WO2017068153A1 - Procédé de fabrication d'un composant à base de cermet ou de carbure cémenté - Google Patents

Procédé de fabrication d'un composant à base de cermet ou de carbure cémenté Download PDF

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Publication number
WO2017068153A1
WO2017068153A1 PCT/EP2016/075449 EP2016075449W WO2017068153A1 WO 2017068153 A1 WO2017068153 A1 WO 2017068153A1 EP 2016075449 W EP2016075449 W EP 2016075449W WO 2017068153 A1 WO2017068153 A1 WO 2017068153A1
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WO
WIPO (PCT)
Prior art keywords
granules
spherically shaped
process according
powder
sintered
Prior art date
Application number
PCT/EP2016/075449
Other languages
English (en)
Inventor
Fredrik Meurling
Christopher Thompson
Original Assignee
Sandvik Intellectual Property Ab
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sandvik Intellectual Property Ab filed Critical Sandvik Intellectual Property Ab
Publication of WO2017068153A1 publication Critical patent/WO2017068153A1/fr

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Classifications

    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/1208—Containers or coating used therefor
    • B22F3/1216—Container composition
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/026—Spray drying of solutions or suspensions
    • 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
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • 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
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present disclosure relates to a Hot Isostatic Pressing (HIP) process for manufacturing a component of a hard metal powder by using a capsule of zirconium (Zr) or Zr-alloy.
  • HIP Hot Isostatic Pressing
  • Hot isostatic pressing is a known method used for preparing solid articles.
  • Components comprising cemented carbides or cermets (hard metal) are usually difficult to machine.
  • HIP near-net- shape techniques to manufacture such components is an attractive alternative as the desired object can be obtained almost without any or with very limited machining.
  • the obtained objects will also have a higher material yield than when manufactured by traditional pressing, green- machining, sintering or post- sintering machining.
  • Eta-phase is a brittle phase and is detrimental to the strength of the component as it may initiate cracks.
  • the present disclosure is aiming at solving or at least reducing the above-mentioned problems and furthermore, the present disclosure provides an effective and cost efficient method for producing components of hard metal.
  • the present disclosure relates to a process of manufacturing a cemented carbide or cermet component by using a HIP process.
  • the cemented carbide powder or cermet powder used in the process is a free flowing dense or semi-dense powder.
  • the obtained components will have enhanced hardness and wear resistance and will also have a fully dense net- or near net shape.
  • the present disclosure relates to the following process for manufacturing a cemented carbide or cermet component comprising the following steps: a) providing spherically shaped granules comprising metallic binder and hard constituents with an organic binder;
  • HIP Hot Isostatic Pressing
  • the form is made of zirconium or a zirconium alloy,.
  • zirconium or a zirconium alloy is used as capsule material, a layer comprising zirconium carbide (ZrC) is formed in the contact interface between the capsule and the cemented carbide or cermet.
  • This carbide layer is dense and has almost no cracks and will therefore prevent most of the interdiffusion between the capsule and the powder.
  • this ZrC layer will limit the loss of carbon from the cemented carbide or the cermet to the capsule material whereby the chemical balance and stability of the cemented carbide or cermet are maintained and thus the degradation of the cemented carbide or cermet is reduced, thereby , this carbide layer (ZrC) provides conditions to avoid formation of low carbon containing carbides such as e.g. M2C, M6C and M12C.
  • Different grades of the Zr (Zirconium) alloys may be used for capsule material, however it is necessary that the grades comprise the amount of zirconium to allow the above-mentioned carbide layer to be formed.
  • Figure 1 discloses SEM image of the product according to one embodiment obtained after step c).
  • the magnitude of the image is xlOOO:
  • Figure 2 discloses a SEM image of the powder according to one embodiment obtained after step e);
  • Figure 3 discloses a SEM image of the micro structure in the component according to one embodiment of the present disclosure
  • Figure 4 discloses a SEM image of the microstructure at the interface between the obtained component and the capsule according to one embodiment of the present disclosure.
  • ceramic is herein intended to denote a material comprising a ceramic phase, i.e. hard constituents, and a metallic binder phase.
  • cemented carbide is herein intended to denote a material comprising a ceramic phase, i.e. hard constituents, which are selected from WC, TiC, TaC, MoC, , TiN, Ti(C,N) NbC, Mo 2 C or a mixture thereof and a metallic binder phase, comprising Co, Ni, Fe, Cr, Mo, V or a mixture thereof.
  • the amount of metallic binder is in the range of from 5 to 30 weight , such as of from 10 to 25 weight , such as of from 15 to 20 weight , such as 20 to 25 weight .
  • granule refers to the agglomerated state of a mixture that is produced by e.g. spray drying. After sintering, the granules are named “sintered granules"
  • sintering is a generic term for a process wherein heating under controlled atmosphere is conducted in order to minimize the surface of a particulate system, which mostly is associated with generation of bonds between neighboring particles or granules resulting in the fusion of neighboring particles and minimizing of inter- particle voids.
  • green body refers to a body comprising granules that are bonded by organic binder.
  • solidus refers to a certain temperature that when being exceeded leads to the inception of liquid phase formation.
  • the present disclosure relates to a process for manufacturing a cemented carbide component or cermet comprising the following steps:
  • HIP Hot Isostatic Pressing
  • the form is made of zirconium or a zirconium alloy.
  • the forming of spherically shaped granules comprising metal, hard constituents and organic binder may be performed by spray drying.
  • the advantage of using spray drying is that the granules will not be exposed to pre-pressing and breaking.
  • the organic binder may for example be PEG (polyethylene glycol).
  • the metallic binder is selected from Cobalt (Co), Nickel (Ni), Iron (Fe), Chromium (Cr), Molybdenium (Mo), Vanadium (V) or a mixture thereof.
  • the hard constituents are selected from WC, TiC, TiN, Ti(C,N), TaC, MoC, Mo 2 C, NbC or a mixture thereof.
  • the metallic binder is selected from Ni, Fe or Co.
  • the step of providing the granules with a spherical shape is important since the subsequent heating process will ideally make the granules to shrink but preserve their original spherical shape.
  • the hard constituents and the metallic binder may be in the form of particles which do not contain any organic binder, thus also other methods than spray drying may be used for obtaining the particles.
  • the step of heat-treating the mixture of spherically shaped granules in the furnace chamber at a sintering temperature is performed in order to remove the organic binder from the spherically shaped granules and to sinter the hard constituents with the metallic binder in each spherically shaped granule whereby the granules will be bound together by the metallic binder and form a friable material.
  • the organic binder will evaporate and leave the spherically shaped granules by degassing.
  • the sintering performed in the present disclosure is an inter-granule sintering which causes the sintered granules to stick together and thereby form co-sintered granule agglomerates or a sintered cake of the granules.
  • the bonded spherically shaped sintered granules will form a sintered cake meaning that all the spherically shaped granules which have been loaded in the furnace have been loosely bound together by the metallic binder.
  • the sintering is usually performed at temperatures in the range of from 1200 to 1500 °C. The sintering temperature to be used depends on which element(s) is(are) used as metallic binder and also on the amount of metallic binder comprised in the spherically shaped granules. Further, the sintering is usually performed, in vacuum, in a vacuum furnace at pressures of 2 x 10 "1 - 2 x 10 "4 Bar.
  • the step of unloading the bonded spherically shaped granules from the furnace chamber may be performed after a cooling step wherein the bonded spherically shaped sintered granules have reached a temperature of about room temperature.
  • the obtained bonded spherically shaped sintered granules, i.e. the granule agglomerates or the sintered cake is milled to a cermet or cemented carbide powder by using a mill, such as a ball mill.
  • the continuous particle size distribution of the spherically shaped granules size may be in the range of from about 5 to about 500 ⁇ , such as about 10 to about 200 ⁇ .
  • a wide granule size distribution may be advantageous in applications such as in HIP, when a capsule is being filled with powder having a wide distribution will obtain a higher packing density compared to a more narrowly distributed granule size.
  • the free flowing properties are of prime interest for the given application a narrow distribution can be preferred.
  • the heat treatment in the furnace chamber is performed at a sintering temperature above the solidus temperature of the metal in the spherically shaped granules.
  • the sintering temperature is above the solidus temperature, liquid phase is formed.
  • a form which is sealable.
  • more than one form may also be provided.
  • the terms “form” and “capsule” are used herein interchangeably, the term “mould” could be used as well.
  • the form is manufactured from zirconium or a zirconium alloy and may be a manufactured of e.g. sheets or tubes, which are welded together.
  • the form may have any shape.
  • the form may also define a portion of the final component.
  • the powder is poured/filled into the form which is thereafter sealed, for example by welding.
  • air Prior to sealing the form, air is evacuated from the form.
  • the air is removed (evacuated) as air contains argon and/or oxygen, which may have negative effect on density, ductility and toughness.
  • the evacuation is usually performed by using vacuum pump(s), thus ensuring the removal of oxygen and argon.
  • the capsule may, after the evacuation, be backfilled with a gas such as nitrogen.
  • the filled, evacuated, and thereafter sealed form is then subjected to HIP in a heatable pressure chamber, normally referred to as a Hot Isostatic Pressing-chamber at a predetermined temperature, a predetermined isostatic pressure and a
  • the heating chamber is pressurized with gas, e.g. argon gas, to a predetermined pressure (isostatic pressure) of above 500 bar.
  • gas e.g. argon gas
  • isostatic pressure is of from about 900 to about 1500 bar, such as of from 1000 to 1200 bar.
  • the heating chamber is heated to a predetermined and suitable temperature allowing said powder particles to metallurgically bond and consolidate and thereby allowing the voids in-between the powder particles to close, whereby a component having a dense structure is obtained.
  • the consolidation process slows down and the obtained component will contain residual porosity and the
  • the predetermined temperature may be above 900°C, such as of from about 900 to about 1350°C, such as about 1100 to about 1350°C.
  • the form is held in the heating chamber at said predetermined pressure and said predetermined temperature for a predetermined time period.
  • the diffusion processes that take place between the powder particles during HIP are time dependent so long times are preferred.
  • the form should be HIP treated for a time period of about 0.5 to about 3 hours, such as about 1 to about 2 hours, such as about 1 hour.
  • the size of the component and also the composition of the powder comprising cermet or cemented carbide will determine the preferred time period.
  • a cermet or cemented carbide component obtained according to the process as defined hereinabove or hereinafter may be used in any product requiring good wear resistant properties and/or high stiffness. Examples of, but not limited to, components which may be manufactured by using the process as defined
  • a tungsten carbide grade with 10% Co metallic binder was selected as spherically shaped granules.
  • the spherically shaped granules were made by mixing tungsten carbide powder with cobalt powder and PEG. The obtained mixture was spray dried to produce the spherically shaped granules.
  • the spherically shaped granules were spread onto graphite trays and placed in a vacuum furnace.
  • the granules were sintered by raising the temperature of the furnace to 1300°C and keeping the furnace at that temperature for 30 minutes under vacuum conditions. Before sintering, the furnace was slowly heated and at 250°C, hydrogen was added to the furnace to aid the removal of organic binder. Vacuum was then applied to the furnace again. Upon cooling, 2 bar pressure of nitrogen was added to the furnace from 900°C. This was to speed up the cooling process.
  • the caked lumps were placed in a ball mill with a half charge of 10 mm diameter tungsten carbide media. The mill was run for 30 minutes without fluid. The resultant powder was passed through a 500 ⁇ aperture sieve to remove any residual agglomerates.
  • the resulting powder from this process was free flowing and had retained the spherical like granule shape of the starting spray dried powder (see figure 2).
  • the obtained powder was filled in a cylindrical zirconium tube capsule (dimensions OD 25.4 x ID 20.4 x L 120 mm) which was sealed in both ends with zirconium disks.
  • the capsule was evacuated and then backfilled with nitrogen gas before sealing.
  • the capsule was placed in a HIP equipment and argon gas was used to create the pressure to rise simultaneously with the temperature to finally reach a pressure of 1500 bar and a temperature of 1300°C.
  • the holding time was one hour then the temperature and pressure was reduced to normal pressure and room temperature.
  • Figure 3 and 4 show the microstructure in the obtained component ( Figure 3) and at the interface with the capsule ( Figure 4).
  • Figure 3 shows a HIPed compacted cemented carbide granule.
  • the metal binder (1) is pointed out with arrows.
  • Figure 4 shows the interface with the granule, the metal binder (1) is pointed out with arrows and also the reaction zone (2). Further, the wall of the zirconium capsule (3) is also shown.
  • the cemented carbides particles have been consolidated to form one dense body.
  • the metal binder (cobalt is the metallic binder) is seen between some of the cemented carbide powder particles.
  • the area named reaction zone comprises ZrC and as in figure 3, the metal binder (cobalt is the metallic binder) is seen between some of the cemented carbide granules.

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

Abstract

La présente invention concerne un procédé de compression isostatique à chaud (HIP) permettant de fabriquer un composant en métal dur solide et dense à partir d'une poudre de métal dur, à l'aide d'une capsule de zirconium ou d'alliage de zirconium.
PCT/EP2016/075449 2015-10-23 2016-10-21 Procédé de fabrication d'un composant à base de cermet ou de carbure cémenté WO2017068153A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EPEP15191269.8 2015-10-23
EP15191269 2015-10-23

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WO2017068153A1 true WO2017068153A1 (fr) 2017-04-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019218589A (ja) * 2018-06-18 2019-12-26 三菱マテリアル株式会社 ＴｉＮ基焼結体およびＴｉＮ基焼結体製切削工具
US11007571B2 (en) 2018-02-27 2021-05-18 Rolls-Royce Plc Method of manufacturing an austenitic iron alloy
CN115106530A (zh) * 2022-06-28 2022-09-27 四川一然新材料科技有限公司 一种硬质合金异形喷管的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007251A (en) * 1972-09-19 1977-02-08 Allmanna Svenska Elektriska Aktiebolaget Method of manufacturing powder bodies of borides, carbides or nitrides
US4983339A (en) * 1987-08-05 1991-01-08 Commissariat A L'energie Atomique Process for shaping a material by hot isostatic pressing and titanium sheath usable in this process
US20140345423A1 (en) * 2010-06-30 2014-11-27 Kennametal Inc. Carbide pellets for wear resistant applications
EP2821166A1 (fr) * 2013-07-04 2015-01-07 Sandvik Intellectual Property AB Procédé de fabrication d'un composant résistant à l'usure comprenant un corps en carbure cémenté mécaniquement verrouillé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007251A (en) * 1972-09-19 1977-02-08 Allmanna Svenska Elektriska Aktiebolaget Method of manufacturing powder bodies of borides, carbides or nitrides
US4983339A (en) * 1987-08-05 1991-01-08 Commissariat A L'energie Atomique Process for shaping a material by hot isostatic pressing and titanium sheath usable in this process
US20140345423A1 (en) * 2010-06-30 2014-11-27 Kennametal Inc. Carbide pellets for wear resistant applications
EP2821166A1 (fr) * 2013-07-04 2015-01-07 Sandvik Intellectual Property AB Procédé de fabrication d'un composant résistant à l'usure comprenant un corps en carbure cémenté mécaniquement verrouillé

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11007571B2 (en) 2018-02-27 2021-05-18 Rolls-Royce Plc Method of manufacturing an austenitic iron alloy
JP2019218589A (ja) * 2018-06-18 2019-12-26 三菱マテリアル株式会社 ＴｉＮ基焼結体およびＴｉＮ基焼結体製切削工具
JP7008249B2 (ja) 2018-06-18 2022-02-10 三菱マテリアル株式会社 ＴｉＮ基焼結体およびＴｉＮ基焼結体製切削工具
CN115106530A (zh) * 2022-06-28 2022-09-27 四川一然新材料科技有限公司 一种硬质合金异形喷管的制备方法
CN115106530B (zh) * 2022-06-28 2024-04-12 四川一然新材料科技有限公司 一种硬质合金异形喷管的制备方法

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