrees C and a pH value in the range of 3 to 5.5, in particular a pH value of 4. DE-A1-1 914 052 refers to an alkaline metal phosphating process when using an application with roller coating with a solution containing 5 to 20 g / L of phosphate ions and 3 to 12.5 g / L of chlorate at a temperature of 54.5 to 60 degrees C with an extraordinarily unconventional pH value in the range of 1 to 3.5 , which contacts a coil within 30 seconds and compression. EP-B1-0 968 320 protects a process for alkaline metal phosphating for radiators by using a solution rich in surfactant of a pH value in the range of 4 to 6 at a temperature in the range of 35 to 60 degrees C and in special grade of at least 50 degrees C. FR-A-1,155,705 refers to an alkaline metal phosphating process using a solution containing ammonium silicon hexafluoride and nitroguanidine, with a pH value in the range of 3 to 6 at a temperature range of 50 to 76 degrees C. GB-A-1 388 435 reports an alkaline metal phosphating process using a solution containing chlorate and fluoride free of a pH value in the range of 3 to 6 at a temperature in the range of 50 to 80 degrees C, especially used with a pH value in the range of 3.65 to 4.4. US-A-2, 665, 231 reports an alkaline metal phosphating process by using a solution containing fluoro with a pH value in the range of 3 to 5.8 at a temperature in the range of 60 to 82 degrees C, in special used with a pH value in the range of 4.25 to 5.5. EP 0 411 606 A2 describes methods for surface treatment of aluminum or its alloys, by applying aqueous compositions containing niobium and / or tantalum together with fluoride and optionally with titanium and / or zirconium as well as phosphate. The addition of phosphate from 0.01 to 0.5 g / L should be used as an agent for pH adjustment. These compositions should help in preventing the blackening of cans during the treatment in boiling water. EP 0 121 155 Al shows processes for the preparation of iron or steel surfaces for painting by applying alkali metal phosphating solutions containing dihydrogen phosphate and nitrobenzenesulfonate which have a pH in the range of 4.2 to 6. DE 1942 156 A1 describes processes for the treatment of metal surfaces, especially of iron and steel surfaces, by applying solutions of alkali metal phosphate respectively, solutions containing ammonium phosphate and benzoate at a pH in the range from 3 to 5.5 at high pressures and at temperatures of about 60 degrees C. An object of the invention is to provide an alkali metal phosphating process with very stable bath conditions and with excellent coating appearances and coating qualities using at least one accelerator as nitroguanidin. A further object is to offer a phosphating process with improved corrosion resistance, compared to currently used alkali metal phosphating processes. Furthermore, an object is to provide an alkaline metal phosphating process which is stable, well suited for industrial application, for coils, parts and wires as well as easier and more economical as compared to processes currently employed. Surprisingly, it was observed that it is possible to "phosphatize" a metal surface with an unusually low or even zero phosphate content. Even acids other than acids containing phosphorus can be used without loss of quality of the coating properties. However, the term "phosphating" is used here for all types of coating processes and coatings independent of whether they contain phosphorus or not.

SUMMARY OF THE INVENTION According to the present invention, a process is provided for coating metal surfaces with a phosphating coating by contacting metal surfaces at a temperature not exceeding 45 degrees C and at a pH value of less than 3.5 with a dispersion solution. of aqueous acidic alkali metal phosphating containing: At least one compound of at least one phosphorus-containing acid and / or at least one of its derivatives such as asters and salts, in a total content of all types of acids and all its derivatives as esters and salts together less than 20 g / L calculated on a molar basis as orthophosphate, whereby the content of said compounds / ions containing phosphorus is at least 50 weight percent in comparison with all these compounds / ions and at least one ion is selected from the group consisting of at least one alkali metal ion and ammonium ion, wherein the phosphating solution or dispersion is chromate free , molybdates, niobates, tantalates and tungstates, wherein the phosphate coating has a coating composition with phosphorus content not greater than 8 atomic percent as measured by Secondary Neutral Mass Spectroscopy (SNMS) and En where the phosphate coating has a coating weight in the range from 0.01 to 0.5 g / m2. According to the present invention, a phosphating coating is provided on a metal surface prepared by contacting metal surfaces with an aqueous acidic alkali metal phosphating solution or dispersion having a coating thickness not greater than 0.15 finite and having good protection to corrosion for the protected metallic material. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES It has been found that for steel panels treated with an alkali metal phosphating solution based on a conventional composition, dried and subsequently painted with polyester paint, they show a corrosion inhibition effect as measured by the Corrosion test with salt spray (fog) clearly depending on the pH value of the alkaline metal phosphating solution. At a solution pH value of about 7, the salt spray corrosion test (SS = spray salt) showed results of about 5, at a pH value of about 5 SS values of about 2.5, and at a pH value of approximately 2.5 SS values (mm of plastoformation per cut-off marker) of approximately 1.5 or even less. More details are found in the examples. Tests were performed to identify the phases of different alkali metal phosphate coatings, but there was no X-ray diffraction result capable of identifying the phases. Thus, it is considered that the thin coatings are amorphous or almost amorphous. Then, the elemental content of the coatings is analyzed by X-ray Photoelectron Spectroscopy (XPS = X-ray Photoelectron Spectroscopy), which can be used as a routine measurement method to control the different coatings, but which is a method of measurement insufficient for these coatings to identify the content of the element, depending on the depth of the coating. Only the upper 8 nm of the surface at depth can be analyzed and therefore there is influence of surface impurities. The measurement of the content of phosphorus and other elements in the coating was performed by X-ray Photoelectron Spectroscopy with a 5700LSci instrument from Physical Electronics, with a monochromatic aluminum X-ray source, a power source of 350 Watts, a region of analysis of 2 x 0.8 mm, an angle of exit of 65 degrees, a correction of load for C- (C, H) in C ls in spectrums to 284.8 eV and a neutralization of load by gun of flood of electrons. Finally, the elemental content of the coatings is analyzed by Secondary Neutral Mass Spectroscopy (SNMS) with a SNMS-Leybold INA3 electron gas apparatus, which is an accurate measurement method for identifying the depth-dependent elemental content of the coating. said thin alkali metal phosphating coatings. The samples are electro-deposited with Ar ions with 1040 eV energy and at a current density of approximately 1.2 mA / cm2. An area of 5 mm in diameter was electro-deposited and analyzed. During the measurement, the atoms of the upper surface layer evaporate and the following lower atomic layers were analyzed, until the total coating was removed in the electro-deposited area during the analysis. In the 10 seconds of electro-deposition, approximately 10 nm was removed from the top of the coating. The measurement method could only be calibrated in a certain amount to the composition of the coatings analyzed. The results showed less dependence on roughness or surface roughness that was considered in the evaluation. For both analyzes, XPS and SNMS, the same four samples of cold-rolled steel panels were analyzed: 1) a panel only clean, but uncoated, 2) a typical conventional iron phosphate coating according to the state of the technique, as it occurs in current practice when first cleaning and then contacting the panel with an iron phosphating solution containing phosphate, sodium and chlorate at a pH value of 4.5 at a temperature of 50 degrees C generating a coating of approximately 0.16 to 0.22 μt thick, 3) a very thin yellow iron phosphating coating according to the invention, generated after having cleaned the panel by contacting it with an iron phosphating solution containing phosphate, sodium and 0.2 g / L of nitroguanidine at a pH value of 3.0 with a total acid value of 6 points at a temperature of 37 degrees C with a coating of approximately 0.02 to 0.1 / root thickness, 4) a coating of brazing iron phosphating, thin, according to the invention, generated after having cleaned the panel by contacting it with an iron phosphating solution containing phosphate, sodium and 0.2 g / L nitroguanidine at a pH value of 3.0 at a temperature of 37 degrees C with a coating with an approximate thickness of 0.06 to 0.12 μta, but the value for total acid fell below 3 points. Table 1: Element content of samples 1) to 4) as measured by XPS in atomic percent: The results of Table 1 show that there is a considerable difference in the composition between the uncoated sample 1), the sample coated according to the state of the art 2) and the coated samples 3) and 4) according to the invention . The figures show the elemental distribution in atomic percent as analyzed by Secondary Neutral Mass Spectroscopy (SNMS) depending on the depth of the coating that was analyzed from the surface (left) in the massive steel material (medium to right) in nm . Figure 1 for the clean but uncoated sample 1) shows the impurity effect of the surface region and then the composition of the cold rolled steel material. Figure 2 for Sample 2) covered with a typical current conventional iron phosphating coating indicates by the Fe content the thickness of the iron phosphating coating. As illustrated in the following figures, the oxygen and phosphorus content curves are - in the logarithmic graph - more or less proportional ("parallel"). There is a level in the upper and middle parts of the coating of about 30 atomic percent of Fe, of about 50 atomic percent of 0 and about 9 atomic percent of P. Figures 3 and 4 for Samples 3) and 4) with the coating according to the invention do not show levels of clear content. The coating of Sample 4) which is some percentage thicker than the coating of Sample 3), indicates a content of about 50 atomic percent Fe, about 35 atomic percent O and about 6 atomic percent of P in the upper parts of the coating. Figure 5 represents the results of Sample 5) that are comparable with Sample 3) but shows superior surface roughness data and therefore higher signal output. Figure 6 represents the results of Sample 6) that are comparable with Sample 4) but have higher surface roughness data and therefore higher signal output, as well. Figure 7 represents the curves of the P content of Samples 1) to 4) in comparison, but now - as a linear graph - it shows clearly different phosphor contents depending on the depth analyzed in the coating. Therefore, it is clearly demonstrated that the composition of the conventional iron phosphate coatings is significantly different from the composition of the iron phosphating coatings according to the invention. The roughness or surface roughness of all the samples was measured with a white light interferometer NT3300 from Wyko, of each panel coated in three areas. For Samples 1) to 4), the average Ra data per panel varied between 0.89 and 1.02 μ a, the average R2 data per panel varied between 1.11 and 1.22 μ p? and the average Rt data per panel varied between 6.17 and 7.25 μp ?. Compared to Samples 3) and 4), Samples 5) and 6) have been coated in the same manner and under almost the same conditions, but showed surface roughness data almost twice as high as Samples 3) and - 4): the average Ra data per panel varied to approximately 1.79 μt ?, the average Rz data per panel varied approximately 11.7 jim and the average Rt data per panel varied in the range of 11.4 to 12.1 μt ?. Sample 3) has to be compared with a Sample 5) by the difference in surface roughness and element content; similarly, Sample 4) should be compared with Sample 6). The rougher the surfaces allow a higher quantity of measured neutral parts than from more uniform surfaces, the more uniform surfaces should be used for analytical research and evaluation. Preferably, the content of P is less than 8 atomic percent at a depth of 0.05 μ? below the (original) surface of the alkaline metal phosphating coating as analyzed by Secondary Neutral Mass Spectroscopy (SNMS) or less than 6 or even less than 4 atomic percent at the depth of 0.1 μ? below the surface of the alkali metal phosphating coating or less than 3 or less than 2 atomic percent at a depth of 0.1 μm less than the surface of the alkali metal phosphating coating. Preferably, the phosphating coating according to the invention has a thickness not greater than or less than 0.15 μt ?, more preferred not greater than 0.12 μt ?, much more preferred not greater than 0.10 μp? . The process according to the invention can preferably be characterized in that the temperature of the phosphating solution or dispersion can be during contact of the metal surfaces in the range of 10 to 42 degrees C or less than 40 degrees C and more is preferred when minus 15 degrees C or up to 38 or up to 35 degrees C. The pH value can preferably be selected in the range starting from 1.8 respectively reaching up to 3.3, more preferred from at least 2 or up to 3.1, especially from at least 2.5 or up to 2.9. The weight of the coating can preferably be chosen in the range from 0.03 to 0.4 g / m2, more preferred is at least 0.05 or up to 0.36 g / m2, more preferred is at least 0.1 or up to 0.32 g / m2. As acids for use in the phosphating solution or dispersion, most organic and inorganic acids as well as their water-soluble and / or water-dispersible derivatives, especially salts and / or esters, can be used, but hydrochloric acid and chlorides they are not recommended as they can cause significant corrosion of cracks or crevices. It is also possible to use mixtures a) of acids, b) of at least one acid with at least one of salts and / or with at least one of ethers or c) of at least one of salts and / or at least one of ethers. Preferably, at least one acid is used as orthophosphoric acid, diphosphoric acid, monophosphoric acid, at least one of phosphonic acids, for example especially at least one with at least one aliphatic and / or aromatic group, especially at least one of diphosphonic acids, phosphonous acids, phosphorous acids, molybdate phosphoric acid, tungstophosphoric acid and / or at least one of its derivatives such as ester (s) and / or salt (s), especially at least one of monoester (s), of diester (en) and / or of triester (s) of a phosphorus-containing acid such as orthophosphoric acid, more preferred in admixture with at least one phosphorus-containing acid. Preferably, at least one sulfur-containing acid and / or at least one of its derivatives such as ester (s) and / or salt (s) is used as sulfuric acid, sulfamatic acid, at least one of sulfonic acids such as nitrosulfonic acid respectively , at least one of its derivatives, such as ester (s) and / or salt (s).

Preferably, at least one nitrogen-containing acid and / or at least one of its derivatives, such as ester (s) and / or salt (s), is used as nitric acid, at least one acid having at least one nitro group and / or at least one amino group respectively, at least one of its derivatives as ester (s) and / or salt (s). Preferably, at least one organic acid and / or at least one of its derivatives such as ester (s) and / or salt (s) is used as at least one of aromatic organic acids, hydroxycarboxylic acids, oxo acids, peracids and / or oxocarboxylic acids, respectively, at least one of their derivatives, such as ester (s) and / or salt (s), in particular, acetic acid, benzoic acid, citric acid, formic acid, gluconic acid, hydroxy acetic acid, lactic acid, malic acid, acid oxalic acid, succinic acid, tartaric acid and / or its or its water-soluble and / or water-dispersible derivatives such as ester (s) and / or salt (s) can be used. Any acid, its derivative, acid mixture and / or mixture with at least one of its derivatives such as ester (s) and / or salt (s) can be used, especially at least one or any mixture that is capable of displaying a value. of pH for example of about 2.4, of about 2.9, of about 3.4, of about 3.9 and / or of about 4.4 and that it is capable of generating - at least together with the cations present - a thin coating, but a high amount of Hydrochloric and chloride acid is not favorable to be used due to its very strong corrosive effect. Of these acids and derivatives, especially phosphoric acid and phosphate esters / dissolved salts are especially favorable. To accelerate the phosphating process, reduction and / or oxidation accelerators can be added, but they should not be applied. Said accelerator (s) may be favorable for improving the process, the quality of the coating and / or influencing the oxidation situation. In the process according to the invention, the phosphating solution or dispersion contains in many, but not in all cases, at least one accelerator as such based on chlorate, guanidine of an organic compound with at least one nitro group such as nitroguanidine. and / or nitrobenzensulfonic acid and its derivatives, hydrogen peroxide, hydroxylamine, nitrate and / or other nitrogen-containing accelerators; more preferred are nitroguanidine, nitrobenzensulfonic acid and / or its derivatives, such as salt or salts. All the accelerators together show a content in the range from 0.005 to 10 g / L, preferably in the range of 0.01 to 6 g / L, more preferred in the range from 0.02 to 3 g / L, especially preferred of at least 0.03 or up to 1 g / L, more is preferred of at least 0.05 or up to 0.7 g / L. Surprisingly it was observed that it is possible to use the process according to the invention without adding any accelerator. The quality of the solutions or dispersions of free accelerator phosphating as well as the coating process and the quality of the resulting coatings was the same as with a content of at least one accelerator. It can only be that the pickling speed of the accelerator free solution or dispersion is somewhat reduced so that the coating speed is decreased and the contact time has to be increased by a small amount. In the process according to the invention, an amount of Fe2 + ions can be added to the phosphating solution or dispersion, preferably in the range from 0.01 to 1 g / L, more preferred in the range from 0.02 to 0.8 g / L. , it is specifically preferred in the range of 0.03 to 0.5 g / L, more preferred is at least 0.05 or up to 0.3 g / L. The addition can be a phosphate-dissolved. This addition helps in some cases, especially for non-ferrous metal surfaces such as hot-dip galvanized (electro-galvanized) or electrogalvanized (EGG) materials, to generate better corrosion inhibition performance. In the case of the coating - especially free of accelerator - of steel surfaces, it is favorable to take care that the phosphating solution or dispersion does not contain more than approximately 0.5, 1 or 1.5 g / L of Fe2 + ions, depending on the current phosphating conditions; the iron content can then be reduced by adding an oxidizing agent - which can in some cases be an accelerator - and / or by using a cation exchange material, for example a suitable resin. In favorable embodiments, the phosphate solution or dispersion contains free fluoride, preferably in the range from 0.01 to 1 g / L and / or complex fluoride, in particular aluminum, boron, silicon, titanium and / or zirconium, preferably each one in the range from 0.01 to 1 g / L. In such cases, it is more preferred that the content of each free fluorine respectively of each of the complex fluoride (s) is in the range of 0.02 to 0.8 g / L, specifically preferred in the range of 0.03 to 0.5 g. / L, more is preferred of at least 0.05 or up to 0.3 g / L. The content of free fluoride and / or at least one complex fluoride improves the pickling effect, especially on galvanized metal surfaces, as well as on aluminum-rich surfaces, since the oxide contents can be more easily removed from the metal surface; in addition, it improves the performance and the quality of the corrosion inhibition and the paint adhesion of the coating thus formed for all the bases of metallic materials. In the process according to the invention, an amount of P04 ions can be added to the phosphating solution or dispersion, preferably in the range from 0.1 to 18 g / L, more preferred in the range of 0.5 to 15 g / L. , especially at least 1 and / or up to 12 g / L, in particular at least 2 g / L and / or up to 9 g / L P04 ions are preferred. The phosphate content can provide the acidity necessary for the primary pickling effect. It can also help in certain cases to remove excess heavy metal content as an iron content outside the solution, which can be predominantly a total result of pickling. The orthophosphoric acid can be added as an acid, as a monoacid and / or as a polyacid salt of an alkali metal and / or ammonium group or in a small amount as an iron phosphate. Instead of or partially in place of orthophosphoric acid, its or its esters and / or its or its salts, a phosphonic acid and / or another phosphorus-containing acid? /? at least one of its salts and / or esters may be added to the solution or dispersion, especially at least one water-soluble ester of phosphoric acid. In the process according to the invention, the phosphating solution or dispersion may contain an amount of S04 ions in the range of 0.1 to 10 or 18 g / L, preferably of at least 0.5 and / or up to 15 g / L, more preferred in the range of 1 to 12 g / L, even more preferred is at least 2 g / L and / or up to 9 g / L of S04 ions. The sulfate content can provide the acidity necessary for the primary pickling effect. The sulfuric acid can be added as an acid or as an alkali metal sulfate and / or ammonium group or in a small amount as an iron sulfate. In particular a mixture of at least one phosphorus-containing acid and / or its or its salts and / or its or its asters with at least one sulfur-containing acid and / or its or its salts and / or its or its asters can be added to the solution or dispersion; preferably, the content of these phosphorus-containing compounds should be at least 50 weight percent of all these acids, salts and esters. In the process according to the invention, the phosphating solution or dispersion may contain an amount of N03 ions in the range from 0.1 to 18 or up to 10 g / L, preferably of at least 0.5 and / or up to 15 g / L , more preferred is at least 1 and / or up to 12 g / L, even more preferred is at least 2 g / L and / or up to 9 g / L of N03 ions. The nitrate content can provide the acidity necessary for the primary pickling effect. Nitric acid can be added as an acid, as nitrate of at least one alkali metal and / or ammonium or a small amount as an iron nitrate. In particular a mixture of at least one phosphorus-containing acid and / or its salt (s) and / or its ester (s) thereof with at least one nitrogen-containing acid and / or its salt (s) and / or its ester (s) may be added to the solution or dispersion; preferably, the content of the phosphorus-containing compounds should be at least 50 weight percent of all these acids, salts and esters. In the process according to the invention, the phosphating solution or dispersion may contain an amount of groups, ions and compounds as a whole of one or more organic acids and / or their derivative (s) in the range of 0.1 to 10 or 18. g / L, preferably at least 0.5 and / or up to 15 g / L, more preferred in the range from 1 to 12 g / L, even more preferred is at least 2 g / L and / or up to 9 g / L L of these groups, ions and compounds. In addition, the phosphating solution or dispersion may contain an amount of nitroguanidine and / or other accelerators based on guanidine such as acetate guanidine, aminoguanidine, carbonate guanidine, raelanilinoguanidine, nitratoguanidine and ureidoguanidine in the total range from 0.01 to 5 g / L, preferably in the range of 0.015 to 3 g / L, more preferred in the range of 0.01 to 1.2 g / L, even more preferred is at least 0.02 g / L and / or up to 0.6 g / L of the guanidine compound (s) . Nitroguanidine has shown in several cases that it gives the best results of all the accelerators tested. In comparison to the use of aminoguanidine, the addition of nitroguanidine was a small amount more favorable especially for the inhibition of corrosion. In the process according to the invention, the phosphating solution or dispersion may contain at least one surfactant, especially when the cleaning and phosphating are carried out with the same solution or dispersion, then preferably with an amount of all the surfactants together in the range from 0.01 to 10 g / L. If at least one surfactant is used in the phosphating solution, care is taken that no foam is generated. In certain cases, it may be favorable to add a defoamer. This total surfactant content may preferably vary in the range of 0.1 to 7 g / L, more preferred in the range of 0.3 to 5 g / L, even more preferred is at least 0.5 g / L and / or up to 3 g / L of the surfactant (s). Especially in a bath processes, cleaning and phosphating can be carried out in the same bath container with the same solution or dispersion, so that in the first time to contact the metal components with the phosphating solution or dispersion , the cleaning and pickling effect of the solution or dispersion may preponderate, while in the future contact time, the coating process with the phosphating coating formation may predominate. In general, almost all types of surfactants respectively surfactant mixtures are suitable for addition to the phosphating solution or dispersion, especially surfactants respectively surfactant mixtures with low foaming or nonfoaming properties and with a cloud point in the range from 25 to 40 degrees C, whereby mixtures of surfactants can be free of constituents in addition to surfactants. The phosphating solution is preferably free or almost free of other heavy metals than those that are cleaved from the metal surface, probably except for titanium and / or zirconium, especially in the presence of fluoride or complex fluorides. It is preferred free of chromates, molxbdates and tungstates. In the process according to the invention, the phosphating solution or dispersion may contain at least one solvent such as a propylene glycol and / or a glycol ether; in addition, it may contain at least one biocide, at least one stabilizing agent for a surfactant such as a condensed sulphonic salt, at least one stabilizing agent for the accelerator such as a fine particle, clay or clay type silicate material and / or at least one stabilizing agent for the solution or dispersion itself as a biopolymer. A solvent can preferably be used to improve the cleaning effect of the metal surface, especially in combination with at least one surfactant. It is favorable to use a guanidine compound in the form of a suspension containing a stabilizing agent, especially nitroguanidine. In the process according to the invention, a phosphating coating is produced which shows to be primarily colorless, slightly colored, silvery, golden, yellowish, yellowish-brown, yellowish-reddish and / or bluish. If the coating according to the invention is bluish, it seems that often a phosphorus content of the coating is not as low as is typical for such coatings and less than excellent corrosion inhibition results must often be found. This coating may in several cases be less than intense in color or may show a less glossy and / or even matte appearance than conventional coatings. This coating typically can have a coating thickness in the range of up to 1 μt ?, primarily only up to 0.6 μ, often only up to 0.3 μ a. In the process according to the invention, a clean and / or pickled metal surface is contacted with the solution or dispersion respectively. The metal surface can be contacted with the solution respectively dispersion by dip, spray, steam phosphating, roller coating and / or compression. All the varieties of application except phosphating with steam, are often used for continuous pre-coating. The coated metal surface is dried after being contacted with the solution or dispersion or subsequent solution after at least one successive rinsing step, by air drying, oven drying and / or infra-red drying, especially at temperatures in the range of 20 to 250 degrees C. At least two coatings can be applied one after the other on the metal surface, whereby at least one of them is applied with an alkali metal phosphating solution respectively dispersion and with at least one other coating can be applied optionally with a conversion coating solution such as phosphating rich in zinc and / or manganese. In the process according to the invention, first an alkali metal phosphating coating is generated on a metal surface and then a coating selected from the group consisting of a conversion coating as a phosphate coating rich in zinc and / or manganese, A stearate coating and / or an organic polymer coating is applied especially for cold forming. In the process according to the invention, a metallic surface essentially consisting of metallic materials of aluminum, chromium, titanium, and / or zinc as well as at least one alloy containing aluminum, chromium, copper such as brass or bronze, iron, magnesium , tin, titanium and / or zinc in alloys, is covered with a coating of a phosphating solution or dispersion. The coating prepared with a process according to the invention can be used for short-term passivation, for the treatment before at least one layer of successive paint, layer of any other organic coating and / or adhesive coating, as a lubricant carrier or as one of the lubricant coatings before cold forming.

The respective lubricant carrier can be used favorably for cans, for machining, for wire drawing and / or for lubricating the moving chains. The process can be varied successfully by covering the phosphating coating derived according to the invention with a first solution respectively seal dispersion. The results of the salt spray corrosion test show that a second, third and / or fourth coating on the metallic surface generated by contacting the phosphate panels in this way with the solution or respective final seal dispersion, significantly improve the resistance to corrosion, although said final seal coatings are very thin. Preferably, said final seal coatings can be generated with a final seal solution / dispersion containing at least one rare earth element compound such as a cerium compound, at least one resin component such as acrylic acid and / or at least one silane. The coating prepared with a process according to the invention can be used for the inhibition of corrosion and / or lubrication of metal surfaces, especially for use in the aerospace industry, the automotive industry, rail transport, ship construction, metal forming, metal work as machining and / or rectification, in metal containers and especially can introduction, in the coil industry for metal sheet applications, wire production, appliances, alloys, machine and building construction. EXAMPLES The following examples illustrate, in detail, embodiment of the invention. The following examples and comparison examples will help clarify the invention, but are not intended to resist its scope. Group 1. Comparison Examples 1 to 6: The first tests were performed where an aqueous acidic solution such as standard chlorate and accelerated alkali metal phosphate concentrate with methanedi-benzene sulfonate (SNBS) A containing: I.3 percent by weight of phosphoric acid, II .7 weight percent of monosodium phosphate, 1.0 weight percent of SNBS, 10.0 weight percent of sodium chlorate and the rest is deionized water. Compared with another aqueous acidic solution of an alkaline metal phosphating concentrate B accelerated only in nitroguanidine containing: 1.3 weight percent phosphoric acid, 11.7 weight percent monosodium phosphate and the rest is deionized water. Starting from these concentrates, the baths with these solutions were prepared at 3 volume percent for both formulations, this means that solution A at 3.58 weight percent respectively for solution B 3.30 weight percent of the concentrate. To solution B, 0.2 g / L nitroguanidine stabilized with a small content of clay type material was added further. The pH value of both phosphating baths was adjusted to 4.5 respectively 2.8 with the addition of sodium hydroxide. Cold rolled steel panels (CRS = cold rolled steel) were cleaned with Okemclean® at 3 percent by volume and 54.4 degrees C for 30 seconds by spraying. The panels were then rinsed and then passed in phosphate bath A or B for 60 seconds when sprayed at various temperatures. This was followed by rinsing and drying with compressed air. The panels were finally painted with a Dupont TGIC polyester powder paint and subjected to a corrosion test with salt spray (fog) strictly in accordance with ASTM B 117 for 336 hours for evaluation of corrosion inhibition properties strictly in accordance with a ASTM B 1654 rating with ten as the best and zero the worst. Table 2. Composition of the coatings of the different groups Contents in g / L P043"Na + C103" BS Nitro-Amino-Examples / Examples of guani- guani-Comparison dyna dina Carbonate 108, 0.12 0.02 - - 0.02 _ 61, 64, 67, 0.58 0.12 - - 0.2 - 70, 73, 76, 0.58 0.12 - 0.2 82, 84, 92, 1.16 0.25 - - 0.02 - 62, 65, 68, 1.16 0.25 - - 0.2 - 71, 74, 77, 1.16 0.25 - - 0.2 83, 85, 95, 1.16 0.25 0.6 - 106, 3.01 0.64 - 0.5 - 88, 91, 94, 97, 3.01 1.38 2.37 0.90 1-3, 11-14, 19-22, 27- 3.48 0.74 0.2 30, 35- 38, 51-53, 63, 66, 69, 54-56, 72, 75, 78, 3.48 0.74 - - - 0.2 4-6,15-18, 23-26, 31-34, 3.78 1.61 2.81 0.32 - -39-42, 79, 110, 111 107, 4.41 0.94 - - 0.8 -Contents in g / L P043"Na + IO3- NBS Nitro-Amino- Examples / E] guaníguani-Comparisons dina dina carbonate 86.93, 96, 102, 5.80 1.23 - - 0.02 - 101, 5.80 1.23 - 0.5 81, 87, 89, 90, 5.80 1.23 - - 0.6 - Table 3: Coating Weight and Salt Spray Corrosion Test Ratings in CRS for a high pH value dependent on the temperature of the coating function is different accelerated alkali metal phosphate systems.

Com . Accelerator TempePeso value of pH rating for coating Coating ASTM D 1654 for corrosion test with salt spray ((g / m2) 550 h 1008 h degrees C) CE 1 Nitroguanidine 4.5 54.4 0.18 6 6 CE 2 65.6 0.24 5 4 CE 3 82.2 0.34 3 Comp. Accelerator Value TempePeso of pH Rating ratura Coating ASTM D 1654 for corrosion test with salt spray CE 4 Chlorate-SNBS 4.5 54.4 0.32 3 0 CE 5 p 65.6 0.52 0 1 CE 6 82.2 0.46 1 The higher the rating values, especially after a longer test time, the better the corrosion inhibition results. As the temperature increased in the accelerated bath with nitroguanidine B, the coatings became more uniform and changed from gray-brown to blue. Lower temperature treatments and lower coating weights were correlated with better salt spray performance. The accelerated system with nitroguanidine B showed a better and more homogeneous appearance of the coatings and a better inhibition of corrosion than the system accelerated with chlorate-SNBS A. The coating for the panels was homogeneous and went from blue to gold as the temperature increased. Group 2: Comparison Examples 11 to 42 The same formulations of base bath were used for the following tests with the accelerator system with chlorate-SNBS standard A and with the accelerator system with nitroguanidine B as in group 1. Panels of cold rolled steel (CRS) galvanized steel with immersion in hot (HDG) electro galvanized steel (EG) and aluminum alloy ?? 6061, were cleaned with Gardoclean® 5206, rinsed, treated in phosphate baths A or B and then rinsed and dried with compressed air. Based on Group 1, the covered temperature range was changed to lower temperatures employed. The panels were finally painted with Morton Corvel Black powder paint and subjected to corrosion testing with salt fog (fog) for 250 hours in accordance with ASTM B 117. The plastoformation of cut marking was measured according to the rating of 0 to 10 in accordance with ASTM D 1654; The higher the SS values, the better the results. Table '4: Salt spray corrosion test results for different metal surfaces depending on the temperature of the coating solution of different accelerated alkaline metal phosphating systems in a different way for a pH value of 4.5.

Com . Accelerator Substrate TempePeso of qualification ratura Examination of test of (degrees (g / m2) corrosion with C) salt spray for 250 h CE 11 Nitroguanidine CRS 26.7 0.02 7 CE 12 43.3 0.14 2 CE 13 54.4 0.26 3 EC 14 65.6 0.33 3 CE 15 Chlorate-SNBS CRS 26.7 0.23 1 EC 16 43.3 0.23 2 EC 17 54.4 0.50 3 EC 18 65.6 0.27 2 CE 19 Nitroguanidine HDG 26.7 - 3 CE 20 43.3 - 2 CE 21 54.4 - 3 EC 22 65.6 - 1 CE 23 Chlorate-SNBS HDG 26.7 - 3 EC 24 43.3 - 3 EC 25 54.4 - 3 EC 26 65.6 - 4 CE 27 Nitroguanidine EG 26.7 - 2 CE 28 43.3 - 3 Comp. Accelerator Substrate TempePeso of qualification ratura Test coating of (degrees (g / m2) corrosion with C) salt spray for 250 h CE 29 54. 4 - 2 CE 30 65.6 - 0 CE 31 Chlorate - ???? EG 26.7 - 4 EC 32 43.3 - 3 CE 33 54.4 - 2 CE 34 65.6 - 0 CE 35 Nitroguanidine AA 6061 26.7 - 10 EC 36 43.3 - 10 EC 37 54.4 - 10 EC 38 65.6 - 10 CE 39 Chlorate-SNBS AA 6061 26.7 - 10 EC 40 43.3 - 10 EC 41 54.4 - 10 EC 42 65. S - 10 The test results of these test series show that the results are partially better at lower temperatures, but the results depend heavily on the metallic material of the contacted surface. Excellent results can be achieved with all the aluminum alloy panels. Nitroguanidine showed good corrosion inhibition results, so it was very surprising that this could be achieved with such a thin coating. Again, all the panels were homogeneous. For the invention, the CRS panels went from gray-brown to blue as the temperature increased. HDG and EG panels showed a mordant appearance in all cases, but without color. The aluminum panels were bright without seemingly visible coating. For the chlorate samples, the CRS panels went from blue to gold as the temperature increased, the HDG and EG panels had an iridescent appearance and the aluminum panels had a tan or light transparent tan. Group 3: Comparison Examples 43 or 44 The cold-rolled steel panels were treated with aqueous acidic phosphating solutions C containing only a very small amount well below 1 g / L of phosphoric acid only to adapt the pH value of the mixed solution listed at 2.5 respectively 4.5, 0.2 g / L nitroguanidine and 0.2 g / L aminoguanidine bicarbonate. If aminoguanidine was added in all the examples, it was added as bicarbonate, although not always indicated. The panels were cleaned with Gardoclean® S 5206 and rinsed before nitro- and aminoguanidine were added. The panels were contacted with the phosphated emulsions for the test with a pH value of 2.5 at room temperature and for the test with a pH value of 4.5 to 49 degrees C. This was followed by rinsing and drying the panels with compressed air . The panels thus coated had a golden appearance and showed a homogeneous coating. The panels were then painted with a polyester powder paint and Ferro TGIC. Finally, the panels were verified for adhesion to paint by scratching and direct impact. There was significant loss of paint when these tests were performed and were not acceptable. The panels were then also subjected to corrosion tests with salt spray (fog) for 250 hours in accordance with ASTM B 117. The panels were rated zero in accordance with ASTM D 1654 for all cases after 250 hours, which also It is a bad result. Since the solutions do not contain alkali metal ions or ammonium ions, they were not damped and lacked a significant acid content. Group 4: Comparison Examples 51 to 56: The comparison examples illustrate the effect of low and very high pH values of the phosphating solution using 0.2 g / L of nitroguanidine and 0.2 g / L of aminoguanidine carbonate as accelerators and using the base bath solution B of Group 1 containing 3 volume percent of the concentrate containing 1.3 weight percent of phosphoric acid, 11.7 weight percent of monosodium phosphate and the rest being deionized water. The C S panels were cleaned as in the previous examples. Starting with a very acidic bath, the addition of NaOH resulted in very high pH values. The panels were sprayed with this conversion coating solution, for 60 seconds at 48.9 degrees C. An unpainted panel of each test was placed in a 100 percent humidity test chamber for a water fog test in accordance with ASTM D 1735 for 72 hours and subsequently the percent red surface oxide was graded. The rest of the panel was painted with a Ferro TGIC polyester powder paint and placed in a salt spray corrosion test chamber in accordance with ASTM B 117 for 250 hours and for a saline fog (fog) corrosion test with acetic acid accelerated with copper (CASS = copper accelerated acetic acid salt spray) strictly in accordance with General Motors Engineering Standards (General Motors engineering standards) June 1997 for 72 hours.

The results of corrosion test with salt spray and CASS test results were measured in mm of plate of plastoformation of cutting marking. The panels of tests 3 and 6 do not produce any visible coating and therefore were not tested further. The nitroguanidine bath was not stable on a pH value of about 7. Table 5: Results of the humidity tests, corrosion with salt spray and CASS depending on the pH value of the coating solutions of accelerated alkali metal phosphating systems in different ways.

Com . Accelerator Corrosion Moisture Value CASS in mm PH percent with salt spray in mm EC 51 Nitroguanidine 2.8 10-25 0.1 0.2 CE 52 7.0 10-25 0.2 0.4 CE 53 9.0 CE 54 Carbonate of 2.8 100 0.2 0.3 Aminoguanidine CE 55 4.5 40 0.1 < 0.1 CE 56 6.5 The corrosion inhibition was only for the EC 51 sample with a good pH value of 2.8 and another medium quality. No coating weights were measured for this group. The coatings in all cases were homogeneous. Both coatings generated with nitro and aminoguanidine showed a golden color at a low pH value and were blue at a high pH. Group 5: Examples and examples and comparison examples 61 to 79: Cold-rolled steel panels were cleaned and found as in the previous examples and comparison examples. The phosphating baths were prepared with varying amounts of the base bath formulations starting from group 1 and varying the accelerator concentrations of A and B. The conversion coating baths were operated at 26.7 degrees C and primarily at a pH value of 4.5. by spraying for 60 seconds. The last comparison example 79 was accelerated alkali metal phosphating-by-SNBS-chlorate standard as established in group 1, but only this was operated at a pH value of 4.5 and at a temperature of 48.9 degrees C for 80 seconds of Dew. The corrosion rating with salt spray was evaluated in accordance with ASTM D 1654 after the corrosion test with saline fog (fog) of 500 hours in accordance with ASTMB 117. Table 6: Results of the corrosion test with salt spray and the weight of coating dependent on the amount of accelerator of the coating solutions of different systems of accelerated alkali metal phosphating and the pH value at a temperature of 26.7 degrees C; * bathroom without accelerator content Ex./ Accelerator AcceleConcentra Weight Rating Value Com . PH coating coating (g / L) Bath * Corrosion corrosion Volume (g / m2) with saline fog for 500 hours CE 61 Nitroguanidine 0.02 0.5 4.5 0.06 0 CE 62 1 0.14 0 EC 63 3 0.07 0 CE 64 0.2 0.5 0.16 0 CE 65 1 0.13 0 CE 66 3 0.01 0 CE 67 0.4 0.5 0.16 0 CE 68 1 0.14 0 CE 69 3 0.11 0 Ex ./ Accelerator AcceleConcentra Weight Weight Rating Com . pH adjustment coating (g / D) Bath * corrosion corrosion Volume (g / m2) with saline fog for 500 hours CE 70 Carbonate 0.2 0.5 0.11 0 Aminoguanidine CE 71 1 0.30 0 E 72 3 2.8 0.15 3 CE 73 0.1 0.5 4.5 0.03 2 CE 74 1 0.19 0 E 75 3 2.8 0.16 3 CE 76 .. 0.05 0.5 4.5 0.03 2 CE 77 .. 1 0.10 1 E 78 .. 3 2.8 0.01 3 CE 79 SNBS-Chlorate 3 4.5 0.45 1 The examples according to the invention, E 72, E 75 and E 78, show significantly better corrosion results than most other samples. The coatings were uniform in a gold color at a low pH value and a blue color at a high pH value for coatings generated with amino- or nitroguanidine respectively.

Group 6: Examples and comparison examples 81 to 97: In this group, a so-called multimetal formulation was used. The bath solution contains fluoride to treat cold rolled steel, hot dip galvanized, electro galvanized and aluminum. The base solution B of group 1 was used with an additional content of free fluoride, with which the content of all the components of this bath is varied to a temperature of 38 degrees C. A high number of solutions and tests were made to generate data for intensive studies with experimental evaluation design. For these experiments, the metal surfaces, the fluoride content (50-200 mg / L), the added Fe2 * content (0-200 mg / L), the content of sodium phosphate and monophosphate together (1.4-7.2 g) / L), the nitroguanidine content as the only accelerator (0.02-0.6 g / L) as well as the pH value (2.8-4.5) were systematically varied within the limits mentioned, with only the examples according to the invention are cited in Table 7. In comparison, an accelerated-by-SNBS-chlorate solution of a pH value of 4.5 was tested at 49 degrees C with CE 88, CE 91, CE 94 and CE 97, while the others Comparison examples belong strictly to the data set as shown for the rest of the examples according to the invention. The number of examples and comparison examples tested were reduced from this general review, so that the typical results are represented here. From these experiments, systematic calculations were performed and regions of respectively good, respectively stable, excellent behavior were selected. The panels were painted with a Ferro TGIC 38 polyester powder paint at 51 μt thickness and placed in a corrosion proof chamber with saline mist (SS) according to ASTM B 117 for 250 hours, resulting in the results of Test were measured in mm of plastoformation of cut-off marker. In addition, adhesion was tested in accordance with ASTM D 3359, whereby 5B means that no flaking occurred in the cross-sectional area which is the best possible test result while for example 2B means that there was a certain amount of flaking in the Cross section area. Table 7: Results of the corrosion test with salt fog (fog) depending on the chemical composition of the phosphating solutions and the pH value at a temperature of 32 degrees C; * bathroom without accelerator content Ex. / Superricie Accelerator Concentration Fluoride Fe2 + Com. Metallic Bath * (g / L) (g / L) (mg / L) (mg / L) E 81 CRS 7.2 0.6 200 0 E 82 1.4 0.02 50 200 E 83 1.4 0.6 200 200 E 84 1.4 0.02 200 0 CE 85 1.4 0.6 200 0 E 86 7.2 0.02 200 200 CE 87 7.2 0.6 200 200 EC 88 4.1 4.4 310 0 E 89 HDG 7.2 0.6 50 200 ? 90 7.2 0.6 200 0 EC 91 4.1 4.4 310 0 E 92 EG 1.4 0.02 50 200 E 93 7.2 0.02 200 200 CE 94 4.1 4.4 310 0 E 95 AI 6061 1.4 0.6 50 0 E 96 7.2 0.02 50 0 CE 97 4.1 4.4 310 0 (CONTINUATION TABLE 7) Ex. / ASTM value of Adhesion Qualification SS Cal. pH 3359 SS for 240 h for 500 h E 81 2.8 5B 1 2.5 E 82 5B 0.5 2 E 83 5B 0.5 1 E 84 4B 1 1.5 CE 85 4.5 5B 2.5 4 E 86 2.8 5B 1 1.5 EC 87 4.5 4B 4 9 EC 88 4.5 2B 4.5 7 E 89 2.8 3B 3.5 4 E 90 3B 4 5 CE 91 4.5 2B 10 18 E 92 2.8 5B 2 2.5 E 93 5B 1.5 3 CE 94 4.5 2B 3.5 4 E 95 2.8 4B 0.5 0.5 E 96 4B 0.5 0.5 CE 97 4.5 4B 0.5 1 Almost all the examples according to the invention showed very good corrosion inhibition results respectively for the HDG corrosion sensitive material, even excellent results compared with the results of the comparison examples. The higher the values of the adhesion tests, the better the results. The coatings were uniform in all cases. CRS panels according to the invention were gray, HDG panels were of a faint gold, EG panels were gray and aluminum panels were not of significant color. For the control, the CRS panels were gilded, the EG and HDG panels were transparent and iridescent and the aluminum panels were light blue. Group 7: Examples and comparison examples 101 to 111: In this group, only cold-rolled steel panels were used and different influences were verified, including the influence of the bath temperature. The solutions were free of fluoride and Fe2 +. All other contents and conditions of the coatings were the same as Group 6. In addition, samples CE 109 and CE 110 were coated with Bonderite® 1000 (CE 109) for having an additional thin chrome end seal cover that covers the phosphate coating respectively Cryscoat® 547 for having an additional thin chrome-free final seal covering the phosphate coating (CE 110) and the latter having no additional final seal (CE111) -each one coated in a typical form. These coatings can be used as typical industrial standards to obtain a comparison of current conventional conventional phosphating iron coatings. Table 8: Results of the corrosion test with salt fog (fog) in the three CRS panels, each one dependent on the chemical composition of the coating solutions, the pH value, the contact time and the temperature; * bathroom without accelerator content Ex. / Bath * Accelerate time (s) temp. qualification Com . Conc. pH (of degrees C) SS for the (g / D (g / D contact pertormation of 240 n ram E 101 7.2 0.5 2.8 30 32 1 E 102 7.2 0.02 2.8 105 32 1.1 E 103 4.3 0.2 3.0 60 37 0.5 E 104 0.14 0.02 2.8 180 37 1.2 E 105 0.14 1.0 2.8 30 44 1.0 CE IOS 3.7 0.5 4.9 105 44 1.6 CE 107 5.4 0.8 6.0 68 54 8.1 CE 108 0.14 0.02 4.9 180 60 9.3 CE 109 _ - _ - - 0.2,0.5 CE 110 4. S 3.9 4.5 52 SO 2 CE 111 4.6 3.9 4.5 52 60 5 The examples according to the invention showed very good corrosion inhibition results compared to the results of the comparison examples. The comparison examples vary with respect to the quality of corrosion inhibition depending on whether there is additional seal or not and especially if this final seal is a layer containing chromium. CE 109 shows that layer containing additional chromium that covers the phosphate layer, should show the best properties of corrosion inhibition. However, it is surprising that the best panels according to the invention were able to achieve the excellent corrosion inhibiting properties of CE 109 which is the best industrial standard material based on iron phosphate known in the art., which in this case is even covered by a final rinsing layer of strong corrosion inhibition. The coatings were uniform in all cases. The color changed from gold to blue when either the pH or the temperature increased. Contact time, bath concentration and accelerator concentration have no apparent effect on appearance.

The results of the design of experiments clearly showed a wide region of unusually stable working conditions for an alkali metal phosphating solution below a pH value of 3.5 and surprisingly very consistent coating properties. The results of phosphating in 6061 aluminum alloy were better at an F-content lower than 200 ppm and at a Fe2 + content less than 120 ppm. In hot dip galvanized steel (HDG = hot dip galvanized), they were better at lower Fe ^ content than 360 ppm and at a Fe + content greater than 80 ppm, although the results were-as is usual with HDG in these comparison-worse than for the other materials tested. In electrogalvanized steel (EG), they were better at a very low P04 content and at a F ~ content of less than 200 ppm. In cold-rolled steels (CRS), they were better at an F-content of less than 250 ppm.For a prolonged performance study, it was confirmed that these working conditions as well as the coating properties could be maintained almost without any variation throughout the The appearance of the coatings at the end was as good as the good alkaline phosphated metal coatings used in the market, and nitroguanidine was identified as the best accelerator during all these studies. Alkali metal phosphating process with the slightly modified working conditions for the solutions according to the invention are all well suited for industrial applications of coils, parts and wires.The use of phosphating solutions at a significantly lower temperature than the current usual for contacting metal surfaces helps reduce costs and heating considerably. The phosphating process proposed here is easier than the processes currently used since it is quite sufficient to control only the free and total acid content, but no other parameters of the bath within the short life times since the bathing behavior is very stable. Finally, this process is not only superior because it requires less heating and therefore is more economical compared to processes currently used since there is a significantly lower consumption of all the chemical compounds in the solution than usual. Group 8: Examples 112 to 119: For this investigation, cold-rolled steel panels supplied by Q panel were used as the substrates. Table 9 below cites the bath composition for each variation. Examples 117 to 119 were rinsed with a final seal instead of rinsing with DI water. CrysCoat UltraSeal is a product of Chemetall Oakite based on water, silane and alcohol. The pre-treated panels were painted using TGIC polyester powder paint supplied by Rohm & Haas. Simple cut marker panels were placed in salt spray corrosion tests according to ASTM B 117 for 240 hours. The panels were scraped with a metal spatula and the amount of cut marker paint loss was measured in mm. All variations were subjected to crosslinking adhesion in accordance with ASTM D 3359 and direct and inverse impact in accordance with ASTM D 2794. In all cases, the score for the scratch adhesion test was 5B (no loss of adhesion) and for the direct and inverse impact, without cracking or other loss of paint is seen up to 1.84 kilograms / meter2 (160 pounds / inch2). The panels were pre-treated as described below: 1. Gardoclean S 5206.3 v / v percent b.v. , 49-52 degrees C (120-125 degrees F), 60-second spray 2. Rinse running water, room temperature, 30 seconds spray 3. Conversion coating, 30-33 degrees C (86-92 degrees F) 4. Rinsing of running water, room temperature, 30-second spray 5. DI water rinse, 10 seconds or final seal, room temperature, 30 seconds immersion 6. Oven-dried, 107 degrees C (225 degrees C) F), 5-10 minutes Table 9: Chemical compositions of Examples 112 to 119 in g / L; addition of cerium nitrate calculated as Ce; CCU = CrysCoat UltraSeal; * Final seal bath Ex. ¾ 'Acid Acid Nitro- NaOH Ce Acid CCU Value P04 Lactic Glycolic guani- Acrylic pH dina E 112 2.2 2.0 0.2 1.0 - - 3.0 E 113 2.2 1.7 0.2 1.8 - - - 3.0 E 114 4.6 - 0.2 2.1 0.4 - - 2.9 E 115 4.6 - 0.2 2.1 0.4 2.0 - 3.1 E 116 4.3 - - 0.2 1.7 - - - 2.8 E 117 4.3 0.2 1.7 - - 2.8 E - - - - - - - 1.6 * 2.85 * 117 * E 118 4.3 0.2 1.7 - - - 2.8 E - - - - - 2.0 * - - 4.3 * 118 * E 119 4.3 - - 0.2 1.7 - - - 2.8 Ex. H3 Acid Acid Nitro- NaOH Ce Acid CCU Valor Lactic Glycolic guani- Acrylic pH dina E - - | - - - 2.0 * 2.0 * - 2.9 * 119 * Table 10: Results of the corrosion test on salt fog (fog) as well as the visual appearance of the panels and the weight of the coating of the coatings Extruded Additions Qualification Appearance Weight of Extra SS for Visual coating plasto panels (g / m2) deformation by 240, mm E 112 Lactic acid 1.0 Color gray- 0.02 uniform toasted E 113 Acid 1.2 Toasted color 0.07 Uniform glycol E 114 Ce Nitrate 2.0 Primarily 0.01 uniform E 115 Ce nitrate 1.2 Gold color 0.14 and Intense acid Acrylic Extruded Additions Qualification Appearance Weight of Extra SS for Visual coating plasto panels (g / m2) deformation by 240 h, mm E 116 - 1.5 Toasted color 0.06 uniform E 117 -; seilo 0.3 Toasted color 0.08 additional uniform finish ·. CCU E 118 - stamp 0.3 color toasted - 0.01 final light gray additional: uniform nitrate of Ce E 119 -; seal 0.3 Gray color to 0.07 final toasting with additional: Ce nitrate patches and acrylic acid The panels showed excellent thin coatings more or less tan and good or even excellent corrosion inhibition. In comparison, the best standard for an iron phosphate coating coated with a final chrome seal achieved a salt fog corrosion test rating of 240 h of 0.2 mm plastformation. Within range and avoiding poisonous chromium compounds, the results are excellent.

Claims (20)

1. CLAIMS 1. Process for coating metal surfaces with a phosphating coating by contacting metal surfaces at a temperature not higher than 45 degrees C and at a pH value below 3.5 with an aqueous acidic alkaline metal phosphating solution or dispersion, which contains: at least one compound of at least one phosphorus-containing acid and / or at least one of its ester-type derivatives and salts in a total content of all types of acids and all their derivatives as asters and salts together less than 20 g / L calculated on the basis of moles as orthophosphate, whereby the content of these compounds / ions containing phosphorus is at least 50 weight percent compared to all these compounds / ions and at least one ion selected from the group consisting of when less an ion of alkali metal and ammonium ion, whereby the phosphating solution or dispersion is free of chromates, moliderates, niobates, tantalates and tunstates, with which the The phosphating compound has a coating composition with a phosphorus content not greater than 8 atomic percent as measured by secondary neutral mass spectroscopy (SNMS) and whereby the phosphating coating has a coating weight in the range of 0.01. at 0.5 g / m2. 2. Process according to claim 1, characterized in that the phosphating solution or dispersion contains at least one accelerator based on chlorate, guanidine, of an organic compound with at least one nitro group such as nitroguanidine and / or nitrobenzensulfonic acid and its derivatives, hydrogen peroxide, hydroxylamine, nitrate and / or other nitrogen-containing accelerators. Method according to claim 1 or 2, characterized in that the phosphating solution or dispersion contains an amount of P04 ions in the range from 0.1 to 10 g / L. Method according to any of the preceding claims, characterized in that the phosphating solution or dispersion contains an amount of S04 ions in the range of 0.1 to 10 g / L. Method according to any of the preceding claims, characterized in that the phosphating solution or dispersion contains a quantity of ions G03 in the range from 0.1 to 10 g / L. Method according to any of the preceding claims, characterized in that an amount of Fe2 + ions is added to the phosphating solution or dispersion, preferably in the range from 0.01 to 1 g / L. 7. Process according to any of the preceding claims, characterized in that the phosphating solution or dispersion contains free fluoride, preferably in the range from 0.01 to 1 g / L, and / or complex fluoride, especially aluminum, boron, silicon, titanium , and / or zirconium, preferably in the range from 0.01 to 1 g / L. Method according to any of the preceding claims, characterized in that the phosphating solution or dispersion contains an amount of nitroguanidine and / or other accelerators based on guanidine in the total range from 0.01 to 5 g / L. 9. Method according to any of the preceding claims, characterized in that the phosphating solution or dispersion contains at least one surfactant, especially when cleaning and phosphating are carried out with the same solution or dispersion, preferably with an amount of all the surfactants together in the range from 0.01 to 10 g / L. 10. Method according to any of the preceding claims, characterized in that the phosphating solution or dispersion contains at least one solvent such as propylene glycol and / or a glycol ether, at least one biocide, at least one stabilizing agent for a surfactant such as a condensed sulphonic salt, at least one stabilizing agent for the accelerator as a clay material or silicate clay type, in fine particles and / or at least one stabilizing agent for the solution itself or dispersion as a biopolymer. 11. Procedure according to any of the preceding claims, characterized in that a phosphating coating is produced which is colorless, of faint coloration, silver, yellowish, golden, yellowish-brown, yellowish-red and / or bluish. Method according to any of the preceding claims, characterized in that a clean metal surface, a clean and / or pickled surface is contacted with the solution or dispersion respectively. 13. Any of the preceding claims, characterized in that the metal surface is contacted with the solution respectively dispersion by dip, spray, steam phosphating, roller coating and / or compression. 14. Any of the preceding claims, characterized in that the coated metal surface is dried after contact with the solution respectively dispersion or after at least one step of susceptible rinsing or air drying, oven drying and / or infrared drying, especially at temperatures in the intervals from 20 to 250 degrees C. 15. Any of the preceding claims, characterized in that at least two coatings are applied one after the other on the metal surface whereby at least one of them is applied with a phosphating dispersion solution respectively and with which at least one other coating can functionally apply with a conversion coating solution such as phosphate rich in zinc and / or manganese. 16. Any of the preceding claims, whereby first an alkali metal phosphating coating is generated on a metal surface and then a coating selected from the group consisting of a conversion coating as a zinc rich phosphate coating and / or Manganese, a stearate coating and an organic polymer coating are applied on top, especially for cold forming. 17. Any of the preceding claims, whereby a metal surface consisting essentially of metallic materials of aluminum, chromium, titanium and / or zinc, as well as at least one alloy containing aluminum, chromium, copper, iron, magnesium, tin , titanium and / or zinc in alloys is covered with a coating of a phosphating solution or dispersion. 18. Any of the preceding claims, whereby the metal surface - after coating with the solution of claim 1 - is contacted with a final seal solution or dispersion, especially with a final seal solution / dispersion containing at least one compound of elemental element of rare earth, at least one component of resin and / or at least one silane. 19. Method for using the coating prepared with a process according to one of claims 1 to 18, for short-term passivation, for the pre-treatment before at least one layer of successive paint, layer of any other organic coating and / or adhesive coating, as a lubricant carrier or as one of the lubricant coatings, for example before cold forming. Method for using the coating prepared with a process according to one of claims 1 to 18, for the inhibition of corrosion and / or lubrication of metal surfaces, especially for use in the aerospace industry, automotive industry, rail transport, construction of vessels, metal forming, metal working (machining, rectification), metal containers and especially can production, coil industry, for sheet metal applications, wire production, appliances, housings, machines and building construction.