EP1218555A1 - Powder metallurgical method for in-situ production of a wear-resistant composite material - Google Patents

Powder metallurgical method for in-situ production of a wear-resistant composite material

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Publication number
EP1218555A1
EP1218555A1 EP00964181A EP00964181A EP1218555A1 EP 1218555 A1 EP1218555 A1 EP 1218555A1 EP 00964181 A EP00964181 A EP 00964181A EP 00964181 A EP00964181 A EP 00964181A EP 1218555 A1 EP1218555 A1 EP 1218555A1
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Prior art keywords
powder
particles
carbon
ferrotitanium
metal matrix
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Granted
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EP00964181A
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German (de)
French (fr)
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EP1218555B1 (en
Inventor
Hans Berns
Birgit Wewers
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Maschinenfabrik Koeppern GmbH and Co KG
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Maschinenfabrik Koeppern GmbH and Co KG
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0207Using a mixture of prealloyed powders or a master alloy

Definitions

  • HT hard particles
  • AT abrasive particles
  • the effectiveness of HT is optimal if it (a) is harder than the attacking ones AT, (b) larger than the furrow cross section, (c) dispersed in the metal matrix (MM) and (d) firmly connected to the MM IM
  • a dispersion of the HT means that they are arranged at a medium distance from each other in the MM and consequently do not touch each other. This leads to the shortest average grooving length in the matrix and to the greatest fracture toughness of the composite material. Setting a dispersion is not trivial and depends on the volume and diameter ratio of the HT and MM powders IM
  • the bond between HT and MM is formed by interdiffusion during hot compacting. It is generally stronger for HT made of metal / metalloid compounds than eg for metal oxides. B, C and N are used as metalloids, some are used as metals the subgroups of the 4 to 6 period, with titanium being of particular interest because of its availability and because of the high stability and hardness of its metalloid compounds.
  • the requirements (a) to (d) can only be met together with a metal matrix-particle composite.
  • Ferro alloys are used to alloy steel. In order to reduce the refining costs, an iron content remains in the ferro alloys, which is why they are not only inexpensive, but also brittle after solidification and can be comminuted to a desired powder grain size.
  • carbide particles TiC, NbC, VC
  • the external shape and size as well as the distribution of the carbide particles in the MM corresponds to that of the ferroalloy particles. Local melting can occur in the core of the carbide particles formed in situ tongues occur
  • the carbon required for carbide formation is not mixed in, but is added to the matrix powder, ( ⁇ ) the carbon required for carbide formation is added to the powder mixture by carburizing in a gas phase, ( ⁇ ) instead of carburizing, an embroidery in a gas phase carried out to convert the ferroalloy particles into nitrides (TiN, NbN, VN)
  • the process according to the invention is distinguished from known processes by the following advantages (1)
  • the HT formed in-situ reach a high hardness of 2000 to 3000 HV (2) They are produced in-situ from inexpensive ferroalloy particles and in a size that is known as carbide or Nitrides are only available as agglomerated powder, but agglomerated HT do not have sufficient internal strength to withstand furring abrasive particles (3)
  • the high wear resistance of the composite material according to the invention, formed in situ, is explained in comparison to known composite materials using an exemplary embodiment.
  • the hardenable steel 56NiCrMoV7 with an average powder grain size of 55 ⁇ m was used as the matrix powder.
  • the hot isostatic pressing of the evacuated powder capsules to full density took place at 1100 ° C for 3 hours an all-round pressure of 140 MPa instead of Subsequent hardening and tempering, a matrix hardness of around 700 HV was set
  • Chromium diboride is in Comparably coarse grit available, but tends to dissolve in the matrix and achieves a lower wear resistance (B) Titanium diboride is even harder than titanium carbide, but does not offer increased wear resistance (C) due to the too small particle size.
  • FIG. 1 shows the same in-situ formation of TiC particles as for A.
  • c, d schematic representation and description of the phase components, the fields labeled Fe, Ti (appearing bright in (a) and (b)) contain more iron , and less carbon than TiC and are partly eutectically solidified. At lower temperatures there are no liquid components.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

In accordance with the method according to the present invention, particles consisting of ferrotitanium, ferroniobium or ferrovanadium are dispersed and hot compacted in a metal matrix powder consisting of hardening steel or heat-resistant alloys. In so doing, titanium, niobium or vanadium carbide is obtained in situ by a solid-state reaction, i.e. without melting, from the carbon admixed or contained in the matrix powder and the ferroalloy particles. Carbon can also be absorbed from the gaseous phase and it may be substituted by nitrogen. This method permits a reasonably-priced introduction of hard particles into the composite material, the hard particles having a size that is necessary as a protection against scoring wear.

Description

Verfahren zur pulvermetallurgischen in-situ Herstellung eines verschleißbeständigen Process for powder metallurgical in-situ production of a wear-resistant
VerbundwerkstoffesComposite
Ein bekannter Weg zur Erhöhung des Widerstandes metallischer Werkstoffe gegen furchenden Verschleiß ist die Einlagerung von harten Teilchen (HT), die sich der Furchung durch abrasive Teilchen (AT) entgegenstellen Die Wirksamkeit der HT ist dann optimal, wenn sie (a) harter als die angreifenden AT, (b) großer als der Furchenquerschnitt, (c) in der Metallmatrix (MM) dispergiert und (d) fest mit der MM verbunden sind IMA well-known way to increase the resistance of metallic materials to grooving wear is the inclusion of hard particles (HT), which oppose the grooving by abrasive particles (AT). The effectiveness of HT is optimal if it (a) is harder than the attacking ones AT, (b) larger than the furrow cross section, (c) dispersed in the metal matrix (MM) and (d) firmly connected to the MM IM
Zu (a): Als AT treten z B naturliche Minerale auf, von denen die meisten eine Harte von < 1000 HV besitzen, Quarz mit ~ 1200 HV und Korund mit ~ 2000 HV, aber deutlich harter sind Die Harte synthetischer Abrasive liegt zum Teil noch darüber Um gerade von härteren AT nicht gefurcht zu werden, sollten die HT eine Harte von 2000 bis 3000 HV aufweisenRegarding (a): For example, natural minerals occur as AT, most of which have a hardness of <1000 HV, quartz with ~ 1200 HV and corundum with ~ 2000 HV, but are significantly harder. The hardness of synthetic abrasives is partly still present above In order not to be feared by harder AT, the HT should have a hardness of 2000 to 3000 HV
Zu (b): Nach Erosion findet man Furchenbreiten von meist wenigen μm, nach Korngleit- und Furchungsverschleiß jedoch häufig solche von einigen 10 μm Es besteht daher Bedarf an HT mit einer mittleren Große zwischen 30 und 130 μm, die als mittlerer Durchmesser oder als Siebgroße zu verstehen istRegarding (b): After erosion, furrow widths of mostly a few μm are found, but after grain sliding and grooving wear often those of a few 10 μm is to be understood
Zu (c): Eine Dispersion der HT bedeutet, dass sie in einem mittleren Abstand voneinander in der MM angeordnet sind und sich folglich nicht berühren Das führt zur kürzesten mittleren Furchungslange in der Matrix und zur größten Bruchzahigkeit des Verbundwerkstoffes Die Einstellung einer Dispersion ist nicht trivial und hangt vom Volumen- und vom Durchmesserverhaltnis der HT- und MM-Pulver ab IMTo (c): A dispersion of the HT means that they are arranged at a medium distance from each other in the MM and consequently do not touch each other. This leads to the shortest average grooving length in the matrix and to the greatest fracture toughness of the composite material. Setting a dispersion is not trivial and depends on the volume and diameter ratio of the HT and MM powders IM
Zu (d): Die Bindung zwischen HT und MM wird durch Interdiffusion beim Heißkompaktieren geknüpft Sie ist in der Regel für HT aus Metall/Metalloid- Verbindungen fester als z B für Metalloxide Als Metalloide werden B, C und N verwendet, als Metalle einige aus den Nebengruppen der 4 bis 6 Periode, wobei Titan wegen seiner Verfügbarkeit sowie wegen der hohen Stabilität und Harte seiner Metalloidverbindungen besonderes Interesse gilt Die Forderungen (a) bis (d) sind gemeinsam nur mit einem Metallmatrix- Teilchenverbundwerkstoff zu erfüllen IM Bekannt ist das Mischen von Karbid-, Borid- oder Nitridpulver mit Metallmatrixpulver 12-41 und anschließendes Heißkompaktieren Die Bildung von Titanborid, -karbid und -kabonitrid aus Titanpulver und Bor oder Ruß ggf unter Stickstoff verlauft exotherm bis zum Schmelzen 15-11 Diese Reaktion wurde bereits genutzt, um in-situ aus Titanteilchen vermischt mit Metalloid und MM-Pulver durch Hochtemperatursynthese einen Verbundwerkstoff zu fertigen /SV Anstelle von Titan- wurde auch Ferrotitanpulver verwendet III, wobei das lokale Aufschmelzen durch die in-situ Bildung von TiC zu feinen μm großen Ausscheidungen führteRegarding (d): The bond between HT and MM is formed by interdiffusion during hot compacting. It is generally stronger for HT made of metal / metalloid compounds than eg for metal oxides. B, C and N are used as metalloids, some are used as metals the subgroups of the 4 to 6 period, with titanium being of particular interest because of its availability and because of the high stability and hardness of its metalloid compounds The requirements (a) to (d) can only be met together with a metal matrix-particle composite. IM It is known to mix carbide, boride or nitride powder with metal matrix powder 12-41 and then hot compact the formation of titanium boride, carbide and carbonitride made of titanium powder and boron or soot, possibly under nitrogen, exothermic until melting 15-11 This reaction has already been used to produce a composite material from titanium particles mixed with metalloid and MM powder by high-temperature synthesis / SV Instead of titanium, too Ferrotitanium powder uses III, whereby the local melting caused by the in-situ formation of TiC to fine microns precipitates
Ferrolegierungen werden verwendet, um Stahle zu legieren Zur Senkung der Raffinationskosten verbleibt in den Ferrolegierungen ein Eisenanteil, weshalb sie nicht nur kostengünstig, sondern nach der Erstarrung auch spröde sind und sich auf eine gewünschte Pulverkorngroße zerkleinern lassen Beim erfindungsgemaßen Verfahren werden Teilchen aus handelsüblichem Ferrotitan, Ferroniob oder Ferrovanadin so mit MM-Pulver und Kohlenstoffstaub vermischt, dass sie in der Pulverschuttung dispergiert vorliegen Beim anschließende Heißkompaktieren der Pulvermischung wird die Temperatur so niedrig gehalten, dass durch die Diffusion von Kohlenstoff in die Ferrolegierungsteilchen nicht aufgeschmolzene Karbidteilchen (TiC, NbC, VC) entstehen, die im Kern mit dem Eisenanteil der Ferrolegierung angereichert sind Die äußere Form und Große sowie die Verteilung der Karbidteilchen in der MM entspricht der der Ferrolegierungsteilchen Im Kern der in-situ gebildeten Karbidteilchen können lokale Anschmelzungen auftretenFerro alloys are used to alloy steel. In order to reduce the refining costs, an iron content remains in the ferro alloys, which is why they are not only inexpensive, but also brittle after solidification and can be comminuted to a desired powder grain size. In the process according to the invention, particles made from commercially available ferrotitanium, ferroniob or Ferrovanadin mixed with MM powder and carbon dust in such a way that they are dispersed in the powder spill. When the powder mixture is subsequently hot compacted, the temperature is kept so low that carbide particles (TiC, NbC, VC) do not melt due to the diffusion of carbon into the ferroalloy particles , which are enriched in the core with the iron portion of the ferroalloy. The external shape and size as well as the distribution of the carbide particles in the MM corresponds to that of the ferroalloy particles. Local melting can occur in the core of the carbide particles formed in situ tongues occur
In weiteren Ausfuhrungsformen des erfindungsgemaßen Verfahrens wird (α) der zur Karbidbildung benotigte Kohlenstoff nicht zugemischt, sondern dem Matrixpulver zulegiert, (ß) der zur Karbidbildung benotigte Kohlenstoff durch Aufkohlen der Pulvermischung in einer Gasphase zugeführt, (γ) anstatt Aufkohlen ein Aufsticken in einer Gasphase durchgeführt, um die Ferrolegierungsteilchen in Nitride (TiN, NbN, VN) umzuwandelnIn further embodiments of the method according to the invention (α) the carbon required for carbide formation is not mixed in, but is added to the matrix powder, (β) the carbon required for carbide formation is added to the powder mixture by carburizing in a gas phase, (γ) instead of carburizing, an embroidery in a gas phase carried out to convert the ferroalloy particles into nitrides (TiN, NbN, VN)
Das erfindungsgemaße Verfahren hebt sich durch folgende Vorzuge von bekannten Verfahren ab (1) Die in-situ gebildeten HT erreichen eine hohe Harte von 2000 bis 3000 HV (2) Sie entstehen in-situ aus kostengünstigen Ferrolegierungsteilchen und in einer Große, die als Karbide oder Nitride z T nur als agglomeriertes Pulver erhältlich sind Agglomerierte HT verfügen aber nicht über eine ausreichende innere Festigkeit, um furchenden Abrasivpartikeln stand zu halten (3) DieThe process according to the invention is distinguished from known processes by the following advantages (1) The HT formed in-situ reach a high hardness of 2000 to 3000 HV (2) They are produced in-situ from inexpensive ferroalloy particles and in a size that is known as carbide or Nitrides are only available as agglomerated powder, but agglomerated HT do not have sufficient internal strength to withstand furring abrasive particles (3)
HT sind in der metallischen Matrix dispergiertHT are dispersed in the metallic matrix
Im Vergleich dazu scheiden sich nach der Hochtemperatursynthese sehr feinkornige Karbidteilchen aus, die weniger Furchungswiderstand bieten Die erfindungsgemaßen groben HT bieten dem Furchungsverschleiß dann den besten Widerstand, wenn sie von einer hochfesten Metallmatrix gestutzt werden Als MM-Pulver eignen sich daher besonders solche aus hartbaren Stahlen und für erhöhte Anwendungstemperaturen solche aus warmfesten Stahlen sowie Nickel- und CobaltlegierungenIn comparison, after the high-temperature synthesis, very fine-grained carbide particles are separated, which offer less grooving resistance. The coarse HT according to the invention offer the best resistance to grooving wear when they are trimmed by a high-strength metal matrix. Those made of hardenable steel and are therefore particularly suitable as MM powders for higher application temperatures, those made of heat-resistant steel as well as nickel and cobalt alloys
Der hohe Verschleißwiderstand des erfindungsgemaßen, in-situ gebildeten Verbundwerkstoffes wird im Vergleich zu bekannten Verbundwerkstoffen anhand eines Ausfuhrungsbeispieles erläutert Zur Herstellung der vorgestellten Werkstoffe kam als Matrixpulver der hartbare Stahl 56NiCrMoV7 mit einer mittleren Pulverkorngroße von 55 μm zur Anwendung Im erfindungsgemaßen Fall wurden 10 Vol% Ferrotitanteilchen mit rund 70 Masse% Titan hinzugemischt sowie Kohlenstoffstaub im Molverhaltnis Ti/C = 1/1 Für die Herstellung der bekannten Verbundwerkstoffe erfolgte eine Zumischung von 10 Vol% Boridteilchen Das heißisostatische Pressen der evakuierten Pulverkapseln auf volle Dichte fand bei 1100 °C, 3 h unter einem allseitigen Druck von 140 MPa statt Durch nachfolgendes Harten und Anlassen wurde eine Matrixharte von rund 700 HV eingestelltThe high wear resistance of the composite material according to the invention, formed in situ, is explained in comparison to known composite materials using an exemplary embodiment. For the manufacture of the materials presented, the hardenable steel 56NiCrMoV7 with an average powder grain size of 55 μm was used as the matrix powder. In the case according to the invention, 10% by volume ferrotitanium particles were used mixed with about 70 mass% titanium and carbon dust in the molar ratio Ti / C = 1/1. 10 vol% boride particles were added for the production of the known composite materials. The hot isostatic pressing of the evacuated powder capsules to full density took place at 1100 ° C for 3 hours an all-round pressure of 140 MPa instead of Subsequent hardening and tempering, a matrix hardness of around 700 HV was set
So hergestellte Proben wurden unter einem Flachendruck von 1 32 MPa über 50 m gegen Korund-Schleifpapier 80er Komung bewegt und der dimensionslose Verschleißwiderstand w"1 bestimmt Dabei ergaben sich als Mittel dreier Messungen folgende Resultate erfindungsgemaß in-situ gebildet, ' MittelwertSamples produced in this way were moved under a surface pressure of 1 32 MPa over 50 m against corundum sandpaper from the 80s and the dimensionless wear resistance w "1 determined. The results of the following were obtained as the average of three measurements formed in situ according to the invention, 'mean value
Der Vergleich zeigt, dass bereits 10 Vol% an harten Teilchen eine deutliche Veränderung des Verschleißwiderstandes gegenüber der reinen Metallmatrix ohne harte Teilchen (D) bewirken und der erfindungsgemaße in-situ mit Ferrotitanteilchen und Kohlenstoff gebildete Verbundwerkstoff (A) den höchsten Verschleißwiderstand aufweist Chromdiborid ist in vergleichbar grober Körnung erhaltlich, neigt aber zur Auflosung in der Matrix und erreicht einen geringeren Verschleißwiderstand (B) Titandiborid ist zwar noch harter als Titankarbid, bietet aber aufgrund der zu geringen Teilchengroße keinen erhöhten Verschleißwiderstand (C) Da aufgrund des ungunstigen Korngroßenverhaltnisses zwischen MM- und HT-Pulver keine Dispersion der TiB2, sondern eine netzförmige Verteilung in der Matrix vorliegt, nimmt der Verschleißwiderstand wegen der damit einhergehenden Werkstoffversprodung im Vergleich zu D sogar ab Das ungunstige Verhalten von C ist auch für das Zumischen von handelsüblich feinem TiC-Pulver zu erwarten Die in-situ Bildung grober TiC-Teilchen aus groben Ferrotitanteilchen und Kohlenstoff in einem Verbundwerkstoff stellt einen neuen Weg dar, um die hervorragenden Eigenschaften des Hartstoffs TiC in Verbundwerkstoffen auch bei tiefergehender furchender Beanspruchung nutzen zu könnenThe comparison shows that already 10% by volume of hard particles cause a clear change in the wear resistance compared to the pure metal matrix without hard particles (D) and that the composite material (A) according to the invention which is formed in situ with ferrotitanium particles and carbon has the highest wear resistance. Chromium diboride is in Comparably coarse grit available, but tends to dissolve in the matrix and achieves a lower wear resistance (B) Titanium diboride is even harder than titanium carbide, but does not offer increased wear resistance (C) due to the too small particle size. Because of the unfavorable grain size ratio between MM and HT powder is not a dispersion of TiB 2 , but a network-like distribution in the matrix, the wear resistance even decreases compared to D due to the associated material brittleness. The unfavorable behavior of C is also fine for mixing commercially available m TiC powder to be expected The in-situ formation of coarse TiC particles from coarse ferrotitanium particles and carbon in a composite material represents a new way to be able to use the excellent properties of the hard material TiC in composite materials even with deeper furrowing loads
In einem weiteren Ausfuhrungsbeispiel wird gezeigt, dass anstelle einer Zumischung von Kohlenstoff, dieser auch aus einem kohlenstoffreichen Matrixpulver zur TiC-Bildung abgezogen werden kann Dazu wurde als Matrixpulver legiertes Gußeisen X 330 NiCr 4-2 mit Ferrotitanpulver ohne Kohlenstoffzugabe gemischt und durch heißisostatisches Pressen kompaktiert (E). In Bild 1 ist die gleiche in-situ Entstehung von TiC Teilchen zu erkennen wie für A.Another exemplary embodiment shows that instead of adding carbon, this can also be drawn off from a carbon-rich matrix powder to form TiC.For this purpose, alloyed cast iron X 330 NiCr 4-2 was mixed with ferrotitanium powder without carbon addition and by hot isostatic pressing compacted (E). Figure 1 shows the same in-situ formation of TiC particles as for A.
Bild lPicture l
In-situ aus Ferrotitanteilchen gebildete TiC-Teilchen nach heißisostatischem Pressen bei 1100°C. (a) Matrixpulver X330CrNi4-2, (b) Mtrixpulver 56NiCrMoV7 mit Graphitzugabe, (c,d) schematische Darstellung und Bezeichnung der Phasenanteile, die mit Fe, Ti bezeichneten Felder (in (a) und (b) hell erscheinend) enthalten mehr Eisen, und weniger Kohlenstoff als TiC und liegen z.T. eutektisch erstarrt vor. Bei niedrigerer Temperatur treten keine Flüssiganteile auf. TiC particles formed in situ from ferrotitanium particles after hot isostatic pressing at 1100 ° C. (a) Matrix powder X330CrNi4-2, (b) Mtrix powder 56NiCrMoV7 with graphite addition, (c, d) schematic representation and description of the phase components, the fields labeled Fe, Ti (appearing bright in (a) and (b)) contain more iron , and less carbon than TiC and are partly eutectically solidified. At lower temperatures there are no liquid components.
Literaturliterature
IM H Berns (Hgb ) Hartlegierungen und Hartverbundwerkstoffe Springer- Verlag, Berlin 1998 121 S Franco Wechselwirkung zwischen Matrix und Hartphasen beim WarmverschleißIM H Berns (Hgb) Hard alloys and hard composite materials Springer-Verlag, Berlin 1998 121 S Franco Interaction between matrix and hard phases during hot wear
Fortschr -Ber VDI Reihe 5, Nr 437, VDI- Verlag, Dusseldorf, 1996 ßl Nguyen van Chuong Hartbare PM-Hartlegierungen mit gradierter Struktur Fortschr -BerProgress-VDI Series 5, No. 437, VDI-Verlag, Dusseldorf, 1996 ßl Nguyen van Chuong Hardable PM hard alloys with graded structure Progress-
VDI-Reihe 5, Nr 192, VDI- Verlag, Dusseldorf, 1990 141 G Wang Hartbare nichtrostende PM-Stahle und Stahlverbunde mit hohem StickstoffgehaltVDI series 5, No. 192, VDI publishing house, Dusseldorf, 1990 141 G Wang Hardenable, rustproof PM steel and steel composites with a high nitrogen content
Fortschr -Ber VDI-Reihe 5, Nr 277, VDI- Verlag, Dusseldorf, 1992 151 P D Zavitsanos, J R Morris Jr Synthesis of Titanium Diboride by a Self-PropagatingProgr -Ber VDI series 5, No. 277, VDI- Verlag, Dusseldorf, 1992 151 P D Zavitsanos, J R Morris Jr Synthesis of Titanium Diboride by a Self-Propagating
Reaction Ceramic engin and science proc 4 (1983), pp 624-633 161 Q Fan, H Chai, Z Jin Microstructural evolution in the combustion synthesis of titanium carbide J Mat Science 31 (1996), pp. 2573-2577 III H Lehuy, G Gliche, S Dallaire Synthesis and characterization of Ti(C,N)-Fe cermets produced by direct reaction Mat Sei and Engin 125 (1990), L11-L14 /8/ O N Dogan, D E Alman, J A Hawk Wear Resistant, Powder Processed, in-situ Iron-Reaction Ceramic engin and science proc 4 (1983), pp 624-633 161 Q Fan, H Chai, Z Jin Microstructural evolution in the combustion synthesis of titanium carbide J Mat Science 31 (1996), pp. 2573-2577 III H Lehuy, G Gliche, S Dallaire Synthesis and characterization of Ti (C, N) -Fe cermets produced by direct reaction Mat Sei and Engin 125 (1990), L11-L14 / 8 / ON Dogan, DE Alman, JA Hawk Wear Resistant, Powder Processed, in-situ Iron-
Matrix TiC Composites Proc of the 1996 World Congr on Powder Metallurgy and Particulate Mat June 16-21, 1996, Washington, pp 16-83 - 16-96 Matrix TiC Composites Proc of the 1996 World Congr on Powder Metallurgy and Particulate Mat June 16-21, 1996, Washington, pp 16-83 - 16-96

Claims

Ansprüche Expectations
1. Verfahren zur pulvermetallurgischeπ Herstellung verschleißbeständiger Verbundwerkstoffe, bei dem Pulver aus Ferrotitan und/oder Ferroniob und/oder Ferro- vanadin durch Mischen in einem Metallmatrixpulver mit einem Anteil von weniger als 50 % des Gesamtpulvervolumens dispergiert wird oder werden und Kohlenstoff und/oder Stickstoff zugegeben bzw. zugeführt wird oder werden, dadurch gekennzeichnet, dass die Pulvermischung durch Heißkompaktieren zu einem Metallmatrix-Teilchen-Verbundwerkstoff verdichtet wird und die dispergierten Pulverteilchen des Ferrotitans und/oder Ferroniobs und/oder Ferrovanadins in-situ zu Karbid- und/oder Nitridteilchen im Wesentlichen ohne Aufschmelzen der Pulverteiichen umgewandelt werden.1. Process for powder metallurgical production of wear-resistant composite materials, in which powders of ferrotitanium and / or ferroniob and / or ferrovanadin are or are dispersed by mixing in a metal matrix powder with a proportion of less than 50% of the total powder volume and carbon and / or nitrogen are added or is supplied, characterized in that the powder mixture is compacted by hot compacting to a metal matrix-particle composite and the dispersed powder particles of ferrotitanium and / or ferroniob and / or ferrovanadin essentially in situ to carbide and / or nitride particles can be converted without melting the powder particles.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als Metallmatrixpulver zumindest als Hauptbestandteil Pulver aus härtbarem Stahl eingesetzt wird.2. The method according to claim 1, characterized in that the metal matrix powder is used at least as the main constituent powder made of hardenable steel.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Molgehalt des zugegebenen bzw. zugeführten Kohlenstoffs und/oder des Stickstoffs dem Molgehalt des Titans und/oder des Niobs und/oder des Vanadins im Ferrotitan oder Ferroniob oder Ferrovanadin entspricht.3. The method according to claim 1 or 2, characterized in that the molar content of the added or supplied carbon and / or nitrogen corresponds to the molar content of titanium and / or niobium and / or vanadium in ferrotitanium or ferroniob or ferrovanadin.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Kohlenstoff und/oder der Stickstoff in Pulverform der Pulvermischung beigemischt wird oder werden.4. The method according to any one of claims 1 to 3, characterized in that the carbon and / or nitrogen is or are added in powder form to the powder mixture.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Titangehalt im Ferrotitan oder der Niobgehalt im Ferroniob oder der Vaπadinge- halt im Ferrovanadin 70 ± 5 Masse% beträgt.5. The method according to any one of claims 1 to 4, characterized in that the titanium content in the ferrotitanium or the niobium content in the ferroniob or the Vaπadinge- content in the Ferrovanadin is 70 ± 5 mass%.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die mittlere Siebkorngröße des Ferrotitans oder des Ferroniobs oder des Ferrovanadins zwischen 30 und 130 μm beträgt. 6. The method according to any one of claims 1 to 5, characterized in that the average sieve grain size of ferrotitanium or ferroniob or ferrovanadin is between 30 and 130 microns.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Heißkompaktieren durch hießisostatisches Pressen vorgenommen wird.7. The method according to any one of claims 1 to 6, characterized in that the hot compacting is carried out by hot isostatic pressing.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der zur in-situ Bildung von Karbidteilchen und/oder Nitridteilchen erforderliche Kohlenstoff oder Stickstoff im Metallmatrixpulver auf Eisenbasis in einer solchen Menge enthalten ist, dass davon die Bildung des Karbids und/oder Nitrids ohne eine wesentliche Einbuße der Härtbarkeit in der Matrix gespeist wird.8. The method according to any one of claims 1 to 7, characterized in that the carbon or nitrogen required for the in-situ formation of carbide particles and / or nitride particles is contained in the metal matrix powder on an iron basis in such an amount that the formation of the carbide and / or nitride is fed without a significant loss of curability in the matrix.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass Kohlenstoff vor oder während des Heißkompaktierens durch Aufkohlen in einer Gasphase der Pulvermischung zugeführt wird.9. The method according to any one of claims 1 to 8, characterized in that carbon is supplied to the powder mixture by carburizing in a gas phase before or during the hot compacting.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass Stickstoff vor oder während des Heißkompaktierens durch Aufsticken in einer Gasphase der Pulvermischung zugeführt wird.10. The method according to any one of claims 1 to 9, characterized in that nitrogen is supplied to the powder mixture by embroidering in a gas phase before or during the hot compacting.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass als Metallmatrixpulver zumindest als Hauptbestandteil Pulver aus einer warmfesten Eisen-, Nickel- und/oder Kobaltlegierung eingesetzt wird.11. The method according to any one of claims 1 to 10, characterized in that the metal matrix powder is used at least as the main component powder from a heat-resistant iron, nickel and / or cobalt alloy.
12. Verfahren nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass der Verbundwerkstoff beim Heißkompaktieren als Schicht mit einem metallischen Substrat zu einem Schichtverbund gefügt wird.12. The method according to any one of claims 1 to 11, characterized in that the composite material is joined during hot compacting as a layer with a metallic substrate to form a layer composite.
13. Verschleißbeständiger Verbundwerkstoff, hergestellt durch ein Verfahren nach einem der Ansprüche 1 bis 12, der in eine Metallmatrix eingelagerte Karbid- und/oder Nitridteilchen in einer durchschnittlichen Größe von 30 bis 130 μm aufweist. 13. Wear-resistant composite material, produced by a method according to one of claims 1 to 12, which has carbide and / or nitride particles embedded in a metal matrix in an average size of 30 to 130 μm.
EP00964181A 1999-09-16 2000-09-15 Powder metallurgical method for in-situ production of a wear-resistant composite material Expired - Lifetime EP1218555B1 (en)

Applications Claiming Priority (3)

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DE19944592 1999-09-16
DE19944592A DE19944592A1 (en) 1999-09-16 1999-09-16 Process for the powder-metallurgical in-situ production of a wear-resistant composite material
PCT/EP2000/009055 WO2001020049A1 (en) 1999-09-16 2000-09-15 Powder metallurgical method for in-situ production of a wear-resistant composite material

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DE60111565T2 (en) * 2000-12-20 2006-05-11 Sandvik Intellectual Property Ab Method of making a metal matrix composite and metal matrix composite
DE10320393A1 (en) * 2003-05-06 2004-11-25 Hallberg Guss Gmbh Production of tribological cast parts, especially engine blocks, made from iron alloys comprises adding hard stable particles to the melt shortly before, during or after casting to obtain embedded particles in the solidified structure
JP7100320B2 (en) * 2018-08-07 2022-07-13 国立大学法人広島大学 Fe-based sintered body, manufacturing method of Fe-based sintered body, and hot pressing die
CN109852871B (en) * 2019-01-31 2021-02-05 株洲华斯盛高科材料有限公司 Nitrogen-containing steel bonded hard alloy prepared from titanium nitride carbide
CN109852870B (en) * 2019-01-31 2021-02-05 株洲华斯盛高科材料有限公司 Preparation method of nitrogen-containing steel bonded hard alloy
CN111607789B (en) * 2020-04-27 2021-06-15 矿冶科技集团有限公司 Laser cladding in-situ authigenic carbide particle reinforced iron-based cladding layer and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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GB781083A (en) 1954-10-01 1957-08-14 Gregory Jamieson Comstock Improvements relating to high speed tool forms and their production
JPS5134363B2 (en) 1971-08-28 1976-09-25
JPS6188701A (en) * 1985-09-20 1986-05-07 Japanese National Railways<Jnr> Copper sintered current collecting slide material
JPH02270944A (en) * 1989-04-13 1990-11-06 Hitachi Metals Ltd Roll stock having wear resistance and resistance to surface roughness and its production
GB2257985A (en) * 1991-07-26 1993-01-27 London Scandinavian Metall Metal matrix alloys.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0120049A1 *

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ATE272724T1 (en) 2004-08-15
DE19944592A1 (en) 2001-03-22
JP2003531959A (en) 2003-10-28
JP3837332B2 (en) 2006-10-25
WO2001020049A1 (en) 2001-03-22

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