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WO2016034390A1 - Corps moulés à haute résistance, absorbant l'énergie mécanique et résistants à la corrosion composés d'alliages de fer et procédé de production desdits corps moulés à haute résistance - Google Patents

Corps moulés à haute résistance, absorbant l'énergie mécanique et résistants à la corrosion composés d'alliages de fer et procédé de production desdits corps moulés à haute résistance Download PDF

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Publication number
WO2016034390A1
WO2016034390A1 PCT/EP2015/068723 EP2015068723W WO2016034390A1 WO 2016034390 A1 WO2016034390 A1 WO 2016034390A1 EP 2015068723 W EP2015068723 W EP 2015068723W WO 2016034390 A1 WO2016034390 A1 WO 2016034390A1
Authority
WO
WIPO (PCT)
Prior art keywords
shaped body
advantageously
corrosion
phase
body according
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.)
Ceased
Application number
PCT/EP2015/068723
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German (de)
English (en)
Inventor
Josephine Zeisig
Julia Hufenbach
Uta KÜHN
Jürgen Eckert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
Original Assignee
Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV filed Critical Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
Priority to EP15756862.7A priority Critical patent/EP3189172B8/fr
Publication of WO2016034390A1 publication Critical patent/WO2016034390A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium 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
    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Definitions

  • the present invention relates to the field of materials science and relates to high strength, mechanical energy absorbing and corrosion resistant iron alloy bodies.
  • Such moldings can be used as moldings in vehicle, machine and plant construction, as well as in the food industry or in plastics processing.
  • martensitic iron alloys are distinguished by their high hardness (> 50 HRC) and mechanical strength and are preferably used for components subject to high mechanical stress and wear, such as ball bearings, press plates or as tool steels for cutting and punching tools [DIN EN ISO 4957].
  • cast (martensitic) iron alloys can be alloyed similar to the high speed steels and these shaped bodies can be used as cutting tools [AS Chaus et al .: International Journal of Advances in Machining and Forming Operations, Vol. 1 (2010) p. 35-53]. It is also known that vanadium contents of about 0.5 to about 6% by weight with wear-resistant cast steel and white cast iron improve the material properties, such as, for example, toughness and wear resistance [A. Todic et al .: Materials and Manufacturing Processes, 27 (2012) p. 1 193-1 197; A. Todic et al .: Journal of Mechanics Engineering and Automation, 3 (2013) p. 168-172; J.
  • the alloys according to EP 1 728 884 A1 contain silicon and manganese and the C content is at most 0.8% by mass.
  • the alloys according to WO 2004 067793 A3 have a Cr content of at most 1 1% by mass with a high carbon content, in order to achieve high wear resistance.
  • a commercial stainless martensitic cast steel usually has a chromium content of 1 1, 5 to 17% by mass with less than 0.15 mass% of carbon, 1 to 2 Mass% manganese and 0.8 to 1.5 mass% silicon and additionally contains nickel and molybdenum.
  • delta ferrite can remain in the microstructure, which can decompose by introducing heat (for example during a heat treatment) into austenite and doped phases such as, for example, the sigma phase. This can adversely affect toughness as well as corrosion properties [J.R. Davis: Stainless Steel (ASM Specialty Handbook). ASM International, (1995), p. 137, 446].
  • a corrosion-resistant cast steel contains metastable austenite
  • TRIP Induced Plasticity Transformation induced by phase transformation or TWIP (Plasticity induced by twinning)
  • TWIP Plasticity induced by twinning
  • Twinning Induced Plasticity may have improved mechanical properties, such as high strength values with good toughness.
  • These materials usually have high levels of austenite-stabilizing elements such as manganese (up to 25% by mass) and / or nickel (up to 12% by mass).
  • martensitic stainless steel cast alloys may exhibit tensile strengths of 590 to 1100 MPa and elongations at break of up to 15% only after a heat treatment consisting of quenching (950 ° C to 1070 ° C) and tempering (460 ° C to 750 ° C) [ DIN EN 10283]. Also known is the production technology for molded parts, wherein by using pure starting elements and the rapid solidification of the melt in a copper mold (increased solidification rates of 10 to 70 K / s) crystalline iron alloys can be produced.
  • solidification rate is understood to mean the average rate at which a material is cooled from the molten state to complete solidification.
  • a disadvantage of known solutions of the prior art is that conventional tools, wear-resistant and stainless steels usually have to undergo a time-consuming and expensive heat treatment (annealing, hardening and tempering) in order to set the required mechanical properties and / or minimize susceptibility to cracking to be able to [DE 000001558656A; GB 1469706A; JP 000H08120418A; WO 03035921 A1; A.S. Chaus et al .: International Journal of Advances on Machining and Forming Operations, Vol. 2, no. 1 (2010) p. 35-53].
  • annealing, hardening and tempering in order to set the required mechanical properties and / or minimize susceptibility to cracking to be able to
  • the invention has for its object to provide mechanical energy absorbing moldings of iron alloys, which are high-strength and corrosion resistant than previously known iron alloys and to provide a method for producing these moldings, which is inexpensive and easy to implement.
  • the high-strength, energy-absorbing and corrosion-resistant shaped bodies of iron alloys according to the invention have a
  • E1 one or more elements of group V, W,
  • E2 one or more elements of the group Mo, Ti, Nb, Ni,
  • the low, production-related additives and impurities may have and have a microstructure with a homogeneous microstructure consisting of at least one cubic surface-centered (fcc) phase and at least one cubic and / or tetragonal space-centered (krz / trz) phase and at least one carbide phase.
  • the structure further boridic and / or nitridic phases, advantageously with a volume fraction of a total of ⁇ 15%, on.
  • the microstructure comprises austenite with at least 5 to 40% by volume, advantageously 10 to 20% by volume, as the cubic-area-centered phase.
  • the microstructure has a volume fraction of the carbidic phase of 3 to 15% by volume.
  • the molding has a hardness between 50 and 65 HRC, a compressive strength between 3500 and 5500 MPa with a fracture upset of between 15 and 30% and a tensile strength greater than or equal to 1000 MPa. It is also advantageous if the shaped body has a passivation of the surface in halide-free solutions and is thus resistant to corrosion and shows resistance to corrosion in halide-containing solutions.
  • the shaped body contains additives, and impurities such as silicon, calcium, phosphorus, sulfur and / or manganese, as manufacturing-related additives.
  • the starting materials are mixed and melted, then poured into a mold and cooled at a solidification rate of> 1 K / s until complete solidification or the starting materials are mixed and melted, then poured into a mold and cooled at a solidification rate of> 1 K / s until complete solidification and then subjected to at least one heat treatment consisting of a hardening (austenitizing and cooling) with or without subsequent tempering.
  • the melting is realized by means of induction, laser or electron beam, wherein this is still advantageously realized at temperatures of 1400 to 1500 ° C, and / or also advantageously under an inert atmosphere, such as under argon atmosphere, realized.
  • the melting between 1300 and 1700 ° C is realized.
  • the melt of the starting materials is poured into a copper mold and cooled therein, wherein the thickness of the cast in the copper mold molded body is still advantageously 1 to 30 mm, or even more advantageously in the range of 10 to 20 mm or 12 to 20 mm is. It is also advantageous if the heat treatment is carried out with tempering.
  • the high-strength, energy-absorbing, and corrosion-resistant shaped bodies of iron alloys according to the invention are used according to the invention when a material property combination of high mechanical stress, mechanical energy absorption capacity, low wear rate and resistance in corrosive media is required.
  • the combination of the alloying elements according to the invention with the higher chromium content than in DE 10 2006 024 358 A1 and DE 10 2010 041 366 A1 sufficient chromium can accumulate in the matrix, whereby the corrosion resistance of the alloys of the invention compared to alloys according to DE 10 2006 024 358 A1 and DE 10 2010 041 366 A1 could be improved.
  • the high-tensile, mechanical energy-absorbing and corrosion-resistant shaped bodies of iron alloys according to the invention have a microstructure with a homogeneous microstructure consisting of at least one cubic surface-centered (fcc) phase and at least one cubic and / or tetragonal space-centered (krz / trz) phase and at least one carbidic phase.
  • fcc cubic surface-centered
  • krz / trz space-centered
  • carbidic phase at least one carbidic phase.
  • boridic and / or nitridic phases may also be present.
  • the moldings contain a relatively high volume fraction (50 to 80% by volume) of martensite and / or bainite.
  • Martensite may occur as a cubic and / or tetragonal space-centered (krz / trz) phase.
  • Bainite is a phase mixture of cubic space-concentrated (krz) and carbide phase.
  • the moldings advantageously have a volume fraction of austenite (kfz phase) of 10 to 20%. Due to the proportion of austenitic phase according to the invention significantly improved properties are achieved.
  • the moldings advantageously have a volume fraction of 3 to 15% by volume of the carbidic and / or boride phases.
  • a stable complex enriched with carbide carbide network is formed, which is embedded in austenitic phase, advantageously additionally carbide and / or boride phase (s) in the nanometer range (particle size ⁇ 1 ⁇ ) is present / present.
  • the structure has the features of a dendritic to globular microstructure.
  • the detection of the krz, trz, kfz and carbide and / or boridic and / or nitridic phases and the determination of the size and the Volume fraction of these phases can be done by X-ray diffraction, scanning electron microscopy or transmission electron microscopy.
  • the carbide formers Ti, V, Nb, W, and Mo more prefer to bind carbon than chromium because they are significantly more affine to C. Due to the inventively higher chromium content, sufficient chromium can accumulate in the matrix in order to improve the corrosion resistance. It may form a complex carbide network of Cr-rich and / or V-rich and / or W-rich and / or Mo-rich and / or Ti-rich and / or Nb-rich carbides.
  • boron forms borides and / or boron carbides and / or boron nitrides, which can lead to a significant increase in hardness and an improvement in strength but can lower toughness.
  • the shaped articles of the iron alloys according to the invention have high mechanical strengths with high plastic deformability, high hardness and good toughness and are resistant to wear and corrosive media.
  • the moldings according to the invention have a compressive strength between 3500 and 5000 MPa with a fracture compression between 15 and 30% and a tensile strength greater than or equal to 1000 MPa.
  • the macrohardness of the iron alloys according to the invention is between 50 and 65 HRC.
  • Inventive moldings show improved corrosion resistance by passivation of the surface in acidic solutions and in contact with chloride-containing solutions.
  • the process according to the invention for producing the high-strength, energy-absorbing and corrosion-resistant shaped bodies made of iron alloys according to the invention takes place by means of mixing and melting of the alloy constituents in the proportions necessary according to the desired composition. Both starting materials and their proportions are determined by the formula given in claim 1. After the starting materials have melted, the melt is poured into a mold. The cooling of the melt in the mold must be realized with a solidification rate of> 1 K / s, advantageously between 10 and 1 000 K / s, more preferably between 10 and 200 K / s, so that the structure of the invention is realized. The cooling can also be followed according to the invention of at least one subsequent heat treatment of the form body. This involves hardening (austenitizing and cooling) with / without subsequent tempering of the material.
  • the inventive method is inexpensive and easy to implement.
  • the starting materials used should be as free of impurities and additives as possible and by melting and casting of the alloy should also be introduced as little impurities and additives in the melt and thus in the molding.
  • the iron alloy according to the invention pure elements are advantageously used, so that no oxides and / or sulfides in the inventive Alloy arise, which can adversely affect the material properties (in particular the toughness).
  • the melting of the starting materials can be advantageously carried out advantageously in an induction furnace at temperatures of 1400 to 1500 ° C advantageously under inert atmosphere, such as argon atmosphere, being used as crucible advantageously AI2O3.
  • inert atmosphere such as argon atmosphere
  • the starting materials are advantageously heated to temperatures of 1300-1700 ° C and poured at temperatures between 1400 and 1500 ° C in the mold.
  • such molds made of copper so-called copper molds, since copper has a high thermal conductivity.
  • a composite-like microstructure consisting of non-equilibrium phases and the complex carbide network according to the invention forms, which improves the properties against abrasive wear.
  • the formation of the martensitic phase is promoted by the high solidification rates.
  • the solidification rate of the molten alloy is controlled by the choice of the size of the mold.
  • the width (B) and length (L) of the molded article to be produced play only a minor role. Decisive for the control of the solidification rate is above all the thickness of the shaped body to be produced. In this case, the smaller the thickness (D) of the molded article to be produced, the greater is the speed of solidification occurring with the same casting mold volume. Therefore, the solidification speed 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.
  • the alloy according to the invention can be re-sharpened and rapidly solidified.
  • the microstructure according to the invention can likewise be formed with a homogeneous dendritic to globular microstructure consisting of cubic and / or tetragonal space-centered (krz / trz) phase, a cubic-surface-centered (kfz) phase and carbidic and / or boridic and / or nitridic phases, as a result of which improved properties can be achieved.
  • the (re) melting of the alloy composition according to the invention can be effected by means of induction, laser or electron beam.
  • the solidification rate is advantageously between 1 and 1 000 K / s.
  • An advantage of the present invention is further that a subsequent mechanical deformation or heat treatment of the cast iron alloy molded body are not necessary to achieve sufficiently high strengths with high plastic deformability and resistance to corrosion.
  • the shaped bodies of the iron alloy according to the invention can be processed by forming technology.
  • the resulting thin-walled cast iron alloy body consists of a high-strength cubic cavity-centered phase, a metastable cubic-surface-centered phase, and mainly eutectic, nano- and microcrystalline carbide phases of the M 7 C3 (M ... Cr, V) type and nanocrystalline carbide phases of the type MC (M ... Cr, V).
  • the volume fraction of the cubic space-centered phase is 78%
  • the volume fraction of the austenitic phase is 18%
  • the volume fraction of the carbide phases is 4%.
  • the resulting thin-walled cast iron alloy body consists of a cubic space-centered phase, a metastable, cubic-surface-centered phase and carbide phases such as the eutectic carbides of type M 7 C 3 (M ... Cr, V) and MC carbides ( ⁇ ... ⁇ , Cr, V, Mo).
  • carbide phases such as the eutectic carbides of type M 7 C 3 (M ... Cr, V) and MC carbides ( ⁇ ... ⁇ , Cr, V, Mo).
  • the volume fraction of the cubic space-centered phase is 71%
  • the volume fraction of the austenitic phase is 25%
  • the volume fraction of the carbide phases is 4%.

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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 Articles (AREA)

Abstract

L'invention se rapporte au domaine de la science des matériaux et concerne les corps moulés qui peuvent être utilisés en tant que pièces moulées dans la construction de véhicules, de machines et d'installations, ainsi que dans l'industrie alimentaire ou dans le traitement des matières plastiques. L'invention vise à mettre au point des corps moulés qui présentent une plus haute résistance et sont plus résistants à la corrosion. Cet objectif est atteint par des corps moulés composés d'alliages de fer, hautement résistants, absorbant l'énergie mécanique et résistants à la corrosion, qui comportent une composition selon la formule Fea Crb Cc E1d E2e E3f, E1 étant un élément ou plusieurs éléments du groupe V, W ; E2 un ou plusieurs éléments du groupe Mo, Ti, Nb, Ni ; E3 B et/ou N, avec a = 100-(b+c+d+e+f), b = 13 à 20, c = 0,8 à 1,6, d = 0,5 à 5, e = 0 à 8, f = 0 à 0,5 (a, b, c, d, e, f % en masse).
PCT/EP2015/068723 2014-09-01 2015-08-14 Corps moulés à haute résistance, absorbant l'énergie mécanique et résistants à la corrosion composés d'alliages de fer et procédé de production desdits corps moulés à haute résistance Ceased WO2016034390A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP15756862.7A EP3189172B8 (fr) 2014-09-01 2015-08-14 Corps moulés à haute résistance, absorbant l'énergie mécanique et résistants à la corrosion composés d'alliages de fer et procédé de production desdits corps moulés à haute résistance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014217369.8A DE102014217369A1 (de) 2014-09-01 2014-09-01 Hochfeste, mechanische energie absorbierende und korrosionsbeständige formkörper aus eisenlegierungen und verfahren zu deren herstellung
DE102014217369.8 2014-09-01

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WO2016034390A1 true WO2016034390A1 (fr) 2016-03-10

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EP (1) EP3189172B8 (fr)
DE (1) DE102014217369A1 (fr)
WO (1) WO2016034390A1 (fr)

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CN119506721B (zh) * 2024-11-01 2025-10-28 任丘市华凯通信设备有限公司 一种高强度抱箍及其制备方法

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DE1553806B1 (de) 1966-01-04 1971-12-09 Sandvikens Jernverks Ab Verwendung eines stahles fuer rasierklingen und deren her stellung
DE1558656A1 (de) 1967-04-19 1970-06-04 Thyssen Huette Ag Rost- und korrosionsbestaendiger Stahlguss
GB1469706A (en) 1973-04-25 1977-04-06 Armco Steel Corp Heat-hardened stainless steel article and process of producing it
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JPH08120418A (ja) 1994-10-19 1996-05-14 Nippon Steel Corp 耐摩耗性高クロム鋳鋼
EP1106706B1 (fr) 1999-11-05 2003-06-25 Nisshin Steel Co., Ltd. Acier austénitique inoxydable et métasable à haute résistance mecanique contenant de titane et procédé pour son fabrication
WO2003035921A1 (fr) 2001-10-19 2003-05-01 Sumitomo Metal Industries, Ltd. Acier inoxydable martensitique et procede de fabrication
WO2003069004A1 (fr) 2002-02-15 2003-08-21 Uddeholm Tooling Aktiebolag Acier d'outillage riche en carbure et en chrome, fabrique selon les techniques de la metallurgie des poudres, et outil fait de cet alliage
WO2004067793A2 (fr) 2003-01-29 2004-08-12 L.E. Jones Company Alliage resistant a la corrosion et a l'usure
WO2005123975A2 (fr) 2004-05-21 2005-12-29 Industeel Creusot Acier a haute resistance mecanique et a l'usure
EP1728884A1 (fr) 2005-06-02 2006-12-06 Daido Steel Co.,Ltd. Acier pour moule matière plastique
DE102006024358A1 (de) 2006-05-17 2007-11-22 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Hochfeste, bei Raumtemperatur plastisch verformbare Formkörper aus Eisenlegierungen
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