EP1029111B1 - Korrosionsschutz von verzinkten und legierungsverzinkten stahlbändern - Google Patents

Korrosionsschutz von verzinkten und legierungsverzinkten stahlbändern Download PDF

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Publication number
EP1029111B1
EP1029111B1 EP98959815A EP98959815A EP1029111B1 EP 1029111 B1 EP1029111 B1 EP 1029111B1 EP 98959815 A EP98959815 A EP 98959815A EP 98959815 A EP98959815 A EP 98959815A EP 1029111 B1 EP1029111 B1 EP 1029111B1
Authority
EP
European Patent Office
Prior art keywords
ions
treatment solution
steel strips
zinc
alloy
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.)
Expired - Lifetime
Application number
EP98959815A
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German (de)
English (en)
French (fr)
Other versions
EP1029111A1 (de
Inventor
Jörg Riesop
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
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Publication of EP1029111A1 publication Critical patent/EP1029111A1/de
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • 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
    • C23C22/364—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 also manganese cations

Definitions

  • the invention relates to a new method for corrosion protection of galvanized and galvanized steel strips.
  • the method causes one Temporary corrosion protection for transport and storage purposes.
  • Temporary corrosion protection should be understood to mean that the metal surfaces are effectively protected against corrosion for transport and storage times, until they are covered with a permanent anti-corrosion layer such as a Paint to be coated.
  • the method according to the invention serves as Pretreatment of the metal surfaces before painting, immediately after the application of the method according to the invention to the metal surfaces can be done.
  • galvanized or alloy-galvanized steel strips are either simply oiled or phosphated or chromated if higher corrosion loads are expected.
  • these measures are not sufficient in the case of particularly high corrosive loads such as ship transport in a salty sea atmosphere or storage in a tropical environment.
  • the best temporary corrosion protection measure known in the prior art is chromating, in which the metal surfaces are coated with a layer containing chromium (III) and / or chromium (VI) with a layer coating of generally about 5 to about 15 mg / m 2 Chrome plated. Because of the known toxicological problems of chromium compounds, this process is disadvantageous and complex from the aspects of occupational safety, ecology and the necessary disposal.
  • chromated sheets are not very suitable for subsequent phosphating because on the one hand they lead to a chromium load on the cleaning solutions and on the other hand the metal surfaces cannot generally be phosphated over the entire area.
  • Phosphating as an alternative measure to temporary corrosion protection can undesirably change the appearance of the metal surfaces.
  • phosphating is complex in terms of plant technology, since depending on the substrate material it requires an additional activation step and, as a rule, a passivation step after the phosphating step. Passivation is often carried out using chromium-containing treatment solutions, which also results in the disadvantages mentioned above of using chromium-containing treatment solutions.
  • the invention has for its object a method for protecting against corrosion to provide galvanized and alloy galvanized steel strips that is less ecologically problematic and technically easier to implement than the aforementioned corrosion protection measures.
  • This new process is supposed to the conventional methods with regard to paintability or paint adhesion be at least equivalent, but corrosion protection for storage purposes improve.
  • US-A-4,264,378 describes a chromium-free phosphating process, the Metal surface with an acidic, aqueous phosphate-containing solution that a pH of 1.5 to 3.0 is treated.
  • This solution contains a divalent or higher cation as well as molybdate, tungstate, niobate or Tantalate ions.
  • divalent or higher cations for example Ca, Mg, Ba, Al, Zn, Cd, Fe, Ni, Co and / or Mn in question.
  • the Solution can also be finely divided silicon or film-forming organic polymers, as they are common in paint manufacturing, for example polyacrylates.
  • the treatment solution is on the metal surface without rinsing dried up.
  • the present invention relates to a method for the corrosion protection of galvanized or alloy-galvanized steel strips, characterized in that the galvanized or alloy-galvanized steel strips are brought into contact with an aqueous treatment solution with a pH in the range from 1.5 to 3.5, which releases is of soluble molybdate, tungstate, vanadate, niobate and / or tantalate ions and the 1 to 20 g / l manganese (II) ions, 1 to 150 g / l phosphate ions and up to 150 g / l of one or more polymers or copolymers of polymerizable carboxylic acids selected from acrylic acid, methacrylic acid, maleic acid and their esters with alcohols having 1 to 6 carbon atoms contains, and the solution dries without intermediate rinsing.
  • an aqueous treatment solution with a pH in the range from 1.5 to 3.5, which releases is of soluble molybdate, tungstate, vanadate, n
  • the Steel strips can also be alloy galvanized, i. that is, an electrolytic or in Apply hot-dip zinc alloy layer.
  • the most important alloy components for zinc are iron, nickel and / or Aluminum.
  • the thickness of the zinc layer or the zinc alloy layer lies here usually in the range between about 2 and about 20 microns, in particular between about 5 and about 10 microns.
  • the applied treatment solution is dried without intermediate rinsing. Methods of this type are known in the art under no-rinse methods or dry-in-place methods.
  • the treatment solutions can be sprayed onto the metal surfaces or applied by passing the steel strips through the treatment bath.
  • the desired amount of the treatment solution remaining on the metal surface which leads to the desired layer coverage of 1 to 5 g / m 2 , can be adjusted by squeezing rollers.
  • the treatment solution for the process according to the invention contains 1 to 150 g / l, preferably 10 to 70 g / l phosphate ions.
  • the phosphate content is here as Phosphate ions calculated.
  • the pH to be set according to the invention in the range from 1.5 to 3.5 is only a very high low proportion of the phosphate is present as triple negatively charged phosphate ions. Rather, there is a balance of free phosphoric acid, primary and secondary phosphate ions, which is determined by the acid constants of phosphoric acid for the different protolysis levels and depends on the specifically chosen pH value. Most of the phosphate is in the free pH range Phosphoric acid and as primary and secondary phosphate ions.
  • the treatment solution also contains up to 150 g / l, preferably between 60 and 125 g / l of one or more polymers or copolymers polymerizable Carboxylic acids selected from acrylic acid, methacrylic acid and maleic acid and their esters with alcohols with 1 to 6 carbon atoms. If here Generally speaking of “treatment solution”, it means that the organic polymers, depending on the type, also as a suspension in the active ingredient solution can be present. The same applies here, depending on the acid constants used Carboxylic acids at the pH value of the treatment solution as a mixture of free acids and acid anions. Especially it is preferred to use one or more polymeric carboxylic acids together at least one of the optional components zinc, nickel, Use titanium, silicon and fluoride.
  • Manganese and, if desired, zinc and nickel can be more water soluble in the form Salts, for example as nitrates, are introduced into the treatment solution.
  • Manganese, zinc and nickel are therefore preferably used in the form of the oxides or carbonates, so that they are ultimately present in the treatment solution as phosphates. It is also preferred to use titanium, silicon and fluoride in the form of hexafluoro acid. At most, the silicon can be introduced in the form of finely dispersed silicas, which preferably have a specific surface area in the range from 150 to 250 m 2 / g.
  • the temperature of the treatment solution on contact with the metal surface should preferably in the range from about 20 to about 40 ° C. Lower temperatures slow down the reaction rate and lead to an increasing weaker corrosion protection, higher temperatures shorten the Exposure time due to drying too quickly and are therefore also disadvantageous.
  • the treatment solution is through Dried up temperature increase. This can be done by Metal surfaces are treated with infrared radiation. However, it is easier to use the Treatment solution to drive wetted metal strips through a drying oven. This should have such a temperature that the object temperature, that is Temperature of the metal surface, ranging from about 60 to about 120 ° C established. In Anglo-Saxon usage, this object temperature is also called "Peak Metal Temperature" called.
  • the invention was tested on test sheets made of hot-dip galvanized steel. Since these were covered with an anti-corrosion oil, they were first cleaned with a commercially available alkaline cleaner. In the practical application of the method in belt systems, however, the cleaning step can be omitted if the method according to the invention immediately follows the process of galvanizing or alloy galvanizing.
  • sample sheets pretreated according to the invention and untreated or chrome-plated comparison sheets were subjected to a constant alternating climate test according to DIN 50017 and a salt spray test according to DIN 50021 SS. The number of days until the sample sheets reached a visually estimated level of rust 5 was recorded. The results are shown in Tables 2 and 3.

Landscapes

  • 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)
  • Laminated Bodies (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Coating With Molten Metal (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP98959815A 1997-11-08 1998-10-30 Korrosionsschutz von verzinkten und legierungsverzinkten stahlbändern Expired - Lifetime EP1029111B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19749508 1997-11-08
DE19749508A DE19749508A1 (de) 1997-11-08 1997-11-08 Korrosionsschutz von verzinkten und legierungsverzinkten Stahlbändern
PCT/EP1998/006889 WO1999024638A1 (de) 1997-11-08 1998-10-30 Korrosionsschutz von verzinkten und legierungsverzinkten stahlbändern

Publications (2)

Publication Number Publication Date
EP1029111A1 EP1029111A1 (de) 2000-08-23
EP1029111B1 true EP1029111B1 (de) 2002-07-24

Family

ID=7848097

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98959815A Expired - Lifetime EP1029111B1 (de) 1997-11-08 1998-10-30 Korrosionsschutz von verzinkten und legierungsverzinkten stahlbändern

Country Status (12)

Country Link
US (1) US6537387B1 (ja)
EP (1) EP1029111B1 (ja)
JP (1) JP2001522941A (ja)
AT (1) ATE221144T1 (ja)
AU (1) AU735849B2 (ja)
BR (1) BR9813180A (ja)
CA (1) CA2309581C (ja)
DE (2) DE19749508A1 (ja)
ES (1) ES2180217T3 (ja)
HU (1) HUP0100106A3 (ja)
WO (1) WO1999024638A1 (ja)
ZA (1) ZA9810120B (ja)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6743302B2 (en) * 2000-01-28 2004-06-01 Henkel Corporation Dry-in-place zinc phosphating compositions including adhesion-promoting polymers
DE10010355A1 (de) * 2000-03-07 2001-09-13 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
DE10022352A1 (de) * 2000-05-08 2001-11-22 Georg Gros Verfahren zur Beschichtung von elektrolytisch- oder feuerverzinkten Blechen
WO2002024344A2 (de) * 2000-09-25 2002-03-28 Chemetall Gmbh Verfahren zur vorbehandlung und beschichtung von metallischen oberflächen vor der umformung mit einem lackähnlichen überzug und verwendung der derart beschichteten substrate
MY117334A (en) * 2000-11-10 2004-06-30 Nisshin Steel Co Ltd Chemically processed steel sheet improved in corrosion resistance
DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
US20050072495A1 (en) * 2002-11-15 2005-04-07 Jasdeep Sohi Passivation composition and process for zinciferous and aluminiferous surfaces
DE102005027567A1 (de) † 2005-06-14 2006-12-21 Basf Ag Verfahren zum Passivieren von metallischen Oberflächen mit Säuregruppen aufweisenden Polymeren
JP4970773B2 (ja) * 2005-11-18 2012-07-11 日本パーカライジング株式会社 金属表面処理剤、金属材の表面処理方法及び表面処理金属材
JP5241075B2 (ja) * 2006-03-06 2013-07-17 日本パーカライジング株式会社 金属材料表面処理用のノンクロメート水系表面処理剤
CN101516728B (zh) * 2006-07-31 2011-10-19 佛罗里达大学研究基金公司 微型飞行器的无翼悬停
DE102007061109B4 (de) * 2007-12-19 2013-01-17 Henkel Ag & Co. Kgaa Behandlungslösung zum Beschichten eines Stahlbandes, ein Verfahren zum Aufbringen derselben sowie ein Stahlband mit einer Beschichtung erhalten aus der Behandlungslösung zur Verbesserung des Umformverhaltens
CN106222639B (zh) * 2016-08-17 2018-07-13 安徽红桥金属制造有限公司 一种弹簧钢铸件表面防锈预处理溶液

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2905535A1 (de) * 1979-02-14 1980-09-04 Metallgesellschaft Ag Verfahren zur oberflaechenbehandlung von metallen
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals
US5378292A (en) * 1993-12-15 1995-01-03 Henkel Corporation Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator
DE4433946A1 (de) 1994-09-23 1996-03-28 Henkel Kgaa Phosphatierverfahren ohne Nachspülung
DE4443882A1 (de) 1994-12-09 1996-06-13 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen

Also Published As

Publication number Publication date
WO1999024638A1 (de) 1999-05-20
DE59804925D1 (de) 2002-08-29
DE19749508A1 (de) 1999-05-12
ZA9810120B (en) 1999-05-10
ES2180217T3 (es) 2003-02-01
JP2001522941A (ja) 2001-11-20
HUP0100106A3 (en) 2004-06-28
ATE221144T1 (de) 2002-08-15
US6537387B1 (en) 2003-03-25
BR9813180A (pt) 2000-08-22
EP1029111A1 (de) 2000-08-23
CA2309581A1 (en) 1999-05-20
HUP0100106A2 (hu) 2001-05-28
CA2309581C (en) 2007-04-10
AU1558399A (en) 1999-05-31
AU735849B2 (en) 2001-07-19

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