Method for producing high strength steel parts with improved ductility and parts obtained by said method

Abstract

To provide a steel sheet with both high mechanical strength and improved ductility, and a method for producing the same.SOLUTION: A rolled steel sheet for press hardening is provided, having a chemical composition with 0.24%≤C≤0.38%, 0.40%≤Mn≤3%, 0.10%≤Si≤0.70%, 0.015%≤Al≤0.070%, 0%≤Cr≤2%, 0.25%≤Ni≤2%, 0.015%≤Ti≤0.10%, 0%≤Nb≤0.060%, 0.0005%≤B≤0.0040%, 0.003%≤N≤0.010%, 0.0001%≤S≤0.005%, and 0.0001%≤P≤0.025% in wt.%, where the titanium and nitrogen contents satisfy Ti / N>3.42, where the chemical composition optionally has one or more of 0.05%≤Mo≤0.5%, 0.001%≤W≤0.30%, and 0.0005%≤Ca≤0.005%, and where the remainder is iron and unavoidable impurities resulting from the processing.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a steel sheet designed to obtain parts with very high mechanical strength after press hardening. [Background technology]

[0002] Press hardening is known to involve heating a blank to a temperature sufficient to cause an austenitic transformation, followed by hot stamping the blank by holding the blank in a press to obtain a quenched microstructure. In a variant of this process, the blank can be subjected to a cold pre-stamping prior to heating and press hardening. These blanks can be pre-coated, for example with an aluminum or zinc alloy. In this case, during heating in a furnace, the pre-coat integrates with the steel substrate by diffusion to form a compound that protects the surface of the part against decarburization and scale formation. This compound is suitable for hot forming.

[0003] The resulting parts are used as structural elements in automobiles to provide anti-intrusion or energy absorption functions. Examples of applications include bumper cross members, door or center pillar reinforcements, or side rails. Such press-hardened parts can also be used in the manufacture of tools or parts for, for example, agricultural machinery.

[0004] The need to reduce automotive fuel consumption is driving efforts to achieve even greater vehicle weight reductions using components with ever-higher levels of mechanical strength, i.e., strengths Rm exceeding 1800 MPa. However, such levels of resistance are typically associated with a microstructure that is entirely or almost entirely martensitic. This type of microstructure has poor resistance to delayed cracking after press hardening, and the resulting components may actually crack or fracture after a certain time.

[0005] International Publication WO2016016707 discloses a method for producing cold-rolled steel sheets and components for press hardening, which simultaneously achieves high mechanical strength (Rm) of 1800 MPa or more, high resistance to delayed cracking after press hardening, and a wide range of thicknesses for the cold-rolled steel sheets. To achieve this, the nickel content in the chemical composition of the steel sheet is 0.25% to 2%, and is concentrated in a specific form on the surface of the steel sheet or its components. This nickel enrichment creates a barrier to hydrogen penetration, thereby slowing the diffusion of hydrogen.

[0006] More specifically, the steel plate of International Publication WO2016016707 has a chemical composition including, in weight percent, 0.24%≦C≦0.38%, 0.40%≦Mn≦3%, 0.10%≦Si≦0.70%, 0.015%≦Al≦0.070%, 0%≦Cr≦2%, 0.25%≦Ni≦2%, 0.015%≦Ti≦0.10%, 0%≦Nb≦0.060%, 0.0005%≦B≦0.0040%, 0.003%≦N≦0.010%, 0.0001%≦S≦0.005%, and 0.0001%≦P≦0.025%, wherein the titanium and nitrogen contents satisfy: Ti / N>3.42, and the carbon, manganese, chromium, and silicon contents are:

[0007]

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[0008]

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[0009]

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[0010] Furthermore, International Publication WO2016016707 discloses a method for producing a hot-rolled steel sheet, which includes a step of heating a slab at a temperature between 1250°C and 1300°C for 20 to 45 minutes. This specific slab heating temperature range and holding time ensures nickel diffusion to the boundary between the formed oxide layer and the steel substrate, resulting in the appearance of a nickel-enriched layer.

[0011] Due to their extremely high strength, the steel parts obtained using the chemical compositions and methods disclosed in WO2016016707 are particularly suitable for the manufacture of anti-intrusion parts for motor vehicles.

[0012] Certain parts or portions of parts of automotive structural components must have advantageous functions related to their ability to absorb energy, particularly in the event of an impact. This is particularly true for the lower parts of the side rails and center pillar reinforcements.

[0013] International Publication WO2017006159 discloses a steel sheet and an associated manufacturing method for producing a steel sheet with very good ductility characterized by bending angles of more than 80°.

[0014] The resulting parts are particularly suitable for forming impact-resistant structural elements or parts of automotive structural elements. However, the mechanical strength of the steel sheets of WO2017006159 is significantly lower than 1800 MPa, which does not meet the highest requirements in terms of anti-intrusion properties.

[0015] Thus, several automotive structural elements having one part whose priority function is mechanical strength and another part whose priority function is energy absorption can be manufactured by welding together, for example, a part obtained according to WO2016016707 and a part obtained according to WO2017006159.

[0016] However, welding requires additional manufacturing operations for the part, which increases costs and manufacturing time. In addition, it must be ensured that the welding does not reduce the durability of the final part in the area around the weld, which requires precise control of the welding parameters. Therefore, there is a need to manufacture monolithic elements that combine the features of high mechanical strength and high energy absorption capacity.

[0017] There is also a need for hot stamped parts that have satisfactory ductility, in other words, bend angles of 50 degrees or greater. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] International Publication No. 2016 / 016707 [Patent Document 2] International Publication No. 2017 / 006159 Summary of the Invention [Problem to be solved by the invention]

[0019] For this reason, the primary objective of the present invention is to produce a steel sheet having both high mechanical strength, characterized by a high tensile strength Rm of more than 1800 MPa, and improved ductility, two characteristics that are inherently difficult to reconcile, since it is well known that an increase in mechanical strength leads to a decrease in ductility.

[0020] Another desirable property for automotive safety components and structural elements is a reduced susceptibility to various forms of hydrogen damage, including stress corrosion in both aqueous and saline environments.

[0021] For this reason, the present invention also aims to produce steel sheets having improved resistance to stress corrosion.

Means for Solving the Problems

[0022] For this purpose, the rolled steel sheet of the present invention, which is intended to be press-hardened, substantially has a chemical composition that, expressed as contents by weight, 0.24% ≦ C ≦ 0.38% and 0.40% ≦ Mn ≦ 3%, or 0.38% < C ≦ 0.43% and 0.05% ≦ Mn < 0.4% 0.10% ≦ Si ≦ 1.70% 0.015% ≦ Al ≦ 0.070% 0% ≦ Cr ≦ 2% 0.25% ≦ Ni ≦ 2% 0.015% ≦ Ti ≦ 0.10% 0% ≦ Nb ≦ 0.060% 0.0005% ≦ B ≦ 0.0040% 0.003% ≦ N ≦ 0.010% 0.0001% ≦ S ≦ 0.005% 0.0001% ≦ P ≦ 0.025% characterized by including where the titanium and nitrogen contents are: Ti / N > 3.42 and the carbon, manganese, chromium and silicon contents

[0023]

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[0024]

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[0025]

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[0026] The rolled steel sheet of the present invention may also have any of the following properties, individually or in all technically possible combinations: Composition by weight: 0.39%≦C≦0.43% 0.09%≦Mn≦0.11% Contains Composition by weight: 0.95%≦Cr≦1.05% Contains Composition by weight: 0.48%≦Ni≦0.52% Contains Composition by weight: 1.4%≦Si≦1.70% Contains The microstructure of the steel plate is ferrite-pearlite.

[0027] The steel plate is hot rolled steel plate.

[0028] The steel plate is cold-rolled and annealed.

[0029] The steel sheet is pre-coated with an aluminum or aluminum alloy or aluminum-based metal layer.

[0030] The steel sheet is pre-coated with zinc or zinc alloy or zinc-based metal.

[0031] The steel sheet is pre-coated with one or more layers of an intermetallic alloy containing aluminum and iron, optionally silicon, the pre-coating comprising free aluminum, Fe3Si2Al in the τ5 phase, 12 , and does not contain the τ6 phase Fe2Si2Al9.

[0032] The invention also relates to a part obtained by press hardening of a steel sheet having a composition according to either the martensite or martensite-bainite structure of the above-mentioned embodiments and having a mechanical strength Rm of 1800 MPa or more, provided that the surface density D of all the grains i and the surface density D of particles larger than 2 micrometers (>2μm) to a depth of at least 100 micrometers near the surface of the steel plate, D i +6.75D (>2μm) <270 It is assumed that D i and D (>2μm) is 1 mm 2 It is expressed in number of particles per unit area.

[0033] The component according to the invention may also comprise any of the following characteristics, either individually or in all technically possible combinations: The part has a bend angle in the rolling direction that is greater than 50°.

[0034] The manganese, phosphorus, chromium, molybdenum, and silicon content of the part is [455Exp(-0.5[Mn+25P])+[390Cr+50Mo]+7Exp(1.3Si)][6-1.22x10 -9 σ γ 3 ][C scc ]≧750 and the yield strength σ γ is between 1300MPa and 1600MPa, C scc is equal to 1 for uncoated steel sheets and 0.7 for coated steel sheets.

[0035] Manganese, phosphorus, chromium, molybdenum and silicon content: [455Exp(-0.5[Mn+25P])+[390Cr+50Mo]+7Exp(1.3Si)] [6-1.22x10 -9 σ γ 3 ][C scc ]≧1100 Meet the following.

[0036] Parts have a nominal nickel content of Ni nom The nickel content in the vicinity of the surface of the steel is surf Ni up to a depth Δ nom Greater than, and Ni max denotes the maximum nickel content within Δ,

[0037]

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[0038]

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[0039] The parts are coated with aluminum or aluminum-based alloys, or zinc or zinc-based alloys, which are formed by diffusion between the steel substrate and the precoat during the press-hardening heat treatment.

[0040] The present invention also relates to a method for producing a hot rolled steel sheet, comprising the following successive steps: - preparing a liquid steel to which manganese, silicon, niobium and chromium are added, the addition being carried out in a vacuum chamber, then desulfurizing the liquid metal without increasing its nitrogen content, then adding titanium, said addition being carried out so as to obtain a liquid metal of the chemical composition previously defined, then Casting the semi-finished product, then Heating the semi-finished product at a temperature between 1250°C and 1300°C for a holding time between 20 minutes and 45 minutes; hot rolling the semi-finished product to a rolling finish temperature TFL between 825°C and 950°C to obtain a hot-rolled steel sheet; - coiling the hot-rolled steel sheet at a temperature between 500°C and 750°C to obtain a hot-rolled coiled steel sheet; and The step of pickling the oxide layer formed in the previous step.

[0041] The present invention also relates to a method for producing hot-rolled, then cold-rolled and annealed steel sheet, in particular comprising the following successive steps: providing a hot-rolled coiled pickled steel sheet manufactured by the above method; cold rolling the hot-rolled coiled pickled hot-rolled steel sheet to obtain a cold-rolled steel sheet; Annealing the cold-rolled steel sheet at a temperature between 740°C and 820°C to obtain a cold-rolled annealed steel sheet.

[0042] The present invention also relates to a method for producing a pre-coated steel sheet, in which a rolled steel sheet according to either of the two processes defined above is provided, after which a successive pre-coating is carried out by immersion, said pre-coating being aluminum or an aluminum alloy or an aluminum-based alloy, or zinc or a zinc alloy or a zinc-based alloy.

[0043] The present invention also relates to a method for producing a precoated and prealloyed steel sheet, by which: - Rolled steel sheets are provided according to one of the two processes defined above, and then subjected to a continuous pre-coating with tempered aluminum alloys or aluminum-based alloys, and then Precoat is free aluminum, τ5 phase Fe3Si2Al 12 The pre-coated steel sheet is subjected to a thermal pretreatment so as to be free of the τ6 phase Fe2Si2Al9.

[0044] The present invention also relates to a method for manufacturing a press-hardened part as defined above, comprising the following successive steps: providing a steel sheet manufactured by a method such as that previously defined, cutting the steel plate to obtain a blank; and Optionally, carrying out a shaping step by cold stamping said blank, then heating the blank to a temperature between 810°C and 950°C to obtain a fully austenitic structure in the steel; Transferring the blank to the press, then hot stamping the blank to obtain a part; and The part is held in a press and hardened by martensitic transformation of the austenitic structure.

[0045] Finally, the invention relates to the use of a press-hardened part as defined above or produced by the method for producing a hardened part as defined above, for the production of structural or reinforced parts for motor vehicles.

[0046] Other features and advantages of the present invention will become apparent from the following description, given by way of example and taken in conjunction with the accompanying drawings, in which: [Brief explanation of the drawings]

[0047] [Figure 1] FIG. 1 shows the surface density of all particles as a function of the surface density of medium-sized particles greater than 2 micrometers under five test conditions for hot stamped parts with tensile strength greater than 1800 MPa. [Figure 2] 1 shows the bend angle of hot stamped parts with tensile strength greater than 1800 MPa as a function of a parameter that quantifies the density of particles present in the hot stamped part. This parameter depends on the surface density of all particles as well as the density of medium-sized particles greater than 2 micrometers; these were evaluated for the same five test conditions. [Figure 3] FIG. 1 shows particle surface density as a function of particle size for five test conditions. DETAILED DESCRIPTION OF THE INVENTION

[0048] The thickness of the steel sheet used in the method of the present invention is preferably between 0.5 mm and 4 mm, which is a thickness range particularly used for the manufacture of structural or reinforced parts for the automotive industry. It can be obtained by hot rolling or subsequent cold rolling and annealing. This thickness range is suitable for industrial press hardening tools, especially hot stamping presses.

[0049] Advantageously, the steel contains the following elements (composition expressed by weight): When the manganese content is between 0.4% and 3%, the carbon content should be between 0.24% and 0.38%. Carbon plays a key role in the hardenability and mechanical strength achieved after cooling after austenitization. Below 0.24% by weight, a mechanical strength of 1800 MPa cannot be achieved without the addition of expensive elements after press hardening. When the manganese content is between 0.4% and 3%, a content exceeding 0.38% by weight increases the risk of delayed cracking and can cause the ductile-brittle transition temperature to exceed -40°C, as measured using a Charpy notched bend test, indicating a significant decrease in toughness. A carbon content between 0.32% and 0.36% by weight consistently maintains a satisfactory level of weldability, reducing manufacturing costs while achieving the desired properties. A carbon content between 0.24% and 0.38% provides particularly good spot weldability.

[0050] If the manganese content is reduced to between 0.05% and 0.4%, the carbon content is increased to between 0.38% and 0.43% in order to obtain a steel part with increased resistance to stress corrosion. For manganese contents between 0.09% and 0.11%, the carbon content is preferably between 0.39% and 0.43%. The reduction in manganese content is thus compensated for by the increase in carbon content, which gives the steel part a high resistance to stress corrosion.

[0051] As discussed below, the carbon content should also be defined in conjunction with the manganese, chromium, and silicon contents.

[0052] In addition to its role as a deoxidizer, manganese also plays a role in hardenability.

[0053] When the carbon content is between 0.24% and 0.38%, the manganese content should be greater than 0.40% by weight to obtain a sufficiently low Ms at the onset of the transformation (austenite → martensite) during press cooling, which helps increase the resistance Rm. A manganese content limit of 3% results in increased resistance to delayed cracking. Manganese segregates at austenite grain junctions and, in the presence of hydrogen, increases the risk of intergranular fracture. On the other hand, as explained below, resistance to delayed cracking is primarily due to the presence of a nickel-rich surface layer. Without being bound by theory, it is believed that excessive manganese content leads to the formation of a thick oxide layer during slab heating, which means that nickel does not have time to diffuse sufficiently to its position beneath this layer of iron and manganese oxides.

[0054] Alternatively, an increased manganese content of between 0.05% and 0.4% is expected along with an increased carbon content of between 0.38% and 0.43%. The reduced manganese content provides improved pitting corrosion resistance, thereby resulting in steel sheets and components with improved stress corrosion resistance. Maintaining high mechanical strength is achieved by significantly increasing the carbon content.

[0055] The manganese content is preferably defined together with the carbon content and, optionally, the chromium content: A carbon content of between 0.32% and 0.36% by weight, in conjunction with a manganese content of between 0.40% and 0.80% and a chromium content of between 0.05% and 1.20%, simultaneously results in excellent resistance to delayed cracking due to the presence of a particularly effective nickel-enriched surface layer, and very good mechanical cutting properties of the steel sheet. To combine high mechanical strength with resistance to delayed cracking, a manganese content of between 0.50% and 0.70% is ideal.

[0056] Spot weldability is particularly good when the carbon content is between 0.24% and 0.38% in combination with a manganese content between 1.50% and 3%.

[0057] A carbon content between 0.38% and 0.43% in combination with a manganese content between 0.05% and 0.4%, and more preferably between 0.09% and 0.11%, significantly increases the resistance to corrosion under stress, as will be seen hereinafter.

[0058] These composition ranges result in a transformation (austenite → martensite) on cooling start temperature Ms of approximately 320°C to 370°C, which makes it possible to ensure that the heat-hardened parts have sufficiently high resistance.

[0059] The silicon content of steel should be between 0.10% and 1.70% by weight: silicon contents greater than 0.10% provide additional hardening and contribute to deoxidation of the liquid steel. The silicon content can be increased up to 1.70%, while avoiding the presence of excessive surface oxides that can affect the deposition of coatings. However, this increase in silicon content requires pickling of the hot-rolled coil and exposure to a suitable annealing atmosphere to suppress oxide formation.

[0060] For carbon contents between 0.24% and 0.38%, the silicon content is preferably greater than 0.50% to avoid softening of the new martensite, which may occur when the part is held in the press tool after the martensitic transformation.

[0061] For a carbon content between 0.38% and 0.43% and a manganese content between 0.05% and 0.4%, the silicon content is preferably between 0.10% and 1.70% in order to reduce the pitting rate, which increases the resistance to corrosion under stress.

[0062] The silicon content can be increased up to 1.70%, provided that the other alloying elements present in the steel allow a transformation temperature Ac3 (ferrite + pearlite → austenite) on heating below 880°C in order to accommodate industrial practice for austenitization before the hot pressing step.

[0063] In amounts above 0.015%, aluminum is an element that promotes deoxidation and nitrogen precipitation in the liquid metal during production. If its content exceeds 0.070%, coarse aluminates may form during production, which tends to reduce ductility. Its content is best between 0.020% and 0.060%.

[0064] Chromium contributes to improving hardenability and achieving the desired level of mechanical tensile strength Rm after press hardening. Above a content of 2% by weight, the effect of chromium on the homogeneity of the mechanical properties of press-hardened parts saturates. Preferably, in amounts between 0.05% and 1.20%, this element contributes to improving resistance. At carbon contents between 0.24% and 0.38%, the addition of chromium between 0.30% and 0.50% is preferred to achieve the desired effect on mechanical strength and delayed cracking without incurring additional costs. When the manganese content is adequate, i.e., between 1.50% and 3% Mn, the addition of chromium is considered optional, and the hardenability provided by manganese is considered adequate.

[0065] Alternatively, at carbon contents between 0.38% and 0.43%, an increased chromium content of more than 0.5%, more preferably between 0.950% and 1.050%, is preferred to increase pitting corrosion resistance and therefore stress corrosion resistance.

[0066] In addition to the conditions for each of the elements C, Mn, Cr, and Si defined above, these elements are also

[0067]

number

[0068] As explained in International Publication WO2016016707, under these conditions, the rate of self-tempering of martensite is extremely limited under the conditions held in the press tool, and therefore a very large amount of unannealed martensite leads to high mechanical strength values. It has been shown that if tensile strength values ​​Rm of greater than 1800 MPa are desired, the parameter P1 ≧ 1.1.

[0069] Titanium has a strong affinity for nitrogen. Taking into account the nitrogen content of the steel of the present invention, the titanium content must be 0.015% or more to obtain effective precipitation. At amounts greater than 0.020% by weight, titanium protects boron, allowing this element in its free form to fully exert its effect on hardenability. Its content must be greater than 3.42N, a value determined by the stoichiometry of TiN precipitation to avoid the presence of free nitrogen. However, above 0.10%, there is a risk of coarse titanium nitrides forming in the liquid steel, which has a detrimental effect on toughness. The titanium content is preferably between 0.020% and 0.040% to form fine nitrides that suppress the growth of austenite grains when the blank is heated before hot pressing.

[0070] In amounts exceeding 0.010% by weight, niobium forms niobium carbonitrides, which can also suppress the growth of austenite grains during heating of the blank. However, its content should be limited to 0.060% due to its ability to limit recrystallization during hot rolling, which increases the rolling effort and manufacturing difficulties. The optimum effect is obtained when the niobium content is between 0.030% and 0.050%.

[0071] In amounts above 0.0005% by weight, boron significantly increases hardenability. Boron exerts a favorable effect by diffusing at the junctions of austenite grains, preventing the intergranular segregation of phosphorus. Above 0.0040%, this effect saturates.

[0072] Nitrogen contents exceeding 0.003% result in the aforementioned precipitation of TiN, Nb(CN), or (Ti,Nb)(CN), which inhibits the growth of austenite grains. However, the content should be limited to 0.010% to avoid the formation of coarse precipitates.

[0073] Optionally, the steel sheet may contain molybdenum in an amount between 0.05% and 0.65% by weight, this element forming co-precipitates with niobium and titanium. These precipitates are very thermally stable and enhance the restriction of austenite grain growth during heating. The optimum effect is obtained with a molybdenum content between 0.15% and 0.25%.

[0074] Optionally, the steel may also contain tungsten in an amount between 0.001% and 0.30% by weight. In the amounts indicated, this element increases the hardenability and the susceptibility to hardening by carbide formation.

[0075] Optionally, the steel may also contain calcium in an amount between 0.0005% and 0.005%: in combination with oxygen and sulfur, calcium prevents the formation of large inclusions that are detrimental to the ductility of the steel sheet or part thus produced.

[0076] In excess amounts, sulfur and phosphorus lead to increased embrittlement. For this reason, the sulfur content is limited to 0.005% by weight to avoid excessive sulfide formation. However, achieving extremely low sulfur contents, i.e., less than 0.001%, would be unnecessarily costly unless it provided some additional benefit.

[0077] For similar reasons, the phosphorus content is between 0.001% and 0.025% by weight: in excessive amounts, this element segregates at austenite grain junctions, increasing the risk of delayed cracking due to intergranular fracture.

[0078] Nickel is a key element of the present invention: the inventors have shown that when this element, in amounts between 0.25% and 2% by weight, is concentrated on the surface of a steel sheet or component in a specific form, the susceptibility to delayed fracture is significantly reduced.

[0079] In addition, and as disclosed in International Publication WO2016016707, the steel part has a maximum of two parameters of Ni in the vicinity of its surface. max The alloy is enriched with nickel up to 10 ...

[0080] The first parameter P2 is

[0081]

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[0082] This first parameter characterizes the total nickel content in the enriched layer Δ.

[0083] The second parameter P3 is

[0084]

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[0085] This second parameter characterizes the average nickel concentration gradient, in other words the strength of enrichment within the Δ layer.

[0086] By meeting these two parameters, the steel part has an extremely high resistance to delayed cracking.

[0087] A method for producing a steel sheet according to the present invention is now described: a semi-finished product having the aforementioned composition is cast in the form of liquid steel. Unlike conventional methods in which elements are added during ladle casting from a converter, the inventors have demonstrated that this addition must be carried out in the absence of air, which would increase the nitrogen content in the liquid metal. In the method of the present invention, the addition of elements such as manganese, silicon, niobium, and chromium is carried out in a sealed vessel under a vacuum atmosphere. After this vacuum treatment, the liquid metal is desulfurized by mixing the metal with slag under conditions that do not increase the nitrogen content. After determining the nitrogen content of the liquid metal, titanium is added, for example, in the form of ferrotitanium. In this way, titanium is added at the end of the secondary metallurgical step. This reduces the amount of nitrogen introduced during the addition process and suppresses the formation of particles that can adversely affect the ductility of the steel part. In this way, the introduction of additional elements reduces the amount of precipitated particles at the end of solidification, thereby improving the ductility of the steel sheet and the resulting steel part, as will be explained in detail below.

[0088] The semi-finished product obtained after casting is usually in the form of a slab between 200 mm and 250 mm thick, or a thin slab, usually several tens of millimeters thick, or in any other suitable form. It is heated to a temperature between 1250 °C and 1300 °C and maintained at this temperature range for 20 to 45 minutes. By reacting with oxygen in the furnace atmosphere, an oxide layer is formed, which in the steel composition of the present invention is substantially rich in iron and manganese. The solubility of nickel in this oxide layer is extremely low, so nickel remains in metallic form. Simultaneously, as this oxide layer grows, nickel diffuses toward the interface between the oxide and the steel substrate, resulting in the appearance of a nickel-rich layer in the steel. At this stage, the thickness of this layer depends, inter alia, on the nominal nickel content of the steel and the temperature and holding conditions described above.

[0089] During subsequent production cycles, this enriched initial phase - thickness reduction due to the rolling ratio imparted by the subsequent rolling step, Increase in thickness due to exposure of the steel plate to high temperatures during subsequent manufacturing steps, However, this increase occurs to a lesser extent than during the slab heating stage.

[0090] The manufacturing cycle for hot rolled steel sheets is typically: Hot rolling steps (roughing and finishing) at temperatures ranging from 1250°C to 825°C, A coiling step at a temperature in the range of 500°C to 750°C.

[0091] The inventors have shown that variations in the hot rolling and coiling parameters within the ranges defined by this invention do not significantly alter the mechanical properties, so that the process can tolerate certain variations within these ranges without significantly affecting the resulting product.

[0092] At this stage, the hot rolled steel sheet, which may typically be 1.5 mm to 4.5 mm thick, is pickled in a manner known per se, but this only removes the oxide layer, so that the nickel-enriched layer is located near the surface of the steel sheet.

[0093] If thinner steel sheets are required, cold rolling is carried out with an appropriate reduction ratio, for example between 30% and 70%, followed by annealing, usually at temperatures between 740°C and 820°C, to recrystallize the hardened metal. After this heat treatment, the steel sheet can be cooled, according to methods known per se, to obtain an uncoated steel sheet, or it can be continuously coated by passing it through a quenching bath and finally cooled.

[0094] As explained in International Publication WO2016016707, the step that primarily affects the properties of the nickel-enriched layer on the final steel sheet is the slab heating step within a specific temperature range and holding time. Conversely, the annealing cycle of cold-rolled steel sheet, with or without a coating step, only has a secondary effect on the properties of the nickel-enriched surface layer. In other words, except for the cold-rolling reduction ratio, which reduces the thickness of the nickel-enriched layer by a similar amount, the nickel-enriched properties of this layer are approximately the same on hot-rolled steel sheet and on steel sheet that has undergone cold rolling and annealing, regardless of whether a pre-coating step is included.

[0095] The precoat may be aluminum, an aluminum alloy (having more than 50% aluminum) or an aluminum-based alloy (where aluminum is the predominant element). The precoat is conveniently an aluminum-silicon alloy containing 7% to 15% by weight silicon, 2% to 4% by weight iron, optionally between 15 ppm and 30 ppm calcium, the balance being aluminum and unavoidable impurities resulting from processing.

[0096] The precoat may also be an aluminum alloy containing 40% to 45% Zn, 3% to 10% Fe, 1% to 3% Si, the balance being aluminum and unavoidable impurities resulting from processing.

[0097] As a variant, the precoat can be an aluminum alloy coating, which is in the form of an intermetallic compound containing iron. This type of precoat is obtained by carrying out a thermal pretreatment of the precoated aluminum or aluminum alloy steel sheet. This thermal pretreatment is carried out at a temperature θ1 for a holding time t1, so that the precoat no longer contains the free aluminum τ5 phase Fe3Si2Al 12 and is free of the τ phase FeSiAl. This type of precoat then allows the blank to be heated at a much faster rate before the hot stamping step, thereby minimizing the time required to keep the blank at high temperature during heating, in other words reducing the amount of hydrogen adsorbed during this blank heating step.

[0098] Alternatively, the precoat may be a galvanized or galvanized alloy, in other words a galvanized alloy having an iron content of between 7% and 12% after the heat treatment of the alloy carried out under industrial conditions immediately after the galvanizing bath.

[0099] The precoat may also consist of a stack of layers deposited during subsequent stages, at least one of which may be aluminum or an aluminum alloy.

[0100] After the above-mentioned production, the steel sheet is cut or punched by methods known per se to obtain blanks whose shape is related to the final shape of the part to be stamped and hard-pressed. As explained above, cutting of steel sheets containing between 0.32% and 0.36% C, between 0.40% and 0.80% Mn, and between 0.05% and 1.20% Cr is particularly easy due to the low mechanical strength associated with the ferrite-pearlite or ferrite-pearlite microstructure at this stage [sic].

[0101] These blanks are heated to temperatures between 810°C and 950°C to fully austenitize the steel substrate, and then held in a press tool and hot stamped to obtain the martensitic transformation. The deformation rate applied during the hot stamping stage can be more or less important, depending on whether a cold forming step (stamping) is performed before the austenitization treatment. The inventors have shown that a thermal heating cycle for press hardening, which involves heating the blanks near the transformation temperature Ac3 and then maintaining them at this temperature for several minutes, also does not result in any significant changes in the nickel-enriched layer.

[0102] In other words, the properties of the nickel-rich surface layer on the steel sheet before press hardening and on the part obtained from this steel sheet after press hardening are similar.

[0103] The composition of the present invention, which has a lower Ac3 transformation temperature than conventional steel compositions, allows the blanks to be austenitized at lower temperatures and shorter holding times, thereby reducing the possible adsorption of hydrogen in the furnace.

[0104] The inventors have discovered that in order to obtain steel parts with improved ductility, in addition to the advantageous properties of mechanical strength and resistance to delayed cracking described above, the density of particles present near the steel sheet surface must also meet certain conditions. In the context of the present invention, these particles refer to all pure oxides, sulfides, nitrides, or complex types such as oxysulfides and carbonitrides present in the steel matrix. Some particles have been shown to be at the site of initial damage that reduces bendability. In the context of the present invention, near the surface refers to the region between the steel sheet and 100 micrometers below.

[0105] In particular, the density of the particles and especially the density of the medium sized particles greater than 2 micrometers must meet certain criteria.

[0106] Tables 1 and 2 below and Figures 1 and 2 show the tests and measurements that led to the establishment of the particle density based parameters.

[0107] Five types of steel sheets, A, B, C, D, and E, were manufactured, and their chemical compositions are shown in Table 1. The composition is expressed in weight percent, with the remainder consisting of iron and impurities resulting from processing.

[0108] These steel plates were obtained from steels produced in the liquid state by different methods: for test A (reference test), the additive elements (manganese, silicon, chromium and niobium) were added under air during ladle casting from a converter.

[0109] Tests B, C, D, and E were carried out under the conditions of the present invention, where the additive elements were added during the RH treatment in a Ruhrstahl Heraeus tank under reduced pressure. The subsequent desulfurization treatment was carried out without nitrogen recovery in the liquid steel. Titanium was added as ferrotitanium at the end of the secondary metallurgical process.

[0110] After casting in the form of semi-finished products, slabs of these various steels were heated to a temperature of 1275°C and held at this temperature for 45 minutes. They were then rolled to a rolling finish temperature of 950°C and coiled at a temperature of 650°C. After pickling, the steel sheets were cold rolled to a thickness of 1.5 mm. They were then annealed by aluminizing at a temperature of 760°C and then continuously aluminized by immersion in a bath containing 9% by weight of silicon and 3% by weight of iron, the balance being aluminium and unavoidable impurities.

[0111] After heating to a temperature of 900° C. and a total holding time in the furnace of 6 minutes 30 seconds, the cut steel sheets were hot stamped.

[0112] [Table 1]

[0113] After press hardening, three samples were measured using a scanning electron microscope. 2 Particles larger than 0.5 micrometers in size were visualized over a surface area of ​​more than 100 micrometers near the surface of the part.

[0114] The first type of measurement is the density D of all particles present in the steel matrix, i.e. pure oxides, sulfides, nitrides or complex types such as oxysulfides and carbonitrides. i The second type of measurement is to evaluate the density D of these same particles larger than 2 micrometers in size. (>2μm) In Table 2 below, reference tests D1, D2, E1 and E2 correspond to steel sheets of compositions D and E shown in Table 1 below, respectively, originating from two different steel coils.

[0115] The bending angle is 60x60mm, supported by two rollers, according to the standard VDA-238. 2 The bending force was measured on hardened parts of 1000 mm. The bending force was applied by a punch with a radius of 0.4 mm. The distance between the roller and the punch was equal to the thickness of the tested part, and a gap of 0.5 mm was applied. The appearance of cracks was detected as a coincidence of a drop in load on the load-displacement curve. The test was stopped when the load dropped more than 30 N from its maximum value. The bending angle for each reference test was measured at the maximum load position. The results shown in Table 2 below correspond to seven samples taken in the rolling direction. We then obtained the average bending angle value.

[0116] [Table 2]

[0117] To meet the industrial requirements for ductility during impact, a satisfactory part in terms of tensile strength has a bend angle of more than 50°. Hot-stamped parts under Reference Test A, which have elements added using conventional methods, have a bend angle of less than 50°.

[0118] Figure 3 shows the particle distribution by average particle size and density for the seven reference tests in Table 2. Reference test A has a particle density distribution by particle size that is substantially different from the other reference tests. First, the density of average particle sizes less than 2 micrometers for Reference A is significantly lower than that of the other reference tests. The processing conditions according to the invention allow a significant reduction in all particles, especially particles larger than 2 micrometers in size. This favorable distribution can be seen on the steel sheet as well as on the hot stamped parts produced from this steel sheet.

[0119] In each reference test in Table 2, the density D of medium-sized particles larger than 2 micrometers (>2μm) and the density of all particles D i was plotted in Figure 1. Considering that only Reference A does not meet the desired criteria of bending angles greater than 50°, the density Di and density D (>2μm) There is a relationship between the equation of line D: Y=-6.75(X-40) is obtained based on

[0120] Considering that parts with possible bend angles greater than 50° are located in the shaded area F below line D, the criteria for satisfying good bend ductility are as follows: D i +6.75D (>2μm) <270 D i and D (>2μm) Both are 1mm 2 It is expressed in number of particles per unit area.

[0121] This criterion shows the significant effect of medium-sized grains larger than 2 micrometers on the ductility of hot stamped parts.

[0122] In Table 3 and Figure 2 below, the defined criteria D i +6.75D (>2μm) The bend angles obtained for the seven test conditions A, B, C, D1, D2, E1, and E2 are shown. The grey area G in Figure 2 defines the region according to the invention, where the parts have bend angles greater than 50° and the criteria are less than 270. In this region G, the parts have improved ductility and mechanical strength Rm greater than 1800 MPa.

[0123] [Table 3]

[0124] The underlined values ​​are not according to the present invention. The inventors have also discovered that a reduction in manganese content accompanied by a large increase in carbon content can substantially increase the stress corrosion resistance of steel components while maintaining high mechanical strength in excess of 1800 MPa.

[0125] Measurement of susceptibility to stress corrosion is Immersion of steel parts stressed in this manner in a salt solution at room temperature for 30 days, or Spraying salt water onto stressed steel parts at 35°C for 4 hours, repeated over 20 days, It is known that the test is carried out by a method using a four-point constant load bending test according to the method described above.

[0126] However, these methods do not adequately replicate the environmental conditions that steel parts may encounter.

[0127] For this reason, another so-called cyclic method provides for alternation of wet and dry saline phases. The saline phase is applied for 2% of the test period in an atmosphere of 1% by weight NaCl at pH 4. The subsequent wet phase is applied for 28% of the test period at a temperature of 35°C and 90% relative humidity. The final dry phase is applied for 70% of the test period at a temperature of 35°C and 55% relative humidity. This cyclic test is applied for 42 days.

[0128] However, this cycle method is not rigorous enough to ensure that the steel parts have satisfactory stress corrosion resistance for the intended application. Therefore, a new cycle method, called the VDA (German Association of the Automotive Industry) method, was applied. In this method, the stressed steel parts are exposed to more severe corrosion conditions. The test period, or cycle, is one week.

[0129] In this VDA method, a saline phase is applied for 5% of the test period (rather than 2% for the cyclic method) in an atmosphere of 1% by weight NaCl at pH 7. A subsequent wet phase is applied for 25% of the test period at a temperature of 35°C and a relative humidity of 95% (rather than 90% for the cyclic test). A final dry phase is applied for 65% of the test period at a temperature of 35°C and a relative humidity of 70% (rather than 55% for the cyclic test). The VDA method is applied over 6 cycles, or in other words, for 6 weeks or 42 days.

[0130] In the present invention, a steel component is considered to meet the stress corrosion criteria if no material failure occurs for at least 42 days.

[0131] Four test conditions H, I, J and K were investigated and their chemical compositions are shown in Table 4 below. The compositions are expressed in weight percent, with the remainder of the composition being iron and impurities resulting from processing.

[0132] Four test conditions, H, I, J, and K, meet the above criteria for particle density and surface nickel enrichment.

[0133] [Table 4]

[0134] The steel plate produced under condition H has a temperature Ac3 of 829°C, which is evaluated by the Andrews' formula, which is known per se. The steel plate produced under test condition I has a temperature Ac3 of 820°C calculated by Andrews' formula, the steel plate produced under test condition J has a temperature Ac3 of 807°C calculated by Andrews' formula, and the steel plate produced under test condition K has a temperature Ac3 of 871°C calculated by Andrews' formula.

[0135] Reference Test J therefore has an austenitizing temperature that is particularly favorable for production in an industrial environment.

[0136] The Ms temperatures (martensitic transformation start temperatures during cooling) calculated by Andrews' formula are 362°C, 345°C, 353°C and 348°C for the steel plates produced under conditions H, I, J and K, respectively.

[0137] The steel plates of reference tests H, I, J and K were manufactured under the following conditions: Heat to a temperature of 1275°C for 30 minutes Hot rolling up to the rolling finish temperature TFL of 900℃ Winding temperature: Reference test H was wound at 540°C, reference tests I and J at 550°C, and reference test K at 580°C. Cold rolling at a reduction ratio of 58%, Annealing at a temperature of 760 ° C to obtain recrystallization of the hardened metal, and ·cooling.

[0138] In reference test H, the steel sheets were coated with an AlSi alloy as described above, whereas the steel sheets produced under conditions I, J and K were not coated.

[0139] The result is a steel plate 1.5 mm thick for conditions H, I and K, and a steel plate 1.3 mm thick for condition J.

[0140] After cutting the steel sheet to obtain the blank, it is heated in a furnace at 900°C for 6 minutes and 30 seconds (total holding time in the furnace), which causes a full austenite transformation in the steel. The blank is then quickly transferred to a device that simulates hot pressing. The transfer is completed in less than 10 seconds, so that austenite transformation does not occur during this step. The pressure applied by the press tool is 5000 MPa. The part is held in the press and hardens by the martensitic transformation of the austenitic structure. The steel sheet then undergoes a heat treatment at 170°C for 20 minutes, which corresponds to the baking cycle of the paint applied to the hot-stamped part.

[0141] The mechanical tensile properties (yield strength σ) measured on stamped parts H, I, J and K γ and mechanical strength Rm) are shown in Table 5 below.

[0142] [Table 5]

[0143] Three specimens from the hot stamped parts for each of the reference tests H, I, J and K were subjected to the above VDA stress corrosion test. The bending stress applied to the specimens on the outer surface between the two rollers was 750 MPa.

[0144] The results are shown in Table 6 below.

[0145] [Table 6]

[0146] In test condition H, two parts failed during the second cycle and the third part failed during the third cycle.

[0147] In Reference Test I, the first part failed during the third cycle and the other two parts failed during the fourth cycle.

[0148] No parts failed at the end of the sixth cycle for Reference Tests J and K. Thus, Reference Test J with its low manganese content and Reference Test K with its high silicon content provide excellent resistance to corrosion under stress.

[0149] Without being bound by theory, the inventors have defined a criterion formula that ensures corrosion resistance under stresses sufficient to pass the VDA test for hot stamped components having a yield strength of 1300 MPa to 1600 MPa.

[0150] This criterion depends on three parameters: parameter P1 depending on the composition of the part, parameter P2 depending on the applied stress, and parameter P3 depending on the presence or absence of a coating on the hot stamped part.

[0151] The parameter P1 is a function of the manganese, phosphorus, chromium, molybdenum and silicon content and is expressed as follows: P1=455Exp(-0.5[Mn+25P])+[390Cr+50Mo]+7Exp(1.3Si), The content is expressed as % by weight.

[0152] The parameter P2 is expressed as: P2=[6-1.22x10 -9 σ γ 3 ] In the formula, σ γmeans the yield strength expressed in MPa, which is between 1300 MPa and 1600 MPa.

[0153] Parameter P3 is parameter C scc This is quantified by: If the uncoated part is bare, this value is equal to 1, and if the part is coated, it is 0.7.

[0154] Therefore, the stress corrosion failure threshold Xo is defined as: Xo = P1 x P2 x P3.

[0155] The stress corrosion failure thresholds Xo determined in this way for stamped parts H, I, J and K are given in Table 7.

[0156] [Table 7]

[0157] Therefore, the inventors have demonstrated that if Xo is 750 or more, preferably 790 or more, the corresponding steel plate or part passes the VDA stress corrosion resistance test.

[0158] The following criteria are defined which, if passed, guarantee good resistance to stress corrosion of steel plates and components:

[0159]

number

[0160] Preferably, the value of Xo is greater than or equal to 790, and most preferably greater than 1100 to obtain very high resistance to stress corrosion.

[0161] In addition to the evidence that reducing the Mn content can increase stress corrosion resistance, it can be seen that increasing the chromium content (0.33% for Reference Test H, 0.51% for Reference Test I, and about 1% for Reference Tests J and K) also improves the stress corrosion resistance of the parts. Reference Test K also shows that a silicon content of 1.53% provides high stress corrosion resistance.

[0162] The present invention therefore provides a method for producing press-hardened parts that simultaneously provide high mechanical tensile properties, good toughness and high resistance to stress corrosion, which parts are advantageously used as structural or reinforced parts in the automotive industry.

Claims

1. A rolled steel plate for press hardening, the chemical composition of which is expressed by weight content: 0.32%≦C≦0.36% 0.40%≦Mn≦0.80% 0.10%≦Si≦1.70% 0.015%≦Al≦0.070% 0.05%≦Cr≦1.2% 0.25%≦Ni≦2% 0.015%≦Ti≦0.10% 0%≦Nb≦0.060% 0.0005%≦B≦0.0040% 0.003%≦N≦0.010% 0.0001%≦S≦0.005% 0.0001%≦P≦0.025% Including, The titanium and nitrogen contents Ti / N>3.42 and The carbon, manganese, chromium and silicon contents [Equation 1] Fulfilling The chemical composition optionally comprises the following elements: 0.05%≦Mo≦0.65%, 0.001%≦W≦0.30% 0.0005%≦Ca≦0.005% and The balance is iron and unavoidable impurities resulting from processing. The steel plate has a nickel content Ni at any position of the steel up to a depth Δ near the surface of the steel plate. ｓｕｒｆ where: Ni ｓｕｒｆ >Ni ｎｏｍ and Ni ｎｏｍ means the nominal nickel content of said steel, And Ni ｍａｘ means the maximum nickel content within Δ [Equation 2] where: [Equation 3] and said depth Δ is the nickel enrichment depth of the steel part expressed in micrometers, The Ni ｍａｘ and Ni ｎｏｍ The content is expressed in % by weight, and the surface density D of all particles ｉ and the surface density D of particles larger than 2 μm （＞２μｍ） to a depth of at least 100 micrometers near the surface of the steel sheet, <h2 style=";text-align:left;direction:ltr">D<h2 style=";text-align:left;direction:ltr"> ｉ <h2 style=";text-align:left;direction:ltr"> +6.75D<h2 style=";text-align:left;direction:ltr"> （＞２μｍ） <h2 style=";text-align:left;direction:ltr"> 2250 Fulfilling D ｉ and D （＞２μｍ） is expressed as the number of particles per square millimeter, said particles meaning all oxides, sulfides and nitrides, pure or complex, present in the steel matrix.

2. A steel plate as described in claim 1, wherein the particles represent oxysulfides and carbonitrides.

3. Composition by weight: 0.95%≦Cr≦1.05% The steel sheet according to claim 1 or 2, characterized in that it contains

4. Composition by weight: 0.48%≦Ni≦0.52% The steel sheet according to claim 3, characterized in that it comprises:

5. Composition by weight: 1.4%≦Si≦1.70% The steel sheet according to claim 3, characterized in that it comprises:

6. The steel sheet according to any one of claims 1 to 3, characterized in that the microstructure is ferrite-pearlite.

7. The steel sheet according to any one of claims 1 to 3, characterized in that the steel sheet is a hot-rolled steel sheet.

8. The steel sheet according to any one of claims 1 to 3, characterized in that the steel sheet is a cold-rolled and annealed steel sheet.

9. 4. The steel sheet according to claim 1, which is precoated with an aluminum or aluminum-based metal layer.

10. 4. The steel sheet according to claim 1, which is pre-coated with a zinc or zinc-based metal layer.

11. precoated with one or more layers of an intermetallic alloy comprising aluminum and iron, and optionally silicon, said precoated layer or layers containing free aluminum, τ ５ Phase Fe ３ Si ２ Al １２ and τ ６ Phase Fe ２ Si ２ Al ９ The steel sheet according to any one of claims 1 to 3, characterized in that it does not contain

12. A part obtained by press hardening a steel plate having a composition according to any one of claims 1 to 5, which has a martensite or martensite-bainite structure, a mechanical strength Rm of 1800 MPa or more, and a surface density D of all particles. ｉ and the surface density D of particles larger than 2 micrometers （＞２μｍ） to a depth of at least 100 micrometers near the surface of the steel plate <h2 style=";text-align:left;direction:ltr">D<h2 style=";text-align:left;direction:ltr"> ｉ <h2 style=";text-align:left;direction:ltr"> +6.75D<h2 style=";text-align:left;direction:ltr"> （＞２μｍ） <h2 style=";text-align:left;direction:ltr"> 2250 Fulfilling D ｉ and D （＞２μｍ） But, 1 mm ２ is expressed as the number of particles per The steel has a nickel content Nisurf anywhere in the steel to a depth Δ near the surface of the steel plate, where: Nisurf>Ninom and Ninom means the nominal nickel content of the steel; And Nimax means the maximum nickel content in Δ [Equation 4] where: [Equation 5] and said depth Δ is the nickel enrichment depth of the steel part expressed in micrometers, The Nimax and Ninom contents are expressed in weight percent; Component characterized in that said particles mean all oxides, sulfides and nitrides, in pure or complex form, present in the steel matrix.

13. The part of claim 12, wherein the particles are oxysulfides and carbonitrides.

14. 14. A part according to claim 12 or 13, characterized in that it has at least a bending angle in the rolling direction of more than 50°.

15. manganese, phosphorus, chromium, molybdenum and silicon contents [455Exp(-0.5[Mn+25P])+[390Cr+50Mo]+7Exp(1.3Si)][6-1.22x10 －９ σ γ ３ ][C ｓｃｃ ]≧750 Fulfilling σ γ is the yield strength between 1300 MPa and 1600 MPa, C ｓｃｃ Component according to any one of claims 12 to 14, characterized in that is equal to 1 for uncoated steel sheets and is equal to 0.7 for coated steel sheets.

16. Manganese, phosphorus, chromium, molybdenum and silicon contents: [455Exp(-0.5[Mn+25P])+[390Cr+50Mo]+7Exp(1.3Si)][6-1.22x10 －９ σ γ ３ ][C ｓｃｃ ]≧1100 16. The part according to claim 15, wherein:

17. Nominal nickel content Ni ｎｏｍ 15. A component according to any one of claims 12 to 14, comprising a nickel content Ni in the vicinity of the surface of the steel. ｓｕｒｆ Ni up to a depth Δ ｎｏｍ and Ni ｍａｘ denotes the maximum nickel content within Δ, [Equation 6] and [Equation 7] characterized in that wherein the depth Δ is expressed in micrometers; The Ni ｍａｘ and Ni ｎｏｍ A part characterized in that the content is expressed in % by weight.

18. A part according to any one of claims 12 to 14, wherein the steel sheet has been precoated with one or more layers of aluminium, or an aluminium alloy, or an aluminium-based alloy, or zinc, or a zinc alloy, or a zinc-based alloy, and the press-hardened part is coated with an aluminium alloy or zinc alloy resulting from diffusion between the steel substrate and the precoated layer or layers during the press-hardening heat treatment.

19. A method for producing a hot-rolled steel sheet according to any one of claims 1 to 5, comprising the following successive steps: - producing liquid steel to which manganese, silicon, niobium and chromium are added, said additions being carried out in a vacuum chamber, then desulfurizing the liquid metal without increasing its nitrogen content, then a step of adding titanium, said addition being carried out so as to obtain a liquid metal having a chemical composition according to any one of claims 1 to 5, then Casting the semi-finished product, then heating the semi-finished product at a temperature between 1250°C and 1300°C for a holding time between 20 minutes and 45 minutes, then hot rolling the semi-finished product to a rolling finish temperature TFL between 825°C and 950°C to obtain a hot-rolled steel sheet; - coiling the hot-rolled steel sheet at a temperature between 500 ° C and 750 ° C to obtain a hot-rolled coiled steel sheet; and then pickling the oxide layer formed in the previous step; A method comprising:

20. 1. A method for producing cold rolled and annealed steel sheet, comprising the following successive steps: - Providing a hot rolled pickled steel sheet in coil form produced by the method of claim 19; - cold rolling the hot-rolled coiled pickled hot-rolled steel sheet to obtain a cold-rolled steel sheet; Annealing the cold-rolled steel sheet at a temperature between 740°C and 820°C to obtain a cold-rolled annealed steel sheet; A method comprising:

21. 21. A method for producing a pre-coated steel sheet, wherein a rolled steel sheet produced by the method according to claim 19 or 20 is provided, and then a continuous pre-coating is carried out by immersion, the pre-coating being aluminum or an aluminum alloy, or zinc or a zinc alloy.

22. 1. A method for producing a precoated and prealloyed steel sheet, comprising: - a rolled steel sheet is provided according to the method of claim 20 or 21, and then a continuous pre-coating with tempered aluminum alloy is carried out, and then The precoat contains free aluminum, τ ５ Phase Fe ３ Si ２ Al １２ and τ ６ Phase Fe ２ Si ２ Al ９ wherein the thermal pretreatment of the pre-coated steel sheet is carried out so as not to include

23. A method for manufacturing a component according to any one of claims 12 to 18, comprising the following successive steps: - Providing a steel sheet manufactured by the method according to any one of claims 19 to 22, then - cutting the steel plate to obtain blanks, then Optionally, carrying out a forming step by cold stamping said blank, then heating the blank to a temperature between 810°C and 950°C to obtain a fully austenitic structure in the steel, then transferring the blank to a press, then hot stamping said blank to obtain a part, then - holding the part in a press and hardening it by martensitic transformation of the austenitic structure; A method comprising:

24. Use of a part as claimed in any one of claims 12 to 18 or produced according to the method of claim 23 for the production of structural or reinforcing parts for motor vehicles.

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