US3620949A - Metal pretreatment and coating process - Google Patents

Metal pretreatment and coating process Download PDF

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Publication number
US3620949A
US3620949A US20016A US3620949DA US3620949A US 3620949 A US3620949 A US 3620949A US 20016 A US20016 A US 20016A US 3620949D A US3620949D A US 3620949DA US 3620949 A US3620949 A US 3620949A
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US
United States
Prior art keywords
iron
liquid
metal
coating
zinc
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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.)
Expired - Lifetime
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US20016A
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English (en)
Inventor
Alexander Robley Morrison
Heinz Dieter Herrmann
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Dulux Australia Ltd
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Dulux Australia Ltd
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • METAL PRE'I'REATMENT AND COATING PROCESS This invention relates to a process of pretreating and painting the surface of zinc-based metals.
  • zinc-based metals we mean zinc itself and alloys of zinc with minor proportions of other alloying materials, together with those impurities known to the art to occur therein.
  • the metal may be zinc sheet, formed zinc strip or zinc-based die-casting alloys, typically containing 90 percent or more by weight of zinc.
  • the metal surface to be treated may be a zinc coating applied to an iron or steel substrated, for example by hot dipping or electrodeposition and usually referred to as galvanized iron or steel.
  • the zinc surface may also be passivated by, for example, subjecting it to the action of an aqueous solution of certain chromium salts, to further increase its corrosion resistance.
  • Metal surfaces of the above type are frequently found to provide unfavorable surfaces on which to deposit paint films, a commonly observed defect being that of poor adhesion between the paint and the metal substrate.
  • paint films of surprisingly strong adhesion can be applied to zinc-based metals by a multistage process in which the metal is drenched in an aqueous conditioning bath as hereinunder defined, water rinsed conversion coated with a zinc phosphate conversion coating and then a paint film applied to the surface by electrophoretic deposition.
  • a process of coating the surface of zinc-based metal by successively a. drenching the surface of the metal with an aqueous conditioning liquid comprising a solution in water of 1.5 to 10.0 percent by weight of sodium or potassium hydroxide together with at least 0.05 percent by weight concentration each of a source of iron ions (calculated as total added Fe) and a sequestering agent for iron at the pH of the liquid which shall be at least 13 b. rinsing aqueous conditioning liquid from the metal with water c. depositing a zinc phosphate conversion coating on the metal surface and d. electrophoretically depositing a paint film thereon.
  • the metal to be treated is first drenched with the aqueous conditioning liquid which is applied to it by, for example, spraying, flow-coating or a dipping process.
  • the metal may be given a preliminary cleaning in a suitable bath before drenching to avoid buildup of deposits in the dipping tank, although it is not essential to do so.
  • the surface of the metal takes on a dark grey to black appearance and drenching is judged to be completed when a color change has been observed over the whole surface of the metal, usually within 2-5 minutes. The color change need not be uniform; some areas may appear to become darker than others, possibly due to a nonuniform composition or physical state of the untreated metal surface.
  • the conditioning liquid may be heated to accelerate the drenching process.
  • Zinc phosphate conversion coating processes are well known and consist essentially of aqueous treatment baths in which the metal to be treated is subjected to reaction with solutions of zinc phosphates, usually in the presence of accelerators and optionally grain refining compounds. it is usual for the process to be carried out in a number of stages including, for example, prerinse and final rinse stages.
  • the metal is then electrophoretically coated with the desired paint.
  • the coating of an electrically conductive article by electrophoretic deposition in a well-known process A conductive article as one electrode is immersed in an aqueous bath of coating composition and an electric current passed between the article and a counterelectrode in electrical contact with the bath until a desired coating is produced on the article.
  • the deposited coating is conventionally dried or baked to produce a hard, adherent coating on the article.
  • the coating composition will normally contain a polycarboxylic acid resin as a binder for the coating to be electrophoretically deposited.
  • the polycarboxylic acid resin is solubilized or stably dispersed in the aqueous bath by at least partially neutralizing it with a base, e.g. ammonia, a water-soluble amine, sodium hydroxide or potassium hydroxide.
  • a base e.g. ammonia, a water-soluble amine, sodium hydroxide or potassium hydroxide.
  • the composition of the polycarboxylic acid resin is not critical, but to achieve consistently good results we have found it preferable for the carboxylic acid resin to have an acid value in the range of 30-200 mg. KOH per gm. and for 30-100 percent of the carboxylic acid groups to be neutralized in the coating bath by a water-soluble base.
  • a particular advantage of our process is that it permits a tightly adhering paint film to be applied to zinc-based metals which have been chromate passivated, an objective which is not readily accomplished by other means.
  • the concentration of sodium or potassium hydroxide in the conditioning liquid is not critical. At lower concentrations, conditioning rates are unacceptably slow, while at higher concentrations, excessive pitting and erosion of the zinc-based metal have been observed.
  • Iron is provided in the conditioning liquid by adding to it at the required concentration a source of iron ions, the nature of the source being relatively unimportant.
  • a source of iron ions the nature of the source being relatively unimportant.
  • the material chosen must be able, in the presence of the liquid of pH at least 13, to provide ions of either ferrous or ferric iron in the liquid.
  • the source of iron may be a soluble iron salt or a solid component suspended in the alkaline aqueous solution and from which iron in a soluble form leaches into the solution.
  • suitable materials are powdered iron, iron oxides and hydroxides and soluble iron salts, e.g. ferrous sulfate, ferric chloride and ferric citrate.
  • the iron content of the conditioning liquid is calculated on the basis of the total iron (calculated as Fe) added to the alkaline aqueous liquid and not on the concentration of iron which passes into solution.
  • the concentration of iron added to the liquid should not exceed 2.5 percent by weight.
  • the conditioning liquid must have a pH of at least 13, we have found that provided the iron is not introduced into the liquid in a virtually insoluble form, sufficient ions of iron leach into the solution for the process to be operative, without it being necessary to control the lower concentration limit of iron ions actually present in the liquid.
  • the sequestering agent is chosen from those materials known to sequester iron in the presence of water at a pH of at least l3.
  • suitable sequestering agents are certain hydroxy acids, for example gluconic, heptonic and tartaric acids and their sodium and potassium salts, and triethanolamine.
  • Other useful sequestering agents are certain hexitols, for example sorbitol and mannitol, although they tend to be less reliable than the above agents within the stipulated pH range and must usually be employed in combination with e.g. ethylenediamine tetraacetic acid to maintain their effectiveness for prolonged working periods.
  • the conditioning liquid should preferably contain a slight excess, e.g. -10 percent by weight, of sequestering agent over the concentration of soluble iron in the liquid; which is readily determined by standard analytical techniques.
  • the conditioning liquid may comprise anionic and/or nonionic surface active agents to promote rapid and even wetting of the surface of the metal to be treated.
  • drenching action is demonstrably operative at all concentrations within our specified limits, but if the initial concentration of sodium or potassium hydroxide is very low, drenching may be somewhat sluggish. Although drenching will take place slowly at sodium or potassium hydroxide concentrations as low as 0.5 percent by weight of the conditioning liquid, the rate of drenching is slower than is desirable for a commercial process and we prefer to limit the concentration of the hydroxide to a minimum of 1.5 percent by weight. in general, drenching rates are improved by increasing the temperature of the liquid, typically to l50-l 80 F.
  • the conditioning liquid When the conditioning liquid is to be applied to the metal by manual or spray methods, we prefer for simplicity of operation to use a soluble iron salt as the source of iron.
  • a soluble iron salt As the source of iron.
  • our practical requirements are less restrictive and water-insoluble iron compounds provide cheap and satisfactory alternatives. if the drenching is carried out at such a rate that the conditioning liquid is rapidly depleted of iron ions, due to a low leaching rate of iron into the liquid, this is simply overcome by using a more readily solubilized source of iron. Also, if the initial concentration of iron and sequestering agent is very low, the liquid may quickly become deficient in these constituents.
  • Example 1 Preparation of aqueous conditioning liquid in which the source of iron is a water-soluble iron salt.
  • the pH of the liquid in each case was greater than 13.
  • Example 2 Preparation of an aqueous conditioning liquid in which the source of iron is a water-insoluble iron compound.
  • Galvanized iron test panels (unannealed hot dip galvanized) were immersed for 3 minutes in a bath of conditioning liquid No. 2 of example 1 at room temperature and then water rinsed. The surface of the conditioned panels acquired a black matte appearance. One-half of the group was set aside as control group A. The remaining panels together with an equal number of cleaned but not conditioned panels (control group B) were then coated with a crystalline zinc phosphate conversion coating in standard commercial phosphating equipment and water rinsed.
  • the three groups of panels were then coated with a red oxide undercoat in a standard electrophoretic coating bath, dried and stoved.
  • the undercoat binder was an epoxy-estertype polycarboxylic acid resin of acid value mg. KOH per g. neutralized in the coating bath to the extent of about 60 percent with caustic potash. The overall appearance of all undercoated panels was satisfactory, the paint films being hard and of uniform texture.
  • the undercoat was not afiected on the panels treated according to the invention, but onthe control panels about 40 percent of the area of undercoat film lying under the tape was removed with the tape, thus demonstrating once more the superior adhesion of a paint film to the metal treated according to the invention.
  • Example 4 The effect of the pH of the conditioning liquid on the performance of the process of the invention is demonstrated.
  • a conditioning liquid was prepared to the general formula of liquid No. l of example l but with the sodium hydroxide content reduced to give a liquid of pH approximately 12.5 (3.0 parts of sodium hydroxide).
  • Example 5 Application of a paint film to zinc-coated panels by the process of the invention and in which the source of iron in the conditioning liquid is iron filings.
  • Unannealed hot dip galvanized steel panels were coated with a paint film and tested by the method described in exampie 3, using the above mixture as the conditioning liquid.
  • the adhesion of paint to the metal on the panels treated according to the invention was markedly superior to that of the control panels.
  • a process of coating the surface of zinc-based metal by successively a. drenching the surface of the metal with an aqueous conditioning liquid comprising a solution in water of 1.5 to 10.0 percent by weight of sodium or potassium hydroxide together with at least 0.05 percent by weight concentration each of a source of iron ions (calculated as total added Fe) and a sequestering agent for iron at the pH of the liquid which shall be at least 13 b. rinsing aqueous conditioning liquid from the metal with water c. depositing a zinc phosphate conversion coating on the metal surface and d. electrophoretically depositing a paint film thereon.
  • the source of iron is at least one member selected from the group consisting of powdered iron, an iron oxide and an iron hydroxide.
  • the sequestering agent is at least one member selected from the group consisting of a sodium salt of any one of gluconic, heptonic and tartaric acids, a potassium salt of any one of the aforesaid acids and triethanolamine.
  • the electrophoretically deposited paint film comprises a polycarboxylic acid resin binder having an acid value in the range of 30-200 mg. KOH per g. and from 30-100 percent of the carboxylic acid groups neutralized in the coating bath by a water soluble base.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
US20016A 1969-04-11 1970-03-16 Metal pretreatment and coating process Expired - Lifetime US3620949A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
AU5338069 1969-04-11

Publications (1)

Publication Number Publication Date
US3620949A true US3620949A (en) 1971-11-16

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Country Status (9)

Country Link
US (1) US3620949A (fr)
BE (1) BE748819A (fr)
BR (1) BR7018177D0 (fr)
DE (1) DE2017327B2 (fr)
FR (1) FR2043216A5 (fr)
GB (1) GB1241538A (fr)
NL (1) NL7005220A (fr)
SE (1) SE351442B (fr)
ZA (1) ZA701902B (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864230A (en) * 1974-01-09 1975-02-04 Kaiser Aluminium Chem Corp Pretreating and Electrocoating Metal Products
US3988231A (en) * 1974-07-09 1976-10-26 Nippon Paint Co., Ltd. Method for coating a conductive material
US4165242A (en) * 1977-11-21 1979-08-21 R. O. Hull & Company, Inc. Treatment of metal parts to provide rust-inhibiting coatings by phosphating and electrophoretically depositing a siccative organic coating
US4213839A (en) * 1978-04-14 1980-07-22 Centro Sperimentale Metallurgico S.P.A. Process for improving the adhesion of paint to steel sheets
US5288377A (en) * 1991-06-05 1994-02-22 Macdermid, Incorporated Process for the manufacture of printed circuits using electrophoretically deposited organic resists
US5385655A (en) * 1992-10-30 1995-01-31 Man-Gill Chemical Company Treatment of metal parts to provide rust-inhibiting coatings
US5753316A (en) * 1997-01-14 1998-05-19 Ppg Industries, Inc. Treatment of metal parts to provide improved sealcoat coatings
WO2001076811A1 (fr) * 2000-04-07 2001-10-18 Whyco Technologies, Inc. Procede de masquage de revetements et objet resultant
US20060289089A1 (en) * 2005-06-14 2006-12-28 Cape Thomas W Method for treatment of chemically passivated galvanized surfaces to improve paint adhesion
US20130202911A1 (en) * 2011-02-08 2013-08-08 Henkel Ag & Co. Kgaa Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
CN104271799A (zh) * 2011-10-24 2015-01-07 凯密特尔有限责任公司 用多组分水性组合物涂覆金属表面的方法
US9228088B2 (en) 2010-02-09 2016-01-05 Henkel Ag & Co. Kgaa Composition for the alkaline passivation of zinc surfaces
US9534301B2 (en) 2011-03-22 2017-01-03 Henkel Ag & Co. Kgaa Multi-stage anti-corrosion treatment of metal components having zinc surfaces
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2560894B1 (fr) * 1984-03-07 1988-11-18 Parker Ste Continentale Procede de preparation de surfaces de zinc, d'alliages de zinc et d'acier recouvert de ces materiaux, destinees a recevoir des peintures ou des vernis
DE3630246A1 (de) * 1986-09-05 1988-03-10 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
JPH04224684A (ja) * 1990-12-25 1992-08-13 Nippon Parkerizing Co Ltd アルミニウム板およびその複合物の表面処理法
GB9211567D0 (en) * 1992-05-15 1992-07-15 Wednesbury Diecasting And Meta Improvements relating to electrophoretic coatings
GB2309980B (en) * 1996-02-06 1998-12-16 Abbey Treatment of ferrous metal surfaces

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3420762A (en) * 1964-01-24 1969-01-07 Ici Ltd Electrocoating process with pretreatment of articles
US3544440A (en) * 1963-06-15 1970-12-01 Hamburger Flugzeugbau Gmbh Process for coating conductive substrates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544440A (en) * 1963-06-15 1970-12-01 Hamburger Flugzeugbau Gmbh Process for coating conductive substrates
US3420762A (en) * 1964-01-24 1969-01-07 Ici Ltd Electrocoating process with pretreatment of articles

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864230A (en) * 1974-01-09 1975-02-04 Kaiser Aluminium Chem Corp Pretreating and Electrocoating Metal Products
US3988231A (en) * 1974-07-09 1976-10-26 Nippon Paint Co., Ltd. Method for coating a conductive material
US4165242A (en) * 1977-11-21 1979-08-21 R. O. Hull & Company, Inc. Treatment of metal parts to provide rust-inhibiting coatings by phosphating and electrophoretically depositing a siccative organic coating
US4213839A (en) * 1978-04-14 1980-07-22 Centro Sperimentale Metallurgico S.P.A. Process for improving the adhesion of paint to steel sheets
US5288377A (en) * 1991-06-05 1994-02-22 Macdermid, Incorporated Process for the manufacture of printed circuits using electrophoretically deposited organic resists
US5385655A (en) * 1992-10-30 1995-01-31 Man-Gill Chemical Company Treatment of metal parts to provide rust-inhibiting coatings
US5603818A (en) * 1992-10-30 1997-02-18 Man-Gill Chemical Company Treatment of metal parts to provide rust-inhibiting coatings
US5753316A (en) * 1997-01-14 1998-05-19 Ppg Industries, Inc. Treatment of metal parts to provide improved sealcoat coatings
WO2001076811A1 (fr) * 2000-04-07 2001-10-18 Whyco Technologies, Inc. Procede de masquage de revetements et objet resultant
US20060289089A1 (en) * 2005-06-14 2006-12-28 Cape Thomas W Method for treatment of chemically passivated galvanized surfaces to improve paint adhesion
US8309177B2 (en) * 2005-06-14 2012-11-13 Henkel Ag & Co. Kgaa Method for treatment of chemically passivated galvanized surfaces to improve paint adhesion
US9228088B2 (en) 2010-02-09 2016-01-05 Henkel Ag & Co. Kgaa Composition for the alkaline passivation of zinc surfaces
US20130202911A1 (en) * 2011-02-08 2013-08-08 Henkel Ag & Co. Kgaa Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
US9573162B2 (en) * 2011-02-08 2017-02-21 Henkel Ag & Co., Kgaa Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
US9534301B2 (en) 2011-03-22 2017-01-03 Henkel Ag & Co. Kgaa Multi-stage anti-corrosion treatment of metal components having zinc surfaces
CN104271799A (zh) * 2011-10-24 2015-01-07 凯密特尔有限责任公司 用多组分水性组合物涂覆金属表面的方法
CN104271799B (zh) * 2011-10-24 2017-03-08 凯密特尔有限责任公司 用多组分水性组合物涂覆金属表面的方法
US10378120B2 (en) 2011-10-24 2019-08-13 Chemetall Gmbh Method for coating metallic surfaces with a multi-component aqueous composition
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

Also Published As

Publication number Publication date
DE2017327B2 (de) 1977-07-07
ZA701902B (en) 1971-10-27
BR7018177D0 (pt) 1973-02-15
DE2017327A1 (de) 1971-01-21
NL7005220A (fr) 1970-10-13
FR2043216A5 (fr) 1971-02-12
GB1241538A (en) 1971-08-04
BE748819A (fr) 1970-10-12
SE351442B (fr) 1972-11-27

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