EP0132424B1 - Fil d'acier à revêtements superposés résistant à la corrosion - Google Patents
Fil d'acier à revêtements superposés résistant à la corrosion Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- wire
- zinc
- bath
- alloy
- corrosion
- 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.)
- Expired
Links
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)
- Conductive Materials (AREA)
- Non-Insulated Conductors (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.
- 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.
- Ces revêtements sont obtenus par un procédé de fabrication à deux stades.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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).
- De plus, la couche de zinc pur de la première galvanisation disparaît complètement pour donner la couche d'alliage A2 (AI-Zn-Fe).
- Ces refroidissements réalisent ainsi un traitement thermochimique de diffusion contrôlée.
- Ces deux couches ont pour analyse globale respective: A1 et 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.
- Le procédé visé par l'invention permet donc une diffusion contrôlée de AI et 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...).
- 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.
- 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 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.
-
- Les échantillons ont été enroulés sur un mandrin de 10 mm de diamètre avant le test.
- Les fils à faible revêtement de zinc (10 pm) présentent de la rouille rouge après 3 jours d'exposition.
- 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.
- 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.
- 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.
- 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.
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8310660A FR2548216B1 (fr) | 1983-06-28 | 1983-06-28 | Fil d'acier a revetements superposes resistant a la corrosion |
FR8310660 | 1983-06-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0132424A1 EP0132424A1 (fr) | 1985-01-30 |
EP0132424B1 true EP0132424B1 (fr) | 1989-04-12 |
Family
ID=9290246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84401266A Expired EP0132424B1 (fr) | 1983-06-28 | 1984-06-19 | Fil d'acier à revêtements superposés résistant à la corrosion |
Country Status (7)
Country | Link |
---|---|
US (1) | US4605598A (fr) |
EP (1) | EP0132424B1 (fr) |
JP (1) | JPS6052568A (fr) |
AU (1) | AU567948B2 (fr) |
DE (1) | DE3477676D1 (fr) |
ES (1) | ES533776A0 (fr) |
FR (1) | FR2548216B1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63134653A (ja) * | 1986-11-22 | 1988-06-07 | Nippon Steel Corp | 耐食性および加工性にすぐれた合金めつき鋼材の製造法 |
US4830184A (en) * | 1988-04-21 | 1989-05-16 | Tri-Steel Industries Inc. | Metal wire spacer for use in the bundling of nested stacks of metal pieces |
JP2777902B2 (ja) * | 1989-04-06 | 1998-07-23 | 新日本製鐵株式会社 | 耐食性に優れた複層めっき鋼板 |
CH685065A5 (it) * | 1991-07-10 | 1995-03-15 | Alian Int Ag | Dado autobloccante. |
TW259820B (fr) * | 1992-07-01 | 1995-10-11 | Shinko Wire Co Ltd | |
JPH07109556A (ja) * | 1993-10-08 | 1995-04-25 | Shinko Kosen Kogyo Kk | 合金層被覆鋼線およびその製造方法 |
US5849408A (en) * | 1993-12-27 | 1998-12-15 | Nippon Mining & Metals Co., Ltd. | Hot-dip zinc plating product |
DE29814074U1 (de) * | 1998-08-07 | 1999-12-09 | Pfeifer Seil Hebetech | Preßfitting aus Stahl |
FR2788499B1 (fr) | 1999-01-20 | 2001-02-16 | Sagem | Dispositif de fermeture de boitier et boitier le comportant |
US6610423B2 (en) | 2000-02-29 | 2003-08-26 | Nippon Steel Corporation | Plated steel product having high corrosion resistance and excellent formability and method for production thereof |
EP1441400B1 (fr) * | 2003-01-17 | 2009-11-04 | Greatbatch Ltd. | Pile bouton hermétiquement scellée |
US20070119715A1 (en) * | 2005-11-25 | 2007-05-31 | Sacks Abraham J | Corrosion Resistant Wire Products and Method of Making Same |
EP1837097B1 (fr) * | 2006-03-13 | 2008-12-10 | Wolfgang Schmauser | Grillage soudé pour gabions |
ES2322740B1 (es) * | 2007-05-10 | 2010-04-06 | Asociacion Española De Fabricantes De Ladrillos Y Tejas De Arcilla Cocida, Hispalyt | Lamina flexible de ladrillos para la construccion de elementos arquitectonicos, y procedimiento de fabricacion de dicha lamina. |
US7901769B2 (en) * | 2008-11-21 | 2011-03-08 | Brow Richard K | Corrosion-resistant glasses for steel enamels |
JP2010165529A (ja) * | 2009-01-14 | 2010-07-29 | Sumitomo Electric Ind Ltd | アルミニウム合金線 |
JP2019096492A (ja) * | 2017-11-23 | 2019-06-20 | 株式会社オートネットワーク技術研究所 | アルミニウム系素線、撚線導体、編組線、および、ワイヤーハーネス |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE315712C (fr) * | ||||
US1307853A (en) * | 1919-06-24 | Assigwob | ||
US1468905A (en) * | 1923-07-12 | 1923-09-25 | Joseph L Herman | Metal-coated iron or steel article |
US2069658A (en) * | 1933-12-09 | 1937-02-02 | Robert F Renkin | Method of coating strip steel and product |
US2068904A (en) * | 1934-05-07 | 1937-01-26 | Northwestern Barb Wire Company | Galvanizing process |
BE440257A (fr) * | 1940-03-29 | 1941-02-28 | Kohle Und Eisenforschung Gmbh | |
US3190768A (en) * | 1961-07-24 | 1965-06-22 | Nat Steel Corp | Method for galvanizing steel |
US3320040A (en) * | 1963-08-01 | 1967-05-16 | American Smelting Refining | Galvanized ferrous article |
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 |
DK134571B (da) * | 1970-09-17 | 1976-11-29 | Fredericia Galvaniseringsansta | Fremgangsmåde til varmgalvanisering af jern- og ståloverflader med en zinklegering. |
US4152472A (en) * | 1973-03-19 | 1979-05-01 | Nippon Steel Corporation | Galvanized ferrous article for later application of paint coating |
US3952120A (en) * | 1974-05-31 | 1976-04-20 | Bethlehem Steel Corporation | Aluminum-zinc coated low-alloy ferrous product and method |
FR2306275A1 (fr) * | 1975-04-02 | 1976-10-29 | Garphytte Bruk Ab | Procede de fabrication de cables et de fils elastiques en acier au carbone presentant une resistance a la corrosion amelioree |
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 |
US4202921A (en) * | 1976-02-24 | 1980-05-13 | Aktiebolaget Garphytte Bruk | Process for the preparation of rope and spring wire of carbon steel with an improved corrosion resistance |
US4350539A (en) * | 1979-11-08 | 1982-09-21 | Bethlehem Steel Corporation | Method of improving the ductility of the coating of an aluminum-zinc alloy coated ferrous product |
US4287008A (en) * | 1979-11-08 | 1981-09-01 | Bethlehem Steel Corporation | Method of improving the ductility of the coating of an aluminum-zinc alloy coated ferrous product |
US4287009A (en) * | 1979-11-08 | 1981-09-01 | Bethlehem Steel Corporation | Method of producing an aluminum-zinc alloy coated ferrous product to improve corrosion resistance |
EP0037143B1 (fr) * | 1980-03-25 | 1985-03-20 | CENTRE DE RECHERCHES METALLURGIQUES CENTRUM VOOR RESEARCH IN DE METALLURGIE Association sans but lucratif | Procédé de revêtement à chaud |
AU544400B2 (en) * | 1980-03-25 | 1985-05-23 | International Lead Zinc Research Organization Inc. | Zinc-aluminum alloys and coatings |
LU82598A1 (fr) * | 1980-07-09 | 1982-02-17 | Arbed | Procede et installation pour la metallisation a chaud d'objets en metal |
EP0111039A1 (fr) * | 1982-12-07 | 1984-06-20 | James W. Hogg | Procédé de galvanisation et de recuit en continu à grande vitesse d'un fil métallique |
-
1983
- 1983-06-28 FR FR8310660A patent/FR2548216B1/fr not_active Expired
-
1984
- 1984-06-19 EP EP84401266A patent/EP0132424B1/fr not_active Expired
- 1984-06-19 DE DE8484401266T patent/DE3477676D1/de not_active Expired
- 1984-06-26 US US06/624,961 patent/US4605598A/en not_active Expired - Lifetime
- 1984-06-26 AU AU29894/84A patent/AU567948B2/en not_active Ceased
- 1984-06-27 ES ES533776A patent/ES533776A0/es active Granted
- 1984-06-28 JP JP59132127A patent/JPS6052568A/ja active Granted
Non-Patent Citations (1)
Title |
---|
"La galvanisation des fils tréfilés" UNIREC (1987) * |
Also Published As
Publication number | Publication date |
---|---|
ES8601327A1 (es) | 1985-10-16 |
FR2548216A1 (fr) | 1985-01-04 |
AU2989484A (en) | 1985-01-03 |
JPH0573824B2 (fr) | 1993-10-15 |
EP0132424A1 (fr) | 1985-01-30 |
ES533776A0 (es) | 1985-10-16 |
US4605598A (en) | 1986-08-12 |
JPS6052568A (ja) | 1985-03-25 |
AU567948B2 (en) | 1987-12-10 |
FR2548216B1 (fr) | 1988-10-21 |
DE3477676D1 (en) | 1989-05-18 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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AK | Designated contracting states |
Designated state(s): BE DE FR GB IT LU NL |
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17P | Request for examination filed |
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