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EP1444381B2 - Method for the production of dark protective layers on flat objects made from titanium zinc - Google Patents

Method for the production of dark protective layers on flat objects made from titanium zinc Download PDF

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Publication number
EP1444381B2
EP1444381B2 EP02787688A EP02787688A EP1444381B2 EP 1444381 B2 EP1444381 B2 EP 1444381B2 EP 02787688 A EP02787688 A EP 02787688A EP 02787688 A EP02787688 A EP 02787688A EP 1444381 B2 EP1444381 B2 EP 1444381B2
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EP
European Patent Office
Prior art keywords
zinc
titanium
weight
content
alloy
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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.)
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EP02787688A
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German (de)
French (fr)
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EP1444381A1 (en
EP1444381B1 (en
Inventor
Marianne SCHÖNNENBECK
Adolf Stradmann
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Rheinzink GmbH and Co KG
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Rheinzink GmbH and Co KG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the invention relates to a process for the production of protective coatings of dark hue by pickling rolled flat products of titanium-zinc alloys for use in construction, wherein the flat products pickled in an aqueous pickling bath with mixed acid containing sulfuric acid and nitric acid and passivated after rinsing to form a protective layer become.
  • the invention also relates to protective products provided with protective layers.
  • very dark colored surface layers are desired for the construction industry, in particular in the area of roof coverings and façade coverings to keep the contrast of the pre-weathered zinc sheets to other building materials used there, for example black slate shingles or roof tiles, or to create a strong contrast to white surfaces.
  • a titanium-zinc alloy is used with an increased copper content of 1.1 to 2.0 wt .-%, but containing the aforementioned proportions of titanium and aluminum.
  • the patina consists in particular of zinc carbonate with copper traces.
  • the resulting matte black coloration allows such patinated building materials to be particularly harmoniously inserted into roofing with black pans or shingles or where contrasts are desired, resulting in a clear gradation black and white. Even a content of preferably 1.1 to 1.4 wt .-% copper in the alloy is sufficient.
  • the majority of the alloy consists of zinc, ie, depending on the content of the alloying elements titanium, aluminum and copper about 97.7 to 98.9 wt .-% zinc of purity level 99.995 wt .-%.
  • An existing from a zinc alloy with increased copper content band of 0.8 mm thickness and 600 mm width is degreased by rinsing with an alkaline degreasing solution at a temperature of about 60 ° C and a rinsing pressure of about 2.5 bar and then with a Water spray sprayed with a temperature of about 65 ° C and a pressure of about 2.5 bar.
  • the strip is brushed in the final rinse step.
  • the strip is in a pickling plant with a pickling bath temperature of 30 ... 80 ° C, preferably about 50 ° C, pickled.
  • the pickling bath contains a mixed acid of about 30 ... 60 g / l sulfuric acid and about 20 ... 50 g / l nitric acid in water.
  • 25 to 80 g / l, preferably about 50 g / l, zinc ions are present dissolved.
  • the rate of the pickling reaction is essentially dependent on the free acid content.
  • the reduction of nitric acid is the dominant reaction and prevents hydrogen evolution.
  • Another influence on the Beizzle results in the ratio of acid contents.
  • a mixed acid with 2 ... 10 vol .-% sulfuric acid and 2 ... 10 vol .-% nitric acid is used, wherein the mixing ratio of sulfuric acid: nitric acid is less than or equal to 3: 1, and the free acid content of 25 to 100 g / l.
  • a further protective layer is preferably produced by applying and drying chromate-containing polymer dispersions as follows.
  • a polymer dispersion is understood as meaning, for example, a mixture of styrene-acrylate, aliphatic polyester and polyurethane.
  • the method of the invention thus obtains a titanium-zinc alloy flat product containing mainly zinc of high purity and, in addition, a copper content of 1.1 to 2.0% by weight, a titanium content of 0.07 to 0, 12 wt .-% and an aluminum content of not more than 0.015 wt .-% and has a dull black patina.
  • the latter is preferably coated with a protective layer having a thickness of 0.4-3.0 ⁇ m, which in the exemplary embodiment was obtained after application and drying of a chromate-containing polymer dispersion; Accordingly, the basis weight of the overlay is 5 ... 40 mg / m 2 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention relates to the production of protective coatings with a dark color by pickling rolled flat objects, made from titanium zinc, for use in construction. The flat objects are pickled in an aqueous pickling bath containing a mixed acid of sulphuric acid and nitric acid and passivated after rinsing by application of a protective layer. Rolled flat objects such as those made from a titanium zinc alloy are used. The alloy comprises mainly zinc of high purity with additionally a copper content of 1.0 to 2.0 wt. %, a titanium content of 0.06 to 0.2 wt. % and a maximum aluminum contant of 0.015 wt. %.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Schutzschichten dunkler Farbtönung durch Beizen von gewalzten Flacherzeugnissen aus Titan-Zink-Legierungen zur Verwendung im Bauwesen, wobei die Flacherzeugnisse in einem wäßrigen Beizbad mit Schwefelsäure und Salpetersäure enthaltender Mischsäure gebeizt und nach dem Spülen unter Bildung einer Schutzschicht passiviert werden. Die Erfindung bezieht sich außerdem auf mit Schutzschichten versehene Flächenerzeugnisse.The invention relates to a process for the production of protective coatings of dark hue by pickling rolled flat products of titanium-zinc alloys for use in construction, wherein the flat products pickled in an aqueous pickling bath with mixed acid containing sulfuric acid and nitric acid and passivated after rinsing to form a protective layer become. The invention also relates to protective products provided with protective layers.

Ein solches Verfahren ist aus der DE 196 36 370 A1 bzw. EP 827785 A2 der Anmelderin, auf deren Inhalt hier vollständig Bezug genommen wird, bekannt. Mit der dort offenbarten Behandlung von Titanzinkblechen aus einer Titan-Zink-Legierung mit 0,07 bis 0,12 Gew.-% Titan, bis zu 0,015 Gew.-% Aluminium, 0,08 bis 0,17 Gew.-% Kupfer bzw. 0,08 bis 1,0 Gew.-% gemäß EP 827785 A2 und dem Rest aus 99,995-prozentigem Zink werden homogene, graue Schutzschichten auf der Oberfläche der Titanzinkbleche erhalten, wobei die graue Färbung in ästhetischer Hinsicht als besonders vorteilhaft empfunden wird, da sie der natürlichen Patina von Zink entspricht. Die in der DE 196 36 370 A1 offenbarte Legierung entspricht in ihrer Zusammensetzung den Kriterien eines "Quality Zinc"-Kataloges der TÜV Produkt und Umwelt GmbH, Institut für Umweltschutz und Energietechnik, Am grauen Stein, 51105 Köln.Such a method is from the DE 196 36 370 A1 respectively. EP 827785 A2 the applicant, the content of which is fully incorporated herein by reference. With the disclosed therein treatment of titanium zinc plates from a titanium-zinc alloy with 0.07 to 0.12 wt .-% titanium, up to 0.015 wt .-% aluminum, 0.08 to 0.17 wt .-% copper or 0.08 to 1.0% by weight according to EP 827785 A2 and the remainder of 99.995% zinc, homogeneous, gray protective layers are obtained on the surface of the titanium zinc sheets, the gray coloration being aesthetically particularly advantageous since it corresponds to the natural patina of zinc. The in the DE 196 36 370 A1 In its composition, the alloy disclosed meets the criteria of a "Quality Zinc" catalog of TÜV Product and Environment GmbH, Institute for Environmental Protection and Energy Technology, Am grau Stein, 51105 Cologne.

Es hat sich jedoch gezeigt, dass mit dem bekannten Verfahren eine dunklere Färbung der Bleche, die in manchen Fällen erwünscht ist, nur geringfügig und zwar durch Verwendung stärker konzentrierter Säuren erreicht werden kann. Hier ergibt sich das Problem, dass mit zunehmender Stärke der Säuren, d.h. niedrigerem pH-Wert des Beizbades, die Substanz der Legierung angegriffen wird und die Metalldicke sich verringert. Insbesondere führt der Einsatz eines sehr niedrigen pH-Wertes der Mischsäure zu einem unerwünschten Schichtaufbau auf der Oberfläche, da sich schlecht haftende Schichten von sogenanntem Beizschlamm bilden. Somit sind einer noch stärkeren Dunkelfärbung von Titanzinkblechen mit dem bekannten Verfahren Grenzen gesetzt. Gewünscht werden jedoch für das Bauwesen auch sehr dunkel gefärbte Oberflächenschichten, um insbesondere im Bereich der Dacheindeckungen und Fassadenabdeckungen den Kontrast der vorbewitterten Zinkbleche zu anderen dort verwendeten Baustoffen, beispielsweise schwarzen Schieferschindeln oder Dachpfannen, gering zu halten oder gerade einen starken Kontrast zu weißen Oberflächen hervorzurufen.However, it has been found that with the known method, a darker coloration of the sheets, which is desired in some cases, can be achieved only slightly by using more concentrated acids. Here there is the problem that with increasing strength of the acids, i. lower pH of the pickle bath, the substance of the alloy is attacked and the metal thickness decreases. In particular, the use of a very low pH of the mixed acid leads to an undesirable layer structure on the surface, since poorly adhering layers of so-called pickling sludge form. Thus, an even stronger darkening of titanium zinc sheets with the known method limits. However, very dark colored surface layers are desired for the construction industry, in particular in the area of roof coverings and façade coverings to keep the contrast of the pre-weathered zinc sheets to other building materials used there, for example black slate shingles or roof tiles, or to create a strong contrast to white surfaces.

Bekannt sind auch Verfahren zur Herstellung einer dunklen Oberfläche bei Titanzink durch Phosphatierung (vergl. DIN 50 942). Hierdurch wird jedoch die metallische Oberflächenstruktur in unerwünschter Weise verändert, wenn die Oberfläche nicht weiter mit Lacken beschichtet werden soll.Also known are methods for producing a dark surface in titanium zinc by phosphating (see DIN 50 942). As a result, however, the metallic surface structure is undesirably changed when the surface is not to be further coated with paints.

Es stellt sich daher die Aufgabe, ein Verfahren der eingangs genannten Art so weiter zu entwickeln, dass Titanzinkbleche mit einer sehr dunklen bis schwarzen Färbung der Oberfläche hergestellt werden können, wobei die natürliche Struktur der Metalloberfläche erhalten bleiben soll.It is therefore an object to develop a method of the type mentioned so that titanium zinc sheets can be produced with a very dark to black coloration of the surface, while the natural structure of the metal surface is to be preserved.

Diese Aufgabe wird dadurch gelöst, dass entgegen der eingangs genannten Legierungsvorschrift eine Titan-Zink-Legierung mit einem erhöhten Kupfergehalt von 1,1 bis 2,0 Gew.-% verwendet wird, die jedoch die vorgenannten Anteile an Titan und Aluminium enthält.This object is achieved in that contrary to the aforementioned alloy specification, a titanium-zinc alloy is used with an increased copper content of 1.1 to 2.0 wt .-%, but containing the aforementioned proportions of titanium and aluminum.

Überraschenderweise wird mit diesem erhöhten Kupfergehalt im Zusammenhang mit dem an sich bekannten weiteren Legierungsbestandteilen und Behandlungsverfahren eine dunklere Patina erhalten als bei der Verwendung von Legierungen mit üblichem, niedrigem Kupfergehalt. Nach bisherigen Erkenntnissen besteht die Patina insbesondere aus Zinkcarbonat mit Kupfer-Spuren.Surprisingly, with this increased copper content, a darker patina is obtained in connection with the other alloying constituents and treatment processes known per se than with the use of alloys of conventional, low copper content. According to previous findings, the patina consists in particular of zinc carbonate with copper traces.

Die erhaltene mattschwarze Färbung erlaubt es, dass sich derartig patinierte Baustoffe insbesondere harmonisch in Dacheindeckungen mit schwarzen Pfannen oder Schindeln einfügen lassen oder dort, wo Kontraste erwünscht sind, sich eine deutliche Abstufung schwarz-weiß ergibt. Schon ein Gehalt von vorzugsweise 1,1 bis 1,4 Gew.-% Kupfer in der Legierung reicht aus. Das erfindungsgemäße Verfahren wird nachstehend durch ein Ausführungsbeispiel näher erläutert:The resulting matte black coloration allows such patinated building materials to be particularly harmoniously inserted into roofing with black pans or shingles or where contrasts are desired, resulting in a clear gradation black and white. Even a content of preferably 1.1 to 1.4 wt .-% copper in the alloy is sufficient. The method according to the invention is explained in more detail below by means of an exemplary embodiment:

Es wird eine Titan-Zink-Legierung, verwandt, die 0,06 bis 0,2 Gew.-% Titan und max. 0,015 Gew.-% Aluminium enthält. Erfindungsgemäß wird ein Kupfergehalt von 1,1 Gew.-% bis zu 2,0 Gew.-%, vorzugsweise von 1,1 bis 1,3 Gew.-% Cu, vorgesehen. Der Hauptanteil der Legierung besteht aus Zink, also je nach Gehalt der Legierungselemente Titan, Aluminium und Kupfer etwa 97,7 bis 98,9 Gew.-% Zink der Reinheitsstufe 99,995 Gew.-%.It is a titanium-zinc alloy, used, the 0.06 to 0.2 wt .-% titanium and max. Contains 0.015 wt .-% aluminum. According to the invention, a copper content of 1.1 wt .-% up to 2.0 wt .-%, preferably from 1.1 to 1.3 wt .-% Cu, provided. The majority of the alloy consists of zinc, ie, depending on the content of the alloying elements titanium, aluminum and copper about 97.7 to 98.9 wt .-% zinc of purity level 99.995 wt .-%.

Ein aus einer Zinklegierung mit erhöhtem Kupfergehalt bestehendes Band von 0,8 mm Dicke und 600 mm Breite wird durch Spülen mit einer alkalischen Entfettungslösung bei einer Temperatur von ca. 60°C und einem Spüldruck von ca. 2,5 bar entfettet und anschließend mit einem Wassersprühstrahl mit einer Temperatur von ca. 65°C und einem Druck von ca. 2,5 bar abgespritzt. Zur Unterstützung des Spülvorgangs und zur Oberflächenaufrauung wird in der letzten Spülstufe das Band gebürstet. Anschließend wird das Band in einer Beizanlage mit einer Beizbadtemperatur von 30 ... 80°C, vorzugsweise ca. 50 °C, gebeizt. Das Beizbad enthält eine Mischsäure aus ca. 30 ... 60 g/l Schwefelsäure und ca. 20 ... 50 g/l Salpetersäure in Wasser. Zusätzlich sind 25 ... 80 g/l, vorzugsweise ca. 50 g/l, Zink-Ionen gelöst vorhanden.An existing from a zinc alloy with increased copper content band of 0.8 mm thickness and 600 mm width is degreased by rinsing with an alkaline degreasing solution at a temperature of about 60 ° C and a rinsing pressure of about 2.5 bar and then with a Water spray sprayed with a temperature of about 65 ° C and a pressure of about 2.5 bar. To assist the rinse and surface roughening, the strip is brushed in the final rinse step. Subsequently, the strip is in a pickling plant with a pickling bath temperature of 30 ... 80 ° C, preferably about 50 ° C, pickled. The pickling bath contains a mixed acid of about 30 ... 60 g / l sulfuric acid and about 20 ... 50 g / l nitric acid in water. In addition, 25 to 80 g / l, preferably about 50 g / l, zinc ions are present dissolved.

Die Geschwindigkeit der Beizreaktion ist im wesentlichen abhängig von dem Gehalt an freier Säure. Die Reduktion der Salpetersäure ist die dominierende Reaktion und verhindert eine Wasserstoff-Entwicklung. Einen weiteren Einfluss auf das Beizergebnis übt das Verhältnis der Säuregehalte aus.The rate of the pickling reaction is essentially dependent on the free acid content. The reduction of nitric acid is the dominant reaction and prevents hydrogen evolution. Another influence on the Beizzle results in the ratio of acid contents.

Vorzugsweise wird eine Mischsäure mit 2 ... 10 Vol.-% Schwefelsäure und 2 ... 10 Vol.-% Salpetersäure verwandt, wobei das Mischungsverhältnis von Schwefelsäure : Salpetersäure kleiner oder gleich 3:1 ist, und der Gehalt an freier Säure 25 bis 100 g/l beträgt.Preferably, a mixed acid with 2 ... 10 vol .-% sulfuric acid and 2 ... 10 vol .-% nitric acid is used, wherein the mixing ratio of sulfuric acid: nitric acid is less than or equal to 3: 1, and the free acid content of 25 to 100 g / l.

Das aus der Beizanlage austretende Band wird wie oben beschrieben gespült. Anschließend wird vorzugsweise eine weitere Schutzschicht durch Auftragen und Trocknen von chromathaltigen Polymerdispersionen wie folgt erzeugt.The strip leaving the pickling line is rinsed as described above. Subsequently, a further protective layer is preferably produced by applying and drying chromate-containing polymer dispersions as follows.

Nach Entfernung des Restwassers wird auf das Band mittels Walzen ein Gemisch aus 65 ... 98 Vol.-%, vorzugsweise 95 Vol.-%, Polymerdispersion und 2 ... 35 Vol.-%, vorzugsweise 5 Vol.-%, wässrige Chromatlösung aufgebracht. Dieser Auftrag wird bei ca. 80 - 120 °C getrocknet. Die Schichtdicke des erzeugten Films beträgt im getrockneten Zustand ca. von 0,4 bis 3,0 µm, vorzugsweise 1,5 µm.After removal of the residual water is on the belt by rolling a mixture of 65 ... 98 vol .-%, preferably 95 vol .-%, polymer dispersion and 2 ... 35 vol .-%, preferably 5 vol .-%, aqueous Applied chromate solution. This job is dried at about 80-120 ° C. The layer thickness of the film produced in the dried state is about 0.4 to 3.0 microns, preferably 1.5 microns.

Dabei wird unter einer Polymerdispersion beispielsweise ein Gemisch aus Styrol-Acrylat, aliphatischem Polyester und Polyurethan verstanden.In this case, a polymer dispersion is understood as meaning, for example, a mixture of styrene-acrylate, aliphatic polyester and polyurethane.

Bevorzugt wird mit dem Verfahren der Erfindung so ein Flacherzeugnis aus einer Titan-Zink-Legierung erhalten, die hauptsächlich Zink hoher Reinheitsstufe und daneben einen Kupfergehalt von 1,1 bis 2,0 Gew.-%, einen Titangehalt von 0,07 bis 0,12 Gew.-% und einen Aluminium-Gehalt von maximal 0,015 Gew.-% aufweist und eine mattschwarze Patina besitzt. Letztere ist vorzugsweise mit einer Schutzschicht mit einer Dicke von 0,4 - 3,0 µm überzogen, die im Ausführungsbeispiel nach Auftragen und Trocknen einer chromathaltigen Polymerdispersion erhalten wurde; entsprechend beträgt das Flächengewicht der Auflage 5 ... 40 mg/m2.Preferably, the method of the invention thus obtains a titanium-zinc alloy flat product containing mainly zinc of high purity and, in addition, a copper content of 1.1 to 2.0% by weight, a titanium content of 0.07 to 0, 12 wt .-% and an aluminum content of not more than 0.015 wt .-% and has a dull black patina. The latter is preferably coated with a protective layer having a thickness of 0.4-3.0 μm, which in the exemplary embodiment was obtained after application and drying of a chromate-containing polymer dispersion; Accordingly, the basis weight of the overlay is 5 ... 40 mg / m 2 .

Claims (7)

  1. A process for the production of protective coatings of dark coloration by pickling rolled flat products consisting of titanium zinc, for use in building construction, the flat products being pickled in an aqueous pickling bath with mixed acid containing sulphuric acid and nitric acid, and being passivated by the application of a protective coating after rinsing, characterised in that use is made of rolled flat products consisting of a titanium zinc alloy, which alloy comprises mainly zinc of a high degree of purity and in addition a copper content of 1.1 to 2.0% by weight, a titanium content of 0.06 to 0.2% by weight and an aluminium content of maximum 0.015% by weight.
  2. A process according to claim 1, characterised in that the copper content is between 1.1 and 1.4% by weight.
  3. A process according to claim 1 or 2, characterised in that the degree of purity of the zinc is 99.995% by weight in the alloy.
  4. A process according to claims 1 to 3, characterised in that in addition to water the pickling bath contains 30 to 60 g/l sulphuric acid (H2SO4) and 20 to 50 g/l nitric acid (HNO3).
  5. A process according to any one of the preceding claims, characterised in that another protective coating is produced by the application and drying of a chromate-containing polymer dispersion.
  6. A flat product consisting of a titanium zinc alloy which consists mainly of zinc of a high degree of purity and in addition a copper content of 1.1 to 2.0% by weight, a titanium content of 0.07 to 0.12% by weight and an aluminium content of maximum 0.015% by weight and is pickled in a pickling bath with sulphuric acid and nitric acid and is passivated with a dark protective coating.
  7. A flat product according to claim 6, characterised in that the passivating protective coating is covered by another protective coating by the application and drying of a chromate-containing polymer dispersion.
EP02787688A 2001-11-16 2002-11-15 Method for the production of dark protective layers on flat objects made from titanium zinc Expired - Lifetime EP1444381B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK02787688T DK1444381T4 (en) 2001-11-16 2002-11-15 Process for the preparation of dark protective layers on titanium zinc surface products

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10156475 2001-11-16
DE10156475A DE10156475A1 (en) 2001-11-16 2001-11-16 Process for the production of dark protective layers on flat products made of titanium zinc
PCT/EP2002/012800 WO2003048417A1 (en) 2001-11-16 2002-11-15 Method for the production of dark protective layers on flat objects made from titanium zinc

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EP1444381A1 EP1444381A1 (en) 2004-08-11
EP1444381B1 EP1444381B1 (en) 2005-01-12
EP1444381B2 true EP1444381B2 (en) 2008-09-10

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US (1) US6916546B2 (en)
EP (1) EP1444381B2 (en)
JP (1) JP2005511896A (en)
CN (1) CN100374621C (en)
AT (1) ATE286993T1 (en)
AU (1) AU2002352012A1 (en)
DE (2) DE10156475A1 (en)
ES (1) ES2236604T5 (en)
WO (1) WO2003048417A1 (en)

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ES2236604T5 (en) 2009-03-01
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CN100374621C (en) 2008-03-12
ATE286993T1 (en) 2005-01-15
EP1444381B1 (en) 2005-01-12
JP2005511896A (en) 2005-04-28
WO2003048417A1 (en) 2003-06-12
DE10156475A1 (en) 2003-06-05
CN1585834A (en) 2005-02-23
US6916546B2 (en) 2005-07-12
US20050003091A1 (en) 2005-01-06
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HK1072785A1 (en) 2005-09-09
AU2002352012A1 (en) 2003-06-17

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