WO2004046420A1 - Couche de conversion exempte de chrome free pour aluminium - Google Patents

Couche de conversion exempte de chrome free pour aluminium Download PDF

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Publication number
WO2004046420A1
WO2004046420A1 PCT/US2003/035660 US0335660W WO2004046420A1 WO 2004046420 A1 WO2004046420 A1 WO 2004046420A1 US 0335660 W US0335660 W US 0335660W WO 2004046420 A1 WO2004046420 A1 WO 2004046420A1
Authority
WO
WIPO (PCT)
Prior art keywords
recited
acid
composition
aluminum
aminosilane
Prior art date
Application number
PCT/US2003/035660
Other languages
English (en)
Inventor
Edward A. Rodzewich
Philip D. Deck
Original Assignee
Ge Betz, Inc.
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 Ge Betz, Inc. filed Critical Ge Betz, Inc.
Priority to AU2003287590A priority Critical patent/AU2003287590A1/en
Publication of WO2004046420A1 publication Critical patent/WO2004046420A1/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
    • C23C22/73—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
    • C23C22/34—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
    • 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 invention relates generally to non-chromate coatings for aluminum and aluminum based alloys that improve the adhesion of siccative coatings to the aluminum surfaces and provides corrosion protection, while maintaining the bright appearance of the metal.
  • Non-chromate alternatives have been provided to enhance the adherence of paints, lacquers, inks, varnishes, resins, etc. (hereinafter "siccative" coatings) and to provide corrosion inhibition.
  • sicative coatings many of these treatments are not suitable in the aluminum wheel market as they result in a dulling or discoloration of the substrate metal and are unacceptable, especially when the wheels are coated with the now popular clear coat paints.
  • the inventors have endeavored to discover a chromate free conversion coating composition and method that provides corrosion protection and siccative coating adherence comparable to conventional chromate based systems.
  • an acidic aqueous treatment solution comprising (a) a water soluble fluoacid of a Group IVB metal or mixtures of such acids (b) fluoboric acid (c) boric acid and (d) gluconic acid or salt thereof is provided.
  • the metal surface is contacted with this treatment solution and, optionally, with a topping agent (e) that is selected to provide enlianced adhesion of siccative coatings (i) and/or enhanced corrosion resistance (ii).
  • an aminosilane may be used as component (e)(i) and an organophosphonate may serve as the component (e)(ii).
  • an organophosphonate may serve as the component (e)(ii).
  • the aluminum or aluminum alloy part is first cleaned in a mild alkaline cleaning solution, such as those conventional in the art, to remove surface contaminants and to assure that the metal is receptive to the coating. Care must be taken in cleaning the part so as not to dull or discolor the metal.
  • a mild alkaline cleaning solution such as those conventional in the art
  • the metal part is rinsed with water and then treated with a chemical deoxidizer to remove excess aluminum oxide and to remove alloying elements from the metal surface.
  • This deoxidizer can be a strong acid solution typically comprising sulfuric or nitric acid combined with an oxidizing species such as ferric ion.
  • the parts are again rinsed before treatment with the non- chromate conversion coating treatment of the invention.
  • the parts are typically rinsed to prevent puddling and the like.
  • the quality of the water used for the conversion coating treatment and subsequent rinse must be good to avoid undesirable accumulation of soluble salts on the metal surface.
  • siccative coating such as paint, lacquer, varnish, ink, etc.
  • a concentrated aqueous solution of: (1) water soluble fluoacid of a Group IVB metal or metals or mixtures of such fluoacids; (2) fluoboric acid; (3) boric acid; (4) gluconic acid or salt thereof and (5) pH regulators such as nitric acid and ammonium hydroxide is prepared.
  • This concentrate is then diluted to make an aqueous solution comprising about 1-10 %v/v of the concentrate.
  • the desired adhesion promoter preferably an aminosilane, an amount of about 50 to 500 ppm.
  • a corrosion inhibitor enhancer such as an organophosphonate may be added. Alternatively, these latter components may be added directly to the concentrate.
  • the thus formed conversion coating solution can be applied to the requisite aluminum surface by any suitable method.
  • the surface can be immersed in the solution, or the coating solution can be applied via spray techniques. Additionally, flow-coating techniques can be employed where convenient.
  • the treatment temperature ranges from about 70°F to about 170°F.
  • the temperature of the coating solution can be adjusted to above about 100°F, and the contact time for the treatment solution to the metal s ⁇ bstrate is normally between about 15 seconds to 2 minutes.
  • the thus coated substrate is rinsed with water and then dried, typically in an oven having forced circulation of hot air. After drying, the desired siccative coating is applied.
  • fluoacid of a Group IVB metal fluozirconic acid H 2 ZrF 6 , and fluotitanic acid H 2 TiF 6 are preferred.
  • a combination of H 2 ZrF 6 and H TiF 6 is preferred.
  • These acids may be present in a molar amount of 1:3 to 3:1 of H 2 ZrFo:H 2 TiF 6 .
  • a 1 :1 molar ratio is preferred.
  • Fluoboric acid and boric acid are also added, as necessary to minimize etching of the aluminum. To maintain the bright appearance of aluminum articles such as wheels, it is required that aluminum etch be minimized.
  • the pH of the diluted, working solutions will be on the order of about 0.5-5 with a range of about 1-3 even more preferred.
  • aminosilane compounds that may be used, it is desirable to use gamma- aminopropyltriethoxysilane (D-APS) due to its efficacy and commercial availability.
  • D-APS gamma- aminopropyltriethoxysilane
  • other alkoxylated aminoalkylsilanes such as aminopropyltrimethoxy silane, etc., can also be mentioned.
  • U.S. Patent 6,203,854 can be reviewed for a more complete listing of the alkoxylated aminoalkylsilanes.
  • organophosphonates that may be employed, amino tri (methylene phosphonic acid) (ATMP) is presently preferred due to commercial availability, but other organophosphonates such as l-hydroxy-l,l-diphosphonic acid; ethylene diamine tetra (methylene phosphonic acid); hexamethylene diamine terra (methylene phosphoic acid) and diethylenetriamine penta (methylene phosphonic acid) can be mentioned.
  • ATMP amino tri (methylene phosphonic acid)
  • organophosphonates such as l-hydroxy-l,l-diphosphonic acid; ethylene diamine tetra (methylene phosphonic acid); hexamethylene diamine terra (methylene phosphoic acid) and diethylenetriamine penta (methylene phosphonic acid) can be mentioned.
  • compositions in accordance with the invention include the following:
  • the concentrates are diluted in deionized, distilled, reverse osmosis, or other suitably high purity water to about 0.5-10%v/v solutions, preferably about 1- 2%v/v of the concentrate (concentrate/total solution).
  • the aminosilane may be added in small amounts.
  • DAPS is added in an amount of about 5 to 500 ppm into the diluted working solution.
  • the organophosponate may be added in amounts similar to those of the addition levels of the aminosilane.
  • the bath, or working solution, that is used to contact the aluminum part thus includes the following active components given in terms of ppm.
  • preclean hot water rinse, 30 s
  • Treated sections are allowed to cool overnight and then powder painted.
  • the wheel sections are baked in accordance with the paint manufacturers' recommendations.
  • Typical powder curing conditions include a metal temperature of 320°F for 17 min (typically 30-40 min in oven set at 360°F). Dry film thickness is 2.5 mils on average.
  • Painted wheel sections are allowed to. "age” for at least three days prior to any performance testing.
  • the procedure is similar to GM 9682P.
  • Wheel sections are scribed using a carbide tip scribe as prescribed in ASTM D 1654.
  • the scribe is made with the aid of a straight edge and using a moderate, even pressure over the length of the ⁇ 10 cm scribe.
  • the scribe is made perpendicular to the machining marks. Wheel sections are placed into the CAASS chamber within 30 minutes of being scribed.
  • the sections Upon removal from the CAASS chamber, the sections are rinsed by immersion in deionized water.
  • the wheel section is immersed straight into the water, rotated a quarter turn right and then a half turn left and pulled from the water; the total dip time taking ⁇ 3 s.
  • the wheel sections are then placed in a humidity chamber.
  • a Blue M Model # FRS 09C maintained at 140°F and 80% RH is used.
  • the sections are placed in the chamber with an orientation similar to that of the CAASS exposure.
  • Wheel sections are exposed in a chamber for at least two weeks, more typically three weeks. Filiform is rated by recording the maximum filament length (to the nearest 0.5 mm), and the quantity of visible filaments along the scribe. For sections providing better performance, we further rate the wheel section by developing a histogram of the quantity of filaments in 0.5 mm length increments and by noting any design flaws.
  • Scribing and exposure conditions are the same as described in the corrosion inoculation portion of the filiform test.
  • the duration of the test is 168 ⁇ 3 hours.
  • This procedure is used to determine the resistance to coating adhesion loss of coated surfaces of aluminum when subjected to a wet steam blast similar to that produced by vehicle wash equipment.
  • the test consists of cooling the wheel part to minus 29°C for three hours, then scribing the painted part with an X scribe and subjecting this area to a steam blast. Paint loss, or paint blushing (whitening, loss of gloss) and the average distance of paint adhesion loss from the scribe line is reported.
  • Formulations A, B, and C were diluted to l%v/v in deionized water, pH adjusted to 3.0 using ammonium hydroxide or left at native solution pH of 2.0, and further modified by the addition of 150, 300, or 450 ppm D- APS. These solutions were used to treat aluminum wheels as set forth under Protocol #1 above. Treated wheels were painted with a clear coat acrylic powder from PPG and performance tested by CAASS and filiform test conditions.
  • Cast and polished aluminum wheel sections and panels were prepared in accordance with Protocol #1 above using solutions D, E, and clirome controls F. Non-chrome treatments were evaluated with and without the addition of D-APS or Dequest 2000. The wheel sections were painted with a clear coat acrylate powder from PPG.
  • Tests were conducted using formulation O, modified by the addition of either 300 ppm D-APS or 300 ppm of an acrylic acid / vinyl phosphonic acid co-polymer.
  • Sections of cast aluminum wheels and cast and polished aluminum wheels were treated in accordance with pretreatment Protocol #1. Wheel sections were painted with clear coat acrylic powder paint and evaluated by CAASS and filiform corrosion resistance.
  • Sections of cast aluminum wheels were treated in accordance with Protocol #1.
  • the treated wheel sections were painted with clear coat acrylic powder.
  • a variety of additives, as shown, were added to the basic formulation listed in Example 5.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une couche de conversion exempte de chromate pour des métaux à base d'aluminium. L'invention concerne également des procédés d'utilisation associés. Les compositions comprennent (a) des fluoacides hydrosolubles de métaux du groupe IVB, (b) de l'acide fluoborique, (c) de l'acide borique, (d) de l'acide gluconique et, éventuellement, (e) un promoteur d'adhésion aminosilane ou un inhibiteur de corrosion organophosphonate. Dans le procédé décrit dans cette invention, la partie métallique voulue est mise en contact avec la composition, par exemple, par immersion ou par pulvérisation.
PCT/US2003/035660 2002-11-18 2003-11-10 Couche de conversion exempte de chrome free pour aluminium WO2004046420A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003287590A AU2003287590A1 (en) 2002-11-18 2003-11-10 Chrome free conversion coating for aluminium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/298,459 2002-11-18
US10/298,459 US20040094235A1 (en) 2002-11-18 2002-11-18 Chrome free treatment for aluminum

Publications (1)

Publication Number Publication Date
WO2004046420A1 true WO2004046420A1 (fr) 2004-06-03

Family

ID=32297459

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/035660 WO2004046420A1 (fr) 2002-11-18 2003-11-10 Couche de conversion exempte de chrome free pour aluminium

Country Status (4)

Country Link
US (1) US20040094235A1 (fr)
AU (1) AU2003287590A1 (fr)
TW (1) TW200419009A (fr)
WO (1) WO2004046420A1 (fr)

Cited By (1)

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CN104109855A (zh) * 2014-06-19 2014-10-22 锐展(铜陵)科技有限公司 一种隔热铝合金表面处理剂

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CA2454042C (fr) * 2002-12-24 2012-04-03 Nippon Paint Co., Ltd. Methode de pretraitement de revetement
US20060151070A1 (en) 2005-01-12 2006-07-13 General Electric Company Rinsable metal pretreatment methods and compositions
EP1906608A1 (fr) * 2006-09-30 2008-04-02 Samsung Electronics Co., Ltd. Appareil et procédé d'interface dans un système de communication
US8398838B2 (en) * 2008-10-10 2013-03-19 Wealtec Bioscience Co., Ltd. Technical measure for gel electrophoresis shaping
DE102009001372B4 (de) 2009-03-06 2011-01-27 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen in einem mehrstufigen Verfahren und Verwendung der nach dem Verfahren beschichteten Produkte
ES2391927T3 (es) * 2009-07-23 2012-12-03 Henkel Ag & Co. Kgaa Composición condensable que contiene agua, para el tratamiento de superficies metálicas
CA2984597C (fr) * 2015-05-01 2020-06-16 Novelis Inc. Procede de pretraitement de bobine continue
CN108330476B (zh) * 2017-12-29 2020-11-03 广东省建筑科学研究院集团股份有限公司 一种免水洗船用铝合金表面金属-有机骨架膜
CN108468049B (zh) * 2018-03-29 2020-03-10 山西银光华盛镁业股份有限公司 一种塑性变形镁合金表面砂面处理液及其应用
CN108411292A (zh) * 2018-04-24 2018-08-17 汤广金 一种提高铝合金制品防腐性能的处理方法
CN108486561A (zh) * 2018-04-24 2018-09-04 汤广金 铝合金用耐腐蚀处理液及其应用方法
CN112376038B (zh) * 2020-10-27 2021-12-21 华南理工大学 一种绿色耐蚀钛锆转化液及其应用

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US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
WO1999014399A1 (fr) * 1997-09-17 1999-03-25 Brent International Plc Procede et compositions permettant de prevenir la corrosion de substrats metalliques
WO2000020657A1 (fr) * 1998-10-08 2000-04-13 Henkel Corporation Procede et composition de revetement par conversion presentant une thermostabilite amelioree

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US4370177A (en) * 1980-07-03 1983-01-25 Amchem Products, Inc. Coating solution for metal surfaces
US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
WO1999014399A1 (fr) * 1997-09-17 1999-03-25 Brent International Plc Procede et compositions permettant de prevenir la corrosion de substrats metalliques
WO2000020657A1 (fr) * 1998-10-08 2000-04-13 Henkel Corporation Procede et composition de revetement par conversion presentant une thermostabilite amelioree

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Publication number Priority date Publication date Assignee Title
CN104109855A (zh) * 2014-06-19 2014-10-22 锐展(铜陵)科技有限公司 一种隔热铝合金表面处理剂

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US20040094235A1 (en) 2004-05-20
AU2003287590A1 (en) 2004-06-15
TW200419009A (en) 2004-10-01

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