EP0048270A1 - Revetements de zinc-aluminium. - Google Patents

Revetements de zinc-aluminium.

Info

Publication number
EP0048270A1
EP0048270A1 EP81901054A EP81901054A EP0048270A1 EP 0048270 A1 EP0048270 A1 EP 0048270A1 EP 81901054 A EP81901054 A EP 81901054A EP 81901054 A EP81901054 A EP 81901054A EP 0048270 A1 EP0048270 A1 EP 0048270A1
Authority
EP
European Patent Office
Prior art keywords
alloy
mischmetal
alloy according
zinc
metal
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
EP81901054A
Other languages
German (de)
English (en)
Other versions
EP0048270A4 (fr
EP0048270B1 (fr
Inventor
Schrade F Radtke
Dimitri Coutsouradis
Jacques Pelerin
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.)
International Lead Zinc Research Organization Inc
Original Assignee
International Lead Zinc Research Organization Inc
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
Priority claimed from BE6/471152A external-priority patent/BE882431A/fr
Application filed by International Lead Zinc Research Organization Inc filed Critical International Lead Zinc Research Organization Inc
Priority to AT81901054T priority Critical patent/ATE14900T1/de
Publication of EP0048270A1 publication Critical patent/EP0048270A1/fr
Publication of EP0048270A4 publication Critical patent/EP0048270A4/fr
Application granted granted Critical
Publication of EP0048270B1 publication Critical patent/EP0048270B1/fr
Expired 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
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon

Definitions

  • the present invention is directed to the appli- cation of zinc coatings to a substrate - commonly sheet steel.
  • hot dip galva ⁇ nizing either continuous or batch type, has long been used for a variety of steel products to protect the products from corrosion.
  • 3,343,930 and 3,393,089) reportedly exhibits a good corrosion resistance but, in view of its high aluminum content does not provide a satis ⁇ factory sacrificial protection of the steel substrate, Subsequent-s-fcudies have been aimed at modifying the composition of molten metal baths in order to form (by hot-dipping) a coating which improves corrosion resistance even in the most varied environ ⁇ ments.
  • One of the aspects of these studies was the influence of the preparation of the surface to be coated on the quality of the product obtained. It thus appears that in order to ensure a quality coating, some of the alloy coatings previously developed required expensive preliminary surface treatments involving expensive equipment.
  • the bath compositions and resultant coatings constitute improvements over known alloy " batha.-and coatings in that they contain additionally mixtures of rare earth elements.
  • the present invention is directed to zinc-aluminu ⁇ compositions or alloys which have added thereto rare earths in the form of mischmetal.
  • the zinc-aluminum alloys be what are commonly referred to as low aluminum zinc alloys which are generally recognized to contain from about 3% to about 15% aluminum.
  • the hot-dip metal baths according to the present invention may vary considerably just as known zinc-aluminum baths and coatings may vary. In each instance, however, it is essential that the bath have added thereto a mischmetal alloy in an amount sufficient to yield the improved results observed and described herein.
  • mischmetal refers to a variety of knovm rare earth alloys.
  • two typical cerium mischmetals might have the following compositions (in weight %) :
  • Ce 45-60 other rare earths 35-50, the balance comprising Fe, Mg, Al, Si and impurities.
  • Typical Lanthanum mischmetals can be defined by the following (in weight %) :
  • mischmetal refers to the above compositions as well as other mischmetal compositions readily apparent to those skilled in the art.
  • the preferred alloy to which mischmetal is to be added is a zinc-aluminum alloy containing from about 3% to about 15% aluminum. Such alloys typically contain about 5% aluminum. These alloys may contain constituents in addition to mischmetal such as Fe, Pb, Sb, Mg, Sn, Cu and Si.
  • one embodiment of the invention comprises a low aluminum (i.e., 3-15%) zinc bath containing Pb or Sn as well as mischmetal.
  • Pb and Sn are known additives to galvanizing baths for modifying the fluidity of the liquid metal or the spangle of the solidified coating.
  • Zinc-aluminum alloys containing lead and also Mg and Cu are reported to be immune to grain boundary corrosion.
  • mischmetal additions have been shown to exhibit a pronounced beneficial effect as regards soundness and uniformity.
  • a Zn-Al alloy containing Mg, Pb, Cu and misch- metal is encompassed by the present invention.
  • a typical composition might contain 3-15% Al, 0.02- 0.15% Mg, 0.02-0.15% Pb and possibly 0.1-0.3% Cu, the balance being Zn with mischmetal additions.
  • mischmetals may be advantageously used according to the invention, including mixtures of mischmetals in a single zinc bath or coating.
  • a La-mischmetal and a Ce-misch ⁇ ietal may be added simultaneously, preferably in an amount such that the total mischmetal concentration is within the ranges described above, i.e. from about 5 ppm to about 1.0% and preferably from about 0.01 to 0.1% by weight.
  • a master alloy may be first prepared and then added to the zinc bath so as to yield the desired mischmetal concentration.
  • Such master alloys might be comprised of 20% Zn and 80% mischmetal or 85-95% Al and 15-5% mischmetal.
  • EXAMPLES 1 Specimens of rimming steel sheet measuring 68 x 120 x 0.7 mm were galvanized in a device simulating a continuous galvanizing bath. They were first pre ⁇ heated in an atmosphere containing 95% N 2 - 5% H 2 at different temperatures from 750 to 800°C for times ranging from 1 to 10 minutes. After this heating stage the specimens were transferred from the hot zone of the furnace, cooled down to about 430°C and then introduced into a zinc alloy bath maintained at 430°C and protected by the 95% 2 - 5% H 2 atmosphere. They were maintained in the zinc bath for periods ranging from 5 to 60 seconds and then removed from the bath and cooled in a jet of 95% l ⁇ - - 5% H 2 gas.
  • This example relates to trials carried out with a pilot continuous annealing and galvanizing plant.
  • 800 kg coils of rimming steel sheet 150 mm wide and 0.25 mm thick were first treated in a Selas type furnace at temperatures ranging from 680 to 860°C.
  • the sheet was then cooled in a controlled atmosphere to about 430°C and then introduced into a seven-ton zinc bath.
  • the sheet was then nitrogen-gas wiped at the exit, jet cooled and finally coiled.
  • the speed of the sheet varied in the range 10 to 30 m/min.
  • the coating was uniform and free of bare spots, uncoated areas or other defects.
  • a Zn - 5% Al bath containing 0.13% Sn and as above 0.05% of cerium mischmetal was also used in the pilot galvanizing line.
  • the coatings obtained had characteristics similar to those described above with a coating somewhat less bright due to a different spangle behavior.
  • An additional bath containing Zn, 5% Al, 0.13% Sn, 0.05% Pb and about 0.05% Ce + La (added as Ce mischmetal or La mischmetal; or added as a master alloy containing about 20% Zn and 80% La and/or Ce mischmetals; or added as a master alloy containing about 90% Al and 10% La and/or Ce misch ⁇ metal) was also used in the pilot galvanizing line.
  • the coatings obtained showed a wide range of thickness, were uniform and again were free of bare spots and uncoated areas.
  • pilot plant conditions are mentioned as examples only and that other condi- tions prevailing in continuous annealing and galva ⁇ nizing lines as regards furnace type, composition of gas, speeds, wiping methods, etc., can be used with advantage with the zinc bath composition according to the invention.
  • bath and coating co posi- tions as described herein may be used in non- continuous (e.g. batch) galvanizing methods.
  • the formabili-fc'y and adherence was evaluated by means of bulge tests and Erichsen tests.
  • the coatings obtained with the isch- metal-containing bath exhibited an adherence and formability equivalent to that of standard galvanized coatings.
  • a 180° bending gave rise to no cracking and in the Erichsen test a depth of 9 mm was made on 0.25 mm thick sheets without peeling of the coating.
  • the corrosion resistance, in a salt spray test, of the Zn-Al coatings containing mischmetal was more than twice that of a standard galvanized coating of the same thickness.
  • the time to first rusting was about 900 hours instead of 350 hours with a conventional galvanized coating of the same thickness.
  • the corrosion resistance in an environment containing 10 ppm S0 2 was shown to be at least 50% greater than that of a conventional- galvanized coating.
  • the galvanic protection of the Zn-Al mischmetal coating was also determined by examining the progress of corrosion around scratches machined on specimens exposed to a S0 2 -containing environment.
  • the galvanic protection of the mischmetal-containing Zn - 5% Al coating was equal to that of a pure zinc coating and far superior to that of a coating containing Zn-55Al-1.5Si.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)

Abstract

Alliages destines a etre utilises dans un bain de galvanisation de zinc comprenant du zinc, de l'aluminium et un alliage contenant une terre rare telle que du mischmetal. Selon les modes preferentiels de realisation, l'alliage contient de 80% a 97% environ de zinc, de 3% a 15% environ d'aluminium et de 5 ppm a 1,0% environ de mischmetal. L'alliage peut aussi contenir un ou plusieurs des elements Fe, Pb, Fb, Mg, Sn, Cu et Si.
EP19810901054 1980-03-25 1981-03-18 Revetements de zinc-aluminium Expired EP0048270B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81901054T ATE14900T1 (de) 1980-03-25 1981-03-18 Zink-aluminium-beschichtungen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
BE47115 1980-03-25
BE6/471152A BE882431A (fr) 1980-03-25 1980-03-25 Procede de formation de revetement zinc-aluminium
BE47373 1981-01-16
BE6047373 1981-01-16

Publications (3)

Publication Number Publication Date
EP0048270A1 true EP0048270A1 (fr) 1982-03-31
EP0048270A4 EP0048270A4 (fr) 1982-07-12
EP0048270B1 EP0048270B1 (fr) 1985-08-14

Family

ID=25662147

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810901054 Expired EP0048270B1 (fr) 1980-03-25 1981-03-18 Revetements de zinc-aluminium

Country Status (6)

Country Link
EP (1) EP0048270B1 (fr)
JP (1) JPH0124221B2 (fr)
BR (1) BR8107944A (fr)
CA (1) CA1175686A (fr)
IN (1) IN156009B (fr)
WO (1) WO1981002748A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE890256A (fr) * 1981-09-07 1982-03-08 Centre Rech Metallurgique Perfectionnements aux procedes de galvanisation des toles ou bandes en acier
EP0148740A1 (fr) * 1983-12-22 1985-07-17 CENTRE DE RECHERCHES METALLURGIQUES CENTRUM VOOR RESEARCH IN DE METALLURGIE Association sans but lucratif Procédé de revêtement à chaud et bain de composition améliorée pour sa mise en oeuvre
EP0958395A1 (fr) * 1996-05-02 1999-11-24 N.V. Bekaert S.A. Fil pour ressort, au chrome et au silicium
JP3343498B2 (ja) * 1997-06-13 2002-11-11 昭和電工株式会社 低温ろう付用ろう材
JP4136286B2 (ja) * 1999-08-09 2008-08-20 新日本製鐵株式会社 耐食性に優れたＺｎ−Ａｌ−Ｍｇ−Ｓｉ合金めっき鋼材およびその製造方法
WO2001064971A1 (fr) * 2000-02-29 2001-09-07 Nippon Steel Corporation Article en acier plaque dote d'une grande resistance a la corrosion ainsi que d'une remarquable aptitude au formage et procede de production
CN115874075B (zh) * 2022-12-16 2023-10-13 佛山市桂源锌合金材料有限公司 一种低杂质且易抛光的锌合金及其制备工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1095832A (en) * 1964-03-06 1967-12-20 Fur Zinkindustrie Ag Improvements in the protection of ferrous constructions against corrosion
FR1570613A (fr) * 1967-04-18 1969-06-13
GB1195904A (en) * 1966-07-11 1970-06-24 Cominco Ltd Process for the production of Coloured Coatings
FR2078812A5 (en) * 1970-02-26 1971-11-05 Centre Nat Rech Metall Malleable binary alloys of zinc and rare - earths

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE926654C (de) * 1951-10-31 1955-04-21 Goldschmidt Ag Th Sicherheitszuendsteine fuer Grubenlampen in schlagwettergefaehrdeten Bergwerksbetrieben
US2829973A (en) * 1953-04-09 1958-04-08 Magnesium Elektron Ltd Magnesium base alloys
FR1155357A (fr) * 1956-08-02 1958-04-25 Treibacher Chemische Werke Ag Procédé de filage d'alliages pyrophoriques de ferrocérium
US3343930A (en) * 1964-07-14 1967-09-26 Bethlehem Steel Corp Ferrous metal article coated with an aluminum zinc alloy
GB1115673A (en) * 1964-07-14 1968-05-29 Bethlehem Steel Corp Zinc-aluminum coated products and methods therefor
US3527601A (en) * 1967-06-14 1970-09-08 Dow Chemical Co Process of making creep-resistant zinc-base alloys
LU55104A1 (fr) * 1967-12-15 1969-07-17
US4152472A (en) * 1973-03-19 1979-05-01 Nippon Steel Corporation Galvanized ferrous article for later application of paint coating
US4056366A (en) * 1975-12-24 1977-11-01 Inland Steel Company Zinc-aluminum alloy coating and method of hot-dip coating
US4029478A (en) * 1976-01-05 1977-06-14 Inland Steel Company Zn-Al hot-dip coated ferrous sheet
US4213799A (en) * 1978-06-05 1980-07-22 Swiss Aluminium Ltd. Improving the electrical conductivity of aluminum alloys through the addition of mischmetal

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1095832A (en) * 1964-03-06 1967-12-20 Fur Zinkindustrie Ag Improvements in the protection of ferrous constructions against corrosion
US3383297A (en) * 1964-03-06 1968-05-14 Eberius Ernst Zinc-rare earth alloy anode for cathodic protection
GB1195904A (en) * 1966-07-11 1970-06-24 Cominco Ltd Process for the production of Coloured Coatings
FR1570613A (fr) * 1967-04-18 1969-06-13
FR2078812A5 (en) * 1970-02-26 1971-11-05 Centre Nat Rech Metall Malleable binary alloys of zinc and rare - earths

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8102748A1 *

Also Published As

Publication number Publication date
JPS57500475A (fr) 1982-03-18
EP0048270A4 (fr) 1982-07-12
CA1175686A (fr) 1984-10-09
IN156009B (fr) 1985-04-27
BR8107944A (pt) 1982-03-09
EP0048270B1 (fr) 1985-08-14
WO1981002748A1 (fr) 1981-10-01
JPH0124221B2 (fr) 1989-05-10

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