US20060042726A1 - Non-chrome passivation of steel - Google Patents

Non-chrome passivation of steel Download PDF

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Publication number
US20060042726A1
US20060042726A1 US10/933,014 US93301404A US2006042726A1 US 20060042726 A1 US20060042726 A1 US 20060042726A1 US 93301404 A US93301404 A US 93301404A US 2006042726 A1 US2006042726 A1 US 2006042726A1
Authority
US
United States
Prior art keywords
recited
composition
metal
fluoacid
polyoxyethylene
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US10/933,014
Other languages
English (en)
Inventor
Andrea Keys
Jeffrey Melzer
Michael Raab
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall Corp
Original Assignee
General Electric Co
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 General Electric Co filed Critical General Electric Co
Priority to US10/933,014 priority Critical patent/US20060042726A1/en
Assigned to GENERAL ELECTRIC COMPANY reassignment GENERAL ELECTRIC COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KEYS, ANDREA, MELZER, JEFFREY I., RAAB, MICHAEL T.
Priority to RU2007111918/02A priority patent/RU2396370C2/ru
Priority to CN2005800294625A priority patent/CN101018888B/zh
Priority to PCT/US2005/031091 priority patent/WO2006028894A2/en
Priority to AU2005282751A priority patent/AU2005282751B2/en
Priority to EP05793978.7A priority patent/EP1838898B1/en
Priority to ES05793978.7T priority patent/ES2573537T3/es
Priority to BRPI0515626A priority patent/BRPI0515626B1/pt
Priority to MX2007002619A priority patent/MX2007002619A/es
Priority to CA2578965A priority patent/CA2578965C/en
Publication of US20060042726A1 publication Critical patent/US20060042726A1/en
Assigned to CHEMETALL CORP. reassignment CHEMETALL CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GE BETZ INTERNATIONAL, INC., GE BETZ, INC., GENERAL ELECTRIC COMPANY
Priority to US12/154,502 priority patent/US8980015B2/en
Abandoned legal-status Critical Current

Links

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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D119/00—Coating compositions based on rubbers, not provided for in groups C09D107/00 - C09D117/00
    • C09D119/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D121/00—Coating compositions based on unspecified rubbers
    • C09D121/02—Latex
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the present invention relates to non-chromate coatings for metals. More particularly, the present invention relates to non-chromate coatings for steel surfaces to improve corrosion resistance and adhesion of paints to the surface.
  • the invention provides a dried in place coating which is particularly effective at treating galvanized steel coil strip.
  • a chromate conversion coating on the surface of galvanized steel are to provide corrosion resistance, improve adhesion of coatings and for aesthetic reasons. Chromate passivation of a galvanized steel surface is done to provide corrosion resistance and for aesthetic reasons on materials which are not to be painted.
  • the conversion coating improves adhesion of coating layers such as paints, inks, lacquers and plastic coatings.
  • Galvanized steel is typically treated with an aqueous composition containing hexavalent or trivalent chromium ions with other additives to create a chromium conversion coating.
  • the present invention provides a method of treating the surface of metals, such as steel or galvanized steel, to provide for the formation of a coating which increases the corrosion resistance and adhesion properties of the metal surface.
  • the passivation or conversion coating formed by the present invention may be dried in place or rinsed.
  • the methods of the invention comprise contacting the requisite metal surface with a chromate free aqueous treatment composition comprising: (a) a film forming latex polymer; (b) a fluoacid; (c) phosphoric acid; and (d) a polyoxyethylene/oxypropylene block copolymer.
  • an improved, non-chromate conversion or passivation coating can be provided on metal surfaces, particularly galvanized steel surfaces, by contacting the surface with an aqueous coating solution or dispersion of:
  • compositions of the invention have been found to provide an aqueous pretreatment agent for the treatment of galvanized metal surfaces which provides improved corrosion resistance and adhesion of latex applied coating when the treatment is dried in place.
  • the film forming latex polymer component this can be chosen from a wide variety of materials such as styrene-butadiene copolymers, acrylate resins, polyvinylacetate, urethanes, amido-amine polymers, and similar materials.
  • Some commercially available latex materials include: Description Type “Neocar” (Union Carbide) Vinyl Ester/Acrylic “Res 3077” (Rohm & Haas) Vinyl Acetate/Acrylic “Airflex” 500 (Air Products) Vinyl Acetate/Ethylene “Airflex 4514 (Air Products) Vinyl Chloride/Amide Terpolymer Airflex 4500 (Air Products) Vinyl Chloride/Amide Terpolymer Flexhane 620 (Air Products) Urethane Vinac 884 (Air Products) Vinyl Acetate Dow 620 (Dow) SBR Airflex 4530 (Air Products) ethylene vinyl chloride Kymene 736 polyamido amine U Car Latex 651 acrylate
  • U Car Latex 651 As the film forming latex polymer component. This is commercially available form Union Carbide and is reportedly an acrylic copolymer resin emulsion having as major latex components butyl acrylate, methyl methacrylate, and methacrylic acid polymers.
  • this is preferably a fluoacid of a Group IVB metal or mixtures thereof.
  • Fluotitanic acid H 2 TiF 6 is presently preferred with fluozirconic acid, H 2 ZrF 6 , also mentioned as exemplary. Combinations of these acids are also used.
  • phosphoric acid As stated above, phosphoric acid, H 3 PO 4 , and salts thereof are also present in the treatment formulation.
  • phosphoric acid refers to both the acid and salt form.
  • a polyoxyethylene/oxypropylene block copolymer is exemplary.
  • the ethylene oxide (EO):propylene oxide (PO) repeat units of the copolymers may be present in a molar ratio of about 1:1-9; preferably 1:5-9; most preferably 1:9. Molecular weights of these block copolymers will range from about 2,000-4,000.
  • These copolymers are commercially available from BASF under the “Pluronic” trademark. Presently, “Pluronic 101” is preferred for use.
  • This specific copolymer has a ratio of EO:PO blocks of about 1:9 and a molecular weight of about 3,300.
  • compositions in accordance with the invention are chromate free and include 0.01-50 wt % film forming latex 0.01-40 wt % H 3 PO 4 0.01-30 wt % fluoacid 0.01-20 wt % non-ionic polymer surfactant wherein the weight of the composition is, in total, 100 wt %.
  • compositions having the following range (in wt %) of the components 1-20 wt % film forming latex 1-50 wt % H 3 PO 4 1-40 wt % fluoacid 0.01-15 wt % non-ionic polymer surfactant remainder water.
  • the sum of all composition components equals 100 wt %.
  • the pH of the compositions may vary from about 1.0 to 2.0.
  • the requisite metal surface may be contacted by the treatment in spray, immersion or roller applications.
  • the treatment is then dried and the metal surface is ready for painting or other coating applications.
  • the conversion or passivation treatment of the present invention is applied to result in a conversion coating weight of greater than about 1 milligram per square foot to treated surface with a weight of 2-150 milligrams per square foot being more preferred.
  • working solutions comprising about 3-100, preferably 10-100 wt % concentrations of the above “More preferred” formulation are used to contact the desired metal surfaces.
  • One tested treatment candidate formulation “A” was a latex emulsion including the following components: 1) U Car Latex 651 5.8 wt % (65% actives) 2) H 3 PO 4 22.0 wt % 3) Fluotitanic acid 10 wt % 4) Pluronic 101 0.5 wt % 5) Water remainder
  • U Car Latex 651 is an acrylic copolymer resin emulsion having a viscosity 20° C., cP (Brookfield, LVT #3, 50 rpm) of 400 and a particle size in microns of 0.45. It is available from the Union Carbide Corporation of Danbury, Conn. Its major constituents are 1) butyl acrylate, methyl methacrylate, methacrylic acid polymers in an amount of ⁇ 65 wt %; 2) water ⁇ 35%; 3) glycols, polyethylene, mono [(1,1,3,3-tetramethylbutyl)phenyl] ether in an amount of less than 2%; and 4) ammonia in 0.2 wt %. It is a white liquid.
  • cP Brookfield, LVT #3, 50 rpm
  • Pluronic 101 is a difunctional block copolymer surfactant terminating in primary hydroxy groups and is available from BASF Corporation in Mount Olive, N.J. It is a block copolymer having hydrophobic propylene oxide (PO) repeat units and hydrophilic ethylene oxide (EtO) repeat units in a molar ratio of about 9:1. The overall molecular weight of the copolymer is about 3300.
  • PO propylene oxide
  • EtO hydrophilic ethylene oxide
  • Test panels for the examples were prepared as follows: G70/70 hot dipped galvanized steel test panels purchased from ACT Laboratories were spray cleaned with a 3% aqueous solution of an alkaline surfactant product and then rinsed with DI water and subsequently coated with the test treatment formulations by spin coat application, followed by forced air drying.
US10/933,014 2004-09-02 2004-09-02 Non-chrome passivation of steel Abandoned US20060042726A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US10/933,014 US20060042726A1 (en) 2004-09-02 2004-09-02 Non-chrome passivation of steel
CA2578965A CA2578965C (en) 2004-09-02 2005-08-30 Method and composition for forming a non-chrome conversion coating on steel surface
ES05793978.7T ES2573537T3 (es) 2004-09-02 2005-08-30 Método y composición para formar un revestimiento de conversión sin cromo sobre una superficie de acero
CN2005800294625A CN101018888B (zh) 2004-09-02 2005-08-30 在钢表面上形成非铬转化涂层的方法和组合物
PCT/US2005/031091 WO2006028894A2 (en) 2004-09-02 2005-08-30 Method and composition for forming a non-chrome conversion coating on steel surface
AU2005282751A AU2005282751B2 (en) 2004-09-02 2005-08-30 Method and composition for forming a non-chrome conversion coating on steel surface
EP05793978.7A EP1838898B1 (en) 2004-09-02 2005-08-30 Method and composition for forming a non-chrome conversion coating on steel surface
RU2007111918/02A RU2396370C2 (ru) 2004-09-02 2005-08-30 Бесхромовая пассивация стали
BRPI0515626A BRPI0515626B1 (pt) 2004-09-02 2005-08-30 método e composição para formar um revestimento de conversão sem cromo em superfície de aço
MX2007002619A MX2007002619A (es) 2004-09-02 2005-08-30 Metodo y composicion para formar un revestimiento de conversacion que no es de cromo sobre una superficie de acero.
US12/154,502 US8980015B2 (en) 2004-09-02 2008-05-23 Non-chrome passivation of steel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/933,014 US20060042726A1 (en) 2004-09-02 2004-09-02 Non-chrome passivation of steel

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/154,502 Continuation US8980015B2 (en) 2004-09-02 2008-05-23 Non-chrome passivation of steel

Publications (1)

Publication Number Publication Date
US20060042726A1 true US20060042726A1 (en) 2006-03-02

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
US10/933,014 Abandoned US20060042726A1 (en) 2004-09-02 2004-09-02 Non-chrome passivation of steel
US12/154,502 Expired - Fee Related US8980015B2 (en) 2004-09-02 2008-05-23 Non-chrome passivation of steel

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/154,502 Expired - Fee Related US8980015B2 (en) 2004-09-02 2008-05-23 Non-chrome passivation of steel

Country Status (10)

Country Link
US (2) US20060042726A1 (zh)
EP (1) EP1838898B1 (zh)
CN (1) CN101018888B (zh)
AU (1) AU2005282751B2 (zh)
BR (1) BRPI0515626B1 (zh)
CA (1) CA2578965C (zh)
ES (1) ES2573537T3 (zh)
MX (1) MX2007002619A (zh)
RU (1) RU2396370C2 (zh)
WO (1) WO2006028894A2 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060169363A1 (en) * 2005-01-14 2006-08-03 Jasdeep Sohi Stable, non-chrome, thin-film organic passivates
WO2012045713A1 (de) * 2010-10-05 2012-04-12 Basf Se Verfahren zum passivieren von metallischen oberflächen mit wässrigen zusammensetzungen enthaltend tenside
US8986467B2 (en) 2010-10-05 2015-03-24 Basf Se Method for passivating metallic surfaces with aqueous compositions comprising surfactants
CN110054956A (zh) * 2019-04-02 2019-07-26 广州市宏彩金属饰品有限公司 一种用于金属表面处理的镀膜剂的制备方法

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CN101619452A (zh) * 2008-07-01 2010-01-06 上海品新冶金设备有限公司 钢铁、锌板、铝及铝合金件和锌及锌合金用的无铬钝化剂
CN101619451A (zh) * 2008-07-01 2010-01-06 上海品新冶金设备有限公司 钢铁、锌板、铝及铝合金件和锌及锌合金用的无铬钝化剂
DE102013107506A1 (de) * 2013-07-16 2015-01-22 Thyssenkrupp Rasselstein Gmbh Verfahren zur Passivierung von bandförmigem Schwarzblech
CN103695888B (zh) * 2013-12-24 2015-12-02 山东建筑大学 邦迪管镀锌无铬军绿色钝化剂i
CN105154861A (zh) * 2015-07-06 2015-12-16 安徽景昌铝业有限公司 铝型材无铬钝化处理工艺
DE102015113878B4 (de) * 2015-08-21 2023-03-16 Thyssenkrupp Ag Verfahren zur thermischen Behandlung eines mit einer Konversionsschicht beschichteten Schwarzblechs
KR102494315B1 (ko) 2016-06-22 2023-02-02 케메탈 게엠베하 강철, 아연도금된 강철, 알루미늄, 마그네슘 및/또는 아연-마그네슘 합금을 함유하는 금속 표면의 부식방지 예비처리를 위한 개선된 방법
CN111218689A (zh) * 2019-12-11 2020-06-02 陈克华 一种钢铁表面锈蚀转化涂液

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US20060169363A1 (en) * 2005-01-14 2006-08-03 Jasdeep Sohi Stable, non-chrome, thin-film organic passivates
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US8986467B2 (en) 2010-10-05 2015-03-24 Basf Se Method for passivating metallic surfaces with aqueous compositions comprising surfactants
CN110054956A (zh) * 2019-04-02 2019-07-26 广州市宏彩金属饰品有限公司 一种用于金属表面处理的镀膜剂的制备方法

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WO2006028894A3 (en) 2006-06-01
CN101018888A (zh) 2007-08-15
AU2005282751A1 (en) 2006-03-16
AU2005282751B2 (en) 2011-07-21
EP1838898B1 (en) 2016-03-16
CA2578965C (en) 2016-08-23
US8980015B2 (en) 2015-03-17
RU2007111918A (ru) 2008-10-10
EP1838898A2 (en) 2007-10-03
MX2007002619A (es) 2007-05-15
BRPI0515626B1 (pt) 2016-11-08
CA2578965A1 (en) 2006-03-16
US20080223490A1 (en) 2008-09-18
WO2006028894A2 (en) 2006-03-16
ES2573537T3 (es) 2016-06-08
CN101018888B (zh) 2012-03-28
BRPI0515626A (pt) 2008-07-29

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