EP0865510A1 - Alloyed zinc strips and plates - Google Patents

Alloyed zinc strips and plates

Info

Publication number
EP0865510A1
EP0865510A1 EP96942345A EP96942345A EP0865510A1 EP 0865510 A1 EP0865510 A1 EP 0865510A1 EP 96942345 A EP96942345 A EP 96942345A EP 96942345 A EP96942345 A EP 96942345A EP 0865510 A1 EP0865510 A1 EP 0865510A1
Authority
EP
European Patent Office
Prior art keywords
zinc
weight
strips
zinc alloy
sheets
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.)
Withdrawn
Application number
EP96942345A
Other languages
German (de)
French (fr)
Inventor
Adolf Stradmann
Frank-Ulrich Dyllus
Volker Brücken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rheinzink GmbH and Co KG
Original Assignee
Rheinzink GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rheinzink GmbH and Co KG filed Critical Rheinzink GmbH and Co KG
Publication of EP0865510A1 publication Critical patent/EP0865510A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc

Definitions

  • the invention relates to strips and sheets made of alloyed zinc based on at least 99.99% zinc with additions of 0.05 to 0.2% by weight of titanium, copper and 0.005 to 0.05% by weight of aluminum, preferably for the building industry .
  • the production of the material is generally carried out using the casting-rolling process, in which strips in a continuous process (melting - casting - rolling - winding) are produced in predetermined thicknesses, which are then cut on scissor lines to narrow strips or sheets.
  • the material is stable in the atmosphere.
  • the surface initially reacts with the oxygen in the air to form zinc oxide.
  • the action of water then forms zinc hydroxide, which, when reacted with the carbon dioxide in the air, converts it into a dense, firmly adhering and water-insoluble cover layer made of basic zinc carbonate. This protective layer is responsible for the high corrosion resistance.
  • the underside of the zinc strips and tablets In contrast to the behavior of the surface of the zinc facing the free atmosphere, the following applies to the underside of the zinc strips and tablets, i.e. on the side facing away from the weather, other criteria.
  • the underside of the zinc strips and sheets if the underside of the zinc strips and sheets is exposed to moisture or condensed water for a long period due to inadequate ventilation, caused by structural or installation errors, it must be subjected to increased corrosion, e.g. due to water inclusions, water ingress, condensation, etc., which ultimately leads to point-by-point deep corrosion (pitting), which can spread out in areas.
  • the object of the present invention to reduce to a minimum the risk of punctiform deep corrosion as a result of physical defects and / or improper laying of strips and sheets consisting of the fine zinc alloy mentioned at the beginning.
  • the solution to this problem is that the copper content of the fine zinc alloy is 0.02 to 0.075% by weight, preferably 0.03 to 0.06% by weight, and in addition a manganese content of 0.075 to 0.75% by weight, preferably 0, 2 to 0.75% by weight of manganese is provided.
  • the samples of the examined zinc sheets consisted of a fine zinc alloy (I) with the composition belonging to the state of the art and of a fine zinc alloy (II) with the composition according to the invention (in% by weight):
  • the sheets made of the known fine zinc alloy (I) showed a surface and local corrosion attack.
  • the corrosion behavior of the fine zinc alloy (II) according to the invention could be influenced in such a way that the attack leading to localized deep corrosion was prevented.
  • the area-related covering number density Z which represents the number of punctiform digits per centimeter, decreases significantly when the manganese content is added and the copper content is limited. Even in the "pre-weathered", ie in the pickled state, no local points of attack on the zinc strips and panels could be determined visually. In addition to the visual impression and the area-related covering number density Z, the area-related mass change can be taken into account as a classification of the fine zinc alloys.
  • Electrolyte Zn (OH) ⁇ - saturated solution with NaCl adjusted to a conductivity of 500 ⁇ m / cm, ⁇ rinsing of the corrosion medium 30 min before
  • the anodic patential profiles of the fine zinc alloys indicate, due to their comparable gradients, that there is no inhibition of the metal dissolution.
  • the conversion of the necessary cathodic partial reaction which takes place in normal aqueous media after the reaction H 2 + V 2 0 2 + 2e " -> 2 (OH " ), can be seen from the curves as a cathodic potential curve depending on the alloy. This shows the positive influence of the addition of manganese already determined under condensation conditions.
  • the cathodic current density (I) show the values of the cathodic current density (I), which were determined at a potential which is 50 mV more negative than the resting potential.
  • the current densities indicate that the cathodic partial reaction of the fine zinc alloy (II) is reduced by approximately 60% compared to the fine zinc alloy (I).
  • the cathodic potential curve of the fine zinc alloy (II) according to the invention is flatter, which is due to an inhibition of the oxygen reduction. If less oxygen is converted, less and less metal will dissolve.

Abstract

In order to prevent pitting, a high-grade zinc alloy with between 0.05 and 0.2 wt.% titanium, copper and between 0.005 and 0.05 wt.% aluminium further contains between 0.075 and 0.75 wt.% manganese, provided that the copper content is between 0.02 and 0.075 wt.%.

Description

Bänder und Tafeln aus legiertem Zink Alloy zinc strips and sheets
Beschreibung:Description:
Die Erfindung betrifft Bänder und Tafeln aus legiertem Zink auf der Basis von wenigstens 99,99% Zink mit Zusätzen von 0,05 bis 0,2 Gew.% Titan, Kupfer und 0,005 bis 0,05 Gew.% Aluminium, vorzugsweise für das Bauwesen.The invention relates to strips and sheets made of alloyed zinc based on at least 99.99% zinc with additions of 0.05 to 0.2% by weight of titanium, copper and 0.005 to 0.05% by weight of aluminum, preferably for the building industry .
Dieser in der DE-C-1 758 498 beschriebene und nach DIN 17 770, Teil 1 genormte Werkstoff wird seit vielen Jahren, insbesondere im Bauwesen, wegen seiner vorzüglichen Werkstoffeigenschaften eingesetzt. Die aus diesem Werkstoff hergestellten Bänder und Tafeln sind unabhängig von der Walzrichtung anrißfrei um 180° faltbar, bleiben bruchfrei beim Wiederaufbiegen und zeichnen sich durch eine hohe Duktilität bei jeder Art Umformung, auch bei Kaltumformung, aus. Die Mindestanforderung an diese mechanisch-technologischen Eigenschaften der aus diesem Werkstoff hergestellten Bänder und Tafeln sind in DIN 17 770, Teil 1 aufgeführt. In DIN 17 770, Teil 2 sind die Maße für solche Bänder und Bleche angegeben.This material described in DE-C-1 758 498 and standardized according to DIN 17 770, Part 1 has been used for many years, particularly in the construction industry, because of its excellent material properties. The strips and sheets made from this material can be folded 180 ° regardless of the rolling direction, remain unbreakable when re-bent and are characterized by high ductility in every type of forming, including cold forming. The minimum requirements for these mechanical-technological properties of the strips and sheets made from this material are listed in DIN 17 770, Part 1. DIN 17 770, Part 2 specifies the dimensions for such strips and sheets.
Die Herstellung des Werkstoffs erfolgt im allgemeinen unter Anwendung des Gieß-Walz-Verfahrens, bei dem in einem ununterbrochenen Verfahrensgang (Schmelzen - Gießen - Walzen - Aufwickeln) Bänder in vorgegebenen Dicken hergestellt werden, die anschließend auf Scherenlinien zu Schmalbändern oder Tafeln geschnitten werden.The production of the material is generally carried out using the casting-rolling process, in which strips in a continuous process (melting - casting - rolling - winding) are produced in predetermined thicknesses, which are then cut on scissor lines to narrow strips or sheets.
ORIGINAL UNTERLAGEN Der Werkstoff ist in der Atmosphäre gut beständig. Die Oberfläche reagiert zunächst unter Bildung von Zinkoxid mit dem Sauerstoff der Luft. Durch Einwirkung von Wasser bildet sich dann Zinkhydroxid, das durch Reaktion mit dem Kohlendioxid der Luft zu einer dichten, festhaftenden und wasserunlöslichen Deckschicht aus basischem Zinkkarbonat umgewandelt wird. Diese Schutzschicht ist verantwortlich für den hohen Korrosionswiderstand.ORIGINAL DOCUMENTS The material is stable in the atmosphere. The surface initially reacts with the oxygen in the air to form zinc oxide. The action of water then forms zinc hydroxide, which, when reacted with the carbon dioxide in the air, converts it into a dense, firmly adhering and water-insoluble cover layer made of basic zinc carbonate. This protective layer is responsible for the high corrosion resistance.
Im Gegensatz zum Verhalten der der freien Atmosphäre zugewandten Oberfläche des Zinks gelten an der Unterseite der Zinkbänder und -tafeln, d.h. auf der von den Witterungseinflüssen abgewandten Seite, andere Kriterien. Wird darüber hinaus die Unterseite der Zinkbänder und -tafeln durch Feuchtigkeit oder Kondenswasser infolge mangelhafter Be- und Entlüftung über einen längeren Zeitraum belastet, verursacht durch bauphysikalische oder verlegungstechnische Fehler, muß mit verstärkter Korrosion, z.B. durch Wassereinschlüsse, Wassereinbrüche, Tauwasser usw. gerechnet werden, die schließlich zu einer punktweisen Tiefenkorrosion (Lochfraß) führt, die sich flächenförmig ausbreiten kann.In contrast to the behavior of the surface of the zinc facing the free atmosphere, the following applies to the underside of the zinc strips and tablets, i.e. on the side facing away from the weather, other criteria. In addition, if the underside of the zinc strips and sheets is exposed to moisture or condensed water for a long period due to inadequate ventilation, caused by structural or installation errors, it must be subjected to increased corrosion, e.g. due to water inclusions, water ingress, condensation, etc., which ultimately leads to point-by-point deep corrosion (pitting), which can spread out in areas.
Um diese Folgen zu vermeiden ist für eine ausreichende Be- und Entlüftung der Unterkonstruktion von Zinkband- oder -tafeldeckungen durch eine Ausführung in Übereinstimmung mit den allgemeinen Vorschriften und Bestimmungen, wie den technischen Vorschriften für Bauleistungen (VOB) , den DIN-Normen, den Fachregeln des Handwerks, den Verordnungen der Baubehörden sowie den Hinweisen des Baustofflieferanten, zu sorgen.In order to avoid these consequences, sufficient ventilation of the substructure of zinc tape or panel coverings must be carried out in accordance with the general regulations and provisions, such as the technical regulations for construction work (VOB), the DIN standards, the technical rules the craft, the ordinances of the building authorities and the instructions of the building material supplier.
Es ist die Aufgabe der vorliegenden Erfindung, die Gefahr einer punktweisen Tiefenkorrosion als Folge bauphysikalischer Fehler und/oder nicht fachgerechter Verlegung von aus der eingangs angeführten Feinzinklegierung bestehenden Bändern und Tafeln auf ein Minimum zu senken. Die Lösung dieser Aufgabe besteht darin, daß der Kupfergehalt der Feinzinklegierung 0,02 bis 0,075 Gew.%, vorzugsweise 0,03 bis 0,06 Gew.% beträgt und zusätzlich ein Mangangehalt von 0,075 bis 0,75 Gew.%, vorzugsweise 0,2 bis 0,75 Gew.% Mangan vorgesehen ist.It is the object of the present invention to reduce to a minimum the risk of punctiform deep corrosion as a result of physical defects and / or improper laying of strips and sheets consisting of the fine zinc alloy mentioned at the beginning. The solution to this problem is that the copper content of the fine zinc alloy is 0.02 to 0.075% by weight, preferably 0.03 to 0.06% by weight, and in addition a manganese content of 0.075 to 0.75% by weight, preferably 0, 2 to 0.75% by weight of manganese is provided.
Zu Vergleichszwecken wurden Korrosionsuntersuchungen an gewalzten 0, 8 mm dicken Zinkblechen unter Anwendungen des Kondenswassertests nach DIN 50 017 KK durchgeführt, bei dem Zinkbleche in einer Kondenswasser-Klimaprüfeinrichtung bei einer Lufttemperatur von 40 °C und einer relativen Luftfeuchte von 100% 7 Tage lang ausgelagert wurden. Nach dieser Explositionsdauer wurden die Massenänderungen und das optische Erscheinungsbild der Korrosion der Zinkbleche ermittelt.For comparison purposes, corrosion tests were carried out on rolled, 0.8 mm thick zinc sheets using the condensation test according to DIN 50 017 KK, in which zinc sheets were stored in a condensation water climate test device at an air temperature of 40 ° C and a relative humidity of 100% for 7 days . After this period of exposure, the changes in mass and the visual appearance of the corrosion of the zinc sheets were determined.
Die Proben der untersuchten Zinkbleche bestanden aus einer Feinzinklegierung (I) mit der zum Stand der Technik gehörenden Zusammensetzung und aus einer Feinzinklegierung (II) mit der erfindungsgemäßen Zusammensetzung (in Gew.%):The samples of the examined zinc sheets consisted of a fine zinc alloy (I) with the composition belonging to the state of the art and of a fine zinc alloy (II) with the composition according to the invention (in% by weight):
Mn Cu Ti AI Zn Feinzinklegierung (I) - 0,13 0,12 0,010 Rest (99,995%) Feinzinklegierung (II) 0,39 0,049 0,12 0,010 Rest (99,995%)Mn Cu Ti AI Zn fine zinc alloy (I) - 0.13 0.12 0.010 balance (99.995%) fine zinc alloy (II) 0.39 0.049 0.12 0.010 balance (99.995%)
Bei den aus der bekannten Feinzinklegierung (I) bestehenden Blechen zeigte sich ein flächenmäßiger und örtlicher Korrosionsangriff. Durch die erfindungsgemäße Zurücknahme des Kupfers und Zugabe von Mangan konnte das Korrosionsverhalten der erfindungsgemäßen Feinzinklegierung (II) derart beeinflußt werden, daß der zur punktuellen Tiefenkorrosion führende Angriff verhindert wurde. Die flächenbezogene Belagszahldichte Z, die die Anzahl von punktuellen Stellen pro Zentimeter wiedergibt, nimmt deutlich bei Zusatz des Mangangehalts und Eingrenzung des Kupfergehalts ab. Selbst im "vorbewitterten" , d. h. im gebeizten Zustand konnten keine örtlichen Angriffsstellen an den Zinkbändern und -tafeln visuell ermittelt werden. Neben dem visuellen Eindruck und der flächenbezogenen Belagszahldichte Z kann die flächenbezogene Massenänderung als Klassifizierung der Feinzinklegierungen berücksichtigt werden. Dazu wurden aus der bekannten Feinzinklegierung (I) und der erfindungsgemäßen Feinzinklegierung (II) bestehende 0,8 mm dicke Bleche gebeizt und anschließend 14 Tage dem Kondenswassertest gemäß DIN 50 017 (Konstantklima) unterzogen. Wie das in Fig. 1 dargestellte Säulendiagramm zeigt, beträgt der flächenbezogene Massenverlust w in mg/cnr bei der Feinzinklegierung (I) 1,2 mg/cm2 und bei der Finzinklegierung (II) nach der Erfindung nur 0,31 mg/cm1.The sheets made of the known fine zinc alloy (I) showed a surface and local corrosion attack. By taking back the copper and adding manganese according to the invention, the corrosion behavior of the fine zinc alloy (II) according to the invention could be influenced in such a way that the attack leading to localized deep corrosion was prevented. The area-related covering number density Z, which represents the number of punctiform digits per centimeter, decreases significantly when the manganese content is added and the copper content is limited. Even in the "pre-weathered", ie in the pickled state, no local points of attack on the zinc strips and panels could be determined visually. In addition to the visual impression and the area-related covering number density Z, the area-related mass change can be taken into account as a classification of the fine zinc alloys. For this purpose, 0.8 mm thick sheets were pickled from the known fine zinc alloy (I) and the fine zinc alloy (II) according to the invention and then subjected to the condensation water test according to DIN 50 017 (constant climate) for 14 days. As the bar chart shown in FIG. 1 shows, the area-related mass loss w in mg / cnr is 1.2 mg / cm 2 for the fine zinc alloy (I) and only 0.31 mg / cm 1 for the fine zinc alloy (II) according to the invention .
Zur Simulierung von Kondenswasserbedingungen wurde alε Korrosionsmedium ein mit Zinkhydroxid gesättigtes, destilliertes Wasser verwendet, wobei Natriumchlorid als Leitsalz zugegeben wurde. Folgende Prüfbedinungen wurden bei allen Proben zugrunde gelegt:To simulate condensation water conditions, a distilled water saturated with zinc hydroxide was used as the corrosion medium, sodium chloride being added as the conductive salt. The following test conditions were used for all samples:
Elektrolyt: Zn (OH)^-gesättigte Lösung mit NaCl auf eine Leitfähigkeit von 500 μm/cm eingestellt, ^-Spülung des Korrosionsmediums 30 min vorElectrolyte: Zn (OH) ^ - saturated solution with NaCl adjusted to a conductivity of 500 μm / cm, ^ rinsing of the corrosion medium 30 min before
Versuchsbeginn eingeschaltet, Elektrolyttemperatur 40°C.Start of experiment switched on, electrolyte temperature 40 ° C.
Die Fig. 2 gibt die Summenstromdichte-Potential-Kurven der Feinzinklegierung (I) und der erfindungsgemäßen Feinzinklegierung (II) wieder.2 shows the total current density-potential curves of the fine zinc alloy (I) and the fine zinc alloy (II) according to the invention.
Die anodischen Patentialverläufe der Feinzinklegierungen deuten aufgrund ihrer vergleichbaren Steigungen darauf hin, daß eine Hemmung der Metallauflösung in keinem Falle vorliegt. Der Umsatz der notwendigen kathodischen Teilreaktion, die in normalen wäßrigen Medien nach der Reaktion H2 + V2 02 + 2e" -> 2(OH") abläuft, kann als kathodischer Potentialverlauf legierungsabhängig aus den Kurven entnommen werden. Hierbei zeigt sich der schon unter Kondenswasserbedingungen ermittelte positive Einfluß des Manganzusatzes. Inwieweit die Reduktion des Sauerstoffes in Abhängigkeit von der LegierungsZusammensetzung verringert wird, zeigen die Werte der kathodischen Stromdichte (I), die bei einem Potential, welches um 50 mV negativer ist als das Ruhepotential, ermittelt wurden. Die Stromdichten lassen erkennen, daß die kathodische Teilreaktion der Feinzinklegierung (II) zu ca. 60 % gegenüber der Feinzinklegierung (I) reduziert ist. Im Vergleich zur Feinzinklegierung (I) verläuft die kathodische Potentialkurve der erfindungsgemäßen Feinzinklegierung (II) flacher, was auf einer Hemmung der Sauerstoffreduktion zurückzuführen ist. Wird weniger Sauerstoff umgesetzt, dann geht immer weniger Metall in Lösung. The anodic patential profiles of the fine zinc alloys indicate, due to their comparable gradients, that there is no inhibition of the metal dissolution. The conversion of the necessary cathodic partial reaction, which takes place in normal aqueous media after the reaction H 2 + V 2 0 2 + 2e " -> 2 (OH " ), can be seen from the curves as a cathodic potential curve depending on the alloy. This shows the positive influence of the addition of manganese already determined under condensation conditions. To what extent the reduction of Oxygen is reduced depending on the alloy composition, show the values of the cathodic current density (I), which were determined at a potential which is 50 mV more negative than the resting potential. The current densities indicate that the cathodic partial reaction of the fine zinc alloy (II) is reduced by approximately 60% compared to the fine zinc alloy (I). In comparison to the fine zinc alloy (I), the cathodic potential curve of the fine zinc alloy (II) according to the invention is flatter, which is due to an inhibition of the oxygen reduction. If less oxygen is converted, less and less metal will dissolve.

Claims

Patentansprüche claims
1. Bänder und Tafeln aus legiertem Zink auf der Basis von Feinzink von wenigsten 99,99% Zink mit Zusätzen von 0,05 bis 0,2 Gew.% Titan, Kupfer und 0,005 bis 0,05 Gew.% Aluminium vorzugsweise für das Bauwesen, dadurch gekennzeichnet, daß der Kupfergehalt 0,02 bis 0,075 Gew.% beträgt und ein Mangangehalt von 0,075 bis 0,75 Gew.% vorgesehen ist.1. Bands and plates made of alloyed zinc based on fine zinc of at least 99.99% zinc with additions of 0.05 to 0.2% by weight of titanium, copper and 0.005 to 0.05% by weight of aluminum, preferably for the building industry , characterized in that the copper content is 0.02 to 0.075% by weight and a manganese content of 0.075 to 0.75% by weight is provided.
2. Bänder und Tafeln nach Anspruch 1 gekennzeichnet durch einen Kupfergehalt von 0,03 bis 0,06 Gew.%2. Ribbons and sheets according to claim 1, characterized by a copper content of 0.03 to 0.06% by weight.
3. Bänder und Tafeln nach einem der Ansprüche 1 und 2 gekennzeichnet durch einen Mangangehalt von 0,20 bis 0,75 Gew.%. 3. Ribbons and sheets according to one of claims 1 and 2, characterized by a manganese content of 0.20 to 0.75% by weight.
EP96942345A 1995-12-06 1996-12-04 Alloyed zinc strips and plates Withdrawn EP0865510A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19545487A DE19545487A1 (en) 1995-12-06 1995-12-06 Alloy zinc strips and sheets
DE19545487 1995-12-06
PCT/EP1996/005415 WO1997020959A1 (en) 1995-12-06 1996-12-04 Alloyed zinc strips and plates

Publications (1)

Publication Number Publication Date
EP0865510A1 true EP0865510A1 (en) 1998-09-23

Family

ID=7779333

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Application Number Title Priority Date Filing Date
EP96942345A Withdrawn EP0865510A1 (en) 1995-12-06 1996-12-04 Alloyed zinc strips and plates

Country Status (5)

Country Link
EP (1) EP0865510A1 (en)
DE (1) DE19545487A1 (en)
PE (1) PE32398A1 (en)
PL (1) PL327029A1 (en)
WO (1) WO1997020959A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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
MX2009006149A (en) * 2009-06-10 2010-12-13 Alberto Manuel Ontiveros Balcazar Alloy for making grounding electrodes and connection method therefor.
CN107385278B (en) * 2017-08-02 2019-10-08 宁波博威合金材料股份有限公司 It is easy to cold-formed deformation zinc alloy material and its preparation method and application

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
GB526619A (en) * 1938-07-26 1940-09-23 Edes Mfg Company Zinc base alloy
DE1138553B (en) * 1960-02-19 1962-10-25 Huettenbetr Wrought zinc alloy and process for its manufacture
DE1274345B (en) * 1962-08-02 1968-08-01 Stolberger Zink Ag Wrought zinc alloy and process for its manufacture and processing
LU53446A1 (en) * 1967-04-18 1968-12-11
CA932158A (en) * 1970-07-27 1973-08-21 F. Redden Robert Method of producing zinc alloy
JPS5952947B2 (en) * 1980-01-29 1984-12-22 三菱マテリアル株式会社 Zinc alloy for hot-dip plating
JPH06228686A (en) * 1993-01-29 1994-08-16 Nisso Kinzoku Kagaku Kk Zinc base alloy wire and production of zinc alloy wire

Non-Patent Citations (1)

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Title
See references of WO9720959A1 *

Also Published As

Publication number Publication date
PL327029A1 (en) 1998-11-09
WO1997020959A1 (en) 1997-06-12
DE19545487A1 (en) 1997-06-12
PE32398A1 (en) 1998-08-08

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