PRE-COATED SHEETS THAT ENABLE THE PRODUCTION OF PRESS-HARDENED COATED STEEL PARTS

Description

[0001] The description relates to a method for manufacturing parts from cold-rolled and annealed steel sheets, pre-coated, heated, stamped and then hardened during cooling obtained by holding within a press tool; these parts are intended in particular to be used as structural elements in motor vehicles to provide anti-intrusion or energy absorption functions. Such parts can also be used, for example, for the manufacture of tools or parts of agricultural machinery.

[0002] In this type of application, the aim is to produce steel parts that combine high mechanical strength, high impact resistance, good corrosion resistance, and good dimensional accuracy. This combination is particularly desirable in the automotive industry, where significant vehicle weight reduction is required. Anti-intrusion parts or parts contributing to the safety of motor vehicles, such as bumper cross members, door or center pillar reinforcements, require, for example, the qualities mentioned above. This can be achieved, in particular, using steel parts with a martensitic or bainito-martensitic microstructure.

[0003] The manufacture of such parts is known from publications FR2780984 and FR2807447 according to which a blank cut from a steel sheet for heat treatment, pre-coated with a metal or a metal alloy, is heated in a furnace and then hot deformed. The pre-coating can be aluminum or an aluminum alloy, zinc or a zinc alloy. During heating in the furnace, the pre-coating provides protection for the steel surface against decarburization and the formation of scale. During heating in the furnace, this pre-coating combines with the steel substrate to form a compound suitable for hot forming and which does not cause damage to the tooling. Holding the part in the tooling after forming has been carried out allows rapid cooling which leads to the production of hardened microstructures with very high mechanical characteristics.Such a process is known as press hardening.

[0004] As a general rule, the mechanical characteristics of the parts thus obtained are evaluated by means of tensile and hardness tests. The aforementioned documents thus disclose manufacturing processes making it possible to obtain a mechanical strength (or tensile breaking strength) Rm of 1500 MPa from a steel blank having an initial strength Rm of 500 MPa before heating and rapid cooling.

[0005] However, the service conditions of some hardened and coated parts require not only a high value of resistance Rm, but also good bending ability. This parameter appears to be more relevant than the elongation at break measured in tension, to ensure that the part has sufficient ductility to absorb deformations or shocks without risk of rupture, particularly in areas corresponding to local stress concentrations due to the geometry of the part or the possible presence of micro-defects on the surface of the parts.

[0006] Document WO2009080292 discloses a method for increasing the bend angle of a hardened part: according to this method, a steel sheet is heated in an annealing furnace at a temperature between 650 and 800°C so as to obtain an oxide layer with a thickness significantly greater than 0.3 micrometers. Certain alloying elements of the steel are oxidized under this oxide layer. This oxide layer is then partially reduced so that it has a thickness greater than 0.3 micrometers. The extreme surface of the reduced oxide layer is made of pure iron. The sheet is then coated by dipping. After this step, the sheet comprises the following successive layers: the steel substrate comprising oxidized elements in the vicinity of the surface (internal oxidation), this substrate being topped with a partially reduced oxide layer, itself topped with the coating deposited by dipping.During the subsequent austenitizing stage of the blank, and / or during shaping and cooling, a thin ductile layer forms under the coating, so that cracks formed during coating during shaping propagate less easily into this underlying layer.

[0007] However, the oxide layer that is present when the sheet metal is immersed in the metallic coating bath can prove detrimental to the adhesion of the coating to the dip on this layer.

[0008] Document WO2011 / 069906 discloses a method for manufacturing a sheet metal. A manufacturing method is therefore sought that would not have this drawback and that would make it possible to simultaneously obtain, after hardening by quenching in a press, high tensile and bending characteristics. Furthermore, it is known that industrial manufacturing conditions inevitably involve a certain variability: for example, the temperature cycle during annealing of the sheet metal before coating, the composition and / or the dew point of the atmosphere of continuous annealing furnaces, may vary slightly during the same manufacturing sequence, or vary from one manufacturing campaign to another.Even if the greatest precautions are taken to minimize these variations, we seek to have a manufacturing process such that the mechanical characteristics, and in particular the bending ability, obtained after hardening by quenching in a press, are very little sensitive to this possible variation in manufacturing conditions. We also seek a manufacturing process leading to good isotropy of the parts after hot stamping, that is to say, whose bending ability depends little on the direction of stress in relation to the rolling direction of the sheet.

[0009] Furthermore, it is known that the length of time blanks remain in the furnaces during the austenitization stage before hot stamping can influence the mechanical characteristics of the parts. We are therefore seeking a manufacturing process that is not very sensitive to the length of time spent in the furnace in order to achieve high reproducibility of the mechanical characteristics of the parts.

[0010] In the case of parts manufactured from pre-coated zinc or zinc alloy sheets, the aim is to have a process allowing welding of these parts without risk of weakening the grain boundaries by penetration of liquid zinc.

[0011] The present invention aims to solve the above-mentioned problems by means of an economical manufacturing method.

[0012] Surprisingly, the inventors demonstrated that a high bendability of the parts was obtained when a decarburized zone of a specific thickness was present under the metallic pre-coating, before the press quench hardening of the part. Surprisingly, this specific decarburization before hardening leads to bending results which depend little on the continuous annealing conditions before coating, and which reflect good isotropy with respect to the rolling direction, high bending values ​​are obtained despite the presence of oxides in this decarburized zone, which corresponds to an oxygen enrichment in this zone.

[0013] The subject of the invention is a first manufacturing method according to claim 1. The first manufacturing method preferably comprises the characteristics of any one of claims 2 or 3. The subject of the invention is also a second manufacturing method according to claim 4. The second manufacturing method preferably comprises the characteristics of any one of claims 5 or 6.

[0014] The invention also relates to a third manufacturing process according to claim 7. The third manufacturing process preferably comprises the features of claim 8. The manufacturing processes according to the invention preferably comprise the features of any one of claims 9 to 15.

[0015] Other characteristics and advantages of the invention will appear during the description below given by way of example and made with reference to the following attached figures: There figure 1 shows the microstructure of a pre-coated steel sheet according to the invention, intended for the manufacture of parts hardened by press quenching. The figure 2 schematically illustrates the definition of the depth of the softened zone d measured by microhardness under the coating of a part hardened by quenching in a press. The figure 3 This schematically illustrates the definition, for a pre-coated sheet or blank, of the surface decarburization depth p 50%, measured by glow discharge spectroscopy, under the pre-coating of the sheet or blank before hardening by press quenching. figure 4 presents the variation of the critical bending angle α c of a coated part hardened by quenching under pressure, as a function of the depth of the surface softened zone, this being measured by microhardness under the coating. The figure 5 presents the variation of the critical bending angle α c of a coated part hardened by quenching under pressure, as a function of the decarburization depth p 50%, this being measured on the pre-coated blank before hot stamping and quenching. The figure 6 shows the influence of the dew point in a particular zone of the furnace during annealing before pre-coating, on the critical bending angle of the part after hot stamping. The figure 7 shows the influence of the dew point in a particular zone of the furnace during annealing before pre-coating, on the decarburization depth p 50%, this last parameter being measured on the pre-coated blank before hot stamping and quenching. The figure 8 shows the microstructure of the steel under the zinc coating, after hardening by pressure quenching, at a dew point of -27°C. figure 9 It also illustrates the microstructure of the steel under the zinc coating, after hardening by pressure quenching, for a dew point of -7°C. figure 10 illustrates the variation, prior to hot stamping, of the carbon content of the steel substrate of two pre-coated steel sheets, in the vicinity of their interface with the pre-coating, the annealing of the sheets having been carried out in an A2a atmosphere with a dew point of -27°C or -7°C. figure 11 illustrates the variation in carbon content of two hot-drawn steel parts, near the interface with the coating of these parts, the annealing of the sheets used to manufacture these parts having been carried out in an A2a atmosphere with a dew point of -27°C or -7°C. figures 12 et 13 illustrate internal oxides formed during annealing in the steel substrate, near the surface. figures 14 et 15 present two X-ray energy dispersion analysis spectra of these oxides. The figure 16 illustrates the variation of the relative oxygen content (O / O 0 ) under the pre-coating, in sheets manufactured according to the invention.

[0016] The thickness of the cold-rolled steel sheet used in the process according to the invention is preferably between approximately 0.5 and 2.6 mm, a thickness range used in particular in the manufacture of structural or reinforcement parts for the automotive industry.

[0017] Steel is a heat-treatable steel, that is, a steel capable of hardening after austenitization and rapid cooling by quenching. Advantageously, the steel contains the following elements, the composition being expressed by weight: A carbon content of between 0.07 and 0.5%, preferably between 0.09 and 0.38% by weight, and most preferably between 0.15 and 0.25% by weight. This element plays a significant role in hardenability and the mechanical strength obtained after cooling following the austenitizing treatment. Below a content of 0.07% by weight, hardenability is reduced and mechanical strength is insufficient after press hardening. A content of 0.15%C ensures sufficient hardenability in the areas most deformed under heat. Above a content of 0.5% by weight, the risk of defect formation is increased during hardening, particularly for thicker parts. It also becomes difficult to guarantee ductility when bending parts after press hardening.A carbon content of between 0.09 and 0.38% makes it possible to obtain a resistance Rm of between approximately 1000 and 2050 MPa when the microstructure of the part is totally martensitic. In addition to its role as a deoxidizer, manganese also has a significant effect on hardenability, particularly when its content by weight is greater than 0.5%, and preferably greater than 0.8%. However, it is preferable to limit its addition to 3% by weight, and very preferably to limit it to 1.5% so as to avoid excessive segregation. The silicon content of the steel must be between 0.02 and 0.5% by weight, and preferably between 0.1 and 0.35%. In addition to its role in the deoxidation of liquid steel, this element contributes to the hardening of the steel, but its content must be limited to avoid excessive formation of oxides and to avoid impairing the quenchability.Above a content of 0.01%, chromium increases hardenability and contributes to achieving significant strength after hot forming. Above a content of 1% (preferably 0.3%), the effect of chromium on the homogeneity of mechanical properties in the part is saturated. Aluminum promotes deoxidation and nitrogen precipitation. In excessive quantities, coarse aluminates are formed during manufacturing, which tend to decrease ductility, thus limiting the aluminum content to 0.25% by weight. A minimum content of 0.001% allows for the deoxidation of steel in its liquid state during manufacturing. In excessive quantities, sulfur and phosphorus lead to increased brittleness. Therefore, it is preferable to limit their respective contents to 0.05% and 0.1% by weight.Boron, the content of which must be between 0.0005 and 0.010 wt%, and preferably between 0.002 and 0.005 wt%, plays an important role in hardenability. Below a content of 0.0005%, a sufficient effect on hardenability is not achieved. The full effect is obtained at a content of 0.002%. The maximum boron content must be less than 0.010%, and preferably 0.005%, to avoid degrading toughness. Titanium has a strong affinity for nitrogen. It protects the boron so that this element remains in its free form to exert its full effect on hardenability. Above 0.2%, however, there is a risk of forming coarse titanium nitrides in the liquid steel, which have a detrimental effect on toughness. It is preferably between 0.02 and 0.1%.Optionally, the steel can also contain calcium in quantities between 0.0005 and 0.005%: by combining with oxygen and sulfur, calcium helps prevent the formation of large inclusions which are harmful to the ductility of the sheets or parts thus manufactured.

[0018] The rest of the steel's composition is made up of iron and unavoidable impurities resulting from production, in particular oxygen, present in the form of oxides.

[0019] A preferred steel is 22MnB5 containing 0.20-0.25%C, 1.1-1.35%Mn, 0.15-0.35%Si, 0.02-0.06%AI, 0.02-0.05%Ti, 0.02-0.25%Cr, 0.002-0.004%B, the balance being iron and unavoidable impurities.

[0020] The inventors first sought the conditions that would allow for good bendability after pressure hardening. This characteristic is measured by subjecting the part to three-point bending. The part is bent progressively on rollers in three-point bending, with the applied load being measured simultaneously. The critical bend angle αc is measured when cracks appear in the part, accompanied by an instantaneous decrease in the applied load. Such test conditions are described in DIN VDA 238-100. For a tensile strength Rm of approximately 1300-1600 MPa, a critical bend angle greater than 55° is required to meet specifications. A critical bend angle greater than 60° is even preferred for more demanding operating conditions.

[0021] Using a manufacturing process that will be detailed below, the inventors manufactured parts from 1.2mm thick 22MnB5 steel blanks pre-coated with galvanized-alloy zinc ("galvannealed"), hot-stamped after heating to 880°C and holding for 5 minutes, differing only in the presence of a more or less significant softened layer located under the coating. The method for determining the depth of this softened zone is illustrated schematically in figure 2 : after hardening by quenching in a press, the part consists of a steel substrate for heat treatment 6, a coating 4 separated from the substrate by the interface 5. It should be noted that this diagram is not intended to reproduce the respective dimensions of the different zones. Hardness measurements are carried out under a very low load (for example Vlckers hardnesses under a load of 50 grams, HV0.05) in the substrate from the interface 5, so as to obtain curve 7 illustrating the microhardness profile. The value d is deduced from this, which characterizes the depth of the softened zone. figure 4 The critical bend angle αc is measured for values ​​of d varying approximately between 30 and 40 micrometers. For a shallow swaged zone depth, hot-drawn parts do not meet the requirement αc ≥ 55°. However, for deeper swaged zones, the relationship is found to be highly variable: for a given value of d, for example 35 micrometers, it is not possible to determine with certainty whether the hot-drawn part will meet the required criterion. It has also been observed that the microstructures corresponding to these swaged zones of varying width are very similar after press hardening. Furthermore, the microstructure of these swaged zones can be entirely martensitic, meaning that it cannot be easily distinguished by conventional optical microscopy.In other words, the inventors have demonstrated that neither the depth of softened areas measured on press-hardened parts, nor the optical microstructural observation of softened areas on these parts, are parameters that can reliably guarantee a minimum value for the bending angle.

[0022] Surprisingly, the inventors demonstrated that the decarburization depth should be determined not on the press-hardened part, but on the pre-coated sheet metal or blank before hardening, to obtain the desired result. The determination method is illustrated in the figure 3 whose diagram does not aim to reproduce to scale the respective dimensions of the different zones: the sheet, or the blank are made up of a steel substrate 10, a pre-coating 8 separated from the substrate by the interface 9. From this interface, we measure, by glow discharge spectroscopy (or GDOES, "Glow Discharge Optical Emission Spectrometry, a technique known in itself) the depth p 50% at which the carbon content is equal to 50% of the nominal carbon content C 0 of the substrate 10. The concentration profile can show a regular decrease in carbon from the substrate to the interface (profile 11) or a minimum located a short distance from the interface (profile 12) This last case reflects a localized carbon enrichment in the vicinity of the extreme surface which has no influence in practice on the mechanical properties after hot stamping.In the case of profile 12, the depth p 50% to be taken into account is located beyond this very superficial enrichment, as shown in . figure 3 . Using a manufacturing process that will be detailed below, the inventors manufactured 1.2mm thick 22MnB5 sheets pre-coated with galvanized-alloyed zinc ("galvannealed"), differing in the presence of a more or less significant decarburized layer located under the pre-coating. These sheets were cut to obtain blanks that were heated in a furnace at 880°C for 5 minutes, then hot-stamped to obtain parts. These were subjected to bending tests, the results of which are illustrated in figure 5 The bending during folding occurs either in a direction parallel to the rolling direction (curve 13) or in a perpendicular direction (curve 14). Contrary to the results presented in the figure 4 , it is observed that the depth of the decarburized zone before hardening by quenching in the press, allows to satisfactorily predict the properties of the part after hardening by quenching in the press. To obtain a critical bending angle value α c ≥ 55° (bending direction parallel to rolling), the depth of the decarburized zone p 50% must not be less than 6 micrometers. For this condition to be met regardless of the orientation with respect to the rolling direction, the depth of decarburization p 50% must not be less than 9 micrometers. To obtain a value α c ≥ 55°, regardless of the orientation with respect to the rolling direction, the depth of decarburization p 50% must not be less than 12 micrometers.Surprisingly, however, it is observed that beyond a depth p 50% of 30 micrometers, the bending ability is not improved, or even slightly reduced when bending is exerted in the direction perpendicular to the rolling. In addition, the difference in bending ability between the direction parallel and the direction perpendicular to the rolling tends to increase. Thus, to satisfy the mechanical requirements, the value of p 50% must be between 6 and 30 micrometers, preferably between 9 and 30, and very preferably between 12 and 30 micrometers.

[0023] The method according to the invention will now be described: first of all, a steel is supplied for heat treatment, as indicated above. This is in the form of a flat, cold-rolled sheet. The annealing heat treatment described below is intended in particular to cause recrystallization of the microstructure hardened by cold rolling. After optional degreasing and electrolytic cleaning to obtain a pollution-free surface, a decarburization depth p 50% of between 6 and 30 micrometers can be obtained using the following methods: according to a first method, the sheet is subjected to a heat treatment in a furnace heated by means of radiant tubes (or "RTF", radiant tube furnace), or by resistance, or by induction, or by any combination of these different means.These furnaces are characterized by the fact that the atmosphere in the different parts of the furnace can be adjusted independently of the heating elements. The furnace comprises several zones (preheating, heating, holding, cooling) where different temperature and / or atmospheric conditions prevail: the sheet metal is preheated to a temperature T1a in a zone where the atmosphere (designated A1) contains 2 to 15% hydrogen by volume, preferably 3-5% hydrogen by volume, the remainder being nitrogen and unavoidable impurities in the gas, with a dew point between -60 and -15°C. It is known that the dew point characterizes the oxidation potential of the atmosphere in question.The moving sheet then passes into another zone of the furnace where, from a temperature T1a, water in liquid or vapor form, or oxygen, or a combination of these different elements, is injected in order to increase the atmospheric dew point. The injection must not be carried out at a temperature T1a lower than 600°C which would lead to oxidation of the iron at low temperature. Preferably, the injection is carried out at a temperature T1a higher than Ac1, the temperature at which the austenitic transformation of the steel begins upon heating. Indeed, above this temperature, the carbon is in solid solution in the austenite, i.e. in a form more suitable for the decarburization phenomenon which will occur. The injection is preferably carried out at a temperature T1a lower than or equal to Ac1+40°C.This temperature range above Ac1 will be preferred to obtain a decarburization depth p 50% greater, for example greater than 9 or 12 micrometers. Beyond Ac1+40°C, there is a risk of increasing the austenitic grain size and causing the formation of bainitic and / or martensitic compounds in the steel substrate during cooling following annealing.

[0024] The injection is carried out so that the dew point PR of the atmosphere A2a of this section of the furnace is between -15°C and the dew point temperature Te of the thermodynamic equilibrium Iron / iron oxide. In the temperature range considered, the iron oxide formed can be FeO or Fe3O4. The lowest equilibrium temperature Te corresponding to the formation of one or the other oxide will be chosen. This temperature Te can be determined for example from the publication: JANAF Thermomechanical Tables, 3rd Edition, Part II, Journal of Physical and Chemical Reference Data, Volume 14, 1985, supplement n°1, published by the American Chemical Society and the American Institutes of Physics for the National Bureau of Standards. Under these injection conditions, an internal selective oxidation of certain addition elements present in the steel (Mn, Si, Al, Cr, Ti) is created without any superficial oxidation of the iron occurring.Internal oxidation can occur up to about 5 micrometers below the surface for Mn, Si, Al and Cr. Oxygen enrichment occurs in this surface zone, the average oxygen content of which is designated O m . If the nominal oxygen content of the steel substrate is designated O 0 , the O m / O 0 ratio that characterizes the surface oxygen enrichment is greater than 15.

[0025] The oxides are located between 0 and 5 micrometers below the interface between the pre-coating and the substrate. For a dew point (PR) above -15°C, the density of oxides with a diameter greater than 1 micrometer in this zone is greater than 50 / mm². The diameter is defined as follows: from a metallographic cross-section, the diameter of the circle that would have the same surface area is determined for each oxide. It is known that oxides generally have an adverse influence on ductility, due to their role as fracture initiation sites. As will be seen later, the specific nature of the internal oxides formed under the conditions of the invention does not have a detrimental effect on the bendability after press hardening.

[0026] Surface decarburization occurs under these conditions. When the dew point is higher than the dew point temperature Te corresponding to the iron / iron oxide equilibrium, the atmosphere becomes oxidizing for iron. During the subsequent annealing steps, there is then a possible risk of not completely reducing the iron oxide and causing the local appearance of coating defects corresponding to the local presence of unreduced surface oxides. The temperature Te is a function of the temperature and the hydrogen content of the atmosphere. As a guide, for an atmosphere containing 97.5% nitrogen and 2.5% hydrogen, Te=+9°C at 800°C. For an atmosphere containing 95% nitrogen and 5% hydrogen, Te=+18°C at 800°C. The sheet then leaves the section in which the injection was carried out, at a temperature T2a between 720 and 860°C to enter a holding zone at a temperature Tm between T2a and T2a+40°C.The time interval between the instant when the sheet is at temperature T1a and the instant when it reaches temperature T2a must be at least 30 seconds in order to obtain a decarburization depth p 50% of between 6 and 30 micrometers.

[0027] Optionally, the atmosphere in the beginning of the holding zone can be identical to that of the previous zone, i.e. have a dew point between -15 and Te. The sheet can then either be cooled or maintained at temperature Tm under an A3 atmosphere containing 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities in the gas, with a dew point between -60 and -15°C, these conditions being reducing for the iron. The following cooling step will be described below.

[0028] According to a second method, the manufacturing process begins in the same way as that just described up to the injection step at the temperature T1a between 600°C and Ac1+40°C, preferably higher than Ac1. At this temperature, a quantity of water, steam or oxygen is injected so as to obtain in this zone of the furnace an atmosphere designated by A2b, oxidizing for the iron. These conditions cause total oxidation of the surface, that is to say of the iron and certain addition elements (Mn, Si, Al, Cr, Ti). Under this oxide layer, internal oxides of Mn, Si, Al, Cr, or Ti are formed, an enrichment in oxygen occurs. A surface decarburization occurs at the same time as the oxidation of the iron. The sheet then leaves the injection section at a temperature T2a between 720 and 860°C to enter a holding zone at a holding temperature Tm between T2a and T2a+40°C.The time interval between the instant when the sheet is at temperature T1a and the instant when it reaches temperature T2a must be at least 30 seconds in order to obtain a decarburization depth p 50% of between 6 and 30 micrometers. Beyond this, in the holding zone, the sheet is held at temperature Tm in an atmosphere A3 which is reducing for iron, the conditions being chosen so that complete reduction of the iron oxide layer occurs at the latest at the end of the holding at temperature Tm. For this purpose, for example, an atmosphere containing 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities in the gas, with a dew point of between -60 and -15°C, may be chosen for a sufficiently long period for complete reduction of the surface layer of iron oxide to occur in this zone.After reduction of this iron oxide layer, the sheet contains oxides of Mn, Si, Al or Cr located between 0 and 5 micrometers below the surface, the density of oxides with a diameter greater than 1 micrometer in this zone being greater than 50 / mm 2 < . The local enrichment in oxygen is such that the ratio O m / O 0 is greater than 15.

[0029] The following cooling step will be described below.

[0030] According to a third mode, the thermal cycle of annealing the sheet combines different heating means; the preheating step is carried out in a zone of a direct flame furnace (or "DFF": "direct flame fumace"): the sheet is preheated in the flow to a temperature T1b of between 550 and 750°C in a zone where the atmosphere results from the combustion of a mixture of air and natural gas. According to the invention, the air / gas ratio is between 1 and 1.2, it being understood that the air-gas combustion in a stoichiometric ratio is 1. These preheating conditions lead to the formation of a surface layer of iron oxide whose thickness is between 0.10 and 0.25 micrometers. Under this oxide layer, internal oxides of Mn, SI, Al, Cr, or Ti are formed, an oxygen enrichment occurs.At the exit of this preheating zone by DFF furnace, the sheet enters a second zone of furnace heated by radiant tubes (RTF) or by resistances, or by induction, or by any combination of these different means. The atmosphere contains from 3 to 40% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, the dew point below -30°C. In this second zone, the sheet is heated to a temperature T2b between 760 and 830°C. Preferably, T2b is higher than Ac1, which allows a faster decarburization due to the presence of carbon in solid solution in the austenite. The time interval between the moment when the sheet metal is at temperature T1b and the moment when it reaches temperature T2b must be at least 30 seconds in order to obtain a decarburization depth p 50% between 6 and 30 micrometers.These conditions lead to a total reduction of the surface layer of iron oxide created in the previous step, and to the targeted surface decarburization. After reduction of the iron oxide layer, the sheet contains oxides of Mn, Si, Al or Cr located between 0 and 5 micrometers below the surface, the density of oxides with a diameter greater than 1 micrometer in this area being greater than 50 / mm 2 < . The local enrichment in oxygen is such that the ratio O m / O 0 is greater than 15. . The sheet metal then enters a holding zone at a holding temperature Tm between T2b and T2b+40°C.

[0031] The rest of the process is identical in the three modes described above: the sheet is cooled to a temperature T3 in an atmosphere A4 such that no surface reoxidation of the iron occurs. For example, an atmosphere containing 2 to 70% by volume of hydrogen can be used, the balance being nitrogen and unavoidable impurities in the gas, with a dew point between -60 and -30°C. The sheet which subsequently enters the pre-coating bath is therefore completely free of surface iron oxide. The temperature T3 is close to that of Tbm, the temperature of the pre-coating bath, in order to avoid thermal disturbance of the bath. For this reason, the temperature T3 will be between Tbm-10°C and Tbm+50°C. Thus, for a zinc pre-coating, the temperature T3 will be between 450 and 510°C. For pre-coating in a so-called aluminum-silicon bath, the temperature T3 will be between 660 and 720°C.The pre-coating may be aluminum or an aluminum-based alloy. In the latter case, the pre-coating, preferably manufactured by continuous dipping, is advantageously an aluminum-silicon alloy comprising by weight 7-15% silicon, 3 to 20% iron, optionally between 15 and 30 ppm calcium, the remainder being aluminum and unavoidable impurities resulting from the production.

[0032] The pre-coating may also be zinc or a zinc alloy. This may be, in particular, of the continuous dip galvanized type ("GI"), containing 0.25-0.70% AI, 0.01-0.1% Fe, the balance being zinc and unavoidable impurities resulting from the processing. The pre-coating may also be galvanized-alloyed ("GA") containing 0.15-0.4% AI, 6-15% Fe, the balance being zinc and unavoidable impurities resulting from the processing. The pre-coating may also be a zinc-aluminum-magnesium alloy containing 1-15% AI, 0.5-5% Mg, 0.01-0.1% Fe, the balance being zinc and unavoidable impurities resulting from the processing. This pre-coating can still be an alloy containing 4-6% AI, 0.01-0.1% Fe, the balance being zinc and unavoidable impurities resulting from the elaboration.

[0033] The pre-coating can also be an aluminum-zinc alloy, containing 40-45% Zn, 3-10% Fe, 1-3% Si, the balance being aluminum and unavoidable impurities resulting from the elaboration.

[0034] The pre-coating can also be composed of a superposition of layers: for example, after dip-deposition of a layer of aluminum or aluminum alloy, one or more subsequent deposits of zinc or zinc alloy can be carried out, for example by electrodeposition or by vacuum deposition: PVD (Physical Vapor Deposition) and / or CVD (Chemical Vapor Deposition), these deposition processes being known in themselves.

[0035] At this stage, using the processes described above, a sheet is obtained consisting of a steel substrate whose decarburization depth p 50% is between 6 and 30 micrometers, topped with a pre-coating, without a layer of iron oxide present between the substrate and the pre-coating. figure 1 presents an example of such a sheet, where the steel substrate 1 has a specific surface decarburized zone 2 topped with a galvanized-alloyed zinc-plated pre-coating 1.

[0036] This sheet is then cut to obtain a blank whose geometry is related to the final geometry of the intended part. Optionally, it is possible to cold stamp it so as to approximate to a greater or lesser degree the final geometry of the intended part. In the case of low cold deformation, this can be supplemented by hot deformation, as will be explained later.

[0037] This flat or pre-drawn blank is heated to a temperature TR suitable for giving a partially or totally austenitic structure to the steel substrate. TR can be between A c1 (temperature at which the steel begins to transform into an austenitic substance when heated) and A c3 (temperature at which the austenitic transformation ends), particularly when the aim is to obtain bainito-martensitic microstructures after cooling in the press. The temperature TR will be higher than A c3 if the aim is rather a predominantly martensitic microstructure in the final part. The blanks are preferably heated in a furnace under ordinary atmosphere; during this stage, alloying takes place between the substrate steel and the pre-coating. The term "pre-coating" refers to the alloy before heating, and "coating" refers to the alloyed layer formed during heating immediately preceding hot stamping.The heat treatment in a furnace thus modifies the nature and geometry of the pre-coating, since the thickness of the final coating is greater than that of the pre-coating. The alloyed coating protects the underlying steel from oxidation and further decarburization and proves suitable for subsequent hot forming, particularly in a stamping press. The alloying process occurs throughout the entire thickness of the coating. Depending on the composition of the pre-coating, one or more intermetallic phases are formed within this alloyed layer and / or an alloy in solid solution form. The iron enrichment of the coating leads to a rapid increase in its melting point. The resulting coatings also have the advantage of being adherent and suitable for any subsequent hot forming and rapid cooling operations.

[0038] The blank is kept at temperature TR to ensure temperature uniformity within it. Depending on the thickness of the blank, for example between 0.5 and 2.6 mm, the holding time at temperature T 1 can vary from 30 seconds to 15 minutes.

[0039] The heated blank is then removed from the furnace and transferred into a tool, this transfer being carried out quickly so as not to cause any transformation of the austenite upon cooling. According to a variant, the blank is heated in the vicinity of the tool and then hot deformed without transfer. The blank is then hot-drawn to obtain the final geometry of the part. Other hot-forming methods are also possible, for example forming between rollers, usually referred to as "roll forming". In the case where the blank has already been cold-drawn beforehand, the step following the extraction of the blank from the furnace may simply be a shaping within a press tool. In this case, the shaping is characterized by a lower force applied by the tool to the part and aims to complete the final geometry of the part and to avoid any possible deformations upon cooling.Optionally, it is also possible to heat only part of the blank, or to cool the stamped part differently in its different zones, these variants leading to the production of parts hardened in a non-uniform manner, some zones being hardened significantly, other zones having lower mechanical resistance but higher ductility.

[0040] After the stamping or forming stage, the part is held in the tooling, possibly cooled, so as to ensure its efficient cooling by thermal conduction.

[0041] Depending on the cooling rate and the hardenability of the substrate steel, the final microstructure is martensitic or bainito-martensitic.

[0042] By way of non-limiting example, the following results will show the advantageous characteristics conferred by the invention. Exemple 1 :

[0043] A 1.2mm thick cold-rolled steel sheet was supplied, the composition of which, expressed in weight content (%), is as follows, the remainder being iron and unavoidable impurities resulting from the production: C Mn Si Cr Ti Al S P B O 0,22 1,17 0,24 0,19 0,040 0,032 0,003 0,013 0,003 0,0014

[0044] The Ac1 temperature of this steel composition is 724°C. The sheet was preheated in a radiant tube furnace under an A1 atmosphere of nitrogen containing 4.7% by volume of hydrogen with a dew point of -31°C, up to a temperature T1a of 600°C from which water is injected to obtain an A2a atmosphere with a dew point PR. Different tests were carried out by modifying the flow rate of water injected into the furnace, so as to vary the dew point PR between -27°C (obtained thanks to a relatively small quantity of injected water) and +2°C. In all tests, the sheet metal was then heated from temperature T1a to temperature T2a equal to 780°C in atmosphere A2a for a duration of 110 s., which leads to decarburization and internal selective oxidation of Mn, Si, Al, Cr and Ti, these oxides being formed in the immediate vicinity of the surface of the sheet metal.At temperature T2a, the dew point of the iron / iron oxide equilibrium is +17°C. The sheet then enters a zone of the furnace where it is maintained at a temperature Tm of 780°C under an A3 atmosphere containing nitrogen and 7% hydrogen, reducing for iron. The sheet is then cooled in another zone of the furnace under an A4 atmosphere containing 10% hydrogen, up to a temperature T3 of 470°C and pre-coated by dipping in a bath at a temperature Tm of 462°C containing zinc and 0.125% aluminum as well as unavoidable impurities. No surface reoxidation of the iron occurs during the stages of maintaining and cooling in the A4 atmosphere. Immediately after pre-coating, the sheet is reheated to a temperature of 540°C to obtain a galvanized-alloyed (“GA”) pre-coating, i.e. containing 9% iron.This results in a sheet metal that does not contain a layer of iron oxide between the steel substrate and the said galvanized-alloy pre-coating. The . figure 12 illustrates observations made under the conditions of the invention, of oxides formed during selective internal oxidation, visible in the steel substrate immediately under the pre-coating. These oxides can be isolated or aligned along the grain boundaries. Through an analysis of the energy dispersion of the X-rays of these oxides ("EDS"), it is shown that these are oxides of manganese, silicon, and aluminum as illustrated by figures 14 et 15 highlighting the characteristic peaks corresponding to these elements. The iron peak is due to the matrix surrounding the oxides.

[0045] There figure 13 illustrates the presence of oxides with a diameter greater than 1 micrometer, with a density greater than 50 / mm 2< in the area between 0 and 5 micrometers below the surface of the steel sheet.

[0046] There figure 16 illustrates the variation of the relative oxygen content (O / O 0 ) under the pre-coating in the substrate, measured by Glow Discharge Spectrometry, O 0 denoting the nominal oxygen content of the substrate. This variation was measured for dew point PR values ​​of -3°C and +2°C. The depth p=0 corresponds to the interface between the substrate and the pre-coating. In a zone located between 0 and 5 micrometers below the surface of the substrate, an increase in the oxygen content is noted, corresponding to the presence of the oxides mentioned above.

[0047] The local oxygen enrichment in this zone is such that the O m / O 0 ratio is greater than 15: it is equal to 15.1 for PR=-3°C and to 17.4 for PR=+2°C.

[0048] The pre-coated sheets are then cut to obtain blanks suitable for stamping. These were heated to a temperature of 880°C in a furnace under ordinary atmosphere. After a total stay of 5 minutes in the furnace (including a duration of 4 minutes for the heating phase), the blanks were extracted and stamped immediately. After hot stamping, the parts were cooled in a press at a rate greater than 30°C / s so as to obtain a totally martensitic structure in the steel substrate. The tensile strength Rm obtained on the hardened parts is typically of the order of 1500 MPa.

[0049] The critical bending angle α c of these parts was measured by three-point bending test carried out with two external rollers of 30 mm diameter and a central knife of very small radius.

[0050] There figure 6 shows the variation of the critical angle α c as a function of the dew point PR after water injection from the temperature T1a: when PR is lower than -15°C, the bending angle obtained has a value lower than 55°, which is unsatisfactory. When PR exceeds the temperature Te by +17°C, there is a possible risk of not completely reducing the iron oxide during subsequent maintenance, thus causing the local appearance of coating defects corresponding to the local presence of unreduced surface oxides. In the field of the invention, the bending angle varies little as a function of the dew point: between -15 and -7°C, the increase is 0.79° per °C on average, while the variation is greater below - 15°C (1.05° per °C). When PR is between -15 and -10°C, a particularly interesting area is highlighted since the bending angle is practically independent of the dew point.In other words, in this particular range, any unwanted fluctuation in the amount of water injected during furnace annealing has no effect on the bendability after hot stamping, thus ensuring high stability of characteristics on stamped and press-hardened parts. It will also be observed that this good bendability is achieved despite the presence of oxides formed under the pre-coating. Without being bound by any theory, it is believed that the initiation of damage from these oxides tends to be delayed by the intrinsic toughness of the reduced carbon zone in which they are found.

[0051] Furthermore, tests were carried out by simultaneously varying PR and the temperature T1a, the latter being 720°C (i.e. Ac1-4°C) or 760°C (Ac1+36°C). figure 7 illustrates the influence of the temperature T1a and the dew point PR on the decarburization depth p 50% before hot stamping, measured by glow discharge spectroscopy: when the dew point is too low, the decarburized depth does not reach the value required by the invention (result marked “A” on the figure 7 ). A sufficiently high dew point, with a temperature T1a slightly lower than Ac1, allows the required depth to be reached (result “B”). Heating to a higher temperature T1a (Ac1+36°C) allows the decarburization depth to be significantly increased by 50% (result “C”).

[0052] After polishing and etching the hot stamped parts obtained with Nital reagent, the microstructure under the coating resulting from the diffusion alloying between the zinc of the initial pre-coating and the steel of the substrate was observed by optical microscopy: figure 8 thus illustrates the coating 15 and the underlying steel 16, for annealing with a dew point PR=-27°C. figure 9 illustrates the coating 17 and the underlying steel 18, for annealing with a dew point PR=-7°C. Despite the significant difference in bendability between the two samples (20°), no significant microstructural differences are found between the two samples after hot stamping, despite the difference in decarburization between them before hot stamping: The figure 10 illustrates the variation, before hot stamping, of the carbon content of the two annealed sheets in an A2a atmosphere with a PR dew point of -27°C or -7°C. This variation, measured by glow discharge spectrometry in the steel substrate, is expressed as figure 10 depending on the depth below the interface between the steel and the pre-coating.

[0053] The measured local content (C) was related to the nominal carbon content C 0 in order to obtain the variation of the relative carbon content C / C 0 . It is observed that the decarburized zones are very different in the two annealing conditions, the decarburization depth p 50% being 15 micrometers for PR=-7°C and 3 micrometers for PR=-27°C. If we consider the entire decarburized zone, the decarburization depth measured after annealing with PR=-7°C is approximately 35 micrometers greater than that measured after annealing under PR=-27°C.

[0054] After hot stamping these sheets, the variation in carbon content under the coating of the parts thus obtained was determined by the same method. figure 11 illustrates the variation in the relative carbon content C / C 0 of these parts. It is then shown that the decarburized zone is substantially identical in the two annealing conditions. This indicates that the heating in the furnace prior to the hardening treatment by quenching in the press, leads to a diffusion of carbon towards the decarburized surface of the steel. The determination of decarburization after hot stamping does not allow us to determine that annealing with PR = -7 ° C will lead to satisfactory bending results while annealing with PR = -27 ° C will not meet the required level. Although incomplete, this homogenization of the carbon nevertheless makes it possible to obtain in the steel located immediately under the coating, a sufficient carbon content to cause martensitic quenching under the cooling conditions linked to hot stamping, as illustrated in figures 8 et 9 However, the intrinsic toughness characteristics of the martensite created under these conditions depend on the decarburization conditions, which result in particular from the choice of the PR temperature. Thus, effective control of the bendability of hot-drawn parts must be carried out on the sheets or blanks before the hot-drawing operation, and not after, contrary to what would be expected by those skilled in the art. Furthermore, hot-drawn parts made from pre-coated zinc or zinc alloy sheets decarburized according to the invention exhibit a particular suitability for resistance spot welding: indeed, after heating and then hot-drawing, a decarburized layer is observed under the coating. It is known that resistance welding leads to a very significant local temperature rise since melting occurs within the molten core that forms the bond between the welded elements.In welded joints made on conventional hot-stamped parts, embrittlement of the austenitic grain boundaries may occur due to penetration of the zinc in the coating, which is then liquid due to the rise in temperature during welding. According to the invention, the presence of a highly carbon-depleted zone under the coating leads to a local increase in the Ac3 to austenite transformation temperature during heating. Depending on the carbon content, the high-temperature structure then consists of a ferrite microstructure or a mixture of ferrite and austenite. In the presence of liquid zinc, this microstructure is less sensitive to cracking than the austenitic structure. Exemple 2 :

[0055] Zn-precoated sheets were manufactured by the method described above, except that they were 1.8 mm thick and were not reheated to 540°C after dip-coating, so that their coating was galvanized and not galvanized-alloyed.

[0056] The manufacturing conditions were chosen to obtain a sheet with a decarburized depth p 50% of 6 micrometers. These sheets were cut to obtain blanks which were austenitized at a temperature of 880°C in a furnace under ordinary atmosphere. After a total stay of up to 10 minutes in the furnace, the blanks were extracted, immediately hot-drawn and press-hardened. The following table shows the variation of the critical bending angle α c as a function of the total stay time of the part in the furnace. durée de séjour (minutes) Angle de pliage α c (°) 5,5 57,5 7 55 10 54

[0057] It thus appears that the blanks can remain in the furnace for up to 7 minutes before hot stamping, while still meeting the required specifications. This resolves the problems encountered on hot stamping lines when an incident on the line forces the blanks to remain in the furnace longer than planned. The invention provides this flexibility, avoiding the need to reject blanks. Furthermore, it will be observed that beyond 7 minutes, the increased residence time results in only a very slight decrease in the bend angle, indicating that the process according to the invention offers strong safety guarantees in the event of deviations from the nominal heat treatment parameters during hot stamping, and ensures high reproducibility of the mechanical characteristics of the parts.

[0058] Thus, the invention enables the manufacture of pre-coated sheets and coated parts with very high strength and bending properties, with good isotropy, under very favorable economic conditions. These parts will be used advantageously as structural or reinforcing components in the automotive industry.

Claims

1. A method of manufacturing a metal sheet, comprising the successive steps according to which: - a cold-rolled sheet of steel for heat treatment containing a Co carbon content of between 0.07% and 0.5% is supplied, the composition of said steel substrate comprising, the contents being expressed by weight: 0.07 % ≤ C ≤ 0.5 % 0.5 % ≤ Mn ≤ 3 % 0.02 % ≤ Si ≤ 0.5 % 0.01 % ≤ Cr ≤ 1 % Ti ≤ 0.2 % Al ≤ 0.25 % S ≤ 0.05 % P ≤ 0.1 % 0.0005 % ≤ B ≤ 0.010 % , optionally 0.0005 % ≤ Ca ≤ 0.005 % , the remainder of the composition consisting of iron and unavoidable impurities resulting from the production method, then - said rolled sheet is annealed so as to obtain, at the end of the annealing, a decarburisation of the surface of said sheet over a depth p5o% of between 6 and 30 micrometres, p50% being the depth at which the carbon content is equal to 50% of said Co content, the depth p50% being measured by glow discharge spectroscopy, and so as to obtain a sheet totally devoid of an iron oxide layer on its surface, the annealing conditions comprise the following successive steps: * after having supplied the said cold-rolled sheet with steel, the said rolled sheet is preheated in a radiant tube furnace, or a resistance furnace, or an induction furnace, or a furnace combining at least any two of these means, to a temperature T1 a of between 600°C and Ac1+40°C, Ac1 designating the temperature at which austenitic transformation begins on heating of the said steel, in a zone of the said furnace in which the atmosphere A1 contains from 2 to 15% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, with a dew point of between -60 and -15°C, then * said metal sheet is heated from temperature T1a to a temperature T2a of between 720 and 860°C, an injection of at least one element chosen from liquid water, water vapour or oxygen being carried out in the said furnace from the said temperature T1a in order to obtain, in the section of the furnace lying between the said temperature T1a and the said temperature T2a, an atmosphere A2a with a dew point PR between - 15°C and the dew point temperature Te of the iron / iron oxide equilibrium, the time interval between the moment when the sheet is at temperature T1a and the moment when said sheet reaches temperature T2a being greater than or equal to 30 seconds, then * the said sheet is kept at a temperature Tm of between T2a and T2a+40°C, in a reducing atmosphere A3 for the iron, then * said sheet is cooled in an atmosphere A4 such that no surface reoxidation of the iron occurs, to a temperature T3, then - a pre-coating of metal or metal alloy is applied to the said annealed metal sheet acting as substrate by dipping in a metal bath at the temperature Tbm, it being understood that the said temperature T3 is between Tbm-10°C and Tbm+50°C, the said metal precoating being aluminium or an aluminium alloy, or zinc or a zinc alloy, or is composed of a layer of aluminium or an aluminium alloy, surmounted by a layer of zinc or a zinc alloy.

2. A manufacturing method according to claim 1, characterised in that said dew point PR is between -15 and +17°C.

3. A manufacturing method according to claim 1, characterised in that said dew point PR is between -15 and -10°C.

4. A method of manufacturing a metal sheet, comprising the successive steps according to which: - a cold-rolled sheet of steel for heat treatment containing a Co carbon content of between 0.07% and 0.5% is supplied, the composition of said steel substrate comprising, the contents being expressed by weight: 0.07 % ≤ C ≤ 0.5 % 0.5 % ≤ Mn ≤ 3 % 0.02 % ≤ Si ≤ 0.5 % 0.01 % ≤ Cr ≤ 1 % Ti ≤ 0.2 % Al ≤ 0.25 % S ≤ 0 .05 % P ≤ 0.1 % 0.0005 % ≤ B ≤ 0.010 % , optionally 0.0005 % ≤ Ca ≤ 0.005 % , the remainder of the composition consisting of iron and unavoidable impurities resulting from the production method, then - said rolled sheet is annealed so as to obtain, at the end of the annealing, a decarburisation of the surface of said sheet over a depth p50% of between 6 and 30 micrometres, p50% being the depth at which the carbon content is equal to 50% of said Co content, the depth p50% being measured by glow discharge spectroscopy, and so as to obtain a sheet totally devoid of an iron oxide layer on its surface, the annealing conditions comprise the following successive steps: * after having supplied said cold-rolled sheet with steel, said rolled sheet is preheated in a radiant tube furnace, or a resistance furnace, or an induction furnace, or a furnace combining at least any two of these means, to a temperature T1 a of between 600°C and Ac1+40°C, Ac1 designating the temperature at which austenitic transformation begins on heating of said steel, in a zone of said furnace in which the atmosphere A1 contains from 2 to 15% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, with a dew point of between -60 and -15°C, then * said metal sheet is heated from temperature T1a to a temperature T2a of between 720 and 860°C, an injection of at least one element chosen from liquid water, water vapour or oxygen being carried out in the said furnace from the said temperature T1a in order to obtain, in the section of the furnace between said temperature T1a and said temperature T2a, an oxidising atmosphere A2b for the iron, the time interval between the moment when the sheet is at temperature T1a and the moment when said sheet reaches temperature T23 being greater than or equal to 30 seconds, then * said metal sheet is maintained at a temperature Tm of between T2a and T2a+40°C, in a reducing atmosphere A3 for the iron, the complete reduction of the layer of iron formed in said atmosphere A2b taking place at the latest at the end of the maintenance at said temperature Tm, then * said sheet is cooled in an atmosphere A4 such that no surface reoxidation of the iron takes place, to a temperature T3, then - a pre-coating of metal or metal alloy is applied to the said annealed metal sheet acting as substrate by dipping in a metal bath at the temperature Tbm, it being understood that the said temperature T3 is between Tbm-10°C and Tbm+50°C, the said metal precoating being aluminium or an aluminium alloy, or zinc or a zinc alloy, or is composed of a layer of aluminium or an aluminium alloy, surmounted by a layer of zinc or a zinc alloy.

5. A manufacturing method according to any one of claims 1 to 4, characterised in that said temperature T1a is greater than Ac1, the austenitic transformation temperature on heating of said steel substrate.

6. A manufacturing method according to any one of claims 1 to 5, characterised in that atmosphere A1 contains 3-5% by volume of hydrogen.

7. A method of manufacturing a metal sheet, comprising the successive steps according to which: - a cold-rolled sheet of steel for heat treatment containing a Co carbon content of between 0.07% and 0.5% is supplied, the composition of said steel substrate comprising, the contents being expressed by weight: 0.07 % ≤ C ≤ 0.5 % 0.5 % ≤ Mn ≤ 3 % 0.02 % ≤ Si ≤ 0.5 % 0.01 % ≤ Cr ≤ 1 % Ti ≤ 0.2 % Al ≤ 0.25 % S ≤ 0.05 % P ≤ 0.1 % 0.0005 % ≤ B ≤ 0.010 % , optionally 0.0005 % ≤ Ca ≤ 0.005 % , the remainder of the composition consisting of iron and unavoidable impurities resulting from the production method, then - said rolled sheet is annealed so as to obtain, at the end of the annealing, a decarburisation of the surface of said sheet to a depth p50% of between 6 and 30 micrometres, p50% being the depth at which the carbon content is equal to 50% of the said Co content, the depth p50% being measured by glow discharge spectroscopy, and so as to obtain a sheet totally devoid of an iron oxide layer on its surface, said annealing conditions comprise the following successive steps: * after having supplied said cold-rolled steel sheet, said sheet is preheated in a furnace, said preheating being carried out in a zone of a furnace heated with direct flames, said sheet being preheated to a temperature T1b of between 550 and 750°C in an atmosphere resulting from the combustion of a mixture of air and natural gas, the air / gas ratio of which is between 1 and 1.2, and then * said sheet is heated from the temperature T1b to a temperature T2b of between 760 and 830°C within a second furnace zone heated by radiant tubes, or by resistors, or by induction, or by any combination of at least two of these means, the atmosphere of which contains from 3 to 40% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, the dew point being less than -30°C, the time interval between the moment when the sheet is at said temperature T1b and the instant when said sheet reaches said temperature T2b, being at least 30 seconds, then * said sheet is kept at a temperature Tm of between T2b and T2b+40°C, in a reducing atmosphere A3 for the iron, then * said sheet is cooled in an atmosphere A4 such that no surface reoxidation occurs, to a temperature T3, then - a pre-coating of metal or metal alloy is applied to the said annealed metal sheet acting as substrate by dipping in a metal bath at the temperature Tbm, it being understood that the said temperature T3 is between Tbm-10°C and Tbm+50°C, the said metal precoating being aluminium or an aluminium alloy, or zinc or a zinc alloy, or is composed of a layer of aluminium or an aluminium alloy, surmounted by a layer of zinc or a zinc alloy.

8. A manufacturing method according to claim 7, characterised in that said temperature T2b is higher than Ac1.

9. A manufacturing method according to any one of claims 1 to 8, characterised in that said depth p50% is between 9 and 30 micrometres, preferably between 12 and 30 micrometres.

10. A manufacturing method according to any one of claims 1 or 9, characterised in that the composition of said steel substrate comprises, the contents being expressed by weight: 0.09 % ≤ C ≤ 0.38 % 0.8 % ≤ Mn ≤ 1.5 % 0.1 % ≤ Si ≤ 0.35 % 0.01 % ≤ Cr ≤ 0.3 % 0.02 % ≤ Ti ≤ 0.1 % , 0.001 ≤ Al ≤ 0.25 S ≤ 0 .05% P ≤ 0 .1% 0.002 % ≤ B ≤ 0.005 % , optionally 0 .0005% ≤ Ca ≤ 0.005 % , the remainder of the composition consisting of iron and unavoidable impurities resulting from the production method11. A manufacturing method according to any one of claims 1 or 10, characterised in that the composition of said steel substrate comprises, the content being expressed by weight: 0.15 % ≤ C ≤ 0.25 %12. A manufacturing method according to any one of claims 1 or 11, characterised in that the composition of said steel substrate comprises, the contents being expressed by weight: 0.20 % ≤ C ≤ 0.25 % 1.1 % ≤ Mn ≤ 1.35 % 0.15 % ≤ Si ≤ 0.35 % 0.02 % ≤ Al ≤ 0.06 0.02 % ≤ Ti ≤ 0.05 % 0.02 % ≤ Cr ≤ 0.25 % 0.002 % ≤ B ≤ 0.004 % , the remainder of the composition consisting of iron and unavoidable impurities resulting from the manufacturing method.

13. A method of manufacture according to any one of claims 1 to 12, characterised in that said cold-rolled steel sheet has an oxygen O0 content of and in that the said cold-rolled sheet is annealed so as to obtain in the substrate, at the end of the annealing, under the interface between the precoating and the said substrate, to a depth of between 0 and 5 micrometres from the said interface, an average oxygen Om, Om / O0 content being greater than 15.

14. A manufacturing method according to any one of claims 1 to 13, characterized in that said cold-rolled sheet is annealed so as to obtain in the substrate at the end of the annealing, under the interface between the precoating and said substrate, to a depth of between 0 and 5 micrometres from said interface, oxides comprising at least one element selected from a group consisting of titanium, silicon, manganese, aluminium, chromium, the density of said oxides of diameter greater than 1 micrometre in this zone being greater than 50 / mm2.

15. A manufacturing method according to any one of claims 1 to 14, characterised in that the sheet is between 0.5 and 2.6 mm thick.