Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
• • 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
  • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
• • 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

Definitions

• the invention relates to the manufacture of hot and cold rolled sheets of austenitic iron-carbon-manganese steels having very high mechanical characteristics, and in particular a high mechanical strength combined with an excellent resistance to delayed cracking.
• the patent FR 2 829 775 discloses, for example, austenitic alloys having as main elements: iron-carbon (up to 2%) manganese (between 10 and 40%) capable of being hot-rolled or cold-rolled, exhibiting a resistance that may exceed 1200 MPa.
• the deformation mode of these steels depends only on the stacking fault energy: for a sufficiently high stacking fault energy, a mechanical deformation mode is observed by twinning, which makes it possible to obtain a large capacitance. hardening.
• the twins participate in increasing the flow limit.
• the stacking fault energy exceeds a certain threshold, the sliding of the perfect dislocations becomes the dominant deformation mechanism and the work hardening capacity is less.
• the aforementioned patent therefore discloses Fe-C-Mn steel grades whose stacking failure energy is such that a high work-hardening is observed, combined with a very high mechanical strength.
• the object of the invention is therefore to provide a hot-rolled or cold-rolled steel sheet or product of economical manufacture, having a resistance greater than 900 MPa, an elongation at break greater than 50%, particularly suitable for cold forming and having a very high resistance to delayed cracking, without the particular need for a specific heat treatment for degassing.
• the subject of the invention is an austenitic iron-carbon-manganese steel sheet, the chemical composition of which comprises the contents being expressed by weight: 0.45% ⁇ C ⁇ 0.75%, 15% ⁇ Mn ⁇ 26%, Si ⁇ 3%, Al ⁇ 0.050%, S ⁇ 0.030%, P ⁇ 0.080%, N ⁇ 0.1% at least one metal element selected from vanadium, titanium, niobium, chromium, molybdenum: 0.050% ⁇ V ⁇ 0.50%, 0.040% ⁇ Ti ⁇ 0.50%, 0.070% ⁇ Nb ⁇ 0, 50%, 0.070% ⁇ Cr ⁇ 2%, 0.14% ⁇ Mo ⁇ 2% and optionally one or more elements selected from 0.0005% ⁇ B ⁇ 0.003%, Ni ⁇ 1%, Cu ⁇ 5%, the remainder of the composition consisting of iron and unavoidable impurities resulting from the preparation, the quantity of metal elements in the form of carbides, nitri
• the composition of the steel comprises: 0.50% ⁇ C ⁇ 0.70% According to a preferred embodiment, the composition of the steel comprises: 17% ⁇ Mn ⁇ 24%
• the composition of the steel comprises 0.070% ⁇ V ⁇ 0.40%, the amount of vanadium in the form of carbides, nitrides or carbonitrides precipitated being 0.070% ⁇ V p ⁇ 0.140%
• the composition of the steel comprises 0.060% ⁇ Ti ⁇ 0.40%, the amount of titanium in the form of carbides, nitrides or carbonitrides precipitated being: 0.060% ⁇ Ti p ⁇ 0.110%
• composition of the steel advantageously comprises 0.090% ⁇ Nb ⁇ 0.40%, the amount of niobium in the form of carbides, nitrides or carbonitrides precipitated being: 0.090% ⁇ Nb p ⁇ 0.200%
• the composition of the steel comprises 0.20% ⁇ Cr ⁇ 1.8%, the amount of chromium in the form of precipitated carbides being 0.20% ⁇ Cr p ⁇ 0.5%
• the composition of the steel comprises 0.20% ⁇ Mo ⁇ 1.8%, the quantity in molybdenum in the form of precipitated carbides being 0.20% ⁇ Mo p ⁇ 0.35%
• the average size of the precipitates is between 5 and 25 nanometers, and more preferably between 7 and 20 nanometers
• at least 75% of the population of said precipitates is located in intragranular position.
• the invention also relates to a method of manufacturing a sheet metal cold-rolled austenitic iron-carbon-manganese steel according to which is supplied a steel whose chemical composition comprises, the contents being expressed by weight:
• the parameters Vc, Tm, tm, Vr, Tu, t u are adjusted so that the average size of the carbide, nitride or carbonitride precipitates after the annealing is between 5 and 25 nanometers, and preferentially between 7 and 20 nanometers.
• Vc, Tm, tm, Vr, Tu, t u are advantageously adjusted such that at least 75% of the population of the precipitates after the annealing is located in the intragranular position.
• a steel whose chemical composition comprises 0.050% ⁇ V ⁇ 0.50% is supplied with heat, the semi-finished product is heated to a rolling end temperature of greater than or equal to 950.degree. the sheet is reeled at a temperature below 500 ° C., the sheet is cold-rolled with a reduction ratio greater than 30%, an annealing heat treatment is carried out with a heating rate Vc of between 2 and 10 ° C / s, at a temperature Tm between 700 and 870 ° C for a time between 30 and 180 s, and the sheet is cooled at a speed between 10 and 50 ° C / s.
• the heating rate Vc is preferably between 3 and 7 ° C./s.
• the holding temperature Tm is between 720 and 850 ° C.
• the casting of the semi-finished product is advantageously carried out in the form of casting slabs or thin strips between counter-rotating steel rolls.
• the invention also relates to the use of an austenitic steel sheet described above or manufactured by a method described above, for the manufacture of structural parts, reinforcing elements or external parts. , in the automotive field.
• carbon plays a very important role in the formation of the microstructure and the mechanical properties: it increases the stacking fault energy and promotes the stability of the austenitic phase. In combination with a manganese content ranging from 15 to 26% by weight, this stability is obtained for a carbon content greater than or equal to 0.45%. However, for a carbon content greater than 0.75%, it becomes difficult to avoid excessive precipitation of carbides during certain thermal cycles during industrial manufacture, a precipitation which degrades the ductility.
• the carbon content is between 0.50 and 0.70% by weight so as to obtain sufficient strength combined with optimum precipitation of carbides or carbonitrides.
• the manganese content is between 17 and 24% so as to optimize the stacking fault energy and to avoid the formation of martensite under the effect of a deformation. Moreover, when the manganese content is greater than 24%, the mode of deformation by twinning is less favored compared to the sliding mode of perfect dislocations.
• Aluminum is a very effective element for the deoxidation of steel. Like carbon, it increases the stacking fault energy. However, its excessive presence in steels with a high manganese content has a disadvantage: in fact, manganese increases the solubility of nitrogen in the liquid iron. If too much aluminum is present in the steel, the nitrogen combining with the aluminum precipitates in the form of aluminum nitrides hindering the migration of the grain boundaries during the hot transformation and increases very significantly the risk of occurrence of cracks in continuous casting. In addition, as will be explained later, a sufficient amount of nitrogen must be available to form fine carbo-nitride precipitates for the most part. An Al content less than or equal to 0.050% avoids precipitation of AlN and maintains a sufficient nitrogen content for the precipitation of the elements mentioned below.
• the nitrogen content must be less than or equal to 0.1% in order to prevent this precipitation and the formation of volume defects (blowholes) during solidification.
• the nitrogen content in the presence of elements capable of precipitating in the form of nitrides, such as vanadium, niobium or titanium, the nitrogen content must not exceed 0.1% otherwise the risk of obtaining an ineffective coarse precipitation will be observed. with respect to the trapping of hydrogen.
• Silicon is also an effective element for deoxidizing steel as well as for hardening in the solid phase. However, beyond a content of 3%, it decreases the elongation, tends to form undesirable oxides during certain assembly processes and must therefore be kept below this limit.
• Sulfur and phosphorus are impurities that weaken the grain boundaries. Their respective content must be less than or equal to 0.030 and 0.080% in order to maintain sufficient hot ductility.
• boron may be added in an amount of from 0.0005 to 0.003%. This element segregates at the austenitic grain boundaries and reinforces their cohesion. Below 0.0005%, this effect is not obtained. Above 0.003%, boron precipitates as borocarbons, and the effect is saturated.
• Nickel can be used as an option to increase the strength of the steel by hardening in solid solution. Nickel contributes to a high elongation break and increases in particular the toughness. However, it is also desirable for cost issues to limit the nickel content to a maximum content of less than or equal to 1%.
• addition of copper to a content of less than or equal to 5% is a means of hardening the steel by precipitation of metallic copper. However, beyond this content, copper is responsible for the appearance of surface defects hot sheet.
• the metal elements capable of forming precipitates such as vanadium, titanium, niobium, chromium, molybdenum, play an important role in the context of the invention.
• delayed cracking is caused by an excessive local concentration of hydrogen, in particular at the austenitic grain boundaries.
• the inventors have demonstrated that certain types of precipitates, the nature, quantity, size and distribution of which are precisely defined according to the invention, significantly reduce the sensitivity to delayed cracking, and this without reducing the properties ductility and tenacity.
• the inventors firstly demonstrated that carbides, nitrides or carbonitrides precipitated from vanadium, titanium or niobium, were very effective as hydrogen traps. Chromium carbides or molybdenum carbides can also play this role. At room temperature, the hydrogen is then irreversibly trapped at the interface between these precipitates and the matrix. It is however necessary, in order to ensure the trapping of the residual hydrogen which could be encountered under certain industrial conditions, that the quantity of metal elements in the form of precipitates is greater than or equal to a critical content, depending on the nature of the precipitates.
• the quantity of metal elements in the form of precipitates of carbides, nitrides, or carbonitrides is designated by V p , Ti p , Nb p , respectively for vanadium, titanium and niobium, and Cr p , Mo p for chromium and molybdenum carbides.
• the minimum value expressed for these various elements corresponds to a quantity of addition necessary to form precipitates taking into account the thermal cycles of manufacture.
• a preferred minimum content (for example 0.070% for vanadium) is recommended, so as to obtain a larger quantity of precipitates.
• the maximum value expressed for these various elements corresponds to excessive precipitation, or in an inappropriate form, deteriorating the mechanical properties, or to an uneconomic implementation of the invention.
• a preferred maximum content (for example of 0.40% for vanadium) is recommended, so as to optimize the addition of the element.
• the minimum value of metallic elements in the form of precipitates corresponds to a quantity of precipitates for very effectively reducing the sensitivity to delayed cracking.
• a preferred minimum amount (for example 0.070% in the case of vanadium) is recommended, so as to obtain a particularly high resistance to delayed cracking.
• the maximum value of metallic elements in the form of precipitates marks a deterioration of the ductility or the tenacity, the rupture starting on the precipitates. Moreover, beyond this maximum value, intense precipitation occurs, which can prevent total recrystallization during thermal treatments of continuous annealing after cold rolling.
• a preferred maximum content in the form of precipitates (for example 0.140% for vanadium) is recommended, so that the ductility is preserved as much as possible and that the precipitation obtained is compatible with the recrystallization under the usual annealing conditions. recrystallization.
• mean size of precipitates is the size that can be measured, for example, from replicates with extraction, followed by observations by transmission electron microscopy: the diameter is measured (in the case of spherical or quasi-spherical precipitates) or the largest length (in the case of irregularly shaped precipitates) of each precipitate, then establishes a histogram of size distribution of these precipitates, the average of which is calculated from the count of a statistically representative number of particles. Beyond an average size of 25 nanometers, the efficiency of hydrogen scavenging decreases due to the decrease in the interface between precipitates and matrix.
• an average size of precipitates exceeding 25 nanometers also decreases the density of precipitates present, thereby excessively increasing the inter-site trapping distance.
• the trapping interfacial surface for hydrogen is also reduced.
• the average size of precipitates is less than 20 nanometers in order to trap the largest amount of hydrogen possible.
• the precipitates are advantageously located in the intragranular position in order to reduce the sensitivity to delayed cracking: in fact, when at least 75% of the population of precipitates is located in the intragranular position, the distribution of hydrogen possibly present is more homogeneous, without accumulation at the austenitic grain boundaries which are potential sites of embrittlement.
• the addition of one of the aforementioned elements, in particular chromium, makes it possible to obtain a precipitation of various carbides such as MC, M 7 C 3 , M 23 C 6 , M 3 C where M denotes not only the metallic element but also Fe or Mn, elements present in the matrix.
• M denotes not only the metallic element but also Fe or Mn, elements present in the matrix.
• the presence of iron and manganese within the precipitates makes it possible to increase the quantity of precipitates at a lower cost, thus reinforcing the efficiency of the precipitation.
• the object of the invention is to simultaneously dispose of steels with very high mechanical characteristics and insensitive to delayed fracture.
• the steel should be completely recrystallized after the annealing cycle. Too early precipitation, for example at the stage of casting, hot rolling or winding, will be a potential brake on recrystallization and may harden the metal and increase the hot or cold rolling forces. It will also be less effective because it will intervene significantly on the austenitic grain boundaries. The size of these precipitates formed at high temperature will be larger, often greater than 25 nanometers.
• vanadium additions are particularly desirable insofar as the precipitation of this element hardly occurs during hot rolling or winding.
• the precipitation takes place in the form of VC and in the form of nanometric VN or V (CN) homogeneously distributed, the vast majority of the precipitates being located in the intragranular position, ie in the most desirable form for the entrapment of the nanoparticles. 'hydrogen.
• this fine precipitation limits the growth of the grain, a finer austenitic grain size can thus be obtained after annealing.
• a steel is produced whose composition comprises: 0.45% ⁇ C ⁇ 0.75% 15% ⁇ Mn ⁇ 26%, Si ⁇ 3%, Al ⁇ 0.050%, S ⁇ 0.030, P ⁇ 0.080%, N ⁇ 0.1%, one or more elements selected from 0.050% ⁇ V ⁇ 0.50%, 0.040% ⁇ Ti ⁇ 0.50%, 0.070% ⁇ Nb ⁇ 0.50%, 0.070% ⁇ Cr ⁇ 2%, 0.14% ⁇ Mo ⁇ 2%, and optionally one or more elements selected from 0.0005% ⁇ B ⁇ 0.003%, Ni ⁇ 1%, Cu ⁇ 5%, the rest being iron and unavoidable impurities from the elaboration.
• This development can be followed by casting in ingots, or continuously in the form of slabs of thickness of the order of 200 mm. It is also possible to advantageously perform the casting in the form of thin slabs, a few tens of millimeters thick, or thin strips of a few millimeters.
• certain addition elements according to the invention such as titanium or niobium are present, the casting in the form of thin products will lead more particularly to a precipitation of nitrides or very thin and thermally stable carbonitrides, the presence of which reduces sensitivity to delayed cracking.
• These cast half-products are first brought to a temperature of between 1100 and 1300 ° C. This is intended to achieve in all points temperature areas favorable to high deformations that will undergo the steel during rolling.
• the reheat temperature must not be higher than 1300 ° C, otherwise it will be too close to the solidus temperature that could be reached in any zones enriched locally with manganese and / or carbon and cause a passage local by a liquid state that would be harmful for hot shaping.
• the hot rolling step of these semi-products starting between 1300 and 1000 ° C can be done directly after casting without going through the intermediate heating step.
• the semi-finished product is hot-rolled, for example to obtain a thickness of hot rolled strip 2 to 5 millimeters thick, or even 1 to 5 mm in the case of semi-finished product from a thin slab casting. , or 0.5 to 3 mm in the case of a casting of thin strips.
• the low aluminum content of the steel according to the invention makes it possible to avoid excessive precipitation of AlN which would adversely affect the hot deformability during rolling.
• the end-of-lamination temperature In order to avoid any problem of cracking due to lack of ductility, the end-of-lamination temperature must be greater than or equal to 890 ° C.
• the strip After rolling, the strip must be wound at a temperature such that a precipitation of carbides, essentially intergranular cementite (Fe, Mn) 3 C), does not take place significantly, which would lead to a reduction of certain mechanical properties. This is achieved when the winding temperature is below 580 ° C.
• the conditions of elaboration will also be chosen so that the product obtained is completely recrystallized.
• the product Before the optional phase of keeping the temperature Tu, the product can be optionally cooled to room temperature. This phase of maintaining the temperature You can possibly be carried out within a separate device, for example a furnace for the static annealing of steel coils.
• Vc, Tm, tm, Vr, Tu, t u is usually carried out in such a way that the desired mechanical properties are obtained, in particular thanks to a complete recrystallization.
• the person skilled in the art will adjust in particular according to the cold rolling ratio, these so that the amount of metal elements (V, Ti, Nb, Cr, Mo) present in the form of carbides, nitrides or carbonitrides precipitated after annealing is included within the contents mentioned above ((V p , Ti p , Nb p , Cr p , Mo p )
• a composition steel will be produced: 0.45% ⁇ C ⁇ 0.75%, 15% ⁇ Mn ⁇ 26%, Si ⁇ 3%, Al ⁇ 0.050%, S ⁇ 0.030%, P 0,0 0.080%, N ⁇ 0.1%, 0.050% ⁇ V ⁇ 0.50%, and optionally one or more elements selected from 0.0005% ⁇ B ⁇ 0.003%, Ni ⁇ 1%, Cu ⁇ 5%, optimally a steel sheet according to the invention by casting a half-product, bringing it to a temperature of between 1100 and 1300 ° C, by hot rolling this half-product to a temperature of end of rolling greater than or equal to 950 ° C and then winding at a temperature below 500 ° C.
• the sheet is cold rolled with a reduction rate greater than 30% (the reduction ratio being defined by: (thickness of the sheet before cold rolling - thickness of the sheet after cold rolling) / (thickness of the front plate
• the rate of 30% corresponds to a minimum deformation so as to obtain a recrystallization.
• An annealing heat treatment is then carried out with a heating rate Vc of between 2 and 10 ° C./s (preferably between 3 and 7 ° C.). ° C / s), at a temperature Tm between 700 and 870 ° C (preferably between 720 and 850 ° C) for a time between 30 and 180s and the sheet will be cooled at a speed between 10 and 50 ° C / s
• compositions expressed as a weight percentage in addition to the steels I1 and I2 according to the invention, the composition of reference steels was indicated by way of comparison:
• R1 steel has a very low vanadium content
• Table 1 Composition of steels Steel VS mn Yes S P al Cu Or NOT B V 11 0,635 21.79 0.01 0,003 0,007 0.005 ⁇ 0.002 ⁇ 0.01 0,003 ⁇ 0.0005 0,160 12 0.595 21,80 0,200 0.006 0,007 0,004 ⁇ 0.002 ⁇ 0.01 0,003 0.0023 0,225 R1 0,600 21.84 0.198 0,007 0.006 0.005 ⁇ 0.002 ⁇ 0.01 0,003 ⁇ 0.0005 0,013 R2 0.625 21.65 0.01 0,003 0,007 0.005 ⁇ 0.002 ⁇ 0.01 0,003 ⁇ 0.0005 0.405 R3 0.625 21.64 0.01 0,003 0,007 0.005 ⁇ 0.002 ⁇ 0.01 0,003 ⁇ 0.0005 0.865 I1-2: according to the invention.
• R1-3 Reference
• Semi-finished products of these steels were heated to 1180 ° C, hot rolled to a temperature of 950 ° C to bring them to a thickness of 3 mm and then wound at a temperature of 500 ° C.
• the steel sheets thus obtained were then cold-rolled with a reduction rate of 50% to a thickness of 1.5 mm, and then annealed under the conditions presented in Table 2.
• Table 3 shows the mechanical tensile properties: strength and elongation at break, obtained under these conditions.
• circular blanks with a diameter of 55 mm were cut in the cold-rolled and annealed sheets. These blanks were then embossed by swallowing in the form of flat-bottomed cups (swift shrinkage tests) using a 33mm diameter punch.
• the factor ⁇ characterizing the severity of the test is 1.66.
• the possible presence of micro-cracks was then noted either immediately after shaping, or after a waiting period of 3 months, thus characterizing a possible sensitivity to delayed cracking. The results of these observations were also reported in Table 3.
• Table 3 Mechanical tensile characteristics obtained on cold-rolled and annealed sheets, and characteristics of drawability and sensitivity to delayed cracking Steel Strength (MPa) Elongation at break (%) observed after stamping Cracks observed after a waiting time of 3 months I1 1071 55 No No I2 1090 58 No No R1 1074 63 No Yes R2 1168 35 No No R3 1417 28 nd nd nd: not determined
• the steels I1 and I2 according to the invention comprise precipitates of suitable size and nature. These are located at more than 75% in intragranular position. These steels combine excellent mechanical characteristics (resistance greater than 1000 MPa, elongation greater than 55% and a high resistance to delayed fracture. This last property is obtained even without specific heat treatment of degassing.
• the hot-rolled or cold-rolled sheets according to the invention are advantageously used in the automobile industry in the form of structural parts, reinforcing elements or external parts which, because of their very high strength and their high ductility, contribute to a very effective reduction of vehicle weight while increasing safety in case of impact.

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• Chemical & Material Sciences (AREA)
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• Mechanical Engineering (AREA)
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• Organic Chemistry (AREA)
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• Heat Treatment Of Sheet Steel (AREA)
• Heat Treatment Of Steel (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Treatment Of Steel In Its Molten State (AREA)
• Heat Treatment Of Strip Materials And Filament Materials (AREA)

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• 2005
  • 2005-01-21 FR FR0500637A patent/FR2881144B1/fr not_active Expired - Fee Related
• 2006
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