EP0851039B1 - Stainless steel wire and process for production - Google Patents

Stainless steel wire and process for production Download PDF

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Publication number
EP0851039B1
EP0851039B1 EP97402907A EP97402907A EP0851039B1 EP 0851039 B1 EP0851039 B1 EP 0851039B1 EP 97402907 A EP97402907 A EP 97402907A EP 97402907 A EP97402907 A EP 97402907A EP 0851039 B1 EP0851039 B1 EP 0851039B1
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EP
European Patent Office
Prior art keywords
wire
diameter
equal
wire according
mpa
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EP97402907A
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German (de)
French (fr)
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EP0851039A1 (en
Inventor
Joel Marandel
Jean-Michel Hauser
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ugitech
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Sprint Metal Societe de Production Internationale de Trefiles
Ugine Savoie Imphy SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/902—Metal treatment having portions of differing metallurgical properties or characteristics
    • Y10S148/908—Spring
    • 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
    • Y10T428/12431—Foil or filament smaller than 6 mils

Definitions

  • the present invention relates to a stainless steel wire of small diameter having high mechanical characteristics, usable in particular for the manufacture of springs or elastomer reinforcement wires.
  • fine drawn wires having very mechanical characteristics high, made of unstable austenitic stainless steel type 1.4310 (according to standards EN 10088 and Pr EN 10270.3) including chemical analysis comprises, by weight, from 16 to 19% of chromium, from 6 to 9.5% of nickel, at most 0.8 % molybdenum, at most 0.11% nitrogen and 0.05 to 0.15% carbon.
  • the mechanical characteristics obtained for the drawn wire result from both the work hardening and the formation of martensite ⁇ 'generated by work hardening resulting from wire drawing.
  • These wires can be used for the manufacture of springs which are obtained by shaping the wire then thermal relaxation treatment and hardening. This technique has at least one drawback which results from very significant consolidation during the wire drawing. Because of the importance of this consolidation, when the diameter of the wire is small, it cannot be obtained in several cycles alternating drawing and heat treatment of hyperemperance. This complicates manufacturing and increases its cost.
  • fine drawn wires having characteristics very high mechanical properties, usable in particular for the manufacture of springs, made of austenitic stainless steel with secondary hardening by NiAl precipitation, type 1.4568 (according to EN 10088 and Pr EN 10270) the chemical analysis of which comprises, by weight, from 16 to 18% of chromium, from 6.5 to 7.8% nickel and 0.7-1.5% aluminum.
  • This technique has the advantage of making it possible to manufacture the springs from a wire with mechanical characteristics significantly lower than desired mechanical characteristics for the spring, which facilitates the carrying out the shaping operation. Indeed, the characteristics final mechanical can be obtained by heat treatment of aging which causes precipitation hardening.
  • this technique has the disadvantage of using steel grades containing easily oxidizable or nitriding elements which generate the formation of harmful inclusions for the fatigue strength of the springs, on the other hand these grades of steel lead, as in the previous case, to a very significant consolidation during wire drawing, which also requires way, a succession of cycles alternating drawing and treatment of hyper quenching.
  • Document DE-A-2 338 282 describes a steel for the manufacture of very long wire, the composition of which overlaps that claimed.
  • the object of the present invention is to remedy these drawbacks by offering a precipitation hardenable austenitic stainless steel wire, having, in the strain-hardened state before aging, a tensile strength greater than 2200 MPa for a diameter between 0.4 and 0.5 mm, greater than 2225 MPa for a diameter between 0.3 and 0.4 mm, greater than 2250 MPa for a diameter between 0.2 and 0.3 mm, greater than 2275 mm for a diameter less than 0.2 mm, and which is easy to draw or cold roll.
  • This wire can be of round, oval or polygonal cross section, for example of triangular, square, rectangular or hexagonal section.
  • its dimension is defined by its diameter
  • its section is not round, its dimension is defined by the diameter of a wire whose section would have the same surface. In all cases, we will talk about the diameter of the wire.
  • the subject of the invention is a stainless steel wire, of diameter less than 2 mm and of tensile strength greater than 2100 MPa, consisting of a steel whose chemical composition comprises, by weight: 0% ⁇ C ⁇ 0.03% 0% ⁇ Mn ⁇ 2% 0% ⁇ If ⁇ 0.5% 8% ⁇ Ni ⁇ 9% 17% ⁇ Cr ⁇ 18% 0% ⁇ Mo ⁇ 0.4% 3% ⁇ Cu ⁇ 3.5% 0% ⁇ N ⁇ 0.03% S ⁇ 0.01% P ⁇ 0.04% the remainder being iron and impurities resulting from processing.
  • This wire can be used in particular to make a spring, make a cable or can constitute the core of an elastomer reinforcement wire.
  • the invention also relates to a method for manufacturing the yarn according to the invention.
  • the process consists of sourcing a wire rod of diameter greater than or equal to 5 mm made of an austenitic steel whose composition chemical complies with what is indicated above, to submit it to a hyperhardening treatment to give it an entirely austenitic structure, pickling and shaping it by cold plastic deformation, generally without intermediate heat treatment, or, for the smallest diameters, with an intermediate hyperemperation followed by a reduction in section greater than 300.
  • the purpose of cold plastic deformation is to in particular, to reduce the section and, possibly, to give the section of the wire the desired shape (round, square, triangle, etc.).
  • This plastic deformation can be made by wire drawing, rolling or any other manufacturing process of a wire by cold plastic deformation.
  • the invention relates to an austenitic stainless steel, the chemical composition of which comprises, by weight: 0% ⁇ C ⁇ 0.03% 0% ⁇ Mn ⁇ 2% 0% ⁇ If ⁇ 0.5% 8% ⁇ Ni ⁇ 9% 17% ⁇ Cr ⁇ 18% 0% ⁇ Mo ⁇ 0.4% 3% ⁇ Cu ⁇ 3.5% 0% ⁇ N ⁇ 0.03% S ⁇ 0.01% P ⁇ 0.04% the remainder being iron and impurities resulting from processing.
  • this steel exhibits the advantage of achieving high mechanical characteristics by drawing and structural hardening without the need for intermediate annealing, even for diameter reductions greater than 20 times.
  • a wire is produced by hot rolling machine with a diameter greater than or equal to 5 mm which is subjected to a treatment hyperhardening consisting of heating to a temperature between 800 ° C and 1250 ° C followed by air cooling, or faster, in order to impart an entirely austenitic structure, then it is pickled.
  • a treatment hyperhardening consisting of heating to a temperature between 800 ° C and 1250 ° C followed by air cooling, or faster, in order to impart an entirely austenitic structure, then it is pickled.
  • the hyper-soaked and pickled wire rod thus obtained is then drawn until a diameter of less than 2 mm, in one or more stages of several passes each, without the need for any intermediate heat treatment, at month as long as the ratio of the initial section to the final section remains below 485.
  • To manufacture the smallest diameters, especially the smaller diameters at 0.25 mm it may be necessary to make an intermediate overflow intended to restore the deformation capacity of the metal.
  • the final work hardening i.e. carried out after the intermediate overheating, must correspond to a section reduction greater than 300 (final section / initial section ⁇ 1/300).
  • This aging treatment consists of heating for a time between 5 min and 3 hours, at a temperature between 400 and 475 ° C It generates a hardening resulting from the precipitation of Cu ⁇ (c.f.c.) in a centered cubic structure ( ⁇ 'martensite induced by wire drawing deformation). This hardening is, all other things being equal, the higher the Martensite content is higher.
  • the aging treatment can be performed either directly after drawing or after carrying out operations additional on the wire, for example after having shaped it to manufacture a spiral spring.
  • drawn wire of 1 mm, 0.5 mm and 0.25 mm diameter was produced in accordance with the invention, starting with a machine wire 5.5 mm in diameter made up of a austenitic stainless steel, the chemical composition of which was as follows (in% by weight): VS Mn Yes Or Cr Mo Cu NOT S P 0.011 1.83 0.4 8.08 17.24 0.36 3.24 0.027 0.004 0.025
  • the wire rod was hyper-soaked by reheating to 1080 ° C and water cooling then pickled.
  • wires thus obtained were used to manufacture springs such as indicated above which have the advantage of having characteristics at least equal to those of springs manufactured in standard grade 1.4310, with a equal or even improved relaxation, while being simpler and less costly to to manufacture.
  • the yarns according to the invention can also be used to make elastomeric reinforcing threads, for example example for making reinforcements of tires.
  • These reinforcing threads comprise a core consisting of a drawn wire according to the invention coated, by example, by nickel plating and brass plating (this coating is intended to ensure good bond with rubber).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)
  • Metal Extraction Processes (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Wire Processing (AREA)
  • Ropes Or Cables (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

Stainless steel contains by weight 0-0.03% carbon, 0-2% manganese, 0-0.5% silicon, 8-9% nickel, 17-18% chromium, 0-0.4% molybdenum, 3-3.5% copper, 0-0.03% nitrogen, less than 0.01% sulphur and less than 0.04% phosphorous, the rest being iron and impurities. Also claimed are wire made of this steel, less than 2 mm. in diameter and with tensile strength over 2100 MPa, also heating a preformed wire of such steel with a diameter of at least 5 mm. and fast-quenching it to produce an austenitic structure, then cold-drawing it to a diameter below 2 mm.

Description

La présente invention concerne un fil en acier inoxydable de petit diamètre ayant des caractéristiques mécaniques élevées, utilisable notamment pour la fabrication de ressorts ou de fils de renforcement d'élastomères.The present invention relates to a stainless steel wire of small diameter having high mechanical characteristics, usable in particular for the manufacture of springs or elastomer reinforcement wires.

On connaít des fils tréfilés fins, ayant des caractéristiques mécaniques très élevées, constitués d'un acier inoxydable austénitique instable du type 1.4310 (selon les normes EN 10088 et Pr EN 10270.3) dont l'analyse chimique comprend, en poids, de 16 à 19 % de chrome, de 6 à 9,5 % de nickel, au plus 0,8 % de molybdène, au plus 0,11 % d'azote et de 0,05 à 0,15 % de carbone. Les caractéristiques mécaniques obtenues pour le fil tréfilé résultent à la fois de l'écrouissage et de la formation de martensite α' engendrée par l'écrouissage résultant du tréfilage. Ces fils peuvent être utilisés pour la fabrication de ressorts qui sont obtenus par mise en forme du fil puis traitement thermique de relaxation et de durcissement. Cette technique présente au moins un inconvénient qui résulte de la consolidation très importante durant le tréfilage. Du fait de l'importance de cette consolidation, lorsque le diamètre du fil est petit, il ne peut être obtenu qu'en plusieurs cycles alternant tréfilage et traitement thermique d'hypertrempe. Cela complique la fabrication et augmente son coût.We know fine drawn wires, having very mechanical characteristics high, made of unstable austenitic stainless steel type 1.4310 (according to standards EN 10088 and Pr EN 10270.3) including chemical analysis comprises, by weight, from 16 to 19% of chromium, from 6 to 9.5% of nickel, at most 0.8 % molybdenum, at most 0.11% nitrogen and 0.05 to 0.15% carbon. The mechanical characteristics obtained for the drawn wire result from both the work hardening and the formation of martensite α 'generated by work hardening resulting from wire drawing. These wires can be used for the manufacture of springs which are obtained by shaping the wire then thermal relaxation treatment and hardening. This technique has at least one drawback which results from very significant consolidation during the wire drawing. Because of the importance of this consolidation, when the diameter of the wire is small, it cannot be obtained in several cycles alternating drawing and heat treatment of hyperemperance. This complicates manufacturing and increases its cost.

On connaít également des fils tréfilés fins, ayant des caractéristiques mécaniques très élevées, utilisables notamment pour la fabrication de ressorts, constitués d'un acier inoxydable austénitique à durcissement secondaire par précipitation de NiAl, du type 1.4568 (selon la norme EN 10088 et Pr EN 10270) dont l'analyse chimique comprend, en poids, de 16 à 18 % de chrome, de 6,5 à 7,8 % de nickel et de 0,7 à 1,5 % d'aluminium.We also know fine drawn wires, having characteristics very high mechanical properties, usable in particular for the manufacture of springs, made of austenitic stainless steel with secondary hardening by NiAl precipitation, type 1.4568 (according to EN 10088 and Pr EN 10270) the chemical analysis of which comprises, by weight, from 16 to 18% of chromium, from 6.5 to 7.8% nickel and 0.7-1.5% aluminum.

Cette technique présente l'avantage de permettre de fabriquer les ressorts à partir d'un fil de caractéristiques mécaniques sensiblement inférieure aux caractéristiques mécaniques souhaitées pour le ressort, ce qui facilite la réalisation de l'opération de mise en forme. En effet, les caractéristiques mécaniques finales peuvent être obtenues par un traitement thermique de vieillissement qui engendre un durcissement par précipitation. Par contre, cette technique présente d'une part l'inconvénient d'utiliser des nuances d'acier contenant des éléments facilement oxydables ou nitrurables qui engendrent la formation d'inclusions néfastes pour la tenue en fatigue des ressorts, d'autre part ces nuances d'acier conduisent, comme dans le cas précédant, à une consolidation très importante pendant le tréfilage ce qui nécessite, de la même façon, une succession de cycles alternant tréfilage et traitement d'hypertrempe.This technique has the advantage of making it possible to manufacture the springs from a wire with mechanical characteristics significantly lower than desired mechanical characteristics for the spring, which facilitates the carrying out the shaping operation. Indeed, the characteristics final mechanical can be obtained by heat treatment of aging which causes precipitation hardening. However, this technique has the disadvantage of using steel grades containing easily oxidizable or nitriding elements which generate the formation of harmful inclusions for the fatigue strength of the springs, on the other hand these grades of steel lead, as in the previous case, to a very significant consolidation during wire drawing, which also requires way, a succession of cycles alternating drawing and treatment of hyper quenching.

Le document DE-A-2 338 282 décrit un acier pour la fabrication de fil de grande longueur dont la composition recoupe celle revendiquée.Document DE-A-2 338 282 describes a steel for the manufacture of very long wire, the composition of which overlaps that claimed.

Le but de la présente invention est de remédier à ces inconvénients en proposant un fil en acier inoxydable austénitique durcissable par précipitation, ayant, à l'état écroui avant vieillissement, une résistance à la traction supérieure à 2200 MPa pour un diamètre compris entre 0,4 et 0,5 mm, supérieure à 2225 MPa pour un diamètre compris entre 0,3 et 0,4 mm, supérieure à 2250 MPa pour un diamètre compris entre 0,2 et 0,3 mm, supérieure à 2275 mm pour un diamètre inférieur à 0,2 mm, et qui soit facile à tréfiler ou à laminer à froid.The object of the present invention is to remedy these drawbacks by offering a precipitation hardenable austenitic stainless steel wire, having, in the strain-hardened state before aging, a tensile strength greater than 2200 MPa for a diameter between 0.4 and 0.5 mm, greater than 2225 MPa for a diameter between 0.3 and 0.4 mm, greater than 2250 MPa for a diameter between 0.2 and 0.3 mm, greater than 2275 mm for a diameter less than 0.2 mm, and which is easy to draw or cold roll.

Ce fil peut être de section ronde, ovale ou polygonale, par exemple de section triangulaire, carrée, rectangulaire ou hexagonale. Lorsqu'il est de section ronde, sa dimension est définie par son diamètre, lorsque sa section n'est pas ronde, sa dimension est définie par le diamètre d'un fil dont la section aurait la même surface. Dans tous les cas, on parlera du diamètre du fil.This wire can be of round, oval or polygonal cross section, for example of triangular, square, rectangular or hexagonal section. When it is of section round, its dimension is defined by its diameter, when its section is not round, its dimension is defined by the diameter of a wire whose section would have the same surface. In all cases, we will talk about the diameter of the wire.

A cet effet, l'invention a pour objet un fil en acier inoxydable, de diamètre inférieur à 2 mm et de résistance à la traction supérieure à 2100 MPa, constitué d'un acier dont la composition chimique comprend, en poids : 0% ≤ C ≤ 0,03 % 0% ≤ Mn ≤ 2% 0% ≤ Si ≤ 0,5% 8% ≤ Ni ≤ 9% 17% ≤ Cr ≤ 18% 0% ≤ Mo ≤ 0,4 % 3% ≤ Cu ≤ 3,5% 0 % ≤ N ≤ 0,03 % S ≤ 0,01 % P ≤ 0,04% le reste étant du fer et des impuretés résultant de l'élaboration.To this end, the subject of the invention is a stainless steel wire, of diameter less than 2 mm and of tensile strength greater than 2100 MPa, consisting of a steel whose chemical composition comprises, by weight: 0% ≤ C ≤ 0.03% 0% ≤ Mn ≤ 2% 0% ≤ If ≤ 0.5% 8% ≤ Ni ≤ 9% 17% ≤ Cr ≤ 18% 0% ≤ Mo ≤ 0.4% 3% ≤ Cu ≤ 3.5% 0% ≤ N ≤ 0.03% S ≤ 0.01% P ≤ 0.04% the remainder being iron and impurities resulting from processing.

Ce fil peut être utilisé notamment pour fabriquer un ressort, confectionner un cable ou peut constituer l'âme d'un fil de renforcement d'élastomère.This wire can be used in particular to make a spring, make a cable or can constitute the core of an elastomer reinforcement wire.

L'invention concerne également un procédé pour la fabrication du fil selon l'invention. Le procédé consiste à s'approvisionner en un fil machine de diamètre supérieur ou égal à 5 mm constitué d'un acier austénitique dont la composition chimique est conforme à ce qui est indiqué ci-dessus, à le soumettre à un traitement d'hypertrempe pour lui conférer une structure entièrement austénitique, à le décaper et à le mettre en forme par déformation plastique à froid, généralement sans traitement thermique intermédiaire, ou, pour les plus petits diamètres, avec une hypertrempe intermédiaire suivie d'une réduction de section supérieure à 300. La mise en forme par déformation plastique à froid a pour but, notamment, de réduire la section et, éventuellement, de donner à la section du fil la forme souhaitée (rond, carré, triangle, etc.). Cette déformation plastique peut être effectuée par tréfilage, par laminage ou par tout autre procédé de fabrication d'un fil par déformation plastique à froid. On peut compléter le procédé par un traitement thermique de vieillissement, effectué sur le fil fortement écroui, et constitué d'un maintien pendant une durée comprise entre 5 mn et 3 heures à une température comprise entre 400 et 475 °C.The invention also relates to a method for manufacturing the yarn according to the invention. The process consists of sourcing a wire rod of diameter greater than or equal to 5 mm made of an austenitic steel whose composition chemical complies with what is indicated above, to submit it to a hyperhardening treatment to give it an entirely austenitic structure, pickling and shaping it by cold plastic deformation, generally without intermediate heat treatment, or, for the smallest diameters, with an intermediate hyperemperation followed by a reduction in section greater than 300. The purpose of cold plastic deformation is to in particular, to reduce the section and, possibly, to give the section of the wire the desired shape (round, square, triangle, etc.). This plastic deformation can be made by wire drawing, rolling or any other manufacturing process of a wire by cold plastic deformation. We can complete the process with a heat treatment of aging, carried out on the highly hardened wire, and consisting of maintenance for a period of between 5 min and 3 hours at a temperature between 400 and 475 ° C.

L'invention concerne enfin un acier inoxydable austénitique dont la composition chimique comprend, en poids : 0% ≤ C ≤ 0,03% 0% ≤ Mn ≤ 2% 0% ≤ Si ≤ 0,5% 8% ≤ Ni ≤ 9% 17% ≤ Cr ≤ 18% 0 % ≤ Mo ≤ 0,4 % 3% ≤ Cu ≤ 3,5% 0 % ≤ N ≤ 0, 03% S ≤ 0,01 % P ≤ 0,04% le reste étant du fer et des impuretés résultant de l'élaboration.Finally, the invention relates to an austenitic stainless steel, the chemical composition of which comprises, by weight: 0% ≤ C ≤ 0.03% 0% ≤ Mn ≤ 2% 0% ≤ If ≤ 0.5% 8% ≤ Ni ≤ 9% 17% ≤ Cr ≤ 18% 0% ≤ Mo ≤ 0.4% 3% ≤ Cu ≤ 3.5% 0% ≤ N ≤ 0.03% S ≤ 0.01% P ≤ 0.04% the remainder being iron and impurities resulting from processing.

L'invention va maintenant être décrite de façon plus précise, mais non limitative, et illustrée par les exemples qui suivent.The invention will now be described in more detail, but not limiting, and illustrated by the examples which follow.

Pour fabriquer un fil tréfilé fin de diamètre inférieur ou égal à 2 mm, on utilise un fil machine de diamètre supérieur ou égal à 5 mm en acier inoxydable austénitique dont la composition chimique comprend, en poids :

  • moins de 0,03 % de carbone car, au delà, la martensite présente en grande proportion dans le fil tréfilé devient sensible à la rupture différée et les ressorts peuvent, alors, se fissurer sous l'effet des contraintes résiduelles de formage ; en général la teneur en carbone est supérieure à 0,005 % car il est extrêmement difficile de descendre en dessous lors des opérations d'affinage ;
  • de 0 %à 2 %, et de préférence plus de 0,2 %, de manganèse pour fixer le soufre et éviter la formation de sulfures de chrome à bas point de fusion ; au delà de 2 % l'acier devient très difficile à décarburer sans réoxyder le manganèse, ce qui augmente de façon très importante les coûts de fabrication ;
  • de 0 % à 0,5 % de silicium dont la présence (en général plus de 0,1 %) résulte de l'élaboration de l'acier, durcit fortement la martensite présente dans les fils écrouis ; afin d'éviter un durcissement excessif avant l'opération de mise en forme, on limite sa teneur à 0,5 % ;
  • de 8 % à 9 % de nickel, pour garantir une structure austénitique pendant le laminage à chaud et après le traitement d'hypertrempe ;
  • de 17 % à 18 % de chrome pour obtenir une résistance à la corrosion suffisante sans engendrer trop de difficultés de décapage après le laminage à chaud ;
  • de 0 % à 0,4 % de molybdène pour améliorer la tenue à la corrosion sans détériorer les autres propriétés ;
  • de 3 % à 3,5 % de cuivre pour permettre le durcissement par précipitation au cours du traitement de vieillissement après tréfilage ; la teneur est limitée à 3,5 % car, au delà, le cuivre engendre des difficultés de laminage à chaud ;
  • de 0 % à 0,03 % d'azote qui résulte de l'élaboration ; sa teneur est généralement supérieure à 0,005 %, mais doit rester inférieure à 0,03 % pour éviter des risques de fissuration en différé ;
  • moins de 0,01 % de soufre qui est une impureté dont la teneur doit être limitée car, en trop grande quantité, elle rend cassants les fils tréfilés ;
  • moins de 0,04 % de phosphore qui est une impureté pouvant créer des défauts lors du laminage à chaud ;
le reste étant du fer et des impuretés résultant de l'élaboration.To manufacture a thin drawn wire of diameter less than or equal to 2 mm, a machine wire of diameter greater than or equal to 5 mm is used in austenitic stainless steel, the chemical composition of which comprises, by weight:
  • less than 0.03% of carbon because, beyond, the martensite present in large proportion in the drawn wire becomes sensitive to deferred rupture and the springs can, then, crack under the effect of the residual stresses of forming; in general the carbon content is greater than 0.005% because it is extremely difficult to descend below during the refining operations;
  • from 0% to 2%, and preferably more than 0.2%, of manganese to fix the sulfur and avoid the formation of chromium sulfides with low melting point; beyond 2% the steel becomes very difficult to decarburize without reoxidizing the manganese, which significantly increases the manufacturing costs;
  • from 0% to 0.5% silicon, the presence of which (in general more than 0.1%) results from the production of steel, strongly hardens the martensite present in the work hardened wires; in order to avoid excessive hardening before the shaping operation, its content is limited to 0.5%;
  • from 8% to 9% nickel, to guarantee an austenitic structure during hot rolling and after the hyperhardening treatment;
  • from 17% to 18% chromium to obtain sufficient corrosion resistance without causing too much pickling difficulty after hot rolling;
  • from 0% to 0.4% molybdenum to improve the corrosion resistance without deteriorating the other properties;
  • from 3% to 3.5% copper to allow precipitation hardening during the aging treatment after wire drawing; the content is limited to 3.5% because, beyond, copper causes difficulties in hot rolling;
  • from 0% to 0.03% nitrogen which results from the production; its content is generally greater than 0.005%, but must remain less than 0.03% to avoid the risk of delayed cracking;
  • less than 0.01% of sulfur which is an impurity the content of which must be limited because, in too large a quantity, it makes the drawn wires brittle;
  • less than 0.04% of phosphorus which is an impurity which can create defects during hot rolling;
the remainder being iron and impurities resulting from processing.

L'ensemble des éléments a un effet sur la stabilité de la structure austénitique pendant le laminage à chaud et après hypertrempe, mais , également, sur la structure de solidification. Les domaines de composition pour chacun des éléments ont été choisis de telle sorte que cette structure de solidification soit ferritique et exempte de fortes ségrégations.All the elements have an effect on the stability of the structure austenitic during hot rolling and after hyper quenching, but, also, on the solidification structure. Composition areas for each of the elements have been chosen so that this structure of solidification is ferritic and free of strong segregation.

Comme l'ont observé de façon inattendue les inventeurs, cet acier présente l'avantage de permettre d'atteindre des caractéristiques mécaniques élevées par tréfilage et durcissement structural sans nécessiter de recuit intermédiaire, même pour des réduction de diamètre supérieures à 20 fois.As the inventors have unexpectedly observed, this steel exhibits the advantage of achieving high mechanical characteristics by drawing and structural hardening without the need for intermediate annealing, even for diameter reductions greater than 20 times.

Avec l'acier qui vient d'être défini, on fabrique par laminage à chaud un fil machine de diamètre supérieur ou égal à 5 mm qui est soumis à un traitement d'hypertrempe consistant en un chauffage à une température comprise entre 800 °C et 1250 °C suivi d'un refroidissement à l'air, ou plus rapide, afin de lui conférer une structure entièrement austénitique, puis il est décapé.With the steel which has just been defined, a wire is produced by hot rolling machine with a diameter greater than or equal to 5 mm which is subjected to a treatment hyperhardening consisting of heating to a temperature between 800 ° C and 1250 ° C followed by air cooling, or faster, in order to impart an entirely austenitic structure, then it is pickled.

Le fil machine hypertrempé et décapé ainsi obtenu est alors tréfilé jusqu'à un diamètre inférieur à 2 mm, en une ou plusieurs étapes de plusieurs passes chacune, sans qu'il soit nécessaire de faire de traitement thermique intermédiaire, au mois tant que le rapport de la section initiale à la section finale reste inférieur à 485. Pour fabriquer les plus petits diamètres, notamment les diamètres inférieurs à 0,25 mm, il peut être nécessaire de faire une hypertrempe intermédiaire destinée à restaurer la capacité de déformation du métal. Cependant, dans ce cas, pour obtenir les caractéristiques mécaniques souhaitées, l'écrouissage final, c'est à dire effectué après l'hypertrempe intermédiaire, doit correspondre à une réduction de section supérieure à 300 (section finale / section initiale ≤ 1 / 300).The hyper-soaked and pickled wire rod thus obtained is then drawn until a diameter of less than 2 mm, in one or more stages of several passes each, without the need for any intermediate heat treatment, at month as long as the ratio of the initial section to the final section remains below 485. To manufacture the smallest diameters, especially the smaller diameters at 0.25 mm, it may be necessary to make an intermediate overflow intended to restore the deformation capacity of the metal. However, in this case, to obtain the desired mechanical characteristics, the final work hardening, i.e. carried out after the intermediate overheating, must correspond to a section reduction greater than 300 (final section / initial section ≤ 1/300).

Pour obtenir les propriétés mécaniques souhaitées en final, c'est à dire, une résistance à la traction, fonction du diamètre, conformément à la norme, reprise au tableau ci-dessous, on effectue un traitement thermique de vieillissement. résistance à la traction minimale imposée par les normes Φ mm 1,5/1,75 1,25/1,5 1/1,25 0,8/1 0,65/0,8 0,5/0,65 0,4/0,5 0,3/0,4 0,2/0,3 < 0,2 R MPa 1950 2000 2050 2100 2125 2150 2200 2225 2250 2275 To obtain the final desired mechanical properties, that is to say, a tensile strength, a function of the diameter, in accordance with the standard, listed in the table below, an aging heat treatment is carried out. minimum tensile strength required by standards Φ mm 1.5 / 1.75 1.25 / 1.5 1 / 1.25 0.8 / 1 0.65 / 0.8 0.5 / 0.65 0.4 / 0.5 0.3 / 0.4 0.2 / 0.3 <0.2 R MPa 1950 2000 2050 2100 2125 2150 2200 2225 2250 2275

Ce traitement de vieillissement consiste en un chauffage pendant un temps compris entre 5 mn et 3 heures, à une température comprise entre 400 et 475 °C Il engendre un durcissement résultant de la précipitation de Cu ε (c.f.c.) dans une structure cubique centrée (martensite α' induite par la déformation de tréfilage). Ce durcissement est, toutes choses égales par ailleurs, d'autant plus élevé que la teneur en martensite a' est plus élevée.This aging treatment consists of heating for a time between 5 min and 3 hours, at a temperature between 400 and 475 ° C It generates a hardening resulting from the precipitation of Cu ε (c.f.c.) in a centered cubic structure (α 'martensite induced by wire drawing deformation). This hardening is, all other things being equal, the higher the Martensite content is higher.

Selon l'application envisagée, le traitement de vieillissement peut être effectué soit directement après tréfilage, soit après avoir effectué des opérations supplémentaires sur le fil, par exemple après l'avoir mis en forme pour fabriquer un ressort spirale.Depending on the intended application, the aging treatment can be performed either directly after drawing or after carrying out operations additional on the wire, for example after having shaped it to manufacture a spiral spring.

A titre d'exemple, on a fabriqué des fils tréfilés de 1 mm, 0,5 mm et 0,25 mm de diamètre conforme à l'invention en partant d'un fil machine de 5,5 mm de diamètre constitué d'un acier inoxydable austénitique dont la composition chimique était la suivante (en % en poids) : C Mn Si Ni Cr Mo Cu N S P 0,011 1,83 0,4 8,08 17,24 0,36 3,24 0,027 0,004 0,025 By way of example, drawn wire of 1 mm, 0.5 mm and 0.25 mm diameter was produced in accordance with the invention, starting with a machine wire 5.5 mm in diameter made up of a austenitic stainless steel, the chemical composition of which was as follows (in% by weight): VS Mn Yes Or Cr Mo Cu NOT S P 0.011 1.83 0.4 8.08 17.24 0.36 3.24 0.027 0.004 0.025

Le fil machine a été hypertrempé par réchauffage à 1080 °C et refroidissement à l'eau puis décapé.The wire rod was hyper-soaked by reheating to 1080 ° C and water cooling then pickled.

Le fil machine a alors été tréfilé selon les schémas suivants :

  • fil de 1 mm de diamètre : en une descente de 5,5 mm à 1 mm, en 12 passes ;
  • fil de 0,5 mm de diamètre :à partir du fil écroui de 1 mm, en une descente de 8 passes de 1 mm à 0,5 mm ;
  • fil de 0,25 mm de diamètre : à partir du fil écroui de 1 mm, en une descente de 5 passes de 1 mm à 0,7 mm suivie d'une descente de 8 passes de 0,7 mm à 0,25 mm; sans traitement thermique intermédiaire.
The wire rod was then drawn according to the following diagrams:
  • wire 1 mm in diameter: in a descent from 5.5 mm to 1 mm, in 12 passes;
  • wire of 0.5 mm in diameter: from the hardened wire of 1 mm, in a descent of 8 passes from 1 mm to 0.5 mm;
  • 0.25 mm diameter wire: from the 1 mm work hardened wire, in a 5-pass descent from 1 mm to 0.7 mm followed by an 8-pass descent from 0.7 mm to 0.25 mm ; without intermediate heat treatment.

Après tréfilage le fil a été vieilli par maintient à 435°C pendant 1 heure.After drawing the wire was aged by maintaining at 435 ° C for 1 hour.

Les caractéristiques mécaniques (résistance à la rupture Rm, et résistance pour une déformation plastique de 0,2 % Rp0,2) obtenues avant et après vieillissement, ainsi que le taux de martensite α', étaient :

Figure 00060001
The mechanical characteristics (tensile strength Rm, and resistance to plastic deformation of 0.2% Rp 0.2 ) obtained before and after aging, as well as the rate of martensite α ', were:
Figure 00060001

Les fils ainsi obtenus ont été utilisés pour fabriquer des ressorts comme indiqué ci-dessus qui ont l'avantage de présenter des caractéristiques au moins égales à celles des ressorts fabriqués en nuance standard 1.4310, avec une relaxation égale, voire améliorée, tout en étant plus simples et moins coûteux à fabriquer.The wires thus obtained were used to manufacture springs such as indicated above which have the advantage of having characteristics at least equal to those of springs manufactured in standard grade 1.4310, with a equal or even improved relaxation, while being simpler and less costly to to manufacture.

Du fait de leurs caractéristiques, les fils selon l'invention peuvent également être utilisés pour fabriquer des fils de renforcement d'élastomères, par exemple pour réaliser des armatures de pneumatiques. Ces fils de renforcement comportent une âme constituée d'un fil tréfilé selon l'invention revêtue, par exemple, par nickelage et laitonnage (ce revêtement est destiné à assurer une bonne liaison avec le caoutchouc).Owing to their characteristics, the yarns according to the invention can also be used to make elastomeric reinforcing threads, for example example for making reinforcements of tires. These reinforcing threads comprise a core consisting of a drawn wire according to the invention coated, by example, by nickel plating and brass plating (this coating is intended to ensure good bond with rubber).

Claims (13)

  1. Stainless steel wire of diameter smaller than 2 mm and with a tensile strength higher than 2100 MPa, characterized in that it consists of a steel whose chemical composition includes, by weight: 0 % ≤ C ≤ 0.03 % 0 % ≤ Mn ≤ 2 % 0 % ≤ Si ≤ 0.5 % 8 % ≤ Ni ≤ 9 % 17 % ≤ Cr ≤ 18 % 0 % ≤ Mo ≤ 0.4 % 3 % ≤ Cu ≤ 3.5 % 0 % ≤ N ≤ 0.03 % S ≤ 0.01 % P ≤ 0.04 % the remainder being iron and impurities resulting from the production.
  2. Wire according to Claim 1, characterized in that its diameter is smaller than or equal to 0.5 mm and its tensile strength higher than or equal to 2200 MPa.
  3. Wire according to Claim 1 or 2, characterized in that its diameter is smaller than or equal to 0.3 mm and its tensile strength higher than or equal to 2250 MPa.
  4. Wire according to Claim 1, 2 or 3, characterized in that its diameter is smaller than or equal to 0.2 mm and its tensile strength higher than or equal to 2275 MPa.
  5. Spring characterized in that it consists of a wire according to any one of Claims 1 to 4.
  6. Wire for elastomer reinforcement comprising at least one core made of stainless steel, characterized in that the core consists of a wire according to any one of Claims 1 to 4.
  7. Process for the manufacture of a wire according to Claim 1, characterized in that:
    a supply is obtained of a machine wire of diameter greater than or equal to 5 mm made of a steel whose chemical composition includes, by weight: 0 % ≤ C ≤ 0.03 % 0 % ≤ Mn ≤ 2 % 0 % ≤ Si ≤ 0.5 % 8 % ≤ Ni ≤ 9 % 17 % ≤ Cr ≤ 18 % 0 % ≤ Mo ≤ 0.4 % 3 % ≤ Cu ≤ 3.5 % 0 % ≤ N ≤ 0.03 % S ≤ 0.01 % P ≤ 0.04 % the remainder being iron and impurities resulting from the production,
    a hyperquenching is performed on the machine wire in order to obtain an entirely austenitic structure,
    and a forming by cold plastic deformation is performed to obtain a diameter smaller than 2 mm.
  8. Process according to Claim 7, characterized in that the forming by cold plastic deformation is performed without intermediate heat treatment.
  9. Process according to Claim 7, characterized in that the forming by cold plastic deformation is performed with an intermediate hyperquenching and in that the reduction in section performed after the intermediate hyperquenching is greater than 300.
  10. Process according to Claim 8 or Claim 9, characterized in that, in addition, an aging heat treatment is performed, consisting of a hold at a temperature of between 400°C and 475°C for a period of between 5 min and 3 hours.
  11. Steel for the manufacture of a wire according to Claim 1, characterized in that its chemical composition includes, by weight: 0 % ≤ C ≤ 0.03 % 0 % ≤ Mn ≤ 2 % 0 % ≤ Si ≤ 0.5 % 8 % ≤ Ni ≤ 9 % 17 % ≤ Cr ≤ 18 % 0 % ≤ Mo ≤ 0.4 % 3 % ≤ Cu ≤ 3.5 % 0 % ≤ N ≤ 0.03 % S ≤ 0.01 % P ≤ 0.04 % the remainder being iron and impurities resulting from the production.
  12. Wire according to any one of Claims 1 to 4, characterized in that its section is round.
  13. Process according to any one of Claims 7 to 9, characterized in that the forming by cold plastic deformation is a wiredrawing in several passes.
EP97402907A 1996-12-31 1997-12-03 Stainless steel wire and process for production Expired - Lifetime EP0851039B1 (en)

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FR9616250A FR2757878B1 (en) 1996-12-31 1996-12-31 STAINLESS STEEL STEEL WIRE AND MANUFACTURING METHOD

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US7166174B2 (en) 2001-07-20 2007-01-23 Nv Bekaert Sa Bundle drawn stainless steel fibers

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ATE235369T1 (en) * 1998-07-30 2003-04-15 Aster COMPOSITE WIRE WITH A CARBON STEEL CORE AND A STAINLESS STEEL OUTER LAYER
FR2781814B1 (en) * 1998-07-30 2000-09-22 Aster COMPOSITE WIRE COMPRISING A CARBON STEEL CORE AND A STAINLESS STEEL OUTER LAYER
US20010045411A1 (en) * 2000-01-20 2001-11-29 Bailey Edwin C. High tensile strength stainless steel screen and method of making thereof
KR100382994B1 (en) * 2000-11-21 2003-05-09 유성권 A stainless steel wire mesh
KR100666727B1 (en) * 2005-04-19 2007-01-09 포스코신기술연구조합 304H austenite stainless steel for spring
CN100497710C (en) * 2007-11-21 2009-06-10 江阴康瑞不锈钢制品有限公司 High intensity corrosion resistant antibiotic type stainless steel wire for brassieres and manufacturing method thereof
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JP2013047367A (en) * 2011-08-29 2013-03-07 Nippon Koshuha Steel Co Ltd Method for producing ultrafine wire of high-strength stainless steel
UA111115C2 (en) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. cost effective ferritic stainless steel
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