EP0044351A1 - Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy - Google Patents
Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy Download PDFInfo
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- EP0044351A1 EP0044351A1 EP80104274A EP80104274A EP0044351A1 EP 0044351 A1 EP0044351 A1 EP 0044351A1 EP 80104274 A EP80104274 A EP 80104274A EP 80104274 A EP80104274 A EP 80104274A EP 0044351 A1 EP0044351 A1 EP 0044351A1
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 33
- 239000000956 alloy Substances 0.000 title claims abstract description 33
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 12
- 239000000126 substance Substances 0.000 title abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 12
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 150000001247 metal acetylides Chemical class 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- -1 platinum metals Chemical class 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910001339 C alloy Inorganic materials 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910002839 Pt-Mo Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- 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
-
- 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
- C22C29/067—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 comprising a particular metallic binder
Definitions
- the invention relates to a hard alloy consisting of one or more hard materials and a binary binder metal alloy which contains a metal from group 8b of the periodic table of the elements.
- Hard metals or hard alloys have already been described in R. Kieffer, F. Benesovsky “Hartmetalle” (1965), pages 216 to 223.
- Hard metals with a base carbide made of chromium carbide (Cr 3 c 2 ) with 12% or 15% nickel binder have good wear resistance and high corrosion resistance.
- Such chromium carbide hard metals are relatively brittle, which has to be taken into account in the case of impact loads. With increasing nickel content, the corrosion resistance of Cr 3 C 2 hard metals also decreases. The low toughness and poor resistance to temperature changes preclude the use of Cr 3 C 2 hard metals as high-temperature materials.
- the invention is therefore based on the object of providing a material with high strength, high hardness and high wear resistance, which is largely resistant to corrosive (sometimes also oxidizing) media.
- the process of its manufacture should be simple.
- Advantageous configurations of the hard alloy are characterized by hard material-to-binder metal alloy ratios in the range between 90% by volume of hard material / 10% by volume of binder metal alloy and 5% by volume of hard material / 95% by volume of binder metal alloy .
- a further development of the hard alloy is characterized in that the proportion of the 4b, 5b, 6b transition metal in the binder metal alloy is in the range between 2 mol% and 60 mol%.
- the carbide in the hard alloy has a composition which corresponds to a transition metal to carbon ratio in the range from 1: 1 to 2: 1.
- the proportion of platinum metal in the binder metal alloy is replaced by up to 90 atomic% by iron, cobalt or nickel.
- chrome powder is mixed with a powder of one or more of the metals from the group Ru, Rh, Ir and Pt and with carbon powder in a ratio that corresponds to the formulas from these resulting mixing formulas, mixed and sintered the mixture after pressing to form the intermediate carbide or at temperatures above the decomposition temperatures of the respective multi-component carbides.
- molybdenum powder is mixed with a powder of one or more metals from the group Re, Ru, Rh, Os, Ir, Pt and with carbon powder in a ratio that corresponds to the formulas corresponds to these resulting mixing formulas, mixed and the mixture melted after pressing to form the intermediate carbide or sintered at temperatures above the decomposition temperatures of the respective multicomponent carbides.
- tungsten powder is mixed with a powder of one or more of the metals from the group Ru, Rh, Os and Pt and with carbon powder in a ratio which corresponds to the formulas from these resulting mixing formulas, mixed and the mixture melted after pressing to form the intermediate carbide or sintered at temperatures above the decomposition temperatures of the respective multicomponent carbides.
- alloys could be produced which are characterized by very finely divided carbides in a solid, tough and corrosion-resistant metal matrix.
- Chromium, molybdenum and tungsten carbides are particularly suitable as carbides. as metal phase alloys based on (Pt-Cr), (Pt-Mo), (Pt-W7, (Pd-Cr), (Pd-Mo), (Pd-W), (Ru-Cr), (Ru -Mo), (Ru-W) or other platinum metals with Cr, Mo and W.
- the invention is characterized in that ternary high-temperature carbides are obtained which, upon cooling or during heat treatment at medium temperatures (approx. 1273 K to 1575 K), form a carbide phase and a solid platinum metal alloy fall.
- the heat treatment can be controlled in such a way that extremely fine-grained microstructures with uniform carbide distribution are created. This brings with it a high level of hardness and strength and is the basis for favorable wear behavior.
- a hard alloy with 63 vol .-% metal phase and 37 vol .-% carbide (Mo 2 C) still has a hardness of lo6o HV and, according to the crack length method, a very high toughness.
- the hard alloys according to the invention are fine-grained composite materials with a total composition of the square a-b-c-d in FIG. 1 consisting of a carbide phase and metal alloys with the components shown in FIG. 1.
- the production method is also an essential component of the invention: a high-temperature sintering or melting process produces a ternary carbide, which is decomposed into a binary carbide phase and a binary metal phase at lower temperatures.
- a material based on molybdenum carbide (Mo, Pt) alloy was obtained by melting or sintering above 1575 K of a mixture of Mo / Pt / C 5o / 35/15 at.%. Such a sample lies at the end of the ternary carbide (Mo, Pt) C ⁇ 0.1 in the isothermal diagram of the system Mo-Pt-C at 1773 K. Subsequent annealing at 1373 K led to decay according to the phase relationships in the diagram at 1373 K in MO 2 C and ⁇ - (Mo, Pt). The contents of the metallic or carbide phase can be varied as required. WC- (W, Ir) or WC (W, Pt) alloys with very high metal contents have also been produced.
- a W / Pt / C alloy with 5o at.% W, 4o at.% Pt and lo At. % C is melted or sintered at 2273 K, cooled rapidly and then homogenized at temperatures around 1373 K. The finest WC and W 2 C particles are then dissolved in a (W, Pt) matrix.
- a W / Rh / C alloy with 4o at.% W, 4o at.% Rh and 2o at.% C is melted or sintered at 2273 K, quickly cooled and then homogenized at 1773 K.
- the microstructure shows WC and W 2 C particles of approximately 1 to 2 ⁇ m, homogeneously distributed in a (W, Rh) alloy.
- Wear and corrosion-resistant hard metals of the specified type can be used in tools and parts subject to wear in particularly corrosive (and / oxidation-prone) environments.
- neutron radiation e.g. Pt
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- Powder Metallurgy (AREA)
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Abstract
Description
Die Erfindung betrifft eine Hartlegierung, bestehend aus einem oder mehreren Hartstoffen und einer binären Bindemetall-Legierung, die ein Metall aus der Gruppe 8b des Periodensystems der Elemente enthält.The invention relates to a hard alloy consisting of one or more hard materials and a binary binder metal alloy which contains a metal from group 8b of the periodic table of the elements.
Hartmetalle bzw. Hartlegierungen sind bereits in R.Kieffer, F.Benesovsky "Hartmetalle" (1965), Seiten 216 bis 223, beschrieben worden. Gute Verschleißfestigkeit und hohe Korrosionsbeständigkeit weisen Hartmetalle mit einem Basiscarbid aus Chromcarbid (Cr3c2) mit 12 % oder 15 % Nickel-Binder auf. Solche Chromcarbid-Hartmetalle sind aber verhältnismäßig spröde,was beiSchlagbeanspruchungen zu berücksichtigen ist. Mit steigendem Nickel-Gehalt nimmt auch die Korrosionsbeständigkeit von Cr3C2-Hartmetallen ab. Die geringe Zähigkeit und schlechte Temperaturwechselbeständigkeit schließt die Verwendung von Cr3C2-Hartmetallen als Hochtemperaturwerkstoffe aus. Versuche, Cr3c2 teilweise durch Mo2C, WC, TiC und TaC sowie Nickel durch Kobalt, Kupfer, Eisen oder Molybdän zu ersetzen, haben keine wesentlichen Eigenschaftsverbesserungen gebracht. Eine andere Möglichkeit zu korrosionsfesten Hartmetallen zu gelangen, besteht darin, in WC-Co- oder WC-TiC-Co-Legierungen das Kobalt durch korrosionsbeständige Binder-Legierungen zu ersetzen. Hierzu wurden Nickel-Chrom-Legierungen im Verhältnis 80:20 oder 7o:3o verwendet. In der Praxis kommen 6 bis 2o %, vorzugsweise 8 bis lo % Binder-Legierung in Frage. Platin gebundenes WC-Hartmetall wurde ebenfalls hergestellt. Dieses wird im Reaktorbau, wo starke Neutronenstrahlungauftritt empfohlen [Kieffer, Benesovsky 1965].Hard metals or hard alloys have already been described in R. Kieffer, F. Benesovsky "Hartmetalle" (1965), pages 216 to 223. Hard metals with a base carbide made of chromium carbide (Cr 3 c 2 ) with 12% or 15% nickel binder have good wear resistance and high corrosion resistance. Such chromium carbide hard metals are relatively brittle, which has to be taken into account in the case of impact loads. With increasing nickel content, the corrosion resistance of Cr 3 C 2 hard metals also decreases. The low toughness and poor resistance to temperature changes preclude the use of Cr 3 C 2 hard metals as high-temperature materials. Attempts to partially replace Cr 3 c 2 with Mo 2 C, WC, TiC and TaC and nickel with cobalt, copper, iron or molybdenum have not brought about any significant improvements in properties. Another way to obtain corrosion-resistant hard metals is to replace the cobalt in WC-Co or WC-TiC-Co alloys with corrosion-resistant binder alloys. To this end, nickel-chromium alloys were in the ratio 8 0: 20 or 7o: 3o used. In practice, 6 to 20%, preferably 8 to 10%, binder alloy are suitable. Platinum-bonded toilet carbide was also made. This is used in reactor construction where strong neutron radiation occurs recommended [Kieffer, Benesovsky 1965].
Die Nachteile der bekannten Hartlegierungen sind in ihrer verhältnismäßig geringen Festigkeit und/ oder in ihrem hohen spezifischen Gewicht zu sehen.The disadvantages of the known hard alloys can be seen in their relatively low strength and / or in their high specific weight.
Der Erfindung liegt daher die Aufgabe zugrunde, einen Werkstoff mit höher Festigkeit, hoher Härte und hoher Verschleißfestigkeit, der gegen korrodierende (teilweise auch oxidierende) Medien weitgehend resistent ist, bereitzustellen. Das Verfahren seiner Herstellung soll einfach sein.The invention is therefore based on the object of providing a material with high strength, high hardness and high wear resistance, which is largely resistant to corrosive (sometimes also oxidizing) media. The process of its manufacture should be simple.
Die Aufgabe wird erfindungsgemäß gelöst durch eine Hartlegierung, bestehend aus einem oder mehreren Hartstoffen und einer binären Bindemetall-Legierung, die ein Metall aus der Gruppe 8b des Periodensystems der Elemente enthält und die dadurch gekennzeichnet ist, daß
- a) eine feindisperse homogene Verteilung des Hartstoffes in der Bindemetall-Legierung vorliegt,
- b) die Hartstoffe aus Carbiden der Ubergangsmetalle der Gruppen4b, 5b und 6b des Periodensystems der Elemente bestehen und
- c) die Bindemetalle aus festen Legierungen der Übergangsmetalle der Gruppen 4b, 5b und 6b des Periodensystems der Elemente mit Rhenium (Re) oder einem der Platinmetalle (Ru, Rh, Pd, Os, Ir,. Pt) bestehen.
- a) there is a finely dispersed, homogeneous distribution of the hard material in the binder metal alloy,
- b) the hard materials consist of carbides of the transition metals of groups 4b, 5b and 6b of the periodic table of the elements and
- c) the binding metals consist of solid alloys of the transition metals of groups 4b, 5b and 6b of the periodic table of the elements with rhenium (Re) or one of the platinum metals (Ru, Rh, Pd, Os, Ir ,. Pt).
Vorteilhafte Ausbildungen der Hartlegierung sind gekennzeichnet durch Hartstoff-zu-Bindemetall-Legierungs-Verhältnisse im Bereich zwischen 9o Vol.-% Hartstoff/lo Vol.-% Bindemetall-Legierung und 5 Vol.-% Hartstoff/95 Vol.-% Bindemetall-Legierung. Eine Weiterbildung der Hartlegierung ist dadurch gekennzeichnet, daß der Anteil des 4b,5b, 6b-Ubergangsmetalles in der Bindemetall-Legierung im Bereich zwischen 2 Mol.-% und 60 Mol.-% liegt. Das Carbid in der Hartlegierung weist eine Zusammensetzung auf, die einem Übergangsmetall-zu-Kohlenstoff-Verhältnis im Bereich von 1:1 bis 2:1 entspricht. In einer vorteilhaften Weiterbildung der Hartlegierung ist der Anteil des Platinmetalls in der Bindemetall-Legierung bis zu 90 Atom- % durch Eisen, Kobalt oder Nickel ersetzt.Advantageous configurations of the hard alloy are characterized by hard material-to-binder metal alloy ratios in the range between 90% by volume of hard material / 10% by volume of binder metal alloy and 5% by volume of hard material / 95% by volume of binder metal alloy . A further development of the hard alloy is characterized in that the proportion of the 4b, 5b, 6b transition metal in the binder metal alloy is in the range between 2 mol% and 60 mol%. The carbide in the hard alloy has a composition which corresponds to a transition metal to carbon ratio in the range from 1: 1 to 2: 1. In an advantageous further development of the hard alloy, the proportion of platinum metal in the binder metal alloy is replaced by up to 90 atomic% by iron, cobalt or nickel.
Das Verfahren zur Herstellung der erfindungsgemäßen Hartlegierungen ist dadurch gekennzeichnet, daß
- a) ein Pulver eines Übergangsmetalls aus einer der Gruppen 4b, 5boder 6b mit einem Pulver des Metalls Rhenium oder eines Platinmetalls und mit Kohlenstoffpulver in stöchiometrischem Verhältnis, das Carbiden mit 2 oder mehr Metallkomponenten entspricht, gemischt werden,
- b) daß Pulvergemisch aus a) zu Preßlingen gepreßt wird,
- c) die Preßlinge bei Temperaturen von 1575 K oder darüber, jedoch in jedem Einzelfall bei Temperaturen oberhalb der Zerfallstanperstur des jeweiligen mehrkomponentigen Carbids geschmolzen oder gesintert und
- .d) danach einer Ausscheidungs- oder Homogenisierungs-Glühung unterzogen und abgekühlt werden.
- a) a powder of a transition metal from one of groups 4b, 5b or 6b is mixed with a powder of the metal rhenium or a platinum metal and with carbon powder in a stoichiometric ratio which corresponds to carbides with 2 or more metal components,
- b) that powder mixture from a) is pressed into compacts,
- c) the compacts are melted or sintered at temperatures of 1575 K or above, but in each individual case at temperatures above the decay structure of the respective multicomponent carbide and
- . d) then subjected to a precipitation or homogenization annealing and cooled.
In einer Ausbildung des erfindungsgemäßen Verfahrens wird Chrompulver mit einem Pulver eines oder mehrerer der Metalle aus der Gruppe Ru, Rh, Ir und Pt und mit Kohlenstoffpulver in einem Verhältnis das den Formeln
In einer anderen Ausbildung des erfindungsgemäßen Verfahrens wird Molybdänpulver mit einem Pulver eines oder mehrerer Metalle aus der Gruppe Re, Ru, Rh, Os, Ir, Pt und mit Kohlenstoffpulver in einem Verhältnis, das den Formeln
In'einer weiteren Ausbildung des erfindungsgemäßen Verfahrens wird Wolframpulver mit einem Pulver eines oder mehrerer der Metalle aus der Gruppe Ru, Rh, Os und Pt und-mit Kohlenstoffpulver in einem Verhältnis, das den Formeln
Eine andere erfindungsgemäße Verfahrensweise zur Herstellung einer Hartlegierung gemäß der Erfindung ist dadurch gekennezeichnet, daß
- a) ein Pulver eines vorgefertigten Carbids eines Übergangsmetalles aus einer der Gruppen 4b, 5b oder 6b mit einem Pulver eines Übergangsmetalles aus einer der Gruppen 4b, 5b oder 6b und mit einem Pulver des Metalles Re oder eines der Platinmetalle in stöchiometrischem Verhältnis, das Carbiden mit 2 oder mehr Metallkomponenten entspricht, gemischt wird,
- b) das Pulvergemisch aus a) zu Preßlingen gepreßt wird,
- c) die Preßlinge bei Temperaturen von 1575 K oder darüber, jedoch in jedem Einzelfall bei Temperaturen oberhalb der Zerfallstemperatur des jeweiligen mehrkomponentigen Carbids geschmolzen oder gesintert und
- d) danach einer Ausscheidungs- oder Homogenisierungs-Glühung unterzogen und abgekühlt werden.
- a) a powder of a prefabricated carbide of a transition metal from one of the groups 4b, 5b or 6b with a powder of a transition metal from one of the groups 4b, 5b or 6b and with a powder of the metal Re or one of the platinum metals in a stoichiometric ratio, the carbide corresponds to 2 or more metal components, is mixed,
- b) the powder mixture from a) is pressed into compacts,
- c) the compacts are melted or sintered at temperatures of 1575 K or above, but in each individual case at temperatures above the decomposition temperature of the respective multicomponent carbide and
- d) then subjected to a precipitation or homogenization annealing and cooled.
In allen Fällen wurde nach dem Schmelz- oder Sintervorgang eine Ausscheidungsglühung durchgeführt. Auf diese Weise konnten Legierungen hergestellt werden, die sich durch feinstverteilte Carbide in einer festen, zähen und korrosionsbeständigen Metallmatrix auszeichnen. Als Carbide kommen insbesondere Chrom-, Molybdän- und Wolframcarbide in.Frage; als Metallphase Legierungen auf der Basis von (Pt-Cr), (Pt-Mo), (Pt-W7, (Pd-Cr), (Pd-Mo), (Pd-W), (Ru-Cr), (Ru-Mo), (Ru-W) bzw. anderer Platinmetalle mit Cr, Mo und W.In all cases, precipitation annealing was carried out after the melting or sintering process. In this way, alloys could be produced which are characterized by very finely divided carbides in a solid, tough and corrosion-resistant metal matrix. Chromium, molybdenum and tungsten carbides are particularly suitable as carbides. as metal phase alloys based on (Pt-Cr), (Pt-Mo), (Pt-W7, (Pd-Cr), (Pd-Mo), (Pd-W), (Ru-Cr), (Ru -Mo), (Ru-W) or other platinum metals with Cr, Mo and W.
Die Erfindung zeichnet sich dadurch aus, daß ternäre Hochtemperaturcarbide erhalten werden, die beim Abkühlen oder bei Wärmebehandlung bei mittleren Temperaturen (ca. 1273 K bis 1575 K) in eine Carbidphase und eine feste Platinmetall-Legierung zeffallen. Die Wärmebehandlung läßt sich so steuern, daß äußerst feinkörnige Gefügestrukturen mit gleichmäßiger Carbidverteilung entstehen. Dies bringt eine hohe Härte und Festigkeit mit sich und ist die Grundlage für günstiges Verschleißverhalten. Beispielsweise weist eine Hartlegierung mit 63 Vol.-% Metallphase und 37 Vol.-% Carbid (Mo2C) so noch eine Härte von lo6o HV auf und, nach dem Rißlängen-Verfahren zu schließen, eine sehr hohe Zähigkeit.The invention is characterized in that ternary high-temperature carbides are obtained which, upon cooling or during heat treatment at medium temperatures (approx. 1273 K to 1575 K), form a carbide phase and a solid platinum metal alloy fall. The heat treatment can be controlled in such a way that extremely fine-grained microstructures with uniform carbide distribution are created. This brings with it a high level of hardness and strength and is the basis for favorable wear behavior. For example, a hard alloy with 63 vol .-% metal phase and 37 vol .-% carbide (Mo 2 C) still has a hardness of lo6o HV and, according to the crack length method, a very high toughness.
Die erfindungsgemäßen Hartlegierungen stellen feinkörnige Verbundwerkstoffe dar mit einer Gesamtzusammensetzung aus dem Viereck a-b-c-d in Fig. 1 bestehend aus einer Carbidphase und Metallegierungen mit den in Fig. 1 angegebenen Komponenten. Wesentlicher Bestandteil der Erfindung ist ferner die Herstellungsmethode: Durch Hochtemperatursinterung oder Erschmelzung wird ein ternäres Carbid hergestellt, welches bei tieferen Temperaturen zum Zerfall in eine binäre Carbidphase und eine binäre Metallphase gebracht wird.The hard alloys according to the invention are fine-grained composite materials with a total composition of the square a-b-c-d in FIG. 1 consisting of a carbide phase and metal alloys with the components shown in FIG. 1. The production method is also an essential component of the invention: a high-temperature sintering or melting process produces a ternary carbide, which is decomposed into a binary carbide phase and a binary metal phase at lower temperatures.
Folgende Tabelle zeigt Zusammensetzungen solcher ternärer Carbidphasen mit übergangsmetallen der 6. Gruppe, deren Zerfall erfindungsgemäß genutzt wird.The following table shows compositions of such ternary carbide phases with transition metals of the 6th group, the decay of which is used according to the invention.
Ternäre kubisch flächenzentrierte Carbide der Übergangsmetalle Cr, Mo und W mit Rhenium und Platinmetallen
Die Erfindung wird im folgenden anhand einiger Ausführungsbeispiele, die die Erfindung jedoch nicht einschränken sollen, näher erläutert.The invention is explained in more detail below with the aid of a few exemplary embodiments, which, however, are not intended to restrict the invention.
Ein Werkstoff auf der Basis Molybdäncarbid-(Mo,Pt)Legierung wurde erhalten durch Erschmelzen oder Sinterung oberhalb 1575 K einer Mischung von Mo/Pt/C 5o/35/15 At.%. Eine solche Probe liegt am Ende des ternären Carbids (Mo,Pt)C ~0.1 im Isothermen-Schauhild des Systems Mo-Pt-C bei 1773 K. Eine nachfolgende Glühung bei 1373 K führte zum Zerfall gemäß den Phasenbeziehungen im Schaubild bei 1373 K in MO2C und η-(Mo,Pt). Die Gehalte der metallischen bzw. der Carbidphase können nach Bedarf variiert werden. WC-(W,Ir)-bzw. WC-(W,Pt)-Legierungen mit sehr hohen Metallgehalten sind ebenfalls hergestellt worden.A material based on molybdenum carbide (Mo, Pt) alloy was obtained by melting or sintering above 1575 K of a mixture of Mo / Pt / C 5o / 35/15 at.%. Such a sample lies at the end of the ternary carbide (Mo, Pt) C ~ 0.1 in the isothermal diagram of the system Mo-Pt-C at 1773 K. Subsequent annealing at 1373 K led to decay according to the phase relationships in the diagram at 1373 K in MO 2 C and η- (Mo, Pt). The contents of the metallic or carbide phase can be varied as required. WC- (W, Ir) or WC (W, Pt) alloys with very high metal contents have also been produced.
Eine W/Pt/C-Legierung mit 5o At.% W, 4o At.% Pt und lo At. % C wird erschmolzen oder bei 2273 K gesintert, schnell abgekühlt und anschließend bei Temperaturen um 1373 K homogenisiert. Feinste WC- und W2C-Teilchen sind sodann in einer (W,Pt)-Matrix gelöst.A W / Pt / C alloy with 5o at.% W, 4o at.% Pt and lo At. % C is melted or sintered at 2273 K, cooled rapidly and then homogenized at temperatures around 1373 K. The finest WC and W 2 C particles are then dissolved in a (W, Pt) matrix.
Eine W/Rh/C-Legierung mit 4o At.% W, 4o At.% Rh und 2o At.% C wird erschmolzen oder bei 2273 K gesintert, schnell abgekühlt und anschließend bei 1773 K homogenisiert. Das Mikrogefüge zeigt WC- und W2C-Partikel von etwa 1 bis 2/um, homogen in einer (W,Rh)-Legierung verteilt.A W / Rh / C alloy with 4o at.% W, 4o at.% Rh and 2o at.% C is melted or sintered at 2273 K, quickly cooled and then homogenized at 1773 K. The microstructure shows WC and W 2 C particles of approximately 1 to 2 μm, homogeneously distributed in a (W, Rh) alloy.
Verschleiß- und korrosionsbeständige Hartmetalle der angegebenen Art können in Werkzeugen und Verschleißteilweise teilen unter besonders korrosiver (und/oxidationsanfälliger) Umgebung eingesetzt werden. Auch in der Kerntechnik ergeben sich günstige Anwendungsmögliehkeiten infolge der Kurzlebigkeit der bei Neutronenstrahlung auftretenden Isotopen von manchen Platinmetallen,z.B. Pt, im Gegensatz zu dem konventionellen Bindemetall Co.Wear and corrosion-resistant hard metals of the specified type can be used in tools and parts subject to wear in particularly corrosive (and / oxidation-prone) environments. In nuclear technology, too, there are favorable application possibilities due to the short-lived nature of the isotopes of some platinum metals that occur with neutron radiation, e.g. Pt, in contrast to the conventional binder metal Co.
Claims (10)
Chrompulver mit einem Pulver eines oder mehrerer der Metalle aus der Gruppe Ru, Rh, Ir und Pt und mit Kohlenstoffpulver in einem Verhältnis, das den Formeln
Chrome powder with a powder of one or more of the metals from the group Ru, Rh, Ir and Pt and with carbon powder in a ratio that the formulas
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT80104274T ATE11574T1 (en) | 1980-07-19 | 1980-07-19 | HARD ALLOY CONSISTING OF ONE OR MORE HARD MATERIALS AND A BINDER METAL ALLOY, AND PROCESS FOR MAKING SUCH ALLOY. |
| EP80104274A EP0044351B1 (en) | 1980-07-19 | 1980-07-19 | Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy |
| DE8080104274T DE3070055D1 (en) | 1980-07-19 | 1980-07-19 | Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy |
| US06/286,376 US4432794A (en) | 1980-07-19 | 1981-07-17 | Hard alloy comprising one or more hard phases and a binary or multicomponent binder metal alloy |
| JP56112046A JPS5751239A (en) | 1980-07-19 | 1981-07-17 | Hard alloy and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP80104274A EP0044351B1 (en) | 1980-07-19 | 1980-07-19 | Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0044351A1 true EP0044351A1 (en) | 1982-01-27 |
| EP0044351B1 EP0044351B1 (en) | 1985-01-30 |
Family
ID=8186725
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80104274A Expired EP0044351B1 (en) | 1980-07-19 | 1980-07-19 | Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4432794A (en) |
| EP (1) | EP0044351B1 (en) |
| JP (1) | JPS5751239A (en) |
| AT (1) | ATE11574T1 (en) |
| DE (1) | DE3070055D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121769A1 (en) * | 1983-03-15 | 1984-10-17 | Stellram S.A. | Sintered alloy based on carbides, and article made from this alloy |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4746363A (en) * | 1982-12-30 | 1988-05-24 | Corning Glass Works | Reaction sintered cermet |
| DE3584475D1 (en) * | 1984-05-18 | 1991-11-28 | Sumitomo Electric Industries | METHOD FOR SINTERING CERAMIC BODIES AND CERAMIC BODIES PRODUCED BY SAME WITH A DISTRIBUTED METAL REINFORCEMENT. |
| US4731115A (en) * | 1985-02-22 | 1988-03-15 | Dynamet Technology Inc. | Titanium carbide/titanium alloy composite and process for powder metal cladding |
| SE456428B (en) * | 1986-05-12 | 1988-10-03 | Santrade Ltd | HARD METAL BODY FOR MOUNTAIN DRILLING WITH BINDING PHASE GRADIENT AND WANTED TO MAKE IT SAME |
| US4810314A (en) * | 1987-12-28 | 1989-03-07 | The Standard Oil Company | Enhanced corrosion resistant amorphous metal alloy coatings |
| US5134039A (en) * | 1988-04-11 | 1992-07-28 | Leach & Garner Company | Metal articles having a plurality of ultrafine particles dispersed therein |
| US4950328A (en) * | 1988-07-12 | 1990-08-21 | Mitsubishi Metal Corporation | End mill formed of tungsten carbide-base sintered hard alloy |
| US5236789A (en) * | 1991-07-01 | 1993-08-17 | Olin Corporation | Palladium alloys having utility in electrical applications |
| US5139891A (en) * | 1991-07-01 | 1992-08-18 | Olin Corporation | Palladium alloys having utility in electrical applications |
| JPH07503997A (en) * | 1992-02-20 | 1995-04-27 | ザ・ダウ・ケミカル・カンパニー | Rhenium bonded tungsten carbide composite |
| JPH07268709A (en) * | 1994-03-23 | 1995-10-17 | Kinzoku Kogyo Kenkyu Hatten Chushin | Cloth gripper |
| US6197253B1 (en) | 1998-12-21 | 2001-03-06 | Allen Broomfield | Lead-free and cadmium-free white metal casting alloy |
| US6987339B2 (en) * | 2002-05-03 | 2006-01-17 | Honeywell International, Inc. | Flywheel secondary bearing with rhenium or rhenium alloy coating |
| US6946096B2 (en) * | 2002-05-03 | 2005-09-20 | Honeywell International, Inc. | Use of powder metal sintering/diffusion bonding to enable applying silicon carbide or rhenium alloys to face seal rotors |
| US6749803B2 (en) | 2002-05-03 | 2004-06-15 | Honeywell International, Inc. | Oxidation resistant rhenium alloys |
| US6821313B2 (en) * | 2002-05-31 | 2004-11-23 | Honeywell International, Inc. | Reduced temperature and pressure powder metallurgy process for consolidating rhenium alloys |
| US6911063B2 (en) * | 2003-01-13 | 2005-06-28 | Genius Metal, Inc. | Compositions and fabrication methods for hardmetals |
| US20070034048A1 (en) * | 2003-01-13 | 2007-02-15 | Liu Shaiw-Rong S | Hardmetal materials for high-temperature applications |
| US7645315B2 (en) * | 2003-01-13 | 2010-01-12 | Worldwide Strategy Holdings Limited | High-performance hardmetal materials |
| US7857188B2 (en) * | 2005-03-15 | 2010-12-28 | Worldwide Strategy Holding Limited | High-performance friction stir welding tools |
| KR20080053468A (en) * | 2005-08-19 | 2008-06-13 | 지니어스 메탈, 인크 | Hardmetal materials for high-temperature applications |
| US8512882B2 (en) * | 2007-02-19 | 2013-08-20 | TDY Industries, LLC | Carbide cutting insert |
| US8440314B2 (en) * | 2009-08-25 | 2013-05-14 | TDY Industries, LLC | Coated cutting tools having a platinum group metal concentration gradient and related processes |
| US9340852B2 (en) * | 2011-09-26 | 2016-05-17 | National Tsing Hua University | Elevated refractory alloy with ambient-temperature and low-temperature ductility and method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2008461B2 (en) * | 1969-02-26 | 1977-07-07 | Aerojet-General Corp, El Monte, Calif. (V.St.A.) | EUTECTIC SOLID CARBIDE HARD ALLOY |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB828877A (en) * | 1957-10-04 | 1960-02-24 | Engelhard Ind Inc | Improvements in or relating to spinerettes |
| US3395013A (en) * | 1965-03-29 | 1968-07-30 | Gen Telepohone And Electronics | High-temperature ductile alloys |
| US3379520A (en) * | 1967-03-23 | 1968-04-23 | Gen Electric | Tantalum-base alloys |
| US3554737A (en) * | 1968-05-21 | 1971-01-12 | Battelle Development Corp | Cast refractory alloy |
| GB1309634A (en) * | 1969-03-10 | 1973-03-14 | Production Tool Alloy Co Ltd | Cutting tools |
| US3628921A (en) * | 1969-08-18 | 1971-12-21 | Parker Pen Co | Corrosion resistant binder for tungsten carbide materials and titanium carbide materials |
| CA986337A (en) * | 1971-05-28 | 1976-03-30 | Brian A. Mynard | Ruthenium or osmium on hard metal |
| US4097275A (en) * | 1973-07-05 | 1978-06-27 | Erich Horvath | Cemented carbide metal alloy containing auxiliary metal, and process for its manufacture |
| US4067742A (en) * | 1976-04-01 | 1978-01-10 | Nasa | Thermal shock and erosion resistant tantalum carbide ceramic material |
-
1980
- 1980-07-19 AT AT80104274T patent/ATE11574T1/en active
- 1980-07-19 DE DE8080104274T patent/DE3070055D1/en not_active Expired
- 1980-07-19 EP EP80104274A patent/EP0044351B1/en not_active Expired
-
1981
- 1981-07-17 US US06/286,376 patent/US4432794A/en not_active Expired - Fee Related
- 1981-07-17 JP JP56112046A patent/JPS5751239A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2008461B2 (en) * | 1969-02-26 | 1977-07-07 | Aerojet-General Corp, El Monte, Calif. (V.St.A.) | EUTECTIC SOLID CARBIDE HARD ALLOY |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121769A1 (en) * | 1983-03-15 | 1984-10-17 | Stellram S.A. | Sintered alloy based on carbides, and article made from this alloy |
| US4574011A (en) * | 1983-03-15 | 1986-03-04 | Stellram S.A. | Sintered alloy based on carbides |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0044351B1 (en) | 1985-01-30 |
| US4432794A (en) | 1984-02-21 |
| ATE11574T1 (en) | 1985-02-15 |
| DE3070055D1 (en) | 1985-03-14 |
| JPS5751239A (en) | 1982-03-26 |
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