EP1444381A1 - 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

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Publication number
EP1444381A1
EP1444381A1 EP02787688A EP02787688A EP1444381A1 EP 1444381 A1 EP1444381 A1 EP 1444381A1 EP 02787688 A EP02787688 A EP 02787688A EP 02787688 A EP02787688 A EP 02787688A EP 1444381 A1 EP1444381 A1 EP 1444381A1
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EP
European Patent Office
Prior art keywords
zinc
titanium
weight
content
protective layer
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
EP02787688A
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German (de)
French (fr)
Other versions
EP1444381B1 (en
EP1444381B2 (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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Application filed by Rheinzink GmbH and Co KG filed Critical Rheinzink GmbH and Co KG
Priority to DK02787688T priority Critical patent/DK1444381T4/en
Publication of EP1444381A1 publication Critical patent/EP1444381A1/en
Publication of EP1444381B1 publication Critical patent/EP1444381B1/en
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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 method for producing protective layers of dark color tint by pickling rolled flat products made of titanium-zinc alloys for use in construction, the flat products being pickled in an aqueous additive containing mixed acid containing sulfuric acid and nitric acid and after rinsing to form a Protective layer can be passivated.
  • the invention also relates to surface products provided with protective layers.
  • the alloy disclosed in DE 196 36 370 AI corresponds in their composition the criteria of a "Quality Zinc” catalog from TÜV Arts und reactor GmbH, Institute for Environmental Protection and Energy Technology, Am grau Stein, 51105 Cologne.
  • very dark colored surface layers are desired for the construction industry, in order to keep the contrast of the pre-weathered zinc sheets to other building materials used there, for example black slate shingles or roof tiles, low or to provide a strong contrast, especially in the area of roof coverings and facade covers white surfaces.
  • the patina consists in particular of zinc carbonate with traces of copper.
  • the matt black color obtained allows building materials patinated in this way to be inserted particularly harmoniously into roof coverings with black pans or shingles or, where contrasts are desired, there is a clear gradation in black and white.
  • a content of preferably 1.1 to 1.4% by weight of copper in the alloy is sufficient.
  • a titanium-zinc alloy is used, the 0.06 to 0.2 wt .-% titanium and max. Contains 0.015 wt .-% aluminum.
  • a copper content of over 1.0% by weight up to 2.0% by weight, preferably from 1.1 to 1.3% by weight of Cu, is provided.
  • the main part 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% by weight of zinc in the 99.995% purity level.
  • a band consisting of a zinc alloy with an increased copper content of 0.8 mm thickness and 600 mm width 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 sprayed at a temperature of approx. 65 ° C and a pressure of approx. 2.5 bar.
  • the belt is brushed in the last rinsing step to support the rinsing process and to roughen the surface.
  • the strip is then processed in a pickling line with a pickling bath temperature of 30 ...
  • the pickling bath contains a mixed acid of approx. 30 ... 60 g / 1 sulfuric acid and approx. 20 ... 50 g / 1 nitric acid in water. In addition, 25 ... 80 g / 1, preferably approx. 50 g / 1, of zinc ions are present in solution.
  • 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 the development of hydrogen.
  • the ratio of the acid contents has a further influence on the pickling result.
  • a mixed acid with 2 ... 10% by volume sulfuric acid and 2 ... 10% by volume nitric acid is preferably used, the mixing ratio of sulfuric acid: nitric acid acid is less than or equal to 3: 1, and the free acid content is 25 to 100 g / 1.
  • the strip emerging from the pickling line is rinsed as described above.
  • Another protective layer is then preferably produced by applying and drying chromate-containing polymer dispersions as follows.
  • This application is dried at approx. 80 - 120 ° C.
  • the layer thickness of the film produced in the dried state is approximately from 0.4 to 3.0 ⁇ m, preferably 1.5 ⁇ m.
  • a polymer dispersion is understood to mean, for example, a mixture of styrene-acrylate, aliphatic polyester and polyurethane.
  • a flat product of a titanium-zinc alloy which mainly contains zinc of a high purity level and also a copper content of 1.0 to 2.0% by weight, a titanium content of 0.07 to 0%.
  • the latter is preferably covered with a protective layer with 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; the basis weight of the edition is accordingly 5 ... 40 mg / m 2 .

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

Verfahren zur Herstellung von dunklen Schutzschichten auf Flacherzeugnissen aus Titanzink Process for the production of dark protective layers on flat products made of titanium zinc
Die Erfindung betrifft ein Verfahren zur Herstellung von Schutzschichten dunkler Farbtönung durch Beizen von gewalzten Flacherzeugnissen aus Titan-Zink-Legierungen zur Ver- wendung 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 method for producing protective layers of dark color tint by pickling rolled flat products made of titanium-zinc alloys for use in construction, the flat products being pickled in an aqueous additive containing mixed acid containing sulfuric acid and nitric acid and after rinsing to form a Protective layer can be passivated. The invention also relates to surface products provided with protective layers.
Ein solches Verfahren ist aus der DE 196 36 370 AI 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.Such a method is known from DE 196 36 370 AI by the applicant, the content of which is hereby incorporated by reference. With the treatment of titanium zinc sheets made of 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% by weight of copper and the rest of 99, 995 percent zinc, homogeneous, gray protective layers are obtained on the surface of the titanium zinc sheets, the gray coloring being perceived as being particularly advantageous from an aesthetic point of view, since it corresponds to the natural patina of zinc.
Die in der DE 196 36 370 AI 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.The alloy disclosed in DE 196 36 370 AI corresponds in their composition the criteria of a "Quality Zinc" catalog from TÜV Produkt und Umwelt 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 Dacheinde- ckungen und Fassadenabdeckungen den Kontrast der vorbewit- terten 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 coloring of the metal sheets, which is desirable in some cases, can only be achieved to a minor extent by using more concentrated acids. The problem arises here that with increasing strength of the acids, i.e. lower pH of the pickling 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 build-up on the surface, since poorly adhering layers of so-called pickling sludge form. There are limits to an even stronger darkening of titanium zinc sheets with the known method. However, very dark colored surface layers are desired for the construction industry, in order to keep the contrast of the pre-weathered zinc sheets to other building materials used there, for example black slate shingles or roof tiles, low or to provide a strong contrast, especially in the area of roof coverings and facade covers 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. 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.Methods for producing a dark surface in titanium zinc by phosphating are also known (cf. DIN 50 942). This, however, undesirably changes the metallic surface structure if the surface is not to be coated further with lacquers. It is therefore the task of developing a method of the type mentioned at the outset in such a way that titanium zinc sheets can be produced with a very dark to black color on the surface, the natural structure of the metal surface being retained.
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 alloy specification mentioned at the outset, a titanium-zinc alloy with an increased copper content of 1.0 to 2.0% by weight is used, but which contains 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 in connection with the further alloy components and treatment methods known per se, a darker patina is obtained than when using alloys with the usual, low copper content. According to current knowledge, the patina consists in particular of zinc carbonate with traces of copper.
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 matt black color obtained allows building materials patinated in this way to be inserted particularly harmoniously into roof coverings with black pans or shingles or, where contrasts are desired, there is a clear gradation in black and white. A content of preferably 1.1 to 1.4% by weight of copper in the alloy is sufficient. The method according to the invention is explained in more detail below using 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 Reinheitsstu- fe 99,995 Gew.-%.A titanium-zinc alloy is used, the 0.06 to 0.2 wt .-% titanium and max. Contains 0.015 wt .-% aluminum. According to the invention, a copper content of over 1.0% by weight up to 2.0% by weight, preferably from 1.1 to 1.3% by weight of Cu, is provided. The main part 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% by weight of zinc in the 99.995% purity level.
Ein aus einer Zinklegierung mit erhöhtem Kupfergehalt bestehendes Band von 0,8 mm Dicke und 600 mm Breite wird durch Spülen mit einer alkalischen Entfettungslδsung 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 ...A band consisting of a zinc alloy with an increased copper content of 0.8 mm thickness and 600 mm width 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 sprayed at a temperature of approx. 65 ° C and a pressure of approx. 2.5 bar. The belt is brushed in the last rinsing step to support the rinsing process and to roughen the surface. The strip is then processed in a pickling line with a pickling bath temperature of 30 ...
80°C, vorzugsweise ca. 50 °C, gebeizt. Das Beizbad enthält eine Mischsäure aus ca. 30 ... 60 g/1 Schwefelsäure und ca. 20 ... 50 g/1 Salpetersäure in Wasser. Zusätzlich sind 25 ... 80 g/1, vorzugsweise ca. 50 g/1, Zink-Ionen gelöst vor- handen .80 ° C, preferably about 50 ° C, pickled. The pickling bath contains a mixed acid of approx. 30 ... 60 g / 1 sulfuric acid and approx. 20 ... 50 g / 1 nitric acid in water. In addition, 25 ... 80 g / 1, preferably approx. 50 g / 1, of zinc ions are present in solution.
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 the development of hydrogen. The ratio of the acid contents has a further influence on the pickling result.
Vorzugsweise wird eine Mischsäure mit 2 ... 10 Vol.-% Schwefelsäure und 2 ... 10 Vol.-% Salpetersäure verwandt, wobei das Mischungsverhältnis von Schwefelsäure : Salpeter- säure kleiner oder gleich 3:1 ist, und der Gehalt an freier Säure 25 bis 100 g/1 beträgt.A mixed acid with 2 ... 10% by volume sulfuric acid and 2 ... 10% by volume nitric acid is preferably used, the mixing ratio of sulfuric acid: nitric acid acid is less than or equal to 3: 1, and the free acid content is 25 to 100 g / 1.
Das aus der Beizanlage austretende Band wird wie oben beschrieben gespült. Anschließend wird vorzugsweise eine wei- tere Schutzschicht durch Auftragen und Trocknen von chromathaltigen Polymerdispersionen wie folgt erzeugt.The strip emerging from the pickling line is rinsed as described above. Another protective layer is then 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, a mixture of 65 to 98% by volume, preferably 95% by volume, polymer dispersion and 2 to 35% by volume, preferably 5% by volume, is aqueous on the belt by means of rollers Chromate solution applied. This application is dried at approx. 80 - 120 ° C. The layer thickness of the film produced in the dried state is approximately from 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.A polymer dispersion is understood to mean, 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 1,0 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 Ausführungsbei- spiel nach Auftragen und Trocknen einer chromathaltigen Polymerdispersion erhalten wurde; entsprechend beträgt das Flächengewicht der Auflage 5 ... 40 mg/m2. With the method of the invention, a flat product of a titanium-zinc alloy is preferably obtained which mainly contains zinc of a high purity level and also a copper content of 1.0 to 2.0% by weight, a titanium content of 0.07 to 0%. Has 12 wt .-% and an aluminum content of 0.015 wt .-% and has a matt black patina. The latter is preferably covered with a protective layer with 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; the basis weight of the edition is accordingly 5 ... 40 mg / m 2 .

Claims

Patentansprüche :Claims:
1) Verfahren zur Herstellung von Schutzschichten dunkler Farbtönung durch Beizen von gewalzten Flacherzeugnis- sen aus Titanzink zur Verwendung im Bauwesen, wobei die Flacherzeugnisse in einem wässrigen Beizbad mit Schwefelsäure und Salpetersäure enthaltender Mischsäure gebeizt und nach dem Spülen durch Auftragen einer Schutzschicht passiviert werden, dadurch gekennzeich- net, dass gewalzte Flacherzeugnisse aus einer Titan- Zink-Legierung verwendet werden, welche Legierung hauptsächlich Zink hoher Reinheitsstufe und daneben einen Kupfergehalt von 1,0 bis 2,0 Gew.-%, einen Titangehalt von 0,06 bis 0,2 Gew.-% und einen Aluminium- Gehalt von maximal 0,015 Gew.-% aufweist.1) Process for the production of protective layers of dark tint by pickling rolled flat products made of titanium zinc for use in construction, the flat products being pickled in an aqueous pickling bath with mixed acid containing sulfuric acid and nitric acid and passivated after rinsing by applying a protective layer - net that rolled flat products made of a titanium-zinc alloy are used, which alloy is mainly zinc of high purity and also a copper content of 1.0 to 2.0% by weight, a titanium content of 0.06 to 0.2% by weight .-% and has an aluminum content of at most 0.015 wt .-%.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Kupfergehalt zwischen 1,1 und 1,4 Gew.-% liegt.2. The method according to claim 1, characterized in that the copper content is between 1.1 and 1.4 wt .-%.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Reinheitsstufe des Zinks 99,995 Gew.-% in der Legierung ist.3. The method according to claim 1 or 2, characterized in that the purity level of the zinc is 99.995 wt .-% in the alloy.
4. Verfahren nach Anspruch 1 bis 3, dass das Beizbad ne- ben Wasser 30 ... 60 g/1 Schwefelsäure (H2S0) und4. The method according to claim 1 to 3, that the pickling bath in addition to water 30 ... 60 g / 1 sulfuric acid (H 2 S0) and
20 ... 50 g/1 Salpetersäure (HN03) enthält.Contains 20 ... 50 g / 1 nitric acid (HN0 3 ).
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß eine weitere Schutzschicht durch Auftragen und Trocknen einer chromathaltigen Polymerdispersion erzeugt wird.5. The method according to any one of the preceding claims, characterized in that a further protective layer is generated by applying and drying a chromate-containing polymer dispersion.
Flächenerzeugnis aus einer Titan-Zink-Legierung, die hauptsächlich aus Zink hoher Reinheitsstufe besteht und daneben einen Kupfergehalt von 1,0 bis 2,0 Gew.-%, einen Titan-Gehalt von 0,07 bis 0,12 Gew.-% und einen Aluminium-Gehalt von maximal 0,015 Gew.-% aufweist und in einem Beigabt mit Schwefelsäure und Salpetersäure gebeizt und mit einer dunklen Schutzschicht passiert ist .Surface product made of a titanium-zinc alloy, which mainly consists of zinc of high purity level 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 has an aluminum content of at most 0.015% by weight and was stained in addition with sulfuric acid and nitric acid and passed through with a dark protective layer.
7. Flächenerzeugnis nach Anspruch 6, dadurch gekennzeichnet, daß die passierende Schutzschicht mit einer weiteren Schutzschicht durch Auftragen und Trocknen aus einer chromathaltigen Polymerdispersion abgedeckt ist. 7. Surface product according to claim 6, characterized in that the passing protective layer is covered with a further protective layer by application and drying from 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
DE10156475A DE10156475A1 (en) 2001-11-16 2001-11-16 Process for the production of dark protective layers on flat products made of titanium zinc
DE10156475 2001-11-16
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

Publications (3)

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

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EP02787688A Expired - Lifetime EP1444381B2 (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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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
GB2460618B (en) * 2007-04-27 2012-07-04 Shine Metal Hot Galvanization Entpr Lead-free hot-dip galvanising method and product thereof
US8463279B2 (en) * 2007-09-26 2013-06-11 Qualcomm Incorporated Methods and apparatus for application network-server determination for removable module-based wireless devices
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
US8831575B2 (en) * 2007-09-26 2014-09-09 Qualcomm Incorporated Apparatus and methods associated with open market handsets
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03048417A1 *

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DE50202024D1 (en) 2005-02-17
HK1072785A1 (en) 2005-09-09
EP1444381B1 (en) 2005-01-12
ES2236604T5 (en) 2009-03-01
US20050003091A1 (en) 2005-01-06
AU2002352012A1 (en) 2003-06-17
ES2236604T3 (en) 2005-07-16
CN100374621C (en) 2008-03-12
WO2003048417A1 (en) 2003-06-12
EP1444381B2 (en) 2008-09-10
DE10156475A1 (en) 2003-06-05
CN1585834A (en) 2005-02-23
ATE286993T1 (en) 2005-01-15
US6916546B2 (en) 2005-07-12
JP2005511896A (en) 2005-04-28

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