EP1444381B1 - 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
EP1444381B1
EP1444381B1 EP20020787688 EP02787688A EP1444381B1 EP 1444381 B1 EP1444381 B1 EP 1444381B1 EP 20020787688 EP20020787688 EP 20020787688 EP 02787688 A EP02787688 A EP 02787688A EP 1444381 B1 EP1444381 B1 EP 1444381B1
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Prior art keywords
zinc
weight
titanium
content
alloy
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EP20020787688
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German (de)
French (fr)
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EP1444381B2 (en
EP1444381A1 (en
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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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    • 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 preparation of Protective layers of dark hue by pickling rolled Flat products of titanium-zinc alloys for use in construction, with the flat products in one aqueous Beigeabt with sulfuric acid and nitric acid containing Stained mixed acid and after rinsing under formation a protective layer passivated.
  • the invention also refers to protective coatings Surface products.
  • Patina is in particular made of zinc carbonate Copper traces.
  • the obtained matte black color allows that such patinated building materials in particular harmonious in Insert roofing with black pans or shingles let or, where contrasts are desired, itself a clear gradation black and white results.
  • a salary of preferably 1.1 to 1.4% by weight of copper in the alloy sufficient.
  • titanium-zinc alloy related to the 0.06 to 0.2% by weight of titanium and max. Contains 0.015 wt .-% aluminum.
  • a copper content of more than 1.0% by weight up to 2.0% by weight, preferably from 1.1 to 1.3% by weight of Cu, intended.
  • the majority of the alloy is zinc, So depending on the content of the alloying elements titanium, aluminum and copper about 97.7 to 98.9 wt% zinc of the purity step 99.995% by weight.
  • Strip of 0.8 mm thickness and 600 mm width is by rinsing with an alkaline degreasing solution a temperature of approx. 60 ° C and a rinsing pressure of approx. Degreased 2.5 bar and then with a water spray with a temperature of about 65 ° C and a pressure hosed from about 2.5 bar.
  • 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 approx. 30 ...
  • the rate of the pickling reaction is essentially depending on the content of free acid.
  • the reduction of Nitric acid is the dominant reaction and prevents a hydrogen evolution.
  • Another influence on the pickling result exerts the ratio of the acid contents.
  • a mixed acid with 2 ... 10 vol .-% Sulfuric acid and 2 ... 10% by volume of nitric acid, the mixing ratio of sulfuric acid: nitric acid is less than or equal to 3: 1, and the content of free Acid is 25 to 100 g / l.
  • a polymer dispersion for example, a Mixture of styrene-acrylate, aliphatic polyester and polyurethane Understood.
  • 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 1.0 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 Vapour Deposition (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (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 Beigabt 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 preparation of Protective layers of dark hue by pickling rolled Flat products of titanium-zinc alloys for use in construction, with the flat products in one aqueous Beigeabt with sulfuric acid and nitric acid containing Stained mixed acid and after rinsing under formation a protective layer passivated. The invention also refers to protective coatings Surface products.

Ein solches Verfahren ist aus der DE 196 36 370 A1 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 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 known from DE 196 36 370 A1 of the applicant, the contents of which are fully incorporated herein by reference becomes known. With the disclosed there treatment of titanium zinc sheets from a titanium-zinc alloy with 0.07 to 0.12% by weight of titanium, up to 0.015% by weight of aluminum, 0.08 to 0.17 wt .-% copper and the remainder of 99.995 percent zinc become homogeneous, gray protective layers on the surface obtained the titanium zinc sheets, wherein the gray color in aesthetically perceived as particularly advantageous because it corresponds to the natural patina of zinc. The alloy disclosed in DE 196 36 370 A1 corresponds in their composition the criteria of a "Quality Zinc "catalog of TÜV product and environment GmbH, Institute for environmental protection and energy technology, At the gray stone, 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 shown that with the known method a darker coloration of the sheets, which in some cases is desired, only slightly by use more concentrated acids can be achieved. Here The problem arises that with increasing strength of the Acids, i. lower pH of the pickling bath, the substance the alloy is attacked and the metal thickness decreases. In particular, the use of a very leads low pH of the mixed acid to an undesirable Layer structure on the surface, since poorly adhering Form layers of so-called pickling sludge. Thus are an even stronger darkening of titanium zinc sheets with the known method limits. Desired however, for the construction industry also very dark colored surface layers, especially in the area of roofing and facade cladding the contrast of the pre-weathered Zinc sheets to other building materials used there, for example black slate shingles or roof tiles, low or just a strong contrast to to cause 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 of titanium zinc by phosphating (see DIN 50 942). As a result, however, the metallic surface structure undesirably changed when the surface should not 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 the task of a method of the beginning so mentioned that titan zinc plates with a very dark to black coloring of Surface can be produced, the natural Structure of the metal surface should be preserved.

Diese Aufgabe wird dadurch gelöst, dass entgegen der eingangs genannten Legierungsvorschrift eine Titan-Zink-Legierung mit einem erhöhten Kupfergehalt von 1,0 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 beginning mentioned alloying rule a titanium-zinc alloy with an increased copper content of 1.0 to 2.0 Wt .-% is used, but the aforementioned proportions Contains 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 in connection with the known further alloying components and treatment procedure a darker Patina obtained when using alloys with usual, low copper content. According to previous findings the patina is in particular made of zinc carbonate 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 obtained matte black color allows that such patinated building materials in particular harmonious in Insert roofing with black pans or shingles let or, where contrasts are desired, itself a clear gradation black and white results. Already a salary of preferably 1.1 to 1.4% by weight of copper in the alloy sufficient. The inventive method is explained in more detail below by 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 über 1,0 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, related to the 0.06 to 0.2% by weight of titanium and max. Contains 0.015 wt .-% aluminum. According to the invention, a copper content of more than 1.0% by weight up to 2.0% by weight, preferably from 1.1 to 1.3% by weight of Cu, intended. The majority of the alloy is zinc, So depending on the content of the alloying elements titanium, aluminum and copper about 97.7 to 98.9 wt% zinc of the purity step 99.995% by weight.

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 of a zinc alloy with increased copper content Strip of 0.8 mm thickness and 600 mm width is by rinsing with an alkaline degreasing solution a temperature of approx. 60 ° C and a rinsing pressure of approx. Degreased 2.5 bar and then with a water spray with a temperature of about 65 ° C and a pressure hosed from about 2.5 bar. To support the rinsing process and the surface roughening is in the last Rinse the tape brushed. Subsequently, the tape 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 approx. 30 ... 60 g / l sulfuric acid and approx. 20 ... 50 g / l nitric acid in water. In addition, 25 ... 80 g / l, preferably about 50 g / l, zinc ions dissolved present.

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 depending on the content of free acid. The reduction of Nitric acid is the dominant reaction and prevents a hydrogen evolution. Another influence on the pickling result exerts the ratio of the 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% by volume of nitric acid, the mixing ratio of sulfuric acid: nitric acid is less than or equal to 3: 1, and the content of free Acid is 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 emerging from the pickling band is as described above rinsed. Subsequently, preferably another Protective layer by applying and drying chromate-containing Polymer dispersions produced 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 tape by means of Rolling a mixture of 65 ... 98 vol .-%, preferably 95 Vol .-%, polymer dispersion and 2 ... 35 vol .-%, preferably 5 vol .-%, applied aqueous chromate solution. this contract is dried at about 80-120 ° C. The layer thickness of the film produced in the dried state of about 0.4 to 3.0 μm, preferably 1.5 μm.

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

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 1,0 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 1.0 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 1.0 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)

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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 true EP1444381B1 (en) 2005-01-12
EP1444381B2 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)
HK (1) HK1072785A1 (en)
WO (1) WO2003048417A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) * 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
WO2008131585A1 (en) * 2007-04-27 2008-11-06 Shine Metal Hot-Galvanization Enterprise A method for hot dip galvanizing and the product obtained therefrom
US8831575B2 (en) * 2007-09-26 2014-09-09 Qualcomm Incorporated Apparatus and methods associated with open market handsets
US20090082004A1 (en) * 2007-09-26 2009-03-26 Qualcomm Incorporated Apparatus and methods of open market handset identification
US8442507B2 (en) * 2007-09-26 2013-05-14 Qualcomm Incorporated Methods and apparatus for dynamic source determination of provisioning information on a per-network service basis for open market wireless devices
CN103849868A (en) * 2014-02-14 2014-06-11 浙江工业大学 Blackening liquid for chromium-free titanium-zinc panel surface and using method of blackening liquid
EP3211113A1 (en) * 2016-02-25 2017-08-30 Rautaruukki Oyj Galvanized product & method
CN114000136A (en) * 2021-10-28 2022-02-01 苏州市祥冠合金研究院有限公司 Preparation method of zinc alloy surface coating
CN115433932B (en) * 2022-08-29 2023-09-12 武汉大学 Pure titanium surface gradient micro-nano TiZn 3 -TiZn X Composite coating and preparation method thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2510985A1 (en) * 1975-03-13 1976-09-23 Rheinisches Zinkwalzwerk Gmbh PROCESS FOR MANUFACTURING DEEP-DRAWABLE SHEET METALS AND STRIPS FROM A DURABLE AND FOLDABLE ZINC-COPPER-TITANIUM ROLLED ALLOY
DE2757592C2 (en) * 1977-12-23 1985-03-28 Rheinzink GmbH, 4354 Datteln Process for the production of cover layers on molded bodies made of zinc-copper-titanium alloys
DE3311334A1 (en) * 1983-03-29 1984-10-04 Rheinzink GmbH, 4354 Datteln Device for improving the corrosion resistance of components for roof-drainage systems
US5160552A (en) * 1986-11-21 1992-11-03 Nippon Mining Co., Ltd. Colored zinc coating
DE3718829A1 (en) * 1987-06-05 1988-12-15 Metallgesellschaft Ag APPLICATION OF ELECTRODIALYSIS FOR THE REGENERATION OF ACID SOLUTIONS
DE4446771A1 (en) * 1994-12-24 1996-06-27 Rheinzink Gmbh Alloy zinc strips and sheets
DE19545487A1 (en) * 1995-12-06 1997-06-12 Rheinzink Gmbh Alloy zinc strips and sheets
DE19636370B4 (en) * 1996-09-09 2005-04-14 Rheinzink Gmbh Process for the production of protective coatings on flat products of titanium zinc and flat products
DE10014519A1 (en) * 2000-03-23 2001-10-11 Rheinzink Gmbh Use of pipes made of titanium zinc according to EN 988 and bending processes for the production of pipe bends

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WO2003048417A1 (en) 2003-06-12
CN1585834A (en) 2005-02-23
DE10156475A1 (en) 2003-06-05
ES2236604T3 (en) 2005-07-16
AU2002352012A1 (en) 2003-06-17
US20050003091A1 (en) 2005-01-06
DE50202024D1 (en) 2005-02-17
ES2236604T5 (en) 2009-03-01
ATE286993T1 (en) 2005-01-15
HK1072785A1 (en) 2005-09-09
JP2005511896A (en) 2005-04-28
US6916546B2 (en) 2005-07-12
EP1444381B2 (en) 2008-09-10
EP1444381A1 (en) 2004-08-11
CN100374621C (en) 2008-03-12

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