EP2402484B1 - Procédé de fabrication d'une couche de protection sur des produits plats en zinc de titane - Google Patents

Procédé de fabrication d'une couche de protection sur des produits plats en zinc de titane Download PDF

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Publication number
EP2402484B1
EP2402484B1 EP20110005194 EP11005194A EP2402484B1 EP 2402484 B1 EP2402484 B1 EP 2402484B1 EP 20110005194 EP20110005194 EP 20110005194 EP 11005194 A EP11005194 A EP 11005194A EP 2402484 B1 EP2402484 B1 EP 2402484B1
Authority
EP
European Patent Office
Prior art keywords
copper
treatment
protective coating
zinc alloy
solution
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.)
Not-in-force
Application number
EP20110005194
Other languages
German (de)
English (en)
Other versions
EP2402484A1 (fr
Inventor
Ralf Prof. Dr.-Ing Feser
Marianne Dr. Schönnenbeck
Andreas Friedrich
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.)
Rheinzink GmbH and Co KG
Original Assignee
Rheinzink GmbH and Co KG
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Publication date
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Application filed by Rheinzink GmbH and Co KG filed Critical Rheinzink GmbH and Co KG
Publication of EP2402484A1 publication Critical patent/EP2402484A1/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
    • C23C22/05—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
    • C23C22/46—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 oxalates
    • C23C22/47—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 oxalates containing also phosphates
    • 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
    • C23C22/10—Orthophosphates containing oxidants

Definitions

  • the invention relates to a method for producing a protective layer in gray tinting on rolled flat products made of a titanium-zinc alloy and the semifinished product produced therefrom.
  • a process for the preparation of uniform hue protective coatings on flat zinc products has been made DE 196 36 370 known.
  • the flat products are pickled in a pickling bath with mixed acid containing sulfuric acid and nitric acid and, after rinsing, passivated by applying chromate-containing polymers to form a protective layer.
  • the aforementioned method requires, in addition to the treatment with strong acids, the aftertreatment with chromate-containing polymers, which encounters environmental protection concerns.
  • Zinc oxalate coatings on zinc layers with relatively low concentration oxalate solutions are used in the EP 1 252 367 B4 described, wherein the Oxalationsaten Cu 2+ ions are attached.
  • the result of the treatment of the zinc surface is a "lubrication pre-coating" (prelubrification). A certain shade of zinc oxalate coatings is not sought.
  • the object of the invention is to provide a method using a coating solution "can be provided with the titanium zinc sheets and other products and products produced therefrom with a homogeneous, textured gray protective layer, which works without the use of chromate polymers and in which the resulting product no
  • different shades of gray should be producible with the components of the same overall composition of the coating solution.
  • the correspondingly treated titanium-zinc alloy flat products show a protective layer of uniform gray hue, in which the natural microstructure of the surface becomes visible as a texture after the treatment.
  • the alloy can remain unchanged, only the composition of the treatment solution is varied within the limits listed above.
  • oxalic acid HOOC-COOH
  • malonic acid HOOC- (CH 2 ) -COOH
  • the color is slightly lighter.
  • the acids can be used mixed. By appropriate mixing ratios of oxalic acid and malonic acid then different shades of color can be produced.
  • Copper compounds which form Cu + or Cu 2+ ions in the coating solution are preferably copper (I) oxides or copper (II) oxides and copper nitrate. Copper sulfate can be used as another copper salt at the expense of color deviations.
  • a rolled strip consisting of a zinc alloy in accordance with the European standard EN 988 is degreased by rinsing with an alkaline degreasing solution at a temperature of approx. 60 ° C and a rinsing pressure of approx. 2.5 bar and then with a water spray jet at a temperature of about 65 ° C and a pressure of about 2.5 bar hosed. To assist the rinse and surface roughening, the strip is brushed in the final rinse step.
  • the strip is treated in a treatment bath at room temperature with an aqueous treatment solution with a proportionate 35 g / l phosphoric acid, 40 g / l oxalic acid, 3 g / l ammonium nitrate and 0.5 g / l copper oxide, wherein the residence time of the respective band section in the bath 60 seconds.
  • the pH of the treatment solution is at pH 2.5.
  • the treatment is carried out at a bath temperature of about 40 ° C. The result is a gray color of the surface.
  • the color of the deposited color protective layer is essentially dependent on the pH of the solution and the component ratios. Uniform shades between light gray and dark gray can be produced for the same alloy composition of the substrate.
  • the emerging from the treatment bath band is rinsed with water.
  • the tape thus obtained shows a similar resistance to white discoloration due to white rust formation in the condensation climate humidity change test as untreated titanium-zinc alloy flat products. Electrochemical investigations confirm the corrosion protection effect of the protective layer obtained. Kelvin probe measurements show that the protective layer inhibits zinc dissolution.
  • an existing from a zinc alloy according to the European standard EN 988 tape was treated according to Example 1, wherein instead of oxalic acid, the same molar mass of malonic acid was used.
  • the ratio of the molecular weights is about 65 to 83, ie per 1 of water about 51 g of malonic acid were used.
  • As Cu 2+ -forming salt 3.0 g / l copper nitrate [Cu (NO 3 ) 2 ] was added.
  • the resulting ribbon showed the same properties as described above, with the color being slightly lighter than the oxalic acid treated ribbon.
  • a band consisting of a zinc alloy according to the European standard EN 988 was treated according to Example 1, using a mixture of 15 g / l oxalic acid and 20 g / l malonic acid.
  • the resulting ribbon showed the same properties as described above, with the color assuming an intermediate tone between the staining according to Examples 1 and 2.
  • the invention further relates to a flat rolled semi-finished product of a titanium-zinc alloy with a gray-tinted protective layer produced by means of one of the appended method claims.
  • the thickness of the protective layer is preferably between 0.1 and 10 microns.
  • a finished part for example a downpipe or roof share made of a titanium-zinc alloy according to the European standard EN 988, is prepared according to the invention from a flat product treated in an aqueous treatment solution of the type mentioned above and in the examples and thereby with a protective layer uniformly gray, but variably adjustable color tint is provided.
  • the flat product thus obtained exhibits the natural surface structure and has a comparable sensitivity to whitening by the formation of white rust as naturally patinated titanium-zinc alloy flat products, so that it is suitable for many uses, even in a free atmosphere.

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)

Claims (8)

  1. Procédé d'élaboration d'une couche de protection de couleur grise sur des produits laminés plats réalisés en un alliage de zinc et titane ainsi que sur des corps fabriqués à partir desdits produits plats, dans lequel le traitement est effectué dans une solution acide acqueuse, caractérisé en ce que, pour élaborer la solution de traitement, l'on additionne à un volume d'eau de 1.000 cm3, proportionnellement :
    a. 20 à 50 g d'acide phosphorique ;
    b. 20 à 50 g d'acide saturé oxalique ou malonique ou un mélange de ces deux acides ;
    c. 2 à 5 g de nitrate d'ammonium ;
    d. 0,1 à 5,0 g de cuivre, additionné en un composé qui forme dans la solution de traitement des ions Cu+ ou Cu2+.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on ajoute comme composés formant dans la solution de traitement des ions Cu+ ou Cu2+, un ou plusieurs oxydes de cuivre(I) ou de cuivre (II), ou du nitrate de cuivre.
  3. Procédé selon la revendication 1, caractérisé en ce que l'alliage de zinc et titane est un composé conforme à la norme européenne EN 988 sur le zinc dans la construction.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le traitement est effectué à une température de bain comprise entre 20 et 55°C.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la valeur pH de la solution de traitement est comprise entre pH 1,0 et pH 4,0.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la durée du traitement est comprise entre 15 secondes et 15 minutes.
  7. Demi-produit plat laminé, réalisé en un alliage de zinc et titane et recouvert d'une couche de protection de couleur grise, ladite couche étant élaborée selon un procédé conforme aux revendications 1 à 6.
  8. Demi-produit selon la revendication 7, caractérisé en ce que l'épaisseur de la couche de protection est comprise entre 0,1 et 1 0 µm.
EP20110005194 2010-06-30 2011-06-27 Procédé de fabrication d'une couche de protection sur des produits plats en zinc de titane Not-in-force EP2402484B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE201010025707 DE102010025707A1 (de) 2010-06-30 2010-06-30 Verfahren zur Herstellung von Schutzschichten auf Flacherzeugnissen aus Titanzink

Publications (2)

Publication Number Publication Date
EP2402484A1 EP2402484A1 (fr) 2012-01-04
EP2402484B1 true EP2402484B1 (fr) 2012-10-24

Family

ID=44587594

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20110005194 Not-in-force EP2402484B1 (fr) 2010-06-30 2011-06-27 Procédé de fabrication d'une couche de protection sur des produits plats en zinc de titane

Country Status (3)

Country Link
EP (1) EP2402484B1 (fr)
DE (1) DE102010025707A1 (fr)
ES (1) ES2395005T3 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103849868A (zh) * 2014-02-14 2014-06-11 浙江工业大学 一种钛锌板表面无铬发黑处理液及使用方法
CN103849866A (zh) * 2014-02-14 2014-06-11 浙江工业大学 一种钛锌板表面灰色保护层及制备方法
CN114000132A (zh) * 2021-10-28 2022-02-01 苏州市祥冠合金研究院有限公司 一种锌合金表面灰色保护层及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT143280B (de) * 1930-08-21 1935-10-25 Metal Finishing Res Corp Verfahren zur Herstellung von Schutzschichten auf Metallgegenständen.
US1954744A (en) * 1932-06-07 1934-04-10 Delaney Chemical Company Method and solution for treating metal surfaces
NL120662C (fr) 1962-01-26
US3767478A (en) * 1971-09-14 1973-10-23 Ball Corp Method for producing patina on a zinc surface and article so formed
DE2757592C2 (de) 1977-12-23 1985-03-28 Rheinzink GmbH, 4354 Datteln Verfahren zur Herstellung von Deckschichten auf aus Zink-Kupfer-Titan-Legierungen bestehenden Formkörpern
ATA143280A (de) 1980-03-17 1981-03-15 Eumig Filmvorratsanzeiger
JP2668555B2 (ja) * 1988-06-30 1997-10-27 日本ペイント株式会社 化成処理剤及び化成処理浴
DE19636370B4 (de) * 1996-09-09 2005-04-14 Rheinzink Gmbh Verfahren zur Herstellung von Schutzschichten auf Flacherzeugnissen aus Titanzink und Flacherzeugnis
FR2803855B1 (fr) * 2000-01-13 2002-05-31 Usinor Procede d'oxalatation de la surface zinguee d'une tole

Also Published As

Publication number Publication date
ES2395005T3 (es) 2013-02-07
EP2402484A1 (fr) 2012-01-04
DE102010025707A1 (de) 2012-01-05

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