EP2976441A1 - Iron-based shape memory alloy - Google Patents

Iron-based shape memory alloy

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Publication number
EP2976441A1
EP2976441A1 EP13741745.7A EP13741745A EP2976441A1 EP 2976441 A1 EP2976441 A1 EP 2976441A1 EP 13741745 A EP13741745 A EP 13741745A EP 2976441 A1 EP2976441 A1 EP 2976441A1
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EP
European Patent Office
Prior art keywords
group
shape memory
alloy
elements
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13741745.7A
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German (de)
French (fr)
Other versions
EP2976441B1 (en
Inventor
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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Priority to EP13741745.7A priority Critical patent/EP2976441B1/en
Publication of EP2976441A1 publication Critical patent/EP2976441A1/en
Application granted granted Critical
Publication of EP2976441B1 publication Critical patent/EP2976441B1/en
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Classifications

    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • 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
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/01—Shape memory effect
    • 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

Definitions

  • the invention relates to an iron-based shape memory alloy.
  • Shape memory alloys are known from different material systems. Also iron based, i. Shape memory alloys consisting essentially of the element iron are known from the prior art. For example, European Patent Application EP 2 194 154 A1 discloses a
  • a patent application proposes to consider a certain combination of the elements of the group Mn, Si, Cr and Ni in addition to Fe in the alloy.
  • Japanese Unexamined Patent Publication JP-A 2003/268502 moreover discloses an iron-based shape memory alloy with Ni contents which is intended to form precipitates during the production process by adding titanium in the alloy.
  • this has the disadvantage that the Ni-Ti precipitates, the properties of the nickel with respect to the shape memory effect due to its binding to titanium can not be used.
  • Shape memory alloy based on an Fe-Mn-Si alloy system to which the elements Nb and C have been additionally added is known from the published patent application EP 1 348 772 A1. The ones added to these legi sys te n s
  • Precipitation types are described in the following documents, for example Va n d i u m co o st e ff e ff e d i n ds ngen in CN 1280444 C.
  • Ti-Nb-V-N carbides / nitrides and Ni 3 Ti as precipitation types are described in the Japanese documents
  • European patent application EP 2 141 251 A1 discloses vanadium nitrogen and vanadium carbon precipitates used for the shape memory alloying effect.
  • the Chinese patent application CN 101215678 B relates to a so-called Ti-Nb-C-N system.
  • An Nb-Ti-V-C system for forming precipitates is known from CN 100523263 C.
  • Russian Patent RU 2270267 Cl discloses a V-Nb-W-C precipitation system for imaging the
  • iron-based shape memory alloy systems are of interest in terms of a reduction in manufacturing costs, an increase in the activation or
  • the present invention has for its object, a
  • Iron-based shape memory alloy that provides a one-way shape memory effect that requires reduced manufacturing costs, has an increased activation temperature compared to copper and nickel base alloys, and that has a corrosion and mildew properties compared to nickel-free and chromium-containing concepts are improved.
  • the above object is achieved according to a first teaching of the present invention by a shape memory alloy consisting of an alloy with the following alloy components in weight percent:
  • group 2 of the elements Ti, Nb, W, V, Zr with the following contents
  • Alloy constituents Mn, Si, Cr, Ni and one of the elements of group 1 (N, C, B) and one of the elements of group 2 (Ti, Nb, W, V, Zr) may be the
  • Group 2 alloy components to group 1 excretion formation is particularly favorable and supports the shape memory effect.
  • 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. in the The result is also a negative effect on the reversibility of the
  • Phase transformation i. the reverse transformation of martensite into austenite. If the ratio of the sums of the alloying components formed in this way is greater than 2.0, unwanted solidifications due to the elements of the group 2 occur, which become lodged as free atoms in the microstructure and thus hinder the shape memory effect.
  • the Mangangeh old from 25 wt .-% to 32 wt .-% serves to stabilize the austenite in the structure and has particular influence on the switching temperature of
  • 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 .-% reduces the desired
  • Shape memory alloy at least 3.0 wt .-% Cr.
  • An increase in the Cr content to above 10.0 wt .-% in turn promotes ferrite formation, which, as already stated, has a negative effect on the shape memory effect.
  • 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 4.0% by weight lead to slight improvements only in connection with an increased Cr content
  • Cost savings of Ni content is limited to a maximum of 4.0 wt .-%.
  • the upper limit for all elements of group 1, ie N, C and B is at most 0.1% by weight.
  • the elements of group 2 (Ti, Nb, W, V, Zr) are present at a minimum level of 0.1% by weight, which applies to at least one element of this group.
  • the shape memory effect is positively influenced.
  • Phase transformation can be ensured by an appropriate content of one of the group 2 elements.
  • 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 1.0% by weight, respectively This results in a reduction of unwanted solidifications.
  • the Cr content in weight percent is 3.0% ⁇ Cr ⁇ 8.0%, so that a good
  • Shape memory alloy is achieved.
  • the ferrite formation acts against the
  • the difference in Cr content and Ni content is 0% ⁇ Cr-Ni ⁇ 6.0%.
  • the maximum difference in the contents of Cr and Ni is limited to 6%. 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%, i. that the nickel content is greater than the chromium content, however, may have a negative effect on the switching temperature, in which it is lowered and the
  • a further embodiment of the shape memory alloy comprises N, C and B in the following amount in percent by weight:
  • the shape memory alloy contains the elements N and / or C in amounts of at least 0.005% by weight and / or B in a content of at least 0.0001% by weight, the minimum contents can improve the formation of the precipitates.
  • the content of N and / or C is limited to a maximum of 0.1% by weight, preferably a maximum of 0.07% by weight, so that the precipitates do not become too large and can adversely affect the mechanical properties of the alloy .
  • the alloy contents of the alloying elements of the group 2 elements are limited. According to this
  • 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.
  • Shape memory alloy sulfur, phosphorus and oxygen to contents of not more than 0.1 wt .-%, preferably to a maximum of 0.05 wt .-% and particularly preferably to a maximum of 0.03 wt .-% are limited to their negative influences, for example the corrosion resistance, reduce.
  • Molybdenum, copper and cobalt can be alloyed individually or in different combinations to improve the strength properties. A corresponding influence is limited in each case to contents of not more than 0.5% by weight.
  • Aluminum and magnesium can contribute individually or in combination to improve the corrosion resistance and also cause a reduction in the density of the molten steel. 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 .-%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

The invention relates to an iron-based shape memory alloy. The problem addressed by the invention is providing an iron-based shape memory alloy which provides a one-way shape memory effect, has an increased activation temperature in comparison to copper and nickel-based alloys at reduced production costs and has improved corrosion and forming properties in comparison to nickel-free and chromium-comprising concepts. The problem is solved by an alloy having the features of patent claim 1.

Description

Eisenbasierte Formgedächtnislegierung  Iron-based shape memory alloy
Die Erfindung betrifft eine eisenbasierte Formgedächtnislegierung. The invention relates to an iron-based shape memory alloy.
Formgedächtnislegierungen sind aus unterschiedlichen Materialsystemen bekannt. Auch eisenbasierte, d.h. zu wesentlichen Teilen aus dem Element Eisen bestehende Formgedächtnislegierungen sind aus dem Stand der Technik bekannt. Beispielsweise offenbart die europäische Patentanmeldung EP 2 194 154 A1 eine Shape memory alloys are known from different material systems. Also iron based, i. Shape memory alloys consisting essentially of the element iron are known from the prior art. For example, European Patent Application EP 2 194 154 A1 discloses a
Formgedächtnislegierung, welche einen Zwei-Wege-Effekt aufweist und aus einer kostengünstigen, eisenbasierten Legierung besteht. Die genannte europäische Shape memory alloy, which has a two-way effect and consists of a low-cost, iron-based alloy. The named European
Patentanmeldung schlägt vor hierzu eine bestimmte Kombination der Elemente der Gruppe Mn, Si, Cr und Ni neben Fe in der Legierung zu berücksichtigen. A patent application proposes to consider a certain combination of the elements of the group Mn, Si, Cr and Ni in addition to Fe in the alloy.
Aus der japanischen Offenlegungsschrift JP-A 2003/268502 ist darüber hinaus eine Formgedächtnislegierung auf Eisenbasis mit Ni-Gehalten bekannt, welche durch Zugabe von Titan in der Legierung Ausscheidungen während des Herstellungsprozesses bilden soll. Allerdings ergibt sich hierbei der Nachteil, dass durch die Ni-Ti-Ausscheidungen die Eigenschaften des Nickels in Bezug auf den Formgedächtniseffekt aufgrund dessen Bindung an Titan nicht genutzt werden kann. Eine weitere eisenbasierte Japanese Unexamined Patent Publication JP-A 2003/268502 moreover discloses an iron-based shape memory alloy with Ni contents which is intended to form precipitates during the production process by adding titanium in the alloy. However, this has the disadvantage that the Ni-Ti precipitates, the properties of the nickel with respect to the shape memory effect due to its binding to titanium can not be used. Another iron-based
Formgedächtnislegierung auf Basis eines Fe-Mn-Si-Legierungssystems, welchem zusätzlich die Elemente Nb und C hinzugefügt wurden, ist aus der Offenlegungsschrift EP 1 348 772 A1 bekannt. Die in diesen Legi eru ngs sys te m e n zulegierten Shape memory alloy based on an Fe-Mn-Si alloy system to which the elements Nb and C have been additionally added is known from the published patent application EP 1 348 772 A1. The ones added to these legi sys te n s
Legierungsbestandteile Niob und Kohlenstoff unterstützen die Ausbildung von Alloy components niobium and carbon support the formation of
Ausscheidungen, welche als Keimstellen für Gamma-Epsilon-Phasentransformationen dienen, welche dann Grundlage für den Formgedächtniseffekt ist. Auch die europäische Patentanmeldung EP 1 574 587 A1 beschreibt ein Legierungssystem, welches NbC-Precipitates, which serve as nucleation sites for gamma-epsilon phase transformations, which then form the basis for the shape memory effect. European Patent Application EP 1 574 587 A1 also describes an alloy system which contains NbC-
Ausscheidungen zur Bereitstellung des Formgedächtniseffekts verwendet. In ähnlicher Weise wie die beiden Legierungsbestandteile Niob und Kohlenstoff lassen sich zwei Gruppen von Elementen bilden, welche ähnliche Funktionen aufweisen. Die eine Gruppe enthält dabei Vanadium, Niob, Titan, Wolfram und Zirkon, die andere Gruppe besteht aus Kohlenstoff, Stickstoff und Bor. Die gezielte Nutzung von unterschiedlichen Excreta used to provide the shape memory effect. Similar to the two alloying elements niobium and carbon, it is possible to form two groups of elements which have similar functions. The one group contains vanadium, niobium, titanium, tungsten and zirconium, the other group consists from carbon, nitrogen and boron. The targeted use of different
Ausscheidungstypen sind in den folgenden Dokumenten beschrieben, beispielsweise Va n a d i u m koh l ensto ff- Au ss ch e i d u ngen in der CN 1280444 C. Ti-Nb-V-N-Karbide/Nitride und Ni3Ti als Ausscheidungstypen werden in den japanischen Dokumenten Precipitation types are described in the following documents, for example Va n d i u m co o st e ff e ff e d i n ds ngen in CN 1280444 C. Ti-Nb-V-N carbides / nitrides and Ni 3 Ti as precipitation types are described in the Japanese documents
JP 2004/115864 sowie dem japanischen Patent JP 3970645 B2 offenbart. Die JP 2004/115864 and Japanese Patent JP 3970645 B2. The
europäische Patentanmeldung EP 2 141 251 AI offenbart Vanadiumstickstoff und Vanadiumkohlenstoff-Ausscheidungen, welche für den Formgedächtnislegierungseffekt verwendet werden. Die chinesische Patentanmeldung CN 101215678 B betrifft ein sogenanntes Ti-Nb-C-N-System. Ein Nb-Ti-V-C-System zur Bildung von Ausscheidungen ist aus der CN 100523263 C bekannt. Schließlich offenbart die russische Patentschrift RU 2270267 Cl ein V-Nb-W-C-Aussscheidungssystem zur Darstellung des European patent application EP 2 141 251 A1 discloses vanadium nitrogen and vanadium carbon precipitates used for the shape memory alloying effect. The Chinese patent application CN 101215678 B relates to a so-called Ti-Nb-C-N system. An Nb-Ti-V-C system for forming precipitates is known from CN 100523263 C. Finally, Russian Patent RU 2270267 Cl discloses a V-Nb-W-C precipitation system for imaging the
Formgedächtniseffekts. Die aus dem Stand der Technik bekannten Shape memory effect. Those known from the prior art
Formgedächtnislegierungssysteme auf Eisenbasis sind allerdings im Hinblick auf eine Verringerung der Herstellkosten, einer Erhöhung der Aktivierungs- bzw. However, iron-based shape memory alloy systems are of interest in terms of a reduction in manufacturing costs, an increase in the activation or
Schalttemperatur sowie ihrer Korrosions- und Umformeigenschaften Switching temperature and their corrosion and forming properties
verbesserungswürdig. improvement.
Hiervon ausgehend hat die vorliegende Erfindung sich zur Aufgabe gestellt, eine On this basis, the present invention has for its object, a
Formgedächtnislegierung auf Eisenbasis zur Verfügung zu stellen, welche einen Einweg- Formgedächtniseffekt bereitstellt, die verringerte Kosten zur Herstellung benötigt, eine erhöhte Aktivierungstemperatur im Vergleich zu Kupfer- und Nickelbasislegierungen aufweist und deren Korrosions- und U m f o r m ei ge n s ch a f te n im Vergleich zu nickelfreien und chromhaltigen Konzepten verbessert sind. Die oben genannte Aufgabe wird gemäß einer ersten Lehre der vorliegenden Erfindung gelöst durch eine Formgedächtnislegierung bestehend aus einer Legierung mit folgenden Legierungsbestandteilen in Gewichtsprozent: Iron-based shape memory alloy that provides a one-way shape memory effect that requires reduced manufacturing costs, has an increased activation temperature compared to copper and nickel base alloys, and that has a corrosion and mildew properties compared to nickel-free and chromium-containing concepts are improved. The above object is achieved according to a first teaching of the present invention by a shape memory alloy consisting of an alloy with the following alloy components in weight percent:
wobei mindestens ein Element einer Gruppe 1 von Elementen vorhanden ist, wobei die Gruppe 1 aus den Elementen N, C, B mit folgenden Gehalten wherein at least one element of a group 1 of elements is present, wherein the group 1 of the elements N, C, B having the following contents
besteht und für die Summe der Legierungsbestandteile der Gruppe 1 gilt: und mindestens ein Element einer Gruppe 2 von Elementen vorhanden ist, die Gruppe 2 aus den Elementen Ti, Nb, W, V, Zr mit folgenden Gehalten and for the sum of the alloying components of group 1: and at least one element of a group 2 of elements is present, the group 2 of the elements Ti, Nb, W, V, Zr with the following contents
besteht und für die Summe der Legierungsbestandteile der Gruppe 2 gilt: und für das Verhältnis der Summe der Legierungsbestandteile der Gruppe 1 und der Gruppe 2 jeweils in Atom-% gilt: and for the sum of the alloying components of group 2: and for the ratio of the sum of the alloy constituents of Group 1 and Group 2, both in atomic%, the following applies:
mit Rest Eisen und unvermeidbaren Verunreinigungen. with residual iron and unavoidable impurities.
Neben den Pflichtbestandteilen der Formgedächtnislegierung, der In addition to the compulsory components of the shape memory alloy, the
Legierungsbestandteile Mn, Si, Cr, Ni sowie eines der Elemente der Gruppe 1 (N, C, B) und eines der Elemente der Gruppe 2 (Ti, Nb, W, V, Zr) kann die Alloy constituents Mn, Si, Cr, Ni and one of the elements of group 1 (N, C, B) and one of the elements of group 2 (Ti, Nb, W, V, Zr) may be the
Formgedächtnislegierung zusätzlich die Elemente P, S, Mo, Cu, AI, Mg, O, Ca oder Co optional enthalten, welche bis zu den angegebenen Werten vorteilhafte Wirkungen entfalten können. Die den Formgedächtniseffekt beeinflussenden Ausscheidungen, deren Bildung durch das Verhältnis der beiden Elementgruppen, Gruppe 1 und Gruppe 2, zueinander beeinflusst wird, zeigen einen deutlichen, positiven Einfluss auf den Formgedächtniseffekt, sofern die Summe der Bestandteile der Elemente der Gruppe 2 in Atom-% der Legierung im Verhältnis zu der Summe der Legierungsbestandteile der Gruppe 1 in Atom-% im Bereich von 0,5 bis 2,0 liegt. Hierdurch wird ein gezieltes stöchiometrisches Verhältnis der Elemente der Gruppe 1 zu den Elementen der Gruppe 2 eingestellt Es wurde festgestellt, dass gerade bei diesem Verhältnis der In addition, the shape memory alloy optionally additionally contains the elements P, S, Mo, Cu, Al, Mg, O, Ca or Co, which can develop advantageous effects up to the stated values. The effects on the shape memory effect affecting precipitations, the formation of which is influenced by the relationship of the two element groups, group 1 and group 2, show a significant, positive influence on the shape memory effect, provided that the sum of the constituents of the group 2 elements in atomic% of Alloy in proportion to the sum of the alloy components of Group 1 in atomic% in the range of 0.5 to 2.0. As a result, a targeted stoichiometric ratio of the elements of group 1 to the elements of group 2 is set. It has been found that it is precisely at this ratio of
Legierungsbestandteile der Gruppe 2 zu der Gruppe 1 die Ausscheidungsbildung besonders günstig ist und den Formgedächtniseffekt unterstützt. Ist das angegebene Verhältnis beispielsweise kleiner als 0,5, können die Ausscheidungselemente in Form von N, C und/oder B nicht abgebunden werden und der Formgedächtniseffekt wird reduziert, da die Elemente der Gruppe 1 in gelöster Form im Gefüge vorliegen. Im Ergebnis wird zudem ein negativer Effekt auf die Reversibilität der Group 2 alloy components to group 1 excretion formation is particularly favorable and supports the shape memory effect. For example, if 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. in the The result is also a negative effect on the reversibility of the
Phasentransformation, d.h. der Rückumwandlung von Martensit in Austenit, beobachtet. Wird das so gebildete Verhältnis der Summen der Legierungsbestandteile größer als 2,0 stellen sich unerwünschte Verfestigungen aufgrund der Elemente der Gruppe 2 ein, die sich als freie Atome im Gefüge einlagern und damit wiederum den Formgedächtniseffekt behindern. Phase transformation, i. the reverse transformation of martensite into austenite. If the ratio of the sums of the alloying components formed in this way is greater than 2.0, unwanted solidifications due to the elements of the group 2 occur, which become lodged as free atoms in the microstructure and thus hinder the shape memory effect.
Der Mangangeh alt von 25 Gew.-% bis 32 Gew.-% dient zur Stabilisierung des Austenits im Gefüge und hat insbesondere Einfluss auf die Schalttemperatur des The Mangangeh old from 25 wt .-% to 32 wt .-% serves to stabilize the austenite in the structure and has particular influence on the switching temperature of
Formgedächtnismaterials. Unterhalb eines Mn-Gehalts von 25,0 Gew.-% wird vermehrt Ferrit gebildet, der sich nachteilig auf den Formgedächtniseffekt auswirkt. Erhöht man den Mn-Gehalt oberhalb von 32 Gew.-% verringert sich die gewünschte 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 .-% reduces the desired
Schalttemperatur zu sehr, so dass sich die Schalttemperatur und die möglichen Switching temperature too much, so that the switching temperature and the possible
Einsatztemperaturen eines entsprechenden Bauteils zu stark annähern. Use temperatures of a corresponding component too close.
Silizium dient der Sicherstellung der Reversibilität der Phasenumwandlung von Silicon serves to ensure the reversibility of the phase transformation of
Martensit in Austenit. Unterhalb von 3,0 Gew.-% bewirkt Si eine Reduzierung des Formgedächtniseffekts. Oberhalb von 8 Gew.-% kann eine Versprödung des Materials beobachtet werden. Zudem findet bei Si-Gehalten oberhalb von 8 Gew.-% die vermehrte Ausbildung der ungünstigen ferritischen Gefügebestandteile statt. Martensite in austenite. Below 3.0% by weight, Si causes a reduction in the shape memory effect. Above 8% by weight, embrittlement of the material can be observed. In addition, at Si contents above 8% by weight, the increased formation of the unfavorable ferritic constituents takes place.
Um eine ausreichende Korrosionsbeständigkeit sicherzustellen, enthält die To ensure adequate corrosion resistance, contains
Formgedächtnislegierung mindestens 3,0 Gew.-% Cr. Eine Steigerung des Cr-Gehaltes auf oberhalb von 10,0 Gew.-% begünstigt wiederum die Ferritbildung, welche sich, wie bereits ausgeführt, negativ auf den Formgedächtniseffekt auswirkt. Shape memory alloy at least 3.0 wt .-% Cr. An increase in the Cr content to above 10.0 wt .-% in turn promotes ferrite formation, which, as already stated, has a negative effect on the shape memory effect.
Nickel dient nun schließlich zur Stabilisierung des austenitischen Gefüges und verbessert zudem die Umformbarkeit des Materials. Ein Ni-Gehalt von unterhalb von 0,1 Gew.-% hat allerdings keinen signifikanten Einfluss auf die Eigenschaften des Materials. Ni-Gehalte von mehr als 4,0 Gew.-% führen jedoch lediglich in Zusammenhang mit einem erhöhten Cr-Anteil zu geringfügigen Verbesserungen, so dass zur Kosteneinsparung der Ni-Gehalt auf maximal 4,0 Gew.-% beschränkt wird. Um zu gewährleisten, dass die gewünschten Ausscheidungen erfolgen ohne sich negativ auf weitere Eigenschaften der Formgedächtnislegierung auszuwirken, ist als Obergrenze für alle Elemente der Gruppe 1, also N, C und B je maximal 0,1 Gew.-% vorgesehen. Die Elemente der Gruppe 2 (Ti, Nb, W, V, Zr) sind mit einem Mindestgehalt von 0,1 Gew.-% vorhanden, wobei dies mindestens für ein Element dieser Gruppe gilt. Mit einem Finally, nickel serves to stabilize the austenitic structure and also improves the formability of the material. However, a Ni content below 0.1% by weight has no significant influence on the properties of the material. However, Ni contents of more than 4.0% by weight lead to slight improvements only in connection with an increased Cr content Cost savings of Ni content is limited to a maximum of 4.0 wt .-%. In order to ensure that the desired precipitations take place without having a negative effect on further properties of the shape memory alloy, the upper limit for all elements of group 1, ie N, C and B, is at most 0.1% by weight. The elements of group 2 (Ti, Nb, W, V, Zr) are present at a minimum level of 0.1% by weight, which applies to at least one element of this group. With a
Gewichtsanteil von mindestens 0,1 Gew.-% für Ti, Nb, W, V und/oder Zr wird der Formgedächtniseffekt positiv beeinflusst. Insbesondere die Reversibilität der Weight fraction of at least 0.1 wt .-% for Ti, Nb, W, V and / or Zr, the shape memory effect is positively influenced. In particular, the reversibility of
Phasentransformation kann durch einen entsprechenden Gehalt eines der Gruppe 2 Elemente sichergestellt werden. Bevorzugt überschreitet jedes einzelne Element der Gruppe 2 den maximalen Gehalt von 1,5 Gew.-% nicht, besonders bevorzugt liegt der maximale Gehalt jedes einzelnen Elementes bei 1,2 Gew.-% bzw. bei 1,0 Gew.-%, da hieraus eine Reduktion der unerwünschten Verfestigungen erfolgt. Gemäß einer ersten Ausgestaltung der erfindungsgemäßen Formgedächtnislegierung beträgt der Cr-Gehalt in Gewichtsprozent 3,0 % < Cr < 8,0 %, so dass ein guter Phase transformation can be ensured by an appropriate content of one of the group 2 elements. Preferably, 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 1.0% by weight, respectively This results in a reduction of unwanted solidifications. According to a first embodiment of the shape memory alloy according to the invention, the Cr content in weight percent is 3.0% <Cr <8.0%, so that a good
Kompromiss zwischen Ferritbildung und Korrosionsbeständigkeit der Compromise between ferrite formation and corrosion resistance of
Formgedächtnislegierung erreicht wird. Die Ferritbildung wirkt gegen den Shape memory alloy is achieved. The ferrite formation acts against the
Formgedächtniseffekt, da Ferrit nicht die erwünschte Phasentransformation eingeht. Shape memory effect, since ferrite does not undergo the desired phase transformation.
Gemäß einer weiteren Ausgestaltung der Formgedächtnislegierung gilt für die Differenz des Cr-Gehalts und des Ni-Gehalts: 0 %≤ Cr-Ni≤ 6,0 %. Die maximale Differenz der Gehalte von Cr und Ni ist insofern auf 6 % beschränkt. Es hat sich gezeigt, dass ein Ansteigen der Differenz des Chrom- und Nickelgehaltes auf über 6 Gew.-% zu keinen nennenswerten Verbesserungen der mechanischen Eigenschaften, sondern vielmehr zur Versprödung des Materials führt. Ein Absinken der Differenz auf unterhalb von 0 %, d.h. dass der Nickel-Gehalt größer ist als der Chrom-Gehalt, kann sich dagegen negativ auf die Schalttemperatur auswirken, in dem diese abgesenkt wird und sich der According to another embodiment of the shape memory alloy, the difference in Cr content and Ni content is 0% ≤ Cr-Ni≤6.0%. The maximum difference in the contents of Cr and Ni is limited to 6%. 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%, i. that the nickel content is greater than the chromium content, however, may have a negative effect on the switching temperature, in which it is lowered and the
Einsatztemperatur des Werkstoffes annähert. Gemäß einer weiteren Ausgestaltung der Formgedächtnislegierung gilt für das Operating temperature of the material approaches. According to a further embodiment of the shape memory alloy applies to the
Verhältnis der Summe der Legierungsbestandteile der Gruppe 1 und Gruppe 2 jeweils in Atom-%: Ratio of the sum of the alloy components of Group 1 and Group 2, both in atomic%:
so dass einerseits der Formgedächtniseffekt vollständig gewährleistet werden kann und andererseits Verfestigungen aufgrund von freien Atomen der Gruppe 2 im Gefüge deutlich reduziert werden können. so that on the one hand the shape memory effect can be fully guaranteed and on the other hand solidifications due to free atoms of group 2 in the microstructure can be significantly reduced.
Eine weitere Ausgestaltung der Formgedächtnislegierung weist N, C und B in folgender Menge in Gewichtsprozent: A further embodiment of the shape memory alloy comprises N, C and B in the following amount in percent by weight:
auf. Enthält die Formgedächtnislegierung die Elemente N und/oder C in Gehalten von mindestens 0,005 Gew.-% und/oder B in einem Gehalt von mindestens 0,0001 Gew.-%, kann durch die Mindestgehalte die Bildung der Ausscheidungen verbessert werden. Durch die Obergrenze von 0,1 Gew.-%, vorzugsweise von 0,05 Gew.-%, besonders bevorzugt 0,01 Gew.-% von B, wird gewährleistet, dass die Oxidationsbeständigkeit der Formgedächtnislegierung nicht zu stark herabsinkt. Gleichzeitig wird der Gehalt von N und/oder C auf maximal 0,1 Gew.-%, vorzugsweise maximal 0,07 Gew.-% beschränkt, so dass die Ausscheidungen nicht zu groß werden und diese sich negativ auf mechanischen Eigenschaften der Legierung auswirken können. Bei einer weiteren Ausgestaltung der Legierung werden die Legierungsgehalte der Legierungsbestandteile der Elemente der Gruppe 2 beschränkt. Gemäß dieser on. If the shape memory alloy contains the elements N and / or C in amounts of at least 0.005% by weight and / or B in a content of at least 0.0001% by weight, the minimum contents can improve the formation of the precipitates. The upper limit of 0.1% by weight, preferably 0.05% by weight, particularly preferably 0.01% by weight of B, ensures that the oxidation resistance of the shape memory alloy does not drop too much. At the same time, the content of N and / or C is limited to a maximum of 0.1% by weight, preferably a maximum of 0.07% by weight, so that the precipitates do not become too large and can adversely affect the mechanical properties of the alloy , In a further embodiment of the alloy, the alloy contents of the alloying elements of the group 2 elements are limited. According to this
Ausführungsform betragen die Legierungsbestandteile der Elemente der Gruppe 2 Embodiment are the alloying components of Group 2 elements
wobei bevorzugt die Obergrenze auf 1,0 Gew.-% für jedes einzelne Element der Gruppe 2 herabgesenkt wird. Die Entstehung von Verfestigungen wird hierdurch weiter verringert, so dass die Formgedächtnislegierung ein gutes Umformverhalten aufweist. Schließlich sollten gemäß einer weiteren Ausführungsform der 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. Finally, according to another embodiment of the
Formgedächtnislegierung Schwefel, Phosphor und Sauerstoff auf Gehalte von maximal 0,1 Gew.-%, bevorzugt auf maximal 0,05 Gew.-% und besonders bevorzugt auf maximal 0,03 Gew.-% beschränkt werden, um deren negative Einflüsse, beispielsweise auf die Korrosionsbeständigkeit, zu verringern. Molybdän, Kupfer und Kobalt können einzeln oder in unterschiedlicher Kombination zur Verbesserung der Festigkeitseigenschaften zulegiert werden. Ein entsprechender Einfluss ist jeweils auf Gehalte von maximal 0,5 Gew.-% beschränkt. Aluminium und Magnesium können einzeln oder in Kombination zur Verbesserung der Korrosionsbeständigkeit beitragen und bewirken nebenbei auch eine Dichtereduzierung der Stahlschmelze. Ihr Gehalt ist auf maximal 5 Gew.-%, vorzugsweise auf maximal 2,0 Gew.-%, besonders bevorzugt auf maximal 1,0 Gew.-% beschränkt.  Shape memory alloy sulfur, phosphorus and oxygen to contents of not more than 0.1 wt .-%, preferably to a maximum of 0.05 wt .-% and particularly preferably to a maximum of 0.03 wt .-% are limited to their negative influences, for example the corrosion resistance, reduce. Molybdenum, copper and cobalt can be alloyed individually or in different combinations to improve the strength properties. A corresponding influence is limited in each case to contents of not more than 0.5% by weight. Aluminum and magnesium can contribute individually or in combination to improve the corrosion resistance and also cause a reduction in the density of the molten steel. 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 .-%.
Gemäß einer weiteren Ausgestaltung kann Kalzium zur Abbindung von vorhandenem Schwefel zulegiert werden, um eine unerwünschte Bindung von Schwefel mit Mangan zu MnS zu vermeiden. Um die Korrosionsbeständigkeit nicht zu vermindern und zu große Verunreinigungen durch Ca zu vermeiden, wird der Gehalt: von Ca auf maximal 0,015 Gew.-%, vorzugsweise auf maximal 0,01 Gew.-% beschränkt. In another embodiment, calcium may be added to set sulfur present to avoid undesirable sulfur-manganese to MnS bonding. In order not to reduce the corrosion resistance and too large To avoid contamination by Ca, the content of Ca is limited to a maximum of 0.015 wt .-%, preferably to a maximum of 0.01 wt .-%.
Tabelle 1 zeigt nun verschiedene Ausführungsbeispiele der Erfindung und Table 1 now shows various embodiments of the invention and
Vergleichsbeispiele. An den Ausführungsbeispielen Nr. 1 bis 20 der Erfindung konnte bei ausreichend hoher Schalttemperatur ein ausreichender Formgedächtniseffekt an Proben nachgewiesen werden. Die Vergleichsbeispiele wiesen einerseits Probleme bezüglich Verfestigungen auf, so dass der Formgedächtniseffekt reduziert war Comparative examples. In embodiments Nos. 1 to 20 of the invention could be detected at sufficiently high switching temperature sufficient shape memory effect on samples. On the one hand, the comparative examples had problems with solidification, so that the shape memory effect was reduced
(Vergleichsbeispiel 1). Die beiden anderen Vergleichsbeispiele 2 und 3 zeigten einen deutlich schwächeren Formgedächtniseffekt als die Ausführungsbeispiele der Erfindung. Die erfindungsgemäße eisenbasierte Formgedächtnislegierung lässt sich als (Comparative Example 1). The other two Comparative Examples 2 and 3 showed a significantly weaker shape memory effect than the embodiments of the invention. The iron-based shape memory alloy according to the invention can be described as
Flachprodukt, beispielsweise in Form eines Bandes und/oder Bleches als Langprodukt, beispielsweise in Form eines Drahtes, als Bramme, Knüppel oder dergleichen erzeugen. Produce flat product, for example in the form of a strip and / or sheet as a long product, for example in the form of a wire, as a slab, billets or the like.

Claims

Patentansprüche Patent claims
1. Formgedächtnislegierung bestehend aus einer Legierung mit folgenden 1. Shape memory alloy consisting of an alloy with the following
Legierungsbestandteilen in Gewichtsprozent: Alloy components in percent by weight:
wobei mindestens ein Element einer Gruppe 1 von Elementen vorhanden ist, wobei die Gruppe 1 aus den Elementen N, C, B mit folgenden Gehalten where at least one element of a group 1 of elements is present, where group 1 consists of the elements N, C, B with the following contents
besteht und für die Summe der Legierungsbestandteile der Gruppe 1 gilt: und mindestens ein Element einer Gruppe 2 von Elementen vorhanden ist, die Gruppe 2 aus den Elementen Ti, Nb, W, V, Zr mit folgenden Gehalten and the following applies to the sum of the alloy components of group 1: and at least one element of a group 2 of elements is present, the group 2 consisting of the elements Ti, Nb, W, V, Zr with the following contents
besteht und für die Summe der Legierungsbestandteile der Gruppe 2 gilt: und für das Verhältnis der Summe der Legierungsbestandteile der Gruppe 1 und der Gruppe 2, jeweils in Atom-% gilt: and the following applies to the sum of the alloy components of group 2: and for the ratio of the sum of the alloy components of Group 1 and Group 2, each in atomic percent:
mit Rest Eisen und unvermeidbare Verunreinigungen. with residual iron and unavoidable impurities.
2. Legierung nach Anspruch 1, 2. Alloy according to claim 1,
dadurch gekennzeichnet, dass characterized in that
der Cr-Gehalt in Gewichtsprozent 3,0 %≤ Cr≤ 8,0 % beträgt. the Cr content in percent by weight is 3.0%≤Cr≤8.0%.
3. Legierung nach Anspruch 1 oder 2, 3. Alloy according to claim 1 or 2,
dadurch gekennzeichnet, dass characterized in that
für die Differenz des Cr-Gehalts und des Ni-Gehalts gilt: The following applies to the difference between the Cr content and the Ni content:
4. Legierung nach einem der Ansprüche 1 bis 3, 4. Alloy according to one of claims 1 to 3,
dadurch gekennzeichnet, dass characterized in that
für das Verhältnis der Summe der Legierungsbestandteile der Gruppe 1 und Gruppe 2, jeweils in Atom-% gilt applies to the ratio of the sum of the alloy components of Group 1 and Group 2, each in atomic percent
5. Legierung nach einem der Ansprüche 1 bis 4, 5. Alloy according to one of claims 1 to 4,
dadurch gekennzeichnet, dass characterized in that
die Legierung zusätzlich N, C und/oder B in folgender Mindestmenge Gewichtsprozent enthält: the alloy additionally contains N, C and/or B in the following minimum amount by weight:
6. Legierung nach einem der Ansprüche 1 bis 5, 6. Alloy according to one of claims 1 to 5,
dadurch gekennzeichnet, dass characterized in that
die Legierungsbestandteile der Elemente der Gruppe 2 the alloying components of the elements of group 2
betragen. be.
7. Legierung nach einem der Ansprüche 1 bis 6, 7. Alloy according to one of claims 1 to 6,
dadurch gekennzeichnet, dass characterized in that
die Legierung einen Ca-Gehalt in Gewichtsprozent von maximal 0,015% aufweist. the alloy has a Ca content in percent by weight of a maximum of 0.015%.
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