• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    method of producing a flat steel product with an amorphous, partially amorphous or fine crystalline microstructure and flat steel product with such characteristics. the invention provides methods for producing a 0.8-4.5 mm thick steel strip with an amorphous, partially amorphous or fine crystalline microstructure with a grain size in the range of 10? 10,000 nm, and also a flat steel product with corresponding characteristics. according to the invention, for this purpose, a molten steel is cast by casting in a cast steel strip (b), in a casting device (2), and is cooled at an accelerated speed. together with the faith and impurities that are unavoidable for production reasons, the molten material contains at least two other elements of the group consisting of? si, b, c and p ?. in this case, the following applies to the content of these elements (in% by weight): 1.2 - 7.0%, b: 0.4 - 4.0%, c: 0.5? 4.0%, p: 1.5? 8.0%. with a corresponding composition and a microstructure with corresponding characteristics, a flat steel product according to the invention has a hv0.5 hardness of 760-900.
    公开号:BR112015017627B1
    申请号:R112015017627-5
    申请日:2014-01-24
    公开日:2020-09-15
    发明作者:Dorothée Dorne；Christian Hockling；Harald Hofmann；Matthias Schirmer；Markus Daamen
    申请人:Thyssenkrupp Steel Europe Ag；
    IPC主号:
    专利说明:

    [001] The invention relates to methods of producing a flat steel product with an amorphous, partially amorphous or fine crystalline microstructure, the fine crystalline microstructure having a grain size in the range of 10-10 000 nm, and also to a flat steel product with an amorphous, partially amorphous or fine crystalline microstructure of this type.
    [002] According to a first variant of the method, the molten steel is melted by casting in a molten strip, in a casting device, and is cooled at an accelerated rate.
    [003] According to another variant of the method, to produce a flat steel product with an amorphous, partially amorphous or fine crystalline microstructure, molten steel containing, together with iron and unavoidable impurities for reasons of production, at least two other elements of the group consisting of Si, B, C and P, are cast by casting in a cast strip, in a casting device whose casting area is formed, on at least one of its longitudinal sides, by a wall that moves in the direction of the casting and is cooled during the casting operation. The area of the casting device in which the steel strip is formed is referred to here as the "casting zone".
    [004] WO 2008/049069 A2 discloses that flat steel products of the above type can be produced by strip casting methods. When casting a strip, the molten steel is cast in a casting device, the casting or solidification zone in which the cast strip is formed is delimited, on at least one of its longitudinal sides, by a wall that moves in parallel and continuously during the casting operation.
    [005] An example of such a method of continuous casting in the form of semi-finished product (near-net-shape), or of a casting device to produce a flat steel product, is that known as «two-cylinder casting device », Technically also known as« two-cylinder casting machine ». In the case of a two-cylinder casting device, two casting cylinders or casting cylinders axially aligned, parallel to each other, rotate against each other during the casting operation and in the area where they are closer together they form a casting pit that defines the casting zone. During the casting operation, the casting cylinders are intensively cooled so that the molten material that falls on them solidifies, forming a coating. The direction of rotation of the casting cylinders is chosen so that the molten material and the coatings formed from it on the casting cylinders are transported to the casting pit. The coatings that enter the foundry pit are compacted on a steel strip under sufficient force to form the strip.
    [006] Another casting device for strip molding is based on the principle of «belt casting» technology. In the case of the casting device of the belt casting method, liquid steel is poured over a circulating casting belt, by means of a feeding system. The direction of operation of the belt is chosen so that the molten material moves away from the feed system. Above a first and lower casting belt, there may be a second casting belt, which runs in the opposite direction to the first casting belt.
    [007] Regardless of using one or two casting belts, also in the case of said method, at least one casting belt delimits the mold in which the steel strip is formed. The respective casting belt is in this case intensely cooled, so that the molten material that comes into contact with the casting belt solidifies at the inversion point of the casting belt, away from the feed system, to form a strip that can be removed from the casting belt.
    [008] The steel strip that leaves the respective casting device is removed, cooled and transferred for further treatment. This can include heat treatment and hot rolling. The particular advantage of casting the strip by casting is that subsequent treatment steps can be performed in a continuous sequence, without interruption.
    [009] In the aforementioned WO 2008/049069 A2, it is mentioned that the steels suitable for producing steel strips with an amorphous, partially amorphous or fine crystalline microstructure can be iron-based alloys, with one or more elements of the group constituted by B, C, Si, P and Ga, being possible the additional presence of Cr, Mo, W, Ta, V, Nb, Mn, Cu, Al and Co contents and rare earths together with these elements. Alloys of this composition can be used to produce strips cast by casting, with a fine-grained, nanocrystalline or virtually nanocrystalline microstructure, in which 90% of the grains have a size of 5 Â -1 pm, the melting point of the steel that makes up the molten strip in the range of 800-1500 ° C, the critical cooling rate of steel below 105 K / s and the molten strip containing Fe α and / or Fe y- phases
    [010] WO 2008/049069 A2 is limited to an analysis of the relevant procedural steps for the production of a steel strip with an amorphous, partially amorphous or fine crystalline microstructure.
    [011] Along with the aforementioned prior art, US 6 416 879 B1 discloses a thin amorphous strip based on Fe, with a thickness of 10 to 100 pm and designed to contain, in atomic percentage, 78 - 90% Fe , 2 - 4.5% Si, 5 -16% B, 0.02 - 4% C and 0.2 -12% P, and having optimized magnetic properties. In order to produce the thin strip, under laboratory conditions, a molten material of corresponding composition is poured onto a rapidly rotating cooling cylinder, solidifies there, and is then removed from the cylinder. In this way, casting rates in the range of about 25 m / s are achieved. It is also said that such a thin strip is intended to be produced in a two-cylinder casting machine. However, no further explanation is given, nor is it revealed how to implement this procedure on an industrial scale, where greater sheet thicknesses and other strip properties are desired.
    [012] A state of the art similar to that described above is disclosed by US 4 219 355. The purpose here is also to produce a thin, film-like strip, with a thickness of 30-100 pm and optimized magnetic properties. With this in mind, also in this case a molten material of suitable composition is poured on a rotating cylinder, in which it is cooled at a rate of 105 - 106 ° C / s, in order to produce an amorphous microstructure. However, likewise, nothing is said about how to implement it on an industrial scale, in order to obtain flat products of greater thickness and with a different set of requirements.
    [013] Finally, DE 10 2009 048 165 A1 discloses a method for casting a steel strip with a chromium content greater than 15% by weight, in which molten steel is cast in a horizontal strip casting facility, which comprises a melting furnace, a melting pot and a conveyor belt for receiving and cooling the strip of liquid steel flowing out of the melting pot. The thickness of the steel strips produced in this way is 8 to 25 mm. Nothing is said about the cooling rates achieved at this facility and whether they would be appropriate to produce, for example, one of the aforementioned flat steel products.
    [014] In the context of the aforementioned prior art, the object of the invention was therefore to provide practical methods for manufacturing flat steel products with an amorphous, partially amorphous or fine-grained microstructure.
    [015] In addition, it is intended to provide a flat steel product that can be manufactured at low cost, properly in practice. A flat steel product is understood here as a strip or sheet of laminated or molten steel, and also "largets", sketches or the like obtained from these.
    [016] A method for achieving this object according to the invention is specified in claim 1.
    [017] In relation to the flat steel product, the solution according to the invention to achieve the object specified above allows to obtain a flat steel product with the characteristics referred to in claim 15.
    [018] The various embodiments of the invention mentioned here are based on the common concept that flat steel products formed by steels that solidify in an amorphous, partially amorphous, nanocrystalline or fine crystalline form can be produced by casting molding methods in the form of a semi-finished product. The steels respectively processed according to the invention are composed in such a way that the desired microstructural state is reliably obtained. When «%» values are given for steel alloys, unless otherwise specified, they should always be understood as «% by weight».
    [019] On the other hand, the invention describes operational conditions under which strips melted with an amorphous, partially amorphous or fine crystalline structure can be produced with sufficient reproducibility for practical purposes, from a steel that contains, together with iron and unavoidable impurities, at least two other elements of the Si, B, Cu and P. group
    [020] The method according to the invention for producing a flat steel product with an amorphous microstructure, partially amorphous or fine crystalline, provides that, together with iron and impurities inevitable for production reasons, the molten steel may contain at least two other elements of the group consisting of Si, B, C and P. According to the invention, the content of the at least two elements of the group consisting of Si, B, C and P that are present lies in the following ranges (in % by weight), respectively:
    [021] Si: 1.2 - 7.0%,
    [022] B: 0.4 - 4.0%,
    [023] C: 0.5 - 4.0%,
    [024] P: 1.5 - 8.0%
    [025] In principle, according to the invention, alloys are preferred in which, together with iron and components that are inevitable for production reasons but ineffective with respect to the properties of flat steel products produced according to with the invention, only two other elements of the Si group are present, B, C and P, in the amounts specified according to the invention. In the case of these alloys, together with Fe and the inevitable impurities, only the pairs of alloy elements Si and B, Si and C, Si and P, B and C, B and P or C and P are respectively present in the steel. Steel alloys with this composition are especially suitable for amorphous or partially amorphous solidification. If necessary, the pairs of alloying elements referred to in this case can be complemented, within the specifications according to the invention, by one or two other alloying elements from the group of Si, B, C and P respectively. At the same time, it is also possible that the alloy elements of the group consisting of Si, B, C and P, which are not within the specifications according to the invention, are actually present in measurable quantities, but which, although they may have some effect, contribute insignificantly, if at all, to the formation of the desired microstructure according to the invention. In other words, according to the invention, two elements of the group consisting of Si, B, C and P must be present in the respective quantities specified according to the invention for the manufacture of a flat steel product according to the invention , without excluding the possibility of other elements, respectively from the group of Si, B, C and P, being present in quantities that are outside the specifications according to the invention. The presence of an alloying element from the group of Si, B, C and P respectively, in an amount outside the specifications according to the invention, is possible especially when its content is below the lower limit prescribed according to the invention for the content of the element concerned.
    [026] The broader composition of a steel according to the invention therefore comprises, as mandatory constituents, at least two elements between boron, silicon, carbon and phosphorus, and also, as the remainder, iron and unavoidable impurities. These elements are particularly advantageous because they can be obtained at a relatively low cost. Using contents of these elements as stated in the claims, the production method according to the invention allows a reproducible manufacture of a steel product with an amorphous, partially amorphous or fine crystalline microstructure. A flat steel product manufactured according to the invention has a fine crystalline microstructure, with a grain size in the range of 10-10 000 nm, and it is often the case that the flat steel products produced in practice are restricted to a maximum of 1000 nm of grain size.
    [027] C amounts of up to 4.0% by weight are favorable for the material amortization of flat steel products according to the invention. In order to ensure this effect, the C content may be fixed at least 1.0% by weight, in particular 1.5% by weight.
    [028] Si, B, C and P contents suitable for practical purposes are obtained whenever the following applies to the Si content, namely% Si: 2.0% by weight <Si <6.0% by weight particular 3.0% by weight <Si <5.5% by weight; where the following applies to the B content, namely% B: 1.0% by weight <% B <3.0% by weight, in particular 1.5% by weight <% B <3.0% by weight ; where the following applies to the C content, namely% C: 1.5% by weight <% C <3.0% by weight; or whenever the following applies to the P content, namely% P: 2.0% by weight <% P <6.0% by weight. It may be favorable here, in the respective case, to add one or more elements between Si, B, C and P, in the aforementioned more strictly delimited quantities, while the other elements of the Si, B, C and P group are added within the maximum specifications permitted according to the invention. Likewise, it may be convenient to add, within the strictest limits specified here, each of the elements that are present in the respective amounts according to the invention.
    [029] Even if it is considered advantageous according to the invention to restrict to Si, B, C and P the group of alloy elements of a steel according to the invention, together with Fe and unavoidable impurities, in certain circumstances it may be From the point of view of the specific properties of the flat steel products obtained, optionally add to one steel one or more elements of the group consisting of Cu, Cr, Al, N, Nb, Mn, Ti and V. The intervals to be taken account according to the invention are respectively (in% by weight):
    [030] Cu: up to 5.0%, in particular up to 2.0%
    [031] Cr: up to 10.0%, especially up to 5.0%
    [032] Al: up to 10.0%, in particular up to 5.0%
    [033] N: up to 0.5%, in particular up to 0.2%,
    [034] Nb: up to 2.0%,
    [035] Mn: up to 3.0%,
    [036] Ti: up to 2.0%,
    [037] V: up to 2.0%,
    [038] The addition of Cu allows to increase the ductility of the material, whereas the action of Cr lies mainly in the improvement of the resistance to corrosion. The addition of Al also increases the corrosion resistance, and in addition helps to form an amorphous microstructure. N can be considered as a possible substitute for C. Thus, as observed for the highest levels of C, the presence of N reinforces the conformation of an amorphous microstructure.
    [039] In order to take advantage of the positive effects of the optionally added alloy elements, ie Cu, Cr, Al and N, the molten steel may optionally contain (in% by weight) at least 0.1% Cu, at least 0.5% Cr, at least 1.0% Al and at least 0.005% N, respectively.
    [040] The steel alloy according to the invention can be produced with alloy elements common to the steel industry and comparatively cheap, as mandatory components.
    [041] Due to the high content of “light weight” elements, considerable advantages of a light construction are foreseen, as a result of the reduced density and high strength, in comparison with conventional steels.
    [042] Typical cooling rates, with a view to successfully producing a flat steel alloy product according to the invention, with an amorphous, partially amorphous or fine crystalline microstructure, are in the range of 100 - 1100 K / s. Surprisingly, it was found that with these cooling rates, which can also be carried out on an industrial scale, it is possible to produce, in an operationally reliable way, strips with the desired microstructure, with thicknesses greater than those obtained with the state of the art as described previously.
    [043] According to the explanations given above, a variant of the method according to the invention for producing a steel strip with an amorphous, partially amorphous or fine crystalline microstructure is based on a molten steel with a composition according to invention, which is melted by casting in a strip, in a casting device whose casting zone in which the melted strip is formed is formed, on at least one of its longitudinal sides, by a wall that moves and is cooled during the smelting operation. The boundary wall of the casting zone and which moves during the casting operation can be formed in particular by two casting cylinders that rotate against each other, or by a belt that moves towards the casting during the casting operation. According to the invention, molten steel is cooled by contact with the moving wall, at least 200 K / s.
    [044] The explanations given here about the composition of the steel according to the invention apply to all methods according to the invention presented here and also to a flat steel product according to the invention.
    [045] The conformation of the desired microstructure of the flat steel product can be ensured by rapid cooling, carried out in practice to a temperature below the TG glass transition temperature of the respective steel. In this way, an amorphous or partially amorphous microstructure is initially formed.
    [046] Based on this microstructure, a fine crystalline microstructure can then be produced by a subsequent heat treatment above the crystallization temperature Tx as a result of the consequent crystal nucleation and crystallization. This procedure has the advantage of being able to precisely fix a fine granularity, a very homogeneous grain size distribution, with a very small fluctuation interval due to the large number of crystallization cores formed.
    [047] To ensure that even after leaving the respective melting zone, the molten strip is cooled at a rate sufficient to form an amorphous or partially amorphous microstructure to the respective glass transition temperature of the treated steel, the rapid cooling of the steel strip, which starts in the casting zone, can be maintained after it leaves the casting zone. The continued cooling in this case occurs conveniently after the strip leaves the casting region, so that an accelerated temperature reduction, as much as possible in a continuous way, is ensured in the steel strip until the desired microstructural state is reached.
    [048] An additional cooling device connected directly to the casting zone of the casting device used to shape the strip can be provided for this purpose. Through this cooling device, the molten steel can be cooled to a cooling rate specified in accordance with the invention, to a temperature below the glass transition temperature TG, in order to obtain an amorphous or partially amorphous microstructure in the flat product. cast steel. During the cooling of the molten steel, the additional cooling device ensures that, in cases where there is insufficient heat removal in the casting zone of the casting device itself through contact with the moving and cooled wall of the casting zone, the cooling of the strip is continued so quickly after the casting zone that the microstructural state to be produced according to the invention is reached reliably.
    [049] An additional advantage of the extra cooling that occurs after the casting device is that, through this cooling, a specifically adapted cooling curve can be varied in a controlled manner. This may be convenient in case it is desired that the casting and cooling process yield specific melted strips, with a partially amorphous or fine crystalline microstructure. In this way, the cooling can be carried out in such a way that, although a temperature below the glass transition temperature TG is reached at an accelerated rate, this does not occur at a rate sufficient to form a completely amorphous microstructure.
    [050] Alternatively, the molten strip can be cooled at an accelerated rate according to the specifications according to the invention, but this cooling ends before reaching the glass transition temperature TG of the respective treated steel. This approach represents a first possibility of producing a predetermined fine crystalline microstructure in the obtained flat steel product. The fine crystalline microstructure is here formed directly from the molten material, being possible a controlled crystallization by means of additional cooling.
    [051] Another approach to produce a flat steel product according to the invention, with a fine crystalline microstructure, is to initially produce a strip with an amorphous or partially amorphous microstructure, which is only then transformed into a fine crystalline state through a annealing process and consequent crystallization process. The special feature of this procedure is that crystallization occurs in a large number of crystal cores, and therefore the formed crystal grains are distributed very evenly across the material.
    [052] The crystallization temperature Tx, which is important for the conformation of the fine crystalline microstructure, is on average about 30 - 50 K above the glass transition temperature All the respective treated steel. For the production of a flat steel product according to the invention, with an amorphous or partially amorphous microstructure, it is therefore necessary to cool the molten material to a temperature below TG temperature as quickly as possible, with a cooling rate v> Vcrit , in which, according to the invention, vcrit is 200 K / s. In this way, the amorphous state of the steel is "frozen", while the crystallization of the steel begins during heating to a heat treatment temperature above the temperature Tx.
    [053] The additional cooling device that is provided as a requirement according to the invention can be so formed that the cooling medium is applied directly to the steel strip. This cooling medium can be water, liquid nitrogen or other correspondingly effective cooling liquid. Alternatively or in addition, cooling gases, such as nitrogen gas, hydrogen, a mixture of gas or water mist, can also be applied. Cooling devices suitable for this purpose are known in the state of the art (KR 2008 / 0057755A).
    [054] The cooling rate, which is essential to achieve an amorphous microstructure, depends, among other things, on the composition of the molten steel that is defined respectively. Thus, it may be convenient to provide cooling rates of more than 250 K / s, more than 450 K / s, or even more than 800 K / s.
    [055] Therefore, by the method according to the invention, an alloy strip according to the invention, with an amorphous or partially amorphous microstructure, can be specifically produced.
    [056] A particular aspect of the fine crystalline microstructure steels produced according to the invention is their structural superplasticity capacity. Therefore, on the basis of the flat steel products according to the invention, extremely complex geometric components can be obtained by sliding the grain boundaries at high temperatures (thermal activation).
    [057] As mentioned above, in a possible and particularly reliable way of producing a flat steel product with a fine crystalline microstructure, the molten strip leaves the casting pit of the casting device, then is optionally further cooled, presenting an amorphous or partially amorphous microstructure; the molten strip with these characteristics is then annealed at a temperature corresponding to at least the crystallization temperature Tx of the respective steel, until the desired microstructural state is reached. With steel compositions within the specifications according to the invention, the appropriate annealing temperatures are 500 - WOO'C. To achieve a purely fine crystalline microstructure, annealing times of 2s-2h are usually sufficient, depending respectively on the current composition.
    [058] The rates at which the steel strip leaves the foundry pit are, in practice, normally between 0.3 and 1.7 m / s.
    [059] The thicknesses with which the strip melted and cooled according to the invention leaves the casting pit are usually in the range of 0.8 - 4.5 mm, in particular 0.8 - 3.0 mm .
    [060] After casting the strip and additional cooling which is optionally carried out below, the molten strip can be subjected to hot rolling, in which the initial temperature of the hot rolling should be 500 - 1000 ° C. The continuous hot rolling steps after casting and cooling allow, on the one hand, to reach the desired final thickness of the strip and, on the other hand, to define the surface finish. In addition, they also allow to optimize the microstructure, such as, for example, closing the cavities still present in the molten state. To maintain an amorphous or partially amorphous state of the steel strip, the steel strip can also be hot rolled to a hot strip at an initial hot rolling temperature in the range between the glass transition temperature TG and the temperature of Tx crystallization.
    [061] As a casting device for carrying out the method according to the invention, it is appropriate, for example, a two-cylinder casting device, in which the cylinders rotate against each other on axes aligned axially in parallel, forming respectively a longitudinal chilled wall in the casting zone in which the strip is formed, which moves continuously in parallel in the direction of the casting during the casting operation.
    [062] The methods according to the invention require only minor modifications to the existing methods or devices for the continuous production of flat steel products in semi-finished form.
    [063] The invention is explained in more detail below, based on a figure representing a typical embodiment. This single figure shows, schematically, a device for producing a steel strip, in side view.
    [064] Installation 1 for the production of a steel strip B comprises a casting device 2, which is constructed as a conventional two-cylinder casting device and, as such, comprises two cylinders 3, 4 which rotate against each other. another on its axes X1, X2 axially aligned, parallel to each other and at the same height. The cylinders 3, 4 are arranged at a distance from each other which establishes the thickness D of the molten strip B to be produced and, therefore, delimit a casting area 5 with its longitudinal sides, which is formed as a casting pit in which steel strip B is formed. On its narrow sides, the casting area 5 is sealed in a manner also known as side plates, not visible here, which are pressed against the end surfaces of the cylinders 3, 4.
    [065] During the casting operation, the intensely cooled cylinders 3, 4 rotate forming the longitudinal walls of a casting mold, which consists of the cylinders 3, 4 and the side plates, and the walls rotate continuously during the casting operation. . The direction of rotation of the cylinders 3, 4 in this case is directed in the direction of the gravitational force R towards the casting zone 5, so that, as a result of the rotation movement, the molten material S is transported from the molten portion in the space above from the casting zone 5, between the cylinders 3, 4, to the casting zone 5. In this way, the molten material S solidifies when it comes in contact with the circumferential surface of the cylinders 3, 4, because of the intense heat removal that occurs here, forming a coating. The linings adhering to the cylinders 3, 4 are transported by the rotational movement of the cylinders to the casting zone 5, where they are compressed under the effect of forming force of strip K in the molten strip B. The current cooling at the exit in the zone of casting 5 and the forming force of strip K in this case are optimized so that the molten strip B, which leaves the casting zone 5 continuously, is as completely solidified as possible.
    [066] In order to suppress the effects of crystallization, after melting zone 5, the molten strip B passes to a cooling device 7, which applies a cooling medium to the molten strip B, in order to further cool it . Cooling by the cooling device 7 proceeds directly here after the casting zone 5, in which case it takes place so intensely that the temperature T of the steel strip B decreases continuously, until it is below the glass transition temperature TG of the respective molten material . Any crystallization of the microstructure of the steel strip B is thus suppressed, so that, as before, it is in an amorphous state when it reaches the transport section 6.
    [067] Strip B that leaves the casting zone 5 is initially transported vertically in the direction of the gravitational force R, and then folds in a known manner, in the form of a continuous curve arc, to a horizontally aligned transport section 6 .
    [068] In the transport section 6, the steel strip B can then pass through a heating device 8, in which the strip B is completely heated to an annealing temperature Tre∞zimento above the crystallization temperature Tx of the respective molten steel S, during an annealing time. This heat treatment aims at the controlled conformation, in the steel strip B, of a fine crystalline microstructure, with a grain size in the range of 10 - 10,000 nm. The heat-treated molten strip B is then hot rolled on the hot strip WB in a hot rolling unit 9.
    [069] In installation 1, a steel strip B was produced respectively from three molten steels S with the compositions Z1, Z2, Z3 indicated in Table 1. For each composition Z1, Z2, Z3, the thickness D of the molten strips B from the respective molten steels S, the cooling rate AR achieved respectively when cooling the molten material S in the casting zone 5, the cooling rate ARZ achieved respectively when cooling the molten strip B leaving the casting zone 5 in the additional cooling device 7, and also the target temperature TZ of the additional cooling. In addition, Table 2 shows the microstructural state and the constituents possibly present in the microstructure of the obtained strip.
    [070] Different heat treatments were carried out on the heating device 8, of two samples of the steel strip B produced as explained above, from molten steel S with the composition Z1. The annealing temperature Tre∞zimento and the annealing time of heat treatment, respectively, are compared in table 3.
    [071] It was found that, before the heat treatment, the fused strip B already had a fine crystalline microstructure of Fe α, Fθ2B, FesB and FesSi, with an HV0.5 hardness of 840-900. After heat treatment, the microstructure also consisted of Fe a, Fe2B, FesB and Fes-Si, but the HV0.5 hardness was 760 - 810.
    [072] Obviously, the heat treatment through the heating device 8 and the hot rolling in the hot rolling unit 9 are only optional steps of the method.
    [073] The invention, accordingly, provides methods for producing a steel strip B with an amorphous, partially amorphous or fine crystalline microstructure, with a grain size in the range of 10-10 000 nm, and also a steel product plane with corresponding characteristics. According to the invention, for this purpose, molten steel is cast in a steel strip (B), in a casting device (2), and is cooled in an accelerated way. Along with Fe and impurities that are unavoidable for production reasons, the molten material contains at least two other elements of the Si group, B, C and P. According to a first variant of the method, the following applies to the content of these elements (in% by weight) Si: 1.2 - 7.0%, B: 0.4 - 4.0%, C: 0.5 - 4.0%, P: 1.5 - 8, 0%. According to a second variant of the method, the molten steel containing Si, B, C and P is melted by casting on a steel strip (B), in a casting device (2) whose casting zone (5) is formed , on at least one of its longitudinal sides, by a wall that moves in the direction of the casting (G) and is cooled during the casting operation, and in which the molten steel (S) is cooled by contact with the moving wall and cooled, at a cooling rate of at least 200 K / s.
    [074] DESIGNATIONS 1 Installation for the production of a cast strip B 2 Casting device 3, 4 Casting device cylinders 2 5 Casting zone 6 Transport section horizontally aligned 7 Cooling device 8 Heating device 9 Lamination unit a hot B Cast strip D Cast strip thickness BR Direction of gravitational force S Cast material K Strip forming force X1, X2 Axes of rotation of cylinders 3, 4
    权利要求:
    Claims (15)
    [0001]
    1. Method of production of a flat steel product with an amorphous, partially amorphous or fine crystalline microstructure, characterized in that the fine crystalline microstructure has a grain size in the range of 10-10 000 nm, in which molten steel is melted by casting in a strip of molten steel (B) in a casting device (2) and wherein said molten steel is cooled at an accelerated rate, where the thickness of the molten strip (B) is 0.8-4.5 mm and the molten steel contains, together with iron and unavoidable impurities for production reasons, at least two other elements belonging to the group consisting of “Si, B, C and P”, as follows (in% by weight): Si: 1 , 2 - 7.0%, B: 0.4 - 4.0%, C: 0.5 - 4.0%, P: 1.5 - 8.0% and also, optionally, one or more elements of the group consisting of “Cu, Cr, Al, N, Nb, Mn, Ti and V”, as follows (in% by weight): Cu: up to 5.0%, Cr: up to 10.0%, Al: up to 10 , 0%, N: up to 0.5%, Nb: up to 2.0%, Mn: up to 3.0%, Ti: up to 2.0%, V: up to 2.0%,
    [0002]
    Method according to claim 1, characterized in that the molten steel is cooled at a cooling rate of 100-1100 K / s.
    [0003]
    Method according to claim 1 or 2, characterized in that the molten steel is cooled at a cooling rate of at least 200 K / s, to a temperature below the glass transition temperature TG.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the molten steel is melted by casting in a molten steel strip (B), in a casting device (2) whose casting zone (5) is formed , on at least one of its longitudinal sides, by a wall that moves in the direction of the casting (G) and is cooled during the casting operation, and in which the molten steel (S) is cooled by contact with the moving wall and cooled, at a cooling rate of at least 200 K / s.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the molten strip (B), after leaving the casting zone (5), continues to be cooled at a cooling rate of at least 200 K / s .
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the molten strip (4), which leaves the casting zone (5) is continuously cooled until its temperature is below the TG glass transition temperature of the respective steel .
    [0007]
    Method according to any one of claims 1 to 6, characterized in that the molten strip (B) is hot rolled at an initial hot rolling temperature of 500-1000 ° C, to form a hot strip.
    [0008]
    Method according to any one of claims 1 to 7, characterized in that the amorphous or partially amorphous strip (B) is hot rolled to form the hot strip at an initial hot rolling temperature in the range between the transition temperature glass TG and the crystallization temperature Tx.
    [0009]
    Method according to any one of claims 3 to 7, characterized in that the molten strip (B), which leaves the casting zone (5) of the casting device (2) and is optionally further cooled, has an amorphous microstructure or partially amorphous, and because the molten strip (B) with such characteristics is annealed at an annealing temperature Trecozimento corresponding, at least, to the crystallization temperature Tx of the respective steel.
    [0010]
    Method according to claim 8, characterized in that the annealing temperature Trecozimento is in the range of 500-1000 ° C.
    [0011]
    Method according to any one of claims 3 to 9, characterized in that the molten steel (S) contains, together with at least two elements of the group consisting of Si, B, Ce P, at least one element of the group consisting of Cu, Cr, Al, N, Nb, Mn, Ti and V.
    [0012]
    Method according to claim 10, characterized in that the molten steel (S), together with iron and unavoidable impurities for production reasons, contains (in% by weight) Si: 1.2 - 7.0%, B: 0.4 - 4.0%, C: 0.5 - 4.0%, P: 1.5 - 8.0% and also, optionally, one or more members of the group consisting of Cu, Cr, Al, N , Nb, Mn, Ti and V, as follows: Cu: up to 5.0%, Cr: up to 10.0%, Al: up to 10.0%, N: up to 0.5%, Nb: up to 2.0 %, Mn: up to 3.0%, Ti: up to 2.0%, V: up to 2.0%,
    [0013]
    Method according to any one of claims 1 to 12, characterized in that it applies to at least one of the elements of the group consisting of Si, B, C and P, one of the following, respectively (in% by weight): Si: 2.0 - 6.0%, B: 0.4 - 3.0%, C: 0.5 - 3.0% or P: 2.0 - 6.0%,
    [0014]
    Method according to any one of claims 1 to 13, characterized in that the molten steel, respectively, optionally contains (in% by weight) at least 0.1% Cu, at least 0.5% Cr, at least 1.0% Al and at least 0.005% N.
    [0015]
    15. Flat steel product with a thickness of 0.8-4.5 mm, characterized in that the steel contains, together with iron and unavoidable impurities, at least two other elements in the group consisting of Si, B, C and P, from as follows (in% by weight): Si: 1.2 - 7.0%, B: 0.4 - 4.0%, C: 0.5 - 4.0%, P: 1.5 - 8, 0%, and also, optionally, one or more elements of the group consisting of Cu, “Cr, Al, N, Nb, Mn, Ti and V”, as follows (in% by weight): Cu: up to 5.0 %, Cr: up to 10.0%, Al: up to 10.0%, N: up to 0.5%, Nb: up to 2.0%, Mn: up to 3.0%, Ti: up to 2.0%, V: up to 2.0%, and have an amorphous, partially amorphous or fine crystalline microstructure, with a grain size in the range of 10-10 000 nm, where the HV0.5 hardness of the flat steel product is 760-900 .
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    同族专利:
    公开号 | 公开日
    WO2014114756A1|2014-07-31|
    US10730105B2|2020-08-04|
    KR20150110729A|2015-10-02|
    BR112015017627A2|2017-07-11|
    JP6457951B2|2019-01-23|
    JP2016507383A|2016-03-10|
    CN105143491B|2016-12-14|
    KR102203018B1|2021-01-14|
    CN105143491A|2015-12-09|
    EP2948572A1|2015-12-02|
    US20150360285A1|2015-12-17|
    EP2759614B1|2019-01-02|
    EP2759614A1|2014-07-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE789989A|1971-10-15|1973-02-01|Arbed|
    US4219355A|1979-05-25|1980-08-26|Allied Chemical Corporation|Iron-metalloid amorphous alloys for electromagnetic devices|
    JPH0226768B2|1981-05-23|1990-06-12|Tdk Electronics Co Ltd|
    JPS5964143A|1982-10-04|1984-04-12|Nippon Steel Corp|Production of light-gage amorphous alloy strip for iron core|
    JPS6376842A|1986-09-18|1988-04-07|Kawasaki Steel Corp|Manufacture of amorphous alloy foil for transformer iron core|
    JPH04266460A|1991-02-19|1992-09-22|Nippon Steel Corp|Secondary cooling method in twin roll type strip continuous casting|
    JPH0559483A|1991-08-30|1993-03-09|Kawasaki Steel Corp|Manufacture of amorphous alloy thin strip for commercial frequency band transformer|
    JPH05291019A|1992-04-13|1993-11-05|Nippon Steel Corp|Manufacture of fe-based amorphous alloy|
    JPH06274050A|1993-03-23|1994-09-30|Tokyo Electric Co Ltd|Transfer device|
    JPH06297109A|1993-04-15|1994-10-25|Nippon Steel Corp|Production of cr-ni series stainless steel cast strip excellent in surface characteristic|
    US5958153A|1995-04-11|1999-09-28|Nippon Steel Corporation|Fe-system amorphous metal alloy strip having enhanced AC magnetic properties and method for making the same|
    JPH08283919A|1995-04-11|1996-10-29|Nippon Steel Corp|Iron-base amorphous alloy foil and its production|
    JP3634286B2|2000-11-27|2005-03-30|新日本製鐵株式会社|Fe-based amorphous alloy ribbon and iron core manufactured using it|
    US6416879B1|2000-11-27|2002-07-09|Nippon Steel Corporation|Fe-based amorphous alloy thin strip and core produced using the same|
    JP3929327B2|2002-03-01|2007-06-13|独立行政法人科学技術振興機構|Soft magnetic metallic glass alloy|
    WO2003085150A1|2002-04-05|2003-10-16|Nippon Steel Corporation|Fe-BASE AMORPHOUS ALLOY THIN STRIP OF EXCELLENT SOFT MAGNETIC CHARACTERISTIC, IRON CORE PRODUCED THEREFROM AND MASTER ALLOY FOR QUENCH SOLIDIFICATION THIN STRIP PRODUCTION FOR USE THEREIN|
    WO2004028724A1|2002-09-27|2004-04-08|Postech Foundation|Method and apparatus for producing amorphous alloy sheet, and amorphous alloy sheet produced using the same|
    JP5079498B2|2004-04-28|2012-11-21|ザ・ナノスティール・カンパニー・インコーポレーテッド|Method for producing nanocrystalline metal sheet|
    JP4849545B2|2006-02-02|2012-01-11|Ｎｅｃトーキン株式会社|Amorphous soft magnetic alloy, amorphous soft magnetic alloy member, amorphous soft magnetic alloy ribbon, amorphous soft magnetic alloy powder, and magnetic core and inductance component using the same|
    JP5057551B2|2006-06-21|2012-10-24|株式会社神戸製鋼所|Zr-based metallic glass sheet|
    JP4319206B2|2006-07-20|2009-08-26|独立行政法人科学技術振興機構|Soft magnetic Fe-based metallic glass alloy|
    WO2008049069A2|2006-10-18|2008-04-24|The Nanosteel Company, Inc.|Improved processing method for the production of amorphous/nanoscale/near nanoscale steel sheet|
    PL1918406T3|2006-10-30|2009-10-30|Thyssenkrupp Steel Ag|Process for manufacturing steel flat products from boron microalloyed multi phase steel|
    TWI434944B|2006-12-04|2014-04-21|Amorphous alloy composition|
    KR101354935B1|2006-12-20|2014-01-27|재단법인 포항산업과학연구원|Cooling device for amorphous strip using strip casting|
    EP2163659B1|2008-09-11|2016-06-08|Outokumpu Nirosta GmbH|Stainless steel, cold strip made of same and method for producing cold strip from same|
    DE102009048165A1|2009-10-02|2011-04-07|Sms Siemag Ag|Method for strip casting of steel and plant for strip casting|
    DE102011000089A1|2011-01-11|2012-07-12|Thyssenkrupp Steel Europe Ag|Method for producing a hot rolled flat steel product|
    CN102605293A|2012-04-18|2012-07-25|江苏省沙钢钢铁研究院有限公司|Non-quenched and tempered low-crack sensitivity steel plate with excellent low-temperature toughness, and production method thereof|
    CN102796969B|2012-08-31|2015-08-26|宝山钢铁股份有限公司|A kind of containing boron microalloy weather resisting steel and manufacture method thereof|EP3039168B1|2013-08-28|2018-10-24|Antelope Oil Tool & Mfg. Co., LLC|Chromium-free thermal spray composition, method, and apparatus|
    CN104593701B|2015-01-15|2017-01-04|江苏本安环保科技有限公司|A kind of Fe-based amorphous alloy block blast-proof materials|
    DE102015217627B4|2015-09-15|2017-07-20|Thyssenkrupp Ag|Belt processing device and method for processing a belt|
    DE102015116517A1|2015-09-29|2017-03-30|Thyssenkrupp Ag|Apparatus and method for the continuous production of a band-shaped metallic workpiece|
    CN105838993B|2016-04-05|2018-03-30|宝山钢铁股份有限公司|Lightweight steel, steel plate and its manufacture method with enhancing modulus of elasticity feature|
    MX2019010126A|2017-02-27|2019-10-15|Nucor Corp|Thermal cycling for austenite grain refinement.|
    CN112585287B|2018-08-28|2022-03-01|杰富意钢铁株式会社|Hot-rolled steel sheet, cold-rolled steel sheet, and method for producing same|
    CN109457168B|2018-12-24|2021-07-06|宁波正直科技有限公司|Gas pipe alloy of household gas stove, preparation method thereof and gas pipe|
    CN109719264B|2019-02-26|2020-10-02|安徽智磁新材料科技有限公司|Antirust amorphous alloy and preparation method thereof|
    CN109822067B|2019-04-08|2020-12-18|东北大学|Method for continuously preparing nickel-based amorphous thin strip|
    CN109957732B|2019-04-08|2020-11-27|东北大学|Method for continuously preparing zirconium-based amorphous thin strip|
    CN109967703B|2019-04-08|2020-09-18|东北大学|Method for continuously and efficiently preparing wide amorphous thin strip with thickness of 80-1500 mu m at high cooling speed|
    CN109825781B|2019-04-08|2021-02-05|东北大学|Method for continuously preparing iron-based amorphous thin strip|
    CN110195187B|2019-05-17|2020-06-05|北京科技大学|High-elasticity-modulus automobile steel material and preparation method thereof|
    DE102019004114A1|2019-06-08|2020-06-18|Daimler Ag|Steel alloy, component, in particular for a motor vehicle, and method for producing such a component|
    DE102019122515A1|2019-08-21|2021-02-25|Ilsenburger Grobblech Gmbh|Process for the production of high-strength sheets or strips from a low-alloy, high-strength bainitic steel and a steel strip or sheet steel from this|
    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-04-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13152793.9A|EP2759614B1|2013-01-25|2013-01-25|Method for generating a flat steel product with an amorphous, semi-amorphous or fine crystalline structure and flat steel product with such structures|
    EP13152793.9|2013-01-25|
    PCT/EP2014/051416|WO2014114756A1|2013-01-25|2014-01-24|Methods for creating a flat steel product with an amorphous, partially amorphous or finely crystalline structure and flat steel product of such a type|
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