EP1483068A2 - Method for making a plated steel armouring wire for a flexible tubular pipe transporting hydrocarbons, and armoured pipe - Google Patents

Method for making a plated steel armouring wire for a flexible tubular pipe transporting hydrocarbons, and armoured pipe

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Publication number
EP1483068A2
EP1483068A2 EP03722682A EP03722682A EP1483068A2 EP 1483068 A2 EP1483068 A2 EP 1483068A2 EP 03722682 A EP03722682 A EP 03722682A EP 03722682 A EP03722682 A EP 03722682A EP 1483068 A2 EP1483068 A2 EP 1483068A2
Authority
EP
European Patent Office
Prior art keywords
steel
pipe
quenching
plating
core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03722682A
Other languages
German (de)
French (fr)
Other versions
EP1483068B1 (en
Inventor
François Dupoiron
Philippe Espinasse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technip Energies France SAS
Original Assignee
Technip France SAS
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Filing date
Publication date
Application filed by Technip France SAS filed Critical Technip France SAS
Publication of EP1483068A2 publication Critical patent/EP1483068A2/en
Application granted granted Critical
Publication of EP1483068B1 publication Critical patent/EP1483068B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • B21C37/12—Making tubes or metal hoses with helically arranged seams
    • B21C37/124—Making tubes or metal hoses with helically arranged seams the tubes having a special shape, e.g. with corrugated wall, flexible tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of rods or wire
    • B21C37/042—Manufacture of coated wire or rods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • B21C37/12—Making tubes or metal hoses with helically arranged seams
    • B21C37/126—Supply, or operations combined with supply, of strip material

Definitions

  • the present invention relates to the field of flexible tabular pipes for the transport of hydrocarbons, in particular unbound pipes ("unbonded flexible pipes").
  • unbound pipes are defined in API recommendations 17J and 17B of the American Petroleum Institute and comprise metallic layers and separate polymer layers, that is to say not linked together so as to allow a certain relative displacement between the layers .
  • an unbound pipe of the type contemplated in the invention generally comprises, from the inside to the outside:
  • an internal sealing sheath made of generally polymeric plastic, resistant to the chemical action of the fluid to be transported;
  • the shaped wires have a Z or T section or their derivatives (teta or zeta), U, or I;
  • Such a pipe can be with smooth internal passage when the passage is directly formed by the sealing sheath (it is then called “smooth bore”) or with non-smooth passage ("rough bore") when provision is also made for the 'Inside the internal sealing sheath a carcass consisting of a stapled strip wound in a short pitch which serves to prevent the crushing of the pipe under external pressure.
  • a carcass it is possible for certain applications to do without the pressure vault.
  • the pipe may optionally comprise, in addition to these layers, other particular layers, a metallic hoop (wound at short pitch) and forming part of the pressure vault, intermediate polymer sheaths, etc.
  • the pipe generally comprises both a carcass, a sealing sheath, a pressure vault, sheets of tensile armor, and a sheath external sealing.
  • the armor wires considered are the tensile armor wires of the crossed armor plies or possibly the shaped wires or hoop wires of the pressure vault, which will be called wires. pressure armor.
  • the expression “armouring wire” will also be understood to mean a form wire obtained according to the method of the invention and which would be intended to be used for the manufacture of a carcass.
  • document FR 2 569 461 discloses a flexible rubber hose intended for the transport of corrosive effluents and incorporating for this purpose reinforcements constituted by layers of embedded metallic cables, the cables being made up of steel wires coated with clad aluminum (that is to say in intimate connection with steel, obtained under high application pressure, for example by co-extrusion).
  • This pipe manufactured according to the technology of linked pipes, is therefore of a different constitution from that of non-linked pipes mainly envisaged according to the invention and which are subjected to tensile stresses which are unthinkable with this technology of linked pipes.
  • the object of the invention is to allow the reinforcement of flexible conduits, in particular unbonded conduits, by armor wires resistant to corrosion but also endowed with good mechanical qualities to allow the use of conduits at great depth. More specifically, the object of the invention is to find a process for the intimate coating or plating of the steel of the armor wires, compatible with the requirements of use for a pipe of the aforementioned type used in an acid medium and in large quantities. depth.
  • the invention achieves its object by a process for the manufacture of plated steel armor wires intended for the reinforcement of flexible tabular conduits, in particular unbound, for the transport of hydrocarbons, a process of the type according to which a plating coating is associated. intimately, by high pressure, to a steel core, characterized in that the steel of the core is chosen with average mechanical characteristics and is hardenable, in that the coating is applied to the core and intimately associated, then in that the plated wire obtained undergoes rapid quenching at high temperature followed by tempering, so as to increase the mechanical characteristics of the plated wire.
  • the characteristics of the steel and the plating coating, as well as the temperature and the time of quenching are chosen in a linked manner so as to raise the mechanical characteristics of the hardened wire without destroying the solidity of the plating bond.
  • One of the key factors of the invention is the speed of the heat treatment at high temperature which, in conjunction with the other parameters, makes it possible to minimize the stresses at the level of the connection between the steel and the coating, in particular by avoiding the migration of the carbon and iron . steel in the connection and coating.
  • a steel of medium strength is used for the core of the armor wire, that is to say of which the resistance Rm is between
  • 500 and 1000 MPa advantageously between 800 and 900 MPa. It must be a "quenchable" steel (capable of undergoing a quenching improving its mechanical characteristics, the hardening consisting, as is known, of hardening by heat treatment (austenization + cooling) with carbon, alloyed or weakly alloyed.
  • the anti-corrosion coating is for example made of titanium or titanium alloys, stainless steel, nickel or nickel alloys.
  • the plating is carried out mechanically when cold after adequate preparation (mechanical or chemical deoxidation of the surfaces), using a technique allowing intimate bonding by pressure (for example co-extrusion or co-laminating). - Following this operation, an assembly is obtained which is characterized by a still fragile base / plating connection and by mechanical characteristics degraded by plastic deformation (low elongation). Such a product, at this stage, would not be compatible with shaping to serve as armor for a pipe of the type considered in the invention.
  • the steel thus coated is subjected to a heat treatment comprising a short quenching at high temperature and tempering carried out so as to minimize the stresses at the level of the connection between the steel and the coating.
  • the heat treatment in accordance with the invention makes it possible to improve the characteristics of the bond, to restore the ductility characteristics of the plating and to obtain the high mechanical characteristics of the base metal necessary in the applications envisaged for this type of product.
  • This heat treatment is characterized by a short high temperature thermal cycle (900 ° C to 1100 ° C) (a few seconds to a few tens of seconds) followed by rapid cooling and a tempering treatment at a temperature of from 400 ° C to 700 ° C and which is adjusted according to the desired mechanical characteristics, the tempering taking place over a period of a few minutes, advantageously between 10 and 20 minutes.
  • This heat treatment has the following effects, different depending on the constituents of the armor:
  • the treatment restores ductility without leading to precipitations which are detrimental to the resistance to conosion.
  • the bond allows an improvement of the resistance by relaxation of the constraints of rolling or extrusion and diffusion metallic.
  • the tempering also allows a complementary improvement of the ductility by the relaxation of the differential stresses linked to quenching.
  • the heat treatment will make it possible to obtain a tempered tempered structure combining very high mechanical characteristics (Rm greater than 1000 MPa and preferably at least 1400 MPa) and sufficient ductility for the targeted applications (approximately 5 % elongation).
  • the invention also relates to a flexible tubular pipe for transporting hydrocarbons, incorporating at least certain armor wires produced according to the aforementioned manufacturing process. More specifically, the invention relates to a flexible tubular pipe for the transport of hydrocarbons, of the type comprising polymeric layers and unbound metallic layers, the metallic layers comprising wound armor wires, characterized in that at least some armor wires are produced according to the method of the preceding claims.
  • the invention relates in particular to a pipe of the type comprising at least one carcass, an internal sheath, a pressure vault comprising pressure armor wires, sheets made up of tensile armor wires and an external sheath, characterized in that that at least some of the armor wires are produced according to the process of the invention.
  • FIG. 1 is a perspective view of a pipe of the "rough bore” type, to which the invention applies,
  • Figure 2 is a schematic view illustrating the manufacturing process of the plated armor according to the invention.
  • Figure 3 schematically illustrates various possible sections of plated armor.
  • Figure 1 shows a pipe type "rough bore" which includes from the inside to the outside: a metal carcass 1, generally made by a stapled strip wound in short pitch and intended for resistance to crushing under external pressure ; a polymeric internal sealing sheath 2, a metal pressure vault, constituted here in the traditional way by helical winding with short pitch (winding angle generally close to 90 ° relative to the axis of the pipe) of a stapled metal wire 3 doubled by the helical winding at short pitch of a hoop wire 4, an armor 5 resistant to axial traction in the longitudinal direction of the pipe and conventionally constituted by a pair of crossed plies of tensile armor wires 6,7 of winding with a long pitch (typically less than 55 ° relative to the axis of the pipe), and of a polymeric external sealing sheath 8.
  • the invention relates to the plating of the tensile armor wires 6,7 as well as the pressure armor wires 3, 4 (if applicable), according to a treatment which is illustrated in FIG. 2.
  • the starting wire 20 consists of a core 21 of base metal with medium mechanical characteristics (for example Rm of 800 to 900 MPa) and of a coating 22 of plating metal.
  • the base metal can be, for example, a base steel of the chromium silicon type (55SiCr V) in the globulated state so as to allow plating.
  • the plating metal may for example be a nickel base (NiCrMo 6x series according to AISI) or a nickel alloy (8x series).
  • the starting wire 20 passes through a co-extrusion die 23, from which it emerges by having the coating 22 intimately linked to the core 21.
  • the wire thus plated passes through a station 24 for heat treatment at high temperature, typically at least 800 ° C and preferably at 1100 ° C, for example by heating the wire by induction.
  • This treatment is rapid (from a few seconds to a few minutes at most).
  • austenitization of the base steel There is an austenitization of the base steel.
  • This treatment is followed by rapid quenching in a quenching station (for example by air, water or oil) which is accompanied by a controlled martensitic transformation and therefore allows high mechanical characteristics to be obtained, with an Rm of in the order of 2.00 MPa.
  • the speed of the treatment makes it possible not to allow harmful elements (iron, carbon) to diffuse in the bond which would degrade the quality of the latter and degrade the corrosion resistance of the plating.
  • Induction heating is advantageous not only for its speed but also because it overcomes the problems associated with the possible reflection of the coating.
  • the wire thus obtained then crosses a station 26 for thermal tempering, at a temperature of the order of 450 ° C for about fifteen minutes.
  • the thickness of the cladding is generally of the order of 200 ⁇ m to 500 ⁇ m; it must be thick enough to resist mechanical attack and corrosion. It represents in section less than approximately 10% of the total section of the wire.
  • FIG. 3 illustrates, by way of example, four types of possible sections for the plated armor wires.
  • the round shape 30 is the simplest, but it is also possible to envisage a rectangular shape 31 or a "zeta" 32 or “teta” shape 33, these shapes being in themselves conventional for constituting pipe reinforcement wires.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Ropes Or Cables (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Wire Processing (AREA)
  • Reinforced Plastic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating With Molten Metal (AREA)
  • Laminated Bodies (AREA)

Abstract

A process for manufacturing plated-steel armor wires intended for reinforcement of flexible tubular pipes for transporting hydrocarbons, comprising a plating coating is intimately bonded, by high pressure, to a core made of hardenable steel with moderate mechanical properties, and then the plated wire obtained undergoes a rapid high-temperature hardening step followed by a tempering step.

Description

Procédé de fabrication de fil d'armure en acier plaqué pour conduite tubulaire flexible de transport d'hydrocarbures, et conduite ainsi armée Method of manufacturing clad steel armor wire for flexible tubular hydrocarbon transport pipe, and pipe thus reinforced
La présente invention concerne le domaine des conduites tabulaires flexibles pour le transport d'hydrocarbures, notamment les conduites non liées ("unbonded flexible pipes"). Ces conduites sont définies dans les recommandations API 17J et 17B de l'American Petroleum Institute et comportent des couches métalliques et des couches polymériques séparées, c'est-à-dire non liées entre elles de manière à autoriser un certain déplacement relatif entre les couches.The present invention relates to the field of flexible tabular pipes for the transport of hydrocarbons, in particular unbound pipes ("unbonded flexible pipes"). These pipes are defined in API recommendations 17J and 17B of the American Petroleum Institute and comprise metallic layers and separate polymer layers, that is to say not linked together so as to allow a certain relative displacement between the layers .
Plus précisément, une conduite non liée du type visé dans l'invention comprend généralement, de l'intérieur vers l'extérieur :More specifically, an unbound pipe of the type contemplated in the invention generally comprises, from the inside to the outside:
- une gaine d'étanchéité interne, réalisée en matière plastique généralement polymère, résistant à l'action chimique du fluide à transporter ;- an internal sealing sheath, made of generally polymeric plastic, resistant to the chemical action of the fluid to be transported;
- éventuellement une voûte de pression résistant principalement à la pression développée par le fluide dans la gaine d'étanchéité et constituée par l'enroulement en hélice à pas court (c'est-à-dire avec un angle d'enroulement voisin de 90° par rapport à l'axe de la conduite) autour de la gaine interne, d'un ou plusieurs fils métalliques de forme agrafés (auto- agrafables ou non) ; les fils de forme ont une section en Z ou en T ou leurs dérivés (teta ou zêta), en U, ou en I ;- possibly a pressure vault mainly resistant to the pressure developed by the fluid in the sealing sheath and constituted by the helical winding with short pitch (that is to say with a winding angle close to 90 ° relative to the axis of the pipe) around the internal sheath, of one or more stapled metal wires (self-stapling or not); the shaped wires have a Z or T section or their derivatives (teta or zeta), U, or I;
- au moins une nappe (et généralement au moins deux nappes croisées) de fils d'armure de traction enroulés à pas long ; l'angle d'armage mesuré sur l'axe longitudinal de la conduite est par exemple sensiblement égal à 55°.; et- At least one ply (and generally at least two crossed plies) of tensile armor wires wound in long pitch; the winding angle measured on the longitudinal axis of the pipe is for example substantially equal to 55 ° .; and
- Eventuellement une gaine de protection et d'étanchéité externe en polymère.- Optionally an external polymer protection and sealing sheath.
Une telle conduite peut être à passage interne lisse quand le passage est directement formé par la gaine d'étanchéité (elle est alors dite "smooth bore") ou à passage non-lisse ("rough bore") quand on prévoit en outre à l'intérieur de la gaine d'étanchéité interne une carcasse constituée d'un feuillard agrafé enroulé à pas court qui sert à empêcher l'écrasement de la conduite sous la pression externe. Lorsqu'on utilise une carcasse, il est possible pour certaines applications de se passer de la voûte de pression. La conduite peut éventuellement comprendre en plus de ces couches, d'autres couches particulières, une frette métallique (enroulée à pas court) et faisant partie de la voûte de pression, des gaines polymériques intermédiaires, etc. La constitution exacte, le nombre et l'arrangement des diverses couches sont soigneusement choisis en fonction des applications et des conditions d'utilisation de la conduite, mais on retrouve dans toutes les conduites des couches réalisées par des enroulements de fils dits de renforcement ou d'armure, en acier. Pour les applications en grande profondeur, qui sont les applications principalement visées selon l'invention, la conduite comprend généralement à la fois une carcasse, une gaine d'étanchéité, une voûte de pression, des nappes d'armures de traction, et une gaine d'étanchéité externe.Such a pipe can be with smooth internal passage when the passage is directly formed by the sealing sheath (it is then called "smooth bore") or with non-smooth passage ("rough bore") when provision is also made for the 'Inside the internal sealing sheath a carcass consisting of a stapled strip wound in a short pitch which serves to prevent the crushing of the pipe under external pressure. When using a carcass, it is possible for certain applications to do without the pressure vault. The pipe may optionally comprise, in addition to these layers, other particular layers, a metallic hoop (wound at short pitch) and forming part of the pressure vault, intermediate polymer sheaths, etc. The exact constitution, number and arrangement of the various layers are carefully chosen according to the applications and conditions of use of the pipe, but we find in all the pipes layers produced by windings of so-called reinforcement or armor, steel. For deep water applications, which are the applications mainly targeted according to the invention, the pipe generally comprises both a carcass, a sealing sheath, a pressure vault, sheets of tensile armor, and a sheath external sealing.
Au sens de la présente invention, les fils d'armure considérés sont les fils d'armure de traction des nappes d'armure croisées ou bien éventuellement les fils de forme ou les fils de frette de la voûte de pression, qu'on appellera fils d'armure de pression. Par extension, on entendra également par fil d'armure un fil de forme obtenu selon le procédé de l'invention et qui serait destiné à être utilisé pour la fabrication d'une carcasse.Within the meaning of the present invention, the armor wires considered are the tensile armor wires of the crossed armor plies or possibly the shaped wires or hoop wires of the pressure vault, which will be called wires. pressure armor. By extension, the expression “armouring wire” will also be understood to mean a form wire obtained according to the method of the invention and which would be intended to be used for the manufacture of a carcass.
Lorsque les conduites sont destinées à un milieu corrosif acide (notamment en raison de l'H2S contenu dans les effluents transportés), souvent appelé dans le jargon pétrolier un milieu "sour", il convient d'adopter des mesures spéciales pour garantir la résistance des armures (de traction et de pression) à la corrosion. Ces mesures et les qualités des aciers qui conviennent sont définies dans la norme MRO 1-75 de la NACE (National Association of Coπυsion Engineers) régissant la résistance des aciers et alliages à la corrosion en milieu acide.When the pipes are intended for an acid corrosive medium (in particular due to the H 2 S contained in the transported effluents), often called in petroleum jargon a "sour" medium, it is advisable to adopt special measures to guarantee the resistance of armor (tensile and pressure) to corrosion. These measures and the qualities of suitable steels are defined in standard NRO 1-75 of the NACE (National Association of Coπυsion Engineers) governing the resistance of steels and alloys to corrosion in an acid medium.
Le plus souvent, les aciers permettant une bonne résistance à la corrosion H2S ont des qualités mécaniques relativement faibles (Rm < 850 Mpa). Or, si on envisage des conditions d'utilisation à la fois corrosives et en grande profondeur, il convient de conserver les qualités mécaniques des fils métalliques, notamment des fils d'armure, qui seront soumis à la fois à la corrosion et aux efforts de traction élevés rencontrés (pour une conduite de transport en fonds marin "flowline", ces efforts de traction élevés ne surviennent peut-être pas lors de la vie de la conduite une fois posée, mais au moins au moment de la pose de la conduite). Si l'acier n'a pas de très bonnes qualités mécaniques, on est obligé d'augmenter les épaisseurs d'acier utilisées, ce qui augmente le poids des conduites, la taille des équipements d'enroulement et de pose et donc le coût de revient des conduites.Most often, steels allowing good resistance to H 2 S corrosion have relatively low mechanical qualities (Rm <850 Mpa). However, if we consider conditions of use that are both corrosive and at great depth, it is advisable to retain the mechanical qualities of the metallic wires, in particular armouring wires, which will be subjected to both corrosion and stresses. high traction encountered (for a flowline transport pipeline, these high traction forces do not may not occur during the life of the pipe once laid, but at least when the pipe is laid). If the steel does not have very good mechanical qualities, it is necessary to increase the thicknesses of steel used, which increases the weight of the pipes, the size of the winding and laying equipment and therefore the cost of returns from the pipes.
Selon le document FR 2 775 050 qui concerne une conduite flexible non liée destinée à une utilisation statique en ambiance corrosive, on utilise un acier résistant à la corrosion H2S mais à caractéristiques mécaniques moyennes pour les fils d'armure de la voûte de pression, et un acier à hautes caractéristiques mécaniques mais ne résistant pas à la corrosion acide pour les nappes d'armure de traction. Ce compromis paraît acceptable si la corrosion H2S ne peut atteindre les nappes d'armures de traction ; à cet effet, une gaine intermédiaire de confinement d'H2S sépare la voûte de pression qui sera soumise à la corrosion H2S et les nappes d'armures de traction, qui ne seront en principe pas soumises à cette corrosion. Cependant la sécurité n'est pas garantie à cause des risques de perçage de la gaine intermédiaire. D'autre part, les mauvaises caractéristiques mécaniques de l'acier utilisé pour la voûte de pression entraînent l'obligation de la surdimensionner.According to document FR 2 775 050, which relates to an unbound flexible pipe intended for static use in a corrosive environment, a steel resistant to corrosion H 2 S but with average mechanical characteristics is used for the armor wires of the pressure vault , and a steel with high mechanical characteristics but not resistant to acid corrosion for the tensile armor plies. This compromise seems acceptable if the H 2 S corrosion cannot reach the tensile armor plies; for this purpose, an intermediate H 2 S confinement sheath separates the pressure vault which will be subjected to H 2 S corrosion and the tensile armor plies, which will in principle not be subjected to this corrosion. However, safety is not guaranteed because of the risks of piercing the intermediate sheath. On the other hand, the poor mechanical characteristics of the steel used for the pressure vault entail the obligation to oversize it.
Dans le domaine des conduites liées ("bonded pipes"), on connaît par le document FR 2 569 461 un tuyau souple en caoutchouc destiné au transport d'effluents corrosifs et incorporant à cet effet des renforcements constitués de couches de câbles métalliques noyés, les câbles étant constitués de fils d'acier revêtus d'aluminium plaqué (c'est-à-dire en liaison intime avec l'acier, obtenue sous forte pression d'application, par exemple par co-extrusion). Ce tuyau, fabriqué selon la technologie des conduites liées, est donc d'une constitution différente de celle des conduites non liées' principalement envisagées selon l'invention et qui sont soumises à des contraintes de traction inenvisageables avec cette technologie des conduites liées. Si l'on cherche à retenir l'idée intéressante consistant à utiliser des armures plaquées dans des conduites du type plus particulièrement considéré dans la présente invention, on est amené à envisager le plaquage de fil métallique à hautes caractéristiques mécaniques (Rm supérieur à 1000 MPa et de préférence à 1400 MPa) par un revêtement résistant à la corrosion. Toutefois, l'utilisation de tels fils métalliques à hautes caractéristiques mécaniques revêtus d'un placage anti-corrosion ne donne pas entière satisfaction notamment en raison d'une difficulté tenant au fait que la liaison intime du revêtement avec l'acier est fragile et ne supporte pas les contraintes liées à la fabrication même des conduites.In the field of bonded pipes, document FR 2 569 461 discloses a flexible rubber hose intended for the transport of corrosive effluents and incorporating for this purpose reinforcements constituted by layers of embedded metallic cables, the cables being made up of steel wires coated with clad aluminum (that is to say in intimate connection with steel, obtained under high application pressure, for example by co-extrusion). This pipe, manufactured according to the technology of linked pipes, is therefore of a different constitution from that of non-linked pipes mainly envisaged according to the invention and which are subjected to tensile stresses which are unthinkable with this technology of linked pipes. If we seek to retain the interesting idea of using armor plated in pipes of the type more particularly considered in the present invention, we are led to consider the plating of metal wire with high mechanical characteristics (Rm greater than 1000 MPa and preferably at 1400 MPa) by a coating resistant to corrosion. However, the use of such metallic wires with high mechanical characteristics coated with an anti-corrosion plating is not entirely satisfactory, in particular because of a difficulty due to the fact that the intimate bond of the coating with the steel is fragile and does not not withstand the constraints linked to the actual manufacture of the pipes.
Le but de l'invention est de permettre le renforcement des conduites flexibles, notamment des conduites non liées, par des fils d'armure résistants à la corrosion mais également dotés de bonnes qualités mécaniques pour permettre l'utilisation des conduites en grande profondeur. Plus précisément, le but de l'invention est de trouver un procédé de revêtement intime ou placage de l'acier des fils d'armure, compatible avec les exigences d'une utilisation pour une conduite du type précité utilisée en milieu acide et en grande profondeur.The object of the invention is to allow the reinforcement of flexible conduits, in particular unbonded conduits, by armor wires resistant to corrosion but also endowed with good mechanical qualities to allow the use of conduits at great depth. More specifically, the object of the invention is to find a process for the intimate coating or plating of the steel of the armor wires, compatible with the requirements of use for a pipe of the aforementioned type used in an acid medium and in large quantities. depth.
L'invention atteint son but grâce à un procédé de fabrication de fils d'armure en acier plaqué destinés au renforcement de conduites tabulaires flexibles, notamment non liées, pour le transport d'hydrocarbures, procédé du type selon lequel un revêtement de placage est associé intimement, par forte pression, à une âme en acier, caractérisé en ce que l'acier de l'âme est choisi avec des caractéristiques mécaniques moyennes et est trempàble, en ce que le revêtement est appliqué sur l'âme et associé intimement, puis en ce que le fil plaqué obtenu subit une trempe rapide à haute température suivie d'un revenu, de manière à augmenter les caractéristiques mécaniques du fil plaqué.The invention achieves its object by a process for the manufacture of plated steel armor wires intended for the reinforcement of flexible tabular conduits, in particular unbound, for the transport of hydrocarbons, a process of the type according to which a plating coating is associated. intimately, by high pressure, to a steel core, characterized in that the steel of the core is chosen with average mechanical characteristics and is hardenable, in that the coating is applied to the core and intimately associated, then in that the plated wire obtained undergoes rapid quenching at high temperature followed by tempering, so as to increase the mechanical characteristics of the plated wire.
Les caractéristiques de l'acier et du revêtement de placage, ainsi que la température et le temps de la trempe sont choisies de manière liée de façon à élever les caractéristiques mécaniques du fil trempé sans détruire la solidité de la liaison de placage. Un des facteurs clefs de l'invention est la rapidité du traitement thermique à haute température qui, en liaison avec les autres paramètres, permet de minimiser les contraintes au niveau de la liaison entre l'acier et le revêtement, notamment en évitant la migration du carbone et du fer.de l'acier dans la liaison et le revêtement.The characteristics of the steel and the plating coating, as well as the temperature and the time of quenching are chosen in a linked manner so as to raise the mechanical characteristics of the hardened wire without destroying the solidity of the plating bond. One of the key factors of the invention is the speed of the heat treatment at high temperature which, in conjunction with the other parameters, makes it possible to minimize the stresses at the level of the connection between the steel and the coating, in particular by avoiding the migration of the carbon and iron . steel in the connection and coating.
Selon l'invention, on utilise pour l'âme du fil d'armure un acier de résistance moyenne, c'est-à-dire dont la résistance Rm est comprise entreAccording to the invention, a steel of medium strength is used for the core of the armor wire, that is to say of which the resistance Rm is between
500 et 1000 MPa, avantageusement entre 800 et 900 MPa. Il doit s'agir d'un acier "trempàble" (capable de subir une trempe améliorant ses caractéristiques mécaniques, la trempe consistant, comme on sait, en un durcissement par traitement thermique : austénisation + refroidissement) au carbone, allié ou faiblement allié.500 and 1000 MPa, advantageously between 800 and 900 MPa. It must be a "quenchable" steel (capable of undergoing a quenching improving its mechanical characteristics, the hardening consisting, as is known, of hardening by heat treatment (austenization + cooling) with carbon, alloyed or weakly alloyed.
Le revêtement anti-corrosif est par exemple en titane ou alliages de titane, acier inoxydable, nickel ou alliages de nickel.The anti-corrosion coating is for example made of titanium or titanium alloys, stainless steel, nickel or nickel alloys.
Le placage est réalisé mécaniquement à froid après une préparation adéquate (désoxydation mécanique ou chimique des surfaces),, selon une technique permettant une liaison intime par pression (par exemple co- extrusion ou colaminage). - A la suite de cette opération, on obtient un assemblage caractérisé par une liaison base/placage encore fragile et par des caractéristiques mécaniques dégradées par la déformation plastique (allongement faible). Un tel produit, à ce stade, ne serait pas compatible avec une mise en forme pour servir d'armure à une conduite du type considéré dans l'invention. Selon l'invention, on soumet l'acier ainsi revêtu à un traitement thermique comportant une trempe courte à haute température et un revenu réalisés de manière à minimiser les contraintes au niveau de la liaison entre l'acier et le revêtement.The plating is carried out mechanically when cold after adequate preparation (mechanical or chemical deoxidation of the surfaces), using a technique allowing intimate bonding by pressure (for example co-extrusion or co-laminating). - Following this operation, an assembly is obtained which is characterized by a still fragile base / plating connection and by mechanical characteristics degraded by plastic deformation (low elongation). Such a product, at this stage, would not be compatible with shaping to serve as armor for a pipe of the type considered in the invention. According to the invention, the steel thus coated is subjected to a heat treatment comprising a short quenching at high temperature and tempering carried out so as to minimize the stresses at the level of the connection between the steel and the coating.
Le traitement thermique conforme à l'invention permet d'améliorer les caractéristiques de la liaison, de restaurer les caractéristiques de ductilité du placage et d'obtenir les hautes caractéristiques mécaniques du métal de base nécessaires dans les applications envisagées pour ce type de produit.The heat treatment in accordance with the invention makes it possible to improve the characteristics of the bond, to restore the ductility characteristics of the plating and to obtain the high mechanical characteristics of the base metal necessary in the applications envisaged for this type of product.
Ce traitement thermique est caractérisé par un cycle thermique à haute température (900 °C à 1100°C) court (quelques secondes à quelques dizaines de secondes) suivi d'un refroidissement rapide et d'un traitement de revenu à une température de l'ordre de 400°C à 700°C et qui est ajustée en fonction des caractéristiques mécaniques recherchées, le revenu s'effectuant sur une durée de quelques minutes, avantageusement entre 10 et 20 minutes. Ce traitement thermique a les effets suivants, différents selon les constituants de l'armure :This heat treatment is characterized by a short high temperature thermal cycle (900 ° C to 1100 ° C) (a few seconds to a few tens of seconds) followed by rapid cooling and a tempering treatment at a temperature of from 400 ° C to 700 ° C and which is adjusted according to the desired mechanical characteristics, the tempering taking place over a period of a few minutes, advantageously between 10 and 20 minutes. This heat treatment has the following effects, different depending on the constituents of the armor:
Pour le placage, le traitement restaure la ductilité sans conduire à des précipitations préjudiciables à la tenue à la conosion.For plating, the treatment restores ductility without leading to precipitations which are detrimental to the resistance to conosion.
Pour la liaison, il permet une amélioration de la résistance par relaxation des contraintes de laminage ou d'extrusion et diffusion métallique. Le revenu permet aussi une amélioration complémentaire de la ductilité par la relaxation des contraintes différentielles liées à la trempe.For the bond, it allows an improvement of the resistance by relaxation of the constraints of rolling or extrusion and diffusion metallic. The tempering also allows a complementary improvement of the ductility by the relaxation of the differential stresses linked to quenching.
Pour le métal de base, le traitement thermique va permettre d'obtenir une structure trempée revenue associant de très hautes caractéristiques mécaniques (Rm supérieure à 1000 MPa et de préférence à 1400 MPa au moins) et une ductilité suffisante pour les applications visées (environ 5% d'allongement).For the base metal, the heat treatment will make it possible to obtain a tempered tempered structure combining very high mechanical characteristics (Rm greater than 1000 MPa and preferably at least 1400 MPa) and sufficient ductility for the targeted applications (approximately 5 % elongation).
L'invention concerne aussi une conduite tubulaire flexible pour le transport d'hydrocarbures, incorporant au moins certains fils d'armure fabriqués selon le procédé de fabrication précité. Plus précisément, l'invention concerne une conduite tubulaire flexible pour le transport d'hydrocarbures, du type comportant des couches polymériques et des couches métalliques non liées, les couches métalliques comportant des fils d'armures enroulés, caractérisée en ce qu'au moins certains des fils d'armure sont fabriqués selon le procédé des revendications précédentes. L'invention vise notamment une conduite du type comportant au moins une carcasse, une gaine intérieure, une voûte de pression comportant des fils d'armure de pression, des nappes constituées de fils d'armure de traction et une gaine extérieure, caractérisée en ce qu'au moins certains des fils d'armure sont fabriqués selon le procédé de l'invention.The invention also relates to a flexible tubular pipe for transporting hydrocarbons, incorporating at least certain armor wires produced according to the aforementioned manufacturing process. More specifically, the invention relates to a flexible tubular pipe for the transport of hydrocarbons, of the type comprising polymeric layers and unbound metallic layers, the metallic layers comprising wound armor wires, characterized in that at least some armor wires are produced according to the method of the preceding claims. The invention relates in particular to a pipe of the type comprising at least one carcass, an internal sheath, a pressure vault comprising pressure armor wires, sheets made up of tensile armor wires and an external sheath, characterized in that that at least some of the armor wires are produced according to the process of the invention.
D'autres avantages et caractéristiques seront mis en évidence à la lecture de la description qui suit, en référence aux dessins schématiques annexés sur lesquels :Other advantages and characteristics will be highlighted on reading the description which follows, with reference to the appended schematic drawings in which:
La figure 1 est une vue en perspective d'une conduite de type "rough bore", à laquelle s'applique l'invention,FIG. 1 is a perspective view of a pipe of the "rough bore" type, to which the invention applies,
La figure 2 est une vue schématique illustrant le procédé de fabrication de l'armure plaquée conformément à l'invention.Figure 2 is a schematic view illustrating the manufacturing process of the plated armor according to the invention.
La figure 3 illustre schématiquement diverses sections possibles d'armures plaquées. La figure 1 montre une conduite de type "rough bore" qui comprend de l'intérieur vers l'extérieur : une carcasse métallique 1, généralement réalisée par un feuillard agrafé enroulé à pas court et destinée à la résistance à l'écrasement sous pression externe ; une gaine d'étanchéité interne polymérique 2, une voûte de pression métallique, constituée ici de manière traditionnelle par l'enroulement en hélice à pas court (angle d'enroulement généralement voisin de 90° par rapport à l'axe de la conduite) d'un fil métallique de forme agrafé 3 doublé par l'enroulement en hélice à pas court d'un fil de frette 4, une armure 5 résistant à la traction axiale dans le sens longitudinal de la conduite et classiquement constituée d'une paire de nappes croisées de fils d'armure de traction 6,7 d'enroulement à pas long (typiquement moins de 55° par rapport à l'axe de la conduite), et d'une gaine d'étanchéité externe polymérique 8. D'autres couches telles qu'une autre armure 9 et une gaine intermédiaire 10 peuvent être prévues selon le type et la destination de la conduite. L'invention vise le placage des fils d'armures de traction 6,7 aussi bien que des fils d'armures de pression 3, 4 (le cas échéant), selon un traitement qui est illustré sur la figure 2.Figure 3 schematically illustrates various possible sections of plated armor. Figure 1 shows a pipe type "rough bore" which includes from the inside to the outside: a metal carcass 1, generally made by a stapled strip wound in short pitch and intended for resistance to crushing under external pressure ; a polymeric internal sealing sheath 2, a metal pressure vault, constituted here in the traditional way by helical winding with short pitch (winding angle generally close to 90 ° relative to the axis of the pipe) of a stapled metal wire 3 doubled by the helical winding at short pitch of a hoop wire 4, an armor 5 resistant to axial traction in the longitudinal direction of the pipe and conventionally constituted by a pair of crossed plies of tensile armor wires 6,7 of winding with a long pitch (typically less than 55 ° relative to the axis of the pipe), and of a polymeric external sealing sheath 8. Other layers such as another armor 9 and an intermediate sheath 10 can be provided depending on the type and destination of the pipe. The invention relates to the plating of the tensile armor wires 6,7 as well as the pressure armor wires 3, 4 (if applicable), according to a treatment which is illustrated in FIG. 2.
Le fil 20 de départ est constitué d'une âme 21 en métal de base à caractéristiques mécaniques moyennes (par exemple Rm de 800 à 900 MPa) et d'un revêtement 22 en métal de placage. Le métal de base peut être, par exemple, un acier de base type chrome silicium (55SiCr V) à l'état globulisé de manière à permettre le placage. Le métal de placage peut être par exemple une base nickel (NiCrMo série 6x selon l'AISI) ou un alliage nickel (série 8x). Le fil de départ 20 passe dans une filière de co-extrusion 23, dont il ressort en ayant le revêtement 22 intimement lié à l'âme 21. Le fil ainsi plaqué passe dans un poste 24 de traitement thermique à haute température, typiquement au moins 800 °C et de préférence à 1100 °C, par exemple par un chauffage du fil par induction. Ce traitement est rapide (de quelques secondes à quelques minutes tout au plus). Il s'y produit une austénitisation de l'acier de base. Ce traitement est suivi d'une trempe rapide dans un poste 25 de trempe (par exemple par air, eau ou huile) qui s'accompagne d'une transformation martensitique contrôlée et permet donc l'obtention de hautes caractéristiques mécaniques, avec une Rm de l'ordre de 2Ô00 MPa. Mais la rapidité du traitement pennet de ne pas laisser diffuser des éléments néfastes (fer, carbone) dans la liaison qui dégraderait la qualité de celle-ci et dégraderait la résistance à la corrosion du placage.The starting wire 20 consists of a core 21 of base metal with medium mechanical characteristics (for example Rm of 800 to 900 MPa) and of a coating 22 of plating metal. The base metal can be, for example, a base steel of the chromium silicon type (55SiCr V) in the globulated state so as to allow plating. The plating metal may for example be a nickel base (NiCrMo 6x series according to AISI) or a nickel alloy (8x series). The starting wire 20 passes through a co-extrusion die 23, from which it emerges by having the coating 22 intimately linked to the core 21. The wire thus plated passes through a station 24 for heat treatment at high temperature, typically at least 800 ° C and preferably at 1100 ° C, for example by heating the wire by induction. This treatment is rapid (from a few seconds to a few minutes at most). There is an austenitization of the base steel. This treatment is followed by rapid quenching in a quenching station (for example by air, water or oil) which is accompanied by a controlled martensitic transformation and therefore allows high mechanical characteristics to be obtained, with an Rm of in the order of 2.00 MPa. However, the speed of the treatment makes it possible not to allow harmful elements (iron, carbon) to diffuse in the bond which would degrade the quality of the latter and degrade the corrosion resistance of the plating.
Le chauffage par induction est avantageux non seulement pour sa rapidité mais aussi parce qu'il permet de s'affranchir des problèmes liés à l'éventuelle réflexion du revêtement. Le fil ainsi obtenu traverse ensuite un poste 26 de revenu thermique, à une température de l'ordre de 450 °C pour une quinzaine de minutes.Induction heating is advantageous not only for its speed but also because it overcomes the problems associated with the possible reflection of the coating. The wire thus obtained then crosses a station 26 for thermal tempering, at a temperature of the order of 450 ° C for about fifteen minutes.
Il est possible, après le placage par co-laminage ou co-extrusion du poste 23 et avant le traitement thermique du poste 24, de prévoir un traitement intermédiaire de type revenu par exemple permettant de restaurer la ductilité et la qualité de la liaison.It is possible, after plating by co-lamination or co-extrusion of station 23 and before the heat treatment of station 24, to provide an intermediate treatment of the tempered type for example making it possible to restore the ductility and the quality of the bond.
Il est avantageux de veiller à l'adéquation entre les caractéristiques mécaniques de l'âme 21 et du revêtement 22, que l'on choisira relativement proches. Leur matériaux constitutifs seront préférentiellement choisis de manière que la différence entre leurs caractéristiques respectives de résistance mécanique Rm ne soit pas supérieure à 200 MPa. En maintenant relativement faible cette différence entre le fil et le revêtement, on améliore la régularité de la répartition des épaisseurs du revêtement et on améliore également la qualité de la liaison obtenue. II est possible de prévoir plusieurs couches de placage. L'épaisseur du placage est généralement de l'ordre de 200 μm à 500 μm ; elle doit être suffisamment épaisse pour résister aux agressions mécaniques et à la corrosion. Elle représente en section moins d'environ 10% de la section totale du fil. La figure 3 illustre, à titre d'exemples, quatre types de sections possibles pour les fils d'armures plaqués. La forme ronde 30 est la plus simple, mais on peut aussi envisager une forme rectangulaire 31 ou une forme en "zêta" 32 ou en "teta" 33, ces formes étant en soi classiques pour constituer des fils de renforcement de conduite. It is advantageous to ensure the adequacy between the mechanical characteristics of the core 21 and of the coating 22, which will be chosen relatively close. Their constituent materials will preferably be chosen so that the difference between their respective characteristics of mechanical resistance Rm is not greater than 200 MPa. By keeping this difference between the wire and the coating relatively small, the regularity of the thickness distribution of the coating is improved and the quality of the bond obtained is also improved. It is possible to provide several layers of plating. The thickness of the cladding is generally of the order of 200 μm to 500 μm; it must be thick enough to resist mechanical attack and corrosion. It represents in section less than approximately 10% of the total section of the wire. FIG. 3 illustrates, by way of example, four types of possible sections for the plated armor wires. The round shape 30 is the simplest, but it is also possible to envisage a rectangular shape 31 or a "zeta" 32 or "teta" shape 33, these shapes being in themselves conventional for constituting pipe reinforcement wires.

Claims

REVENDICATIONS
. Procédé de fabrication de fils (20) d'armure en acier plaqué destinées au renforcement de conduites tubulaires flexibles pour le transport d'hydrocarbures, du type selon lequel un revêtement de placage (22) est associé intimement, par forte pression, à une âme en acier (21), caractérisé en ce que l'acier de l'âme (21) est choisi avec des caractéristiques mécaniques moyennes et est trempàble, en ce que le revêtement (22) est appliqué sur l'âme (21) et associé intimement, puis en ce que le fil plaqué obtenu subit une trempe rapide à haute température s'accompagnant d'une transformation martensitique contrôlée, suivie d'un revenu. . Procédé selon la revendication 1, caractérisé en ce que les caractéristiques de l'acier et du revêtement de placage, ainsi que la température et le temps de la trempe sont choisies de façon à élever les caractéristiques mécaniques du fil trempé sans détruire la solidité de la liaison de placage.. Method for manufacturing plated steel armor wires (20) intended for the reinforcement of flexible tubular conduits for the transport of hydrocarbons, of the type according to which a cladding coating (22) is intimately associated, by high pressure, with a core steel (21), characterized in that the steel of the core (21) is chosen with average mechanical characteristics and is hardenable, in that the coating (22) is applied to the core (21) and associated intimately, then in that the plated wire obtained undergoes rapid quenching at high temperature accompanied by a controlled martensitic transformation, followed by tempering. . Method according to claim 1, characterized in that the characteristics of the steel and of the plating coating, as well as the temperature and the time of quenching, are chosen so as to raise the mechanical characteristics of the quenched wire without destroying the solidity of the plating bond.
3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que la trempe à haute température se fait à une température de l'ordre de 800°C à l l00°C.3. Method according to any one of claims 1 or 2, characterized in that the high temperature quenching takes place at a temperature of the order of 800 ° C to l00 ° C.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la trempe à haute température se fait pendant une durée de quelques secondes à quelques minutes tout au plus. 5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la trempe à haute température se fait par induction. 6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le revenu se fait pendant une durée comprise entre 10 min et 20 min. 7. Procédé selon l'une quelconque des revendications là 6, caractérisé en ce que une étape intennédiaire de revenu est introduite avant la trempe rapide. 8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le métal de placage est choisi parmi le titane et ses alliages, l'acier inoxydable, le nickel ou ses alliages. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que les matériaux constitutifs de l'âme (21) et du revêtement (22) sont choisis de manière que la différence entre leurs caractéristiques respectives de résistance mécanique Rm ne soit pas supérieure à 200 MPa. Conduite tubulaire flexible pour le transport d'hydrocarbures, du type comportant des couches polymériques (2, 8) et des couches métalliques (1, 3, 4, 6, 7) non liées, les couches métalliques comportant des fils d'armures enroulés (3, 4, 6, 7), caractérisée en ce qu'au moins certains des fils d'armure (3, 4, 3, 7) sont fabriqués selon le procédé des revendications précédentes. 4. Method according to any one of claims 1 to 3, characterized in that the high temperature quenching takes place for a period of a few seconds to a few minutes at most. 5. Method according to any one of claims 1 to 4, characterized in that the quenching at high temperature is carried out by induction. 6. Method according to any one of claims 1 to 5, characterized in that the tempering takes place for a period of between 10 min and 20 min. 7. Method according to any one of claims 1 to 6, characterized in that an intermediate tempering step is introduced before rapid quenching. 8. Method according to any one of claims 1 to 7, characterized in that the plating metal is chosen from titanium and its alloys, stainless steel, nickel or its alloys. Method according to any one of Claims 1 to 8, characterized in that the materials constituting the core (21) and the covering (22) are chosen so that the difference between their respective characteristics of mechanical resistance Rm is not greater than 200 MPa. Flexible tubular pipe for the transport of hydrocarbons, of the type comprising polymeric layers (2, 8) and metallic layers (1, 3, 4, 6, 7) unbound, the metallic layers comprising coiled armor wires ( 3, 4, 6, 7), characterized in that at least some of the armor wires (3, 4, 3, 7) are produced according to the method of the preceding claims.
EP03722682A 2002-03-05 2003-02-28 Method for making a plated steel armouring wire for a flexible tubular pipe transporting hydrocarbons, and armoured pipe Expired - Lifetime EP1483068B1 (en)

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FR0202793A FR2836847B1 (en) 2002-03-05 2002-03-05 METHOD FOR MANUFACTURING PLATE STEEL ARMOR WIRE FOR FLEXIBLE TUBULAR PIPE FOR TRANSPORTING HYDROCARBONS, AND PIPE THUS REINFORCED
FR0202793 2002-03-05
PCT/FR2003/000657 WO2003074206A2 (en) 2002-03-05 2003-02-28 Method for making a plated steel armouring wire for a flexible tubular pipe transporting hydrocarbons, and armoured pipe

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AU2003229847A1 (en) 2003-09-16

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