EP3019292B1 - Procédé de fabrication d'un produit plat à partir d'un alliage a memoire de forme à base de fer - Google Patents

Procédé de fabrication d'un produit plat à partir d'un alliage a memoire de forme à base de fer Download PDF

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Publication number
EP3019292B1
EP3019292B1 EP13741744.0A EP13741744A EP3019292B1 EP 3019292 B1 EP3019292 B1 EP 3019292B1 EP 13741744 A EP13741744 A EP 13741744A EP 3019292 B1 EP3019292 B1 EP 3019292B1
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Prior art keywords
casting
group
weight
strip
gew
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German (de)
English (en)
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EP3019292A1 (fr
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Rainer FECHTE-HEINEN
Christian Höckling
Lothar Patberg
Jens-Ulrik Becker
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/46—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling metal immediately subsequent to continuous casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/041—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for vertical casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/1206—Accessories for subsequent treating or working cast stock in situ for plastic shaping of strands
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/007—Heat treatment of ferrous alloys containing Co
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/006—Resulting in heat recoverable alloys with a memory effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/46—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling metal immediately subsequent to continuous casting
    • B21B1/463—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling metal immediately subsequent to continuous casting in a continuous process, i.e. the cast not being cut before rolling

Definitions

  • the invention relates to a method for producing a flat product from an iron-based shape memory alloy, in which a melt containing at least as a main component iron, alloying elements and unavoidable impurities, cast in a casting device to a cast strip and thereby cooled.
  • films or wires can be produced by strip casting.
  • strip casting the melt is cast in a casting device in which the casting region or the congestion region in which the cast strip is formed is delimited on at least one longitudinal side by a wall that is continuously moved and cooled during the casting process.
  • twin-roll caster two casting rolls or casting rolls oriented axially parallel to one another rotate in opposite directions and limit a casting gap defining the casting region in the region of their closest spacing.
  • the casting rolls are strongly cooled, so that the melt meeting them solidifies to a shell.
  • the direction of rotation of the casting rolls is chosen so that the melt and with it the shells formed from it on the casting rolls are transported into the casting gap.
  • the trays entering the casting nip are compressed into the cast strip under the effect of sufficient banding force, resulting in at least approximately solidification.
  • Another principle is the so-called "belt caster".
  • liquid steel is poured via a feed system onto a revolving casting belt, whereupon the steel solidifies.
  • the running direction of the belt is chosen so that the melt is conveyed away from the supply system.
  • a further casting belt can be arranged, which rotates in opposite directions to the first casting belt.
  • at least one casting belt also limits the region in which the cast strip is formed, even in the above-mentioned methods.
  • the respective casting belt is cooled intensively, so that the melt coming into contact with the casting belt in question solidifies thereon to form a belt which can be removed from the casting belt.
  • the cast strip emerging from the respective casting device is drawn off, cooled and can be sent for further processing.
  • This further processing may include a heat treatment and / or a hot rolling.
  • JP 62 112 751 A is an iron-based Shape memory alloy, which in addition to iron in particular elements from the group "Mn, Si” and in addition to these elements additional contents of Cr, Ni, Co, Mo, C, Al, Ca and rare earths may be present.
  • Made of alloys of this kind should be produced by tape cast films that are temperature and corrosion resistant.
  • the present invention has the object to provide cost-effective method for the production of flat products of an iron-based shape memory alloy, which are resistant to bending stress and pressure and torsion.
  • a flat product is to be produced, which can be produced inexpensively in a practical way.
  • a flat product is understood to be a cast and / or rolled strip or sheet, as well as blanks, blanks or the like obtained therefrom.
  • the melt is poured into a casting into a belt and cooled, so that a continuous casting operation can be ensured, the thickness of the tape is greater than 1 mm and less than 30 mm, the casting region at least on one of its longitudinal sides is limited by a moving during the casting in the casting and cooled wall.
  • the melt is cooled in contact with the moving wall or casting belt at a cooling rate of in particular at least 20 K / s, preferably 50 K / s, more preferably at least 100 K / s. Due to the high solidification rate, segregation processes, which adversely affect the material properties can be reduced.
  • the cooling rate is chosen so that at the end of the casting process, a solidified, flat product is produced, for example an iron-based strip made of a shape memory alloy.
  • Group 1 + Group 2 contains the melt next to iron and manufacturing impurities manganese with 12 wt .-% to 45 wt .-% and silicon with 1 wt .-% to 12 wt .-% and at least a further element of a group 1, wherein the group 1 comprises the elements N, B, C and applies to the alloy constituents of the group 1 in wt .-%: ⁇ N .
  • the group 2 comprises the elements Ti, Nb, W, V, Zr and applies to the alloy constituents of the group 2 in wt .-%: ⁇ Ti . Nb . W . V . Zr ⁇ 0.01 ⁇ % . prefers ⁇ Ti . Nb . W . V . Zr ⁇ 0.1 ⁇ %
  • the strip emerging from the casting gap of the casting device or solidified on the casting strip and optionally additionally hot-rolled subsequently optionally cold-rolled strip is finally heated to at least the martensite finish (M F ) temperature of the respective alloy.
  • M F martensite finish
  • the flat product thus produced allows the impressing of a component shape by applying a load to the flat product, during which the temperature is increased to at least austenite finish temperature (A F ) and at least 20 seconds the load and the temperature> A F on the Flat product acts.
  • the shape memory effect is thus set in the flat product according to the invention to the desired component shape.
  • the strip thicknesses with which the cast and cooled strip according to the invention leaves the casting gap or onto the casting strip is poured and solidified, amount to between more than 1 mm and 30 mm, in particular between 1.5 mm and 20 mm, more preferably between 2 mm and 10 mm.
  • iron-based shape memory alloys based on Fe-Mn-Si (-Cr (-Ni)) systems can be cast as a flat product by means of a strip casting device. Because of their use preferably for switching purposes, in particular in high-temperature regions, it is necessary to use a material for To provide that meets the respective requirements. Depending on the application, a material is used which has a minimum thickness of> 1 mm in order to achieve the required later component properties, e.g. To ensure resistance to buckling and / or effectiveness in bending stress.
  • a twin-roll caster or a belt caster is used as casting device. It has been found that the melt according to the invention can preferably be produced via the strip casting devices mentioned.
  • the tape casting is ideal for iron-based shape memory alloys, since compared to conventional casting, in particular continuous casting no casting powder must be used, so that can be prevented, in particular when highly reactive alloying components, such as Mn, Si, Cr and / or Al in high If they are present, casting problems will occur.
  • strip casting is advantageous, especially if, for example, high alloy contents are present on strongly segregating elements, such as Mn, Si, Cr and / or Ni. A segregation can essentially be due to a rapid solidification be suppressed.
  • iron-based shape memory alloys have a low high-temperature ductility, so that bending during casting is possible only for small thicknesses or is not absolutely necessary depending on the casting device. It is also characteristic that iron-based shape memory alloys have a high hot forming resistance and are nevertheless essentially thinly molded close to the final dimensions.
  • the devices can be used for energy efficient production of the flat product with shape memory properties.
  • the rollers disposed parallel to the axis each form a cooled boundary of the casting area continuously moving in the casting direction in the casting direction, with which at least two longitudinal sides of the strip are formed.
  • this function takes over a horizontally moving casting belt onto which the melt is poured to make the strip.
  • the advantage of using this strip casting is that other process steps, such as hot rolling, can connect directly and in particular the rolling effort is low because of the low casting thicknesses and due to the compact nature of the corresponding casting a process control with the material side required parameters, especially with respect to the temperature, is particularly advantageous. Since the melt is poured in the Belt-Caster in the horizontal and cooled, the solidified band experiences no deflection and the result In the band itself only low voltages are present, so that in particular the risk of cracking in the high temperature region of the flat product produced is minimized.
  • an alloy-dependent roll pressure expressed by the so-called RSF (roll separating force) or band forming force (BFK)
  • RSF roll separating force
  • BFK band forming force
  • any heat loss which may occur when the strip exits the casting device can be compensated for again and the specific hot rolling temperature can be reliably achieved.
  • the belt speeds with which the cast strip emerges from the casting gap are typically in the range of 0.06 to 3.0 m / s in practice.
  • a particularly effective and economical production method can be provided by continuously feeding the cast strip emerging from the casting area to at least one rolling stand.
  • the casting device can thus directly supply at least one roll stand with a cast strip for rolling, so that no handling of the cast strip between casting and rolling must take place.
  • the cast strip can be cooled accordingly and at a later time if necessary, reheated and rolled.
  • the hot strip is optionally cold rolled, wherein the cold rolling takes place in at least one rolling pass.
  • an annealing treatment in the hot and / or cold rolled state can be carried out at a temperature above the switching temperature for a period of 20 seconds to 48 hours.
  • the cast strip may be subjected to hot rolling in which the hot rolling start temperature should be between -50 ° C and T solidus .
  • the hot rolling steps following the casting and cooling process in-line can, on the one hand, set the desired final thickness of the strip and, on the other hand, improve the surface finish and optimize the microstructure by, for example, closing still existing cavities in the cast state.
  • the hot strip can also be subjected to cold rolling and thus further reduced in thickness.
  • the strip casting method used produces a strip which, for example, owing to the contents of the alloy constituents according to group 1 N, C, B in combination with the elements of group 2 Ti, Nb, W, V, Zr precipitation pairs in the form of carbides, nitrides, Contains borides or their mixed form, which in conjunction with the iron, manganese and silicon content of the alloy provides the desired texture combination to achieve a shape memory effect.
  • the alloy contains at least one of boron, nitrogen and / or carbon and at least one of titanium, niobium, tungsten, vanadium or zirconium, with the remainder iron, manganese, silicon and unavoidable impurities.
  • the elements of group 1 and 2 prove to be particularly advantageous because they lead to the desired precipitations, which serve as germ cells for the desired phase transformation in the appropriate places.
  • the manufacturing method according to the invention enables a reliable production of a flat product with shape memory effect.
  • Manganese in contents of 12% by weight to 45% by weight promotes stabilization of the austenite of the material in the steel flat product produced according to the invention.
  • the Mn content may be between 20% by weight and in particular 35% by weight.
  • Si contents of 1% by weight up to 12% by weight serve to ensure the reversibility of the transformation of martensite into austenite in the flat products according to the invention.
  • Preferred Si contents are from 3% by weight to 10% by weight.
  • the B content is expediently set to max. 0.5 wt .-%, in particular to max. 0.05 wt .-% limited.
  • the N content is expediently reduced to 0.5% by weight, in particular to max. 0.2 wt .-% limited.
  • the content of elements of group 2 (Ti, Nb, W, V, Zr) is preferably increased to max. 2.0 wt .-%, in particular to max. 1.5 wt .-% individually limited.
  • the shape memory effect can be improved, whereas the effect of Cr, Al and Mg alone or in combination is mainly to improve the corrosion resistance.
  • the individually mentioned elements can be added up to 20% by weight, preferably up to 10% by weight. To avoid negative influences of S, P and O, these are limited to max. 0.5% by weight, preferably max. 0.2 wt .-%, more preferably to max. 0.1 wt .-% limited.
  • Ni supports the stabilization of austenite in the structure and improves the formability of the material.
  • Ca can be added in the presence of S with a maximum of 0.5% by weight in order to suppress undesired binding of Mn in the form of MnS. The content is reduced to max. 0.5% by weight, preferably max. 0.2 wt .-%, more preferably to max. 0.1 wt .-% limited.
  • the melt can in each case optionally contain at least 0.1% by weight of Ni and at least 0.2% by weight of Cr.
  • the shape memory alloy may optionally optionally contain the elements P, S, Mo, Cu, Al, Mg, O, Ca, or Co, which may exhibit advantageous effects up to the given values.
  • the ratio given is less than 0.5, the precipitating elements in the form of N, C and / or B can not be set and the shape memory effect is reduced since the group 1 elements are present in dissolved form in the microstructure. As a result, a negative effect on the reversibility of the phase transformation, that is the back transformation of martensite into austenite, is observed. If the ratio of the sums of the alloying components formed in this way is greater than 2, unwanted solidifications due to the elements of group 2 appear, which become lodged as free atoms in the microstructure and thus hinder the shape memory effect.
  • the manganese content of 25 wt .-% to 32 wt .-% serves to stabilize the austenite in the structure and has particular influence on the switching temperature of the shape memory material. Below an Mn content of 25.0 wt .-% ferrite is increasingly formed, which adversely affects the shape memory effect. Increasing the Mn content above 32 wt .-%, the desired decreases Switching temperature too much, so that the switching temperature and the possible operating temperatures of a corresponding component too close.
  • Silicon serves to ensure the reversibility of the phase transformation of martensite into austenite. Contents below 3.0% by weight of Si lead to a reduction of the shape memory effect. Above 10% by weight, embrittlement of the material can be observed. In addition, with Si contents above 10% by weight, the increased formation of the unfavorable ferritic microstructure takes place.
  • the shape memory alloy contains at least 3.0 wt% Cr.
  • Ni serves to stabilize the austenitic structure and also improves the formability of the material.
  • a Ni content below 0.1% by weight has no significant influence on the properties of the material.
  • Ni contents of more than 6.0% by weight lead to slight improvements in the abovementioned properties only in conjunction with an increased Cr content, so that the Ni content is reduced to a maximum of 6.0% by weight, preferably up to cost savings is limited to a maximum of 4.0 wt .-%.
  • each individual element of group 2 does not exceed the maximum content of 1.5% by weight, more preferably the maximum content of each individual element is 1.2% by weight or at most 1.0% by weight, to counteract unwanted solidification.
  • the Cr content in weight percentage is 3.0% by weight ⁇ Cr ⁇ 10.0% by weight, so that a good compromise between ferrite formation and corrosion resistance of the shape memory alloy is achieved.
  • the ferrite formation counteracts the shape memory effect, since ferrite does not undergo phase transformation and prone to premature plastic deformation.
  • the difference between the Cr content and the Ni content is: 0% by weight ⁇ Cr-Ni ⁇ 6.0% by weight.
  • the maximum difference in the contents of Cr and Ni is insofar limited to 6 wt .-%. It has been found that an increase in the difference of the chromium and nickel content to more than 6 wt .-% leads to no appreciable improvements in the mechanical properties, but rather to the embrittlement of the material. A decrease in the difference to below 0 wt .-%, ie that the nickel content is greater than the chromium content On the other hand, it can have a negative effect on the switching temperature, in which it is lowered and approaches the operating temperature of the material.
  • the ratio in atomic% of the sum of the alloy constituents of group 1 and group 2 applies: 0.5 ⁇ ⁇ group 2 ⁇ group 1 ⁇ 1.5 . so that on the one hand the shape memory effect can be completely ensured by sufficient formation of precipitates and on the other hand solidifications due to free atoms of group 2 in the microstructure can be significantly reduced.
  • the content of N and C is limited to a maximum of 0.1 wt .-%, preferably a maximum of 0.07 wt .-%, so that the precipitates are not too large and these can have a negative effect on mechanical properties of the alloy.
  • the alloy contents of the alloying elements of the group 2 elements are limited.
  • the alloying constituents of the elements of group 2 Ti ⁇ 1.2 wt.%, Nb ⁇ 1.2 wt%, W ⁇ 1.2% by weight, V ⁇ 1.2% by weight, Zr ⁇ 1.2 wt.%, preferably, the upper limit is lowered to 1.0% by weight for each individual Group 2 element. The formation of solidifications is thereby further reduced, so that the shape memory alloy has a good forming behavior.
  • sulfur, phosphorus and oxygen should be limited to contents of not more than 0.1% by weight, preferably not more than 0.05% by weight and more preferably not more than 0.03% by weight. to reduce their negative impact, for example on corrosion resistance.
  • Molybdenum, copper and cobalt may be alloyed singly or in combination to improve the shape memory effect. A corresponding influence is in each case on contents of maximally 0.5 Gew. -% limited.
  • Aluminum and magnesium can contribute individually or in combination to improve the corrosion resistance and at the same time also bring about a reduction in the density of the alloy. Their content is limited to a maximum of 5 wt .-%, preferably to a maximum of 2.0 wt .-%, more preferably to a maximum of 1.0 wt .-%.
  • calcium may be added to cure existing sulfur to avoid undesirable sulfur-manganese MnS bonding.
  • the content of Ca is limited to a maximum of 0.015 wt .-%, preferably to a maximum of 0.01 wt .-%.
  • the above-described object is also achieved by a flat product with a shape memory effect consisting of an alloy which, in addition to iron and production-related impurities, contains manganese at 12% by weight to 24% by weight, silicon at 1% by weight. to 12 wt .-%, wherein at least one further element of a group 1 is contained, wherein the group 1 comprises the elements (N, B, C) and applies to the alloy constituents of the group 1 in wt .-%: ⁇ N . C . 10 ⁇ B ⁇ 0.005 ⁇ % .
  • group 2 comprises the elements (Ti, Nb, W, V, Zr) and applies to the alloy components of the group 2 in percent by weight: ⁇ Ti . Nb . W . V . Zr ⁇ 0.01 ⁇ % .
  • FIGS. 1 and 2 each show schematically a device for producing a flat product by strip casting in a schematic sectional view.
  • the exemplary embodiments listed in Table 1 were determined using the in Fig. 1 poured casting device (twin roll caster) poured and checked their shape memory effect. It was found that the embodiments compared to the prior art showed a lower tendency to undesirable solidifications and at the same time a good shape memory effect at sufficiently high switching temperature. In simulation experiments with identical melts, it was found that the embodiments can also be produced by tape casting in a belt caster, as in Fig. 2 shown.
  • the plant 1 for producing a cast strip B comprises a casting device 2, which is constructed as a conventional twin-roll caster and accordingly two mutually aligned around axis-parallel to each other and at the same height axes X1, X2 comprises rotating rollers 3,4.
  • the rollers 3, 4 are arranged with a thickness defining the thickness D of the cast strip B to be produced, and thus define at their longitudinal sides a casting area 5 in the form of a casting gap, in which the cast strip B is formed. On its narrow sides, the casting area 5 is sealed in a likewise known manner by side plates (not visible here), which are pressed against the end faces of the rollers 3, 4.
  • intensively cooled rollers 3, 4 rotate and thus form a boundary of the longitudinal sides of a casting mold formed by the rollers 3, 4 and the side plates, which continuously move in the casting operation.
  • the direction of rotation of the rollers 3,4 is directed in the direction of gravity R in the casting area 5 in, so that as a result of the rotation melt S. is conveyed from one in the space above the casting area 5 between the rollers 3,4 pending melt pool in the casting area 5.
  • the melt S solidifies when it touches the peripheral surface of the rollers 3,4, due to the there taking place intense heat dissipation to one shell.
  • the shells adhering to the rollers 3, 4 are conveyed into the casting region 5 by the rotation of the rollers 3, 4, where they are pressed together under the action of a band-forming force BFK into the cast strip B.
  • the effective cooling in the casting area 5 and the band forming force BFK are coordinated so that the continuously emerging from the casting area 5 cast strip B is largely completely solidified.
  • the emerging from the casting area 5 Band B is initially conveyed vertically in the direction of gravity and then deflected in a known manner in a continuously curved arc in a horizontally oriented conveyor section 6.
  • the cast strip B can then pass through a heating device 8, in which the strip B is heated to at least hot rolling start temperature.
  • the correspondingly heated cast strip B is then rolled in at least one hot rolling stand 9 to hot strip WB.
  • targeted cooling 7 after the hot rolling stand can be influenced on the formation of the structure.
  • By cooling the strip to about 400 ° C, a coarsening of the precipitates can be suppressed.
  • the hot strip WB can be reeled and otherwise prepared for removal.
  • the described heat treatment by means of the heating device 8 as well as the hot rolling with the hot rolling mill 9 or the cooling step using the cooling device 7 are only optional process steps.
  • the in Fig. 2 shown belt Caster 1 uses a casting belt 10, on which the molten steel 11 is poured with the composition of the invention. This takes place in the region of the first deflection roller 10a of the casting belt. About the second guide roller 10b, the highly cooled casting belt is returned. Covering means 12 make it possible for the further transport of the cast strip 13 to take place as far as possible without heat loss and optionally under a protective gas atmosphere for hot rolling 9. Instead of the covering means 12, alternatively, a second casting belt (not shown here) opposite the first casting belt 10 may be provided. Immediately before the hot rolling mill 9 and heating means 8 may be provided which heat the cast strip 13 to at least hot rolling start temperature.
  • a desired microstructure in the band can be adjusted, so that a flat product of a shape memory alloy is formed, which can be coiled or otherwise prepared for removal in the Anschuss.
  • a hot rolling machine as in the Fig. 1 and 2 exemplified, not mandatory.
  • the cast strip emerging from the casting area can be cooled directly without rolling.

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  • Physics & Mathematics (AREA)
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Claims (6)

  1. Procédé pour produire un produit plat à partir d'un alliage à mémoire de forme à base de fer, dans lequel une masse fondue, qui contient au moins, comme constituant principal, du fer, des éléments d'alliage et des impuretés inévitables, est coulée dans une installation de coulée en un feuillard coulé et est refroidie, caractérisé en ce que la masse fondue est coulée en un feuillard dans une installation de coulée et est refroidie, l'épaisseur du feuillard étant supérieure à 1 mm et inférieure à 30 mm, la zone de coulée de laquelle est délimitée, au moins au niveau d'un de ses côtés longitudinaux, par une paroi mobile pendant le fonctionnement de coulée dans la direction de coulée et refroidie, la masse fondue en contact avec la paroi mobile ou la courroie de coulée est refroidie à une vitesse de refroidissement d'au moins 20 K/s, la masse fondue contient, outre du fer et les impuretés provoquées par la fabrication, le manganèse à raison de 12% en poids à 45% en poids et le silicium à raison de 1% en poids à 12% en poids, au moins un autre élément d'un groupe 1, le groupe 1 comprenant les éléments N, B, C et pour les proportions d'alliage du groupe 1, en pour cent en poids, l'équation suivante s'appliquant : ∑ N , C , 10 ⋅ B ≥ 0,005 ⁢ % ,
    Figure imgb0016
     et/ou au moins un autre élément d'un groupe 2 étant contenu, le groupe 2 comprenant les éléments Ti, Nb, W, V, Zr et pour les proportions d'alliage du groupe 2, en pour cent en poids, l'équation suivante s'appliquant : ∑ Ti , Nb , W , V , Zr ≥ 0,01 ⁢ %
    Figure imgb0017
     et éventuellement au moins l'une ou plusieurs des proportions de constituants d'alliage suivantes pouvant être présentes :
    Cu 20% en poids,
    Cr 20% en poids,
    Al 20% en poids,
    Mg 20% en poids,
    Ni 20% en poids,
    O 0,5% en poids,
    Co 20% en poids,
    Mo 20% en poids,
    Ca 0,5% en poids,
    P 0,5% en poids et/ou
    S 0,5% en poids,
    le feuillard sortant de la fente de coulée de l'installation de coulée ou le feuillard solidifié sur la courroie de coulée et ensuite en outre laminé à chaud, éventuellement laminé à froid est enfin réchauffé au moins à la température de finition de martensite (MF) de l'alliage en question.
  2. Procédé selon la revendication 1, caractérisé en ce qu'une machine de coulée à double cylindre ou une machine de coulée à courroie est utilisée comme installation de coulée.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le feuillard passe à travers un dispositif de chauffage avant le laminage à chaud.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le feuillard est sensiblement complètement solidifié après la sortie de la zone de coulée.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le feuillard coulé sortant de la zone de coulée est introduit en continu dans au moins une cage de laminage.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le feuillard coulé sortant de la zone de coulée est refroidi directement.
EP13741744.0A 2013-07-10 2013-07-24 Procédé de fabrication d'un produit plat à partir d'un alliage a memoire de forme à base de fer Not-in-force EP3019292B1 (fr)

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DE102015112889A1 (de) * 2015-08-05 2017-02-09 Salzgitter Flachstahl Gmbh Hochfester manganhaltiger Stahl, Verwendung des Stahls für flexibel gewalzte Stahlflachprodukte und Herstellverfahren nebst Stahlflachprodukt hierzu
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CN105377472B (zh) 2018-01-02
KR20160030505A (ko) 2016-03-18
KR102079847B1 (ko) 2020-02-20
EP3019292A1 (fr) 2016-05-18
WO2015003755A1 (fr) 2015-01-15
JP6434969B2 (ja) 2018-12-05

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