EP0448572B1 - Hard metal composite body and process for producing it - Google Patents
Hard metal composite body and process for producing it Download PDFInfo
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- EP0448572B1 EP0448572B1 EP89913058A EP89913058A EP0448572B1 EP 0448572 B1 EP0448572 B1 EP 0448572B1 EP 89913058 A EP89913058 A EP 89913058A EP 89913058 A EP89913058 A EP 89913058A EP 0448572 B1 EP0448572 B1 EP 0448572B1
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- composite body
- hard metal
- metal composite
- sintering
- reinforcing material
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/08—Iron group metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
Definitions
- the invention relates to a hard metal composite body consisting of hard material phases such as tungsten carbide and / or carbides or nitrides of the elements of the IVa or Va group of the periodic table, of reinforcing materials and of a binding metal phase such as cobalt and / or iron and / or nickel.
- the invention further relates to a method for producing a hard metal composite material by powder metallurgy.
- the single crystals known in principle from the prior art have excellent mechanical properties, such as great tensile and shear strength.
- AT-PS 259 242 describes a sintered hard metal consisting of hard materials and binders, which contains hard materials in the form of acicular single crystals in an amount of at least 0.1%, preferably 0.5 to 1.5% of the total hard material content.
- WC in the form of needle-shaped single crystals is added to the hard material portion before grinding, the hard metal batch being pressed and sintered to form a liquid phase after the addition of a binding metal to the iron group.
- the monocrystalline WC portion largely dissolves in the bandage rabbit (cf. DE-Z "Metall", July 1974, No. 7).
- the proposed hard single crystals do not suffice to obtain a noticeable improvement in wear properties, especially not because only a maximum of single crystals should be added until the hard grain fraction (grains with an average diameter of less than 2 ⁇ m) is replaced is.
- EP 0 289 476 A2 also describes a generic hard metal composite body having the following composition: 5 to 50% by volume of whiskers of nitrides, carbides and carbonitrides of titanium, zirconium and hafnium or mixtures thereof, and also 25 to 82% by volume of hard material phase Carbides and / or nitrides of the IVa, Va and / or VIa group of the periodic system or mixtures thereof and 3 to 25 vol .-% binder made of iron, cobalt and nickel.
- Claim 1 distinguishes two types of reinforcing material, namely single-crystalline platelet-shaped material (also referred to as platelets in English-language literature) and single-crystalline needle-shaped material (whiskers, sometimes also filaments).
- the platelets within the meaning of claim 1 include: borides, carbides, nitrides and / or carbonitrides of the elements from groups IVa to VIa, SiC, Si3N4, Si2N2O, Al2O3, ZrO2, AlN and / or BN or mixtures of the aforementioned platelets.
- the whiskers within the meaning of claim 1 include: SiC, Si3N4, Si2N2O, Al2O3, ZrO2, AlN and / or BN or mixtures of the aforementioned whiskers.
- the US-PS 45 43 345 describes a ceramic (Al2O3 matrix) with embedded SiC whiskers.
- EP 0 067 584 B1 describes a process for producing a composite material from a metallic, ceramic glass or plastic base material and therein substantially homogeneously and uniformly distributed deagglomerated silicon carbide whiskers for reinforcing the base material, in which silicon carbide whiskers are formed in a polar solvent to form a The slurry is stirred and then the slurry is ground to form a slurry of deagglomerated silicon carbide whiskers, the slurry is mixed therefrom with a base material to form a homogeneous mixture, then dried and formed into a blank.
- EP 0 213 615 A2 discloses composite materials in which silicon carbide and silicon nitride whiskers are contained in a metal matrix.
- the platelet-shaped single crystals In contrast to the whiskers, the platelet-shaped single crystals have a much larger width (which is generally referred to as diameter) with a thickness that is in the order of magnitude of the whisker diameter.
- the whiskers should preferably have a length of 3 ⁇ m to 100 ⁇ m and / or a diameter of 0.1 to 10 ⁇ m.
- the platelets are preferably characterized by a thickness of 0.5 ⁇ m to 10 ⁇ m and a diameter (the larger area of the platelet) of 3 ⁇ m to 100 ⁇ m.
- SiC whiskers or platelets are used which have more than 90% of the ⁇ structure.
- the amount of whiskers or platelets is in the range from 2 to 40% by volume, preferably 10 to 20% by volume, as specified in claim 1.
- a particular advantage of an inert whisker or platelet coating is, however, that a targeted strength of the bond with the matrix can be set.
- the storage of coated whiskers or platelets leads to an increase in hardness with a simultaneous increase in toughness, even under high-temperature loads, such as those e.g. take place with cutting materials. This is advantageously also achieved in the case of hard metals which have a low binder content (less than 8% by volume).
- the inert coating has a certain protective function for the coated single crystals, ie the single crystals cannot be dissolved in the binder, in particular toilet single crystals can be used for the first time in an effective proportion based on the hard metal composition.
- Preferred coating material are carbides, nitrides and / or carbonitrides from the VIa group of the periodic table and / or ZrO2, Al2O3 and / or BN.
- the thickness of the coating is between 0.2 ⁇ m and a maximum of 2/10 of the whisker diameter or platelet thickness, preferably between 0.05 ⁇ m and 1/10 of the whisker diameter or platelet thickness.
- the coating of the whiskers and / or platelets is preferably applied using the CVD or PVD method known in principle from the prior art.
- whisker hard metal composites are basically based on known powder metallurgical process steps.
- the reinforcement materials whiskers, platelets
- a basic distinction is made between four compression processes: the usual sintering, a combined sintering / HIP process, in which hot isostatic pressing is carried out at 20 to 100 bar, maximum 200 bar, immediately after the sintering process, and sintering with subsequent hot isostatic Pressing at pressures of around 1000 bar, for example, in a separate system and finally the hot pressing mentioned.
- WC whiskers are disagglomerated and classified Form which have been coated with TiC by means of the CVD process known in principle from the prior art. The entire mixture was then dried, granulated and cold-isostatically pressed into a green compact before the whisker composite was finished by hot pressing.
- the hard metal composite material according to the invention has a greater hardness and higher strength values than composite materials known from the prior art.
- the toughness resilience is higher with a reduced risk of breakage, without having to set higher binding contents.
Abstract
Description
Die Erfindung betrifft einen Hartmetallverbundkörper, bestehend aus Hartstoffphasen, wie Wolframcarbid und/oder Carbiden bzw. Nitriden der Elemente der IVa- oder Va-Gruppe des Periodensystems, aus Verstärkungsmaterialien und aus einer Bindemetallphase, wie Cobalt und/oder Eisen und/oder Nickel. Ferner betrifft die Erfindung ein Verfahren zur Herstellung eines Hartmetallverbundwerkstoffes auf pulvermetallurgischem Weg.The invention relates to a hard metal composite body consisting of hard material phases such as tungsten carbide and / or carbides or nitrides of the elements of the IVa or Va group of the periodic table, of reinforcing materials and of a binding metal phase such as cobalt and / or iron and / or nickel. The invention further relates to a method for producing a hard metal composite material by powder metallurgy.
Die nach dem Stand der Technik im Prinzip bekannten Einkristalle besitzen hervorragende mechanische Eigenschaften, wie z.B. eine große Zug- und Schubfestigkeit.The single crystals known in principle from the prior art have excellent mechanical properties, such as great tensile and shear strength.
In der AT-PS 259 242 wird ein aus Hartstoffen und Bindemitteln bestehendes Sinterhartmetall beschrieben, das Hartstoffe in Form von nadelförmigen Einkristallen in einer Menge von wenigstens 0,1 %, vorzugsweise 0,5 bis 1,5 % des gesamten Hartstoffanteils enthält. Zur Herstellung dieses Sinterhartmetalls wird dem Hartstoffanteil vor dem Vermahlen WC in Form von nadelförmigen Einkristallen zugesetzt, wobei nach Zusatz eines Bindemetalls der Eisengruppe der Hartmetallansatz gepreßt und unter Bildung einer flüssigen Phase gesintert wird. Nachteiligerweise löst sich jedoch der einkristalline WC-Anteil weitgehend in der Bindenhase (vgl. DE-Z "Metall", Juli 1974, Heft 7). Im übrigen reichen die vorgeschlagenen Hartstoff-Einkristalle nicht aus, um eine merkliche Verbesserung der Verschleißeigenschaften zu erhalten, insbesondere auch deshalb nicht, weil maximal nur so viel Hartstoff-Einkristalle zugegeben werden sollen, bis der Hartstoffeinkornanteil (Körner mit mittlerem Durchmesser unter 2 µm) ersetzt ist.AT-PS 259 242 describes a sintered hard metal consisting of hard materials and binders, which contains hard materials in the form of acicular single crystals in an amount of at least 0.1%, preferably 0.5 to 1.5% of the total hard material content. To produce this sintered hard metal, WC in the form of needle-shaped single crystals is added to the hard material portion before grinding, the hard metal batch being pressed and sintered to form a liquid phase after the addition of a binding metal to the iron group. Disadvantageously, however, the monocrystalline WC portion largely dissolves in the bandage rabbit (cf. DE-Z "Metall", July 1974, No. 7). Furthermore, the proposed hard single crystals do not suffice to obtain a noticeable improvement in wear properties, especially not because only a maximum of single crystals should be added until the hard grain fraction (grains with an average diameter of less than 2 µm) is replaced is.
Die EP 0 289 476 A2 beschreibt ferner einen gattungsgemäßen Hartmetallverbundkörper der folgende Zusammensetzung besitzt: 5 bis 50 Vol.-% Whisker aus Nitriden, Carbiden und Carbonitriden des Titans, Zirkoniums und Hafniums oder Mischungen hiervon, ferner 25 bis 82 Vol.-% Hartstoffphase aus Carbiden und/oder Nitriden der IVa-, Va- und/oder VIa-Gruppe des periodischen Systems oder Mischungen hiervon und 3 bis 25 Vol.-% Binder aus Eisen, Kobalt und Nickel.EP 0 289 476 A2 also describes a generic hard metal composite body having the following composition: 5 to 50% by volume of whiskers of nitrides, carbides and carbonitrides of titanium, zirconium and hafnium or mixtures thereof, and also 25 to 82% by volume of hard material phase Carbides and / or nitrides of the IVa, Va and / or VIa group of the periodic system or mixtures thereof and 3 to 25 vol .-% binder made of iron, cobalt and nickel.
Es ist Aufgabe der vorliegenden Erfindung, einen Hartmetallverbundkörper anzugeben, der gegenüber den bisher bekannten Hartmetallverbundkörpern eine höhere Zähigkeitsbelastbarkeit, eine größere Härte, auch bei starker thermischer Belastung des Hartmetallverbundkörpers und eine geringere Bruchanfälligkeit aufweist. Ferner ist es Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung eines solchen Hartmetallverbundkörpers anzugeben.It is an object of the present invention to provide a hard metal composite body which, compared to the previously known hard metal composite bodies, has a higher toughness resistance, greater hardness, even when the hard metal composite body is subjected to high thermal loads, and has a lower susceptibility to breakage. It is also an object of the present invention to provide a method for producing such a hard metal composite body.
Die Aufgabe wird durch einen Hartmetallverbundkörper der im Anspruch 1 genannten Zusammensetzung gelöst.The object is achieved by a hard metal composite body of the composition mentioned in claim 1.
Der Anspruch 1 unterscheidet zwei Sorten von Verstärkungsmaterial, nämlich einkristallines plättchenförmiges Material (in der englischsprachigen Literatur auch als Platelets bezeichnet) und einkristallines nadelförmiges Material (Whisker, bisweilen auch Filaments). Zu den Platelets im Sinne des Anspruches 1 gehören: Boride, Carbide, Nitride und/oder Carbonitride der Elemente der Gruppe IVa bis VIa, SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AlN und/oder BN oder Mischungen der vorgenannten Platelets.Claim 1 distinguishes two types of reinforcing material, namely single-crystalline platelet-shaped material (also referred to as platelets in English-language literature) and single-crystalline needle-shaped material (whiskers, sometimes also filaments). The platelets within the meaning of claim 1 include: borides, carbides, nitrides and / or carbonitrides of the elements from groups IVa to VIa, SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AlN and / or BN or mixtures of the aforementioned platelets.
Zu den Whiskern im Sinne des Anspruches 1 gehören: SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AlN und/oder BN oder Mischungen der vorgenannten Whisker.The whiskers within the meaning of claim 1 include: SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AlN and / or BN or mixtures of the aforementioned whiskers.
Die Verwendung von nadelförmigen Einkristallen, also Whiskern, ist zwar nach dem Stand der Technik bei anderen Stoffen bereits vorgeschlagen worden:The use of acicular single crystals, i.e. whiskers, has already been proposed for other substances according to the prior art:
So z.B. in der US-PS 34 41 392 eine faserverstärkte Metallegierung, die auf pulvermetallurgischem Wege hergestellt worden ist und die beispielsweise Fasern aus α-Aluminiumoxid und Siliciumcarbid enthält.So e.g. in US-PS 34 41 392 a fiber-reinforced metal alloy which has been produced by powder metallurgy and which contains, for example, fibers made of α-aluminum oxide and silicon carbide.
Die US-PS 45 43 345 beschreibt eine Keramik (Al2O3-Matrix) mit eingelagerten SiC-Whiskern.The US-PS 45 43 345 describes a ceramic (Al2O3 matrix) with embedded SiC whiskers.
Aus der DE 33 03 295 A1 ist bekannt, daß die Festigkeits- und Bruchzähigkeitseigenschaften einer siliciumcarbidfaserverstärkten Keramik besser als die der Keramikmatrix sind. Entsprechende Angaben werden auch in der DE-Z ZwF 83 (1988) 7, Seiten 354 bis 359 gemacht.From DE 33 03 295 A1 it is known that the strength and fracture toughness properties of a silicon carbide fiber reinforced ceramic are better than those of the ceramic matrix. Corresponding information is also given in DE-Z ZwF 83 (1988) 7, pages 354 to 359.
Die EP 0 067 584 B1 beschreibt ein Verfahren zur Herstellung eines Verbundwerkstoffes aus einem metallischen, keramischen Glas- oder Kunststoff-Grundmaterial und darin im wesentlichen homogen und gleichmäßig verteilten desagglomerierten Siliciumcarbidwhiskern zur Verstärkung des Grundmaterials, bei dem man Siliciumcarbidwhisker in einem polaren Lösungsmittel zur Bildung einer Aufschlämmung rührt und anschließend die Aufschlämmung zur Bildung einer Aufschlämmung aus desagglomerierten Siliciumcarbidwhiskern vermahlt, die Aufschlämmung hieraus mit einem Grundmaterial zur Bildung einer homogenen Mischung vermischt, anschließend trocknet und zu einem Rohling formt.EP 0 067 584 B1 describes a process for producing a composite material from a metallic, ceramic glass or plastic base material and therein substantially homogeneously and uniformly distributed deagglomerated silicon carbide whiskers for reinforcing the base material, in which silicon carbide whiskers are formed in a polar solvent to form a The slurry is stirred and then the slurry is ground to form a slurry of deagglomerated silicon carbide whiskers, the slurry is mixed therefrom with a base material to form a homogeneous mixture, then dried and formed into a blank.
Schließlich sind aus der EP 0 213 615 A2 Verbundwerkstoffe bekannt, bei denen in einer Metallmatrix Siliciumcarbid- und Siliciumnitridwhisker enthalten sind.Finally, EP 0 213 615 A2 discloses composite materials in which silicon carbide and silicon nitride whiskers are contained in a metal matrix.
Die Einbringung von nadel- oder plättchenförmigen Einkristallen bei Hartmetallen in größeren Mengen wurde jedoch nie durchgeführt, weil bisher eine Lösung der Einkristalle in der flüssigen Bindemittelphase befürchtet worden ist. In der Tat ist die Löslichkeit des WC in einem Bindemittel wie Cobalt groß, was bewirkt, daß die Verwendung von WC-Whiskern - wie in der AT-PS 259 242 vorgeschlagen - keine Verbesserung der Verschleißeigenschaften bringt.However, the introduction of needle-like or platelet-shaped single crystals in hard metals in large quantities has never been carried out because a solution of the single crystals in the liquid binder phase has previously been feared. In fact, the solubility of the toilet in a binder such as cobalt is great, which causes the use of toilet whiskers - as in the AT-PS 259 242 proposed - brings no improvement in wear properties.
Den Whiskern gegenüber besitzen die plättchenförmigen Einkristalle eine wesentlich größere Breite (die i.a. als Durchmesser bezeichnet wird) bei einer Dicke, die in der Größenordnung der Whisker-Durchmesser liegt.In contrast to the whiskers, the platelet-shaped single crystals have a much larger width (which is generally referred to as diameter) with a thickness that is in the order of magnitude of the whisker diameter.
Weiterentwicklungen der Erfindung sind in den Unteransprüchen 2 bis 9 dargelegt.Further developments of the invention are set out in subclaims 2 to 9.
So sollen die Whisker vorzugsweise eine Länge von 3 µm bis 100 µm aufweisen und/oder einen Durchmesser von 0,1 bis 10 µm haben. Die Platelets hingegen sind vorzugsweise durch eine Dicke von 0,5 µm bis 10 µm und einen Durchmesser (der größeren Fläche des Platelet) von 3 µm bis 100 µm gekennzeichnet. In bevorzugten Ausführungsbeispielen werden SiC-Whisker oder Platelets verwendet, die zu mehr als 90 % die β-Struktur aufweisen. Die Menge der Whisker oder Platelets liegt in dem im Anspruch 1 angegebenen Bereich von 2 bis 40 Vol.-%, vorzugsweise 10 bis 20 Vol.-%.For example, the whiskers should preferably have a length of 3 μm to 100 μm and / or a diameter of 0.1 to 10 μm. The platelets, however, are preferably characterized by a thickness of 0.5 µm to 10 µm and a diameter (the larger area of the platelet) of 3 µm to 100 µm. In preferred exemplary embodiments, SiC whiskers or platelets are used which have more than 90% of the β structure. The amount of whiskers or platelets is in the range from 2 to 40% by volume, preferably 10 to 20% by volume, as specified in claim 1.
Ein besonderer Vorteil einer inerten Whisker- oder Platelet-Beschichtung liegt jedoch darin, daß eine gezielte Festigkeit der Bindung mit der Matrix eingestellt werden kann. Insgesamt führt die Einlagerung von beschichteten Whiskern oder Platelets zu einer Härteerhöhung mit einer gleichzeitigen Zähigkeitssteigerung, und zwar auch bei Hochtemperaturbelastungen, wie sie z.B. bei Schneidwerkstoffen stattfinden. Vorteilhafterweise wird dies auch bei solchen Hartmetallen erreicht, die einen geringen Bindemittelgehalt aufweisen (weniger als 8 Vol.-%).A particular advantage of an inert whisker or platelet coating is, however, that a targeted strength of the bond with the matrix can be set. Overall, the storage of coated whiskers or platelets leads to an increase in hardness with a simultaneous increase in toughness, even under high-temperature loads, such as those e.g. take place with cutting materials. This is advantageously also achieved in the case of hard metals which have a low binder content (less than 8% by volume).
Darüber hinaus kommt der inerten Beschichtung eine gewisse Schutzfunktion für die umhüllten Einkristalle zu, d.h. die Einkristalle können nicht im Bindemittel gelöst werden, insbesondere lassen sich erstmalig WC-Einkristalle in einem bezogen auf die Hartmetallzusammensetzung wirkungsvollen Anteil verwenden.In addition, the inert coating has a certain protective function for the coated single crystals, ie the single crystals cannot be dissolved in the binder, in particular toilet single crystals can be used for the first time in an effective proportion based on the hard metal composition.
Bevorzugtes Beschichtungsmaterial sind Carbide, Nitride und/oder Carbonitride der VIa-Gruppe des Periodensystems und/oder ZrO₂, Al₂O₃-und/oder BN. Die Dicke der Beschichtung liegt zwischen 0,2 µm und maximal 2/10 des Whiskerdurchmessers oder der Platelet-Dicke, bevorzugt zwischen 0,05 µm und 1/10 des Whiskerdurchmessers oder der Platelet-Dicke. Die Beschichtung der Whisker und/oder Platelets wird vorzugsweise mit dem im Prinzip nach dem Stand der Technik bekannten CVD- bzw. PVD-Verfahren aufgebracht.Preferred coating material are carbides, nitrides and / or carbonitrides from the VIa group of the periodic table and / or ZrO₂, Al₂O₃ and / or BN. The thickness of the coating is between 0.2 μm and a maximum of 2/10 of the whisker diameter or platelet thickness, preferably between 0.05 μm and 1/10 of the whisker diameter or platelet thickness. The coating of the whiskers and / or platelets is preferably applied using the CVD or PVD method known in principle from the prior art.
Der auf das nach dem Stand der Technik bekannte Verfahren bezogene Aufgabenteil wird durch die im Anspruch 11 angegebenen Merkmale gelöst, wobei insbesondere bei Gehalten bis zu 20 Vol.-% dem normalen Sinter-, dem kombinierten Sinter/HIP-Prozeß oder dem Sintern mit einem nachfolgenden heißisostatischen Pressen in einer getrennten Anlage und bei höheren Verstärkungsmaterialgehalten dem Heißpressen der Vorzug gegeben wird.The part of the task relating to the method known from the prior art is solved by the features specified in claim 11, with the normal sintering process, the combined sintering / HIP process or the sintering with a particularly at contents of up to 20% by volume subsequent hot isostatic presses in a separate plant and with higher reinforcement material, preference is given to hot pressing.
Die Herstellung der Whisker-Hartmetallverbundwerkstoffe lehnt sich grundsätzlich an bekannte pulvermetallurgische Verfahrensschritte an. So werden im Unterschied zum Stand der Technik die Verstärkungsmaterialien (Whisker, Plättchen) zunächst aufbereitet , desagglomeriert und klassifiziert, bevor sie den weiteren Verfahrensschritten unterzogen werden. Grundsätzlich unterscheidet man dabei zwischen vier Verdichtungsverfahren: Dem üblichen Sintern, einem kombinierten Sinter/HIP-Prozeß, bei dem unmittelbar auf den Sintervorgang in der Hitze ein heißisostatisches Pressen bei 20 bis 100 bar, maximal 200 bar, durchgeführt wird, dem Sintern mit nachfolgendem heißisostatischen Pressen bei Drücken um beispielsweise ca. 1000 bar in einer getrennten Anlage und schließlich dem erwähnten Heißpressen.The production of whisker hard metal composites is basically based on known powder metallurgical process steps. In contrast to the prior art, the reinforcement materials (whiskers, platelets) are first prepared, deagglomerated and classified before they are subjected to the further process steps. A basic distinction is made between four compression processes: the usual sintering, a combined sintering / HIP process, in which hot isostatic pressing is carried out at 20 to 100 bar, maximum 200 bar, immediately after the sintering process, and sintering with subsequent hot isostatic Pressing at pressures of around 1000 bar, for example, in a separate system and finally the hot pressing mentioned.
In einem Ausführungsbeispiel der Erfindung sind in einer Mischung aus 4 Vol.-% Co, Rest WC im Anschluß an das Naßmahlen 21 Vol.-% WC-Whisker in desagglomerierter und klassifizierter Form, die mittels des im Prinzip nach dem Stand der Technik bekannten CVD-Prozesses mit TiC beschichtet worden sind, zugegeben worden. Die gesamte Mischung wurde jeweils anschließend getrocknet, granuliert und kaltisostatisch zu einem Grünling vorgepreßt, bevor über das Heißpressen der Whisker-Verbundwerkstoff fertiggestellt wurde.In one embodiment of the invention, in a mixture of 4% by volume of Co and the remainder of the WC, following the wet grinding, 21% by volume of WC whiskers are disagglomerated and classified Form which have been coated with TiC by means of the CVD process known in principle from the prior art. The entire mixture was then dried, granulated and cold-isostatically pressed into a green compact before the whisker composite was finished by hot pressing.
Insgesamt besitzt der erfindungsgemäße Hartmetallverbundwerkstoff eine größere Härte und höhere Festigkeitswerte als nach dem Stand der Technik bekannte Verbundwerkstoffe. Die Zähigkeitsbelastbarkeit ist bei vermindertem Bruchrisiko höher, ohne daß höhere Bindegehalte eingestellt werden mußten.Overall, the hard metal composite material according to the invention has a greater hardness and higher strength values than composite materials known from the prior art. The toughness resilience is higher with a reduced risk of breakage, without having to set higher binding contents.
Claims (13)
- Hard metal composite body consisting of hard metal phases such as tungsten carbide and/or carbides or nitrides of elements of the IVa- or Va-Group of the Periodic System, of reinforcing materials and of a binder metal phase as cobalt and/or iron and/or nickel, characterized in that either a monocrystalline platelets-shaped reinforcing materials of borides and/or carbides and/or nitrides and/or carbonitrides of the elements of the IVa-Group (Ti, Zr, Hf), Va-Group (V, Nb, Ta) or VIa-Group (Cr, Mo, W) or mixtures thereof and/or of SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AIN and/or BN and/or moncrystalline neddle-shaped reinforcing material of SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AlN and/or BN is incorporated, whereby the proportion of the reinforcing material ranges between 2 and 40 % by volume, preferably 10 to 20 % by volume.
- Hard matl composite body according to claim 1, characterized in that the needle-shaped monocrystals (whiskers) have a length of 3 µm to 100 µm.
- Hard metal composite body according to one of the claim 1 or 2, characterized in that the needle-shaped monocrystals have a diameter of 0,1 to 10 µm.
- Hard metal composite body according to claim 1, characterized in that the platelet-shaped monocrystals (platelets) have a thickness of 0,5 µm to 10 µm and a diameter of 3 µm to 100 µm.
- Hard metal composite body according to one of the claim 1 to 4, characterized in that SiC is present in the form of needle-like or platelet-like monocrystals and for more than 90 % is of the β-SiC-structure.
- Hard metal composite body according to claim 1 to 5, characterized in that the reinforcing material is coated with a layer which is inert with respect to the binder metal phase.
- Hard metal composite body according to claim 6, characterized in that the reinforcing material is entirely or partially replaced by borides and/or carbides and/or nitrides and/or carbonitrides of the elements of VIa-Group of the Periodic System or by mixtures thereof.
- Hard metal composite body according to claim 6 or 7, characterized by an inert coating of carbides, nitrides and/or carbonitrides of the IVa-Group (Ti, Zr, Hf) and/or of ZrO₂, Al₂O₃ and/or BN.
- Hard metal composite body according to one of the claim 6 to 8, characterized in that the thickness of the coating is of at least 0,02 µm and of maximum 2/10 of the needle diameter, respectively of the platelet thickness, preferably of 1/10 thereof, respectively at least 0,05 µm.
- Hard metal composite body according to one of claim 6 to 9, characterized in that the inert coating of the needle-shaped and/or platelet-shaped monocrystals is applied to the monocrystals by the CVD (chemical vapor deposition) process or by the PVD (physical vapor deposition) process.
- Process für the production of hard metal composite bodies according to claim 1 to 5 through powder-metallurgical methods, characterized in that the reinforcing material in deagglomerated and graded form is mixed with the ground mixture of hard materials and binder, is then dried, granulated, uniaxially or cold isostatically pressed and the composite body is produced through sintering, through a combined sintering/HIP process, through sintering with a HIP process after an intermediate cooling or through axial hot-pressing.
- Process according to claim 11, characterized in that the reinforcing material in a deagglomerated and graded form is coating by a CVD or a PVD process with carbides, nitrides and/or carbonitrides of IVa-Groups, Va-Groups or VIa-Groups with mixtures thereof and/or SiC, Si₃N₄, Si₂N₂O, Al₂O₃, ZrO₂, AlN and/or BN, before it is blended with the ground mixture of hard materials and binder, then dried, granulated, uniaxially pressed or cold isostatically pressed and the composite body is produced by sintering, by a combined sintering/HIP-process, by sintering followed by a HIP-process after intermediate cooling or through axial hot-pressing.
- Process according to claim 11 or 12, characterized in that in the case of a content of up to 20 % by volume of reinforcing material, normal sintering, sintering followed by high-temperature isostatic pressing after a cooldown or the combined sintering/HIP-process are performed, while in the case of contents higher than 20 % by volume the axial hot-pressing process is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT89913058T ATE90399T1 (en) | 1988-12-16 | 1989-11-27 | CARBIDE COMPOSITE AND PROCESS FOR ITS MANUFACTURE. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3842439 | 1988-12-16 | ||
| DE19883842439 DE3842439A1 (en) | 1988-12-16 | 1988-12-16 | Hard cemented composite and process for the production thereof |
| DE3843219 | 1988-12-22 | ||
| DE19883843219 DE3843219A1 (en) | 1988-12-22 | 1988-12-22 | Hard cemented composite and process for the production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0448572A1 EP0448572A1 (en) | 1991-10-02 |
| EP0448572B1 true EP0448572B1 (en) | 1993-06-09 |
Family
ID=25875237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89913058A Expired - Lifetime EP0448572B1 (en) | 1988-12-16 | 1989-11-27 | Hard metal composite body and process for producing it |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5173107A (en) |
| EP (1) | EP0448572B1 (en) |
| JP (1) | JPH04502347A (en) |
| DE (1) | DE58904666D1 (en) |
| WO (1) | WO1990007017A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6293986B1 (en) | 1997-03-10 | 2001-09-25 | Widia Gmbh | Hard metal or cermet sintered body and method for the production thereof |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0532000B1 (en) * | 1991-09-13 | 1997-07-23 | Tsuyoshi Masumoto | High strength structural member and process for producing the same |
| US5376466A (en) * | 1991-10-17 | 1994-12-27 | Mitsubishi Materials Corporation | Cermet blade member |
| US5579532A (en) * | 1992-06-16 | 1996-11-26 | Aluminum Company Of America | Rotating ring structure for gas turbine engines and method for its production |
| CH686888A5 (en) * | 1993-11-01 | 1996-07-31 | Ufec Universal Fusion Energy C | composite metal-ceramic high tenacity and process for its manufacture. |
| US5672435A (en) * | 1994-12-12 | 1997-09-30 | The Dow Chemical Company | Hard disk drive components and methods of making same |
| US5580666A (en) * | 1995-01-20 | 1996-12-03 | The Dow Chemical Company | Cemented ceramic article made from ultrafine solid solution powders, method of making same, and the material thereof |
| US5842107A (en) * | 1995-08-31 | 1998-11-24 | National Science Council | Sintering process for AIN powder coated with Al film |
| JP4945814B2 (en) * | 1997-05-13 | 2012-06-06 | アロメット コーポレイション | Tough-coated hard powder and its sintered product |
| US20040052984A1 (en) | 1997-05-13 | 2004-03-18 | Toth Richard E. | Apparatus and method of treating fine powders |
| JP2005509739A (en) * | 2001-11-13 | 2005-04-14 | ファンダシオン イナスメット | Product manufacture of structural metal materials reinforced with carbides |
| KR101215656B1 (en) * | 2004-06-10 | 2013-01-10 | 알로메트 코포레이션 | Method for consolidating Tough Coated Hard Powders |
| US7682557B2 (en) * | 2006-12-15 | 2010-03-23 | Smith International, Inc. | Multiple processes of high pressures and temperatures for sintered bodies |
| CA2640206A1 (en) * | 2008-10-02 | 2010-04-02 | Hydro-Quebec | Composite materials for wettable cathodes and use of same for aluminum production |
| US20100104874A1 (en) * | 2008-10-29 | 2010-04-29 | Smith International, Inc. | High pressure sintering with carbon additives |
| CN102373357B (en) * | 2010-08-19 | 2013-09-18 | 比亚迪股份有限公司 | Composition composed of metal and ceramic and its preparation method, cermet and Raymond mill |
| CN111471942A (en) * | 2020-03-25 | 2020-07-31 | 成都美奢锐新材料有限公司 | Nanocrystalline composite material for 3C product and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3139672A (en) * | 1961-02-10 | 1964-07-07 | Bendix Corp | Rocket nozzles and the like |
| AT259242B (en) * | 1964-11-23 | 1968-01-10 | Boehler & Co Ag Geb | Sintered carbide consisting of hard materials and binding metal and process for its production |
| US4007049A (en) * | 1968-08-06 | 1977-02-08 | The United States Of America As Represented By The Secretary Of The Air Force | Thermal shock resistant ceramic composite |
| DE2461801C3 (en) * | 1974-12-30 | 1979-01-04 | Fisitscheskij Institut Imeni P.N. Lebedeva Akademii Nauk Ssr | Refractory material |
| US4259112A (en) * | 1979-04-05 | 1981-03-31 | Dwa Composite Specialties, Inc. | Process for manufacture of reinforced composites |
| JPS6031799B2 (en) * | 1979-11-30 | 1985-07-24 | 黒崎窯業株式会社 | SiC-Si↓3N↓4-based composite heat-resistant ceramic material and its manufacturing method |
| US4268314A (en) * | 1979-12-21 | 1981-05-19 | Union Carbide Corporation | High density refractory composites and method of making |
| JPS57205364A (en) * | 1981-06-08 | 1982-12-16 | Ngk Spark Plug Co | Manufacture of cutting tool ceramics |
| US4463058A (en) * | 1981-06-16 | 1984-07-31 | Atlantic Richfield Company | Silicon carbide whisker composites |
| JPS59121196A (en) * | 1982-12-25 | 1984-07-13 | Tokai Carbon Co Ltd | Preparation of whisker preform for composite material |
| SE451581B (en) * | 1984-04-06 | 1987-10-19 | Sandvik Ab | CERAMIC MATERIAL MAINLY BASED ON SILICON NITRIDE, ALUMINUM NITRIDE AND ALUMINUM OXIDE |
| DE3617055C2 (en) * | 1985-05-21 | 1996-03-07 | Toyoda Chuo Kenkyusho Kk | Fiber material for composite materials, process for its production and use of this fiber material |
| DE3662782D1 (en) * | 1985-06-10 | 1989-05-18 | Ngk Spark Plug Co | Fiber-reinforced compositie material for tools |
| CA1285582C (en) * | 1986-08-04 | 1991-07-02 | Joseph G. Ii Baldoni | Ceramic based composites with improved fracture toughness |
| US4756791A (en) * | 1986-08-25 | 1988-07-12 | Gte Laboratories Incorporated | Chemical vapor deposition process for producing metal carbide or nitride whiskers |
| DE3706000A1 (en) * | 1987-02-25 | 1988-09-08 | Feldmuehle Ag | Cutting tip (cutting insert, cutting tool) |
| SE8701791D0 (en) * | 1987-04-29 | 1987-04-29 | Sandvik Ab | CEMENTED CARBONITRIDE ALLOY WITH IMPROVED TOUGHNESS BEHAVIOUR |
| EP0295228B1 (en) * | 1987-06-09 | 1992-03-25 | Sandvik Aktiebolag | Whisker reinforced ceramic cutting tool |
| JPH01103205A (en) * | 1987-10-15 | 1989-04-20 | Toshiba Ceramics Co Ltd | Tool for working carbon |
-
1989
- 1989-11-27 DE DE8989913058T patent/DE58904666D1/en not_active Expired - Fee Related
- 1989-11-27 US US07/689,237 patent/US5173107A/en not_active Expired - Fee Related
- 1989-11-27 WO PCT/DE1989/000740 patent/WO1990007017A1/en active IP Right Grant
- 1989-11-27 EP EP89913058A patent/EP0448572B1/en not_active Expired - Lifetime
- 1989-11-27 JP JP2500125A patent/JPH04502347A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| CERAM. TRANS., Nr. 2, 1989; S.C.WEAVER et al., Seiten 397-406# * |
| R.Sube et al., WÖRTERBUCH PHYSIK, Verlag Harri Deutsch, 1987; Seiten 608, 988# * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6293986B1 (en) | 1997-03-10 | 2001-09-25 | Widia Gmbh | Hard metal or cermet sintered body and method for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04502347A (en) | 1992-04-23 |
| EP0448572A1 (en) | 1991-10-02 |
| US5173107A (en) | 1992-12-22 |
| WO1990007017A1 (en) | 1990-06-28 |
| DE58904666D1 (en) | 1993-07-15 |
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