EP3535431B1 - Mittelmanganstahlprodukt zum tieftemperatureinsatz und verfahren zu seiner herstellung - Google Patents

Mittelmanganstahlprodukt zum tieftemperatureinsatz und verfahren zu seiner herstellung Download PDF

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EP3535431B1
EP3535431B1 EP17798132.1A EP17798132A EP3535431B1 EP 3535431 B1 EP3535431 B1 EP 3535431B1 EP 17798132 A EP17798132 A EP 17798132A EP 3535431 B1 EP3535431 B1 EP 3535431B1
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optionally
steel
rolling
temperature
steel product
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German (de)
English (en)
French (fr)
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EP3535431A1 (de
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Peter PALZER
Manuel Otto
Kai Köhler
Thomas Evertz
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Salzgitter Flachstahl GmbH
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Salzgitter Flachstahl GmbH
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    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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Definitions

  • the invention relates to a medium-manganese steel product for use at low temperatures and a method for its production in the form of a flat steel product or a seamless tube.
  • the invention relates to the production of a steel product from a medium-manganese steel with excellent low-temperature toughness and / or high strength, for use in temperature ranges up to at least minus 196 ° C, which optionally includes a TRIP (TR Transformation Induced Plasticity) and / or TWIP (TWinning Induced Plasticity) effect.
  • steel products are understood to mean in particular flat steel products such as steel strips (hot or cold rolled) or heavy plates, as well as welded pipes made therefrom, but also seamless pipes.
  • the steel has a notched impact strength of 70 J at -196 ° C and consists of the elements (contents in% by weight and based on the molten steel): C: 0.01 to 0.06; Mn: 2.0 to 8.0; Ni: 0.01 to 6.0; Mo: 0.02 to 0.6; Si: 0.03 up to 0.5; AI: 0.003 to 0.05; N: 0.0015 to 0.01; P: up to 0.02; S: up to 0.01; as well as the remainder iron and unavoidable impurities.
  • a method for producing a flat steel product from the above-described high-strength steel with medium manganese content comprises the following work steps: heating a steel slab to a temperature of 1000 ° C to 1250 ° C, - rolling the slab with a final rolling temperature of 950 ° C or less with a reduction rate (Degree of rolling) of 40% or less, - cooling the rolled steel to a temperature of 400 ° C or less at a cooling rate of 2 ° K / s or more, - and, following the cooling, tempering the steel for 0.5 to 4 hours at a temperature between 550 ° C and 650 ° C.
  • the structure of the steel has martensite as the main phase and 3 to 15% by volume of retained austenite.
  • a medium-manganese steel for a door reinforcement tube which, in addition to iron, contains the following elements: C: 0.15 to 0.25%; Mn: 3.4 to 6.1%; P: 0.03% or less; S: 0.03% or less; Si: 0.6% or less; Al: 0.05%; Ni, Cr, Mo: 0 to 1%; V: 0 to 0.15%.
  • a structural composition of the steel is not described.
  • the U.S. Patent 5,310,431 discloses a corrosion-resistant, martensitic steel which, in addition to iron and impurities, contains the following elements: C: 0.05 to 0.15%; Cr: 2 to 15%; Co: 0.1 to 10%; Ni: 0.1 to 4%, Mo: 0.1 to 2%; Ti: 0.1 to 0.75%; B: ⁇ 0.1%; N: ⁇ 0.02%.
  • the steel described can also contain, for example, ⁇ 5% Mn.
  • the U.S. Patent 4,257,808 discloses a low-manganese steel for low-temperature applications, the composition of which does not contain any nickel.
  • the Chinese patent application CN 103 422 017 A also describes a steel composition for steel pipes used in the low temperature range, the composition containing (in% by weight): C: 0.02-0.13; Si: 0.15-0.4; Mn: 0.2-0.9; P: ⁇ 0.012; S ⁇ 0.007; N ⁇ 0.012; Mo: 0.008-0.12; Ni: 8.5-9.6 with the balance iron including impurities.
  • the steel sheet consists of the following elements (in% by weight): C: 0.03 to 0.35; Si: 0.5 to 3; Mn: 3.5 to 10; P: ⁇ 0.1; S: ⁇ 0.01; N: ⁇ 0.08.
  • a microstructure is specified with more than 30% ferrite and more than 10% residual austenite.
  • WO 2006/011503 A1 describes a steel sheet, the chemical composition of which is given in% by weight as follows: C: 0.0005 to 0.3; Si: ⁇ 2.5; Mn: 2.7 to 5; P: ⁇ 0.15; S: ⁇ 0.015; Mo: 0.15 to 1.5; B: 0.0006 to 0.01; Al: ⁇ 0.15 as well as the remainder iron and unavoidable impurities.
  • Such a steel strip is characterized by a high modulus of elasticity of greater than 230 Gpa in the rolling direction.
  • the European published application EP 2 055 797 A1 relates to a ferromagnetic, iron-based alloy whose composition contains one or more of the following elements in% by weight: Al: 0.01 to 11; Si: 0.01 to 7; Cr: 0.01 to 26, the remainder being iron and unavoidable impurities.
  • the alloy can optionally also contain 0.01 to 5% by weight of Mn and other elements.
  • TRIP steels have already been described, which have a predominantly ferritic basic structure with embedded retained austenite, which can convert to martensite during forming (TRIP effect). Because of its strong work hardening, TRIP steel achieves high values of uniform elongation and tensile strength. TRIP steels are used, among other things, in structural, chassis and crash-relevant components of vehicles as sheet metal blanks and as welded blanks.
  • Hot strips made from TRIP / TWIP steels with manganese contents of 9 to 30% by weight are known, the melt being cast into a pre-strip between 6 and 15 mm via a horizontal strip caster and then rolled out into a hot strip.
  • the present invention is based on the object of specifying a steel product made of a manganese-containing steel, which can be manufactured inexpensively and has an advantageous combination of strength and elongation properties at low temperatures and optionally a TRIP and / or TWIP effect. Furthermore, a method for producing such a steel product is to be specified.
  • this manganese-containing steel product according to the invention with a medium manganese content based on the alloying elements C, Mn, Al, Mo and Si is cost-effective, since it relies on an increased addition of nickel of up to 9% by weight to achieve the low-temperature toughness can generally be dispensed with.
  • the steel product according to the invention has a stable austenite component even at low temperatures down to at least ⁇ 196 ° C., which converts at the earliest when deformed at low temperatures, but is otherwise metastable to stable. This austenite content of at least 2% by volume, which is present at low temperatures, improves the low-temperature toughness and thus the elongation properties.
  • the steel product according to the invention can advantageously be used as a substitute for steels with a high Ni content in low-temperature applications, such as in the areas of shipbuilding, boiler construction / container construction, construction machinery, transport vehicles, crane construction, mining, mechanical and plant engineering, power plant industry, oil field pipes, Petrochemicals, wind turbines, pressure pipelines, precision pipes, pipes in general and for the substitution of high-alloy steels, in particular Cr, CrN, CrMnN, CrNi, CrMnNi steels.
  • the optionally alloyed elements advantageously have the following contents in% by weight: Ti: 0.002 to 0.5; V: 0.006 to 0.1; Cr: 0.05 to 4; Cu: 0.05 to 2; Nb: 0.003 to 0.1; B: 0.0005 to 0.014; Co: 0.003 to 3; W: 0.03 to 2; Zr: 0.03 to 1; Ca: ⁇ 0.004 and Sn: ⁇ 0.5
  • the steel product according to the invention in particular in the form of a seamless tube, has a multiphase structure consisting of 2 to 90% by volume, preferably up to 80% by volume or up to 70% by volume of austenite, less than 40% by volume, preferably less than 20% by volume ferrite and / or bainite and the remainder martensite or tempered martensite and optionally a TRIP and / or TWIP effect.
  • Some of the martensite is in the form of tempered martensite and some of the austenite of up to 90% can be in the form of annealing or deformation twins.
  • the steel can optionally have both a TRIP and a TWIP effect, with part of the austenite being able to convert into martensite during a subsequent deformation / forming / processing of the steel strip, whereby at least 20% of the original austenite must be retained in order to maintain the low-temperature properties to guarantee.
  • the steel product according to the invention is also characterized by an increased resistance to delayed crack formation (delayed fracture) and to hydrogen embrittlement. This is mainly achieved by precipitating molybdenum carbide, which acts as a hydrogen trap.
  • the steel has a high resistance to liquid metal embrittlement (LME) during welding.
  • LME liquid metal embrittlement
  • the steel according to the invention is particularly suitable for producing heavy plate or hot and cold strip as well as welded and seamless tubes which can be provided with metallic or non-metallic, organic or other inorganic coatings.
  • the steel product advantageously has a yield strength Rp0.2 of 450 to 1150 MPa, a tensile strength Rm of 500 to 2100 MPa and an elongation at break A50 of more than 6% to 45% at room temperature, with higher tensile strengths tending to be associated with lower elongation at break and vice versa are.
  • a flat specimen with an initial measurement length of A50 was used in accordance with DIN 50 125.
  • Alloy elements are usually added to steel in order to specifically influence certain properties.
  • An alloy element can influence different properties in different steels. The effect and interaction generally depends considerably on the amount, the presence of other alloying elements and the state of solution in the material. The relationships are varied and complex. In the following, the effect of the alloying elements in the alloy according to the invention will be discussed in more detail.
  • the positive effects of the alloying elements used according to the invention are described below:
  • Carbon C C is required for the formation of carbides, stabilizes the austenite and increases the strength. Higher contents of C worsen the welding properties and lead to a deterioration in the elongation and toughness properties, which is why a maximum content of less than 0.3% by weight is specified. In order to achieve a fine precipitation of carbides, a minimum addition of 0.01% by weight is required.
  • the C content is advantageously set at 0.03 to 0.15% by weight.
  • Mn stabilizes the austenite, increases the strength and the toughness and optionally enables a deformation-induced martensite and / or twin formation in the alloy according to the invention. Contents of less than 4% by weight are not sufficient to stabilize the austenite and thus worsen the elongation properties, while contents of 10% by weight and more, the austenite is stabilized too strongly, so that the deformation-induced mechanisms TRIP and TWIP effect are not sufficiently effective and thereby the strength properties, in particular the 0.2% yield strength, are reduced. For the manganese steel according to the invention with medium manganese contents, a range of 4 to ⁇ 8% by weight is preferred.
  • Aluminum Al is used to deoxidize the melt. An Al content of 0.003% by weight and more is used to deoxidize the melt. This results in a higher effort when potting. Al contents of more than 0.03% by weight completely deoxidize the melt, influence the transformation behavior and improve the strength and elongation properties. Al contents of more than 2.9% by weight deteriorate the elongation properties. Higher Al contents also significantly worsen the casting behavior in continuous casting. Therefore, a maximum content of 2.9% by weight and a minimum content of more than 0.003% by weight are specified. However, the steel preferably has an Al content of 0.03 to 0.4% by weight.
  • Silicon Si The addition of Si in contents of more than 0.02% by weight hinders the carbon diffusion, reduces the specific density and increases the strength and the elongation and toughness properties. Furthermore, an improvement in cold rollability could be observed through the addition of Si. Contents of more than 0.8% by weight lead to embrittlement of the material and have a negative impact on hot and cold rollability and coatability, for example by galvanizing. Therefore, a maximum content of 0.8% by weight and a minimum content of 0.02% by weight are specified. Contents of 0.08 to 0.3% by weight have proven to be optimal.
  • Mo acts as a carbide former, increases strength and increases resistance to hydrogen-induced delayed cracking and hydrogen embrittlement. Contents of Mo of more than 0.8% by weight deteriorate the elongation properties, which is why a maximum content of 0.8% by weight and a minimum content of 0.01% by weight, which is necessary for sufficient effectiveness, are specified. A Mo content of 0.1 to 0.5% by weight has proven to be advantageous in terms of increasing strength in combination with the lowest possible cost.
  • Phosphorus P is a trace or accompanying element from iron ore and is dissolved in the iron lattice as a substitution atom. Phosphorus increases hardness through solid solution strengthening and improves hardenability. As a rule, however, attempts are made to lower the phosphorus content as much as possible, since it is, among other things, highly susceptible to segregation due to its low diffusion rate and to a great extent reduces the toughness. The accumulation of phosphorus at the grain boundaries can cause cracks to appear along the grain boundaries during hot rolling. In addition, phosphorus increases the transition temperature from tough to brittle behavior by up to 300 ° C. For the reasons mentioned above, the phosphorus content is limited to values less than 0.04% by weight.
  • sulfur S is bound as a trace or accompanying element in iron ore or is introduced through coke during production via the blast furnace route. It is generally undesirable in steel because it tends to segregate strongly and has a strong embrittling effect, as a result of which the elongation and toughness properties are impaired. Attempts are therefore made to achieve the lowest possible amounts of sulfur in the melt (e.g. through deep desulphurisation). For the reasons mentioned above, the sulfur content is limited to values less than 0.02% by weight.
  • N is also an accompanying element in steel production. He improves in the dissolved state for steels with a higher manganese content with greater than or equal to 4% weight% Mn, the strength and toughness properties. Lower Mn-alloyed steels with less than 4% by weight tend to have a strong aging effect in the presence of free nitrogen. The nitrogen diffuses at dislocations even at low temperatures and blocks them. It thus causes an increase in strength combined with a rapid loss of toughness.
  • a setting of the nitrogen in the form of nitrides is possible, for example, by adding aluminum and / or titanium as well as Nb, V, B, aluminum nitrides in particular having a negative effect on the forming properties of the alloy according to the invention. For the reasons mentioned above, the nitrogen content is limited to less than 0.02% by weight.
  • Titanium Ti When optionally added, Ti acts as a carbide former to refine the grain, which at the same time improves strength, toughness and elongation properties. Furthermore, Ti reduces intergranular corrosion. Contents of Ti of more than 0.5% by weight deteriorate the elongation properties, which is why a maximum Ti content of 0.5% by weight is specified. A minimum content of 0.002 is optionally specified in order to advantageously eliminate nitrogen with Ti.
  • Vanadium V When optionally added, V acts as a carbide former to refine the grain, which at the same time improves strength, toughness and elongation properties. Contents of V of more than 0.1% by weight give no further advantages, which is why a maximum content of 0.1% by weight is specified. A minimum content of 0.006% by weight is optionally specified, which is necessary for the separation of the finest carbides.
  • Chromium Cr With the optional addition, Cr increases the strength and reduces the corrosion rate, delays the formation of ferrite and pearlite and forms carbides.
  • the maximum content is set at 4% by weight, since higher contents result in a deterioration in the elongation properties.
  • a minimum Cr content for effectiveness is set at 0.05% by weight.
  • Nickel Ni The addition of at least 0.01% by weight of nickel stabilizes the austenite, especially at lower temperatures, and improves the strength and toughness properties and reduces carbide formation. The For reasons of cost, the maximum content is set at 3% by weight. A maximum Ni content of 1% by weight has proven to be particularly economical.
  • a particularly cost-effective alloy system can be achieved if the following condition is met in combination with manganese: 6 ⁇ 1.5 Mn + Ni ⁇ 8.
  • Copper Cu reduces the rate of corrosion and increases strength. Contents of more than 2% by weight worsen the producibility due to the formation of low-melting phases during casting and hot rolling, which is why a maximum content of 2% by weight is specified. In order to achieve a strength-increasing effect through Cu, a minimum of 0.05% by weight is specified.
  • Niobium Nb When optionally added, Nb acts as a carbide former to refine the grain, which at the same time improves strength, toughness and elongation properties. Contents of Nb of more than 0.1% by weight give no further advantages, which is why a maximum content of 0.1% by weight is specified. Optionally, a minimum content of 0.003% by weight is specified, which is necessary for the separation of the finest carbides.
  • Boron B B retards the austenite transformation, improves the hot forming properties of steels and increases the strength at room temperature. It develops its effect even with very low alloy contents. Contents above 0.008% by weight increasingly deteriorate the elongation and toughness properties, which is why the maximum content is set at 0.014% by weight. A minimum content of 0.0005% by weight is optionally specified in order to take advantage of the strength-increasing effect of boron.
  • Co increases the strength of the steel and stabilizes the austenite. Contents of more than 3% by weight worsen the elongation properties, which is why a maximum content of 3% by weight is optionally specified. An optional minimum content of 0.003% by weight is preferably provided, which, in addition to the strength properties, particularly advantageously influences the austenite stability.
  • Tungsten W acts as a carbide former and increases strength. W contents of more than 2% by weight deteriorate the elongation properties, which is why a maximum W content of 2% by weight is specified. An optional minimum content of 0.03% by weight is specified for the effective elimination of carbides.
  • Zirconium Zr acts as a carbide former and improves strength. Contents of Zr of more than 1% by weight deteriorate the elongation properties, which is why a maximum content of 1% by weight is specified. In order to enable the precipitation of carbides, an optional minimum content of 0.03% by weight is specified.
  • Ca is used to modify non-metallic oxidic inclusions, which otherwise could lead to undesired failure of the alloy due to inclusions in the structure, which act as stress concentration points and weaken the metal bond. Furthermore, Ca improves the homogeneity of the alloy according to the invention. Contents above 0.004% by weight Ca do not result in any further advantage in the inclusion modification, impair the producibility and are to be avoided due to the high vapor pressure of Ca in steel melts. Therefore, an optional maximum content of 0.004% by weight is provided.
  • Tin Sn increases the strength, but, like copper, accumulates under the scale and at the grain boundaries at higher temperatures. By penetrating into the grain boundaries, it leads to the formation of low-melting phases and the associated cracks in the structure and to solder brittleness, which is why a maximum content of less than 0.5% by weight is optionally provided.
  • the annealing required to achieve the required low-temperature toughness and thus the setting of the final structure can not be carried out on the hot or cold strip, but optionally only after the Tube production take place, the annealing of the tube in an annealing plant with an annealing time of 0.3 to 24 h and temperatures of 500 ° C to 840 ° C, preferably 520 ° C to 600 ° C with an annealing time of 0.5 to 6 h he follows. If necessary, the tube can be given an organic or inorganic coating on one or both sides after annealing.
  • the usual thickness ranges for pre-strip are 1 mm to 35 mm and for slabs and thin slabs 35 mm to 450 mm. It is preferably provided that the slab or thin slab is hot-rolled into a heavy plate with a thickness of more than 3 mm to 200 mm or a hot strip with a thickness of 0.8 mm to 28 mm, or the pre-strip, cast close to its final dimensions, is hot-rolled into a hot strip with a thickness of 0.8 mm to 3 mm is hot rolled.
  • the cold strip according to the invention has a thickness of at most 3 mm, preferably 0.1 mm to 1.4 mm.
  • a pre-strip produced near net dimensions using the two-roll casting method with a thickness of less than or equal to 3 mm, preferably 1 mm to 3 mm, is already understood as hot strip.
  • the pre-strip produced in this way as hot strip does not have an original cast structure due to the reshaping of the two counter-rotating rolls. Hot rolling thus already takes place inline during the two-roller casting process, so that separate hot rolling can optionally be omitted.
  • the cold rolling of the hot strip can take place at room temperature or advantageously at an elevated temperature before the first rolling pass, in one or more rolling passes.
  • Cold rolling at elevated temperatures is advantageous in order to reduce the rolling forces and to promote the formation of deformation twins (TWIP effect).
  • Advantageous temperatures of the rolling stock before the first rolling pass are 60 ° C to 450 ° C.
  • the steel strip can be skin-pass after cold rolling, whereby the surface structure (topography) required for the end application is set. Passing can be done using the Pretex® process, for example.
  • the flat steel product produced in this way receives a surface refinement, for example by electrolytic galvanizing or hot-dip galvanizing and, instead of galvanizing or in addition, a coating on an organic or inorganic basis.
  • the coating systems can be, for example, organic coatings, plastic coatings or lacquers or other inorganic coatings such as iron oxide layers.
  • the flat steel product produced according to the invention can be used both as sheet metal, sheet metal section or blank or further processed into a pipe that is welded longitudinally or helically.
  • a solid block (round cast bar) is essentially understood to mean a continuously cast section produced by round casting, which section already has a desired length.
  • Warm forming or warm internal high pressure forming is the term used here for forming and internal high pressure forming processes in which at least the first forming step takes place at a temperature above room temperature to below the Ac3 temperature, preferably at 60 ° C to 450 ° C.
  • alloys 1 and 2 not according to the invention with regard to the Ni content and with a standard alloy.
  • the standard alloy and alloys 1 and 2 contain the following elements in the listed contents in% by weight: alloy C. Ni Mn Si P. S. Mon V. B. X8Ni9 / 1.5662 (standard) Max 0.1 8.5-10.0 0.3-0.8 Max. 0.35 Max. 0.02 Max. 0.01 Max 0.1 0.05 max - Leg. 1 0.03 0.004 6.4 0.12 0.023 0.006 0.43 - 0.001 Leg. 2 0.06 0.004 6.3 0.12 0.022 0.006 0.43 - -
  • the elongation at break A50 of the X8Ni9 was converted in accordance with DIN ISO 2566/1 from the elongation at break A5.65 in accordance with the standard to a sample cross-section of 20 mm.
  • the elongation parameters represent the elongation in the rolling direction.

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US20190264297A1 (en) 2019-08-29
CA3042120A1 (en) 2018-05-11
EP3535431A1 (de) 2019-09-11
CN109923233A (zh) 2019-06-21
AU2017353259B2 (en) 2022-12-22
WO2018083035A1 (de) 2018-05-11
US11352679B2 (en) 2022-06-07

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