EP1029111A1 - Protection anti-corrosion de feuillards acier galvanises et galvanises par alliage - Google Patents

Protection anti-corrosion de feuillards acier galvanises et galvanises par alliage

Info

Publication number
EP1029111A1
EP1029111A1 EP98959815A EP98959815A EP1029111A1 EP 1029111 A1 EP1029111 A1 EP 1029111A1 EP 98959815 A EP98959815 A EP 98959815A EP 98959815 A EP98959815 A EP 98959815A EP 1029111 A1 EP1029111 A1 EP 1029111A1
Authority
EP
European Patent Office
Prior art keywords
ions
treatment solution
corrosion protection
alloy
galvanised
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.)
Granted
Application number
EP98959815A
Other languages
German (de)
English (en)
Other versions
EP1029111B1 (fr
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
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1029111A1 publication Critical patent/EP1029111A1/fr
Application granted granted Critical
Publication of EP1029111B1 publication Critical patent/EP1029111B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C23C22/07—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 the corrosion protection of galvanized and alloy-galvanized steel strips.
  • the process provides temporary protection against corrosion for transport and storage purposes.
  • temporary corrosion protection is to be understood in such a way that the metal surfaces are effectively protected against corrosion for transport and storage times until they are coated with a permanent corrosion protection layer, such as, for example, a lacquer before painting, which can take place immediately after the application of the method according to the invention to the metal surfaces.
  • 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 provided with a chromium (III) and / or chromium (VI) -containing layer with a layer coating of generally about 5 to about 15 mg / m chromium be covered. 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, since on the one hand they lead to chromium contamination of the cleaning solutions and on the other hand the metal surfaces generally do not cover the entire surface are phosphatable. Phosphating as an alternative measure for 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 with chromium-containing treatment solutions, which also results in the disadvantages mentioned above of using chromium-containing treatment solutions.
  • the object of the invention is to provide a method for the corrosion protection of galvanized and alloy-galvanized steel strips which is less ecologically problematic and easier to implement in terms of plant technology than the aforementioned corrosion protection measures.
  • This new process is said to be at least equivalent to the conventional processes with regard to paintability or paint adhesion, but should still improve corrosion protection for storage purposes.
  • This object is achieved by a method for the corrosion protection of galvanized or alloy-galvanized steel strips, characterized in that the galvanized or alloy-galvanized steel strips are coated with an aqueous
  • Ibis contains 150 g / 1 phosphate ions, and the solution dries without intermediate rinsing.
  • electrolytically galvanized or hot-dip galvanized steel strips are suitable as substrate materials for the process according to the invention.
  • the steel strips can also be alloy-galvanized, that is to say carry an electrolytically or hot-dip layer of a zinc alloy.
  • the most important alloy components for zinc are iron, nickel and / or aluminum.
  • the thickness of the zinc layer or the zinc alloy layer is generally in the range between approximately 2 and approximately 20 micrometers, in particular between approximately 5 and approximately 10 micrometers.
  • 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, can be adjusted by squeezing rollers.
  • the treatment solution for the process according to the invention contains 1 to 150 g / 1, preferably 10 to 70 g / 1 phosphate ions.
  • the phosphate content is calculated as phosphate ions.
  • the person skilled in the art is aware that at the pH to be set according to the invention in the range from 1.5 to 3.5, only a very small proportion of the phosphate is present as triple negatively charged phosphate ions. Rather, there is an equilibrium of free phosphoric acid, primary and secondary phosphate ions, which depends on the acid constants of the phosphoric acid for the various protolysis stages and on the specifically chosen pH value. In the selected pH range, most of the phosphate is present as free phosphoric acid and as primary and secondary phosphate ions.
  • the corrosion protection to be achieved with the method according to the invention can be further improved if the treatment solution additionally contains one or more of the following components: up to 10 g / 1, preferably between 2 and 4 g / 1 zinc ions, up to 10 g / 1, preferably 3 to 6 g / 1 nickel ions, up to 20 g / 1, preferably between 3 and 7 g / 1 titanium ions, which are preferably used as hexafluorotitanate ions, up to 50 g / 1, preferably between 15 and 25 g / 1 silicon in the form of silicon compounds such as, for example, hexafluorosilicate ions and / or finely dispersed silica with an average particle size below 10 ⁇ m, up to 30 g / 1 Fluoride ions, which can be introduced as free fluoride in the form of hydrofluoric acid or soluble alkali metal or ammonium fluorides or in the form of hexafluoro anions of titanium or silicon. Free fluoride
  • the treatment solution can contain up to 150 g / 1, preferably between 60 and 125 g / 1, of one or more polymers or copolymers of polymerizable carboxylic acids selected from acrylic acid, methacrylic acid and maleic acid and their esters with alcohols having 1 to 6 carbon atoms. If the term "treatment solution” is used generally, this means that the organic polymers can also be present as a suspension in the active ingredient solution, depending on the type.
  • the carboxylic acids used at the pH set in each case Treatment solution as a mixture of free acids and acid anions, It is particularly preferred to use one or more polymeric carboxylic acids together with at least one of the optional components zinc, nickel, titanium, silicon and fluoride mentioned above.
  • Manganese and, if desired, zinc and nickel can be introduced into the treatment solution in the form of water-soluble salts, for example as nitrates. However, it is preferable not to introduce any other foreign ions into the treatment solution other than the above-mentioned components. 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 further preferred to use titanium, silicon and fluoride in the form of hexafluoric 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 be in the range from about 20 to about 40 ° C. Lower temperatures slow down the reaction rate and lead to increasingly weaker corrosion protection, higher temperatures shorten the exposure time by drying too quickly and are therefore also disadvantageous.
  • the treatment solution is dried by increasing the temperature. This can be done by irradiating the metal surfaces with infrared radiation. However, it is easier to drive the metal strips wetted with the treatment solution through a drying oven. This should have a temperature such that the object temperature, that is to say the temperature of the metal surface, is in the range from approximately 60 to approximately 120 ° C. In Anglo-Saxon usage, this object temperature is also referred to as the "peak metal temperature".
  • the invention relates to a metal strip made of galvanized or alloy-galvanized steel with a manganese and phosphate-containing corrosion protection layer, which can be obtained by treating the metal strip with an aqueous treatment solution with a pH in the range from 1.5 to 3 , 5th in contact that
  • Ibis contains 150 g / 1 phosphate ions, and the solution dries without intermediate rinsing.
  • the treatment solution preferably contains one or more of the components listed above and that it is applied in the manner described above.
  • the metal strip can have one or more lacquer layers above the manganese and phosphate-containing corrosion protection layer, as is produced in the method according to the invention. These lacquer layers can be applied, for example, by powder coating or in the so-called “coil coating method”. "Coil coating” means that the lacquer layer or layers are applied to the running metal strips by application rollers and then baked.
  • 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.
  • Table 2 Constant alternating climate test according to DIN 50017: days to rust level 5
  • Table 3 Salt spray test according to DIN 50021 SS: days to rust level 5

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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Coating With Molten Metal (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Laminated Bodies (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

L'invention concerne un procédé pour la protection anti-corrosion de feuillards acier galvanisés ou galvanisés par alliage, caractérisé en ce que l'on met en contact lesdits feuillards acier avec une solution de traitement aqueuse présentant un pH se situant dans la plage de 1,5 à 3,5, cette solution contenant 1 à 20 g/l d'ions d'oxyde manganeux et 1 à 150 g/l d'ions phosphate, et en ce que l'on fait sécher la solution sans rinçage intermédiaire. Cette solution peut éventuellement renfermer en plus: jusqu'à 10 g/l d'ions zinc, jusqu'à 10 g/l d'ions nickel, jusqu'à 20 g/l d'ions titane, jusqu'à 50 g/l de silicium sous forme de composés au silicium, jusqu'à 30 g/l d'ions fluorure, jusqu'à 150 g/l d'un ou de plusieurs polymères ou copolymères d'acides carboxyliques polymérisables choisis parmi l'acide acrylique, l'acide méthacrylique, l'acide maléique et leurs esters avec des alcools possédant 1 à 6 atomes de C. L'invention concerne d'autre part les feuillards métalliques ainsi traités.
EP98959815A 1997-11-08 1998-10-30 Protection anti-corrosion de feuillards acier galvanises et galvanises par alliage Expired - Lifetime EP1029111B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19749508A DE19749508A1 (de) 1997-11-08 1997-11-08 Korrosionsschutz von verzinkten und legierungsverzinkten Stahlbändern
DE19749508 1997-11-08
PCT/EP1998/006889 WO1999024638A1 (fr) 1997-11-08 1998-10-30 Protection anti-corrosion de feuillards acier galvanises et galvanises par alliage

Publications (2)

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

Family

ID=7848097

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98959815A Expired - Lifetime EP1029111B1 (fr) 1997-11-08 1998-10-30 Protection anti-corrosion de feuillards acier galvanises et galvanises par alliage

Country Status (12)

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

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 (fr) * 2000-09-25 2002-03-28 Chemetall Gmbh Procede de pretraitement et d'enduction de surfaces metalliques, avant leur façonnage, au moyen d'un revetement ressemblant a de la peinture, et utilisation de substrats ainsi enduits
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

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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

Non-Patent Citations (1)

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Title
See references of WO9924638A1 *

Also Published As

Publication number Publication date
ZA9810120B (en) 1999-05-10
HUP0100106A2 (hu) 2001-05-28
WO1999024638A1 (fr) 1999-05-20
JP2001522941A (ja) 2001-11-20
ES2180217T3 (es) 2003-02-01
AU735849B2 (en) 2001-07-19
HUP0100106A3 (en) 2004-06-28
CA2309581C (fr) 2007-04-10
DE59804925D1 (de) 2002-08-29
EP1029111B1 (fr) 2002-07-24
BR9813180A (pt) 2000-08-22
DE19749508A1 (de) 1999-05-12
AU1558399A (en) 1999-05-31
ATE221144T1 (de) 2002-08-15
US6537387B1 (en) 2003-03-25
CA2309581A1 (fr) 1999-05-20

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