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EP0195965B1 - Hard metal and process for its manufacture - Google Patents

Hard metal and process for its manufacture Download PDF

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Publication number
EP0195965B1
EP0195965B1 EP86102983A EP86102983A EP0195965B1 EP 0195965 B1 EP0195965 B1 EP 0195965B1 EP 86102983 A EP86102983 A EP 86102983A EP 86102983 A EP86102983 A EP 86102983A EP 0195965 B1 EP0195965 B1 EP 0195965B1
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EP
European Patent Office
Prior art keywords
weight
sintered
hard metal
percent
sintering
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.)
Expired - Lifetime
Application number
EP86102983A
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German (de)
French (fr)
Other versions
EP0195965A3 (en
EP0195965A2 (en
Inventor
Johannes Kolaska
Norbert Dr.-Ing. Reiter
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Fried Krupp AG
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Fried Krupp AG
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Application filed by Fried Krupp AG filed Critical Fried Krupp AG
Priority to AT86102983T priority Critical patent/ATE56483T1/en
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Publication of EP0195965A3 publication Critical patent/EP0195965A3/en
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Classifications

    • 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
    • C22C29/08—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 tungsten carbide
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a hard metal, the hard material phase of tungsten carbide and the binder metal phase of nickel and chromium and which is produced from powdered raw materials by pressing and sintering, and a method for its production.
  • Such hard metals are already known, because US Pat. No. 3,215,510 describes a hard metal which consists of 10 to 30% by weight of a chromium-nickel binding alloy and the remainder tungsten carbide, the weight ratio of chromium to binding metal being between 0.015 and 0. 15 lies, and which is made from powdered raw materials by pressing and sintering.
  • the invention has for its object to provide a hard metal of the type mentioned which, in addition to good corrosion resistance, also has high strength and in particular high toughness. Another object of the invention is to provide a method for producing the hard metal.
  • the hard metal contains, in addition to the hard material phase, 5 to 25% by weight of binder metal phase, which is composed of 5 to 15% by weight of chromium and the rest of nickel, and that the hard metal after sintering during a Time of 20 to 200 minutes in an inert gas atmosphere, preferably an argon atmosphere, at a temperature of 1300 to 1400 ° C and a pressure of 20 to 3000 bar.
  • the hard metal according to the invention is corrosion-resistant and has great strength and great toughness.
  • the strength and toughness of the hard metal according to the invention are even higher than in the case of corresponding tungsten carbide-cobalt hard metals, which according to current knowledge are distinguished by the highest strength and toughness.
  • the hard metal according to the invention is always non-magnetic, which is not always the case with the known hard metals. Because of its good properties, there are many possible uses for the hard metal according to the invention.
  • the tungsten carbide is replaced by titanium carbide, tantalum carbide and / or niobium carbide.
  • the object on which the invention is based is further achieved by a method for producing the hard metal, in which the sintered body is in a noble gas atmosphere, preferably an argon atmosphere, at a temperature of 1300 to 1400 ° C. and a pressure of 20 to 200 minutes 20 to 3000 bar can be treated.
  • a noble gas atmosphere preferably an argon atmosphere
  • the treatment of the sintered bodies according to the invention gives the hard metal good strength and toughness, which is attributed to a high degree of compaction of the hard metal structure.
  • the sintered bodies are cooled and then treated in a separate plant at 100 to 3000 bar or that the sintered bodies are treated in the sintering plant immediately after sintering at 20 to 100 bar. If the treatment of the sintered bodies according to the invention takes place immediately after their sintering, it is possible to work advantageously at particularly low pressure.
  • the powdered raw materials used for hard metal production have a particle size of 0.5 to 5 pm.
  • the hard metal is pressed and sintered according to the known methods.
  • the pressure should not be below 20 bar and the temperature should not be above 1400 ° C., since at a lower pressure there is insufficient compression of the structure and at a higher temperature there is an adverse enlargement of the structure. If the chromium content of the binder metal phase is greater than 15% by weight, chromium carbide precipitates occur in the hard metal structure, as a result of which the properties of the hard metal deteriorate sustainably.
  • the following table contains exemplary embodiments of the hard metal according to the invention and indicates their bending strengths.
  • the flexural strength is a measure of the strength and toughness of hard metals.
  • the table also shows the composition and bending strength of corresponding WC-Co hard metals.
  • the comparison of the bending strengths shows the excellent properties of the hard metal according to the invention.

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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)
  • Conductive Materials (AREA)

Abstract

A sintered tungsten carbide material and method for manufacturing same in which the method includes the steps of combining metal particles composed of from 75 to 95 percent by weight of a composition containing at least 70 percent by weight of tungsten carbide and from 5 to 25 percent by weight of a binder metal composition, the binder metal composition consisting essentially of from 5 to 15 percent by weight of chromium and from 85 to 95 percent by weight of nickel; pressing the metal particles into a pressed body; sintering the pressed body in a sintering chamber for a period ranging from 20 to 200 minutes, at a temperature ranging from 1400 DEG to 1500 DEG C., and in a protective atmosphere which is one of a vacuum, a noble gas, a mixture of noble gases, and hydrogen gas to form a sintered body; and treating the sintered body for a period ranging from 20 to 200 minutes, at a temperature ranging from 1300 DEG to 1400 DEG C., at a pressure ranging from 20 to 3000 bar, and in a noble gas atmosphere. The pressure/temperature treatment step densifies the sintered composition and results in an unexpectedly stronger and tougher sintered metal.

Description

Die Erfindung bezieht sich auf ein Hartmetall, dessen Hartstoffphase aus Wolframcarbid und dessen Bindemetallphase aus Nickel und Chrom besteht und das aus pulverförmigen Rohstoffen durch Pressen und Sintern hergestellt ist, sowie auf ein Verfahren zu seiner Herstellung. Darartige Hartmetalle sind bereits bekannt, denn die US-PS 3 215 510 beschreibt ein Hartmetall, das aus 10 bis 30 Gew.-% einer Chrom-Nickel-Bindelegierung und Rest Wolframcarbid besteht, wobei das Gewichtsverhältnis von Chrom zu Bindemetall zwischen 0,015 und 0,15 liegt, und das aus pulverförmigen Rohstoffen durch Pressen und Sintern hergestellt wird. Ferner offenbart die Veröffentlichung von Kieffer und Benesovsky, Hartmetalle, 1965, Seiten 220, 221 und 228, ein Hartmetall, das aus 90 Gew.-% Wolframcarbid, 8 Gew.-% Nickel und 2 Gew.-% Chrom besteht. Diese bekannten Hartmetalle haben zwar eine gute Korrosionsfestigkeit, aber sie besitzen nur eine geringe Festigkeit und insbesondere eine sehr geringe Zähigkeit, so daß ihre Verwendungsmöglichkeiten stark eingeschränkt sind.The invention relates to a hard metal, the hard material phase of tungsten carbide and the binder metal phase of nickel and chromium and which is produced from powdered raw materials by pressing and sintering, and a method for its production. Such hard metals are already known, because US Pat. No. 3,215,510 describes a hard metal which consists of 10 to 30% by weight of a chromium-nickel binding alloy and the remainder tungsten carbide, the weight ratio of chromium to binding metal being between 0.015 and 0. 15 lies, and which is made from powdered raw materials by pressing and sintering. Furthermore, the publication by Kieffer and Benesovsky, Hartmetalle, 1965, pages 220, 221 and 228, discloses a hard metal which consists of 90% by weight tungsten carbide, 8% by weight nickel and 2% by weight chromium. Although these known hard metals have good corrosion resistance, they have only a low strength and in particular a very low toughness, so that their possible uses are severely restricted.

Der Erfindung liegt die Aufgabe zugrunde, ein Hartmetall der eingangs genannten Art zu schaffen, das neben einer guten Korrosionsfestigkeit auch eine hohe Festigkeit und insbsondere eine hohe Zähigkeit besitzt. Ferner liegt der Erfindung die Aufgabe zugrunde, ein Verfahren zur Herstellung des Hartmetalls zu schaffen.The invention has for its object to provide a hard metal of the type mentioned which, in addition to good corrosion resistance, also has high strength and in particular high toughness. Another object of the invention is to provide a method for producing the hard metal.

Die der Erfindung zugrundeliegende Aufgabe wird dadurch gelöst, daß das Hartmetall neben der Hartstoffphase 5 bis 25 Gew.-% Bindemetallphase enthält, die aus 5 bis 15 Gew.-% Chrom und Rest Nickel zusammengesetzt ist, und daß das Hartmetall nach dem Sintern während einer Zeit von 20 bis 200 Minuten in einer Edelgasatmosphäre, vorzugsweise einer Argonatmosphäre, bei einer Temperatur von 1300 bis 1400°C und einem Druck von 20 bis 3000 bar behandelt worden ist. Das erfindungsgemäße Hartmetall ist korrosionsfest und hat eine größe Festigkeit sowie eine große Zähigkeit. Überraschenderweise hat sich aber gezeigt, daß Festigkeit und Zähigkeit des erfindungsgemäßen Hartmetalls noch höher sind als bei entsprechenden Wolframcarbid-Cobalt-Hartmetallen, die sich nach den heutigen Erkenntnissen durch höchste Festigkeiten und Zähigkeiten auszeichnen. Ferner ist das erfindungsgemäße Hartmetall immer unmagnetisch, was bei den bekannten Hartmetallen nicht immer der Fall ist. Wegen seiner guten Eigenschaften ergeben sich für das erfindungsgemäße Hartmetall vielfältige Verwendungsmöglichkeiten.The object on which the invention is based is achieved in that the hard metal contains, in addition to the hard material phase, 5 to 25% by weight of binder metal phase, which is composed of 5 to 15% by weight of chromium and the rest of nickel, and that the hard metal after sintering during a Time of 20 to 200 minutes in an inert gas atmosphere, preferably an argon atmosphere, at a temperature of 1300 to 1400 ° C and a pressure of 20 to 3000 bar. The hard metal according to the invention is corrosion-resistant and has great strength and great toughness. Surprisingly, however, it has been shown that the strength and toughness of the hard metal according to the invention are even higher than in the case of corresponding tungsten carbide-cobalt hard metals, which according to current knowledge are distinguished by the highest strength and toughness. Furthermore, the hard metal according to the invention is always non-magnetic, which is not always the case with the known hard metals. Because of its good properties, there are many possible uses for the hard metal according to the invention.

Es ist bekannt (FR-A-2 036 654 und 2 387 720) gesinterte Hartmetalle anderer als erfindungsgemäßer Zusammensetzung einer Nachbehandlung bei erhöhter Temperatur und erhöhtem Druck zwecks Verbesserung der mechanischen Eigenschaften zu unterziehen. Es war aber überraschend, daß sich die Zähigkeit des Hartmetalles bei Beibehaltung oder sonstigen Günstigen Eigenschaften im Fall der erfindungsgemäßen Zusammensetzung durch die Nachbehandlung entscheidend verbessert.It is known (FR-A-2 036 654 and 2 387 720) to subject sintered hard metals other than the composition according to the invention to post-treatment at elevated temperature and elevated pressure in order to improve the mechanical properties. However, it was surprising that the toughness of the hard metal while maintaining or other favorable properties in the case of the composition according to the invention is decisively improved by the aftertreatment.

Nach der Erfindung ist ferner vorgesehen, daß 1 bis 30 Gew.-% des Wolframcarbids durch Titancarbid, Tantalcarbid und/oder Niobcarbid ersetzt sind. Hierdurch können die guten Eigenschaften des Hartmetalls variiert und bestimmten Verwendungszwecken angepaßt werden.According to the invention it is further provided that 1 to 30% by weight of the tungsten carbide is replaced by titanium carbide, tantalum carbide and / or niobium carbide. As a result, the good properties of the hard metal can be varied and adapted to specific uses.

Die der Erfindung zugrundeliegende Aufgabe wird ferner durch ein Verfahren zur Herstellung des Hartmetalls gelöst, bei dem die gesinterter Körper während einer Zeit von 20 bis 200 Minuten in einer Edelgasatmosphäre, vorzugsweise einer Argonatmosphäre, bei einer Temperatur von 1300 bis 1400°C und einem Druch von 20 bis 3000 bar behandelt werden. Durch die erfindungsgemäße Behandlung der gesinterten Körper erhält das Hartmetall eine gute Festigkeit und Zähigkeit, was auf einen hohen Verdichtungsgrad des Hartmetallgefüges zurückgeführt wird.The object on which the invention is based is further achieved by a method for producing the hard metal, in which the sintered body is in a noble gas atmosphere, preferably an argon atmosphere, at a temperature of 1300 to 1400 ° C. and a pressure of 20 to 200 minutes 20 to 3000 bar can be treated. The treatment of the sintered bodies according to the invention gives the hard metal good strength and toughness, which is attributed to a high degree of compaction of the hard metal structure.

Nach der Erfindung ist schließlich vorgesehen, daß die gesinterten Körper abgekühlt und dann in einer gesonderten Anlage bei 100 bis 3000 bar behandelt werden oder das die gesinterten Körper unmittelbar nach der Sinterung in der Sinteranlage bei 20 bis 100 bar behandelt werden. Wenn die erfindungsgemäße Behandlung der gesinterten Körper unmittelbar nach ihrer Sinterung erfolgt, kann in vorteilhafter Weise bei besonders niedrigem Druck gearbeitet werden.According to the invention, it is finally provided that the sintered bodies are cooled and then treated in a separate plant at 100 to 3000 bar or that the sintered bodies are treated in the sintering plant immediately after sintering at 20 to 100 bar. If the treatment of the sintered bodies according to the invention takes place immediately after their sintering, it is possible to work advantageously at particularly low pressure.

Die zur Hartmetallherstellung verwendeten pulverförmigen Rohstoffe haben eine Teilchengröße von 0,5 bis 5 pm. Das Pressen und Sintern des Hartmetalls wird nach den bekannten Methoden durchgeführt. Bei der erfindungsgemäßen Druck-Temperatur-Behandlung soll der Druck nicht unter 20 bar und die Temperatur nicht über 1400°C liegen, da bei einem kleineren Druck keine ausreichende Verdichtung des Gefüges und bei einer höheren Temperatur eine nachteilige Vergrößerung des Gefüges eintritt. Wenn der Chromgehalt der Bindemetallphase größer als 15 Gew.-% ist, treten im Hartmetallgefüge Chromcarbidausscheidungen auf, wodurch sich die Eigenschaften des Hartmetalls nachhaltig verschlechtern.The powdered raw materials used for hard metal production have a particle size of 0.5 to 5 pm. The hard metal is pressed and sintered according to the known methods. In the pressure-temperature treatment according to the invention, the pressure should not be below 20 bar and the temperature should not be above 1400 ° C., since at a lower pressure there is insufficient compression of the structure and at a higher temperature there is an adverse enlargement of the structure. If the chromium content of the binder metal phase is greater than 15% by weight, chromium carbide precipitates occur in the hard metal structure, as a result of which the properties of the hard metal deteriorate sustainably.

Die nachfolgende Tabelle enthält Ausführungsbeispiele des erfindungsgemäßen Hartmetalls und gibt deren Biegefestigkeiten an. Die Biegefestigkeit ist ein Maß für die Festigkeit und Zähigkeit von Hartmetallen. Die Tabelle zeigt auch die Zusammensetzung und Biegefestigkeit von entsprechenden WC-Co-Hartmetallen. Der Vergleich der Biegefestigkeiten beweist die ausgezeichneten Eigenschaften des erfindungsgemäßen Hartmetalls.

Figure imgb0001
The following table contains exemplary embodiments of the hard metal according to the invention and indicates their bending strengths. The flexural strength is a measure of the strength and toughness of hard metals. The table also shows the composition and bending strength of corresponding WC-Co hard metals. The comparison of the bending strengths shows the excellent properties of the hard metal according to the invention.
Figure imgb0001

Claims (5)

1. A hard metal whose hard material phase consists of tungsten carbide and whose binder metal phase consists of nickel and chromium and which is produced from pulverulent raw materials by pressing and sintering and contains in addition to the hard material phase 5 to 25% by weight binder metal phase which is made up of 5 to 15% by weight chromium, the residue being nickel, characterized in that following sintering the hard metal has been treated for a period of 20 to 200 minutes in a noble gas atmosphere, preferably an argon atmosphere, at a temperaturre of 1300 to 1400°C and a pressure of 20 to 3000 bar.
2. A hard metal according to Claim 1, characterized in that titanium carbide, tantalum carbide and/or niobium carbide are substituted for 1 to 30% by weight of the tungsten carbide.
3. A process for the production of the hard metal according to Claims 1 and 2, wherein the pulverulent raw materials are pressed into pressings which are then sintered for 20 to 200 minutes in vacuo or in a protective gas atmosphere of noble gases or hydrogen at 1400 to 1450°C, characterized in that the sintered bodies are treated for a period of 20 to 200 minutes in a noble gas atmosphere, preferably an argon atmosphere, at a temperature of 1300 to 1400°C and a pressure of 20 to 3000 bar.
4. A process according to Claim 3, characterized in that the sintered bodies are cooled and then treated in a separate installation of 100 to 3000 bar.
5. A process according to Claim 3, characterized in that immediately following sintering, the sintered bodies are treated in the sintering installation at 20 to 100 bar.
EP86102983A 1985-03-28 1986-03-06 Hard metal and process for its manufacture Expired - Lifetime EP0195965B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86102983T ATE56483T1 (en) 1985-03-28 1986-03-06 CARBIDE AND PROCESS FOR ITS PRODUCTION.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853511220 DE3511220A1 (en) 1985-03-28 1985-03-28 HARD METAL AND METHOD FOR THE PRODUCTION THEREOF
DE3511220 1985-03-28

Publications (3)

Publication Number Publication Date
EP0195965A2 EP0195965A2 (en) 1986-10-01
EP0195965A3 EP0195965A3 (en) 1988-09-21
EP0195965B1 true EP0195965B1 (en) 1990-09-12

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Country Status (5)

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US (1) US4684405A (en)
EP (1) EP0195965B1 (en)
JP (1) JPS61227147A (en)
AT (1) ATE56483T1 (en)
DE (1) DE3511220A1 (en)

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JPS5935974A (en) * 1982-08-24 1984-02-27 Mitsubishi Pencil Co Ltd Printing of paper surface of notebook or the like

Also Published As

Publication number Publication date
EP0195965A3 (en) 1988-09-21
JPS61227147A (en) 1986-10-09
US4684405A (en) 1987-08-04
ATE56483T1 (en) 1990-09-15
EP0195965A2 (en) 1986-10-01
DE3511220A1 (en) 1986-10-09
DE3511220C2 (en) 1989-09-07

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