EP3577242B1 - Method of making a double-structured bimodal tungsten cemented carbide composite material - Google Patents
Method of making a double-structured bimodal tungsten cemented carbide composite material Download PDFInfo
- Publication number
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- final material
- tungsten
- resulting
- grains
- 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.)
- Active
Links
- 230000002902 bimodal effect Effects 0.000 title claims description 27
- 229910052721 tungsten Inorganic materials 0.000 title claims description 16
- 239000002131 composite material Substances 0.000 title claims description 13
- 239000010937 tungsten Substances 0.000 title claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 23
- 150000001247 metal acetylides Chemical class 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 12
- 238000003801 milling Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000003966 growth inhibitor Substances 0.000 claims description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 235000019241 carbon black Nutrition 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229910009043 WC-Co Inorganic materials 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 8
- 238000009770 conventional sintering Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000007373 indentation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- -1 iron group metals Chemical class 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 102100027715 4-hydroxy-2-oxoglutarate aldolase, mitochondrial Human genes 0.000 description 1
- 101001081225 Homo sapiens 4-hydroxy-2-oxoglutarate aldolase, mitochondrial Proteins 0.000 description 1
- 101001109518 Homo sapiens N-acetylneuraminate lyase Proteins 0.000 description 1
- 101000604027 Homo sapiens Nuclear protein localization protein 4 homolog Proteins 0.000 description 1
- 101000974007 Homo sapiens Nucleosome assembly protein 1-like 3 Proteins 0.000 description 1
- 101001099181 Homo sapiens TATA-binding protein-associated factor 2N Proteins 0.000 description 1
- 239000002310 Isopropyl citrate Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 102100022686 N-acetylneuraminate lyase Human genes 0.000 description 1
- 102100038438 Nuclear protein localization protein 4 homolog Human genes 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 101100094105 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) NPL6 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102100038917 TATA-binding protein-associated factor 2N Human genes 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
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
- 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
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
-
- 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)
-
- 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).
Description
- 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 (double-structured bimodal materials) 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. Usually, 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 (WC-Co) 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].
- When it comes to wear resistance, the effects of Co content and WC grain size are not so straightforward. Often only hardness is used in order to evaluate wear resistance of hardmetals, but many researches have pointed out that this approach is invalid, since wear resistance is functionally related to hardmetal plane strain bulk fracture toughness. Abrasive resistance increases when fracture toughness increases. Fracture toughness, KIC of WC-Co alloys is known to increase as binder phase volume fraction, mean carbide grain size, and binder phase mean free path are increased. The hardmetals with coarser carbide grains have higher toughness than finer grained grades yet lower hardness [6]. Generally, concurrent improvement of hardness and toughness has been the main research topic since cemented carbides were invented.
- It is found that introducing coarse grains in otherwise fine-ultrafine structure can increase fracture toughness without sacrificing the hardness [7]. It results in a microstructure where different grain sizes appear simultaneously, a so-called bimodal structure. Bimodal grain size distribution is achieved by mixing together WC-Co sources with different mean carbide particle sizes [8].
- Known is
US5593474 disclosing a cemented metal carbide comprising a plurality of regions of a first type of cemented metal carbide; and a plurality of regions of a second type of cemented metal carbide, the first type of cemented metal carbide having a larger average particle size than the second type of cemented metal carbide and the second plurality of regions being interspersed with the first plurality of regions, the regions collectively forming the body of cemented metal carbide with the two types of regions being approximately uniformly distributed throughout the body. Such a double-structured bimodal material exhibits improved wear resistance without sacrificing toughness. 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. - Also known is
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].
- Known in
US6293986 disclosing a bimodal hard metal or cermet sintering of body consisting of WC-containing hard metal phase and a binder phase, and WC platelets embedded therein as reinforcement produced by microwave-assisted reactive sintering while the given material was having only one type of structure, i.e., it is not double-structured. - WC-Co hardmetals with a bimodal structure have been produced using reactive sintering without microwaves. In [12], 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.
- These and other goals of the invention are achieved by a method for producing a double-structured bimodal tungsten cemented carbide composite material, said method comprising:
- milling of tungsten, carbon (e.g., graphite or carbon black) and cobalt elemental powders, resulting in a first mixture W+C+Co of ultrafine particles, wherein the average W particle size after milling in said first mixture is from 0.1 to 100 nm;
- milling of tungsten carbide powder and cobalt elemental powder, resulting in a second mixture WC+Co of coarse or extra coarse particles, and average WC grain size in said second mixture is from 1 000 to 20 000 nm;
- granulating said second mixture into a granulated second mixture;
- mixing of said first mixture W+C+Co and said granulated second mixture WC+Co, resulting in a third mixture;
- consolidating said third mixture; and
- sintering said consolidated powder mixture, resulting in a final material.
- Preferably, 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.
- In principle, 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. The fact that during reactive sintering 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. The addition of well-known grain-growth inhibitors such as chromium, vanadium, zirconium, tantalum, titanium or their carbides, nitrides, carbonitrides such as VC, Cr3C2, TaC and TiC helps to further refine the microstructure of continuous areas resulting from the first mixture. The fact that grain-growth inhibitors can be added to the first mixture only reduces their possible negative effect due to their segregation along grain boundaries and resulting reduction of fracture toughness. The contiguity ratio of material (measurement of the degree of contacts between ceramic grains) 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 inUS5593474 andUS7384443 since it involves the granulation of only one mixture instead of two. The proposed production method is cheaper than methods described inUS5593474 andUS7384443 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.
- The invention is described in the following figures:
-
Fig.1 shows the structures of conventional, bimodal, and novel double-structured bimodal materials, the latter being produced by the invented method. -
Fig.2 is a flowchart of a method of producing a double-structured bimodal structure of the cemented carbide according to one embodiment of the invention. -
Fig.3 is a SEM image of the composite material produced according to one embodiment of the invention. -
Fig.4 is an enlarged image offig 3 . - According to the one embodiment of the invention, a double-structured bimodal (
Fig 1 ) cemented carbide was prepared. First, 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 µm and the average initial particle size of the graphite powder was 17-19 µm. 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 µm and the average particle size of Co was 2-8 µm. Alcohol was employed as milling medium. The Co weight ratio of the mixture (WC+Co) was 15 wt% alike the first mixture. After milling, 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). - Sintering of specimens was carried out in a vacuum furnace at 1410 °C with a 5 min dwell (
Fig 2 , step 6). The final temperature was reached with a ramp speed of 10 °C/min. Vacuum level during sintering was 0.3-0.9 mbar. - The microstructures were investigated with SEM (Zeiss EVO MA-15). Vickers hardness was measured in accordance to the ASTM Standard E384. The fracture toughness (KIC) was determined by measuring the crack length from the tip of the indentation made by Vickers's indentation (Palmqvist method). Indentation diagonals and crack lengths (emanating from the indentation tip) were measured using the Buehler Omnimet software. The toughness is calculated by the following equation [13]
where P is the load of Vickers indentor (N) and C is half of the diagonal plus crack lengths (in mm). Mechanical properties of experimental grades E2 to E4 as well as reference materials E1 and E5 are exhibited in Table 1.[Table 1] Grade First mixture, W+C+Co, wt% Second mixture, WC+Co, wt% Hardness, HV50 Average crack length, µm Fracture toughness KIC, MPa*m1/2 E1 0 100 1134 (+/-6) 49 (+/- 12) 18.5 (+/- 0.5) E2 25 75 1308 (+/- 6) 42 (+/- 11) 20.8 (+/- 0.6) E3 50 50 1251 (+/- 8) 52 (+/- 10) 19.7 (+/ -0.5) E4 75 25 1211 (+/- 4) 46 (+/- 9) 19.5 (+/- 0.4) E5 100 0 1343 (+/-10) 74 (+/- 10) 19.6 (+/- 0.4) - The wear rate of double-structured bimodal cemented carbide according to sample E2, Table 1 in combined impact-abrasive conditions (where hardness and fracture toughness are both important; see reference [PTL4] for an explanation of the testing method) and when tested by high-velocity (40-140 m/s) impacts of coarse (3.0-5.6 mm) abrasive particles was at least 20 % less than that of conventional (Table 1, E1) or reactive-sintered (Table 1, E5) cemented carbides. Testing of the proposed double-structured bimodal materials by the conventional ASTM G132 method (static sliding against SiC sand paper) has not revealed better wear resistance as compared to conventional or reactive sintered reference grades.
- Citation List follows:
-
-
- NPL1: Schatt, W., Wieters, K. P. Powder Metallurgy: Processing and Materials. European Powder Metallurgy Association (EPMA), Shrewsbury, 1997
- NPL2: Brookes, K. J. A. World Directory and Handbook of Hardmetals and Hard Materials: Sixth Ed. International Carbide Data, East Barnet Hertfordshire, 1996
- NPL3: : Saito, H., Iwabuchi, A., Shimizu, T. Effects of Co Content and WC Grain Size on Wear of WC Cemented carbide Wear 261 2006: pp. 126 - 132, http://dx.doi.org/10.1016/j.wear.2005.09.034
- NPL4: Upadhyaya, G. S. Cemented Tungsten Carbides: Production, Properties, and Testing. Noves Publications, 1998 .
- NPL5: Gille, G., Szesny, B., Dreyer, K., van den Berg, H., Schmidt, J., Gestrich, T., Leitner, G. Submicron and Ultrafine Grained Hardmetals for Microdrills and Metal Cutting Inserts International Journal of Refractory Metals &
- NPL6: Konyashin, I., Ries, B., Lachmann, F. Near-nano WC-Co hardmetals: Will They Substitute Conventional Coarse-Grained Mining Grades? International Journal of Refractory Metals & Hard Materials 28 2010: pp. 489 - 497, http://dx.doi.org/10.1016/j.ijrmhm.2010.02.001
- NPL7: Liu, C., Lin, N., He, Y., Wu, C., Jiang, Y. The Effects of Micron WC Contents on the Microstructure and Mechanical Properties of Ultrafine WC-(micron WC-Co) Cemented Carbides Journal of Alloys and Compounds 594 2014: pp. 76 - 81; http://dx.doi.org/10.1016/j.jallcom.2014.01.090
- NPL8: Petersson, A., Ågren, J. Sintering Shrinkage of WC-Co Materials with Bimodal Grain Size Distribution Acta Materialia 53 2005: pp. 1665 - 1671.
- NPL9: Pirso, J., Viljus, M., Juhani, K., Letunovits, S. Microstructure Evolution in WC-Co Composites During Reactive Sintering From Nanocrystalline Powders Proceedings of the 2008 World Congress on Powder Metallurgy and Particulate Materials CD-ROM.
- NPL10: Juhani, K., Pirso, J., Viljus, M., Letunovits, S., Tarraste, M. The Influence of Cr3C2 and VC as Alloying Additives on the Microstructure and Properties of Reactive Sintered WC-Co Cermets Materials Science (Medziagotyra) 18 (1) 2012: pp. 79 - 83.
- NPL11: Tarraste, M., Juhani, K., Pirso, J., Viljus, M. Erosion Wear of Reactive Sintered WC-TiC-Co Cermets Key Engineering Materials 604 2014: pp. 63 - 66; http://dx.doi.org/10.4028/www.scientific.net/KEM.604.63
- NPL12: Tarraste, M., Juhani, K., Pirso, J., Viljus, M. Reactive Sintering of Bimodal WC-Co Hardmetals Materials Science (Medziagotyra) 21 (3) 2015: pp. 382-385.
- NPL13: Lawn, H. R. and Fuller, E. R. Equilibrium penny-like cracks in indentation fracture Journal of Materials Science 10 1975: pp. 2016-2024.
Claims (12)
- A method for producing a double-structured bimodal tungsten cemented carbide composite material, said method comprises:milling of tungsten, carbon such as graphite or carbon-black, and cobalt elemental powders, resulting in a first mixture W+C+Co for obtaining ultrafine tungsten carbide particles in a final material;milling of tungsten carbide powder and cobalt elemental powder, resulting in the second mixture WC+Co for obtaining coarse or extra coarse tungsten particles in the final material;granulating of said second mixture resulting in a granulated second mixture, wherein said granules comprise a plurality of grains;- mixing of said first mixture W+C+Co and said granulated second mixture WC+Co, resulting in a third mixture;- consolidating said third mixture; and- sintering said consolidated powder mixture resulting in the final material.
- A method as in claim 1, wherein the carbon weight ratio in said first mixture is selected to achieve close to the stoichiometric ratio in the final material.
- A method as in claims 1 to 2, wherein the final material has a microstructure of the tungsten cemented carbide composite material comprising two distinct areas: separate dispersed areas with coarser WC grains in the Co matrix and a continuous area with ultrafine WC grains in the Co matrix.
- A method as in claims 1 to 3, wherein said first mixture is from 1 wt % to 99 wt % of the third mixture.
- A method as in claim 3, wherein said first mixture is from 10 wt % to 50 wt % of the third mixture.
- A method as in claim 3, wherein said first mixture is from 15 wt % to 35 wt % of the third mixture.
- A method as in claims 1 to 6, wherein the Co fraction in the final material is from 3 wt % to 50 wt %.
- A method as in claim 6, wherein the Co fraction in the final material is from 10 wt % to 30 wt %.
- A method as in claim 6, wherein the Co fraction in the final material is from about 12 to about 15 wt %.
- A method as in claims 1 to 9, wherein carbide grain-growth inhibitors are added in said milling step only to the first mixture.
- A method as in claim 9, wherein said grain-growth inhibitors are selected from a group consisting of chromium, vanadium, zirconium, tantalum, titanium, or their carbides, nitrides, carbonitrides.
- A method as in claim 11, wherein the weight fraction of said grain-growth inhibitors in the first mixture is from 0.1 to 5 wt %.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2017/050505 WO2018142181A1 (en) | 2017-01-31 | 2017-01-31 | Method of making a double-structured bimodal tungsten cemented carbide composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3577242A1 EP3577242A1 (en) | 2019-12-11 |
EP3577242B1 true EP3577242B1 (en) | 2022-10-12 |
Family
ID=58213268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17708582.6A Active EP3577242B1 (en) | 2017-01-31 | 2017-01-31 | Method of making a double-structured bimodal tungsten cemented carbide composite material |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3577242B1 (en) |
WO (1) | WO2018142181A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2693415C1 (en) * | 2018-09-12 | 2019-07-02 | Общество с ограниченной ответственностью "Вириал" | Sintered solid alloy based on tungsten carbide and method for production thereof |
CN111378860B (en) * | 2018-12-28 | 2021-12-03 | 自贡硬质合金有限责任公司 | Ultra-fine grain hard alloy and preparation method thereof |
CN110343889B (en) * | 2019-06-28 | 2020-08-07 | 江西江钨硬质合金有限公司 | Extra-thick hard alloy and preparation method thereof |
JP7385829B2 (en) | 2020-02-21 | 2023-11-24 | 三菱マテリアル株式会社 | WC-based cemented carbide cutting tools and surface-coated WC-based cemented carbide cutting tools with excellent plastic deformation resistance and fracture resistance |
CN111455252A (en) * | 2020-05-12 | 2020-07-28 | 江西江钨硬质合金有限公司 | Non-uniform hard alloy prepared by adopting close-packed batching mode and preparation method thereof |
CN113930651A (en) * | 2020-06-29 | 2022-01-14 | 有研工程技术研究院有限公司 | Ultra-coarse WC-Co hard alloy and preparation method thereof |
CN112143953A (en) * | 2020-09-25 | 2020-12-29 | 江西江钨硬质合金有限公司 | High-performance non-uniform structure hard alloy and preparation method thereof |
CN112430770A (en) * | 2020-11-24 | 2021-03-02 | 江西理工大学 | Multi-scale structure non-uniform hard alloy and preparation method thereof |
CN113699406A (en) * | 2021-08-30 | 2021-11-26 | 四川轻化工大学 | High-strength and high-toughness extra-coarse-grain WC hard alloy with average grain size larger than 8 microns and preparation method thereof |
CN114150201B (en) * | 2021-12-02 | 2022-05-17 | 湖南人文科技学院 | Preparation method of superhard CoWB-Co hard alloy |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5593474A (en) | 1988-08-04 | 1997-01-14 | Smith International, Inc. | Composite cemented carbide |
WO1998040525A1 (en) | 1997-03-10 | 1998-09-17 | Widia Gmbh | Hard metal or cermet sintered body and method for the production thereof |
SE9802519D0 (en) * | 1998-07-13 | 1998-07-13 | Sandvik Ab | Method of making cemented carbide |
SE513177C2 (en) * | 1999-01-14 | 2000-07-24 | Sandvik Ab | Methods of making cemented carbide with a bimodal grain size distribution and containing grain growth inhibitors |
US7384443B2 (en) | 2003-12-12 | 2008-06-10 | Tdy Industries, Inc. | Hybrid cemented carbide composites |
CN101338382B (en) * | 2007-07-06 | 2010-05-12 | 湖南世纪特种合金有限公司 | Method for preparing high strength cemented carbide |
EE05780B1 (en) | 2014-06-16 | 2016-10-17 | Tallinna Tehnikaülikool | The device for abrasive wear testing of materials |
-
2017
- 2017-01-31 EP EP17708582.6A patent/EP3577242B1/en active Active
- 2017-01-31 WO PCT/IB2017/050505 patent/WO2018142181A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP3577242A1 (en) | 2019-12-11 |
WO2018142181A1 (en) | 2018-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3577242B1 (en) | Method of making a double-structured bimodal tungsten cemented carbide composite material | |
US20190368011A1 (en) | Cemented carbide material and method of making same | |
EP2691198B1 (en) | Cemented carbide material | |
US7678327B2 (en) | Cemented carbide tools for mining and construction applications and method of making same | |
Liu et al. | Effects of TiC/TiN addition on the microstructure and mechanical properties of ultra-fine grade Ti (C, N)–Ni cermets | |
AU1642092A (en) | Method of making cemented carbide articles | |
US10415120B2 (en) | Cemented carbide material and related producing method | |
Liu et al. | Microstructures and mechanical properties of nanoTiN modified TiC-based cermets for the milling tools | |
Lin et al. | Enhanced mechanical properties and oxidation resistance of tungsten carbide-cobalt cemented carbides with aluminum nitride additions | |
US20030037639A1 (en) | Matrix powder for the production of bodies or components for wear-resistant applications and a component produced therefrom | |
Johnson et al. | Metal injection molding (MIM) of heavy alloys, refractory metals, and hardmetals | |
US20200024702A1 (en) | Cemented carbide containing tungsten carbide and iron alloy binder | |
JP6259978B2 (en) | Ni-based intermetallic compound sintered body and method for producing the same | |
EP0046209B1 (en) | Steel-hard carbide macrostructured tools, compositions and methods of forming | |
Qian et al. | Microstructure and mechanical behavior of functionally graded cemented carbides with CoNiFeCr multi-principal-element alloy binder | |
Tang et al. | Microstructure and mechanical properties improvements in cemented carbides by (Cr, Mo, Ta) 2 (C, N) inhibitors | |
JP5207922B2 (en) | Binderless powder for surface hardening | |
Duran et al. | Liquid-phase sintering and properties of Cr3C2/NiCr cermets | |
Tarraste et al. | Reactive sintering of bimodal WC-Co hardmetals | |
EP1935537A2 (en) | Multiple processes of high pressures and temperatures for sintered bodies | |
JPH07331376A (en) | Non-magnetic or weak-magnetic diamond sintered compact and its production | |
JP4413022B2 (en) | Composite oxide dispersion sintered alloy | |
EP4275815A1 (en) | Double pressed chromium alloyed cemented carbide insert | |
García-Junceda et al. | Novel WC hardmetal with Cr/Fe binder alloy sintered by SPS | |
JP2005194556A (en) | Rare-earth-containing sintered alloy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20190830 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20211105 |
|
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: TALLINN UNIVERSITY OF TECHNOLOGY |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
INTC | Intention to grant announced (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20220426 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602017062565 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1524206 Country of ref document: AT Kind code of ref document: T Effective date: 20221115 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20221116 Year of fee payment: 7 Ref country code: FR Payment date: 20221116 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20221012 Ref country code: EE Ref legal event code: FG4A Ref document number: E022972 Country of ref document: EE Effective date: 20221230 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1524206 Country of ref document: AT Kind code of ref document: T Effective date: 20221012 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230213 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230112 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20230201 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230212 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230113 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: EE Payment date: 20221220 Year of fee payment: 7 Ref country code: DE Payment date: 20221116 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602017062565 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 |
|
26N | No opposition filed |
Effective date: 20230713 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230131 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20230131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221012 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230131 |