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
  • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
• • 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
  • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
  • C21D1/18—Hardening; Quenching with or without subsequent tempering
• • 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
  • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
  • C21D1/18—Hardening; Quenching with or without subsequent tempering
  • C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
  • C21D1/20—Isothermal quenching, e.g. bainitic hardening
• • 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
  • C21D6/002—Heat treatment of ferrous alloys containing Cr
• • 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
  • C21D6/00—Heat treatment of ferrous alloys
  • C21D6/005—Heat treatment of ferrous alloys containing Mn
• • 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
  • C21D6/008—Heat treatment of ferrous alloys containing Si
• • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
  • C21D8/06—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
• • 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
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
• • 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
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
  • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
• • 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
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
  • C21D9/54—Furnaces for treating strips or wire
  • C21D9/56—Continuous furnaces for strip or wire
  • C21D9/58—Continuous furnaces for strip or wire with heating by baths
• • 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
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
  • C21D9/54—Furnaces for treating strips or wire
  • C21D9/64—Patenting furnaces
• • 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
  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
• • 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
  • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
• • 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
  • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
• • 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
  • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
• • 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
  • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
• • 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
  • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
• • 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
  • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
• • 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
• • 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
  • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
• • 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
  • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
• • 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
  • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
• • 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
  • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
• • 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
• • 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
  • 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
  • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
• • 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
  • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
• • 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
  • C21D2211/00—Microstructure comprising significant phases
  • C21D2211/009—Pearlite

Definitions

• the present invention relates to the field of metallurgy dedicated to the exploitation of marine oil. It relates more particularly to steel wires which can be used as reinforcement elements or structural components or as deep water immersed structures, such as flexible offshore pipes.
• These form wires may have a round cross section, obtained by simple drawing from a wire of larger diameter. They can also, after drawing, rolling, or drawing followed by rolling, have a flat section, or profiled U, Z, T, etc.. in such a way that they can fit into each other on the edges, or be stapled together to form articulated reinforcing plies.
• NACE TM 0177 with solution A in this case, due to a high presence of H 2 S in the hydrocarbon transported, especially if the target hardness levels are greater than 28 HRC (more than 900 MPa).
• the document FR-B-2731371 published in 1996 also relates to the production of form wires, made of carbon steel, for the reinforcement of off-shore flexible pipes whose resistance in acidic medium with H 2 S is sought at a temperature of high level from general knowledge about the influence of steel microstructures on its resistance to embrittlement by hydrogen.
• the form wire proposed in this document which contains from 0.05 to 0.8% of C and from 0.4 to 1.5% of Mn, has undergone, after shaping (drawing or drawing-rolling), a temper followed by an income in the end.
• the metal structure obtained is essentially a martensitobarbite returned.
• JP 59001631 A of 1984 (DATA BASE WPI Week 198407 Thomsom Scientific, London, GB, AN 1984-039733) which recommends a final treatment for restoring long-lived yarn, in the form of an annealing that lasts several hours.
• the aim of the invention is to achieve an optimal balance between a good resistance to wet embrittlement by hydrogen under the conditions of use of the shaped wire, and an increased mechanical strength thereof, and this in the framework of an industrial production which will make it possible to offer the yarn on the market in attractive economic conditions.
• the subject of the invention is a wire of low alloy steel shape with high mechanical characteristics and resistant to embrittlement with hydrogen, shaped wire intended to be used as a component of flexible pipes for the sector of off-shore oil exploitation, characterized in that it has the following chemical composition, expressed as weight percentages of the total mass, with Cr ⁇ 0.4%; V ⁇ 0.16%; If ⁇ 1.40% and preferably> 0.15%,
• the shaped wire is obtained by subjecting said starting wire rod first to a thermomechanical treatment according to two successive and ordered steps, namely an isothermal quench (conventionally a lead patenting) which gives it a homogeneous pearlitic microstructure, followed by a mechanical transformation operation to cold (wire drawing, or wire drawing + rolling) carried out with an overall work hardening rate of between approximately 50 and 80% (and, if possible, preferably around 60%) to give the wire its final shape, and in that the shaped wire thus obtained is then subjected to a heat treatment of short duration restoration
• the invention which has just been defined above, is based on the triptique: "steel grade -treatment -application" and can be seen as an optimization of the knowledge acquired by the applicant in the field of wire metallurgy steel intended for use in the deep sea.
• a simplified steel grade namely a carbon steel (at least 0.75%) and manganese, which is therefore in opposition to the much lower carbon content currently retained, and without the addition of elements quenching, but preferably alloyed with dispersoid elements, such as vanadium and chromium, to obtain a homogeneous distribution of fine carbides throughout the metal matrix;
• this grade is produced from a hot-rolled machine wire then cooled to ambient temperature (thus of ordinary ferrito-pearlite structure coming from the austenite of hot rolling), but whose diameter (between 5 and 30 mm about) is reduced compared to the usual practice.
• This arrangement will allow its transformation into final form wire ready for use by gentle mechanical shaping operations, ie without hardening too marked to heart that could create areas of heterogeneity, being specified that It is, of course, the operator in charge of the manufacturing process to adjust the operating parameters (operational parameter settings, choice of dies and splines rolling rolls) to limit the local hardening at the heart of the wire.
• the microstructure to be created by isothermal quenching is perlite. Being easy to obtain industrially, the perlite will ensure a metallurgical structure as homogeneous as possible throughout the mass of the wire obtained and will be able to undergo the deformations applied by drawing and / or rolling
• This wire is a wire shaped, flat, flat or profiled, intended for the offshore oil exploitation to constitute the wire of wire, fret or vault entering the structure of the pipelines and other flexible conduits .
• the steel form son evolve in the pipelines between two layers of extruded polymers in an area called "annular".
• the physicochemical conditions prevalent in this area, when using the hose, are now better known. They depend on the nature of the effluent in the hose (liquid or gaseous hydrocarbons) and the structure of the different layers of the hose. In particular, the pH is higher than previously thought in the years 1990/2000 (on average around 5.5 rather than 4).
• the invention thus finds its primary cause in the discovery of these new, less drastic conditions to be satisfied in the region of the annulus, which allow the use of form wires with higher mechanical strength.
• the NACE quality of today can be expressed quite validly through test results less severe than those provided by the API standard (the applicant has had to adapt the test conditions to the API standard, especially pH, to adapt to the demand).
• the NACE quality can be recognized for a steel wire that has withstood without breakage or internal cracking for one month under a continuous stress of 90% of the Re in an aqueous solution having a pH between 5 and 6.5 and subject to bubbling a gas containing C0 2 and a few millibars of H 2 S.
• Table I shows seven examples of chemical compositions of shades according to the invention, which is identified in the first column by a nomenclature internal to the applicant.
• composition taken from the steel grade referenced C88 (penultimate line of Table I), whose present components meet the following precise weight ratios: C: 0.861%, Mn: 0.644% , P: 0.012%, S: 0.003%, Si: 0.303%, Al: 0.47%, Ni: 0.015%, Cr: 0.032%, Cu: 0.006%, Mo: 0.003%, and V: 0.065%.
• a final wire ready for use of flat form of 9 mm ⁇ 4 mm is produced according to the following successive operations. It is indicated beforehand that, in accordance with the invention, it will not exceed 30 mm in diameter for the starting machine wire taken cold, so as not to have to wrinkle the heart of the wire markedly during drawing subsequent conducted with an overall wrought rate of not more than 80% to achieve the desired final diameter of the form wire ready to use.
• the wire rod is a hot-rolled steel wire, ie in its austenitic range (typically above 900 ° C) which is then rapidly cooled in the hot rolling mill before winding it into a coil to finish cool to room temperature on a storage area awaiting delivery to the customer.
• austenitic range typically above 900 ° C
• this starting wire which is unrolled from its coil, is first subjected, from the ambient temperature, isothermal quenching. Conventionally, it will be a patenting at constant temperature around 520-600 ° C by passing in a bath of molten lead, before cooling. This patenting gives the steel wire a pearlitic microstructure, with possible traces of ferrite, but without bainite or martensite, and that it will keep until the end.
• the wire is then drawn (round or already flat) in a "soft" manner, that is to say, as already mentioned above, so as to limit as much as possible the level of constraints to heart that will confer on it the wrought metal.
• the reason for this is that damage to the microstructure should be limited to the core, which would create sites favorable to a preferential accumulation of hydrogen.
• the wire may then be subjected to a cold rolling final setting, it being specified that the rate of overall hardening (drawing + rolling) will be between 50 and 80% maxi, and, if possible preferably around 60%.
• the intermediate yarn thus obtained has an Rm of about 1900 MPa.
• Table II below gives the final mechanical characteristics obtained for a shaped wire having undergone a fast heat treatment of restoration under the following operating conditions, indicated by the lines A to E: stay of a duration of 5 seconds , at a temperature below the temperature Acl of the grade of steel considered and given in the second column of the table, before brutal cooling with water.
• the other columns indicate respectively the average ultimate limit Rm, the average yield strength Re, the average elongation rate at break A% of the treated wire resulting from the thermomechanical operations applied, and the Re / Rm ratio.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Thermal Sciences (AREA)
• Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Heat Treatment Of Steel (AREA)
• Heat Treatment Of Strip Materials And Filament Materials (AREA)
• Metal Extraction Processes (AREA)
• Heat Treatment Of Articles (AREA)

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• 2010
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