(19)
(11)EP 2 300 194 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
12.12.2018 Bulletin 2018/50

(21)Application number: 09767463.4

(22)Date of filing:  08.06.2009
(51)International Patent Classification (IPC): 
B23K 26/38(2014.01)
A61B 17/06(2006.01)
(86)International application number:
PCT/US2009/046570
(87)International publication number:
WO 2009/155153 (23.12.2009 Gazette  2009/52)

(54)

POST LASER DRILLING STRESS RELIEF OF SURGICAL NEEDLES MADE OF REFRACTORY ALLOYS

SPANNUNGSENTLASTUNG VON CHIRURGISCHEN NADELN AUS HOCHSCHMELZENDEN LEGIERUNGEN NACH DEM LASERBOHREN

RELAXATION DE CONTRAINTE POST-FORAGE LASER D'AIGUILLES CHIRURGICALES RÉALISÉES EN ALLIAGES RÉFRACTAIRES


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR
Designated Extension States:
AL BA RS

(30)Priority: 16.06.2008 US 139744

(43)Date of publication of application:
30.03.2011 Bulletin 2011/13

(73)Proprietor: Ethicon, Inc
Somerville, NJ 08876 (US)

(72)Inventor:
  • MAURER, Robert, E.
    Belle Mead NJ 08502 (US)

(74)Representative: Carpmaels & Ransford LLP 
One Southampton Row
London WC1B 5HA
London WC1B 5HA (GB)


(56)References cited: : 
EP-A- 0 650 698
WO-A-2008/151108
EP-A- 1 396 305
RU-C- 2 218 879
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] The field of art to which this invention pertains is surgical needles, more specifically, methods of manufacturing surgical needles.

    BACKGROUND OF THE INVENTION



    [0002] Surgical needles and methods of manufacturing surgical needles are known in the art. Surgical needles are typically made from conventional biocompatible metals such as stainless steels. The selection of the materials used to manufacture the surgical needles depends upon a variety of factors including manufacturability, machineablility, cost, biocompatibility, and mechanical properties. Conventional surgical needles are made utilizing conventional manufacturing processes. Typically, a wire made from a biocompatible metal is drawn in a conventional wire mill to obtain a wire having a desired diameter or wire size. The wire is then cut into pieces known as needle blanks having a desired length, and the needle blanks are then processed through a series of conventional manufacturing process steps including bending, forming, grinding, polishing, heat treating, coating, etc.

    [0003] A conventional surgical needle has a distal piercing point and a proximal suture mounting section. The proximal suture mounting sections are typically a channel formed in the proximal end or a bore hole drilled into the proximal end. If a bore hole is used, it is typically formed by conventional mechanical drilling or laser drilling processes. Suture mounting is accomplished by inserting an end of a surgical suture into the channel or into the bore hole, and then mechanically compressing a section of the proximal end of the surgical needle about the end of the suture using any of a variety of conventional processes known in the art as swaging. The degree of swaging will depend upon the desired release characteristics, i.e., the amount of force necessary to detach the suture from the channel or bore hole.

    [0004] There is a constant need in this art for improved surgical needles having improved performance characteristics. It is desirable to have a surgical needle made from a wire having a diameter as close as possible to that of the suture to which it is attached . This can be accomplished by having a needle with the smallest cross-section possible (made from a wire having a small wire size) while providing sufficient resistance to bending when a surgeon grasps the needle and passes it through tissue. While existing surgical needles made from conventional stainless steels have such properties, novel needles made from materials such as refractory metal alloys have been developed that have maximized such characteristics. Since these materials are typically harder than conventional stainless steel alloys and have other differing metallurgical characteristics including greater strength, higher elastic modulus, and desirable magnetic properties, novel processes are needed to manufacture such needles and to manufacture needle-suture combinations utilizing such needles. For example, it is known that swaging a surgical suture to a drilled refractory alloy surgical needle may result in cracking about the proximal end of the needle.

    SUMMARY OF THE INVENTION



    [0005] Accordingly, a novel method of processing a laser-drilled surgical needle is disclosed. In the method of the present invention, a surgical needle made from a refractory alloy or stainless steel is provided. The needle has a distal end and a proximal end. A bore hole is drilled into the proximal end of the needle using a laser drilling apparatus. The needle, or just the suture mounting end or section of the surgical needle, is then subjected to an elevated temperature for a sufficient period of time to relieve residual stresses in the metal of the proximal end or section of the surgical needle surrounding the bore hole. The time and temperature are selected to be sufficiently effective such that stress relief is effected without softening the metal.

    [0006] Yet another aspect of the present invention is a novel surgical needle. The surgical needle has a body having a distal piercing point and a proximal suture mounting section. The needle has a bore hole that is laser-drilled in the proximal suture mounting section. The needle is processed using the above-described novel heat treating process to relieve residual stresses.

    [0007] It is now possible, using the process of the present invention, to swage surgical sutures to surgical needles made from refractory metal alloys without attendant cracking of the swaged portion of the needle.

    [0008] These and other aspects and advantages of the present invention will become more apparent from the following description and accompanying drawings.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0009] 

    FIG. 1 is a plan view of a drilled surgical needle made from a refractory alloy.

    FIG. 2 illustrates the needle of FIG. 1 with a suture mounted to the bore hole of the needle after treatment with the process of the present invention.

    FIG. 3 is a schematic diagram illustrating the process of the present invention wherein surgical needles mounted to a strip are heat treated.

    FIG. 3A is a partial plan view of the strip containing needles of FIG. 3.


    DETAILED DESCRIPTION OF THE INVENTION



    [0010] The novel process of the present can be utilized with surgical needles made from alloys of refractory metals including tungsten, molybdenum, niobium, tantalum, and rhenium. Surgical needles made from tungsten-rhenium alloys are disclosed in the following references.
    US Patent No. 5 415 707 discloses sterile surgical needles formed of alloys of tungsten and a second metal selected from the group consisting of rhenium, rhodium and iridium. The needles have a body portion, a distal point and a proximal suture mounting portion and have advantageously high ductility and exhibit improved yield point and elastic modulus in tension.
    US-A-2008/0147117 discloses a method for making curved tungsten alloy suture needles which have a desirable combination of stiffness, strength, ductility and surface colour comprising heating said needle to a temperature below the recrystallization temperature of the alloy.
    US-A-2008/0147118 discloses a medical device, particularly a suture needle, comprising a tungsten alloy having a blue, yellow or black surface colouration.
    US-A-2008/03005552 discloses a method of thermal forming of refractory alloy suture needles comprising heating needle blanks to a temperature which is above the ductile to brittle transition temperature but below the recrystallization temperature of the refractory alloy then forming the needle blanks into a surgical needle.
    US-A-2008/0295927 discloses a method of thermal forming of refractory alloy suture needles comprising heating needle blanks to a temperature which is above the ductile to brittle transition temperature but below the recrystallization temperature of the refractory alloy then forming the needle blanks into a surgical needle. Also disclosed is a fixture and an apparatus for forming refractory alloy surgical needles.
    WO-A-2008/151108, which can be cited for novelty only, discloses a method of thermal forming of refractory alloy suture needles comprising heating needle blanks to a temperature which is above the ductile to brittle transition temperature but below the recrystallization temperature of the refractory alloy then forming the needle blanks into a surgical needle.
    EP-A-1 396 305 discloses a method of laser drilling surgical needles utilizing a diode pulsed laser to produce a laser beam consisting of a train of high energy pulses. The method produces lased drilled chamfered blind bore holes in surgical needles.
    EP-A-0 650 698 discloses a process for progressively manufacturing cutting edge needles or wire members.
    RU-C-2 218 879 discloses a method for manufacturing ophthalmic needles wherein the end piece of the needle is pierced, bent and heat treated before a thread is fixed into the end piece.

    [0011] Although not preferred, the method of the present invention may also be used with laser drilled surgical needles made from conventional stainless steel alloys.

    [0012] Referring now to FIG 1, a drilled surgical needle 10 made from a tungsten-rhenium refractory alloy is illustrated. The needle 10 is seen to have a body 20 made from a tungsten rhenium alloy wire. The needle 10 has a distal piercing point 30 and proximal needle mounting section 40 having end 41. A suture mounting bore hole 50 is contained in section 40. Bore hole 50 is seen to have distal end 52, cavity 54 and proximal end 56 in communication with opening 44 in end 41.

    [0013] The needle 10 may be made using conventional manufacturing processes that are adapted to manufacturing surgical needles made from refractory metal alloys. Typically, in a conventional process, wire made from the desired metal alloy is drawn in a wire mill to a desired diameter. The wire is then cut in conventional wire cutting equipment to produce needle blanks having the desired length. The wire then goes through a series of conventional manufacturing process steps including forming, grinding, polishing, cleaning and drilling.

    [0014] Needle blanks may be drilled in several ways. The blanks may be mounted in a fixture and a conventional mechanical drill may be used to drill out a bore hole in the proximal end of the needle blank. Although mechanical drilling may be useful to drill bore holes in surgical needles, there are limitations associated with such a drilling process. For example, drills wear out and need to be replaced on a constant basis. In addition, the mechanical drilling process is time consuming and is less desirable for high speed, automated production processes. In addition, mechanical drills cannot typically be used in a cost effective manner for drilling needles made from very hard materials, or those that readily work-harden during the drilling operation. Laser drilling systems have been developed for drilling bore holes in surgical needles. These laser systems typically use Nd:YAG lasers, but any laser type capable of providing the required power density and being focused to the required spot size would be acceptable. Specific cycles are utilized to obtain the desired bore hole diameter and depth by controlling laser beam parameters including beam power, energy density, energy density distribution, pulse shape, pulse duration, and the number of pulses.

    [0015] Referring now to FIG. 2, the drilled refractory alloy surgical needle 10 of FIG. 1 is seen having a surgical suture 100 mounted thereto. The surgical suture is seen to have proximal end 110 mounted in cavity 54 of bore hole 50 and free proximal end 120. The surgical suture 110 is mounted to proximal needle mounting section 40 using a conventional mechanical swaging die and process and equivalents. This results in the swage section 45 in needle mounting section 40, which prevents the release of the end 110 from bore hole 50 or provides a controlled release at a predetermined force. The suture 100 can be selected from a variety of conventional surgical sutures.

    [0016] In order to swage a surgical suture to a drilled surgical needle, the needle is mounted in a die and a tool is pressed against a section of the suture mounting section of the needle. This causes a deformation of the metal such that the end of a suture inserted into the drilled bore hole is compressed within the cavity of the hole. Although such a process works well with conventional surgical needles, using such a swaging process with harder metals such as the refractory metal alloys may result in cracking of the needle about the suture mounting bore hole. Such cracking precludes the use of mechanical swaging with such needles. Mechanical swaging is an optimal method of attaching surgical sutures to drilled surgical needles. Other known methods such as glues or cements have disadvantages including lower suture attachment strength, difficulties associated with inserting adhesives into the blind bore hole due to air entrapment, and being an excessively time consuming process.

    [0017] The process of the present invention facilitates laser drilled refractory alloy surgical needles to be processed with mechanical swaging suture attachment processes. The process of the present invention involves heating either the portion of the needle containing the laser drilled hole, or the entire needle, for a sufficient time at a sufficient temperature to effectively relieve residual stresses in the metal surrounding the laser drilled bore hole. These residual stresses are believed to result from the enormously steep thermal gradient experienced during laser drilling, and a very thin layer of recast metal lining the inside surface of the hole. When the recast layer solidifies and cools, it is believed that its thermal contraction is restrained by the relatively unheated metal adjacent to the hole. This results in a state of residual tensile stress within the recast layer.

    [0018] If not relieved, as by the process of the present invention, cracks are likely to originate within this area of residual tensile stress during the mechanical swaging process used for suture attachment. For laser drilled surgical needles made of tungsten-rhenium alloys, the stress relief cycle (in an atmosphere controlled furnace) is preferably ranges from 900 - 1100 degrees Centigrade, for 15 - 60 minutes at temperature. This provides for stress relief, without softening the tungsten- rhenium or inducing microstructural alteration. If it were desired to heat only the region of the surgical needle containing the bore hole for stress relief, as by laser, induction heating or the like, higher temperatures for shorter periods of time would typically be required. To be consistent with the teachings of this invention, temperature-time selection would be bound from above by that which would result in microstructural and/or hardness changes in the needle alloy.

    [0019] An example of an automated process of the present invention for relieving stress in laser drilled needles is schematically illustrated in FIG. 3 and FIG. 3A. As seen in FIGS. 3 and 3A, needle blanks 200 are mounted to a moveable strip 280 by crimps or tabs 290. In place of a strip, the needle blank 200 may be mounted to a conventional fixture. Each needle blank 200 is seen to have distal section 210 with piercing point 215 and proximal needle mounting section 220. A bore hole 230 has been laser-drilled into section 220. A conventional laser drilling system 300 is located proximate to the needle blank 200 and strip 280 such that laser beam 310 may be directed to proximal needle mounting section 220 or the entire length of the needle blank 200 as the strip 280 moves the needle blanks 200 into position in front of beam 310. The beam 310 is moveable and has sufficient energy and is maintained on the section 220 or the entire needle blank 200 for a sufficient amount of time such that the metal in section 220 surrounding bore hole 230 is effectively stress relieved without annealing the metal. Lasers which may be useful in the stress relief process of the present invention will include conventional lasers such as the Nd:YAG, CO2, and fiber lasers, and other equivalent types capable of generating the required amount of heating over the required time interval for residual stress relief. Those skilled in the art will appreciate that the time that the suture mounting sections of the needles are exposed to the laser energy will depend upon several factors, including beam power, energy density, and energy density distribution, for example, and not being limited to any particular range of times, the time that the laser beam energy is applied may range from about 1 milliseconds to about a few seconds. Those skilled in the art will appreciate that the times will vary in accordance with the previously describe parameters. Other methods of heating the metal in the needles useful in the stress relieving process of the present invention will include conventional heating methods such as inductive heating and resistive heating.

    [0020] After being treated by the stress relief process of the present invention, the refractory alloy surgical needles will readily be able to have surgical sutures attached to the suture mounting ends using mechanical swaging without cracking. The metal in the stress relieved area can be metallurgically characterised by being unaltered with respect to microstructure and hardness. In contrast, an annealing process produces a metallurgical profile characterized by reduced hardness. It is surprising and unexpected that the process of the present invention for treating surgical needles would prevent cracking since laser drilled needles made of stainless steel do not exhibit the same propensity to crack during suture attachment by mechanical swaging. Annealing (softening) processes would be disadvantageous for use in treating the suture mounting ends of drilled surgical needles made from tungsten-rhenium alloys, and other refractory alloys, because, counter to the behavior of steels, which exhibit increasing ductility with decreasing hardness, tungsten-rhenium alloys lose ductility with decreasing hardness.

    [0021] The following examples are illustrative of the principles and practice of the present invention although not limited thereto.

    Example 1



    [0022] Tungsten-Rhenium alloy wire having a diameter of 0.25 mm (0.01-inch) was cut into needle blanks using conventional cutting equipment. The alloy composition was 74.25% tungsten + 25.75% rhenium. The needle blanks were pointed, polished and curved in a conventional manner. The proximal ends of the needle blanks were drilled to form bore holes using a conventional needle-drilling Nd:YAG laser. Conventional polyester suture was mounted in the bore holes of the needles, and the proximal suture mounting end of the needles was mechanically swaged using a conventional die and swage apparatus. It was observed that all of the needles exhibited cracking in the proximal suture mounting end about the drilled bore hole.

    Example 2



    [0023] Tungsten-Rhenium alloy needles were prepared in a similar manner to the needles of Example 1. The needles were made from an alloy wire having the same composition as that used in Example 1. After laser drilling and prior to suture mounting and mechanical swaging, the needles were heat treated in a furnace at about 1000°C for about about 30 minutes to effectively stress relieve the metal in needles about the laser-drilled bore holes. The same polyester suture was mounted to the heat treated needles and swaged in an identical manner and using the same equipment as in Example 2. None of the needles exhibited cracking in the proximal needle mounting end about the laser-drilled bore hole.

    [0024] Although this invention has been shown and described with respect to detailed embodiments thereof, it will be understood by those skilled in the art that various changes in form and detail thereof may be made without departing from the scope of the claimed invention.


    Claims

    1. A process for treating surgical needles, comprising:

    providing a surgical needle (10) comprising a metal alloy, the surgical needle (10) having a distal piercing end (30), a proximal suture mounting end (41) and a bore hole (50) that is laser-drilled in the suture mounting end (41), the bore hole (50) having a cavity (54) and an opening (44); followed by,

    heat treating at least the suture mounting end (41) by exposing said end to thermal energy for a sufficient amount of time to provide sufficient energy to effectively stress relieve the metal alloy about the bore hole (50) without annealing the metal alloy.


     
    2. The process of claim 1, wherein the metal alloy comprises a refractory metal alloy.
     
    3. The process of claim 2 wherein the refractory alloy metal is Tungsten-Rhenium.
     
    4. The process of claim 2 wherein the refractory alloy is selected from the group consisting of molybdenum, tantalum and niobium.
     
    5. The process of claims 1-4 comprising the additional steps of mounting an end (110) of a surgical suture (100) in the cavity of the laser-drilled bore hole (50), and swaging the suture mounting end (41) of the needle (10).
     
    6. The process of claims 1-5, wherein the entire needle (10) is heat treated.
     
    7. The process of claims 1-6, wherein the thermal energy is provided by a laser.
     
    8. The process of claims 1-6, wherein the thermal energy is provided by a furnace.
     
    9. The process of claims 1-6, wherein the thermal energy is provided by inductive heating.
     
    10. The process of claims 1-6, wherein the thermal energy is provided by resistive heating.
     
    11. The process of claims 1-5, wherein each needle (10) is mounted in a moveable strip (280), and the strip (280) is moved in front of a laser (300), which directs a beam (310) to contact at least a section of the needle (10) to provide sufficient thermal energy for a sufficient period of time to effectively heat treat the section of the needle (10) by relieving stress without annealing the metal.
     
    12. The process of claim 8, wherein the needle is maintained at a temperature of 900°C to 1100°C.
     
    13. The process of claim 8, wherein the needle is maintained in the furnace for 15 to 60 minutes.
     
    14. The process of claim 1, wherein the metal alloy comprises stainless steel.
     


    Ansprüche

    1. Verfahren zum Behandeln chirurgischer Nadeln, umfassend:

    Bereitstellen einer chirurgischen Nadel (10), die eine Metalllegierung umfasst, wobei die chirurgische Nadel (10) ein distales Durchstechende (30), ein proximales Nahtmaterialmontageende (41) und ein Bohrungsloch (50) aufweist, das in dem Nahtmaterialmontageende (41) lasergebohrt ist, wobei das Bohrungsloch (50) einen Hohlraum (54) und eine Öffnung (44) aufweist, gefolgt von

    Wärmebehandeln mindestens des Nahtmaterialmontageendes (41), indem das Ende für eine ausreichende Zeitdauer Wärmeenergie ausgesetzt wird, um ausreichend Energie zur effektiven Spannungsentlastung der Metalllegierung um das Bohrungsloch (50) herum bereitzustellen, ohne die Metalllegierung zu tempern.


     
    2. Verfahren nach Anspruch 1, wobei die Metalllegierung eine hochschmelzende Metalllegierung umfasst.
     
    3. Verfahren nach Anspruch 2, wobei das hochschmelzende Legierungsmetall Wolfram-Rhenium ist.
     
    4. Verfahren nach Anspruch 2, wobei die hochschmelzende Legierung ausgewählt ist aus der Gruppe bestehend aus Molybdän, Tantal und Niob.
     
    5. Verfahren nach den Ansprüchen 1 bis 4, umfassend die zusätzlichen Schritte des Montierens eines Endes (110) eines chirurgischen Nahtmaterials (100) in dem Hohlraum des lasergebohrten Bohrungslochs (50) und Kaltverformens des Nahtmaterialmontageendes (41) der Nadel (10).
     
    6. Verfahren nach den Ansprüchen 1 bis 5, wobei die gesamte Nadel (10) wärmebehandelt wird.
     
    7. Verfahren nach den Ansprüchen 1 bis 6, wobei die Wärmeenergie durch einen Laser bereitgestellt wird.
     
    8. Verfahren nach den Ansprüchen 1 bis 6, wobei die Wärmeenergie durch einen Ofen bereitgestellt wird.
     
    9. Verfahren nach den Ansprüchen 1 bis 6, wobei die Wärmeenergie durch induktives Erwärmen bereitgestellt wird.
     
    10. Verfahren nach den Ansprüchen 1 bis 6, wobei die Wärmeenergie durch Widerstandserwärmen bereitgestellt wird.
     
    11. Verfahren nach den Ansprüchen 1 bis 5, wobei jede Nadel (10) in einem beweglichen Streifen (280) montiert ist und der Streifen (280) vor einem Laser (300) bewegt wird, der einen Strahl (310) lenkt, um mit mindestens einem Abschnitt der Nadel (10) in Kontakt zu kommen, um für einen ausreichenden Zeitraum ausreichend Wärmeenergie bereitzustellen, um den Abschnitt der Nadel (10) effektiv wärmezubehandeln, indem Spannung entlastet wird, ohne das Metall zu tempern.
     
    12. Verfahren nach Anspruch 8, wobei die Nadel auf einer Temperatur von 900 °C bis 1100 °C gehalten wird.
     
    13. Verfahren nach Anspruch 8, wobei die Nadel 15 bis 60 Minuten in dem Ofen gehalten wird.
     
    14. Verfahren nach Anspruch 1, wobei die Metalllegierung rostfreien Stahl umfasst.
     


    Revendications

    1. Procédé de traitement d'aiguilles chirurgicales, comprenant :

    la fourniture d'une aiguille chirurgicale (10) comprenant un alliage métallique, l'aiguille chirurgicale (10) ayant une extrémité de perçage distale (30), une extrémité de montage de suture proximale (41) et un trou d'alésage (50) qui est percé au laser dans l'extrémité de montage de suture (41), le trou d'alésage (50) ayant une cavité (54) et une ouverture (44) ; suivie par,

    le traitement thermique d'au moins l'extrémité de montage de suture (41) en exposant ladite extrémité à une énergie thermique pendant une durée suffisante pour fournir suffisamment d'énergie pour relaxer de manière efficace les contraintes de l'alliage métallique autour du trou d'alésage (50) sans recuit de l'alliage métallique.


     
    2. Procédé selon la revendication 1, l'alliage métallique comprenant un alliage métallique réfractaire.
     
    3. Procédé selon la revendication 2, le métal d'alliage réfractaire étant du tungstène-rhénium.
     
    4. Procédé selon la revendication 2, l'alliage réfractaire étant choisi dans le groupe constitué par le molybdène, le tantale et le niobium.
     
    5. Procédé selon les revendications 1 à 4, comprenant les étapes supplémentaires de montage d'une extrémité (110) d'une suture chirurgicale (100) dans la cavité du trou d'alésage percé au laser (50), et l'emboutissage de l'extrémité de montage de suture (41) de l'aiguille (10).
     
    6. Procédé selon les revendications 1 à 5, l'ensemble de l'aiguille (10) étant traité thermiquement.
     
    7. Procédé selon les revendications 1 à 6, l'énergie thermique étant fournie par un laser.
     
    8. Procédé selon les revendications 1 à 6, l'énergie thermique étant fournie par un four.
     
    9. Procédé selon les revendications 1 à 6, l'énergie thermique étant fournie par chauffage inductif.
     
    10. Procédé selon les revendications 1 à 6, l'énergie thermique étant fournie par chauffage résistif.
     
    11. Procédé selon les revendications 1 à 5, chaque aiguille (10) étant montée dans une bande mobile (280), et la bande (280) étant déplacée devant un laser (300) qui dirige un faisceau (310) pour venir en contact avec au moins une section de l'aiguille (10) pour fournir une énergie thermique suffisante pendant une période de temps suffisante pour traiter thermiquement de manière efficace la section de l'aiguille (10) en relaxant les contraintes sans recuit du métal.
     
    12. Procédé selon la revendication 8, l'aiguille étant maintenue à une température de 900 °C à 1100 °C.
     
    13. Procédé selon la revendication 8, l'aiguille étant maintenue dans le four pendant 15 à 60 minutes.
     
    14. Procédé selon la revendication 1, l'alliage métallique comprenant de l'acier inoxydable.
     




    Drawing














    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description