EP0827785B1 - Process for making protecting layers on flat shaped products made of titanium zinc - Google Patents
Process for making protecting layers on flat shaped products made of titanium zinc Download PDFInfo
- Publication number
- EP0827785B1 EP0827785B1 EP97114344A EP97114344A EP0827785B1 EP 0827785 B1 EP0827785 B1 EP 0827785B1 EP 97114344 A EP97114344 A EP 97114344A EP 97114344 A EP97114344 A EP 97114344A EP 0827785 B1 EP0827785 B1 EP 0827785B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- chromate
- zinc
- acid
- containing polymer
- 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.)
- Revoked
Links
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
Definitions
- the invention relates to a method for producing Protective layers of uniform tint on rolled Flat products made of titanium zinc in the form of strips, sheets and strips for use in construction.
- titanium zinc initially reacts in the atmosphere with the formation of zinc oxide with the oxygen in the Air. It is formed by the action of rain and moisture then zinc hydroxide, which is caused by the reaction with the carbon dioxide the air into a dense, firmly adhering and water-insoluble Protective layer for basic zinc carbonate, the so-called Patina, is transformed. This protective layer is in generally responsible for the high corrosion resistance of the titanium zinc.
- titanium zinc consists of 0.06 up to 0.2% by weight titanium, max. 0.015% by weight aluminum, 0.08 to 1.0 % By weight copper, balance zinc 99.995% by weight.
- Sulfur dioxide affects at a relative humidity of over 70% the formation of the protective layer of the Titanium zinc.
- the protective layer complements the removal or Damage due to consumption corresponding to this removal of zinc.
- the aggressiveness of the local atmosphere is different and thus the intensity of the atmospheric Corrosion.
- the formation of the protective layer from basic zinc carbonate needs one depending on the season, climate and environmental conditions more or less long period, the training of Zinc carbonate layer is not done regularly and thereby optically negative impression arises.
- Claims 2 to 8 preferably contain and / or others Design options of the method according to claim 1.
- the speed of the pickling reaction is essentially dependent on the free acid content.
- the reduction of nitric acid is the dominant reaction and prevents one Hydrogen development.
- Another influence on the pickling result exerts the ratio of acidity.
- a tape made of titanium zinc 0.8 mm thick and 600 mm Width is achieved by rinsing with an alkaline degreasing solution at a temperature of approx. 60 ° C and a pressure of degreased approx. 2.5 bar and then in a sink with water with a temperature of 65 ° C and a pressure of 2.5 bar hosed.
- the belt is brushed in the last rinse stage.
- the belt is then used in a pickling line a pickling bath temperature of approx. 50 ° C, containing a mixed acid from approx. 30 to 60 g / l sulfuric acid and approx. 20 to 50 g / l nitric acid and approx.
- the Belt emerging from the pickling line is described as above rinsed with water. After removal of the residual water is on the tape by rolling a mixture of 95% polymers and 5% Chromate solution applied and this application at approx. 80 ° C dried.
- the layer thickness of the film produced is dry condition 1.5 ⁇ m. That is under the light microscope Layer not recognizable.
- a condensation test was carried out with two belt sections DIN 50017 (8 hours including warming up at 40 ° C and 100% humidity, then 16 hours cooling with the chamber open) carried out. After repeating this test 10 times no formation of zinc hydroxide was found. On simultaneously tested titanium zinc sheet, which only was pickled by the process according to DE-C-2 757 592, showed extensive formation of zinc hydroxide.
- the deep-drawing behavior of the strip sections treated according to the invention was tested by pulling out the two band sections Blanks were cut using a press Elbow half shells were deep drawn. There were both deep-drawn and non-oiled boards deep-drawn; spalling the passivation layer was not visible anywhere.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Schutzschichten einheitlicher Farbtönung auf gewalzten Flacherzeugnissen aus Titanzink in der Form von Bändern, Blechen und Streifen zur Verwendung im Bauwesen.The invention relates to a method for producing Protective layers of uniform tint on rolled Flat products made of titanium zinc in the form of strips, sheets and strips for use in construction.
In der Atmosphäre reagiert die Oberfläche von Titanzink zunächst unter Bildung von Zinkoxid mit dem Sauerstoff in der Luft. Durch Einwirkung von Regen und Feuchtigkeit bildet sich dann Zinkhydroxid, welches durch die Reaktion mit dem Kohlendioxid der Luft zu einer dichten, festhaftenden und wasserunlöslichen Schutzschicht zu basischem Zinkcarbonat, der sogenannten Patina, umgewandelt wird. Diese Schutzschicht ist im allgemeinen verantwortlich für den hohen Korrosionswiderstand des Titanzinks. Gemäß DIN EN 988 besteht Titanzink aus 0,06 bis 0,2 Gew.% Titan, max. 0,015 Gew.% Aluminium, 0,08 bis 1,0 Gew.% Kupfer, Rest Zink 99,995 Gew.%. The surface of titanium zinc initially reacts in the atmosphere with the formation of zinc oxide with the oxygen in the Air. It is formed by the action of rain and moisture then zinc hydroxide, which is caused by the reaction with the carbon dioxide the air into a dense, firmly adhering and water-insoluble Protective layer for basic zinc carbonate, the so-called Patina, is transformed. This protective layer is in generally responsible for the high corrosion resistance of the titanium zinc. According to DIN EN 988, titanium zinc consists of 0.06 up to 0.2% by weight titanium, max. 0.015% by weight aluminum, 0.08 to 1.0 % By weight copper, balance zinc 99.995% by weight.
Das unter ungünstigen Gegebenheiten die Atmosphäre verunreinigende Schwefeldioxid beeinträchtigt bei einer relativen Luftfeuchtigkeit von über 70 % die Bildung der Schutzschicht des Titanzinks. Die Schutzschicht ergänzt sich bei Abtragung oder Beschädigung durch einen dieser Abtragung entsprechenden Verbrauch von Zink. Die Aggressivität der örtlichen Atmosphäre ist unterschiedlich und damit auch die Intensität der atmosphärischen Korrosion.That which pollutes the atmosphere under unfavorable conditions Sulfur dioxide affects at a relative humidity of over 70% the formation of the protective layer of the Titanium zinc. The protective layer complements the removal or Damage due to consumption corresponding to this removal of zinc. The aggressiveness of the local atmosphere is different and thus the intensity of the atmospheric Corrosion.
Die Ausbildung der Schutzschicht aus basischem Zinkcarbonat benötigt je nach Jahreszeit, Klima und Umweltbedingungen einen mehr oder minder langen Zeitraum, wobei die Ausbildung der Zinkcarbonatschicht nicht regelmäßig erfolgt und dadurch ein optisch negativer Eindruck entsteht.The formation of the protective layer from basic zinc carbonate needs one depending on the season, climate and environmental conditions more or less long period, the training of Zinc carbonate layer is not done regularly and thereby optically negative impression arises.
Es ist deshalb in der DE-C-2 757 592 ein Verfahren zur Herstellung von grauen Schichten einer einheitlichen Farbtönung auf Blechen und Bändern aus Titanzink beschrieben, bei dem diese in einer Lösung, bestehend aus 60 bis 90 Vol.% Wasser, 10 bis 40 Vol.% Salpetersäure und 5 bis 10 Vol.% Schwefelsäure behandelt werden. Mit diesem Verfahren gelingt es, die aus Titanzink bestehenden Bleche, Bänder und Streifen von Anfang an mit einer Schicht zu versehen, die den Oberflächen den optischen Eindruck ähnlich einer natürlichen Patina verleiht. Nachteilig ist jedoch, daß es beispielsweise bei fehlerhafter Stapelung der Bänder, Bleche und Streifen oder bei ungünstigen Witterungseinflüssen zu Zinkhydroxidbildung, dem sogenannten Weißrost, kommt, der die einheitliche Farbtönung der Oberfläche erheblich beeinträchtigt. It is therefore a process for the production in DE-C-2 757 592 of gray layers of a uniform Color tint on sheets and strips made of titanium zinc described, in which this in a solution consisting of 60 up to 90 vol.% water, 10 to 40 vol.% nitric acid and 5 to 10% by volume of sulfuric acid are treated. With this procedure succeeds in making the sheets, strips and titanium zinc To provide the strip with a layer from the start that Surfaces look similar to a natural one Patina gives. The disadvantage, however, is that it is, for example if the strips, sheets and strips are incorrectly stacked or in case of unfavorable weather conditions for zinc hydroxide formation, the so-called white rust, which is the uniform Color tint of the surface significantly impaired.
Es ist die Aufgabe der vorliegenden Erfindung ein Verfahren bereitzustellen, mit dem die durch Beizen erzeugten grauen Schichten einheitlicher Farbtönung auch unter ungünstigen Gegebenheiten, wie z. B. Luftabschluß, nicht zerstört werden.It is the object of the present invention a method with which the gray produced by pickling Layers of uniform color even under unfavorable ones Conditions, such as B. air exclusion, not destroyed become.
Die Lösung dieser Aufgabe erfolgt durch die im Anspruch 1 aufgeführten Verfahresmaßnahmen.This object is achieved by those listed in claim 1 Proceed measures.
Die Ansprüche 2 bis 8 enthalten vorzugsweise und/oder weitere Ausgestaltungsmöglichkeiten des Verfahrens nach Anspruch 1.Claims 2 to 8 preferably contain and / or others Design options of the method according to claim 1.
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 speed of the pickling reaction is essentially dependent on the free acid content. The reduction of nitric acid is the dominant reaction and prevents one Hydrogen development. Another influence on the pickling result exerts the ratio of acidity.
Die Vorteile der auf erfindungsgemäße Art und Weise behandelten Flacherzeugnisse aus Titanzink bestehen darin, daß beim Transport bzw. bei der Montage von Bändern, Blechen und Streifen keine Fingerabdrücke entstehen, das Verformen der Bleche, Bänder und Streifen ölfrei durchführbar ist, die Passivierungsschicht einen permanenten Korrossionsschutz auch unter ungünstigsten Bedingungen gewährleistet, so daß auch eine vollkommene Resistenz gegen alle Wittungseinflüsse gegeben ist. Darüber hinaus ist die Passivierungsschutzschicht mit diversen Beschichtungssystemen lackierbar.The advantages of those treated in the manner according to the invention Flat products made of titanium zinc consist in the fact that Transport or when assembling strips, sheets and strips there are no fingerprints, the sheet metal is deformed, Tapes and strips can be carried out oil-free, the passivation layer permanent corrosion protection even under unfavorable conditions guaranteed, so that a perfect resistance to all weather influences is. The passivation protection layer is also included various coating systems can be painted.
Die Erfindung ist nachstehend näher durch ein Ausführungsbeispiel erläutert. The invention is explained in more detail below by an embodiment explained.
Ein aus Titanzink 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 Druck von ca. 2,5 bar entfettet und anschließend in einer Spüle mit Wasser mit einer Temperatur von 65 °C und einem Druck von 2,5 bar abgespritzt. Zur Unterstützung des Spülvorgangs und zur Oberflächenaufrauhung wird in der letzten Spülstufe das Band gebürstet. Anschließend wird das Band in einer Beizanlage mit einer Beizbadtemperatur von ca. 50 °C, enthaltend eine Mischsäure aus ca. 30 bis 60 g/l Schwefelsäure und ca. 20 bis 50 g/l Salpetersäure sowie ca. 50 g/l Zink-Ionen behandelt. Das aus der Beizanlage austretende Band wird wie oben beschrieben mit Wasser gespült. Nach Entfernung des Restwassers wird auf das Band mittels Walzen ein Gemisch aus 95 % Polymeren und 5 % Chromatlösung aufgebracht und dieser Auftrag bei ca. 80 °C getrocknet. Die Schichtdicke des erzeugten Films beträgt im trockenen Zustand 1,5 µm. Unter dem Lichtmikroskop ist die Schicht nicht zu erkennen.A tape made of titanium zinc 0.8 mm thick and 600 mm Width is achieved by rinsing with an alkaline degreasing solution at a temperature of approx. 60 ° C and a pressure of degreased approx. 2.5 bar and then in a sink with water with a temperature of 65 ° C and a pressure of 2.5 bar hosed. To support the rinsing process and for surface roughening the belt is brushed in the last rinse stage. The belt is then used in a pickling line a pickling bath temperature of approx. 50 ° C, containing a mixed acid from approx. 30 to 60 g / l sulfuric acid and approx. 20 to 50 g / l nitric acid and approx. 50 g / l zinc ions. The Belt emerging from the pickling line is described as above rinsed with water. After removal of the residual water is on the tape by rolling a mixture of 95% polymers and 5% Chromate solution applied and this application at approx. 80 ° C dried. The layer thickness of the film produced is dry condition 1.5 µm. That is under the light microscope Layer not recognizable.
Mit zwei Bandabschnitten wurde eine Schwitzwasserprüfung nach DIN 50017 (8 Stunden incl. Aufwärmen bei 40 °C und 100 % Luftfeuchtigkeit, danach 16 Stunden Abkühlen bei geöffneter Kammer) durchgeführt. Nach 10maliger Wiederholung dieses Tests konnte keine Bildung von Zinkhydroxid festgestellt werden. Ein gleichzeitig dem Test unterzogenes Titanzink-Blech, das nur nach dem Verfahren gemäß DE-C-2 757 592 gebeizt worden war, zeigte flächenhafte Bildung von Zinkhydroxid.A condensation test was carried out with two belt sections DIN 50017 (8 hours including warming up at 40 ° C and 100% humidity, then 16 hours cooling with the chamber open) carried out. After repeating this test 10 times no formation of zinc hydroxide was found. On simultaneously tested titanium zinc sheet, which only was pickled by the process according to DE-C-2 757 592, showed extensive formation of zinc hydroxide.
Das Tiefziehverhalten der erfindungsgemäß behandelten Bandabschnitte wurde getestet, indem aus den beiden Bandabschnitten Platinen geschnitten wurden, die mit einer Presse zur Rohrbogen-Halbschalen tiefgezogen wurden. Es wurden sowohl unbeölte als auch beölte Platinen tiefgezogen; Abplatzungen der Passivierungsschicht waren an keiner Stelle erkennbar.The deep-drawing behavior of the strip sections treated according to the invention was tested by pulling out the two band sections Blanks were cut using a press Elbow half shells were deep drawn. There were both deep-drawn and non-oiled boards deep-drawn; spalling the passivation layer was not visible anywhere.
Zwei weitere Bandabschnitte wurden dem Gitterschnitt-Test nach DIN 53 151 unterzogen; das Ergebnis für beide Bandabschnitte war G 0, d. h. das Haftvermögen der Beschichtung ist als sehr gut zu bezeichnen. Ergänzend wurden nach dem Gitterschnitt-Test die Bandabschnitte einer Runde in der Klimakammer ausgesetzt. Mit bloßem Auge waren keine Veränderungen der Oberflächen erkennbar. Zusätzlich wurden zwei Bandabschnitte einem Gitterschnitt-Test mit anschließender Erichsen-Tiefung gemäß DIN 50 101 unterworfen. Es waren keinerlei Abplatzungen der Schicht zu erkennen.Two other band sections were made after the cross-cut test Subjected to DIN 53 151; the result for both band sections was G 0, i.e. H. the adhesion of the coating is very easy to describe. Complementary were after the cross-cut test the tape sections exposed to a lap in the climatic chamber. With the naked eye there were no changes to the surfaces recognizable. In addition, two tape sections were one Cross-cut test with subsequent Erichsen cupping according to Subject to DIN 50 101. There were no flaking off Layer.
Mit zwei weiteren Bandabschnitten wurden Falttests mit einer Faltung um 180 ° durchgeführt und zwar sowohl längs als auch quer zur Walzrichtung; in beiden Fällen konnten keine Abplatzungen der Passivierungsschicht erkannt werden.With two further belt sections, folding tests with one Folded through 180 °, both lengthways and transverse to the rolling direction; in both cases, flaking failed the passivation layer can be recognized.
Zur Simulierung der Verhältnisse bei fehlerhafter Stapelung wurden mehrere Bandabschnitte gestapelt. Zwischen je zwei Bandabschnitte wurde ein Tropfen destilliertes Wasser gegeben und der Stapel dann fest zusammengepreßt, um den Zutritt von Kohlendioxid zu verhindern. Nach einer Woche wurde der Stapel wieder gelöst.To simulate the conditions in the event of incorrect stacking several band sections were stacked. Between two A drop of distilled water was added to tape sections and then the stack pressed tightly to gain access from To prevent carbon dioxide. After a week the stack became solved again.
Dabei zeigte sich, daß die erfindungsgemäß beschichteten Bleche frei von Zinkhydroxid geblieben waren, während die zu Vergleichszwecken gestapelten Bleche, die gemäß dem Verfahren nach DE-C-2 757 592 gebeizt worden waren, in größerem Umfang Zinkhydroxidbildungen aufwiesen.It was found that the sheets coated according to the invention remained free of zinc hydroxide, while for comparison purposes stacked sheets according to the procedure were stained according to DE-C-2 757 592, to a larger extent Zinc hydroxide formation.
Probebleche von den zwei Bandabschnitten wurden bei erhöhter Temperatur von 60 bis 70 °C unter eine UV-Lampe gelegt, auch nach 5 Wochen war weder ein Abblättern noch eine Verfärbung der Passivierungsschicht zu erkennen.Sample sheets from the two tape sections were raised at Temperature from 60 to 70 ° C placed under a UV lamp, too after 5 weeks there was no flaking or discoloration the passivation layer.
Claims (9)
- A process for the production of protective layers of unitary colour tint by pickling on rolled flat products consisting of titanium zinc, in the form of bands, sheets or strips for use in building construction, characterised in that the flat products are pickled in a pickling bath with mixed acid containing sulphuric acid and nitric acid and after rinsing are passivated by the application of a chromate-containing polymer with the formation of a protective coating.
- A process according to claim 1, characterised in that the mixed acid contains 2 to 10% by volume of sulphuric acid and 2 to 10% by volume of nitric acid, the mixture ratio of sulphuric acid to nitric acid being < 3 and the free acid content being 25 to 100 g/l.
- A process according to claims 1 and 2, characterised in that the pickling bath contains 25 to 80 g/l of zinc ions.
- A process according to any one of claims 1 to 3, characterised in that the chrome-containing polymer consists of a mixture of 65 to 98% polymer and 2 to 35% chromate.
- A process according to any one of claims 1 to 4, characterised in that the organic polymer consists of a mixture of styrene acrylate, aliphatic polyesters and polyurethane.
- A process according to any one of claims 1 to 5, characterised in that the pickling bath has a temperature of 30 to 80°C.
- A process according to any one of claims 1 to 6, characterised in that the rinse water has a temperature of 20 to 80°C.
- A process according to any one of claims 1 to 7, characterised in that the chromate-containing polymer is applied by spraying, dipping, rolling, roller application or the like.
- Flat products of titanium zinc treated by any one of claims 1 to 8, characterised by a protective layer of chromate-containing polymer with a thickness of 0.4 to 3.0 □m, preferably 1 to 2 □m, the chromate thickness being 5 to 40 mg/m2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19636370 | 1996-09-09 | ||
| DE19636370A DE19636370B4 (en) | 1996-09-09 | 1996-09-09 | Process for the production of protective coatings on flat products of titanium zinc and flat products |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0827785A2 EP0827785A2 (en) | 1998-03-11 |
| EP0827785A3 EP0827785A3 (en) | 2000-01-12 |
| EP0827785B1 true EP0827785B1 (en) | 2003-02-26 |
Family
ID=7804917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97114344A Revoked EP0827785B1 (en) | 1996-09-09 | 1997-08-20 | Process for making protecting layers on flat shaped products made of titanium zinc |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0827785B1 (en) |
| DE (2) | DE19636370B4 (en) |
| DK (1) | DK0827785T3 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10156475A1 (en) | 2001-11-16 | 2003-06-05 | Rheinzink Gmbh | Process for the production of dark protective layers on flat products made of titanium zinc |
| US6838572B2 (en) | 2002-09-30 | 2005-01-04 | Degussa Ag | Process for the epoxidation of olefins |
| DE102006051384A1 (en) * | 2006-10-27 | 2008-04-30 | Seppeler Holding Und Verwaltungs Gmbh & Co. Kg | Process for the pre-weathering of metal parts with a predominantly zinc surface |
| IT1393946B1 (en) | 2009-04-21 | 2012-05-17 | Np Coil Dexter Ind Srl | PROCESS OF TREATMENT IN CONTINUOUS PATINATURA / SATINATIMATE CHEMICA OF ZINCO-TITANIUM ALLOYS |
| DE102010025707A1 (en) * | 2010-06-30 | 2012-01-05 | Rheinzink Gmbh & Co. Kg | Process for the preparation of protective coatings on flat titanium zinc products |
| IT201900016901A1 (en) * | 2019-09-20 | 2021-03-20 | Vimar Spa | Method of production of metallic electric plate, and relative plate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1996
- 1996-09-09 DE DE19636370A patent/DE19636370B4/en not_active Expired - Lifetime
-
1997
- 1997-08-20 DE DE59709373T patent/DE59709373D1/en not_active Revoked
- 1997-08-20 EP EP97114344A patent/EP0827785B1/en not_active Revoked
- 1997-08-20 DK DK97114344T patent/DK0827785T3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP0827785A3 (en) | 2000-01-12 |
| DE59709373D1 (en) | 2003-04-03 |
| DK0827785T3 (en) | 2003-06-23 |
| DE19636370A1 (en) | 1998-03-12 |
| EP0827785A2 (en) | 1998-03-11 |
| DE19636370B4 (en) | 2005-04-14 |
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