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WO2001007679A1 - Traitement de surface de metaux - Google Patents

Traitement de surface de metaux Download PDF

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Publication number
WO2001007679A1
WO2001007679A1 PCT/GB2000/002874 GB0002874W WO0107679A1 WO 2001007679 A1 WO2001007679 A1 WO 2001007679A1 GB 0002874 W GB0002874 W GB 0002874W WO 0107679 A1 WO0107679 A1 WO 0107679A1
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WO
WIPO (PCT)
Prior art keywords
concentrate
composition
complex fluoride
silane
composite
Prior art date
Application number
PCT/GB2000/002874
Other languages
English (en)
Inventor
Kevin Brown
Erwin Barry Bines
Original Assignee
Chemetall Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall Plc filed Critical Chemetall Plc
Priority to AU62984/00A priority Critical patent/AU6298400A/en
Publication of WO2001007679A1 publication Critical patent/WO2001007679A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to compositions for conversion coating metal surfaces, concentrates from which such compositions may be made, processes in which the compositions are applied and the products of such processes.
  • the compositions contain a silane, a complex fluoride and phosphate ions.
  • the metal is usually aluminium or zinc and is subsequently coated.
  • the compositions are preferably dry-in-place and are chrome free. It is well known to provide conversion coatings on metal surfaces to improve corrosion resistance and/or to provide a good basis for application of polymeric surface coatings such as of paint, plastics or rubber. Chromate conversion coating compositions are well known to provide excellent corrosion resistance. Chromium is, however, potentially toxic. While the use of dry-in-place compositions, which are not rinsed from the surface after application, provide some environmental protection, it is desirable to avoid the use of chromium containing compositions all together to minimise pollution.
  • Phosphate conversion coatings are also well known, especially for zinc based surfaces. Most phosphating processes require that the surface is rinsed after the conversion coating step and before drying. The rinse water tends to contain potential pollutants.
  • Silanes especially partially hydrolysed trialkoxysilanes, have been used as bonding agents between various substrates including between metal surfaces and polymer coatings. More recently, silanes have been applied to metal surfaces to improve corrosion resistance.
  • a metal substrate is contacted with an aqueous solution containing partially hydrolysed amino silane and a fluorine- containing inorganic compound.
  • the fluorine compound is, for instance, a fluorozirconate.
  • the metal substrate is generally aluminium or an alloy thereof, and may be subsequently coated with a paint, generally a powder paint. The treatment improves corrosion resistance.
  • compositions may be applied in a no-rinse process, that is a process in which there is no rinse step between application of the composition and drying.
  • a two step metal treatment process is described in which, in a first step, a metal is conversion coated by phosphating or chromating, and is subsequently treated with a composition containing an organo silane and a complex fluoride.
  • metal treatment compositions contain chromium in both 6 and 3 valence states, phosphate, a silane coupling agent and, optionally, a complex fluoride such as a fluorozirconate or fluorotitanate. The compositions are dried in place without being rinsed, and the substrate subsequently painted.
  • metal surfaces are treated with a hydrous oxide sol, for instance zirconia sol to improve corrosion resistance or adhesive properties of the surface.
  • the sol may include a silane as an adhesion promoter.
  • the compositions may also contain a complex fluoride or phosphoric acid. There is no suggestion to include both complex fluoride and phosphoric acid.
  • a metal treatment composition comprises a diglycidyl derivative of bisphenol A, a silane coupling agent and a complex fluoride.
  • the composition is applied to a metal surface and dried without intermediate rinsing.
  • the conversion coated metal is subsequently painted.
  • a chrome free metal treatment composition contains a silane or, preferably a mixture of silanes, and phosphoric acid. Following conversion coating, the metal surface is rinsed before being dried. The conversion coated metal is subsequently protected with a paint.
  • a new aqueous metal treatment composition according to the present invention comprises: a) 1 to 50 g/l of a silane derivative having the general formula I XR 2 Si (OR 1 ) 3 I in which each R 1 is selected from hydrogen, C,. 6 -alkyl and C ⁇ -alkanoyl, R 2 is a C,_ 10 -alkanediyl, optionally substituted by amino, hydroxyl or thiol groups and/or interrupted by an amine, an ether or a thioether linkage, and
  • X is a reactive group selected from NH 2 , glycidoxy, (meth)acryloyloxy, vinyloxy, thiol and ureido groups; b) 0.1 to 5 mM of a complex fluoride ion; and c) 0.02 to 5 g/l of a phosphate ion, in which the molar ratio of complex fluoride to phosphate ion is in the range 2:5 to 2:1 , the composition having a pH in the range 2 to 11 , and being substantially free of Cr III and Cr VI.
  • the silane is at least partially hydrolysed.
  • the silane will have the general formula I in which at least some of the groups R 1 are hydrogen. Preferably at least about 50% of the R 1 groups are hydrogen.
  • the remaining R 1 groups are preferably the same, most preferably being selected from C ⁇ -alkyl groups, most preferably methyl or ethyl.
  • the level should generally be enough to confer water solubility.
  • the silane compounds preferably have the group R 2 representing an alkane diyl group which is not interrupted by any of the specified groups, most preferably a (CH 2 ) n group, where n is an integer in the range 2 to 6.
  • Most preferred groups X are NH 2 and glycidoxy groups.
  • the silane should be present in the solution at a concentration in the range 1 to 500 mM, preferably 5 to 200 mM, more preferably 10 to 150 mM. In particular, the silane should preferably be present in a concentration of 1 to 50 g/l, more preferably 2 to 30 g/l, most preferably 5 to 30 g/l.
  • the complex fluoride is preferably a fluoride of a group IV element having an oxidation state of IV such as silicon, titanium, zirconium or hafnium, although it may comprise borofluoride. Most preferably the complex fluoride is of a metal selected from hafnium, zirconium and titanium, and is most preferably a fluorozirconate.
  • the composition For some uses, especially for treatment of aluminium, it is desirable for the composition to contain simple fluoride ions, that is F " . It is generally desirable to include a compound which has a stabilising effect on the complex fluoride, for instance nitric acid.
  • the molar ratio of complex fluoride to phosphate is preferably in the range 3:5 to 1 :1.
  • the complex fluoride is present in the metal treatment composition in a concentration in the range 0.1 to 5mM, preferably 0.2 to 2 mM.
  • Phosphate is generally present in a concentration in the range 0.1 to 1.0 g/l (based on phosphoric acid H 3 PO 4 ), preferably in the range 0.2 to 2 mM, more preferably 0.3 to 1 mM. Any simple fluoride is present in a concentration in the range 0.002 to
  • Nitric acid is generally present in a concentration in the range 0.01 to 2 g/l, most preferably in the range 0.05 to 0.5 g/l.
  • the metal treatment composition of the invention is substantially free of metal cations. If it is necessary to include counterions, for instance where pH adjustment by addition of base is necessary, these are generally provided as ammonium ions.
  • the pH is in the range 2 to 11 , preferably 2.5 to 10. Depending on the nature of the silane, it may be necessary to add a base to achieve the desired pH. Where the silane is an amino silane (X is NH 2 and/or R 2 is interrupted by an amino linkage), pH adjustment by addition of acid or base may be unnecessary. Where the silane is an amino silane the composition usually has a basic pH. For other silanes the pH is preferably acidic.
  • the composition may contain other ingredients such as thickening agents or hydrous oxides.
  • the composition is free of hydrous oxides such as titania, zirconia and silica, since these may destabilise the composition and/or may not benefit the performance.
  • the silane may include a mixture of silanes of the general formula I. Additionally there may be admixed with such silanes, crosslinking silanes having two groups Si(OR 1 ) 3 , joined by an alkanediyl group optionally interrupted by ether, thioether or amine linkages. Examples of such, crosslinking, compounds are 1 ,2-bis(trimethoxy)ethane, 1 ,2- bis(triethoxysilyl)ethane.
  • the composition should be substantially free of chromium. Thus there should be no intentional addition of any chromium compound to the compositions. Chromium may be present as an impurity, however, in components from which the solutions are made up, for instance in an amount less than 10 ppm.
  • the metal treatments composition may be made up by dissolution of individual ingredients directly into water at the desired end use concentration.
  • materials it is more convenient for the materials to be supplied in premixed concentrate form ready for dilution with water to form the metal treatment composition.
  • Such concentrates are generally water-based, preferably being substantially organic solvent-free.
  • a concentrate which is sufficiently storage stable may be made up ready for dilution with water alone to form the metal treatment compositions.
  • a composite concentrate comprising a) a silane of the general formula I
  • each R 1 is selected from hydrogen, C ⁇ -alkyl and C ⁇ -alkanoyl, and R 2 and X are as defined for the novel composition; b) a complex fluoride, and c) a phosphate ion, in which the molar ratio of complex fluoride to phosphate is in the range 2:5 to 2:1 , and which is substantially free of Cr III and Cr VI.
  • the silane in the composite concentrate is generally in the partially or fully hydrolysed form, that is each group R 3 is other than hydrogen.
  • the level of hydrolysis silane is limited since the hydrolysed silanes are generally unstable, tending to react together to form oligomeric or polymeric siloxane compounds. Such compositions have reduced activity and may even gel.
  • a two- part concentrate pack comprising a silane concentrate which comprises the silane of the general formula II
  • each R 3 is selected from C 1-6 -alkyl and C 2 . 6 -alkanoyl, and R 2 and X are as in the compound of the general formula I , and a complex fluoride concentrate, which contains the complex fluoride and phosphate.
  • the silane is generally present at a concentration of at least 10 g/l, preferably in the range 20 to 100 g/l.
  • Complex fluoride is generally present in a concentration of at least 2.5 mM. In a composition concentrate the composition is preferably in the range 5 to 50 mM. In a complex fluoride concentrate of a two pack concentrate, the concentration is preferably at least 25 mM, more preferably in the range 50-200 mM.
  • the phosphate is generally present in the or each concentrate in a concentration of at least 0.2 g/l. In a composition concentrate the concentration is preferably in the range 0.5 to 5 g/l.
  • phosphate is preferably present in the complex fluoride concentrate at a concentration in the range 3 to 30 g/l.
  • nitric acid is included in the composition for treatment of the metal, it may be added after dilution of the concentrate(s), or, preferably, is included in a composite or two part concentrate.
  • the nitric acid is generally present in a concentrate in an amount of at least 0.2 g/l, in a composite concentrate, preferably in a range 0.4 to 2 g/l, and in a two part concentrate in the complex fluoride concentrate in a range 2 to 10 g/l.
  • silane may be provided effectively undiluted, for instance at a concentration of at least 90 or 95%.
  • a composite concentrate it is preferably included in an amount of at least 10 g/l, more preferably in the range 25 to 100 g/l.
  • Phosphate ions are generally incorporated into the compositions, or concentrates as the case may be, from phosphoric acid, H 3 PO 4 .
  • Complex fluoride ions are generally incorporated from the conjugate acids, such as borofluoric, fluorozirconic, fluorotitanic or fluorohafnic acid.
  • the concentrate or concentrates are useful for initially making up the metal treatment composition.
  • the make up is preferably by dilution of the concentrate(s) with water, with optional pH adjustment where necessary.
  • the concentrates may also be of use for replenishing a bath or reservoir containing the composition which is reused and depleted of chemicals.
  • the present invention also comprises a novel metal treatment process in which a metal substrate is contacted in a conversion coating step with the novel metal treatment composition, to form a conversion coating on the substrate surface.
  • the composition may be applied to the surface of the substrate by dipping, spraying, roll coating or brushing or by a combination of such means. Generally the excess solution having contacted the surface is collected and reused. For instance it may be collected directly into the vessel or reservoir from which the composition is applied.
  • the present invention is of particular value in so called dry-in-place processes, that is in which there is no rinsing step between the conversion coating step and the drying step.
  • a drying step is carried out at, for instance, a temperature of at least 60°C, most preferably at least 75°C, up to around 135°C, most preferably in the range 80 to 120°C.
  • the time of drying depends upon the temperature and the shape of the substrate. The period is preferably at least 5 seconds, for instance at least 10 seconds, up to 30 minutes, most preferably in the range 30 seconds to 5 minutes. It may be desirable to use reduced pressure during drying but this is usually found to be unnecessary.
  • the present invention may be used on substantially any metals desired to be treated to improve corrosion resistance and/or to provide improved adhesion of subsequent top coating compositions.
  • the invention is of particular value in treating aluminium, zinc, aluminium alloys and/or zinc alloys.
  • silanes of the general formula I in which X is glycidoxy are very effective for Zn and Al surfaces.
  • Silanes in which X is NH 2 are very effective with aluminium.
  • metal ions from the surface may dissolve into the composition.
  • Monitoring the level of dissolved metal may be desirable in some circumstances. It may be advantageous, to use the levels of dissolved metals to control the concentrations of some or all of the essential components of the composition. For instance, it is believed that the presence of the simple fluoride in the composition may help improve the bath stability where aluminium ions dissolve into the composition during processing. Monitoring the level of aluminium may thus be useful for controlling the level of fluoride ion in the composition.
  • the metal substrate is subjected to cleaning, optionally including an acid or alkaline etch step, and, generally, a rinse step, usually without subsequent drying.
  • the conversion coated surface is generally provided with a protective coating of a polymer, for instance a plastic or rubber coating or, more preferably, a paint.
  • the paint may be applied from a liquid, aqueous or solvent-based, composition, or from a powder. Paints may be any of those conventionally used for coating metals such as based upon epoxy, polyurethane, polyester or polyacrylic polymer compounds. Usually there is no rinse step between the drying of the conversion coating step and any polymer coating step.
  • the present invention has been found to provide conversion coatings on metals which are corrosion resistant and provide a good basis for polymer coatings of many types.
  • the use of a dry-in-place process minimises environmental problems whilst still providing a very good basis for subsequent coatings.
  • the supply of components for forming the metal treatment compositions as concentrates is highly convenient.
  • the following example(s) illustrate the invention:
  • Example 1 Application to hot-dipped galvanised steel Hot-dip galvanised (HDG) panels were spray cleaned in Pyroclean
  • the GPTMS was also used at 1.0, 2.5, 10, 25, 35 and 50 g/l. As a control the silane was omitted. After spin coating the panels were oven dried at 100° C for about 2 mins.
  • GPTMS was hydrolysed as in 1 and fluorozirconic acid (0.058 g/l), phosphoric acid (0.038 g/l) and nitric acid (0.028 g/l) were added.
  • GPTMS (5/gl) was hydrolysed as in 1 and the following compounds were added H 2 TiF 6 (0.23 g/l), H 3 PO 3 (0.18 g/l) and HNO 3 (0.14 g/i).
  • the panels were painted with a solvent based polyester paint using a bar coater to give a dry film thickness (DFT) of 20-23 micrometer and cured at 241 °C pmt (peak metal temperature) for 35 sees.
  • DFT dry film thickness
  • the panels were cross scored and subjected to ASTM B117 salt spray for 528 hours. After salt spray exposure the panels were examined and the amount of paint removal from the cross score was measured.
  • Table 1 shows that the GPTMS containing solutions give good results on HDG. The results of APS on HDG were not good.
  • Aluminium panels (grade 5154 alloy) were cleaned in Pyroclean 71 (a non etch silicate free alkali cleaner), rinsed, etched by immersing in a solution containing 10 g/l H 2 SO 4 and 50 ppm fluoride for 4 secondss at 60°C, rinsed demineralised, rinsed and then the following solutions were applied by spin coating.
  • Pyroclean 71 a non etch silicate free alkali cleaner
  • APS (5 g/l) was added to demineralised water and stirred for 40 minutes to allow it to hydrolyse then the following were added H 2 ZrF 6 (0.29 g/l), H 3 PO 4 (0.19 g/l), HNO 3 (0.14 g/l) HF (0.014 g/l), Aerosil (silicondioxide thickener) 380 (13 g/l) (compelx fluoride:phosphate 3:4 mole). o 10.2-4 As 10.1 but the APS was used at 10, 15 and 20 g/l.
  • the panels were dried at 100°C for about 2 minutes.
  • the panels were then painted with a solvent based polyester paint to a DFT of 20 ⁇ m stoved at 241 °C peak metal temperature and subjected to 5 acetic acid salt spray for 1000 hours.
  • the results are shown in Table 2.
  • Example 3 APS or GPTMS on aluminium Aluminium panels (5154 alloy) were cleaned as in example 2 and treated with the following solutions:
  • Example 5 Two pack concentrate
  • a complex fluoride concentrate has the following composition:- H 2 ZrF 6 1.18%
  • the silane is supplied as such, the concentration being above 95%.
  • the complex fluoride concentrate is diluted 25 times with water and silane added in a suitable amount to give the desired concentration.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

La présente invention concerne une composition aqueuse pour traitement des métaux. Elle comporte de 1 à 50 g, notamment de 1 à 20 g/l, d'un composé de trialcoxy ou trialcanoyloxy silyle portant un substituant réactif tel qu'un groupe alkyle avec un substituant amine, époxy, ou uréide ou thiol éthyléniquement insaturés. Elle comporte également 0,1 à 5 mM, de préférence de 0,2 à 2 mM d'un fluorure de complexe, généralement un ion de complexe d'un élément du groupe IV tel qu'un fluorosilicate, fluorozirconate, fluorotitanate ou fluorohafnate. La composition comporte en outre de 0,02 à 5 g/l, de préférence de 0,1 à 1 g/l d'un ion phosphate, le rapport du fluorure de complexe sur le phosphate se situant dans la plage des 2:5 à 2:1, pour un pH se situant dans la plage de 2 à 11. Cette composition est sensiblement exempte de chrome. Cette composition sert à la réalisation sur une surface métallique d'un revêtement de conversion, généralement selon un procédé à séchage sur place (sans rinçage). Après le séchage, le métal à revêtement de conversion se prête particulièrement à l'application d'une couche de polymère, de préférence de peinture. Cette composition améliore la résistance à la corrosion et/ou l'adhésion des couches de finition de polymère, particulièrement dans le cas des substrats métalliques présentant des surfaces d'aluminium et/ou de zinc, ou en alliages à base de l'un ou de l'autre. L'invention concerne également des concentrés unaires ou binaires à diluer permettant de réaliser les compositions aqueuses de l'invention.
PCT/GB2000/002874 1999-07-26 2000-07-26 Traitement de surface de metaux WO2001007679A1 (fr)

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AU62984/00A AU6298400A (en) 1999-07-26 2000-07-26 Metal surface treatment

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EP99305904.7 1999-07-26
EP99305904 1999-07-26

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Cited By (13)

* Cited by examiner, † Cited by third party
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EP1243668A1 (fr) * 2001-03-21 2002-09-25 Kawasaki Steel Corporation Tôle d'acier étamée
US7833332B2 (en) * 2007-11-02 2010-11-16 Dubois Chemicals, Inc. Coating solution for metal surfaces
US20110008645A1 (en) * 2008-03-11 2011-01-13 Mark Andre Schneider Process for coating metallic surfaces with a passivating agent, the passivating agent and its use
US8609755B2 (en) 2005-04-07 2013-12-17 Momentive Perfomance Materials Inc. Storage stable composition of partial and/or complete condensate of hydrolyzable organofunctional silane
WO2015018873A1 (fr) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Prétraitement de métaux avec des compositions aqueuses acides comprenant des silanes
EP2191042B1 (fr) 2007-08-27 2015-07-22 Momentive Performance Materials Inc. Inhibition de la corrosion d'un métal
US9169466B2 (en) 2003-03-28 2015-10-27 Mesoblast, Inc. Perivascular mesenchymal precursor cell induced blood vessel formation
US10106689B2 (en) 2013-08-06 2018-10-23 Henkel Ag & Co. Kgaa Metal pretreatment compositions comprising silanes and organophosporus acids
CN110520291A (zh) * 2017-05-08 2019-11-29 日本轻金属株式会社 涂装的铝材及其制造方法
WO2019245863A1 (fr) * 2018-06-18 2019-12-26 Chemetall U.S., Inc. Systèmes de combinaison organosilane/organophosphate à fonction amine en tant qu'agents ep/inhibiteurs de corrosion dans des compositions pour le traitement de surfaces métalliques
CN111218172A (zh) * 2020-01-23 2020-06-02 广东省建筑科学研究院集团股份有限公司 一种从源头消除重金属铬和VOCs污染的复合涂层及制备方法
EP3636801A4 (fr) * 2017-05-08 2021-03-03 Nippon Light Metal Company, Ltd. Matériau revêtu d'aluminium pour assemblage et matériau composite aluminium-résine
CN114717543A (zh) * 2022-03-12 2022-07-08 浙江五源科技股份有限公司 增加钢铁无磷转化处理后的涂层耐盐雾性能的组合物制备方法

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EP2191042B1 (fr) 2007-08-27 2015-07-22 Momentive Performance Materials Inc. Inhibition de la corrosion d'un métal
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WO2015018873A1 (fr) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Prétraitement de métaux avec des compositions aqueuses acides comprenant des silanes
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CN110520291A (zh) * 2017-05-08 2019-11-29 日本轻金属株式会社 涂装的铝材及其制造方法
US12060643B2 (en) 2017-05-08 2024-08-13 Nippon Light Metal Company, Ltd. Coated aluminum material and method for producing same
EP3623150A4 (fr) * 2017-05-08 2021-03-03 Nippon Light Metal Company, Ltd. Matériau revêtu d'aluminium et son procédé de production
EP3636801A4 (fr) * 2017-05-08 2021-03-03 Nippon Light Metal Company, Ltd. Matériau revêtu d'aluminium pour assemblage et matériau composite aluminium-résine
WO2019245863A1 (fr) * 2018-06-18 2019-12-26 Chemetall U.S., Inc. Systèmes de combinaison organosilane/organophosphate à fonction amine en tant qu'agents ep/inhibiteurs de corrosion dans des compositions pour le traitement de surfaces métalliques
US11396637B2 (en) 2018-06-18 2022-07-26 Chemetall U.S., Inc. Amine-functionalized organosilane/organophosphate combination systems as EP agents / corrosion inhibitors in compositions for treating metal surfaces
CN111218172B (zh) * 2020-01-23 2022-07-19 广东省建筑科学研究院集团股份有限公司 一种从源头消除重金属铬和VOCs污染的复合涂层及制备方法
CN111218172A (zh) * 2020-01-23 2020-06-02 广东省建筑科学研究院集团股份有限公司 一种从源头消除重金属铬和VOCs污染的复合涂层及制备方法
CN114717543B (zh) * 2022-03-12 2023-06-09 浙江五源科技股份有限公司 增加钢铁无磷转化处理后的涂层耐盐雾性能的组合物制备方法
CN114717543A (zh) * 2022-03-12 2022-07-08 浙江五源科技股份有限公司 增加钢铁无磷转化处理后的涂层耐盐雾性能的组合物制备方法

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