EP3577242B1 - Verfahren zur herstellung eines doppelstrukturierten bimodalen wolframzementierten carbid-verbundstoffes - Google Patents

Verfahren zur herstellung eines doppelstrukturierten bimodalen wolframzementierten carbid-verbundstoffes Download PDF

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EP3577242B1
EP3577242B1 EP17708582.6A EP17708582A EP3577242B1 EP 3577242 B1 EP3577242 B1 EP 3577242B1 EP 17708582 A EP17708582 A EP 17708582A EP 3577242 B1 EP3577242 B1 EP 3577242B1
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mixture
final material
tungsten
resulting
grains
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EP3577242A1 (de
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Marek TARRASTE
Der-Liang YUNG
Maksim ANTONOV
Irina HUSSAINOVA
Renno VEINTHAL
Jüri PIRSO
Philippe KAPSA
Vincent Fridrici
Ousseini MAROU-ALZOUMA
Alexandre TABOULET
Thomas Camus
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Tallinn University of Technology
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Tallinn University of Technology
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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
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
    • 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
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
    • 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

  • This invention relates to the field of cemented carbides and methods of making cemented carbides.
  • Bimodal i.e., having two different distinct sizes of grains in final sintered material
  • cemented carbides can be used in the same applications where conventional cemented carbides are used.
  • Bimodal cemented carbides usually have better mechanical properties and higher resistance against wear.
  • the combination of dispersed areas with predominantly coarse or extra coarse WC grains surrounded by continuous area with predominantly ultrafine WC grains allows to obtain even better properties as required for materials working in demanding impact-abrasive conditions.
  • Cemented carbides are composite materials where one constituent is a hard carbide phase of one or more transition metals and second constituent is a ductile metal phase.
  • the carbides of titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum and tungsten can be used.
  • Ductile metal phase is the cement that binds carbide grains together.
  • iron group metals - iron, cobalt, nickel or their alloys are used as a metal phase in cemented carbides. Different alloying elements may be added to improve different properties.
  • Cemented tungsten carbides with a cobalt binder are the most commercially important among the various carbide-metal combinations due to an excellent combination of mechanical and tribological properties.
  • Tungsten carbide cemented carbides with cobalt binder are still predominant hardmetals since the composition of the hard and brittle tungsten carbide phase that is cemented by the Co-rich binder phase provides an efficient complex of mechanical and tribological properties [1, 2]. Mechanical properties are dependent to a great extent on the Co content and WC grain size [3]. Lower Co content increases hardness and decreases transverse rupture strength (TRS); decreasing WC grain size improves both of these characteristics [4, 5].
  • Bimodal grain size distribution is achieved by mixing together WC-Co sources with different mean carbide particle sizes [8].
  • the material is produced by preparing two grades of WC+Co powders (with different grain size) by milling and granulating it individually and then mixing the two amounts of these granules carefully without breaking down the granules that are followed by consolidation and sintering.
  • US7384443 disclosing a hybrid composite material comprising a cemented carbide dispersed phase and a cemented carbide continuous phase.
  • the contiguity ratio of the dispersed phase of embodiments may be less than or equal to 0.48.
  • the hybrid double-structured bimodal composite material may have a hardness of the dispersed phase that is greater than the hardness of the continuous phase.
  • the method includes making a hybrid cemented carbide composite by blending partially and/or fully sintered granules of the dispersed cemented carbide grade with "green” and/or unsintered granules of the continuous cemented carbide grade to provide a blend that is later consolidated and sintered.
  • Mechanical and thermal activation is a novel method for producing fine and ultrafine grained WC-Co hardmetals by reactive sintering [9-11].
  • WC-Co hardmetals with a bimodal structure have been produced using reactive sintering without microwaves.
  • milled and activated tungsten and graphite powders were mixed with commercial coarse-grained WC-Co powder and then sintered.
  • the microstructure of produced materials was without pores while double-structured material could not be produced because of the breakage of granules and mixing of WC grains from dispersed and continuous areas. What is needed is an alternative method for producing cemented tungsten carbides that combine double-structure with bimodal grain distribution to obtain improved mechanical properties and increased wear resistance in impact-abrasive conditions.
  • the average size of 95 % of WC grains of the dispersed areas of the finished material resulting from the second mixture is from 5 to 50 times larger than average size of 95 % of WC grains of the continuous areas resulting from the first mixture.
  • the invention combines two cemented carbide production methods, i.e., reactive sintering and conventional sintering, in order to achieve a double-structured bimodal microstructure, thereby increase hardness, strength, and wear resistance without compromising the fracture toughness.
  • Two powder mixtures are prepared: 1. elemental powders of W and Co are milled with a carbon source, such as graphite or carbon black, and 2. coarse or extra coarse WC and Co are milled and granulated. Granules are substantially spherical. Then the powder mixture of W+C+Co is mixed together with the granules of WC-Co and consolidated. Following sintering is done using conventional methods. During sintering, the in-situ reaction takes place to form ultrafine WC embedded in Co matrix. Coarse or extra coarse WC grains experience some growth during sintering.
  • the final microstructure has the double-structured bimodal appearance, comprising closed areas of coarse or extra coarse WC-Co (originating from granules of WC-Co) while these areas are surrounded by an ultra-fine grained WC-Co matrix (originating from W+C+Co mixture).
  • the main advantage over conventional methods is that after conventional sintering the WC grain size distribution is unimodal, i.e. close to normal or Gaussian distribution while with the bimodal approach described here a clear distinction is achievable.
  • WC grains formed by reactive sintering from the first mixture have sufficiently smaller size than those obtained from the second mixture.
  • WC grains are first formed (this takes time) and then start to grow enables to obtain finer size than during conventional sintering when existing WC particles activated by preliminary mechanical milling tend to grow intensively during the heating-dwelling-cooling steps of the sintering process.
  • grain-growth inhibitors such as chromium, vanadium, zirconium, tantalum, titanium or their carbides, nitrides, carbonitrides such as VC, Cr 3 C 2 , TaC and TiC helps to further refine the microstructure of continuous areas resulting from the first mixture.
  • the contiguity ratio of material should be as small as possible while magnetic saturation (indicating the presence of Wand C in the Co binder phase) should be as high as possible (indicating the absence of additives in the Co binder) so as to provide the highest possible resistance against impacts.
  • the Co content in the first mixture and in the second mixture can be from 3wt % to 50 wt%, preferably from 10 wt% to 30 wt%, most preferably from 12 wt to 15% to provide final material with best wear resistance in impact-abrasive conditions.
  • the Co content can be same or different in the first and second mixtures.
  • the same Co content in both mixtures provides a reduction of thermal stresses generated during sintering while different contents can result in preferential pre-stressed conditions of either the first or second mixture.
  • the invented method is simpler and could be implemented by most of the companies exploiting a conventional sintering process than the one described in US6293986 since a microwave generator is not required.
  • the invented method allows to produce double-structured bimodal cemented carbide composite materials without breakage of granules of the second mixture as it took place in reference [12] due to the presence of Co in the first mixture that facilitates the pressing (consolidation) process.
  • the given method is simpler that those given in US5593474 and US7384443 since it involves the granulation of only one mixture instead of two.
  • the proposed production method is cheaper than methods described in US5593474 and US7384443 since it uses W for the first mixture instead of the more expensive WC. Additionally, intensive milling required to produce ultrafine WC grains for conventional sintering leads to partial oxidation of these grains and a subsequent higher risk of brittle phases formation, which is avoided in materials obtained by reactive sintering.
  • Another object not part of the invention is a double-structured bimodal tungsten cemented carbide composite material as prepared by the described method.
  • Yet another object not part of the invention is a tool insert for mining, tunnelling, construction and drilling, including earth-boring applications comprising a bimodal tungsten cemented carbide composite material as described above.
  • a double-structured bimodal ( Fig 1 ) cemented carbide was prepared.
  • a mixture of elemental powders of W and Co and graphite as C source were milled for 72 hours in a ball-mill with hardmetal lining and hardmetal balls ( Fig 2 , step 1).
  • Ball-to-powder weight ratio was 10:1.
  • the average initial particle size of W and Co powders was 2-8 ⁇ m and the average initial particle size of the graphite powder was 17-19 ⁇ m.
  • Alcohol was employed as milling medium.
  • the Co weight ratio of the mixture (W+C+Co) was 15 wt%.
  • C weight ratio of W+C was 7.1 wt% which is approximately 1% (depends on sintering methodology and equipment used) over the stoichiometric C content of WC (6.13 wt%). Excess of C is needed to compensate decarburization that occurs during sintering and to achieve stoichiometric ratio in the final material.
  • WC and Co powders were milled for 24 hours in ball-mill with hardmetal lining and hardmetal balls ( Fig 2 , step 2) with ball-to-powder weight ratio 5:1.
  • the average initial particle size of WC was 3-4 ⁇ m and the average particle size of Co was 2-8 ⁇ m.
  • Alcohol was employed as milling medium.
  • the Co weight ratio of the mixture (WC+Co) was 15 wt% alike the first mixture.
  • the second mixture was granulated using organic resin, namely rubber, and spray drying method ( Fig 2 , step 3).
  • Said first mixture (W+C+Co) and granules of said second mixture (WC+Co) were mechanically mixed inside a soft (plastic) rotating container for 24 h ( Fig 2 , step 4). This was done to reduce the fracturing of granules as well as to reduce the refinement of carbides. Steel springs were included in the container to facilitate the mixing procedure.
  • Said first and said second powder mixtures were mixed with the ratios of 1:3 (Table 1, E2), 1:1 (Table 1, E3) and 3:1 (Table 1, E4). After mixing, the organic resin was added to the new powder mixture in order to facilitate the consolidation process.
  • Powder mixtures were consolidated into green specimens using a uniaxial press with a pressure of 90 MPa ( Fig 2 , step 5).
  • Conventional cemented carbide and reactive sintered cemented carbide specimens with 15 wt% Co ratio were prepared as the reference (Table 1, grades E1 and E5 respectively).
  • K IC 0.0726 P C 3 / 2 where P is the load of Vickers indentor (N) and C is half of the diagonal plus crack lengths (in mm).

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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)

Claims (12)

  1. Ein Verfahren zur Herstellung eines bimodalen Wolfram-Sintercarbid-Verbundmaterials mit doppelter Struktur, wobei das Verfahren umfasst:
    Mahlen von Wolfram, Kohlenstoff, wie Graphit oder Ruß, und elementaren Kobaltpulvern, was zu einer ersten Mischung W + C + Co führt, um ultrafeine Wolframcarbidpartikel in einem Endmaterial zu erhalten;
    Mahlen von Wolframcarbidpulver und elementarem Kobaltpulver, was zu der zweiten Mischung WC + Co führt, um grobe oder extra grobe Wolframpartikel im Endmaterial zu erhalten;
    Granulieren der zweiten Mischung, was zu einer granulierten zweiten Mischung führt, wobei die Körner eine Vielzahl von Körnern umfassen;
    - Mischen der ersten Mischung W+C+Co und der granulierten zweiten Mischung WC+Co, was zu einer dritten Mischung führt;
    - Konsolidieren der dritten Mischung; und
    - Sintern der konsolidierten Pulvermischung, was zu dem Endmaterial führt.
  2. Verfahren nach Anspruch 1, wobei das Kohlenstoffgewichtsverhältnis in dem ersten Die Mischung wird so ausgewählt, dass im Endmaterial ein nahezu stöchiometrisches Verhältnis erreicht wird.
  3. Verfahren nach den Ansprüchen 1 bis 2, wobei das Endmaterial a Mikrostruktur des Wolfram-Sintercarbid-Verbundmaterials, umfassend zwei unterschiedliche Bereiche: separate dispergierte Bereiche mit gröberen WC-Körnern in der Co-Matrix und einen kontinuierlichen Bereich mit ultrafeinen WC-Körnern in der Co-Matrix.
  4. Verfahren nach den Ansprüchen 1 bis 3, wobei die erste Mischung 1 Gew.-% bis 99 Gew.-% der dritten Mischung ausmacht.
  5. Verfahren nach Anspruch 3, wobei die erste Mischung 10 Gew.-% bis 50 Gew.-% der dritten Mischung ausmacht.
  6. Verfahren nach Anspruch 3, wobei die erste Mischung 15 Gew.-% bis 35 Gew.-% der dritten Mischung ausmacht.
  7. Verfahren nach den Ansprüchen 1 bis 6, wobei der Co-Anteil im Endmaterial 3 Gew.-% bis 50 Gew.-% beträgt.
  8. Verfahren nach Anspruch 6, wobei der Co-Anteil im Endmaterial 10 Gew.-% bis 30 Gew.-% beträgt.
  9. Verfahren nach Anspruch 6, wobei der Co-Anteil im Endmaterial etwa 12 bis etwa 15 Gew.-% beträgt.
  10. Verfahren nach den Ansprüchen 1 bis 9, wobei Carbidkornwachstumsinhibitoren in dem Mahlschritt nur zu der ersten Mischung zugegeben werden.
  11. Verfahren nach Anspruch 9, wobei die Kornwachstumsinhibitoren ausgewählt sind aus einer Gruppe bestehend aus Chrom, Vanadium, Zirkonium, Tantal, Titan oder ihren Carbiden, Nitriden, Carbonitriden.
  12. Verfahren nach Anspruch 11, wobei der Gewichtsanteil der Kornwachstumsinhibitoren in der ersten Mischung 0,1 bis 5 Gew.-% beträgt.
EP17708582.6A 2017-01-31 2017-01-31 Verfahren zur herstellung eines doppelstrukturierten bimodalen wolframzementierten carbid-verbundstoffes Active EP3577242B1 (de)

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RU2693415C1 (ru) * 2018-09-12 2019-07-02 Общество с ограниченной ответственностью "Вириал" Спечённый твёрдый сплав на основе карбида вольфрама и способ его получения
CN111378860B (zh) * 2018-12-28 2021-12-03 自贡硬质合金有限责任公司 超细晶硬质合金及其制备方法
CN110343889B (zh) * 2019-06-28 2020-08-07 江西江钨硬质合金有限公司 一种特粗硬质合金及其制备方法
JP7385829B2 (ja) * 2020-02-21 2023-11-24 三菱マテリアル株式会社 耐塑性変形性、耐欠損性にすぐれたｗｃ基超硬合金製切削工具および表面被覆ｗｃ基超硬合金製切削工具
CN111455252A (zh) * 2020-05-12 2020-07-28 江西江钨硬质合金有限公司 采用密排配料方式制备的非均匀硬质合金及其制备方法
CN113930651A (zh) * 2020-06-29 2022-01-14 有研工程技术研究院有限公司 一种超粗WC-Co硬质合金及其制备方法
CN112143953A (zh) * 2020-09-25 2020-12-29 江西江钨硬质合金有限公司 一种高性能非均匀结构硬质合金及其制备方法
CN112430770A (zh) * 2020-11-24 2021-03-02 江西理工大学 一种多尺度结构非均匀硬质合金及其制备方法
CN113699406A (zh) * 2021-08-30 2021-11-26 四川轻化工大学 平均晶粒度大于8微米的高强韧性特粗晶wc硬质合金及其制备方法
CN114150201B (zh) * 2021-12-02 2022-05-17 湖南人文科技学院 一种超硬CoWB-Co硬质合金的制备方法
CN116422883B (zh) * 2023-03-23 2025-08-08 湖南和畅新材料有限公司 一种梯度结构耐磨复合材料及其制备方法
CN117701969B (zh) * 2023-11-02 2026-02-10 南昌大学 一种螺纹芯头用双晶高钴硬质合金及其制备方法

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US5593474A (en) 1988-08-04 1997-01-14 Smith International, Inc. Composite cemented carbide
US6293986B1 (en) 1997-03-10 2001-09-25 Widia Gmbh Hard metal or cermet sintered body and method for the production thereof
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EE05780B1 (et) 2014-06-16 2016-10-17 Tallinna Tehnikaülikool Katseseade materjalide abrasiivkulumise uurimiseks

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