EP2619343B1 - A high strength iron-based alloy moulded body being pasticially deformable and having mechanical energy absorption capability at room temperature - Google Patents
A high strength iron-based alloy moulded body being pasticially deformable and having mechanical energy absorption capability at room temperature Download PDFInfo
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- EP2619343B1 EP2619343B1 EP11779110.3A EP11779110A EP2619343B1 EP 2619343 B1 EP2619343 B1 EP 2619343B1 EP 11779110 A EP11779110 A EP 11779110A EP 2619343 B1 EP2619343 B1 EP 2619343B1
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- 229910045601 alloy Inorganic materials 0.000 title claims description 20
- 239000000956 alloy Substances 0.000 title claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 19
- 238000010521 absorption reaction Methods 0.000 title 1
- 229910052742 iron Inorganic materials 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 18
- 229910000734 martensite Inorganic materials 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000005300 metallic glass Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- VHRSUDSXCMQTMA-PJHHCJLFSA-N 6alpha-methylprednisolone Chemical compound C([C@@]12C)=CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2[C@@H](O)C[C@]2(C)[C@@](O)(C(=O)CO)CC[C@H]21 VHRSUDSXCMQTMA-PJHHCJLFSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017870 Cu—Ni—Al Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- UAIXRPCCYXNJMQ-RZIPZOSSSA-N buprenorphine hydrochlorie Chemical compound [Cl-].C([C@]12[C@H]3OC=4C(O)=CC=C(C2=4)C[C@@H]2[C@]11CC[C@]3([C@H](C1)[C@](C)(O)C(C)(C)C)OC)C[NH+]2CC1CC1 UAIXRPCCYXNJMQ-RZIPZOSSSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
Definitions
- the invention relates to the field of materials science and relates to high-strength, at room temperature plastically deformable and energy absorbing mechanical body of iron alloys.
- Such moldings can be used as cutting, punching and splitting tools, in the aerospace industry, aerospace, the automotive industry and generally in mechanical engineering, as well as for mining tools, e.g. Dredger teeth, if particularly high demands on the mechanical loadability, the surface stress (wear) and in particular on the ability to absorb mechanical energy are provided.
- composition ranges of multicomponent alloys in which such metallic glasses can also be produced by casting in solid form for example with dimensions> 1 mm.
- Such alloys are, for example, Pd-Cu-Si, Pd 40 Ni 40 P 20 , Zr-Cu-Ni-Al, La-Al-Ni-Cu ( T. Masumoto: Mater. Sci. Closely. A179 / 180 (1994) 8-16 ; WL Johnson: Mater. Sci. Forum Vol. 225-227, pp. 35-50, Transtec Publications 1996, Switzerl and).
- metallic glass moldings having a particularly high glass-forming ability (in dimensions up to 12 mm castable with vitreous structure) in the compositions Fe 48 Cr 15 Mo 14 Er 2 C 15 B 6 and (Fe 44.3 Cr 5 Co 5 Mo 12, 8 Mn 11.2 C 15.8 B 5.9 ) 98.5 Y 1.5 ( V. Ponnambalam, et al .: J. Mater. Res. 19, 5, (2004) 1320-1323 ; ZP Lu, et al .: Phys. Rev. Let. 92, 24, (2004) 245503-1 - 245503-4 ).
- the invention has for its object to provide high-strength, plastically deformable at room temperature and mechanical energy absorbing moldings of iron alloys, which have macroscopic plasticity and strain hardening compared to moldings of metallic glasses, without thereby other properties such as breaking strength or corrosion behavior are significantly impaired, and compared to moldings of amorphous, semi-crystalline or crystalline metallic alloys have a significant increase in strength while having a comparatively high ductility.
- ferritic and / or bainitic phases are present.
- the volume fraction of the martensitic phase is 50 to 70%.
- the volume fraction of the austenitic phase is 5 to ⁇ 30%, more preferably 10 to 20%.
- the volume fraction of the boridic and / or carbidic and / or nitridic and / or oxidic phases is 5 to 15% by volume.
- the alloying elements are mixed, melted and then poured into a mold, wherein the cooling of the alloy in the mold at a rate of> 20 K / s is realized and the cooling rate is chosen depending on the phase composition to be set, with higher cooling rates promote the formation of the martensitic phase.
- the melting and casting is carried out with the exclusion of oxygen
- molds are used to realize the cooling rates with a small thickness of the molded article to be produced, wherein molds having a thickness of the molded article of 1 to 30 mm, more preferably from 10 to 20 mm or from 12 to 20 mm used.
- the shaped bodies according to the invention have improved properties compared to shaped bodies made of metallic glasses or of metallic alloys, which were not to be expected due to the sometimes small changes in the composition and / or in the production process.
- compositions according to the invention and their preparation according to the invention which have the almost infinite number of possible compositions of metallic glasses or crystalline alloys having these advantageous properties. Alloy compositions also close to the compositions according to the invention show markedly poorer properties.
- the homogeneous microstructure has a relatively high proportion by volume (40 to 80% by volume) of martensitic (tetragonal, body-centered) phase. This high volume fraction of martensitic phase leads to the known properties of iron alloys in general.
- the shaped bodies according to the invention are produced according to the invention by mixing the alloy components and then melting.
- the alloy components and the melting vessel should contain as few additives and impurities as possible.
- the melt After melting, the melt is poured into a mold.
- the cooling of the melt in the mold must be realized according to the invention with a cooling rate of> 20 K / s, advantageously between 20 and 200 K / s, so that the microstructure according to the invention can be achieved.
- the choice of higher cooling rates promotes the formation of the martensitic phase.
- a protective gas atmosphere for example consisting of argon, is used during melting and casting of the shaped body.
- the cooling rate of the molten alloy can be controlled by the choice of the size of the mold.
- the width and length of the casting mold and also of the shaped body to be produced play only a minor role. Decisive for the control of the cooling rate is above all the thickness of the shaped body to be produced. In this case, the smaller the thickness of the shaped body to be produced, the greater the cooling rate. Therefore, the cooling rate can also be controlled with the dimensions of the corresponding mold.
- Advantageous thicknesses of the shaped bodies to be produced are in the range of 1 to 30 mm, advantageously in the range of 10 to 20 mm or 12 to 20 mm. Accordingly, molds having such dimensions can be selected.
- such molds made of copper, so-called copper molds.
- Typical dimensions of such molds are 70 x 120 x 14 mm 3 .
- the melting of the alloy constituents can furthermore advantageously be carried out in an induction furnace, Al 2 O 3 also advantageously being used as the crucible material.
- the alloy constituents used should advantageously be as free as possible of impurities and additives, and as a result of the melting and casting of the alloy, as few impurities and additives as possible should also be introduced into the melt and thus into the shaped body.
- the alloy components are advantageously heated to temperatures of 1400-1900 ° C and poured at temperatures between 1400 and 1500 ° C in the mold.
- the detection of the austenitic, the martensitic, the boridic and / or carbidic and / or nitridic and / or oxidic phases and the determination of the size and the volume fraction of these phases can be carried out by X-ray diffraction, scanning electron microscopy or transmission electron microscopy.
- the cuboidal shaped body obtained consists of a high-strength, microcrystalline, martensitic (trz) phase, a microcrystalline austenitic (kfz) phase, as well as nano- and microcrystalline carbidic phases of the type MC and M 2 C.
- the volume fraction of the martensitic phase is 75%
- the Volume fraction of the austenitic phase is 15%
- the volume fraction of the carbidic phases is 10%.
- the molded article was tested in compression and a technical crushing of 13.6% (true crushing of 15.3%) at a technical breaking strength of 5060 MPa (true breaking strength of 4260 MPa) been determined.
- the elastic compression at the 0.2% proof stress is 1.3% with a strength of 2480 MPa (techn.) Or 2010 MPa (true).
- the modulus of elasticity is 212 GPa.
- a molded body has been produced, which has a good resistance to deformation and a significant increase in strength coupled with good ductility.
- the resulting rectangular shaped body consists of a high-strength, microcrystalline, martensitic (trz) phase, a microcrystalline austenitic (kfz) phase, as well as nano- and microcrystalline carbidic phases of the type MC and M 2 C.
- the volume fraction of the martensitic phase is 70%
- the Volume fraction of the austenitic phase is 18%
- the volume fraction of the carbidic phases is 12%.
- the molding was examined by compression and a technical crushing of 16.3% (true crushing fracture of 18.1%) at a technical breaking strength of 4350 MPa (true breaking strength of 3720 MPa) has been determined.
- the elastic compression at the 0.2% proof stress is 1.2% at a strength of 2140 MPa (techn.) Or 1860 MPa (true).
- the modulus of elasticity is 217 GPa.
- a molded body has been produced, which has a good resistance to deformation and a significant increase in strength coupled with good ductility.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Powder Metallurgy (AREA)
Description
Die Erfindung bezieht sich auf das Gebiet der Materialwissenschaften und betrifft hochfeste, bei Raumtemperatur plastisch verformbare und mechanische Energie absorbierende Formkörper aus Eisenlegierungen. Derartige Formkörper sind einsetzbar als Schneid-, Stanz- und Spaltwerkzeuge, in der Flugzeugindustrie, der Raumfahrt, der Fahrzeugindustrie und allgemein im Maschinen- und Gerätebau, sowie für Gewinnungswerkzeuge, z.B. Baggerzähne, wenn besonders hohe Anforderungen an die mechanische Belastbarkeit, die Oberflächenbeanspruchung (Verschleiß) und insbesondere an das Vermögen mechanische Energie zu absorbieren gestellt werden.The invention relates to the field of materials science and relates to high-strength, at room temperature plastically deformable and energy absorbing mechanical body of iron alloys. Such moldings can be used as cutting, punching and splitting tools, in the aerospace industry, aerospace, the automotive industry and generally in mechanical engineering, as well as for mining tools, e.g. Dredger teeth, if particularly high demands on the mechanical loadability, the surface stress (wear) and in particular on the ability to absorb mechanical energy are provided.
Bekannt ist, dass bestimmte mehrkomponentige metallische Werkstoffe, z.B. FeCuNbSiB (
Bekannt sind auch bestimmte Zusammensetzungsbereiche mehrkomponentiger Legierungen, in denen solche metallischen-Gläser auch in massiver Form, z.B. mit Abmessungen > 1 mm, durch Gießverfahren hergestellt werden können. Solche Legierungen sind z.B. Pd-Cu-Si, Pd40Ni40P20, Zr-Cu-Ni-Al, La-Al-Ni-Cu (
Weiterhin bekannt sind metallische Glas-Formkörper mit besonders hoher Glasbildungsfähigkeit (in Dimensionen bis 12 mm gießbar mit glasartiger Struktur) in den Zusammensetzungen Fe48Cr15Mo14Er2C15B6 und (Fe44,3Cr5Co5Mo12,8Mn11,2C15,8B5,9)98,5Y1,5 (
Ebenfalls bekannt sind hochfeste kristallinen Fe-Legierungen mit metastabilen Phasenanteilen auf Grund hoher Erstarrungsraten in den Zusammensetzungen (Fe84.4Cr5.2Mo5.2Ga5.2)100-xCx mit x = 9 und 17, Fe84.3Cr4.3Mo4.6V2.2C4.6 und Fe88.9Cr4.3V2.2C4.6, (
Der Erfindung liegt die Aufgabe zugrunde, hochfeste, bei Raumtemperatur plastisch verformbare und mechanische Energie absorbierende Formkörper aus Eisenlegierungen anzugeben, die gegenüber Formkörpern aus metallischen Gläsern makroskopische Plastizität sowie Verformungsverfestigung aufweisen, ohne dass dadurch andere Eigenschaften, wie Bruchfestigkeit oder das Korrosionsverhalten wesentlich beeinträchtigt werden, und gegenüber Formkörpern aus amorphen, teilkristallinen oder kristallinen metallischen Legierungen eine signifikante Festigkeitssteigerung bei gleichzeitiger vergleichsweise hoher Duktilität aufweisen.The invention has for its object to provide high-strength, plastically deformable at room temperature and mechanical energy absorbing moldings of iron alloys, which have macroscopic plasticity and strain hardening compared to moldings of metallic glasses, without thereby other properties such as breaking strength or corrosion behavior are significantly impaired, and compared to moldings of amorphous, semi-crystalline or crystalline metallic alloys have a significant increase in strength while having a comparatively high ductility.
Diese Aufgabe wird mit der in den Patentansprüchen angegebenen Erfindung gelöst. Vorteilhafte Ausgestaltungen sind Gegenstand der Unteransprüche.This object is achieved with the invention specified in the claims. Advantageous embodiments are the subject of the dependent claims.
Die erfindungsgemäßen hochfesten, bei Raumtemperatur plastisch verformbaren und mechanische Energie absorbierenden Formkörper aus Eisenlegierungen, bei denen der Werkstoff der Formkörper eine Zusammensetzung
FeaCrc1Moc2Vc3CbYe
mit a = 70-90, b = 3-6, c1 = 3-5, c2 = 3-5, c3 = 1-3, und e = 0,01-0,09 (in Atom-%) oder der Zusammensetzung
FeaCrc1Moc2Vc3CbSidYe
mit a = 70-90, b = 3-6, c1 = 3-5, c2 = 3-5, c3 = 1-3, d = 1-3 und e = 0,01-0,09 (in Atom-%)
aufweist. und Verunreinigungen enthalten können,
weisen ein Gefüge mit einer homogenen Mikrostruktur auf, die
- 40 bis 80 Vol.-% martensitische (trz - tetragonal raumzentriert) Phase
und - 5 bis 35 Vol.- % austenitische (kfz - kubisch flächenzentriert) Phase
und - den Rest an boridischen und/oder carbidischen und/oder nitridischen und/oder oxidischen Phasen
enthält, wobei der Volumenanteil an austenitischer Phase ansteigt, je geringer der Anteil an E2 ist.
Fe a Cr c1 Mo c2 V c3 C b Y e
with a = 70-90, b = 3-6, c1 = 3-5, c2 = 3-5, c3 = 1-3, and e = 0.01-0.09 (in atomic%) or composition
Fe a Cr c1 Mo c2 V c3 C b Si d Y e
with a = 70-90, b = 3-6, c1 = 3-5, c2 = 3-5, c3 = 1-3, d = 1-3 and e = 0.01-0.09 (in atomic %)
having. and may contain impurities,
have a microstructure with a homogeneous microstructure, the
- 40 to 80 vol .-% martensitic (trt - tetragonal body - centered) phase
and - 5 to 35% by volume austenitic (kfz - cubic face centered) phase
and - the remainder of boridic and / or carbidic and / or nitridic and / or oxidic phases
contains, wherein the volume fraction of austenitic phase increases, the lower the proportion of E2.
Vorteilhafterweise sind ferritische und/oder bainitische Phasen vorhanden.Advantageously, ferritic and / or bainitic phases are present.
Weiterhin vorteilhafterweise beträgt der Volumenanteil der martensitischen Phase 50 bis 70 %.Further advantageously, the volume fraction of the martensitic phase is 50 to 70%.
Ebenfalls vorteilhafterweise beträgt der Volumenanteil der austenitischen Phase 5 bis < 30 %, noch vorteilhafterweise 10 bis 20 %.Also advantageously, the volume fraction of the austenitic phase is 5 to <30%, more preferably 10 to 20%.
Und auch vorteilhafterweise beträgt der Volumenanteil der boridischen und/oder carbidischen und/oder nitridischen und/oder oxidischen Phasen 5 - 15 Vol.-%.And also advantageously, the volume fraction of the boridic and / or carbidic and / or nitridic and / or oxidic phases is 5 to 15% by volume.
Bei dem erfindungsgemäßen Verfahren zur Herstellung von hochfesten, bei Raumtemperatur plastisch verformbaren und mechanische Energie absorbierenden Formkörpern aus Eisenlegierungen werden die Legierungselemente gemischt, aufgeschmolzen und anschließend in eine Gussform gegossen, wobei die Abkühlung der Legierung in der Gussform mit einer Geschwindigkeit von > 20 K/s realisiert wird und die Abkühlungsgeschwindigkeit in Abhängigkeit von der einzustellenden Phasenzusammensetzung gewählt wird, wobei höhere Abkühlgeschwindigkeiten die Bildung der martensitischen Phase fördern.In the inventive method for producing high-strength, at room temperature plastically deformable and mechanical energy-absorbing moldings made of iron alloys, the alloying elements are mixed, melted and then poured into a mold, wherein the cooling of the alloy in the mold at a rate of> 20 K / s is realized and the cooling rate is chosen depending on the phase composition to be set, with higher cooling rates promote the formation of the martensitic phase.
Vorteilhafterweise wird zur Realisierung von boridischen und/oder carbidischen und/oder nitridischen Phasen im Gefüge das Aufschmelzen und Formgießen unter Ausschluss von Sauerstoff durchgeführt wird,Advantageously, in order to realize boridic and / or carbidic and / or nitridic phases in the microstructure, the melting and casting is carried out with the exclusion of oxygen,
Ebenfalls werden zur Realisierung der Abkühlgeschwindigkeiten Gussformen mit einer geringen Dicke des herzustellenden Formkörpers eingesetzt, wobei Gussformen mit einer Dicke des herzustellenden Formkörpers von 1 bis 30 mm, noch vorteilhafterweise von 10 bis 20 mm oder von 12 bis 20 mm, eingesetzt.Also molds are used to realize the cooling rates with a small thickness of the molded article to be produced, wherein molds having a thickness of the molded article of 1 to 30 mm, more preferably from 10 to 20 mm or from 12 to 20 mm used.
Die erfindungsgemäßen Formkörper weisen derartig verbesserte Eigenschaften gegenüber Formkörpern aus metallischen Gläsern oder aus metallischen Legierungen auf, die aufgrund der zum Teil geringen Änderungen in der Zusammensetzung und/oder im Herstellungsverfahren nicht zu erwarten gewesen sind.The shaped bodies according to the invention have improved properties compared to shaped bodies made of metallic glasses or of metallic alloys, which were not to be expected due to the sometimes small changes in the composition and / or in the production process.
Es war überraschend, dass gerade die erfindungsgemäßen Zusammensetzungen und ihre erfindungsgemäße Herstellung aus der nahezu unendlichen Anzahl an möglichen Zusammensetzungen von metallischen Gläsern oder kristallinen Legierungen diese vorteilhaften Eigenschaften aufweisen. Legierungszusammensetzungen auch nahe bei den erfindungsgemäßen Zusammensetzungen zeigen deutlich schlechtere Eigenschaften.It was surprising that it is precisely the compositions according to the invention and their preparation according to the invention which have the almost infinite number of possible compositions of metallic glasses or crystalline alloys having these advantageous properties. Alloy compositions also close to the compositions according to the invention show markedly poorer properties.
Hervorzuheben sind bei den verbesserten Eigenschaften der erfindungsgemäßen Formkörper insbesondere, dass sie bei Raumtemperatur in unerwarteter Art und Weise plastisch verformbar sind und gleichzeitig deutlich mehr mechanische Energie absorbieren können. Dies führt zusammen zu einer signifikanten Festigkeitssteigerung der Formkörper.It should be emphasized in the improved properties of the shaped bodies according to the invention in particular that they occur at room temperature in an unexpected manner and Are plastically deformable and at the same time can absorb significantly more mechanical energy. This together leads to a significant increase in strength of the moldings.
Diese deutlich verbesserten Eigenschaften sind neben der konkreten Legierungszusammensetzung vor allem durch Einstellung der erfindungsgemäßen Gefügestruktur erreicht worden. Die homogene Mikrostruktur weist dabei erfindungsgemäß einen relativ hohen Volumenanteil (40 bis 80 Vol.-%) an martensitischer (trz - tetragonal raumzentriert) Phase auf. Dieser hohe Volumenanteil an martensitischer Phase führt zu den bekannten Eigenschaften von Eisenlegierungen allgemein.These significantly improved properties have been achieved in addition to the concrete alloy composition, especially by adjusting the microstructure according to the invention. In accordance with the invention, the homogeneous microstructure has a relatively high proportion by volume (40 to 80% by volume) of martensitic (tetragonal, body-centered) phase. This high volume fraction of martensitic phase leads to the known properties of iron alloys in general.
Durch den erfindungsgemäßen Volumenanteil (5 bis 35 Vol.- %) an austenitischer (kfz - kubisch flächenzentriert) Phase, und durch die weiterhin vorhandenen boridischen und/oder carbidischen und/oder nitridischen und/oder oxidischen Phasen werden dann deutlich verbesserten Eigenschaften erreicht.By virtue of the volume fraction (5 to 35% by volume) according to the invention of austenitic (kfz-cubic face-centered) phase, and by the boridic and / or carbidic and / or nitridic and / or oxidic phases which are still present, significantly improved properties are then achieved.
Dabei ist zu berücksichtigen, dass im Falle einer Legierungszusammensetzung mit einem geringen Anteil an einem oder mehreren Elementen der Gruppe Cr, V, Mo, W, Ti, Ta, Zr, Hf und Nb der Volumenanteil an austenitischer Phase ansteigen muss. Das ist dadurch bedingt, da diese Elemente der austenitischen Phase Kohlenstoff entziehen und carbidische Phasen bilden.It should be noted that in the case of an alloy composition with a small proportion of one or more elements of the group Cr, V, Mo, W, Ti, Ta, Zr, Hf and Nb, the volume fraction of austenitic phase must increase. This is because these elements withdraw carbon from the austenitic phase and form carbide phases.
Ist jedoch der Kohlenstoffgehalt in der austenitischen Phase entsprechend hoch und wird dieser nicht durch die carbidbildenden Elemente entzogen, so führt dies zu einer Austenitstabilisierung durch den Kohlenstoff.However, if the carbon content in the austenitic phase is correspondingly high and is not removed by the carbide-forming elements, this results in austenite stabilization by the carbon.
Die erfindungsgemäßen Formkörper werden erfindungsgemäß hergestellt durch Mischen der Legierungsbestandteile und anschließendem Aufschmelzen. Dabei sollten durch die Legierungsbestandteile und das Schmelzgefäß möglichst wenige Zusätze und Verunreinigungen eingebracht werden.The shaped bodies according to the invention are produced according to the invention by mixing the alloy components and then melting. The alloy components and the melting vessel should contain as few additives and impurities as possible.
Nach dem Aufschmelzen wird die Schmelze in eine Form gegossen. Die Abkühlung der Schmelze in der Form muss dabei erfindungsgemäß mit einer Abkühlgeschwindigkeit von > 20 K/s, vorteilhafterweise zwischen 20 und 200 K/s realisiert werden, damit die erfindungsgemäße Gefügestruktur erreicht werden kann. Dabei wird durch die Wahl von höheren Abkühlgeschwindigkeiten die Bildung der martensitischen Phase gefördert.After melting, the melt is poured into a mold. The cooling of the melt in the mold must be realized according to the invention with a cooling rate of> 20 K / s, advantageously between 20 and 200 K / s, so that the microstructure according to the invention can be achieved. The choice of higher cooling rates promotes the formation of the martensitic phase.
Im Fall, dass im Gefüge keine oxidischen Phasen eingestellt werden sollen, ist es erforderlich, dass das Aufschmelzen und Formgießen der Legierung zu Formkörpern unter Ausschluss von Sauerstoff durchgeführt wird. Im diesem Falle wird bei Erschmelzen und Gießen des Formkörpers eine Schutzgasatmosphäre, beispielsweise bestehend aus Argon, eingesetzt.In the event that no oxide phases are to be set in the structure, it is necessary that the melting and casting of the alloy is carried out to form bodies in the absence of oxygen. In this case, a protective gas atmosphere, for example consisting of argon, is used during melting and casting of the shaped body.
Weiterhin kann vorteilhafterweise die Abkühlungsgeschwindigkeit der geschmolzenen Legierung durch die Wahl der Abmessung der Gussform gesteuert werden. Dabei spielen die Breite und Länge der Gussform und auch des herzustellenden Formkörpers nur eine untergeordnete Rolle. Entscheidend für die Steuerung der Abkühlgeschwindigkeit ist vor allem die Dicke des herzustellenden Formkörpers. Dabei gilt, je geringer die Dicke des herzustellenden Formkörpers ist, umso größer ist die Abkühlgeschwindigkeit. Daher kann auch mit den Abmessungen der entsprechenden Gussform die Abkühlgeschwindigkeit gesteuert werden. Vorteilhafte Dicken der herzustellenden Formkörper liegen im Bereich von 1 bis 30 mm, vorteilhafterweise im Bereich von 10 bis 20 mm oder 12 bis 20 mm. Dementsprechend können Gussformen ausgewählt werden, die solche Abmessungen aufweisen.Furthermore, advantageously, the cooling rate of the molten alloy can be controlled by the choice of the size of the mold. The width and length of the casting mold and also of the shaped body to be produced play only a minor role. Decisive for the control of the cooling rate is above all the thickness of the shaped body to be produced. In this case, the smaller the thickness of the shaped body to be produced, the greater the cooling rate. Therefore, the cooling rate can also be controlled with the dimensions of the corresponding mold. Advantageous thicknesses of the shaped bodies to be produced are in the range of 1 to 30 mm, advantageously in the range of 10 to 20 mm or 12 to 20 mm. Accordingly, molds having such dimensions can be selected.
Vorteilhafterweise bestehen solche Gussformen aus Kupfer, sogenannte Kupferkokillen. Typische Abmessungen derartiger Kokillen sind 70 x 120 x 14 mm3.Advantageously, such molds made of copper, so-called copper molds. Typical dimensions of such molds are 70 x 120 x 14 mm 3 .
Das Aufschmelzen der Legierungsbestandteile kann weiterhin vorteilhafterweise in einem Induktionsofen durchgeführt werden, wobei als Tiegelmaterial auch vorteilhafterweise Al2O3 eingesetzt wird.The melting of the alloy constituents can furthermore advantageously be carried out in an induction furnace, Al 2 O 3 also advantageously being used as the crucible material.
Die eingesetzten Legierungsbestandteile sollen vorteilhafterweise möglichst frei von Verunreinigungen und Zusätzen sein und durch das Aufschmelzen und Gießen der Legierung sollen ebenfalls möglichst wenig Verunreinigungen und Zusätze in die Schmelze und damit in den Formkörper eingebracht werden.The alloy constituents used should advantageously be as free as possible of impurities and additives, and as a result of the melting and casting of the alloy, as few impurities and additives as possible should also be introduced into the melt and thus into the shaped body.
Die Legierungsbestandteile werden vorteilhafterweise bis auf Temperaturen von 1400 - 1900 °C erwärmt und bei Temperaturen zwischen 1400 und 1500 °C in die Form gegossen.The alloy components are advantageously heated to temperatures of 1400-1900 ° C and poured at temperatures between 1400 and 1500 ° C in the mold.
Weiterhin ist es vorteilhaft, dass durch das erfindungsgemäße Verfahren anschließende Wärmebehandlungen überflüssig werden, da der erfindungsgemäße Formkörper seine besonderen mechanischen Eigenschaften bereits im Gusszustand aufweist.Furthermore, it is advantageous that subsequent heat treatments become superfluous as a result of the method according to the invention, since the shaped body according to the invention has its particular mechanical properties already in the cast state.
Der Nachweis der austenitischen, der martensitischen, der boridischen und/oder carbidischen und/oder nitridischen und/oder oxidischen Phasen und die Bestimmung der Größe und des Volumenanteils dieser Phasen kann über Röntgenbeugung, Rasterelektronenmikroskopie oder Transmissionselektronenmikroskopie erfolgen.The detection of the austenitic, the martensitic, the boridic and / or carbidic and / or nitridic and / or oxidic phases and the determination of the size and the volume fraction of these phases can be carried out by X-ray diffraction, scanning electron microscopy or transmission electron microscopy.
Die Erfindung ist nachstehend anhand von mehreren Ausführungsbeispielen näher erläutert.The invention is explained below with reference to several embodiments.
Zur Herstellung einer Legierung mit der Zusammensetzung Fe84,31Cr4,26Mo4,62V2,18C4,61Y0,02 (in Atom-%) werden 849,8 g Fe, 40 g Cr, 80 g Mo, 20 g V, 10 g C und 0,2 g Y eingewogen und gemischt. Diese Mischung wird in einer Induktionsschmelzanlage unter Argonschutzgas bei Temperaturen von 1500° C aufgeschmolzen und in eine rechteckige Kupferkokille mit den Abmessungen 70 x 100 x 14 mm3 abgegossen. Aufgrund der Größe der Kupferkokille und der Abmessungen des Gussteiles beträgt die Abkühlungsgeschwindigkeit 200 K/s.To produce an alloy having the composition Fe 84.31 Cr 4.26 Mo 4.62 V 2.18 C 4.61 Y 0.02 (in atomic%), 849.8 g Fe, 40 g Cr, 80 g Mo, 20 g of V, 10 g of C and 0.2 g of Y weighed and mixed. This mixture is melted in an induction melting plant under argon protective gas at temperatures of 1500 ° C and poured into a rectangular copper mold with the dimensions 70 x 100 x 14 mm 3 . Due to the size of the copper mold and the dimensions of the casting, the cooling rate is 200 K / s.
Der erhaltene quaderförmige Formkörper besteht aus einer hochfesten, mikrokristallinen, martensitischen (trz) Phase, einer mikrokristallinen austenitischen (kfz) Phase, sowie nano- und mikrokristallinen carbidischen Phasen vom Typ MC und M2C. Der Volumenanteil der martensitischen Phase beträgt 75 %, der Volumenanteil der austenitischen Phase beträgt 15 % und der Volumenanteil der carbidischen Phasen beträgt 10 %.The cuboidal shaped body obtained consists of a high-strength, microcrystalline, martensitic (trz) phase, a microcrystalline austenitic (kfz) phase, as well as nano- and microcrystalline carbidic phases of the type MC and M 2 C. The volume fraction of the martensitic phase is 75%, the Volume fraction of the austenitic phase is 15% and the volume fraction of the carbidic phases is 10%.
Nachfolgend ist der Formkörper im Druckversuch untersucht worden und eine technische Bruchstauchung von 13,6 % (wahre Bruchstauchung von 15,3 %) bei einer technischen Bruchfestigkeit von 5060 MPa (wahre Bruchfestigkeit von 4260 MPa) ermittelt worden. Die elastische Stauchung an der 0,2 % Dehngrenze beträgt 1,3 % bei einer Festigkeit von 2480 MPa (techn.) oder 2010 MPa (wahr). Der Elastizitätsmodul beträgt 212 GPa.Subsequently, the molded article was tested in compression and a technical crushing of 13.6% (true crushing of 15.3%) at a technical breaking strength of 5060 MPa (true breaking strength of 4260 MPa) been determined. The elastic compression at the 0.2% proof stress is 1.3% with a strength of 2480 MPa (techn.) Or 2010 MPa (true). The modulus of elasticity is 212 GPa.
Damit ist ein Formkörper hergestellt worden, der eine gute Verformungsfestigkeit und eine deutliche Festigkeitssteigerung bei gleichzeitiger guter Duktilität aufweist.Thus, a molded body has been produced, which has a good resistance to deformation and a significant increase in strength coupled with good ductility.
Zur Herstellung einer Legierung mit der Zusammensetzung Fe81,9Cr4,32Mo4,63V2,15C4,56Si2,34Sm0,10 (in Atom-%) werden 835 g Fe, 41 g Cr, 81 g Mo, 20 g V, 10 g C, 12 g Si und 1 g Sm eingewogen und gemischt. Diese Mischung wird in einer Induktionsschmelzanlage unter Argonschutzgas bei Temperaturen von 1500 ° C aufgeschmolzen und in eine quadratische Kupferkokille mit den Abmessungen 70 x 70 x 18 mm3 abgegossen. Aufgrund der Größe der Kupferkokille und der Abmessungen des Gussteiles beträgt die Abkühlungsgeschwindigkeit 150 K/s.To prepare an alloy having the composition Fe 81.9 Cr 4.32 Mo 4.63 V 2.15 C 4.56 Si 2.34 Sm 0.10 (in atomic%), 835 g of Fe, 41 g of Cr, 81 g Mo, 20 g V, 10 g C, 12 g Si and 1 g Sm weighed and mixed. This mixture is melted in an induction melting plant under argon protective gas at temperatures of 1500 ° C and poured into a square copper mold with the dimensions 70 x 70 x 18 mm 3 . Due to the size of the copper mold and the dimensions of the casting, the cooling rate is 150 K / s.
Der erhaltene quaderförmige Formkörper besteht aus einer hochfesten, mikrokristallinen, martensitischen (trz) Phase, einer mikrokristallinen austenitischen (kfz) Phase, sowie nano- und mikrokristallinen carbidischen Phasen vom Typ MC und M2C. Der Volumenanteil der martensitischen Phase beträgt 70 %, der Volumenanteil der austenitischen Phase beträgt 18 % und der Volumenanteil der carbidischen Phasen beträgt 12 %.The resulting rectangular shaped body consists of a high-strength, microcrystalline, martensitic (trz) phase, a microcrystalline austenitic (kfz) phase, as well as nano- and microcrystalline carbidic phases of the type MC and M 2 C. The volume fraction of the martensitic phase is 70%, the Volume fraction of the austenitic phase is 18% and the volume fraction of the carbidic phases is 12%.
Nachfolgend ist der Formkörper im Druckversuch untersucht worden und eine technische Bruchstauchung von 16,3 % (wahre Bruchstauchung von 18,1 %) bei einer technischen Bruchfestigkeit von 4350 MPa (wahre Bruchfestigkeit von 3720 MPa) ermittelt worden. Die elastische Stauchung an der 0,2 % Dehngrenze beträgt 1,2 % bei einer Festigkeit von 2140 MPa (techn.) oder 1860 MPa (wahr). Der Elastizitätsmodul beträgt 217 GPa.Subsequently, the molding was examined by compression and a technical crushing of 16.3% (true crushing fracture of 18.1%) at a technical breaking strength of 4350 MPa (true breaking strength of 3720 MPa) has been determined. The elastic compression at the 0.2% proof stress is 1.2% at a strength of 2140 MPa (techn.) Or 1860 MPa (true). The modulus of elasticity is 217 GPa.
Damit ist ein Formkörper hergestellt worden, der eine gute Verformungsfestigkeit und eine deutliche Festigkeitssteigerung bei gleichzeitiger guter Duktilität aufweist.Thus, a molded body has been produced, which has a good resistance to deformation and a significant increase in strength coupled with good ductility.
Claims (7)
- High-strength shaped bodies which are plastically deformable and absorb mechanical energy at room temperature and are composed of iron alloys, wherein the material of the shaped body has a composition FeaCrc1Moc2Vc3CbYe
where a = 70-90, b = 3-6, c1 = 3-5, c2 = 3-5, c3 = 1-3 and e = 0.01-0.09 (in atom %)
or the composition
FeaCrc1Moc2Vc3CbSidYe
where a = 70-90, b = 3-6, c1 = 3-5, c2 = 3-5, c3 = 1-3, d = 1-3 and e = 0.01-0.09 (in atom %),
and impurities can be present and the microstructure thereof has a homogeneous structure which contains- from 40 to 80% by volume of martensitic (tbc - tetragonal body-centred) phase
and- from 5 to 35% by volume of austenitic (cfc - cubic face-centred) phase
and- boridic and/or carbidic and/or nitridic and/or oxidic phases as balance,where the proportion by volume of austenitic phase increases, the smaller the proportion of Cr, Mo or V. - Shaped body according to Claim 1, wherein ferritic and/or bainitic phases are present.
- Shaped body according to Claim 1, wherein the proportion by volume of the martensitic phase is from 50 to 70%.
- Shaped body according to Claim 1, wherein the proportion by volume of the austenitic phase is from 5 to < 30%, advantageously from 10 to 20%.
- Shaped body according to Claim 1, wherein the proportion by volume of the boridic and/or carbidic and/or nitridic and/or oxidic phases is 5-15% by volume.
- Process for producing high-strength shaped bodies which are plastically deformable and absorb mechanical energy at room temperature and are composed of iron alloys according to any of Claims 1-5, wherein the alloy elements are mixed, melted and finally poured into a mould, where casting moulds having a thickness of the shaped body to be produced of from 12 to 20 mm are used in order to achieve the cooling rates, and the cooling of the alloy in the casting mould is effected at a rate of > 20 K/s and the cooling rate is selected as a function of the phase composition to be set, with higher cooling rates promoting the formation of the martensitic phase.
- Process according to Claim 6, wherein the melting and casting into a mould is carried out with exclusion of oxygen in order to obtain boridic and/or carbidic and/or nitridic phases in the microstructure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010041366A DE102010041366A1 (en) | 2010-09-24 | 2010-09-24 | High-strength, at room temperature plastically deformable and energy absorbing mechanical body of iron alloys |
| PCT/EP2011/066283 WO2012048993A1 (en) | 2010-09-24 | 2011-09-20 | High-strength shaped bodies which are composed of iron alloys, are plastically deformable at room temperature and absorb mechanical energy |
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| Publication Number | Publication Date |
|---|---|
| EP2619343A1 EP2619343A1 (en) | 2013-07-31 |
| EP2619343B1 true EP2619343B1 (en) | 2014-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP11779110.3A Active EP2619343B1 (en) | 2010-09-24 | 2011-09-20 | A high strength iron-based alloy moulded body being pasticially deformable and having mechanical energy absorption capability at room temperature |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2619343B1 (en) |
| KR (1) | KR101827866B1 (en) |
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| DE102014217122B4 (en) | 2013-08-30 | 2021-02-25 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | Filler material for build-up welding |
| DE102014217369A1 (en) | 2014-09-01 | 2016-03-03 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | HIGH STRENGTH, MECHANICAL ENERGY ABSORBING AND CORROSION-RESISTANT FORM BODIES OF IRON ALLOYS AND METHOD FOR THE PRODUCTION THEREOF |
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| DE3248866A1 (en) * | 1981-06-30 | 1983-06-16 | Foote Mineral Co | Boron alloy additive for continuous casting of borehole |
| KR100374980B1 (en) * | 1999-02-12 | 2003-03-06 | 히다찌긴조꾸가부시끼가이사 | High strength steel for dies with excellent machinability |
| NO310980B1 (en) * | 2000-01-31 | 2001-09-24 | Elkem Materials | Process for grain refining of steel, grain refining alloy for steel and process for the production of grain refining alloy |
| DE102006024358B4 (en) * | 2006-05-17 | 2013-01-03 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | High-strength, at room temperature plastically deformable shaped body made of iron alloys |
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- 2011-09-20 WO PCT/EP2011/066283 patent/WO2012048993A1/en active Application Filing
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| DE102010041366A1 (en) | 2012-03-29 |
| WO2012048993A1 (en) | 2012-04-19 |
| KR20130122627A (en) | 2013-11-07 |
| KR101827866B1 (en) | 2018-02-12 |
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