US20040118483A1 - Process and solution for providing a thin corrosion inhibiting coating on a metallic surface - Google Patents

Process and solution for providing a thin corrosion inhibiting coating on a metallic surface Download PDF

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US20040118483A1
US20040118483A1 US10/328,924 US32892402A US2004118483A1 US 20040118483 A1 US20040118483 A1 US 20040118483A1 US 32892402 A US32892402 A US 32892402A US 2004118483 A1 US2004118483 A1 US 2004118483A1
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coating
phosphating
solution
process according
dispersion
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US10/328,924
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Michael Deemer
Chanard Cooper
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Chemetall GmbH
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Chemetall GmbH
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Priority to US10/328,924 priority Critical patent/US20040118483A1/en
Assigned to CHEMETALL GMBH reassignment CHEMETALL GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COOPER, CHANARD, DEEMER, MICHAEL
Priority to CN200380109959.9A priority patent/CN1754009B/zh
Priority to PCT/EP2003/014577 priority patent/WO2004059034A1/fr
Priority to AU2003293945A priority patent/AU2003293945B2/en
Priority to ES03789349T priority patent/ES2344345T3/es
Priority to ZA200505064A priority patent/ZA200505064B/xx
Priority to AT03789349T priority patent/ATE464404T1/de
Priority to RU2005123323/02A priority patent/RU2358035C2/ru
Priority to CA002511361A priority patent/CA2511361A1/fr
Priority to DE60332161T priority patent/DE60332161D1/de
Priority to MXPA05006897A priority patent/MXPA05006897A/es
Priority to EP03789349A priority patent/EP1579030B1/fr
Priority to BR0316881-6A priority patent/BR0316881A/pt
Publication of US20040118483A1 publication Critical patent/US20040118483A1/en
Abandoned legal-status Critical Current

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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.
  • 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.
  • 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 opposite to coatings of the so called zinc-, zinc-manganese- or manganese-phosphating, mostly or totally amorphous or extraordinarily fine-grained.
  • Alkali metal 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, badly 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 going 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 hureaulithe, 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 3 to 10 mg/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.
  • 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.
  • 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 ion selected from the group consisting of at least one alkali metal ion and ammonium ion,
  • 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
  • the phosphating coating has a coating weight in the range from 0.01 to 0.5 g/m 2 .
  • 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 ⁇ 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.
  • FIG. 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”).
  • FIGS. 3 and 4 for the samples 3) and 4) with the coating according to the invention do not show clear content levels.
  • FIG. 5 represents the results of sample 5) that is comparable with sample 3) but shows higher surface roughness data and therefore higher signal output.
  • FIG. 6 represents the results of sample 6) that is comparable with sample 4) but shows higher surface roughness data and therefore higher signal output, too.
  • FIG. 7 represents the curves of the P content of the samples 1) to 4) in comparison, but now—as linear graph—showing clearly different phosphorus contents dependent from the depth analysed in the coating.
  • composition of the conventional iron phosphating coatings is significantly different from the composition of the iron phosphating coatings according to the invention.
  • 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 derivates, 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 derivates 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 derivates like ester(s)
  • At least one sulfur containing acid and/or at least one of its derivates 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 derivates like ester(s) and/or salt(s).
  • At least one nitrogen containing acid and/or at least one of its derivates 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 derivates like ester(s) and/or salt(s).
  • At least one organic acid and/or at least one of its derivates 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 derivates 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 derivate(s) like ester(s) and/or salt(s) may be used.
  • Any acid, derivate of it, acid mixture and/or mixture with at least one of its derivates 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 too strong corroding effect.
  • these acids and derivates 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.
  • the phosphating solution or dispersion contains in many, but not all cases at least one accelerator like such on the base of chlorate, guanidine, of an organic compound with at least one nitro group like nitroguanidine and/or nitrobenzenesulfonic acid and its derivatives, of hydrogen peroxide, hydroxylamine, nitrate and/or of other nitrogen containing accelerators; more preferred are nitroguanidine, nitrobenzenesulfonic acid and/or its derivate(s) like salt(s).
  • at least one accelerator like such on the base of chlorate, guanidine, of an organic compound with at least one nitro group like nitroguanidine and/or nitrobenzenesulfonic acid and its derivatives, of hydrogen peroxide, hydroxylamine, nitrate and/or of other nitrogen containing accelerators; more preferred are nitroguanidine, nitrobenzenesulfonic acid and/or its derivate(s) like salt(s).
  • All accelerators together show a content in the range from 0.005 to 10 g/L, preferably in the range from 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, most preferred of at least 0.05 or up to 0.7 g/L.
  • 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
  • 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 derivate(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 may contain 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 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 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 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 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
  • 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 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.
  • On hot dip galvanized steel (HDG) they were best at a F ⁇ content of less than 360 ppm and at a Fe 2+ content of more than 80 ppm, although the results were—as usual with HDG in such comparisons—worse than for the other metallic materials tested.

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US10/328,924 2002-12-24 2002-12-24 Process and solution for providing a thin corrosion inhibiting coating on a metallic surface Abandoned US20040118483A1 (en)

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Application Number Priority Date Filing Date Title
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
BR0316881-6A BR0316881A (pt) 2002-12-24 2003-12-18 Processo para provimento de um revestimento fino inibidor de corrosão sobre uma superfìcie metálica
AT03789349T ATE464404T1 (de) 2002-12-24 2003-12-18 Verfahren zum versehen einer metallischen oberfläche mit einer dünnen korrosionsinhibierenden beschichtung
CA002511361A CA2511361A1 (fr) 2002-12-24 2003-12-18 Procede de formation d'un revetement anticorrosion mince sur une surface metallique
AU2003293945A AU2003293945B2 (en) 2002-12-24 2003-12-18 Process for providing a thin corrosion inhibiting coating on a metallic surface
ES03789349T ES2344345T3 (es) 2002-12-24 2003-12-18 Procedimiento para proporcionar un revestimiento delgado, inhibidor de la corrosion, sobre una superficie metalica.
ZA200505064A ZA200505064B (en) 2002-12-24 2003-12-18 Process for providing a thin corrosion inhibiting coating on a metallic surface
CN200380109959.9A CN1754009B (zh) 2002-12-24 2003-12-18 在金属表面上提供薄腐蚀抑制涂层的方法
RU2005123323/02A RU2358035C2 (ru) 2002-12-24 2003-12-18 Способ получения тонкого ингибирующего коррозию покрытия на металлической поверхности
PCT/EP2003/014577 WO2004059034A1 (fr) 2002-12-24 2003-12-18 Procede de formation d'un revetement anticorrosion mince sur une surface metallique
DE60332161T DE60332161D1 (de) 2002-12-24 2003-12-18 He mit einer dünnen korrosionsinhibierenden beschichtung
MXPA05006897A MXPA05006897A (es) 2002-12-24 2003-12-18 Proceso para proporcionar un revestimiento inhibidor de corrosion delgado en una superficie metalica.
EP03789349A EP1579030B1 (fr) 2002-12-24 2003-12-18 Procede de formation d'un revetement anticorrosion mince sur une surface metallique

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BR (1) BR0316881A (fr)
CA (1) CA2511361A1 (fr)
DE (1) DE60332161D1 (fr)
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US10513784B2 (en) 2014-04-30 2019-12-24 Rio Verwaltungs Ag Treatment device and treatment method for pickling and phosphating metal parts

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AU2003293945A1 (en) 2004-07-22
MXPA05006897A (es) 2005-08-18
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RU2005123323A (ru) 2006-02-10
ZA200505064B (en) 2008-09-25
WO2004059034A1 (fr) 2004-07-15
AU2003293945B2 (en) 2009-01-22
BR0316881A (pt) 2005-10-25
ATE464404T1 (de) 2010-04-15
DE60332161D1 (de) 2010-05-27
CA2511361A1 (fr) 2004-07-15
EP1579030B1 (fr) 2010-04-14
CN1754009B (zh) 2011-10-19
CN1754009A (zh) 2006-03-29
ES2344345T3 (es) 2010-08-25

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