EP1579030B1 - Procede de formation d'un revetement anticorrosion mince sur une surface metallique - Google Patents

Procede de formation d'un revetement anticorrosion mince sur une surface metallique Download PDF

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EP1579030B1
EP1579030B1 EP03789349A EP03789349A EP1579030B1 EP 1579030 B1 EP1579030 B1 EP 1579030B1 EP 03789349 A EP03789349 A EP 03789349A EP 03789349 A EP03789349 A EP 03789349A EP 1579030 B1 EP1579030 B1 EP 1579030B1
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coating
phosphating
solution
dispersion
process according
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German (de)
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EP1579030A1 (fr
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Michael Deemer
Chanard Cooper
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Chemetall GmbH
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Chemetall GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates

Definitions

  • This invention relates to a process for coating the surface of a metallic coil, part or 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 relates further on to a phosphating solution to be used in this process for generating excellent corrosion inhibiting coatings on metallic surfaces. In some instances such coating may be used for coldforming of the metallic part.
  • Such solutions are called alkali metal phosphating solutions or, if used on iron-rich surfaces, iron phosphating solutions.
  • the invention is particularly concerned with a coating resp. conversion coating on aluminum, aluminum alloy, iron alloy like steel and stainless steel, magnesium alloy, zinc or zinc alloy as well as with a process, a concentrate and a solution for the formation of a phosphating coating on surfaces of these metallic materials.
  • Such coating solution is especially suitable for the generation of pretreatment coatings on substrate surfaces which will be coated in a second step with at least one organic film, especially at least one film like a thin electrocoating lacquer layer, a paint layer, a silane-rich layer and/or an adhesive layer.
  • the coating may be used for a treatment like a passivation without being covered with a further coating like a paint layer.
  • alkali metal phosphating coatings are described in relatively few cases in comparison to zinc phosphating or manganese phosphating where there is a huge number of publications.
  • Fresh solutions for alkali metal phosphating that had not yet been used show typically only a very low or even practically no content of aluminum, iron and zinc.
  • the fresh aqueous acid alkali metal phosphating solutions contain ions of at least one type of alkali metal ions and/or ammonium ions as well as phosphate ions.
  • the main phases of the alkali metal phosphating coatings are the corresponding phosphates, oxides and/or hydroxides of the metallic constituents of the metallic base material(s).
  • Alkali metal phosphating solutions resp. coatings are called iron phosphating solutions resp. coatings if used on iron alloy surfaces like steel. The same corresponds to aluminum and aluminum alloys where such solutions resp. coatings are described as aluminum phosphating solutions resp. coatings.
  • Often surfaces of very different metallic materials may be coated in the same alkali 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.
  • Such coatings are - in contrast to coatings of the so called zinc-, zinc-manganese- or manganese- phosphating, mostly or totally amorphous or extraordinarily fine-grained.
  • Non-coating phosphatings are described in Werner Rausch: The Phosphating of Metals, ASM International, Finishing Publications Ltd., Teddington, England 1990 (especially pages 94 - 100, 120 - 130 ) in detail and are called the "non-coating phosphating" or in other publications “amorphous phosphating".
  • the term “non-coating phosphating” is misleading, as there will be coatings generated although such coatings will be significantly thinner than created during e.g. zinc phosphating or zinc-manganese phosphating.
  • the very thin alkali metal phosphating coatings are not, poorly or - if coloured or grey - well visible; the coatings may be only visible by colours caused by physical effects, by their kind of grey appearance and/or by their matte appearance.
  • the alkali metal phosphating solution contains always a certain content of at least one alkali metal like sodium, potassium and/or of ammonium.
  • the alkali metal phosphating coatings are typically - in contrary to the well and coursely crystalline coatings of the so-called "coating-forming phosphatings" - more or less amorphous and show under the scanning electron microscope typically no crystalline grain shapes.
  • the alkali metal phosphating coatings are mostly poor, nearly free or totally free of manganese and zinc, if there will not be manganese and/or zinc rich surfaces to be pretreated or treated. They are typically poor, nearly free or totally free of chromium, cobalt, copper, nickel, tin and/or other heavy metals.
  • the phases mainly generated and/or precipitated during iron phosphating, which is performed by contacting iron-rich metallic surfaces with an alkali metal phosphating solution, are iron phosphates, iron oxides and iron hydroxides like e.g. vivianite and/or magnetite.
  • the contents of the ions dissolved from the metallic surface and then carried in the alkali metal phosphating solution, especially of aluminum, chromium, copper, iron, magnesium, tin, titanium, resp. zinc are relatively low as such compounds resp. cations are normally not added to the bath, but are only or nearly only present because of the pickling effect of the aqueous acidic alkali metal phosphating solution to the metallic surfaces of the parts, sheets, strips or wires to be coated.
  • Such contents will precipitate and generate the coating primarily containing phosphates, oxides and/or hydroxides of the metals' content in the solution further on, there may be traces or even low contents of such ions caused by impurities by pickling the bath containers and connecting tubes as well as by dragging in from earlier steps of the process succession.
  • a significant difference of the alkali metal phosphating process in comparison to phosphating processes of the "coating-forming phosphating" is further that the cation(s) necessary for the coating formation during alkali metal phosphating is/are always present in a small percentage, mostly or totally dissolved from the surfaces of the metallic base substrates, whereby during e.g. zinc-, zinc-manganese-, zinc-nickel- or zinc-manganese-nickel-phosphating there will be a relatively high addition of e.g. zinc so that zinc is contained mostly in a content of more than 0.3 g/L resp. often of more than 1 g/L in the phosphating solution.
  • This high zinc content is often caused by addition of zinc compounds of at least 40 %, mostly more than 60 %, often even more than 80 % of the total content to the bath, whereas only the remaining content is mostly generated by the pickling effect to zinciferous surfaces.
  • the coatings generated by zinc-, zinc-manganese-, zinc-nickel- or zinc-manganese-nickel-phosphating show typically the predominantly zinc and/or manganese containing phases hranceaulithe, phosphophyllite, scholzite and/or hopeite in significant crystalline shapes.
  • alkali metal phosphating show significant other properties as such from zinc-rich phosphatings: They have mostly a coating thickness in the range from 0.1 to 0.8 ⁇ m resp. only a coating weight in the range from 0.2 to 1.3 g/m 2 .
  • the much thinner alkali metal phosphatings are mostly transparent or show iridescent colours related to their extremely thin thickness. Then they show the colours of "higher orders" and may be e.g. nearly transparent, yellowish, golden, reddish, a bit violet, greenish or often bluish, partly iridescent.
  • the alkali metal phosphating coatings should have a higher coating weight, especially more than 0.7 and perhaps up to about 1.3 g/m 2 , they may show a more matte-grey appearance.
  • aluminum-rich alkali metal phosphatings may occur silvery or silvery-iridescent.
  • the alkali metal phosphating coatings may be prepared without any later generation of e.g. at least one paint layer and/or another organic paint-like layer. Then this coating process may be called a treatment. If the phosphating coatings should be used for a protection against corrosion for a limited time, then the coatings may be called a passivation. But they can be used under at least one paint layer and/or another organic paint-like layer like a primer, a lacquer, a silane layer, a base coat and/or a topcoat and/or respectively together with an adhesive and may then be called a pretreatment.
  • alkali metal phosphating coatings are produced prior to painting by contacting the aqueous acidic phosphating solution which contains typically at least one mono- and/or orthophosphate and afterwards by electrocoating the phosphated metallic surfaces and/or often by powder painting e.g. of the parts of the metallic construction that are well accessable from outside like radiators and car bodies.
  • alkali metal phosphating processes are carried out with solutions that contain alkali metal and/or ammonium and at least one type of phosphate, mostly orthophosphate, as well as always at least one accelerator, thereby showing a pH value during operating in the range of 4 to 6.
  • aqueous acidic solutions are contacted to the metallic surfaces typically at temperatures in the range from 48 to 72 °C.
  • Their typical coating weights are in the range from 0.3 to 1 g/m 2 .
  • the coatings of today are rich in at least one phosphorus compound, show mostly bluish or light grey coloured coatings and often a coating weight in the range from 0.5 to 1.5 g/m 2 .
  • DE-A1-100 06 338 describes a typical process for iron phosphating where there has been added a small amount of copper ions to solutions of a pH value in the range from 3.5 to 6.5 at a temperature in the range from 30 to 70 °C and especially at a pH value of about 4.8 of about 55 °C.
  • DE-A1-1 942 156 teaches an alkali metal phosphating process by using a high pressure spraying method for contacting the metallic surfaces with solutions of a temperature of 60 °C and of a pH value in the range from 3 to 5.5, especially of a pH value of 4.
  • DE-A1-1 914 052 concerns an alkali metal phosphating process by using a rollcoating application 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 °C with an extraordinarily unconventional pH value in the range of 1 to 3.5 contacting a coil less than 30 seconds and squeegeeing.
  • EP-B1-0 968 320 protects a process for an alkali metal phosphating for radiators by using a surfactant rich solution of a pH value in the range from 4 to 6 at a temperature in the range from 35 to 60 °C and especially of at least 50 °C.
  • FR-A-1.155.705 refers to an alkali metal phosphating process by using an ammonium silicon hexafluoride and nitroguanidine containing solution of a pH value in the range from 3 to 6 at a temperature in the range from 50 to 76 °C.
  • GB-A-1 388 435 reports an alkali metal phosphating process by using a free fluoride and chlorate containing solution of a pH value in the range from 3 to 6 at a temperature in the range from 50 to 80 °C, especially used with a pH value in the range from 3.65 to 4.4.
  • US-A-2,665,231 discloses an alkali metal phosphating process by using a fluoride containing solution of a pH value in the range from 3 to 5.8 at a temperature in the range from 60 to 82 °C, especially used with a pH value in the range from 4.25 to 5.5.
  • EP 0 411 606 A2 describes methods of surface-treating 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 with phosphate.
  • the phosphate addition of 0.01 to 0.5 g/L shall be used as pH-adjusting agent.
  • EP 0 121 155 A1 teaches processes for the preparation of surfaces of iron or steel for painting by applying alkali metal phosphating solutions containing dihydrogen phosphate and nitrobenzolsulfonate that show a pH in the range from 4.2 to 6.
  • DE 1942 156 A1 discloses processes for the treatment of metal surfaces, especially of iron and steel surfaces, by applying alkali metal phosphate resp. ammonium phosphate and benzoate containing solutions at a pH in the range from 3 to 5.5 at high pressures and at temperatures of about 60 °C.
  • 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:
  • a phosphating coating on a metallic surface prepared by contacting metallic surfaces with an aqueous acidic alkali metal phosphating solution or dispersion having a coating thickness of not more than 0.15 ⁇ m and having a good corrosion protection for the protected metallic material.
  • the element content of the coatings was analysed by X-ray Photoelectron Spectroscopy (XPS), which may be used successfully as routine measurement method for controlling the different coatings, but which is an insufficient precise measurement method for such coatings to identify the element content dependent from the depth of the coating. Only the upper 8 nm from the surface into the depth could be analysed and therefore there is an influence of surface impurities.
  • XPS X-ray Photoelectron Spectroscopy
  • the measurement of the content of phosphorus and other elements in the coating was performed by X-ray Photoelectron Spectroscopy with an instrument 5700LSci of Physical Electronics, with an X-ray source of monochromatic aluminum, a power source of 350 Watts, an analysis region of 2 x 0.8 mm, an exit angle of 65 °, a charge correction for C-(C,H) in C 1s spectra at 284.8 eV and a charge neutralization by electron flood gun.
  • the element content of the coatings was analysed by Secondary Neutral Mass Spectroscopy (SNMS) with an INA3 electron gas - SNMS apparatus of Leybold, which is a precise measuring method to identify the element content dependent from the depth of the coating of such thin alkali metal phosphating coatings.
  • the samples were sputtered with Ar ions of 1040 eV energy and at a current density of about 1.2 mA/cm 2 .
  • An area of 5 mm diameter was sputtered and analysed.
  • the atoms of the upper surface layer evaporated and the next atom layers of below were analysed, until the total coating was removed in the sputtered area during the analysis.
  • FIG. 1 for the cleaned, but not coated 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 conventional iron phosphating coating of today indicates via the Fe content the thickness of the iron phosphating coating.
  • the curves of the content of oxygen and phosphorus are - in the logarithmic graph - more or less proportional ("parallel").
  • composition of the conventional iron phosphating coatings is significantly different from the composition of the iron phosphating coatings according to the invention.
  • the surface roughness of all samples was measured with a white light interferometer NT3300 of Wyko, each coated panel on three areas.
  • the average data of R a per panel varied between 0.89 and 1.02 ⁇ m
  • the average data of R z per panel varied between 1.11 and 1.22 ⁇ m
  • the average data of R t per panel varied between 6.17 and 7.25 ⁇ m.
  • the samples 5) and 6) had been coated in the same manner and under nearly the same conditions, but they showed surface roughness data nearly twice as high as the samples 3) and 4):
  • the average data of R a per panel varied at about 1.79 ⁇ m
  • the average data of R z per panel varied at about 11.7 ⁇ m
  • the average data of R t per panel varied in the range from 11.4 to 12.1 ⁇ m.
  • Sample 3 ) has to be compared with sample 5) for the difference in surface roughness and element content; similarly, sample 4) has to be compared with sample 6).
  • the rougher surfaces enable a higher amount of neutral parts measured than from more even surfaces, the more even surfaces shall be used for the analytical investigation and evaluation.
  • the P content is less than 8 atomic% in a depth of 0.05 ⁇ m below the (original) surface of the alkali metal phosphating coating as analysed by Secondary Neutral Mass Spectroscopy (SNMS) or is less than 6 or even less than 4 atomic% in a depth of 0.1 ⁇ m below the surface of the alkali metal phosphating coating or is less than 3 or less than 2 atomic% in a depth of 0.1 ⁇ m below the surface of the alkali metal phosphating coating.
  • the phosphating coating according to the invention has a thickness of not more or less than 0.15 ⁇ m, more preferred of not more than 0.12 ⁇ m, much more preferred of not more than 0.10 ⁇ m.
  • the process according to the invention may preferably be characterized in that the temperature of the phosphating solution or dispersion may be during the contacting of the metallic surfaces in the range from 10 to 42 °C or less than 40 °C and more preferred at least 15 °C or up to 38 or up to 35 °C.
  • the pH value may preferably be selected in the range starting from 1.8 resp. reaching up to 3.3, more preferred of at least 2 or up to 3.1, especially of at least 2.5 or up to 2.9.
  • the coating weight may preferably be selected in the range from 0.03 to 0.4 g/m 2 , more preferred of at least 0.05 or up to 0.36 g/m 2 , most preferred of at least 0.1 or up to 0.32 g/m 2 .
  • 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, may be taken, but hydrochloric acid and chlorides are not recommended as they may cause significant crevice corrosion.
  • hydrochloric acid and chlorides are not recommended as they may cause significant crevice corrosion.
  • 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 of at least one of ethers.
  • At least one acid is used like orthophosphoric acid, diphosphoric acid, monophosphoric acid, at least one of phosphonic acids, e.g. especially at least one with at least one aliphatic and/or aromatic group each, especially at least one of diphosphonic acids, phosphonous acid, phosphorous acid, molybdatophosphoric acid, tungstophosphoric acid and/or at least one of its derivatives like ester(s) and/or salt(s), especially at least one of monoester(s), of diester(s) and/or of triester(s) of a phosphorus containing acid like orthophosphoric acid, more preferred mixed with at least one phosphorus containing acid.
  • phosphonic acids e.g. especially at least one with at least one aliphatic and/or aromatic group each, especially at least one of diphosphonic acids, phosphonous acid, phosphorous acid, molybdatophosphoric acid, tungstophosphoric acid and/or at least one of its derivatives like ester(s) and/
  • At least one sulfur containing acid and/or at least one of its derivatives like ester(s) and/or salt(s) is used like sulfuric acid, sulfamatic acid, at least one of sulfonic acids like nitrosulfonic acid resp. at least one of their derivatives like ester(s) and/or salt(s).
  • At least one nitrogen containing acid and/or at least one of its derivatives like ester(s) and/or salt(s) is used like nitric acid, at least one acid having at least one nitro and/or at least one amino group resp. at least one of its derivatives like ester(s) and/or salt(s).
  • At least one organic acid and/or at least one of its derivatives like ester(s) and/or salt(s) is used like at least one of aromatic organic acids, hydroxocarboxylic acids, oxo acids, peracids and/or oxocarboxylic acids resp. at least one of its derivatives like ester(s) and/or salt(s) especially like acetic acid, benzoic acid, citric acid, formic acid, gluconic acid, hydroxy acetic acid, lactic acid, malic acid, oxalic acid, succinic acid, tartaric acid and/or its water-soluble and/or water-dispersible derivative(s) like ester(s) and/or salt(s) may be used.
  • Any acid, derivative of it, acid mixture and/or mixture with at least one of its derivatives like ester(s) and/or salt(s) may be used, especially at least one or any mixture that is able to show a pH value e.g. of about 2.4, of about 2.9, of about 3.4, of about 3.9 and/or of about 4.4 and that is able to generate - at least together with the cations present - a thin coating, but a high amount of hydrochloric acid and of chloride is not favourable to be used because of its very strong corroding effect.
  • these acids and derivatives especially phosphoric acid and dissolved phosphate esters/salts are especially favourable.
  • reducing and/or oxidizing accelerators may be added, but must not be applied. Such accelerator(s) may be favourable to enhance the process, the coating quality and/or to influence the oxidation situation.
  • an amount of Fe 2+ ions may 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, specifically preferred in the range from 0,03 to 0.5 g/L, most preferred of at least 0.05 or up to 0.3 g/L.
  • the addition may be a dissolved iron phosphate. This addition helps in some cases, especially for nonferrous metal surfaces like such of hot-dip-galvanized (HDG) or electrogalvanized materials (EG), to generate a better corrosion inhibiting performance.
  • HDG hot-dip-galvanized
  • EG electrogalvanized materials
  • the phosphating solution or dispersion does not contain more than about 0.5, 1 or 1.5 g/L of Fe 2+ ions, depending on the actual phosphating conditions; the iron content may then be lowered by addition of an oxidizing agent - which may be in some cases an accelerator - and/or by using a cation exchange material, e.g. an adequate resin.
  • an oxidizing agent - which may be in some cases an accelerator - and/or by using a cation exchange material, e.g. an adequate resin.
  • the phosphating solution or dispersion contains free fluoride, preferably in the range from 0.01 to 1 g/L, and/or complex fluoride, especially of aluminum, boron, silicon, titanium and/or zirconium, preferably each in the range from 0.01 to 1 g/L.
  • the content of each of free fluoride resp. of each of the complex fluoride(s) lies in the range from 0.02 to 0.8 g/L, specifically preferred in the range from 0.03 to 0.5 g/L, most preferred of at least 0.05 or up to 0.3 g/L.
  • the content of free fluoride and/or of the at least one complex fluoride enhances the pickling effect, especially on galvanized metallic surfaces as well as on aluminum-rich surfaces as oxide contents may be easier removed from the metallic surface; further on, it improves the performance and the quality of the corrosion inhibition and paint adhesion of the thereof formed coating for all metallic material bases.
  • an amount of PO 4 ions may be added to the phosphating solution or dispersion preferably in the range from 0.1 to 18 g/L, more preferred in the range from 0.5 to 15 g/L, especially preferred of at least 1 and/or up to 12 g/L, most preferred of at least 2 g/L and/or up to 9 g/L of PO 4 ions.
  • the phosphate content may provide the necessary acidity for the primary pickling effect. It also may help in some cases to remove the excess heavy metal content like an iron content out of the solution, that may predominantly or totally be a result of the pickling.
  • the orthophosphoric acid may be added as acid, as monoacid and/or as poly acid salt of an alkali metal and/or of an ammonium group or in a small amount as an iron phosphate.
  • orthophosphoric acid its ester(s) and/or its salt(s)
  • a phosphonic acid and/or other phosphorus containing acid and/or at least one of their salts and/or esters may be added to the solution or dispersion, especially at least one water-soluble ester of phosphoric acid.
  • the phosphating solution or dispersion may contain an amount of SO 4 ions in the range from 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 from 1 to 12 g/L, much more preferred of at least 2 g/L and/or up to 9 g/L of SO 4 ions.
  • the sulfate content may provide the necessary acidity for the primary pickling effect.
  • the sulfuric acid may be added as acid or as sulfate of an alkali metal and/or of an ammonium group or in a small amount as an iron sulfate.
  • a mixture of at least one phosphorus containing acid and/or its salt(s) and/or its ester(s) with at least one sulphur containing acid and/or its salt(s) and/or its ester(s) may be added to the solution or dispersion; preferably, the content of such phosphorus containing compounds should be at least 50 % by weight of all such acids, salts and esters.
  • the phosphating solution or dispersion may contain an amount of NO 3 ions in the range from 0.1 to 18 or to 10 g/L, preferably of at least 0.5 and/or up to 15 g/L, more preferred of at least 1 and/or up to 12 g/L, much more preferred of at least 2 g/L and/or up to 9 g/L of NO 3 ions.
  • the nitrate content may provide the necessary acidity for the primary pickling effect.
  • the nitric acid may be added as acid, as nitrate of at least one alkali metal and/or ammonium or in a small amount as an iron nitrate.
  • a mixture of at least one phosphorus containing acid and/or its salt(s) and/or its ester(s) 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 such phosphorus containing compounds should be at least 50 % by weight of all such acids, salts and esters.
  • the phosphating solution or dispersion may contain an amount of groups, ions and compounds together of organic acid(s) and/or of its derivative(s) in the range from 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 from 1 to 12 g/L, much more preferred of at least 2 g/L and/or up to 9 g/L of such groups, ions and compounds.
  • the phosphating solution or dispersion contains an amount of nitroguanidine and/or other accelerators on the base of guanidine like acetatoguanidine, aminoguanidine, carbonatoguanidine, melanilinoguanidine, nitratoguanidine and ureidoguanidine in the total range from 0.01 to 5 g/L, preferably in the range from 0.015 to 3 g/L, more preferred in the range from 0.01 to 1.2 g/L, much more preferred of at least 0.02 g/L and/or up to 0.6 g/L of the guanidine compound(s).
  • Nitroguanidine had shown in several instances to give the best results of all accelerators tested. In comparison to the use of aminoguanidine, the addition of nitroguanidine was a small amount more favourable, especially for the corrosion inhibition.
  • the phosphating solution or dispersion may contain at least one surfactant, especially when cleaning and phosphating is carried out with the same solution or dispersion, then preferably with an amount of all surfactants together in the range from 0.01 to 10 g/L. If using at least one surfactant in the phosphating solution, it is preferred to take care not to generate foam. In some cases, it may be favourable to add a defoamer.
  • This total surfactant content may preferably vary in the range from 0.1 to 7 g/L, more preferred in the range from 0.3 to 5 g/L, much more preferred of at least 0.5 g/L and/or up to 3 g/L of surfactant(s).
  • the cleaning and phosphating may be carried out in the same bath container with the same solution or dispersion, so that in the first time of contacting the metallic components with the phosphating solution or dispersion, the cleaning and pickling effect of the solution or dispersion may prevail, whereas in the further time of the contacting, the coating process with the phosphating coating formation may predominate.
  • nearly all types of surfactants resp. surfactant mixtures are suitable to be added to the phosphating solution or dispersion, especially surfactants resp. surfactant mixtures with low-foaming or non-foaming properties and with a cloud-point in the range from 25 to 40 °C, whereby the surfactant mixtures may be free of further constituents than surfactants.
  • the phosphating solution is preferably free or nearly free of other heavy metals than those being pickled out of the metallic surface, perhaps with the exception of titanium and/or zirconium, especially in the presence of complex fluoride(s). It is preferably free of chromates, molybdates and tungstates.
  • the phosphating solution or dispersion may contain at least one solvent like a propylene glycol and/or a glycol ether; further on it may contain at least one biocide, at least one stabilizing agent for a surfactant like a condensed sulfonic salt, at least one stabilizing agent for the accelerator like a fine-particular silicate-, clay- or clay-like material and/or at least one stabilizing agent for the solution or dispersion itself like a biopolymer.
  • a solvent may be preferable for enhancing the cleaning effect of the metallic surface, especially in combination with at least one surfactant. It is favourable to use a guanidine compound in the form of a suspension containing a stabilizing agent, especially the nitroguanidine.
  • a phosphating coating is generated showing mostly a colourless, faintly coloured, silvery, golden, yellowish, yellowish-brownish, yellowish-reddish and/or bluish colour. If the coating according to the invention is bluish, there seems to be often a phosphorus content of the coating being not as low as typical for such coatings and there are to be found often corrosion inhibition results less than of excellence. This coating may in several cases be less intensively coloured or may show a less brighter and/or even a matter appearance than conventional coatings. This coating may typically have a coating thickness in the range of up to 1 ⁇ m, mostly only up to 0.6 ⁇ m, often only up to 0.3 ⁇ m.
  • a clean, a cleaned and/or a pickled metallic surface is contacted with the solution resp. dispersion.
  • the metallic surface may be contacted with the solution resp. dispersion by immersing, spraying, steam-phosphating, roll-coating and/or squeegeeing. All application varieties except of steam-phosphating are often used for coil coating.
  • the coated metallic surface is dried after contacting it with the solution resp. dispersion or later on after at least one thereon succeeding rinsing step, preferably by air-drying, oven-drying and/or infrared-drying, especially at temperatures in the range from 20 to 250 °C.
  • At least two coatings one after the other on the metallic surface whereby at least one of them is applied with an alkali metal phosphating solution resp. dispersion and whereby at least one other coating may optionally be applied with a conversion coating solution like a zinc- and/or manganese-rich phosphating.
  • an alkali metal phosphating coating is generated on a metallic surface and then a coating selected from the group consisting of a conversion coating like a zinc- and/or manganese-rich phosphating coating, a stearate coating and an organic polymer coating is applied thereon, especially for coldforming.
  • a metallic surface consisting essentially of metallic materials of aluminum, chromium, titanium and/or zinc as well as at least one alloy containing aluminum, chromium, copper like brass or bronze, iron, magnesium, tin, titanium and/or zinc alloys is covered with a coating of a phosphating solution or dispersion.
  • the coating prepared with a process according to the invention may be used for the short-term passivation, for the pretreatment prior to at least one succeeding paint layer, layer of any other organic coating and/or adhesive coating, as a lubricant carrier or as one of the lubricating coatings prior to coldforming.
  • the lubricant resp. lubricant carrier may be favourably be used for cans, for machining, for wire drawing and/or for lubricating the moving chains.
  • the process may be successfully varied by coating the thin phosphating coating according to the invention with a final seal solution resp. dispersion.
  • the results of the salt spray testings show that a second, third and/or fourth coating on the metallic surface generated by contacting the panels phosphated in such way with the final seal solution resp. dispersion enhance the corrosion resistance significantly, although such final seal coatings are very thin.
  • such final seal coatings may be generated with a final seal solution/ dispersion containing at least one rare earth element compound like a cerium compound, at least one resin component like acrylic acid and/or at least one silane.
  • the coating prepared with a process according to the invention may be used for the corrosion inhibition and/or the lubrication of metallic surfaces, especially for use in aerospace industry, automobile industry, rail transportation, shipbuilding, metal forming, metal working like machining and/or grinding, in metallic container and especially can production, coil industry, for metal sheet applications, wire production, appliances, housings, machines and construction of buildings.
  • the baths with these solutions were prepared at 3 % by volume for both formulations, this means for the solution A 3.58 % by weight resp. for the solution B 3.30 % by weight of the concentrate.
  • 0.2 g/L nitroguanidine stabilized with a small content of clay-like material was further added.
  • the pH value of both phosphating baths was adjusted to 4.5 resp. to 2.8 with an addition of sodium hydroxide.
  • Panels of cold rolled steel (CRS) were cleaned with Okemclean ® at 3 % by volume and 54.4 °C for 30 seconds by spraying. The panels were then rinsed and afterwards treated in the phosphating bath A or B for 60 seconds by spraying 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 salt spray (fog) test strictly according to ASTM B 117 for 336 hours for the evaluation of the corrosion inhibiting properties strictly according to a ASTM D 1654 rating, with 10 to be the best and 0 the worst.
  • CRS cold rolled steel
  • Table 2 Composition of the coatings of the different groups Contents in g/L Examples/ Comparison Examples PO 4 3- Na + ClO 3 - NBS Nitro-guanidine Amino-guanidine 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, 27-30, 35-38, 51-53, 63, 66, 69, 3.48 0.74
  • the coatings became more uniform and changed from grey-brown to blue.
  • Lower temperature treatments and lower coating weights were correlated with a better salt spray performance.
  • the nitroguanidine-accelerated system B showed a better and more homogeneous appearance of the coatings and a better corrosion inhibition than the chlorate-SNBS-accelerated system A.
  • the coating for the panels was homogeneous and went from blue to golden as the temperature increased.
  • the CRS panels went from grey-brown to blue as temperature increased.
  • the HDG and EG panels showed an etched appearance in all cases, but no colour.
  • the aluminum panels were shiny with no apparently visible coating.
  • the CRS panels went from blue to golden with increasing temperature, the HDG and EG panels had an iridescent appearance and the aluminum panels had a transparent light tan colour.
  • the cold rolled steel panels were treated with aqueous acidic phosphating solutions C containing only a very tiny amount much less of 1 g/L of phosphoric acid only to adapt the pH value of the ready mixed solution to 2.5 resp. 4.5, 0.2 g/L nitroguanidine and 0.2 g/L aminoguanidine bicarbonate. If in all the examples aminoguanidine was added, it was added as bicarbonate, although not always indicated.
  • the panels were cleaned with Gardoclean ® S 5206 and rinsed before the nitro- and the aminoguanidine were added.
  • the panels were contacted with the phosphating solution for the test with a pH value of 2.5 at ambient temperature and for the test with a pH value of 4.5 at 49 °C.
  • 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 % by volume of the concentrate containing 1.3 % by weight of phosphoric acid, 11.7 % by weight of monosodium phosphate and the rest being deionized water.
  • the CRS 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 °C.
  • 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 °C and mostly at a pH value 4.5 for 60 second spraying.
  • the last comparison example 79 was the standard chlorate-SNBS-accelerated alkali metal phosphating as outlined in Group 1, but only this was operated at a pH value of 4.5 and at a temperature of 48.9 °C for 80 seconds of spraying.
  • the salt spray rating was evaluated according to ASTM D 1654 after 500 hours salt spray (fog) test according to ASTM B 117.
  • Table 6 Results of the salt spray test and the coating weight dependent from the accelerator amount of the coating solutions of differently accelerated alkali metal phosphating systems and of the pH value at a temperature of 26.7 °C; * bath without accelerator content Ex./ Comp. Accelerator Accelerator (g/L) Bath * Concentration Vol.
  • E 72, E 75 and E 78 show significantly better corrosion results than most of the other samples.
  • the coatings were even, of a golden colour at a low pH value and of a blue colour at a high pH value for coatings generated with amino- resp. nitroguanidine.
  • the bath solution contained fluoride to treat cold rolled steel, hot dipped galvanized, electrogalvanized and aluminum.
  • the base solution B of Group 1 was used by with an additional content of free fluoride, whereby the content of all components of this bath were varied at a temperature of 38 °C.
  • the panels were painted with a Ferro TGIC polyester powder paint of 38 to 51 ⁇ m thickness and were put into a salt spray (SS) test chamber according to ASTM B 117 for 250 hours, whereby the test results were measured in mm creep from the scribe. Further on, adhesion was tested according to ASTMD 3359, whereby 5B means that no flaking did occur in the cross-cut area which is the best possible test result, whereas e.g. 2B means that there is a certain amount of flaking in the cross-cut area.
  • SS salt spray
  • Table 8 Results of the salt spray (fog) test on three CRS panels each dependent from the chemical composition of the coating solutions, the pH value, the contacting time and the temperature; * bath without accelerator content Examples /Comp. Bath * Concentration (g/L) Accelerator (g/L) pH Value contacting time (s) temperature (° C) SS rating for 240 h mm creep 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 106 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 4.6 3.9 4.5 52 60 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 with the results of the comparison examples.
  • the comparison examples vary with respect to the corrosion inhibition quality depending if there is a further seal or not and especially if this final seal is a chromium containing layer.
  • CE 109 showing such additional chromium containing layer covering the phosphate layer should show the best corrosion inhibition properties. Nevertheless, it is astonishing that the best panels according to the invention were able to reach the excellent corrosion inhibition properties of CE 109 which is the best industry standard material on the base of iron phosphate known in the art which in this case is even covered by a strongly further corrosion inhibiting final rinse layer.
  • the coatings were even in all cases.
  • the contact time, bath concentration and accelerator concentration did not have any apparent effect on the appearance.
  • the results of the design of experiments showed clearly a broad region of unusually stable working conditions for an alkali metal phosphating solution below a pH value of 3.5 and astonishingly very constant coating properties.
  • the phosphating results on aluminum alloy 6061 were best at a F - content of less than 200 ppm and at a Fe 2+ content less than 120 ppm.
  • HDG hot dip galvanized steel
  • electrogalvanized steel (EG) they were best at a very low PO 4 content and at a F - content of less than 200 ppm.
  • the appearance of the coatings was at least as good as for comparable good alkali metal phosphating coatings used in the market. As best accelerator during all these studies, nitroguanidine was identified.
  • the alkali metal phosphating process with the slightly modified working conditions for the solutions according to the invention are well suited for industrial application of coils, parts and wires.
  • the use of the phosphating solution at a significantly lower temperature than today usual for the contacting of metallic surfaces helps to reduce heating costs considerably.
  • the herein proposed phosphating process is easier than the processes used today as it is quite sufficient to control only total and free acid content, but no other parameters of the bath within short time limits, as the bath behaviour is very stable.
  • this process is not only superior because less heating is needed and therefor is cheaper in comparison to actually used processes as there is a significant lower consumption of all chemical compounds of the solution than usual.
  • the panels showed excellent thin coatings of more or less tan colour and good or even excellent corrosion inhibition.
  • the best standard for an iron phosphate coating coated with a chrome final seal reached a salt spray test rating for 240 h of 0.2 mm creep.
  • the results are excellent.

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Claims (18)

  1. Procédé permettant de revêtir des surfaces métalliques avec un revêtement de phosphatation, dans lequel on met des surfaces métalliques en contact avec une solution ou dispersion aqueuse acide de phosphatation à métal alcalin, à une température d'au plus 45 °C et à un pH inférieur à 3,5, laquelle solution ou dispersion contient:
    au moins une composé d'au moins un acide phosphoré et/ou d'au moins un dérivé de tels acides, choisi parmi leurs esters et leurs sels, la concentration totale de tous ces acides et de tous leurs dérivés choisis parmi leurs esters et leurs sels étant inférieure à 20 g/L, valeur calculée en orthophosphate sur base molaire, et la teneur en ces composés et ions phosphorés valant au moins 50 % en poids, en comparaison de tous les composés et ions,
    au moins un ion choisi dans l'ensemble formé par au moins un ion de métal alcalin et l'ion ammonium,
    et au moins un accélérateur à base de guanidine, en une concentration totale située dans l'intervalle allant de 0,01 à 5 g/L,
    dans lequel le revêtement de phosphatation présente une composition de revêtement où la teneur en phosphore, mesurée par SNMS (spectrométrie de masse de particules neutres secondaires), ne vaut pas plus de 8 % en atomes,
    et dans lequel le revêtement de phosphatation présente un poids de revêtement qui vaut de 0,01 à 0,5 g/m2.
  2. Procédé conforme à la revendication 1, dans lequel la solution
    ou dispersion de phosphatation contient des ions phosphate PO4 en une concentration de 0,1 à 10 g/L.
  3. Procédé conforme à la revendication 1 ou 2, dans lequel la solution ou dispersion de phosphatation contient des ions sulfate SO4 en une concentration de 0,1 à 10 g/L.
  4. Procédé conforme à l'une des revendications précédentes, dans lequel la solution ou dispersion de phosphatation contient des ions nitrate NO3 en une concentration de 0,1 à 10 g/L.
  5. Procédé conforme à l'une des revendications précédentes, dans lequel on ajoute à la solution ou dispersion de phosphatation des ions de fer Fe2+, de préférence en une concentration de 0,01 à 1 g/L.
  6. Procédé conforme à l'une des revendications précédentes, dans lequel la solution ou dispersion de phosphatation contient des ions fluorure libres, de préférence en une concentration de 0,01 à 1 g/L, et/ou des ions fluorure complexes, spécialement de ceux formés avec de l'aluminium, du bore, du silicium, du titane et/ou du zirconium, de préférence en une concentration de 0,01 à 1 g/L.
  7. Procédé conforme à l'une des revendications précédentes, dans lequel la solution ou dispersion de phosphatation contient au moins un tensioactif, en particulier si l'on effectue des opérations de nettoyage et de phosphatation avec la même solution ou dispersion, de préférence en une concentration globale de tous les tensioactifs de 0,01 à 10 g/L.
  8. Procédé conforme à l'une des revendications précédentes, dans lequel la solution ou dispersion de phosphatation contient au moins un solvant, comme du propylèneglycol et/ou un éther de glycol, au moins un biocide, au moins un agent de stabilisation pour tensioactif, comme un sel sulfonate condensé, au moins un agent de stabilisation pour l'accélérateur, comme un matériau silicate, argile ou de type argile en fines particules, et/ou au moins un agent de stabilisation pour la solution ou dispersion elle-même, comme un biopolymère.
  9. Procédé conforme à l'une des revendications précédentes, dans lequel on produit un revêtement de phosphatation incolore ou de couleur pâle, argentée, jaunâtre, dorée, jaunâtre-brunâtre, jaunâtre-rougeâtre et/ou bleuâtre.
  10. Procédé conforme à l'une des revendications précédentes, dans lequel c'est une surface métallique propre, nettoyée et/ou décapée que l'on met en contact avec la solution ou dispersion.
  11. Procédé conforme à l'une des revendications précédentes, dans lequel on met la surface métallique en contact avec la solution ou dispersion par immersion, pulvérisation, phosphatation à la vapeur, enduction au rouleau et/ou enduction à la raclette.
  12. Procédé conforme à l'une des revendications précédentes, dans lequel, après avoir mis la surface métallique en contact avec la solution ou dispersion ou après au moins une étape ultérieure de rinçage, on fait sécher la surface métallique revêtue, par séchage à l'air, séchage au four et/ou séchage aux infrarouges, en particulier à des températures situées dans l'intervalle allant de 20 à 250 °C.
  13. Procédé conforme à l'une des revendications précédentes, dans lequel on applique sur la surface métallique au moins deux revêtements, l'un après l'autre, dont au moins l'un est appliqué au moyen d'une solution ou dispersion de phosphatation, et au moins un autre revêtement peut, en option, être appliqué au moyen d'une solution de revêtement de conversion, comme une solution de phosphatation enrichie en zinc et/ou manganèse.
  14. Procédé conforme à l'une des revendications précédentes, dans lequel on applique d'abord, sur une surface métallique, un revêtement de phosphatation contenant un métal alcalin, puis on applique par-dessus, en particulier en vue d'une opération de formage à froid, un revêtement choisi dans l'ensemble formé par un revêtement de conversion, comme un revêtement de phosphate enrichi en zinc et/ou manganèse, un revêtement de stéarate et un revêtement de polymère organique.
  15. Procédé conforme à l'une des revendications précédentes, dans lequel on recouvre d'une couche de solution ou dispersion de phosphatation une surface métallique essentiellement constituée d'un métal ou des métaux aluminium, chrome, titane et/ou zinc, ou d'au moins un alliage contenant de l'aluminium, du chrome, du cuivre, du fer, du magnésium, de l'étain, du titane et/ou du zinc.
  16. Procédé conforme à l'une des revendications précédentes, dans lequel on met la surface métallique, après l'avoir revêtue avec une solution du type indiqué dans la revendication 1, en contact avec une solution ou dispersion finale de colmatage, en particulier une solution ou dispersion finale de colmatage contenant au moins un composé d'élément des terres rares, au moins un composant de type résine et/ou au moins un silane.
  17. Procédé d'utilisation d'un revêtement, préparé selon un procédé conforme à l'une des revendications 1 à 16, pour passivation à court terme, ou pour un traitement préalable à l'application ultérieure d'au moins une couche de peinture ou couche d'un autre revêtement organique et/ou revêtement adhésif, comme support de lubrifiant ou comme l'un des revêtements lubrifiants, par exemple avant une opération de formage à froid.
  18. Procédé d'utilisation d'un revêtement, préparé selon un procédé conforme à l'une des revendications 1 à 16, pour inhibition de la corrosion et/ou lubrification de surfaces métalliques, en particulier celles destinées à servir dans l'industrie aérospatiale, l'industrie automobile, le transport ferroviaire, la construction navale, le formage des métaux, le travail sur métaux (usinage, meulage), la production de récipients métalliques et en particulier de boîtes ou bidons, l'industrie des bobines de tôle enroulée, les applications de tôles métalliques, la production de fils métalliques, les appareils, boîtiers et machines, et la construction de bâtiments.
EP03789349A 2002-12-24 2003-12-18 Procede de formation d'un revetement anticorrosion mince sur une surface metallique Expired - Lifetime EP1579030B1 (fr)

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US10/328,924 US20040118483A1 (en) 2002-12-24 2002-12-24 Process and solution for providing a thin corrosion inhibiting coating on a metallic surface
PCT/EP2003/014577 WO2004059034A1 (fr) 2002-12-24 2003-12-18 Procede de formation d'un revetement anticorrosion mince sur une surface metallique

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CN109563628A (zh) * 2016-08-12 2019-04-02 Prc-迪索托国际公司 密封组合物
PL3392375T3 (pl) * 2017-04-21 2020-05-18 Henkel Ag & Co. Kgaa Sposób fosforanowania cynkowego komponentów metalowych w seriach, tworzącego warstwy, bez powstawania szlamu
DE102017207591A1 (de) * 2017-05-05 2018-11-08 Federal-Mogul Nürnberg GmbH Stahlkolben mit einer Phosphat-Schicht
CN107488849A (zh) * 2017-08-24 2017-12-19 南通市烨达汽车零部件有限公司 一种汽车冲压件表面处理液
CN108085684B (zh) * 2017-11-23 2019-10-08 中国科学院近代物理研究所 用于去除铜表面铌镀层的化学退镀液和退镀方法
CN107966401A (zh) * 2017-12-26 2018-04-27 华测检测认证集团股份有限公司 材料耐腐蚀性能测试装置
CN107966402A (zh) * 2017-12-26 2018-04-27 华测检测认证集团股份有限公司 金属涂层耐磨耐高温性能测试装置
CN108007806A (zh) * 2017-12-26 2018-05-08 华测检测认证集团股份有限公司 金属涂层耐磨耐高温及成份分析设备
CN112011791A (zh) * 2020-08-28 2020-12-01 立邦涂料（重庆）化工有限公司 一种基于磷酸无需表调工序及无需亚钠类促进剂的化成剂及制备方法
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ZA200505064B (en) 2008-09-25
EP1579030A1 (fr) 2005-09-28
ES2344345T3 (es) 2010-08-25
AU2003293945A1 (en) 2004-07-22
ATE464404T1 (de) 2010-04-15
RU2358035C2 (ru) 2009-06-10
US20040118483A1 (en) 2004-06-24
CN1754009A (zh) 2006-03-29
MXPA05006897A (es) 2005-08-18
AU2003293945B2 (en) 2009-01-22
DE60332161D1 (de) 2010-05-27
CN1754009B (zh) 2011-10-19
RU2005123323A (ru) 2006-02-10
WO2004059034A1 (fr) 2004-07-15
CA2511361A1 (fr) 2004-07-15
BR0316881A (pt) 2005-10-25

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