EP3186405A1 - Steel with high wear resistance, hardness and corrosion resistance and low thermal conductivity, and use of such a steel - Google Patents

Steel with high wear resistance, hardness and corrosion resistance and low thermal conductivity, and use of such a steel

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Publication number
EP3186405A1
EP3186405A1 EP15756892.4A EP15756892A EP3186405A1 EP 3186405 A1 EP3186405 A1 EP 3186405A1 EP 15756892 A EP15756892 A EP 15756892A EP 3186405 A1 EP3186405 A1 EP 3186405A1
Authority
EP
European Patent Office
Prior art keywords
steel
steel according
content
weight
particles
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
EP15756892.4A
Other languages
German (de)
French (fr)
Other versions
EP3186405B1 (en
Inventor
Horst HILL
André VAN BENNEKOM
Oliver RIPKENS
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.)
Deutsche Edelstahlwerke Specialty Steel GmbH and Co KG
Original Assignee
Deutsche Edelstahlwerke Specialty Steel GmbH and Co KG
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Publication of EP3186405A1 publication Critical patent/EP3186405A1/en
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Classifications

    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C21D1/32—Soft annealing, e.g. spheroidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/10—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • 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
    • C22C38/40—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
    • C22C38/50—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

Definitions

  • the invention relates to a steel for uses requiring high wear resistance, high hardness, good corrosion resistance and / or low thermal conductivity.
  • Cutting tools perforated plates, sieves, molds and similar components for machines needed in the plastics processing industry.
  • a typical field of application here are machines for the regeneration or recycling of plastic products, which are melted down into a melt for their return into the processing cycle.
  • the melt is forced through a perforated plate, from which it emerges in a large number of single strands.
  • the single strands solidify and then by means of suitable, near the perforated plate rotating knives to individual granules
  • the perforated plates used must have a good corrosion resistance due to the corrosive environment in which they are exposed in use and are exposed to high abrasive wear. Especially for the
  • a known steel intended for this purpose is known under the material number 1.2379 (AISI designation: D2). It contains besides iron and unavoidable Impurities (in wt%) 1.55% C, 12.00% Cr, 0.80 Mo and 0.90% V.
  • Material number 1.3343 (AISI designation: M2) standardized. It contains besides iron and unavoidable
  • Impurities (in wt%) 0.85-0.9% C, 0.25% Mn, 4.1% Cr, 5.0% Mo, 1.9% V and 6.4% W.
  • the highest demands on wear are to be met by the martensitic steel standardized under the material number 1.4110 (AISI designation: 440A), which in addition to iron and unavoidable impurities (in% by weight) 0.6 - 0.75% C, max. 1% Mn, max. 1% Si, max. 0.04% P, max. 0.03% S, 16 - 18% Cr and max. 0.75% Mo contains.
  • This steel achieves a hardness of at least 60 HRC after a suitable heat treatment.
  • a steel known under the trade designation "Ferro-Titanit Nikro 128" which has been specially created for the manufacture of components used in the processing of abrasive plastics, contains besides iron and unavoidable impurities (in% by weight) 13 , 5% Cr, 9% Co, 4% Ni and 5% Mo.
  • the proportion of titanium carbide in the structure of the composite steel is 30 wt .-%, which corresponds to a volume fraction of about 40 vol .-% TiC.
  • the well-known powder metallurgy produced steel achieved after over two to four hours under vacuum annealing at 850 ° C and a subsequent deterrence, in which he was a
  • a subsequent curing treatment in which the steel over six to eight hours at 480 ° C, to a maximum hardness of about 62 HRC can be increased.
  • From this steel are typically perforated plates, granulators, spray nozzles and
  • Screws, rings and other pressing tools for the processing of abrasive plastics as well as components for pumps, filling heads and ring knives, which are required for canning-filling machines see data sheet "Ferro-Titanit Nikro 128"
  • the object of the invention was to provide a steel which is in the
  • the invention provides a steel for applications requiring high wear resistance, high hardness, good corrosion resistance and / or low thermal conductivity.
  • the steel according to the invention achieves a hardness of at least 56 HRC in the cured state and contains in its structure a total of at least 30% by weight of hard phases
  • TiC particles of carbide, Oxide or nitride particles present in addition to the TiC particles of carbide, Oxide or nitride particles exist.
  • the content of TiC particles is
  • the hard phases are in a matrix
  • a steel according to the invention is particularly suitable for the production of components for
  • Hole openings are made microfine to produce correspondingly finely granulated granules.
  • knives for shredding of steel according to the invention can be made
  • a steel according to the invention contains at least 20% by weight of TiC embedded in a matrix which is penetrated by
  • Deterioration contributes to the hardenability of the steel and at the same time is chosen so that a low
  • Thermal conductivity of less than 35 W / mK is guaranteed regardless of the respective heat treatment state.
  • the passive current density of the steel according to the invention is less than 5 ⁇ / cm 2 , measured in oxygen-free 0.5 molar sulfuric acid with a
  • Wear resistance has a corrosion resistance comparable to the corrosion resistance
  • steels is at a temperature of 20 ° C at more than 270 GPa, in particular more than 300 GPa, so that the steel according to the invention or produced therefrom
  • Coefficient of expansion of steel according to the invention is that for applications for the steels according to the invention
  • the steel according to the invention contains at least 20% by weight, corresponding to about 30% by volume of TIC, or at least 28% by weight of TiC, in particular at least 30% by weight of TiC.
  • the TiC content should not exceed an upper limit of 45% by weight. That way you can ensure that yourself
  • Too high a hard phase content leads to increased hardness and wear resistance.
  • a steel according to the invention also contributes that According to the invention further hard phases are present in addition to the TiC particles in the steel matrix, so that the volume fraction of the hard phases in the structure of the steel is at least 30 wt .-% in total. This can be done by separate addition of carbide, nitride or oxide particles in the production of the steel. Alternatively or additionally, the elements forming the weight fractions of the precipitates (Ni, Al, Ti) can also be used within the
  • form steel according to the invention are intermetallic precipitates, in whose formation mainly the elements Ni, Al and Ti are involved. These elements form Ni 3 Al and Ni 3 Ti or mixed forms. These intermetallic phases are present in the structure with grain sizes of the order of 10 nm and are not counted to the total hard phase content. Due to their small size, they afford the
  • intermetallic precipitations an increase in hardness and strength of the metal matrix and thus also contribute to improving the performance properties.
  • Chromium is in the steel of the invention in levels of
  • the Cr content is 12.5-14.5 wt .-%.
  • Molybdenum is contained in the steel according to the invention in amounts of 5.0-9.0 wt .-%, on the one hand to ensure sufficient corrosion resistance, in particular with regard to pitting corrosion and on the other hand to support the formation of intermetallic phases, by the hardness of the steel matrix, in which the hard phases are embedded, is increased.
  • the Mo content of the steel according to the invention is 6.5-7.5% by weight.
  • Cobalt is contained in the steel according to the invention in contents of 6.0 - 11.0 wt .-%, in order to To increase martensite start temperature and on the other hand to reduce the solubility of Mo in the metal matrix. In this way, in the inventive
  • the Co content of the steel according to the invention is 8.0-10.0% by weight
  • Copper is in the steel of the invention in contents of
  • the Cu content of the steel according to the invention is 0.5-1.0% by weight.
  • Nickel is in the steel according to the invention in contents of
  • Nickel is needed in the steel matrix in sufficient quantity to be at a
  • the presence of nickel stabilizes the austenite to such an extent that martensite is safely formed during quenching. If too little nickel is present in the steel matrix provided according to the invention, this effect is not achieved with the necessary certainty. If, on the other hand, too much nickel is present in the steel matrix, no martensite forms, since the austenitic phase is then stable even at room temperature.
  • the second object of nickel in the steel according to the invention is precipitation hardening by formation of intermetallic phases with elements such as Al and Ti. Therefore, in the steel matrix of the invention Steel the contents of Ni, Al and Ti on each other
  • Titanium is in the steel according to the invention in contents of
  • the Ti content of the steel according to the invention is 0.8 to 1.2% by weight.
  • aluminum is contained in the steel of the present invention at levels of 0.1-2.0% by weight to effect precipitation hardening in combination with Ni.
  • the Al content of the steel according to the invention is 1.0 to 1.4% by weight.
  • the steel according to the invention can be hardened with extremely low distortion, since titanium carbide has a low thermal expansion and no transformation.
  • the wear resistance of the steel according to the invention is increased.
  • the NbC particles have a lower thermal conductivity than TiC, which is beneficial to the
  • Tic and NbC are isomorphic carbides and therefore miscible with each other. This leads to
  • the carbide, nitride and oxide particles used according to the invention as hard phases are already supplied as "finished” particles during powder metallurgical production.
  • both the sintering, as well as the HIP (hot isostatic pressing) route can be used.
  • this is also suitable
  • the steel according to the invention can be used to adjust its mechanical properties to a conventional one
  • Steel according to the invention regularly has a hardness of more than 62 HRC after such a heat treatment.
  • Steel according to the invention has a hardness of more than 50 HRC.
  • the invention is based on
  • Fig. 1 shows a detail of a
  • FIG. 2 is a diagram in which the results of
  • Fig. 3 is a diagram with the result of an
  • composition of the steel V corresponded to the composition of the known under the name "Ferro-Titanit Nikro 128", for example, in the above-mentioned publication documented steel.
  • the completed in the powder metallurgical production of both steels E, V operations corresponded to the
  • Heat treatment corresponded.
  • samples PE1 and PV1 were first kept in vacuo at a temperature of 850 ° C. for a period of two to four hours and then quenched under a nitrogen atmosphere pressurized with 1 to 4.5 bar. This is followed by a curing treatment in which the samples PEl, PVl have been stored for six to eight hours at a temperature of 480 ° C.
  • Fig. 1 shows a section of a
  • Metal matrix is recognizable by the bright areas, whereas the TiC inclusions surrounded by the matrix are rendered dark.
  • the hard phase contents were determined on the samples PE1, PV1, PE2, PV2. They were with the from the
  • Comparative steel V produced samples PV1, PV2 had on average only 30 wt .-% hard phases.
  • PEl, PE2, PVl, PV2 five hardness measurements according to DIN EN ISO 6508-1 were carried out.
  • the mean values of the measured values thus acquired for the samples PE1, PE2, PV1, PV2 are in
  • the TiC content of the samples according to the invention PE1, PE2 was, as indicated in Table 1, each more than 30 wt .-%.
  • the modulus of elasticity is determined by means of ultrasound in FIG.
  • PV1 was 294 GPa.
  • FIG. 4 shows, by way of example, the result of a dilatometer measurement on a sample PE 1 produced from the steel according to the invention, which confirms this result.

Abstract

The invention relates to steel for applications which require high wear resistance, a high degree of hardness, good corrosion resistance and/or low thermal conductivity, said steel being reliably producible on an industrial scale. The hardness of the steel according to the invention in the hardened state is at least 56 HRC. In order to obtain said steel, the microstructure of the steel in total contains at least 30 wt.-% hard phases, which, in addition to the TiC particles, consist of further carbide particles, oxide particles or nitride particles. The TiC particle content of the steel according to the invention is at least 20 wt.-%. The hard phase particles are embedded in a matrix that consists of (in wt.-%) 9.0 - 15.0% Cr, 5.0 - 9.0% Mo, 3.0 - 7.0% Ni, 6.0 - 11.0% Co, 0.3 - 1.5% Cu, 0.1 - 2.0% Ti, and 0.1 - 2.0% Al, the remainder being iron and inevitable impurities. The combination of properties makes said steel particularly suitable for the production of structural components, in particular blades or perforated plates which are required for the production and the recycling of plastics.

Description

Stahl mit hoher Verschleißbeständigkeit, Härte und Korrosionsbeständigkeit sowie niedriger Wärmeleitfähigkeit und Verwendung eines solchen Stahls  Steel with high wear resistance, hardness and corrosion resistance as well as low thermal conductivity and use of such a steel
Die Erfindung betrifft einen Stahl für Verwendungen, die eine hohe Verschleißbeständigkeit, eine hohe Härte, eine gute Korrosionsbeständigkeit und/oder eine niedrige Wärmeleitfähigkeit erfordern. The invention relates to a steel for uses requiring high wear resistance, high hardness, good corrosion resistance and / or low thermal conductivity.
Wenn nachfolgend Gehaltsangaben von Stahllegierungen angegeben sind, so sind diese jeweils auf das Gewicht bezogen, soweit nicht ausdrücklich etwas anderes If salary specifications of steel alloys are given below, these are each based on the weight, unless expressly otherwise
angegeben ist. is specified.
Stähle mit dem voranstehend genannten Eigenschaftsprofil eignen sich insbesondere für die Herstellung von Steels with the above-mentioned property profile are particularly suitable for the production of
Schneidwerkzeugen, Lochplatten, Sieben, Formen und vergleichbaren Komponenten für Maschinen, die in der Kunststoff verarbeitenden Industrie benötigt werden. Cutting tools, perforated plates, sieves, molds and similar components for machines needed in the plastics processing industry.
Ein typisches Einsatzgebiet sind hier Maschinen für die Neuerzeugung oder das Recycling von Kunststoffprodukten, die für ihre Rückführung in den Verarbeitungskreislauf zu einer Schmelze eingeschmolzen werden. Um aus der Schmelze ein Granulat zu bilden, wird die Schmelze durch eine Lochplatte gedrückt, aus der sie in einer Vielzahl von Einzelsträngen austritt. Die Einzelstränge erstarren und werden dann mittels geeigneter, nahe der Lochplatte rotierender Messer zu einzelnen Granulatkörnern A typical field of application here are machines for the regeneration or recycling of plastic products, which are melted down into a melt for their return into the processing cycle. To form a granulate from the melt, the melt is forced through a perforated plate, from which it emerges in a large number of single strands. The single strands solidify and then by means of suitable, near the perforated plate rotating knives to individual granules
zerkleinert . crushed.
Um den Erstarrungsvorgang zu beschleunigen, kann das Auspressen der Kunststoffschmelze durch die Lochplatte und das Zerkleinern unter Wasser durchgeführt werden. Dieses Verfahren ist in der KunststoffIndustrie als "Unterwassergranulieren" bekannt . To accelerate the solidification process, the extrusion of the plastic melt through the perforated plate and the crushing can be carried out under water. This process is known in the plastics industry as "underwater granulation".
Sowohl die für das Zerkleinern der Kunststoffe Both for the crushing of plastics
eingesetzten Messer als auch die zum Formen der von den Messern zu zerkleinernden Kunststoffsträngen used for shaping the plastic strands to be comminuted by the knives
eingesetzten Lochplatten müssen aufgrund der korrosiven Umgebung, der sie im Einsatz ausgesetzt sind, eine gute Korrosionsbeständigkeit besitzen und sind dabei hohem abrasiven Verschleiß ausgesetzt. Gerade für die The perforated plates used must have a good corrosion resistance due to the corrosive environment in which they are exposed in use and are exposed to high abrasive wear. Especially for the
Anwendung "Lochplatte" soll gleichzeitig die Application "perforated plate" should simultaneously the
Wärmeleitfähigkeit des Stahls, aus dem die Lochplatte jeweils hergestellt ist, niedrig sein, damit der mit der jeweiligen Lochplatte in Kontakt kommenden Thermal conductivity of the steel from which the perforated plate is made in each case, be low, so that the coming into contact with the respective perforated plate
Kunststoffschmelze nicht zu viel Wärme entzogen und es zu einer vorschnellen Erstarrung der Schmelze kommt, die zu einer Verstopfung der Löcher der Platte führen würde. Diese Anforderung ergibt sich insbesondere dann, wenn es sich bei der Lochplatte um eine so genannte "Micro- Lochplatte" mit Lochdurchmessern von weniger als 1 mm handelt . Plastic melt not withdrawn too much heat and there is a premature solidification of the melt, which would lead to clogging of the holes of the plate. This requirement arises in particular when the perforated plate is a so-called "micro perforated plate" with hole diameters of less than 1 mm.
Ein für diese Zwecke vorgesehener bekannter Stahl ist unter der Werkstoffnummer 1.2379 (AISI-Bezeichnung : D2) bekannt. Er enthält neben Eisen und unvermeidbaren Verunreinigungen (in Gew.-%) 1,55 % C, 12,00 % Cr, 0,80 Mo und 0, 90 % V. A known steel intended for this purpose is known under the material number 1.2379 (AISI designation: D2). It contains besides iron and unavoidable Impurities (in wt%) 1.55% C, 12.00% Cr, 0.80 Mo and 0.90% V.
Ein anderer ebenfalls im Bereich des Kunststoff- Recyclings weit verbreiteter Stahl ist unter der Another steel that is also widely used in the field of plastic recycling is under the
Werkstoffnummer 1.3343 (AISI-Bezeichnung : M2) genormt. Er enthält neben Eisen und unvermeidbaren Material number 1.3343 (AISI designation: M2) standardized. It contains besides iron and unavoidable
Verunreinigungen (in Gew.-%) 0,85 - 0,9 % C, 0,25 % Mn, 4,1 % Cr, 5,0 % Mo, 1,9 % V und 6,4 % W. Impurities (in wt%) 0.85-0.9% C, 0.25% Mn, 4.1% Cr, 5.0% Mo, 1.9% V and 6.4% W.
Höchsten Verschleißanforderungen soll der unter der Werkstoffnummer 1.4110 (AISI-Bezeichnung: 440A) genormte martensitische Stahl standhalten, der neben Eisen und unvermeidbaren Verunreinigungen (in Gew.-%) 0,6 - 0,75 % C, max. 1 % Mn, max. 1 % Si, max. 0,04 % P, max. 0,03 % S, 16 - 18 % Cr sowie max. 0,75 % Mo enthält. Dieser Stahl erreicht nach einer geeigneten Wärmebehandlung eine Härte von mindestens 60 HRC. The highest demands on wear are to be met by the martensitic steel standardized under the material number 1.4110 (AISI designation: 440A), which in addition to iron and unavoidable impurities (in% by weight) 0.6 - 0.75% C, max. 1% Mn, max. 1% Si, max. 0.04% P, max. 0.03% S, 16 - 18% Cr and max. 0.75% Mo contains. This steel achieves a hardness of at least 60 HRC after a suitable heat treatment.
Ein unter der Handelsbezeichnung "Ferro-Titanit Nikro 128" bekannter Stahl, der speziell für die Herstellung von Komponenten, die bei der Verarbeitung von abrasiven Kunststoffen eingesetzt werden, geschaffen worden ist, enthält neben Eisen und unvermeidbaren Verunreinigungen (in Gew.-%) 13,5 % Cr, 9 % Co, 4 % Ni und 5 % Mo. Der Anteil an Titancarbid im Gefüge des so zusammengesetzten Stahls beträgt 30 Gew.-%, was einem Volumenanteil von ca. 40 Vol.-% TiC entspricht. A steel known under the trade designation "Ferro-Titanit Nikro 128", which has been specially created for the manufacture of components used in the processing of abrasive plastics, contains besides iron and unavoidable impurities (in% by weight) 13 , 5% Cr, 9% Co, 4% Ni and 5% Mo. The proportion of titanium carbide in the structure of the composite steel is 30 wt .-%, which corresponds to a volume fraction of about 40 vol .-% TiC.
Der bekannte pulvermetallurgisch hergestellte Stahl erreicht nach einer über zwei bis vier Stunden unter Vakuum durchgeführten Glühung bei 850 °C und einer anschließenden Abschreckung, bei der er einer The well-known powder metallurgy produced steel achieved after over two to four hours under vacuum annealing at 850 ° C and a subsequent deterrence, in which he was a
Stickstoffatmosphäre mit einem Druck von 1 - 4,5 bar ausgesetzt wird, eine Glühhärte von ca. 53 HRC, die durch eine anschließende Aushärtbehandlung, bei der der Stahl über sechs bis acht Stunden bei 480 °C ausgelagert wird, auf eine Maximalhärte von ca. 62 HRC gesteigert werden kann. Aus diesem Stahl werden typischerweise Lochplatten, Granuliermesser, Spritzdüsen sowie Nitrogen atmosphere at a pressure of 1 to 4.5 bar, an annealing hardness of about 53 HRC, which is then removed by a subsequent curing treatment in which the steel over six to eight hours at 480 ° C, to a maximum hardness of about 62 HRC can be increased. From this steel are typically perforated plates, granulators, spray nozzles and
Schnecken, Ringe und sonstige Presswerkzeuge für die Verarbeitung von abrasiv wirkenden Kunststoffen sowie Komponenten für Pumpen, Abfüllköpfe und Ringmesser hergestellt, die für Konserven-Abfüllmaschinen benötigt werden (s. Datenblatt "Ferro-Titanit Nikro 128", Screws, rings and other pressing tools for the processing of abrasive plastics as well as components for pumps, filling heads and ring knives, which are required for canning-filling machines (see data sheet "Ferro-Titanit Nikro 128",
enthalten in der Broschüre "Ferro-Titanit - Die Härte aus Krefeld", 06/2001, veröffentlicht von der Deutsche Edelstahlwerke GmbH) . contained in the brochure "Ferro-Titanit - Die hardness from Krefeld", 06/2001, published by Deutsche Edelstahlwerke GmbH).
Von Horst Hill ist in seiner Dissertation "Neuartige Metallmatrixverbundwerkstoffe (MMC) zur By Horst Hill is in his dissertation "Novel Metal Matrix Composites (MMC) for
Standzeiterhöhung verschleißbeanspruchter Werkzeuge in der polymerverarbeitenden Industrie", Bochum Univ. Diss. 2011, veröffentlicht beim Selbstverlag des Lehrstuhls Werkstofftechnik, Ruhr-Universität Bochum, ISBN 978-3- 943063-08-0, schließlich ein Stahl vorgeschlagen worden, der aus (in Gew.-%) 13,5 % Cr, 1,0 % Mo, 9,0 % Ni, 5,5 % Co, 1,0 % Cu, 2,0 % Ti und 1,25 % AI, Rest Eisen und unvermeidbare Verunreinigungen besteht. Der TiC-Anteil im Gefüge dieses Stahls liegt ebenfalls bei 30 Gew.-%. Zusätzlich sind im Gefüge jedoch 5 Gew.-% NbC als Increasing the service life of tools subject to wear in the polymer processing industry ", Bochum Univ. Diss. 2011, published by the Department of Materials, Ruhr University Bochum, ISBN 978-3- 943063-08-0, finally a steel has been proposed which consists of (in wt %) 13.5% Cr, 1.0% Mo, 9.0% Ni, 5.5% Co, 1.0% Cu, 2.0% Ti and 1.25% Al, balance iron and unavoidable The proportion of TiC in the microstructure of this steel is also 30% by weight, but in addition, 5% by weight of NbC are used in the microstructure
Hartphase vorhanden. Der derart zusammengesetzte Stahl ließ bei seiner Hard phase available. The thus composed steel left at his
Erzeugung im Labormaßstab auf vielversprechendes Laboratory scale production on promising
Potenzial hoffen. Allerdings erwies sich seine Hope for potential. However, his proved
betriebssichere großtechnische Erzeugung als Reliable large-scale production as
problematisch . problematic.
Vor diesem Hintergrund bestand die Aufgabe der Erfindung darin, einen Stahl zu schaffen, der sich im Against this background, the object of the invention was to provide a steel which is in the
industriellen Maßstab unter Anwendung konventioneller Verfahren erzeugen lässt und ein hinsichtlich seiner Eigenschaften optimiertes Profil aufweist. Ebenso sollten praxisgerechte Verwendungen eines solchen Stahls genannt werden. produce industrial scale using conventional methods and has a profile optimized in terms of its properties. Likewise, practical uses of such a steel should be mentioned.
In Bezug auf den Stahl ist diese Aufgabe dadurch gelöst worden, dass ein solcher Stahl erfindungsgemäß die in Anspruch 1 angegebenen Merkmale besitzt. With respect to the steel, this object has been achieved in that such a steel according to the invention has the features specified in claim 1.
Vorteilhafte Ausgestaltungen der Erfindung sind in den abhängigen Ansprüchen angegeben und werden nachfolgend wie der allgemeine Erfindungsgedanke im Einzelnen erläutert . Advantageous embodiments of the invention are specified in the dependent claims and are explained below as the general inventive concept in detail.
Mit der Erfindung steht ein Stahl für Anwendungen, die eine hohe Verschleißbeständigkeit, eine hohe Härte, eine gute Korrosionsbeständigkeit und/oder eine niedrige Wärmeleitfähigkeit erfordern, zur Verfügung. The invention provides a steel for applications requiring high wear resistance, high hardness, good corrosion resistance and / or low thermal conductivity.
Der erfindungsgemäße Stahl erzielt im gehärteten Zustand eine Härte von mindestens 56 HRC und enthält in seinem Gefüge in Summe mindestens 30 Gew.-% Hartphasen The steel according to the invention achieves a hardness of at least 56 HRC in the cured state and contains in its structure a total of at least 30% by weight of hard phases
vorhanden, die neben den TiC-Partikeln aus Karbid-, Oxid- oder Nitrid-Partikeln bestehen. Dabei beträgt im erfindungsgemäßen Stahl der Gehalt an TiC-Partikeln present in addition to the TiC particles of carbide, Oxide or nitride particles exist. In the steel according to the invention, the content of TiC particles is
mindestens 20 Gew.-%. at least 20% by weight.
Erfindungsgemäß sind die Hartphasen in eine Matrix According to the invention, the hard phases are in a matrix
eingebettet, welche (in Gew.-%) aus embedded, which (in wt .-%) out
9,0 - 15,0 % Cr,  9.0 - 15.0% Cr,
5,0 - 9,0 % Mo,  5.0 - 9.0% Mo,
3,0 - 7,0 % Ni,  3.0 - 7.0% Ni,
6,0 - 11,0 % Co,  6.0 - 11.0% Co,
0,3 - 1, 5 % Cu,  0.3-1.5% Cu,
0,1 - 2, 0 % Ti,  0.1-2.0% Ti,
0,1 - 2,0 % AI,  0.1 - 2.0% AI,
Rest Eisen und unvermeidbaren Verunreinigungen  Remaining iron and unavoidable impurities
besteht . consists .
Die Komponenten eines erfindungsgemäßen Stahls sind so eingestellt, dass er höchsten Anforderungen genügt, wie sie an Stähle gestellt werden, die im Bereich der The components of a steel according to the invention are adjusted so that it meets the highest requirements, as they are made of steels that are in the field of
kunststoffverarbeitenden Industrie eingesetzt werden. used in the plastics processing industry.
Dementsprechend eignet sich ein erfindungsgemäßer Stahl insbesondere für die Herstellung von Komponenten zum Accordingly, a steel according to the invention is particularly suitable for the production of components for
Neuerzeugen und zum Recycling von KunststoffProdukten . So lassen sich aus erfindungsgemäßem Stahl beispielweise für das Granulieren von aus abrasiven Kunststoffen gebildeten New generation and recycling of plastic products. Thus, for example, for the granulation of abrasive plastics formed from inventive steel
Schmelzen benötigte Lochplatten, insbesondere Melting required perforated plates, in particular
Mikrogranulierlochplatten, herstellen, die selbst dann noch optimale Gebrauchseigenschaften aufweisen, wenn ihre Mikrogranulierlochplatten produce, even if they have optimal performance characteristics, even if their
Lochöffnungen mikrofein ausgebildet sind, um entsprechend feingekörnte Granulate zu erzeugen. Genauso lassen sich aus erfindungsgemäßem Stahl Messer zum Zerkleinern von Hole openings are made microfine to produce correspondingly finely granulated granules. In the same way, knives for shredding of steel according to the invention can be made
Kunststoffteilen herstellen. Solche Messer werden, wie oben bereits erläutert, ebenfalls bei der Herstellung von Produce plastic parts. Such knives become as above already explained, also in the production of
Granulaten aus erschmolzenen Kunststoffsträngen benötigt, wie sie mit Hilfe von Lochplatten der voranstehend erläuterten Art in Granuliereinrichtungen erzeugt werden. Granules of molten plastic strands required, as they are produced by means of perforated plates of the type described above in Granuliereinrichtungen.
Um das hierzu benötigte Eigenschaftsprofil bereitzustellen, enthält ein erfindungsgemäßer Stahl mindestens 20 Gew.-% TiC, die eingebettet sind in eine Matrix, die durch In order to provide the property profile required for this purpose, a steel according to the invention contains at least 20% by weight of TiC embedded in a matrix which is penetrated by
Äusschexdungsbildung zur Härtbarkeit des Stahls beiträgt und die gleichzeitig so gewählt ist, dass eine niedrige Deterioration contributes to the hardenability of the steel and at the same time is chosen so that a low
Wärmeleitfähigkeit von weniger als 35 W/mK unabhängig vom jeweiligen Wärmebehandlungszustand gewährleistet ist. Thermal conductivity of less than 35 W / mK is guaranteed regardless of the respective heat treatment state.
Die Passivstromdichte des erfindungsgemäßen Stahls ist geringer als 5 μΑ/cm2, gemessen in Sauerstofffreier 0,5 molarer Schwefelsäure mit einer The passive current density of the steel according to the invention is less than 5 μΑ / cm 2 , measured in oxygen-free 0.5 molar sulfuric acid with a
Potenzialänderungsgeschwindigkeit von 600 mV/h gegen eine Kalomel-Bezugselektrode bei 20 °C. Erfindungsgemäßer Stahl weist daher bei hoher Härte und optimiertem  Potential change rate of 600 mV / h against a calomel reference electrode at 20 ° C. Steel according to the invention therefore has high hardness and optimized
Verschleißwiderstand eine Korrosionsbeständigkeit auf, die vergleichbar ist mit der Korrosionsbeständigkeit Wear resistance has a corrosion resistance comparable to the corrosion resistance
konventioneller austenitischer rostfreier Stähle. conventional austenitic stainless steels.
Das gemäß mittels Ultraschallmessung in Abhängigkeit der Schallausbreitungsgeschwindigkeit bestimmte E-Modul The E modulus determined by ultrasound measurement as a function of the sound propagation velocity
erfindungsgemäßer Stähle liegt bei einer Temperatur von 20 °C bei mehr als 270 GPa, insbesondere mehr als 300 GPa, so dass der erfindungsgemäße Stahl bzw. daraus hergestellte According to the invention steels is at a temperature of 20 ° C at more than 270 GPa, in particular more than 300 GPa, so that the steel according to the invention or produced therefrom
Komponenten auch höchste Anforderungen an ihre Festigkeit sicher erfüllen. Der gemäß mittels Dilatometer ermittelte thermische Components also meet the highest demands on their strength. The determined by means of dilatometer thermal
Ausdehnungskoeffizient von erfindungsgemäßem Stahl liegt in dem für Anwendungen, für die erfindungsgemäße Stähle Coefficient of expansion of steel according to the invention is that for applications for the steels according to the invention
vorgesehen sind, bedeutsamen Temperaturbereich von 20 °C bis 600 °C bei 7 x 10"6/K bis 12 x 10~6/K. are provided, significant temperature range from 20 ° C to 600 ° C at 7 x 10 "6 / K to 12 x 10 ~ 6 / K.
Durch die Anwesenheit einer ausreichenden Menge der extrem harten, thermodynamisch stabilen TiC-Partikel, die eine geringe Dichte bei niedriger Wärmeleitfähigkeit besitzen, wird in Kombination mit der erfindungsgemäß vorgesehenen Stahlmatrix, die ebenfalls eine hohe Härte erreicht, eine maximierte Verschleißbeständigkeit bei gleichzeitig The presence of a sufficient amount of the extremely hard, thermodynamically stable TiC particles, which have a low density with low thermal conductivity, in combination with the inventively provided steel matrix, which also achieves a high hardness, a maximized wear resistance at the same time
minimierter Wärmeleitfähigkeit erhalten. Optimalerweise enthält dazu der erfindungsgemäße Stahl mindestens 20 Gew.-%, entsprechend etwa 30 Vol.-% Tic, oder mindestens 28 Gew.-% TiC, insbesondere mindestens 30 Gew.-% TiC. Jedoch sollte der TiC-Gehalt eine Obergrenze von 45 Gew.-% nicht überschreiten. Auf diese Weise lässt sich gewährleisten, dass sich minimized thermal conductivity. Optimally, the steel according to the invention contains at least 20% by weight, corresponding to about 30% by volume of TIC, or at least 28% by weight of TiC, in particular at least 30% by weight of TiC. However, the TiC content should not exceed an upper limit of 45% by weight. That way you can ensure that yourself
erfindungsgemäßer Stahl betriebssicher herstellen und manufacture steel according to the invention reliably and
weiterverarbeiten lässt. Zu hohe Hartphasengehalte führen zwar zu erhöhter Härte und Verschleißbeständigkeit. can be further processed. Too high a hard phase content leads to increased hardness and wear resistance.
Allerdings wird die thermische Ausdehnung reduziert, was die Verbundfertigung mit Stahlsubstraten deutlich erschwert. However, the thermal expansion is reduced, which makes joint production with steel substrates much more difficult.
Zudem bedeutet ein höherer Hartphasengehalt, dass der In addition, a higher hard phase content means that the
Werkstoff spröder und rissempfindlicher wird. Gleichzeitig werden die mechanischen Bearbeitungsmöglichkeiten bei zu hohen Hartphasengehalten signifikant herabgesetzt. Ein Material becomes more brittle and more susceptible to cracking. At the same time, the mechanical processing options are significantly reduced at high hard phase contents. One
Vorteil von erfindungsgemäßem Stahl besteht hier darin, dass auch er konventionell zerspanend bearbeitet werden kann. The advantage of steel according to the invention here is that it too can be machined conventionally by machining.
Zur Optimierung der Härte und Verschleißbeständigkeit eines erfindungsgemäßen Stahls trägt zudem bei, dass erfindungsgemäß zusätzlich zu den TiC-Partikeln in der Stahlmatrix weitere Hartphasen vorhanden sind, so dass der Volumenanteil der Hartphasen am Gefüge des Stahls insgesamt mindestens 30 Gew.-% beträgt. Dies kann durch gesonderte Zugabe von Karbid-, Nitrid- oder Oxid-Partikeln bei der Erzeugung des Stahls erfolgen. Alternativ oder ergänzend dazu können auch die die Gewichtsanteile der Ausscheidungen bildenden Elemente (Ni, AI, Ti) innerhalb der To optimize the hardness and wear resistance of a steel according to the invention also contributes that According to the invention further hard phases are present in addition to the TiC particles in the steel matrix, so that the volume fraction of the hard phases in the structure of the steel is at least 30 wt .-% in total. This can be done by separate addition of carbide, nitride or oxide particles in the production of the steel. Alternatively or additionally, the elements forming the weight fractions of the precipitates (Ni, Al, Ti) can also be used within the
erfindungsgemäßen Vorgaben so eingestellt werden, dass sich im Zuge der bei der Erzeugung des Stahls absolvierten According to the invention specifications are adjusted so that in the course of the completed in the production of steel
Arbeitsschritte zuverlässig eine ausreichende Menge an härtesteigernden Ausscheidungen in der Matrix bildet. Reliably forms a sufficient amount of hardness-increasing precipitates in the matrix.
Gegenüber dem aus der oben schon erwähnten Dissertation von H. Hill bekannten Stahl sind beim erfindungsgemäßen Stahl die Gehalte an Mo und Co deutlich erhöht sowie die Gehalte an Ni und Ti deutlich vermindert. Zudem sind die Vorgaben für die Cu-, AI-, TiC- und NbC-Gehalte einer erfindungsgemäßen Legierung gegenüber dem bekannten In contrast to the steel known from the above-mentioned thesis of H. Hill, the contents of Mo and Co are markedly increased in the steel according to the invention and the contents of Ni and Ti are markedly reduced. In addition, the specifications for the Cu, Al, TiC and NbC contents of an alloy according to the invention over the known
Stahl variiert worden. Durch die erfindungsgemäße Steel has been varied. By the invention
Einstellung der Legierungsgehalte ist es gelungen, einen Stahl im industriellen Maßstab zu erzeugen, der einen hohen Hartphasenanteil besitzt, der in einer Stahlmatrix von ebenfalls hoher Härte eingebettet ist. Ausgehend von den bekannten Stahlkonzepten erforderte dies aufwändige Untersuchungen und Versuche, weil die Wirkweise und die Wechselwirkungen der einzelnen Elemente und Phasen bei Stählen der hier in Rede stehenden Art sehr komplex sind. Der so erhaltene erfindungsgemäße Stahl weist mit seiner hohen Verschleißbeständigkeit, hohen Härte, guten Korrosionsbeständigkeit und niedrigen Wärmeleitfähigkeit eine optimierte Eigenschaftskombination auf. Die Ausscheidungen, die sich in der Stahlmatrix des Adjustment of the alloy contents has succeeded in producing a steel on an industrial scale, which has a high hard phase content, which is embedded in a steel matrix of equally high hardness. Starting from the known steel concepts, this required extensive investigations and experiments, because the mode of action and the interactions of the individual elements and phases are very complex in steels of the type in question here. The steel according to the invention thus obtained has an optimized combination of properties with its high wear resistance, high hardness, good corrosion resistance and low thermal conductivity. The precipitates arising in the steel matrix of the
erfindungsgemäßen Stahls bilden, sind intermetallische Ausscheidungen, an deren Entstehung vor allem die Elemente Ni, AI und Ti beteiligt sind. Diese Elemente bilden Ni3Al und Ni3Ti oder auch Mischformen. Diese intermetallischen Phasen liegen im Gefüge mit Korngrößen in der Größenordnung von 10 nm vor und werden nicht zum Gesamthartphasengehalt gezählt. Aufgrund ihrer geringen Größe leisten sie im form steel according to the invention are intermetallic precipitates, in whose formation mainly the elements Ni, Al and Ti are involved. These elements form Ni 3 Al and Ni 3 Ti or mixed forms. These intermetallic phases are present in the structure with grain sizes of the order of 10 nm and are not counted to the total hard phase content. Due to their small size, they afford the
Vergleich zu den groben Hartphasenpartikeln, wie sie erfindungsgemäß in der Matrix des erfindungsgemäßen Stahls eingebettet sind, keinen größeren Beitrag zur Beständigkeit gegen abrasiven Verschleiß. Jedoch bewirken die Compared to the coarse hard-phase particles, as they are embedded in the matrix of the steel according to the invention, no major contribution to the resistance to abrasive wear. However, the effect
intermetallischen Ausscheidungen eine Steigerung der Härte und Festigkeit der Metallmatrix und tragen so ebenfalls zur Verbesserung der Gebrauchseigenschaften bei. intermetallic precipitations an increase in hardness and strength of the metal matrix and thus also contribute to improving the performance properties.
Chrom ist im erfindungsgemäßen Stahl in Gehalten von Chromium is in the steel of the invention in levels of
9,0 - 15,0 Gew.-% vorhanden, um die geforderte 9.0 - 15.0 wt .-% present to the required
Korrosionsbeständigkeit zu sichern. Optimalerweise liegt dazu der Cr-Gehalt bei 12,5 - 14,5 Gew.-%. To ensure corrosion resistance. Optimally, the Cr content is 12.5-14.5 wt .-%.
Molybdän ist im erfindungsgemäßen Stahl in Gehalten von 5,0 - 9,0 Gew.-% enthalten, um einerseits eine ausreichende Korrosionsbeständigkeit insbesondere im Hinblick auf die Lochkorrosion zu gewährleisten und andererseits die Bildung intermetallischer Phasen zu unterstützen, durch die die Härte der Stahlmatrix, in der die Hartphasen eingelagert sind, erhöht wird. Optimalerweise beträgt der Mo-Gehalt des erfindungsgemäßen Stahls 6,5 - 7,5 Gew.-%. Molybdenum is contained in the steel according to the invention in amounts of 5.0-9.0 wt .-%, on the one hand to ensure sufficient corrosion resistance, in particular with regard to pitting corrosion and on the other hand to support the formation of intermetallic phases, by the hardness of the steel matrix, in which the hard phases are embedded, is increased. Optimally, the Mo content of the steel according to the invention is 6.5-7.5% by weight.
Kobalt ist im erfindungsgemäßen Stahl in Gehalten von 6,0 - 11,0 Gew.-% enthalten, um zum einen die Martensitstarttemperatur zu erhöhen und zum anderen die Löslichkeit von Mo in der Metallmatrix zu reduzieren. Auf diese Weise kann sich das in der erfindungsgemäßen Cobalt is contained in the steel according to the invention in contents of 6.0 - 11.0 wt .-%, in order to To increase martensite start temperature and on the other hand to reduce the solubility of Mo in the metal matrix. In this way, in the inventive
Stahlmatrix enthaltene Mo verstärkter an der Bildung intermetallischer Phasen beteiligen. Optimalerweise beträgt der Co-Gehalt des erfindungsgemäßen Stahls 8,0 - 10,0 Gew.- o Steel matrix contained more intensely involved in the formation of intermetallic phases. Optimally, the Co content of the steel according to the invention is 8.0-10.0% by weight
o · o ·
Kupfer ist im erfindungsgemäßen Stahl in Gehalten von Copper is in the steel of the invention in contents of
0,3 - 1,5 Gew.-% enthalten, um die Ausscheidungshärtung zu beschleunigen. Optimalerweise beträgt der Cu-Gehalt des erfindungsgemäßen Stahls 0,5 - 1,0 Gew.-%. 0.3 - 1.5 wt .-% to accelerate the precipitation hardening. Optimally, the Cu content of the steel according to the invention is 0.5-1.0% by weight.
Nickel ist im erfindungsgemäßen Stahl in Gehalten von Nickel is in the steel according to the invention in contents of
3,0 - 7,0 Gew.-% vorhanden. Nickel wird in der Stahlmatrix in ausreichender Menge benötigt, um bei einem 3.0 - 7.0 wt .-% present. Nickel is needed in the steel matrix in sufficient quantity to be at a
Lösungsglühen, das typischerweise bei ca. 850 °C Solution annealing, typically at about 850 ° C
durchgeführt wird, die austenitische Phase zu is carried out, the austenitic phase too
stabilisieren. Dies ist vor allem dann wichtig, wenn der erfindungsgemäße Werkstoff ausgehend von der stabilize. This is especially important if the material according to the invention, starting from the
Lösungsglühtemperatur abgeschreckt wird. Durch die Solution annealing temperature is quenched. By the
Anwesenheit von Nickel wird hier der Austenit so weit stabilisiert, dass bei der Abschreckung sicher Martensit entsteht. Ist zu wenig Nickel in der erfindungsgemäß vorgesehenen Stahlmatrix vorhanden, so wird dieser Effekt nicht mit der notwendigen Sicherheit erreicht. Ist dagegen zu viel Nickel in der Stahlmatrix vorhanden, bildet sich kein Martensit, da die austenitische Phase dann auch bei Raumtemperatur stabil ist. Die zweite Aufgabe von Nickel im erfindungsgemäßen Stahl ist die Ausscheidungshärtung durch Bildung intermetallischer Phasen mit Elementen wie AI und Ti . Daher sind in der Stahlmatrix des erfindungsgemäßen Stahls die Gehalte an Ni, AI und Ti so aufeinander The presence of nickel stabilizes the austenite to such an extent that martensite is safely formed during quenching. If too little nickel is present in the steel matrix provided according to the invention, this effect is not achieved with the necessary certainty. If, on the other hand, too much nickel is present in the steel matrix, no martensite forms, since the austenitic phase is then stable even at room temperature. The second object of nickel in the steel according to the invention is precipitation hardening by formation of intermetallic phases with elements such as Al and Ti. Therefore, in the steel matrix of the invention Steel the contents of Ni, Al and Ti on each other
abgestimmt, dass zum einen die Martensitbildung gegeben ist und zum anderen die Ausscheidungshärtung ermöglicht wird. Optimalerweise beträgt dazu der Ni-Gehalt des agreed that on the one hand, the martensite is given and on the other the Ausscheidungshärtung is made possible. Optimally, this is the Ni content of the
erfindungsgemäßen Stahls 4,5 - 5,5 Gew.-%. steel according to the invention 4.5 to 5.5 wt .-%.
Titan ist im erfindungsgemäßen Stahl in Gehalten von Titanium is in the steel according to the invention in contents of
0,1 - 2,0 Gew.-% vorhanden, um, wie voranstehend schon erläutert, in Kombination mit Ni die Ausscheidungshärtung zu ermöglichen. Optimalerweise beträgt dazu der Ti-Gehalt des erfindungsgemäßen Stahls 0,8 - 1,2 Gew.-%. 0.1 - 2.0 wt .-% present to allow, as already explained above, in combination with Ni the precipitation hardening. Optimally, the Ti content of the steel according to the invention is 0.8 to 1.2% by weight.
Auch Aluminium ist im erfindungsgemäßen Stahl in Gehalten von 0,1 - 2,0 Gew.-% enthalten, um in Kombination mit Ni die Ausscheidungshärtung zu bewirken. Optimalerweise beträgt dazu der Al-Gehalt des erfindungsgemäßen Stahls 1,0 - 1,4 Gew.-%. Also, aluminum is contained in the steel of the present invention at levels of 0.1-2.0% by weight to effect precipitation hardening in combination with Ni. Optimally, the Al content of the steel according to the invention is 1.0 to 1.4% by weight.
Der erfindungsgemäße Stahl lässt sich äußerst verzugsarm härten, da Titankarbid eine geringe Wärmeausdehnung und keine Umwandlung besitzt. The steel according to the invention can be hardened with extremely low distortion, since titanium carbide has a low thermal expansion and no transformation.
Durch die Zugabe von bis zu 4,5 Gew.-% NbC-Partikeln wird der Verschleißwiderstand des erfindungsgemäßen Stahls erhöht. Gleichzeitig haben die NbC-Partikel eine geringere Wärmeleitfähigkeit als TiC, was sich günstig auf die By adding up to 4.5 wt .-% NbC particles, the wear resistance of the steel according to the invention is increased. At the same time, the NbC particles have a lower thermal conductivity than TiC, which is beneficial to the
Gebrauchseigenschaften des erfindungsgemäßen Stahls Performance characteristics of the steel according to the invention
auswirkt. Darüber hinaus sind Tic und NbC isomorphe Karbide und daher untereinander mischbar. Dies führt bei effect. In addition, Tic and NbC are isomorphic carbides and therefore miscible with each other. This leads
Diffusionsreaktionen zur Bildung von Mischkarbiden. In Folge dessen ergibt sich im Vergleich zur alleinigen Diffusion reactions for the formation of mixed carbides. As a result, compared to the sole
Verwendung von Tic eine Änderung der Valenzelektronenkonzentration und somit die Bildung von Leerstellen im Zwischengitter des Kohlenstoffes. Auch auf diesem Weg wird die Wärmeleitfähigkeit des Using Tic a change of Valence electron concentration and thus the formation of vacancies in the interstitial carbon. Also in this way, the thermal conductivity of the
erfindungsgemäßen Stahls herabgesetzt und die reduced steel according to the invention and the
Gebrauchseignung verbessert. Diese Wirkung kann Fitness for use improved. This effect can
insbesondere dann erzielt werden, wenn im erfindungsgemäßen Stahl mindestens 2,0 Gew.-% NbC vorhanden sind. Ein be achieved in particular if at least 2.0 wt .-% NbC are present in the steel according to the invention. One
optimaler Einfluss ergibt sich dabei dann, wenn der NbC- Gehalt 2,0 - 3,0 Gew.-% beträgt. optimum influence is obtained when the NbC content is 2.0-3.0% by weight.
Indem der erfindungsgemäße Stahl in konventioneller Weise pulvermetallurgisch hergestellt wird, lässt sich By producing the steel according to the invention by powder metallurgy in a conventional manner, it is possible to obtain
gewährleisten, dass sein Gefüge frei von Seigerungen und Faserverläufen ist. Die erfindungsgemäß als Hartphasen verwendeten Karbid-, Nitrid- und Oxidpartikel werden während der pulvermetallurgischen Fertigung bereits als "fertige" Partikel zugeführt. ensure that its structure is free of segregation and fiber progressions. The carbide, nitride and oxide particles used according to the invention as hard phases are already supplied as "finished" particles during powder metallurgical production.
Für die pulvermetallurgische Herstellung lassen sich sowohl die Sinter-, als auch die HIP- (Heiß-Isostatisches Pressen) Route nutzen. Beispielsweise eignet sich auch das For the powder metallurgical production, both the sintering, as well as the HIP (hot isostatic pressing) route can be used. For example, this is also suitable
Supersolidus Flüssigphasensintern auf Basis gasverdüster Stahlpulver für die Erzeugung erfindungsgemäßer Stähle. Supersolidus liquid phase sintering based on gas-atomized steel powder for the production of steels according to the invention.
Eine Beschreibung der üblicherweise bei der A description of the commonly used in the
pulvermetallurgischen Herstellung von Stählen der hier in Rede stehenden Art angewendeten Arbeitsschritte findet sich beispielsweise in Foller, M.; Meyer, H.; Lammer, A. : Wear and Corrosion of Ferro-Titanit and Competing Materials. In: Tool steels in the next Century: Proceedings of the 5th International Conference on Tooling, September 29th - October Ist, University of Leoben, Austria, 1999, S. 1 - 12, in H. Hill, S. Weber, W. Theisen, A. van Bennekom, Optimierung korrosionsbeständiger MMC mit hohem powder metallurgical production of steels of the type in question here applied steps can be found for example in Foller, M .; Meyer, H .; Lammer, A.: Wear and Corrosion of Ferro-Titanite and Competing Materials. In: Tool steels in the next Century: Proceedings of the 5th International Conference on Tooling, September 29th - October Ist, University of Leoben, Austria, 1999, p. 1 - 12, H. Hill, S. Weber, W. Theisen, A. van Bennekom, Optimization of Corrosion-Resistant MMCs with High
Verschleißwiderstand, 30. Hagener Symposium, 24. - 25.11.2011 oder in der oben schon erwähnten Dissertation von Horst Hill. Wear resistance, 30th Hagen Symposium, 24. - 25.11.2011 or in the already mentioned dissertation by Horst Hill.
Der erfindungsgemäße Stahl kann zur Einstellung seiner mechanischen Eigenschaften einer konventionellen The steel according to the invention can be used to adjust its mechanical properties to a conventional one
Wärmebehandlung unterzogen werden, bei der er für Be subjected to heat treatment, during which he for
2 - 4 Stunden erwärmt, anschließend unter einer mit einem Druck von 1 - 4,5 bar beaufschlagten Stickstoffatmosphäre abgeschreckt und schließlich über 6 - 8 Stunden bei 480 °C ausgelagert wird. Erfindungsgemäßer Stahl weist nach einer derartigen Wärmebehandlung regelmäßig eine Härte von mehr als 62 HRC auf. Durch eine Erwärmung unter Vakuum und eine Abschreckung in einer Inertgasatmosphäre werden negative Einflusszonen im Randbereich des für die Wärmebehandlung jeweils aus dem Stahl geformten Halbzeugs vermieden. 2 to 4 hours, then quenched under a nitrogen atmosphere applied at a pressure of 1 to 4.5 bar, and finally removed at 480 ° C. for 6 to 8 hours. Steel according to the invention regularly has a hardness of more than 62 HRC after such a heat treatment. By heating under vacuum and quenching in an inert gas atmosphere negative influence zones are avoided in the edge region of the semi-finished for the heat treatment in each case from the steel.
Beschränkt sich die Wärmebehandlung auf eine Weichglühung bei 850 °C über 2 - 4 Stunden, so besitzt der If the heat treatment is limited to soft annealing at 850 ° C for 2 - 4 hours, then the
erfindungsgemäße Stahl eine Härte von mehr als 50 HRC. Steel according to the invention has a hardness of more than 50 HRC.
Nachfolgend wird die Erfindung anhand von The invention is based on
Ausführungsbeispielen näher erläutert. Die Figuren zeigen : Embodiments explained in more detail. The figures show:
Fig. 1 einen Ausschnitt einer Fig. 1 shows a detail of a
rasterelektronenmikroskopischen Aufnahme eines Schnitts einer erfindungsgemäßen Probe; Fig. 2 ein Diagramm, in dem die Ergebnisse der scanning electron micrograph of a section of a sample according to the invention; Fig. 2 is a diagram in which the results of
Messung der Wärmeleitfähigkeit von  Measurement of the thermal conductivity of
erfindungsgemäßen und zum Vergleich erzeugten Stahlproben dargestellt sind;  shown and produced for comparison steel samples are shown;
Fig. 3 ein Diagramm mit dem Ergebnis einer an Fig. 3 is a diagram with the result of an
erfindungsgemäßen und zum Vergleich erzeugten according to the invention and produced for comparison
Stahlproben durchgeführten Stromdichte-Steel samples carried out current density
Potenzial-Messung; Potential measurement;
Fig. 4 ein Diagramm, das das Ergebnis einer 4 is a diagram showing the result of a
Dilatometermessung an einer aus  Dilatometer measurement on one
erfindungsgemäßem Stahl erzeugten Probe wiedergibt .  reproduces sample produced according to the invention steel.
Zum Vergleich der Eigenschaften eines erfindungsgemäßen Stahls, der für die Herstellung von Lochplatten oder Messern für eine Unterwasser-Granuliermaschine bestimmt ist, mit den Eigenschaften eines bekannten, für To compare the properties of a steel according to the invention, which is intended for the production of perforated plates or knives for an underwater pelletizer, with the properties of a known, for
denselben Verwendungszweck vorgesehenen Stahls sind der erfindungsgemäße Stahl E und der bekannte Stahl V erzeugt worden. Die Zusammensetzung beider Stähle E und V ist in Tabelle 1 angegeben. steel steel E according to the invention and the known steel V have been produced. The composition of both steels E and V is given in Table 1.
Die Zusammensetzung des Stahls V entsprach dabei der Zusammensetzung des unter der Bezeichnung "Ferro-Titanit Nikro 128" bekannten, beispielsweise in der oben bereits genannten Veröffentlichung dokumentierten Stahls. Die bei der pulvermetallurgischen Herstellung beider Stähle E,V absolvierten Arbeitsschritte entsprachen den The composition of the steel V corresponded to the composition of the known under the name "Ferro-Titanit Nikro 128", for example, in the above-mentioned publication documented steel. The completed in the powder metallurgical production of both steels E, V operations corresponded to the
Arbeitsschritten, die üblicherweise bei der Steps that are usually taken at the
pulvermetallurgischen Erzeugung des Stahls "Ferro- Titanit Nikro 128" ausgeführt werden. Sie sind in der oben bereits erwähnten Fachliteratur erläutert. powder metallurgical production of the steel "Ferro Titanit Nikro 128 ", which are explained in the technical literature already mentioned above.
Nach der pulvermetallurgischen Erzeugung sind Proben PEl, PVl der Stähle E und V einer Wärmbehandlung After powder metallurgy production, samples PEl, PVl of steels E and V are heat treated
unterzogen worden, die ebenfalls der beim Stahl Ferro- Titanit Nikro 128 standardmäßig absolvierten which also passed the steel Ferro-Titanit Nikro 128 as standard
Wärmebehandlung entsprach. Dazu sind die Proben PEl und PVl zunächst über eine Dauer von zwei bis vier Stunden im Vakuum bei einer Temperatur von 850 °C gehalten worden und anschließend unter einer mit 1 - 4,5 bar druckbeaufschlagten Stickstoffatmosphäre abgeschreckt worden. Anschließend erfolgt eine Aushärtebehandlung, bei der die Proben PEl, PVl jeweils für sechs bis acht Stunden bei einer Temperatur von 480 °C ausgelagert worden sind. Heat treatment corresponded. For this purpose, samples PE1 and PV1 were first kept in vacuo at a temperature of 850 ° C. for a period of two to four hours and then quenched under a nitrogen atmosphere pressurized with 1 to 4.5 bar. This is followed by a curing treatment in which the samples PEl, PVl have been stored for six to eight hours at a temperature of 480 ° C.
Fig. 1 zeigt einen Ausschnitt einer Fig. 1 shows a section of a
rasterelektronenmikroskopischen Aufnahme eines Schnitts einer Probe PEl des derart standardmäßig Scanning electron micrograph of a section of a sample PEl of such a standard
wärmebehandelten erfindungsgemäßen Stahls E. Die heat treated steel of the invention E. The
Metallmatrix ist durch die hellen Bereiche erkennbar, wogegen die von der Matrix umgebenen TiC-Einschlüsse dunkel wiedergegeben sind. Metal matrix is recognizable by the bright areas, whereas the TiC inclusions surrounded by the matrix are rendered dark.
Andere aus den Stählen E und V bestehende Proben PE2, PV2 sind einer über ebenfalls 2 - 4 Stunden sich Other samples PE2, PV2 consisting of steels E and V are also over 2 to 4 hours
erstreckenden Weichglühung bei 850 °C unterzogen worden. extending soft annealing at 850 ° C.
An den Proben PEl , PVl , PE2 , PV2 sind die Hartphasengehalte bestimmt worden. Sie lagen bei den aus dem The hard phase contents were determined on the samples PE1, PV1, PE2, PV2. They were with the from the
erfindungsgemäßen Stahl PE1,PE2 erzeugten Proben im Mittel bei mehr als 30 Gew.-%, wogegen die aus dem steel according to the invention PE1, PE2 produced in the Mean at more than 30 wt .-%, whereas the from the
Vergleichsstahl V erzeugten Proben PV1,PV2 im Mittel nur 30 Gew.-% Hartphasen aufwiesen. Comparative steel V produced samples PV1, PV2 had on average only 30 wt .-% hard phases.
Zur Bestimmung der Härte der verschiedenen Proben To determine the hardness of the different samples
PEl, PE2, PVl, PV2 wurden fünf Härtemessungen gemäß DIN EN ISO 6508-1 durchgeführt. Die Mittelwerte der so für die Proben PEl, PE2, PVl, PV2 erfassten Messwerte sind in PEl, PE2, PVl, PV2 five hardness measurements according to DIN EN ISO 6508-1 were carried out. The mean values of the measured values thus acquired for the samples PE1, PE2, PV1, PV2 are in
Tabelle 2 angegeben. Es zeigt sich, dass die Härte der erfindungsgemäßen Proben PE1,PE2 jeweils höher lag als die Härte der Vergleichsproben. Table 2 given. It turns out that the hardness of the samples according to the invention PE1, PE2 was higher than the hardness of the comparative samples.
Des Weiteren ist die temperaturabhängige Furthermore, the temperature-dependent
Wärmeleitfähigkeit λ(Τ) mit Hilfe der indirekten Methode bei Raumtemperatur, 100 °C, 200 °C und 300 °C, bestimmt worden : λ(Τ) = a (T) x p(T) x cp(T) mit a(T): Temperaturleitfähigkeit, gemessen mittels  Thermal conductivity λ (Τ) was determined using the indirect method at room temperature, 100 ° C, 200 ° C and 300 ° C: λ (Τ) = a (T) xp (T) x cp (T) with a (T ): Thermal conductivity, measured by means of
Laserflash, wie in Linseis Messgeräte GmbH: Instruction Manual LFA 1250/1600 - Laser Flash: Thermal constant analyser, 2010, oder ASTM International E 1461-01: Standard Test Method for Thermal Diffusivity by the Flash Method, 2001, erläutert;  Laser Flash as described in Linseis Messgeräte GmbH: Instruction Manual LFA 1250/1600 - Laser Flash: Thermal constant analyzer, 2010, or ASTM International E 1461-01: Standard Test Method for Thermal Diffusion by the Flash Method, 2001;
p(T) : die Dichte der jeweiligen Probe, gemessen mit dem Dilatometer;  p (T): the density of each sample measured with the dilatometer;
cp(T): die spezifische isobare Wärmekapazität der  cp (T): the specific isobaric heat capacity of the
Probe, ermittelt durch Dynamische Differenzkalorimetrie ("DSC") . Das Ergebnis dieser Untersuchung ist für die Proben PEl und PV1 in Fig. 2 dargestellt. Es zeigt sich, dass die Wärmeleitfähigkeit bei der aus dem erfindungsgemäßen Stahl E erzeugten Probe PEl jeweils niedriger war als bei der Probe PV1, die aus dem Vergleichsstahl V Sample determined by Differential Scanning Calorimetry ("DSC"). The result of this investigation is shown for samples PE1 and PV1 in FIG. It can be seen that the thermal conductivity of the sample PEl produced from the steel E according to the invention was in each case lower than in the case of the sample PV1, which consisted of the comparative steel V
gefertigt worden ist. Die geringe Wärmeleitfähigkeit der erfindungsgemäßen Probe PEl ist im Hinblick auf den hier vorgesehenen Verwendungszweck der Stähle E und V has been made. The low thermal conductivity of the sample according to the invention PEl is in view of the intended use of steels E and V here
vorteilhaft . advantageous.
Der TiC-Gehalt der erfindungsgemäßen Proben PE1,PE2 betrug, wie in Tabelle 1 angegeben, jeweils mehr als 30 Gew.-%. The TiC content of the samples according to the invention PE1, PE2 was, as indicated in Table 1, each more than 30 wt .-%.
Die Dichte der aus dem erfindungsgemäßen Stahl E The density of the steel E of the invention
erzeugten Proben PE1,PE2 betrug 6,55 g/cm3, womit die theoretische Dichte erreicht wurde. Wie aus Fig. 1 hervorgeht, weist das Gefüge keine Restporösitäten auf. produced samples PE1, PE2 was 6.55 g / cm 3 , whereby the theoretical density was reached. As is apparent from Fig. 1, the structure has no residual porosity.
Das Ergebnis einer an aus dem erfindungsgemäßen Stahl E erzeugten Proben PEl und aus dem Vergleichsstahl V erzeugten Proben PV1 durchgeführten Stromdichte- Potenzial-Messung ist in Fig. 3 dargestellt. Darin ist die für die Proben PEl ermittelte Stromdichte- Potenzialkurve als durchgezogene Linie und die für die Proben PV1 ermittelte Stromdichte-Potenzialkurve als gestrichelte Linie dargestellt. Die Stromdichte- Potenzialkurven wurden in Sauerstofffreier 0,5 molarer Schwefelsäure mit in einer The result of a current density potential measurement carried out on samples PEl produced from steel E according to the invention and samples PV1 produced from comparison steel V is shown in FIG. Therein, the current density potential curve determined for the samples PE1 is shown as a solid line and the current density potential curve determined for the samples PV1 is shown as a dashed line. The current density potential curves were in oxygen-free 0.5 molar sulfuric acid in one
Potenzialänderungsgeschwindigkeit von 600 mV/h gegen eine Kalomel-Bezugselektrode bei 20 °C gemessen. Auch die für die erfindungsgemäßen Proben PEl ermittelten Passivstromdichten lagen jeweils unter 5 μΑ/cm2. Potential change rate of 600 mV / h measured against a calomel reference electrode at 20 ° C. Also the passive current densities determined for the samples according to the invention PEI were in each case below 5 μΑ / cm 2 .
Für die aus dem erfindungsgemäßen Stahl E erzeugten Proben PEl ist das E-Modul mittels Ultraschall in For the samples PEl produced from the steel E according to the invention, the modulus of elasticity is determined by means of ultrasound in FIG
Abhängigkeit von der Schallausbreitungsgeschwindigkeit auf 318 GPa bestimmt worden. Das E-Modul der Depending on the sound propagation speed has been determined to be 318 GPa. The modulus of elasticity of
konventionellen Proben PV1 lag dagegen bei 294 GPa. on the other hand, PV1 was 294 GPa.
Tabelle 3 gibt einen Überblick über die thermische Table 3 gives an overview of the thermal
Ausdehnung des Stahls E. Gemessen wurde diese mittels eines Bähr Dilatometers in Temperaturschritten von Expansion of the steel E. It was measured by means of a Bähr dilatometer in temperature steps of
100 °C bis zu einer Maximaltemperatur von 600 °C. Es ist zu erkennen, dass der thermische Ausdehnungskoeffizient ath in diesem Temperaturbereich zwischen 7 und 12 10-6/K liegt. Ergänzend dazu zeigt Fig. 4 exemplarisch das Ergebnis einer Dilatometermessung an einer aus dem erfindungsgemäßen Stahl erzeugten Probe PEl, die dieses Ergebnis bestätigt. 100 ° C up to a maximum temperature of 600 ° C. It can be seen that the thermal expansion coefficient is a th in this temperature range 7-12 10- 6 / K. In addition, FIG. 4 shows, by way of example, the result of a dilatometer measurement on a sample PE 1 produced from the steel according to the invention, which confirms this result.
Stahl Cr Mo Ni Co Cu Ti AI TiC NbCSteel Cr Mo Ni Co Cu Ti Al TiC NbC
E 13, 5 7,0 5,0 9,0 0,8 1,0 1,2 33 2,5E 13, 5 7.0 5.0 9.0 0.8 1.0 1.2 33 2.5
V 13, 5 5, 0 4,0 9,0 0,8 1,0 1,0 30 -V 13, 5 5, 0 4.0 9.0 0.8 1.0 1.0 30 -
Angaben in Gew.-%, Rest Eisen und unvermeidbare Data in% by weight, balance iron and unavoidable
Verunreinigungen impurities
Tabelle 1 Table 1
Tabelle 2  Table 2
Tabelle 3  Table 3

Claims

P A T E N T A N S P R Ü C H E  P A T E N T A N S P R E C H E
Stahl für Anwendungen, die eine hohe Steel for applications requiring a high
Verschleißbeständigkeit, eine hohe Härte, eine gute Korrosionsbeständigkeit und/oder eine niedrige Wear resistance, high hardness, good corrosion resistance and / or low
Wärmeleitfähigkeit erfordern, Require thermal conductivity,
- wobei der Stahl im gehärteten Zustand eine Härte von mindestens 56 HRC besitzt,  the hardened steel has a hardness of at least 56 HRC,
- wobei im Gefüge des Stahls in Summe mindestens  - in the structure of steel in total at least
30 Gew.-% Hartphasen vorhanden sind, die neben TiC- Partikeln aus weiteren Karbid-Partikeln, Oxid-Partikel oder Nitrid-Partikeln bestehen,  30 wt .-% hard phases are present, which consist in addition to TiC particles of other carbide particles, oxide particles or nitride particles,
- wobei der Gehalt an TiC-Partikeln mindestens 20 Gew. beträgt,  wherein the content of TiC particles is at least 20% by weight,
und and
- wobei die Hartphasen in eine Matrix eingebettet sind die aus (in Gew.-%)  - wherein the hard phases are embedded in a matrix consisting of (in% by weight)
9,0 - 15,0 % Cr,  9.0 - 15.0% Cr,
5,0 - 9,0 % Mo,  5.0 - 9.0% Mo,
3,0 - 7,0 % Ni,  3.0 - 7.0% Ni,
6,0 - 11,0 % Co,  6.0 - 11.0% Co,
0,3 - 1,5 % Cu,  0.3-1.5% Cu,
0,1 - 2,0 % Ti,  0.1-2.0% Ti,
0,1 - 2,0 % AI,  0.1 - 2.0% AI,
Rest Eisen und unvermeidbaren Verunreinigungen besteht . Residual iron and unavoidable impurities persist.
2. Stahl gemäß Anspruch 1, d a d u r c h 2. Steel according to claim 1, d a d u r c h
g e k e n n z e i c h n e t, d a s s sein Cr-Gehalt 12,5 - 14,5 Gew.-% beträgt.  However, its Cr content is 12.5-14.5 wt%.
Stahl nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d Steel according to one of the preceding claims, characterized in that: a
sein Mo-Gehalt 6,5 - 7,5 Gew.-% beträgt.  its Mo content is 6.5-7.5% by weight.
4. Stahl nach einem der voranstehenden Ansprüche, 4. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein Ni-Gehalt 4,5 - 5,5 Gew.-% beträgt.  d a d u r c h e c e n e, e s t e s, its nickel content is 4.5-5.5% by weight.
5. Stahl nach einem der voranstehenden Ansprüche, 5. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein Co-Gehalt 8 - 10 Gew.-% beträgt.  The co-content thereof is 8 to 10% by weight.
6. Stahl nach einem der voranstehenden Ansprüche, 6. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein Cu-Gehalt 0,5 - 1,0 Gew.-% beträgt.  d a d u r c h e s e s e s e c h e s e s, its copper content is 0.5 to 1.0 wt%.
7. Stahl nach einem der voranstehenden Ansprüche, 7. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein Ti-Gehalt 0,8 - 1,2 Gew.-% beträgt.  d a d u r c h e c e n c i n e s, its ti content is 0.8 to 1.2 wt%.
8. Stahl nach einem der voranstehenden Ansprüche, 8. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein Al-Gehalt 1,0 - 1,4 Gew.-% beträgt. characterized in that its Al content is 1.0 - 1.4 wt .-%.
9. Stahl nach einem der voranstehenden Ansprüche, 9. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein TiC-Gehalt mindestens 20 Vol.-% beträgt.  d a d u r c h e c e n c e s, the TiC content thereof is at least 20% by volume.
10. Stahl nach einem der voranstehenden Ansprüche, 10. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s er bis zu 4,5 Gew.-% NbC-Partikel enthält.  It does not contain up to 4.5% by weight of NbC particles.
11. Stahl nach Anspruch 10, d a d u r c h 11. Steel according to claim 10, d a d u r c h
g e k e n n z e i c h n e t, d a s s der Gehalt an NbC-Partikeln mindestens 2,0 Gew.-% beträgt.  In other words, the content of NbC particles is at least 2.0% by weight.
12. Stahl nach einem der voranstehenden Ansprüche, 12. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s der Anteil der Hartphasen an seinem Gefüge mindestens 30 Gew.-% beträgt.  The proportion of hard phases in its microstructure is at least 30% by weight.
13. Stahl nach einem der voranstehenden Ansprüche, 13. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s sein TiC-Gehalt höchstens 45 Gew.-% beträgt.  d a d u r c h e c e n c e n e s, its content of TiC is at most 45% by weight.
14. Stahl nach einem der voranstehenden Ansprüche, 14. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s er nach einer Wärmebehandlung, bei der er für  d a d u r c h g e k e n c e n e s, he s after a heat treatment in which he for
2 - 4 Stunden unter Vakuum erwärmt, anschließend unter einer Stickstoff atmosphäre mit einem Druck von 1 - 4,5 bar abgeschreckt und schließlich über 6 - 8 Stunden bei 480 °C ausgelagert worden ist, eine Härte von mehr als 62 HRC aufweist. Heated for 2 - 4 hours under vacuum, then quenched under a nitrogen atmosphere at a pressure of 1 - 4.5 bar and finally at 6-8 hours at 480 ° C has a hardness of more than 62 HRC.
15. Stahl nach einem der voranstehenden Ansprüche, 15. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s er nach einer bei 850 °C über 2 - 4 Stunden durchgeführten Weichglühung eine Härte von mindestens 50 HRC besitzt.  It has a hardness of at least 50 HRC after soft annealing carried out at 850 ° C for 2 to 4 hours.
16. Stahl nach einem der voranstehenden Ansprüche, 16. Steel according to one of the preceding claims,
d a d u r c h g e k e n n z e i c h n e t, d a s s er pulvermetallurgisch hergestellt ist.  It is not known that it is manufactured by powder metallurgy.
1 . Verwendung eines gemäß einem der voranstehenden 1 . Use of one of the above
Ansprüche beschaffenen Stahls für die Herstellung von Komponenten, die beim Recycling oder der Neuerzeugung von KunststoffProdukten eingesetzt werden.  Claims of procured steel for the production of components used in the recycling or the regeneration of plastic products.
18. Verwendung nach Anspruch 17, d a d u r c h 18. Use according to claim 17, d a d u r c h
g e k e n n z e i c h n e t, d a s s es sich bei der Komponente um eine Lochplatte oder um ein Messer zum Zerkleinern von Kunststoffteilen handelt.  If the component is a perforated plate or a knife for shredding plastic parts, this is not the case.
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EP3263726A1 (en) * 2016-06-29 2018-01-03 Deutsche Edelstahlwerke GmbH Fe basis material and method for its production
JP7287916B2 (en) * 2020-03-12 2023-06-06 株式会社神戸製鋼所 LAMINATED PRODUCT MANUFACTURING METHOD AND LAMINATED PRODUCT
CN111455274A (en) * 2020-04-08 2020-07-28 鞍钢股份有限公司 80 Ksi-grade 9Cr fireflood heat production well pipe and manufacturing method thereof
CN112251749B (en) * 2020-10-23 2023-04-07 黑龙江科技大学 Method for preparing ceramic phase enhanced high-entropy alloy wear-resistant coating of directional array by plasma cladding
KR20220063626A (en) * 2020-11-10 2022-05-17 한국재료연구원 TiC particle-reinforced Fe-based composite material and its manufacturing method

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966423A (en) * 1973-11-06 1976-06-29 Mal M Kumar Grain refinement of titanium carbide tool steel
DE3015709A1 (en) * 1980-04-24 1981-10-29 Thyssen Edelstahlwerke AG, 4000 Düsseldorf HARD MATERIAL ALLOY
JPH0229736B2 (en) * 1984-09-14 1990-07-02 Mitsubishi Metal Corp BUNSANKYOKAGATASHOKETSUGOKINKOSEINETSUKANTAIMAMOBUZAI
JPH0586435A (en) * 1991-09-27 1993-04-06 Hitachi Metals Ltd Tool parts material having high corrosion resistance and high wear resistance
SE9604538D0 (en) * 1996-12-10 1996-12-10 Hoeganaes Ab Agglomerated iron-based powders
JP4279935B2 (en) * 1999-03-25 2009-06-17 株式会社神戸製鋼所 Hard grain dispersed sintered steel and method for producing the same
US6521353B1 (en) * 1999-08-23 2003-02-18 Kennametal Pc Inc. Low thermal conductivity hard metal
SE529041C2 (en) * 2005-08-18 2007-04-17 Erasteel Kloster Ab Use of a powder metallurgically made steel
SE528991C2 (en) * 2005-08-24 2007-04-03 Uddeholm Tooling Ab Steel alloy and tools or components made of the steel alloy
GB2440737A (en) * 2006-08-11 2008-02-13 Federal Mogul Sintered Prod Sintered material comprising iron-based matrix and hard particles
SE533988C2 (en) * 2008-10-16 2011-03-22 Uddeholms Ab Steel material and process for making them
MX345311B (en) * 2010-02-05 2017-01-25 Weir Minerals Australia Ltd Hard metal materials.
RU2443795C2 (en) * 2010-04-16 2012-02-27 Тамара Федоровна Волынова MULTI-FUNCTION ANTIFRICTION NANOSTRUCTURE WEAR-RESISTANT DAMPING ALLOYS WITH SHAPE MEMORY EFFECT ON METASTABLE BASIS OF IRON WITH STRUCTURE OF HEXAGONAL ε-MARTENSITE, AND ITEMS USING THESE ALLOYS WITH EFFECT OF SELF-ORGANISATION OF NANOSTRUCTURE COMPOSITIONS, SELF-STRENGTHENING AND SELF-LUBRICATION OF FRICTION SURFACES, WITH EFFECT OF SELF-DAMPING OF VIBRATIONS AND NOISES
EP2662460A1 (en) * 2012-05-07 2013-11-13 Valls Besitz GmbH Tough bainitic heat treatments on steels for tooling

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US20180119257A1 (en) 2018-05-03
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DE102014112374A1 (en) 2016-03-03
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RU2017106319A3 (en) 2018-08-28
JP2017532434A (en) 2017-11-02

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