EP0132424B1 - Corrosion-resistant steel wire - Google Patents

Corrosion-resistant steel wire Download PDF

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Publication number
EP0132424B1
EP0132424B1 EP84401266A EP84401266A EP0132424B1 EP 0132424 B1 EP0132424 B1 EP 0132424B1 EP 84401266 A EP84401266 A EP 84401266A EP 84401266 A EP84401266 A EP 84401266A EP 0132424 B1 EP0132424 B1 EP 0132424B1
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EP
European Patent Office
Prior art keywords
wire
zinc
bath
alloy
corrosion
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Expired
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EP84401266A
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German (de)
French (fr)
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EP0132424A1 (en
Inventor
Bruno Thomas
Guy Viart
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Trefilunion SA
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Trefilunion SA
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Classifications

    • 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
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • the present invention relates to a hard steel wire with high carbon content, perfectly ductile, used for the manufacture of cables and springs, having a protective coating consisting of several layers of different alloys based on zinc, aluminum and of iron.
  • the wire is characterized in that it is coated with a first internal layer of alloy (AI-Fe-Zn) comprising between 15% and 45% of AI, between 5% and 25% of Fe, the remainder consisting essentially of zinc and small amounts of additions of at least one of the elements from the group Mg, Sn, Ni, Cu, Cr and Mischmetal, the total of which does not exceed 0.5%, and a second outer layer of alloy comprising between 3% and 10% of AI, between 0.5% and 5% of Fe, the remainder consisting essentially of zinc and of small amounts of addition elements not exceeding one 0.5% total, from the group consisting of Mg, Sn, Ni, Cu, Cr, and Mischmetal.
  • a first internal layer of alloy (AI-Fe-Zn) comprising between 15% and 45% of AI, between 5% and 25% of Fe, the remainder consisting essentially of zinc and small amounts of additions of at least one of the elements from the group Mg, Sn, Ni, Cu, Cr and Mischmetal, the total of which does not exceed 0.
  • These coatings are obtained by a two-stage manufacturing process.
  • document EP-AO 037143 describes a process for coating steel consisting of at least two immersions in baths with different temperatures, in particular metal baths of zinc and zinc alloy, such as Zn-AI with an AI content of between 3 and 10% by weight.
  • the first stage of the process according to the invention thus consists of galvanizing with pure zinc by hot immersion in a bath of pure zinc followed by controlled cooling (R1) of 20 ° C / sec.
  • the second stage of this process is an immersion of the first galvanizing coating in a bath of molten zinc-aluminum alloy, having the above-mentioned composition.
  • the layer of pure zinc from the first galvanization disappears completely to give the layer of alloy A2 (AI-Zn-Fe).
  • the process targeted by the invention therefore allows controlled diffusion of AI and Fe.
  • the wire obtained as defined has a significantly improved corrosion resistance compared to the usual galvanized wires, while retaining excellent ductility and deformability characteristics (bending, winding, wire drawing, etc.).
  • the resistance to accelerated corrosion in salt spray according to standard NFX41-002 (August 1975) of the wire according to the invention is at least twice as high as that of a traditional galvanized wire as shown by tests carried out.
  • rust appears after approximately 150 hours on a traditional galvanized wire, and after 400 hours on a wire provided of a coating according to the invention.
  • these times are 300 hours and 800 hours respectively.
  • cathodic protection in a chlorinated medium of the coating according to the invention is at least equal to that of traditional galvanized wire.
  • Corrosion tests were also carried out in an S0 2 atmosphere, at 10 ppm S0 2 , the table of which presents the results expressed in weight loss due to corrosion for various samples exposed in an atmosphere at 10 ppm S0 2 and examined. after 3 days, 1, 2, 3 and 4 weeks.
  • the samples were wound on a 10 mm diameter mandrel before the test.
  • Wires with a low zinc coating (10 ⁇ m) show red rust after 3 days of exposure.
  • the galvanized wires with a coating thickness of 21 ⁇ m are corroded (with attack by the steel) after one week and those with a thickness of 35 ⁇ m reveal rust after two weeks of exposure.
  • the corrosion resistance of the wire obtained according to the invention is greater than that of similar Zn-AI coatings, but deposited in a single operation, without controlled diffusion.
  • the controlled cooling R1 of the wire at the outlet of the first bath was 20 ° C per second
  • the cooling R2 after the second bath was 100 ° C per second.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Description

La présente invention concerne un fil d'acier dur à haute teneur en carbone, parfaitement ductile, utilisé pour la fabrication de câbles et de ressorts, présentant un revêtement protecteur constitué de plusieurs couches d'alliages différents à base de zinc, d'aluminium et de fer.The present invention relates to a hard steel wire with high carbon content, perfectly ductile, used for the manufacture of cables and springs, having a protective coating consisting of several layers of different alloys based on zinc, aluminum and of iron.

Suivant l'invention, le fil est caractérisé en ce qu'il est revêtu d'une première couche interne d'alliage (AI-Fe-Zn) comprenant entre 15% et 45% d'AI, entre 5% et 25% de Fe, le reste étant essentiellement constitué de zinc et d'additions en faible quantité d'au moins un des éléments du groupe Mg, Sn, Ni, Cu, Cr et Mischmetal dont le total n'excède pas 0,5%, et une deuxième couche externe d'alliage comprenant entre 3% et 10% d'AI, entre 0,5% et 5% de Fe, le reste étant essentiellement constitué de zinc et d'éléments d'addition en faible quantité n'excédant pas un total de 0,5%, du groupe constitué de Mg, Sn, Ni, Cu, Cr, et de Mischmetal.According to the invention, the wire is characterized in that it is coated with a first internal layer of alloy (AI-Fe-Zn) comprising between 15% and 45% of AI, between 5% and 25% of Fe, the remainder consisting essentially of zinc and small amounts of additions of at least one of the elements from the group Mg, Sn, Ni, Cu, Cr and Mischmetal, the total of which does not exceed 0.5%, and a second outer layer of alloy comprising between 3% and 10% of AI, between 0.5% and 5% of Fe, the remainder consisting essentially of zinc and of small amounts of addition elements not exceeding one 0.5% total, from the group consisting of Mg, Sn, Ni, Cu, Cr, and Mischmetal.

Ces revêtements sont obtenus par un procédé de fabrication à deux stades.These coatings are obtained by a two-stage manufacturing process.

Depuis longtemps, la préparation de revêtements protecteurs en deux stades est connue, mais les procédés antérieurs ne prévoient pas de traitements thermiques volontaires avant et après les deux immersions.For a long time, the preparation of protective coatings in two stages has been known, but the prior processes do not provide for voluntary heat treatments before and after the two immersions.

Par exemple, le document EP-A-O 037143 décrit un procédé de revêtement d'acier consistant en au moins deux immersions dans des bains dont les températures sont différentes, notamment des bains métalliques de zinc et d'alliage de zinc, tel que Zn-AI avec une teneur en AI comprise entre 3 et 10% en poids.For example, document EP-AO 037143 describes a process for coating steel consisting of at least two immersions in baths with different temperatures, in particular metal baths of zinc and zinc alloy, such as Zn-AI with an AI content of between 3 and 10% by weight.

Le procédé de fabrication du fil selon l'invention est caractérisé par les étapes suivantes:

  • a) on effectue une première immersion du fil dans un bain de zinc pur;
  • b) on refroidit le fil après sa sortie du bain à une vitesse de 20°C/sec.
  • c) on effectue une seconde immersion du fil dans un second bain constitué par un alliage zinc-aluminium de composition: entre 3 et 10% d'AI; Zn faisant la balance avec des additions en faible quantité comme Mg, Sn, Ni, Cu, Cr, Mischmetal;
  • d) on refroidit le fil à la sortie du second bain à une vitesse de 100°C/sec.
The method of manufacturing the wire according to the invention is characterized by the following steps:
  • a) a first immersion of the wire is carried out in a bath of pure zinc;
  • b) the wire is cooled after leaving the bath at a speed of 20 ° C / sec.
  • c) a second immersion of the wire is carried out in a second bath consisting of a zinc-aluminum alloy of composition: between 3 and 10% of AI; Zn balancing with small additions such as Mg, Sn, Ni, Cu, Cr, Mischmetal;
  • d) the wire is cooled at the outlet of the second bath at a speed of 100 ° C / sec.

Le premier stade du procédé selon l'invention consiste ainsi en une galvanisation au zinc pur par immersion à chaud dans un bain de zinc pur suivi d'un refroidissement contrôlé (R1) de 20°C/sec.The first stage of the process according to the invention thus consists of galvanizing with pure zinc by hot immersion in a bath of pure zinc followed by controlled cooling (R1) of 20 ° C / sec.

Le deuxième stade de ce procédé est une immersion du premier revêtement de galvanisation dans un bain d'alliage zinc-aluminium fondu, ayant la composition précitée.The second stage of this process is an immersion of the first galvanizing coating in a bath of molten zinc-aluminum alloy, having the above-mentioned composition.

L'immersion du premier revêtement de galvanisation dans la deuxième cuve, suivie d'un refroidissement contrôlé de 100°C/sec, provoque une modification thermochimique considérable des couches d'alliage obtenues par la première galvanisation pour faire place à l'alliage A1 (AI-Zn-Fe).The immersion of the first galvanizing coating in the second tank, followed by a controlled cooling of 100 ° C / sec, causes a considerable thermochemical modification of the layers of alloy obtained by the first galvanization to make room for the alloy A1 ( AI-Zn-Fe).

De plus, la couche de zinc pur de la première galvanisation disparaît complètement pour donner la couche d'alliage A2 (AI-Zn-Fe).In addition, the layer of pure zinc from the first galvanization disappears completely to give the layer of alloy A2 (AI-Zn-Fe).

Ces refroidissements réalisent ainsi un traitement thermochimique de diffusion contrôlée.These coolings thus carry out a thermochemical treatment of controlled diffusion.

Ces deux couches ont pour analyse globale respective: A1 et A2.These two layers have their respective global analysis: A1 and A2.

On constate donc un très fort enrichissement en aluminium de la couche intérieure, alors que le premier bain ne contient que du zinc pur.There is therefore a very high aluminum enrichment of the inner layer, while the first bath contains only pure zinc.

Le procédé visé par l'invention permet donc une diffusion contrôlée de AI et Fe.The process targeted by the invention therefore allows controlled diffusion of AI and Fe.

Le fil obtenu comme défini, présente une tenue à la corrosion très nettement améliorée par rapport aux fils galvanisés habituels, tout en conservant d'excellentes caractéristiques de ductilité et de déformabilité (pliage, enroulement, tréfilage...).The wire obtained as defined has a significantly improved corrosion resistance compared to the usual galvanized wires, while retaining excellent ductility and deformability characteristics (bending, winding, wire drawing, etc.).

On a établi que la résistance à la corrosion accélérée en brouillard salin suivant la norme ASTM B-117 du fil, objet de la présente invention est au moins le double de celle du fil galvanisé traditionnel.It has been established that the resistance to accelerated corrosion in salt spray according to the ASTM B-117 standard of the wire which is the subject of the present invention is at least twice that of traditional galvanized wire.

D'autre part, la résistance à la corrosion accélérée en brouillard salin suivant la norme NFX41-002 (Août 1975) du fil selon l'invention est au minimum deux fois supérieure à celle d'un fil galvanisé traditionnel comme l'ont montré les essais réalisés. A titre d'exemples numériques indicatifs, pour des revêtements anti-corrosion d'une épaisseur de 20 llm exposés au brouillard salin, la rouille apparaît au bout d'environ 150 heures sur un fil galvanisé traditionnel, et après 400 heures sur un fil pourvu d'un revêtement selon l'invention. Pour des revêtements de 40 llm d'épaisseur, ces temps sont respectivement de 300 heures et 800 heures.On the other hand, the resistance to accelerated corrosion in salt spray according to standard NFX41-002 (August 1975) of the wire according to the invention is at least twice as high as that of a traditional galvanized wire as shown by tests carried out. As indicative numerical examples, for anti-corrosion coatings with a thickness of 20 μm exposed to salt spray, rust appears after approximately 150 hours on a traditional galvanized wire, and after 400 hours on a wire provided of a coating according to the invention. For coatings 40 µm thick, these times are 300 hours and 800 hours respectively.

On a également vérifié que la protection cathodique en milieu chloruré du revêtement selon l'in- ventio est au moins égale à celle du fil galvanisé traditionnel.It has also been verified that the cathodic protection in a chlorinated medium of the coating according to the invention is at least equal to that of traditional galvanized wire.

On a également exécuté des tests de corrosion en atmosphère S02, à 10 ppm S02, dont le tableau ci-dessous présente les résultats exprimés en perte de poids due à la corrosion pour différents échantillons exposés en atmosphère à 10 ppm S02 et examinés après 3 jours, 1, 2, 3 et 4 semaines.

Figure imgb0001
Figure imgb0002
 Corrosion tests were also carried out in an S0 2 atmosphere, at 10 ppm S0 2 , the table of which presents the results expressed in weight loss due to corrosion for various samples exposed in an atmosphere at 10 ppm S0 2 and examined. after 3 days, 1, 2, 3 and 4 weeks.
Figure imgb0001
Figure imgb0002

Les échantillons ont été enroulés sur un mandrin de 10 mm de diamètre avant le test.The samples were wound on a 10 mm diameter mandrel before the test.

Les fils à faible revêtement de zinc (10 pm) présentent de la rouille rouge après 3 jours d'exposition.Wires with a low zinc coating (10 µm) show red rust after 3 days of exposure.

Les fils galvanisés d'épaisseur de revêtement de 21 µm sont corrodés (avec attaque de l'acier) après une semaine et ceux d'épaisseur de 35 µm laissent apparaître la rouille après deux semaines d'exposition.The galvanized wires with a coating thickness of 21 µm are corroded (with attack by the steel) after one week and those with a thickness of 35 µm reveal rust after two weeks of exposure.

Aucune trace de rouille rouge n'a été observée sur les échantillons de fil selon l'invention même sur ceux de faible épaisseur de revêtement (10 µm) après quatre semaines d'exposition.No trace of red rust was observed on the wire samples according to the invention even on those of thin coating thickness (10 μm) after four weeks of exposure.

Enfin, la résistance à la corrosion du fil obtenu selon l'invention est supérieure à celle des revêtements Zn-AI analogues, mais déposés en une seule opération, sans diffusion contrôlée.Finally, the corrosion resistance of the wire obtained according to the invention is greater than that of similar Zn-AI coatings, but deposited in a single operation, without controlled diffusion.

A titre d'exemple, le refroidissement contrôlé R1 du fil à la sortie du premier bain (zinc pur) a été de 20°C par seconde, et le refroidissement R2 après le deuxième bain (alliage zinc + AI + additions) de 100°C par seconde.For example, the controlled cooling R1 of the wire at the outlet of the first bath (pure zinc) was 20 ° C per second, and the cooling R2 after the second bath (zinc alloy + AI + additions) of 100 ° C per second.

Claims (2)

1. Hard steel wire, having superposed coatings and being perfectly ductile and resistant to corrosion, characterized in that it is coated with a first inner layer of alloy (AI-Se-Zn) containing between 15% and 45% of Al, between 5% and 25% of Fe, the balance mainly consisting of zinc and additions in a small amount of at least one of the elements of group Mg, Sn, Ni, Cu, Cr and Mischmetal, the total amount of which does not exceed 0.5%, and a second outer layer of alloy, containing between 3% and 10% of Al, between 0.5 and 5% of Fe, the balance consisting mainly of zinc and additional elements in a small amount from the group formed by Mg, Sn, Ni, Cu, Cr, and Mischmetal, the total amount of which does not exceed 0.5%.
2. Process for manufacturing steel wire according to claim 1, characterized by the following stages:
a. Carrying out a first dipping of the wire in a bath of pure zinc;
b. Cooling the wire at a speed of 20°C per second when it leaves the bath;
c. Carrying out a second dipping of the wire in a second bath of an alloy of zinc-aluminium, containing between 3 and 10% aluminium, the balance consisting of Zn with additions in a small quantity such as Mg, Sn, Ni, Cu, Cr, Mischmetal;
d. Cooling of the wire at a speed of 100°C per second when it leaves the second bath.
EP84401266A 1983-06-28 1984-06-19 Corrosion-resistant steel wire Expired EP0132424B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8310660 1983-06-28
FR8310660A FR2548216B1 (en) 1983-06-28 1983-06-28 STEEL WIRE WITH CORROSION RESISTANT COATINGS

Publications (2)

Publication Number Publication Date
EP0132424A1 EP0132424A1 (en) 1985-01-30
EP0132424B1 true EP0132424B1 (en) 1989-04-12

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US (1) US4605598A (en)
EP (1) EP0132424B1 (en)
JP (1) JPS6052568A (en)
AU (1) AU567948B2 (en)
DE (1) DE3477676D1 (en)
ES (1) ES533776A0 (en)
FR (1) FR2548216B1 (en)

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DE3477676D1 (en) 1989-05-18
FR2548216B1 (en) 1988-10-21
AU567948B2 (en) 1987-12-10
JPH0573824B2 (en) 1993-10-15
ES8601327A1 (en) 1985-10-16
EP0132424A1 (en) 1985-01-30
ES533776A0 (en) 1985-10-16
FR2548216A1 (en) 1985-01-04
JPS6052568A (en) 1985-03-25
US4605598A (en) 1986-08-12
AU2989484A (en) 1985-01-03

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