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EP4385644A1 - Verbundmaterial - Google Patents

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Publication number
EP4385644A1
EP4385644A1 EP23154270.5A EP23154270A EP4385644A1 EP 4385644 A1 EP4385644 A1 EP 4385644A1 EP 23154270 A EP23154270 A EP 23154270A EP 4385644 A1 EP4385644 A1 EP 4385644A1
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EP
European Patent Office
Prior art keywords
diamond
cemented carbide
entities
sccg
granules
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.)
Pending
Application number
EP23154270.5A
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English (en)
French (fr)
Inventor
Clint MCKEACHNIE
Malin MÅRTENSSON
Gustav GRENMYR
Johan SUNDSTRÖM
Tobias GYLLENFLYKT
John DE FLON
Ida BORGH
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Sandvik Mining and Construction Tools AB
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Sandvik Mining and Construction Tools AB
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Publication date
Application filed by Sandvik Mining and Construction Tools AB filed Critical Sandvik Mining and Construction Tools AB
Priority to PCT/EP2023/085347 priority Critical patent/WO2024126484A1/en
Publication of EP4385644A1 publication Critical patent/EP4385644A1/de
Pending legal-status Critical Current

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    • 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
    • B22F3/156—Hot isostatic pressing by a pressure medium in liquid or powder form
    • 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
    • B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • 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
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • 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

Definitions

  • homogenously distributed throughout is herein meant that the diamond entities are evenly distributed throughout the composite material and that no distinguishable pattern in the distribution of the diamond entities can be seen. Examples of distinguishable patterns could be a gradient in either size, volume or number of the diamond entities or that the material contains satellite structures wherein there would be a plurality of the smaller diamond entities surrounding a larger diamond entity.
  • the diamond entities are homogenously distributed throughout the cemented carbide matrix in three dimensions in terms of distance between the neighbouring diamond entities throughout the material.
  • the volume of the diamond entities throughout the material is homogenously distributed, meaning that the diamond entities are evenly distributed throughout the composite material and that no distinguishable pattern in the distribution of the diamond entities can be seen. Examples of distinguishable patterns could be a gradient in either size or number of the diamond entities or that the material contains satellite structures wherein there would be a plurality of the smaller diamond entities surrounding a larger diamond entity. This could be analysed by comparing SEM or LOM images from a near in the bulk of the material and an area near the surface of the material. The difference between the volume of the diamond entities in the area near the surface and the volume of diamond entities in the area in the bulk of the material (i.e.
  • the binder content of the cemented carbide matrix 4 is between 5 - 20 weight percent (wt%).
  • this provides a material with a cemented carbide matrix having an optimal balance between hardness and toughness.
  • the binder content in the cemented carbide part of the matrix is >3 wt%, more preferably >4wt%; most preferably >5 wt%, the binder content is ⁇ 20 wt%, more preferably ⁇ 15wt%, most preferable ⁇ 14 wt%. This is measured by using energy dispersive spectroscopy (EDS) on cemented carbide areas of the sintered sample phase.
  • EDS energy dispersive spectroscopy
  • the diamond entities include single crystal diamond.
  • the average diameter or D50 of the diamond single crystals are between 6 -100 ⁇ m, preferable 6-80 ⁇ m, more preferable 8-60 ⁇ m, even more preferable 10-80 ⁇ m, most preferable 15- 80 ⁇ m or 12-60 ⁇ m.
  • the pores and / or cracks 8 in the diamond entities 6 are filled through infiltration.
  • the elements in the cemented carbide source are tougher compared to the diamond and hence the enhancement is provided by supplying the diamond with a tougher material(s). These element(s) may also improve the retention, i.e. a reduced risk of pull-out, of the diamond to the cemented carbide through increased contact area.
  • a diamond feed stock having existing imperfections such as cracks, cavities etc. or diamond feedstock that is capable of creating such imperfections during the manufacturing process, it allows for the pores and/or cracks to be filled with elements from the cemented carbide matrix.
  • a diamond entity containing pores and/or cracks that are filled with constituent(s) from the cemented carbide matrix are defined as cemented carbide element(s) that are visible in less than or equal to 1kX inside or in the periphery of the diamond entity 6 using a SEM and back scatter electrons.
  • At least 20 %, preferably at least 25 % and even more preferably at least 30 wt% of the diamond entities contains pores and/or cracks that are filled with at least one of the elements from the cemented carbide source.
  • At least 25% of the diamond entities comprise a plurality of crystals having a two or more different orientations wherein having different orientations is defined as two or more substantially neighbouring diamonds crystals having at least 10 degrees difference in orientation.
  • Figure 2 shows an insert 10 for a mining or rock cutting or wear part application comprising the material as described hereinbefore or hereinafter.
  • the Inserts typically comprise a base portion 12; a working tip potion 14 and a core 16. It should however be understood that the insert could have a different form.
  • the insert 10 could for example have a symmetrical or asymmetrical formation.
  • the insert 10 has a domed working tip portion 14 comprising the composite material 2 as described hereinbefore or hereinafter and a base portion 12 comprising cemented carbide.
  • the cemented carbide base portion contains Cr.
  • the cemented carbide base portion has a room temperature hardness between 900 - 1650 Vickers.
  • the cemented carbide base portion has a fracture toughness K1C >10 mPa/m measured with Palmqvist method from 30 kg or 100 kg Vickers indents using Shetty's formula.
  • the binder concentration is between 4-12 wt%, more preferably between 4-10 wt% most preferable 5-8 wt%.
  • the average grain size of the hard metal is between 0.7-5 ⁇ m, more preferably between 1-4 ⁇ m with a room temperature hardness of 1200-1650 HV20.
  • the binder concentration is between 8-20 wt%, more preferably between 8-15 wt%, most preferable 10-15 wt%.
  • the average grain size of the hard metal is between 2-10 ⁇ m, more preferable between 2- 8 ⁇ m most preferable between 2-6 ⁇ m with a room temperature hardness of between 1000-1300 HV20.
  • the binder concentration is between 6-15 wt%, more preferably between 6-12 wt%.
  • the average grain size of the hard metal is between 6-18 ⁇ m, more preferably between 6-15 ⁇ m with a room temperature hardness of 800 - 1100 HV20.
  • the binder concentration is between 3-10 wt%, more preferably between 3-8 wt% most preferable 3-7 wt%.
  • the average grain size of the hard metal is between 0.6- 4 ⁇ m, more preferably between 0.6-3 ⁇ m with a room temperature hardness of 1300-2000 HV20.
  • the diameter of the base portion 12 is between 5-40 mm, more preferable 7-30 mm, most preferable 7-24 mm.
  • the thickness of the tip portion 14 is between 0.1-15 mm more preferable 0.2-10 mm, even more preferable 0.5 - 5 mm, most preferable 0.8 -4 mm when measured along the longitudinal axis.
  • the volume of the tip portion 14 is between 2- 50 vol% of the total volume of the insert 10, more preferable 5-40 vol%, most preferable 8-30 vol%.
  • the insert 10 may be freestanding without a cemented carbide base.
  • the application further relates to a method for making a material as described hereinbefore or hereinafter comprising the steps of:
  • the diamond grains comprise one or more of the following characteristics; the diamond grains have rough surfaces; cavities; pores; cracks; multi/polycrystalline structure; inclusions; crystallographic defects and / or an elongated, irregular, sharp or angular shape. Friable diamond grains have the tendency to break up into smaller fragments when under pressure.
  • diamond feedstock with more friable characteristics examples include grits designed for resin and or vitrified bond system grinding wheels.
  • Another example of diamond feedstock with more friable characteristics are polycrystalline diamond powder, for example those designed for lapping or polishing, that comprise of many smaller crystals bound together to form a larger polycrystalline diamond grain.
  • the friable diamond granules could for example be produced by, but not limited, freeze spray drying or spray drying and have a relative density of about 15-40% compared to the density of diamonds (3.52 g/cm 3 ).
  • Examples of diamond feedstock with more friable characteristics are grits designed for resin and or vitrified bond system grinding wheels. Contribution to the friable characteristics of such grits may be shapes that are more elongated and irregular, rougher surfaces, multi/polycrystalline structure inside such grains, as well as inclusions.
  • Another example of diamond feedstock with more friable characteristics are polycrystalline diamond powder, for example those designed for lapping or polishing, that comprise of many smaller crystals bound together to form a larger polycrystalline diamond grain.
  • the D50 or average diameter of cemented carbide granules is in the range of 5-60 microns.
  • the sintered cemented carbide granules can be manufactured in different ways.
  • Spray dried granules are prepared using conventional means, i.e. preparing a slurry is prepared where powders with the desired composition and WC grain size are mixed with an organic binder, usually PEG and a liquid, usually a water/ethanol blend. The slurry is then spray dried to form granules.
  • the sintering temperature of the cemented carbide granules is used both to control the WC-grain size and the density and is preferable between 1250 - 1550 °C, more preferably between 1270-1500 °C, most preferably between 1300-1500 °C.
  • the sintered cemented carbide granules are preferably fully dense or at least 90% dense, depending on the composition and sintering temperature of the granules.
  • the sintering can be performed in vacuum, or in N 2 /Ar atmosphere, or, at least partly, in a carburizing atmosphere which can be provided by one or more carbon containing gases e.g. CO 2 , CO and CH 4 .
  • the sintering process are usually started with a de-binding step where the organic binder is removed.
  • the de-binding step is usually performed at a temperature between 300 and 600°C.
  • the sintered granules of cemented carbide particles are substantially fully dense.
  • fully dense or near fully dense cemented carbide granules below a certain D50 or D90 is beneficial to controlling the homogeneity when blending diamond which is a lighter material with SCCG which is a heavier material.
  • the cemented carbide granule size also defines the smallest distance to the next diamond entity.
  • the WC grain size within the sintered cemented carbide granules is between 0.6 - 8 ⁇ m.
  • this grain size range provides the means to balance and optimize the hardness and toughness for mining applications.
  • the grain is measured by image analysis on SEM images either from secondary or back-scatter electron images using Jeffries method giving an average grain size or from analysis of an EBSD-image on an ion polished surface using the area D50 value.
  • the average WC grain size in the sintered cemented carbide granules is preferably between 0.6- 8 microns, more preferably between 0.7-5 microns, even more preferably between 0.8-3 microns, most preferably between 0.9-4 microns.
  • the binder phase content, preferable Co, in the SCCG prior to HPHT is between 6-20 wt%, more preferable 7-15 wt% Co, most preferable 8-13 wt% Co.
  • the binder content in the cemented carbide part can thus range from about 3 wt% to about 18 wt%, depending on the amounts of diamonds and the degree of binder infiltration.
  • the binder phase content in the cemented carbide part of the composite after HPHT can be analysed by EDS (energy dispersive spectroscopy) or more preferable WDS (wavelength dispersive spectroscopy) on a sufficient large ion polished area where only cemented carbide is present.
  • the D50 size of SCCG is between 5-60 microns.
  • this range provides good flowability and high powder density and the mass of each SCCG is more equal to the mass of a diamond particle.
  • the D50 size of the cemented carbide granules is preferably between 5-40 microns, even more preferably 5-30 microns.
  • the particle size distribution was measured using laser diffraction fully compliant with ISO 13320 for the complete size range from 0.1 ⁇ m to 8750 ⁇ m from Sympatec GmbH using a Helos BR instrument with Rodos M/Vibri dry sampling unit.
  • the powder is analysed with a combination of R3 (0.9 to 175 ⁇ m) and R5 (4.5 to 875 ⁇ m) measuring ranges. For each measuring range the samples are analysed three times using 0.5g of powder. The results from the two measuring ranges were then combined in the Windox 5.7.2.2 software to cover the range 0.9 to 875 ⁇ m.
  • the D90 size of SCCG is ⁇ 80 ⁇ m, preferably ⁇ 70 ⁇ m, more preferably ⁇ 60 ⁇ m, most preferable ⁇ 50 ⁇ m.
  • this provides a smaller distance to the next diamond entity and is also important for the mass of the granule which should be as close to the mass of the diamonds in the feed as possible to reduce the risk of separation during blending and filling of the cup which will be of great importance for the homogeneity of the final material.
  • the (D90 - D10) range of cemented carbide granules is ⁇ 50 ⁇ m, preferably ⁇ 40 ⁇ m, more preferably ⁇ 30 ⁇ m.
  • a narrow distribution of the sintered cemented carbide granules provides a more homogenous distribution of the diamond entities within the cemented carbide matrix and the distances between the diamond entities within the composite material will be easier to control and thus the properties of the material will be more even.
  • D10, D50 and D90 are calculated using Windox software.
  • D10, D50, or D90 is defined as the size value corresponding to cumulative size distribution at 10%, 50%, or 90% respectively, which represents the size of particles below which 10%, 50%, or 90% of the sample lies.
  • Alternative notations are x10, x50 and x90, as used in Windox software.
  • the powder density of the SCCG powder is >35%, preferably >40%, more preferably >45% compared with the fully dense sintered bodies of such granules.
  • the powder density (or apparent density) is measured by using a Hall flow meter and filling a known volume (Hall density cup) using a funnel placed above where the powder is added.
  • the SCCG powder has a tap density is preferable >40%, more preferably >50%, most preferably >55% relative to a full sintered body.
  • the tap density is obtained when filling a known volume (Hall density cup or similar) with the powder granules and tap or "knock" to make them pack even tighter.
  • a high granule density provides that the diamond grains are fixed in their position after filling the refractory metal cup.
  • it allows a lower shrinkage during HPHT which is beneficial for the shape and size control and also for avoiding sudden pressure drops during HPHT (so called blow-outs) which can result in catastrophic failures of the cemented carbide dies in the HPHT cell.
  • the cemented carbide granules have graphite or other sp 2 -carbon on their surface prior to the HPHT step.
  • this will lower the binder-melting point and ease the infiltration of the diamond grains and will convert into diamond since the HPHT process is carried out at or above the diamond stable region in presence of a catalytic metal (Co).
  • the interior of the cemented carbide granules has a majority of fcc-Co and the binder layer around the remaining granules have a majority of hcp-Co after HPHT.
  • step c) the blending could be done by vibrating, turbola blending or shaking for example in a commercial paint shaker.
  • the refractory metal cup is preferably made from titanium but could also be made from niobium or tantalum or any other suitable refractory metal.
  • the cup is shaped as required by the product being formed.
  • step e) either a refractory metal lid, or, a pre-sintered or a sintered cemented carbide pre-shaped base is inserted on top of the powder blend inside the refractory metal cup in order to close the cup.
  • the choice of the cemented carbide base in terms of grain size and composition is made depending on the target application.
  • pre-sintered is herein meant that the cemented carbide base has not been sintered to full density prior to being placed in the cup. It will reach full density during the subsequent HPHT step.
  • step f) either a refractory metal or a sintered hard metal pre-shaped substrate is inserted on top of the powder blend inside the refractory metal cup in order to close the cup.
  • a hard metal substrate is added this enables a cemented carbide base portion to be formed and the shape of the cutting tip to be designed or adjusted to fit the application for example by allowing a higher amount of cemented carbide granule and diamond blend in one part or one side of the tip.
  • the choice of the cemented carbide base portion in terms of grain size and binder content is made depending on the target application.
  • the tip could have either a symmetric or asymmetric geometry.
  • the pressure media could for example is hBN or an NaCl mixture that becomes molten during the high temperature high pressure stage at or above the diamond stable region.
  • the high pressure container for example could be, but not limited to a natural and synthetically reconstituted pyrophyllite cube or cylinder.
  • a typical HPHT cycle comprises a fast ramp for 50-65 seconds to a max pressure of 52 kBar and a temperature of 1225°C and then a smooth transition into a lower ramp of 200-300 seconds at 52 kBar gradually climbing up to a sintering soak temperature.
  • the typical soaking temperature is between 1350-1425°C for 100-200 seconds a sharp transition into a down ramp with maintained pressure of 52 kBar for 200-400 seconds; an instant cut of electrical power and a natural cooling ramp with cooling water jackets dissipating the heat for 40 seconds and a gradual release of the applied pressure.
  • the temperature is controlled by W-Re thermocouples inside the cube.
  • the full cycle is about 15-25 minutes.
  • the sintering temperature used is typically 1300-1500°C, preferably 1320-1450°C, most preferable 1350- 1420°C.
  • the sintering pressure used is typically 50kBar to 60kBar, preferably 50kBar-55kBar, most preferably 52kBar.
  • the pressure and the contact with the cemented carbide granules will to a large extent break up the diamond and the metal binder, in the cemented carbide melts and infiltrates and fills the cavities in the diamond entities and or cementing the diamond crystals and or enabling the formation of new diamond entities.
  • the outer diamater of the part is then cleaned up using centerless grinding and when needed the cup on the dome is removed either using grinding or by blasting with SiC-grits. If the part is a mining insert it is then ground to the exact dimensions required. If required the inserts can then be subjected to shot blasting and / or tumbling, for example high energy tumbling. The inserts can then be shrink fit to be brazed into a cavity in a drill bit.
  • inventive samples were produced by blending diamonds and sintered cemented carbide granules (SCCG) in the desired composition using a Caulk VARI-MIX II vibrating unit for 2.5 minutes.
  • SCCG sintered cemented carbide granules
  • the amount of powder blend to be filled to the Ti-cups was calculated by the volume of the Ti-cup and the desired height of the cutting layer.
  • the comparable samples were manufactured using only SCCG powder.
  • Cylindrical cemented carbide base portions (substrates) were manufactured using conventional methods and then the desired dome geometry of the tip portion was formed on top.
  • Table 2 shows the summary of the powder blends and substrates used in the samples Table 2: Summary of powder blends and substrates Sample Composition of the SCCG Type of diamond source Diamond feedstock sizes Volume of the diamond (%) Composition and hardness of cemented carbide substrate A (inventive) 13 wt% Co, 0.56 wt% Cr, WC (SCCG1-) Resin bond RVG810 from Hyperion 230/270 US mesh 30 12 wt% Co, 0.5 wt% TiC, 2.5 wt% (Ta,Nb)C, 90.2 HRA B (inventive) 13 wt% Co, 0.56 wt% Cr, WC (SCCG-1) Resin bond RVG810 from Hyperion 230/270 US mesh 50 12 wt% Co, 0.5 wt% TiC, 2.5 wt% (Ta,Nb)C, 90.2 HRA C (comparative) 13 wt% Co, 0.56 wt% Cr, WC (SCCG-1) Freeze dried diamond
  • Sample C is a comparative sample wherein soft freeze spray dried diamond containing granules was used in the powder mixture having a D100 diamond granule size if 500 ⁇ m, having a bi-modal distribution of the diamond grain sizes with maxima at 6 ⁇ m and 25 ⁇ m, a powder density of the granules of 1.11 g/cm 3 and a relative density of the diamond in the diamond containing granules compared to pure diamond of 32%.
  • the soft diamond granules also contained 10 wt% PEG-binder that was removed in a mixture of hydrogen and nitrogen gas up to 500 °C prior to the HPHT-step.
  • Table 3 shows the properties of the cemented carbide granules in the powder mixture: Table 3: Properties of the cemented carbide granules in the powder mixture SCCG source in samples Sintering temp. (°C) Average WC grain size in the sintered cemented carbide granules ( ⁇ m) Sintered density (g/cm3) 1 D50 size of the cemented carbide granules ( ⁇ m) D10 size of the cemented carbide granules ( ⁇ m) D90 size of the cemented carbide granules ( ⁇ m) Powder density of sintered granules (g/cm 3 ) Relative density of sintered cement ed carbide granules (%) Tap density (g/cm 3 ) SCCG-1 used in samples A, B, C, D 2 1360 0.75 14.16 16.7 9.1 28.5 7.9 56 9.0 SCCG-2 used in samples E, F, G, H 2 1350 1.1 2 14.4 18.1 11.0 29.2 7.2 50 8.1 1.2
  • the sintered cemented carbide granules SCCG-3, SCCG-4, SCCG-5 and SCCG-6 have been manufactured using soft spray dried cemented carbide granules with a relative density of about 25% and average granule size around 80-100 microns and with a maximum size of 250 microns.
  • the spray dried granules were placed on yttrium oxide coated graphite trays. 1.5 kg spray dried granules were loaded on each tray that have an inside diameter of 278 mm.
  • the sintering consisted of a de-binding step to remove the PEG from the spray dried granules and then a solid-state sintering step at 1275°C for 60min under a partial pressure of 250 mbar.
  • the partial pressure consisted of equal flow of argon and carbon monoxide. After sintering the granules were deagglomerated using approximately 2kg cylindrical cemented carbide milling bodies in a small ball mill for 20 minutes. The deagglomeration was ran under dry conditions, i.e., no liquid was added to the ball mill.
  • the deagglomerated powder SCCG-3 and SCCG-6 were used as-received after the deagglomeration step and the deagglomerated powder SCCG-4 and SCCG-5 were finally fraction sieved at 63 ⁇ m and using the fraction ⁇ 63 ⁇ m.
  • Samples produced using SCCG-3 and SCCG-6 are comparative samples as the D50 size of the cemented carbide granules is too large.
  • the SCCG and the diamond powder was then blended by using a Caulk VARI-MIX II vibrating unit for 2.5 minutes. Then the powder blend was poured into a titanium refractory metal cup with a wall thickness of 127 ⁇ m. This was followed by providing a sintered cemented carbide base on top of the powder blend to close the cup and thus containing the assembly. The powder blend in the refractory metal cup was pre-compacted by pushing the cemented carbide body on the powder blend. The contained assembly was then surrounded by a pressure media being hexagonal Boron Nitride (hBN); a Carbon Foil Heater, and a cylinder made up of a mixture of carbon lampblack and sodium chloride.
  • hBN hexagonal Boron Nitride
  • Carbon Foil Heater a Carbon Foil Heater
  • Table 4 shows the properties of the HPHT sintering conditions used and the yields post sintering. Following the HPHT sintering the inserts were then ground and / or blasted with SiC to clean the dome. Table 4 also reports the homogeneity of the wear on the dome following the SiC blasting. Table 4: Comments following HPHT sintering and blasting / cleaning of the dome. Sample HPHT max.
  • Table 4 shows that the comparative samples suffer from either or both failure after HPHT sintering due to delamination or non-homogenous wear during SiC-blasting/cleaning of dome, whereas the inventive samples had no failures post HPHT sintering and homogenous wear during SiC-blasting/cleaning of dome.
  • the homogeneous wear during SiC blasting of the dome is an indication of homogeneous material properties, which will lead for better insert performance and provide inserts that will be less prone to cracking.
  • Tables 5 and 6 show the properties of commercially available samples that are considered to be the state of the art and the "benchmark" for the properties for the inserts produced according the invention disclosed herein. These samples have high diamond contents and therefore a much more expensive to produce than the inventive samples. These samples are produced with three layers of diamond in the dome, with each layer having a different concentration of diamond.
  • Table 5 Cemented carbide properties for the comparative benchmark samples Sample D50 WC grain size in diamond layer 1 (cutting layer) from EBSD Co (wt%) content from EDS on WC-Co area in diamond layer 1 D50 diamond grain size by EBSD ( ⁇ m) D50 WC grain size in cemented carbide substrate from EBSD Composition of cemented carbide substrate from EDS (wt%) Q (benchmark) 0.39 5.4 8.32 1.89 8.8 Co, balance WC R (benchmark) 0.45 8.2 9.98 1.64 8.2 Co, Balance WC Table 6: Diamond properties of the comparative benchmark samples Sample Diamond content in layer 1 (cutting layer) by Image analysis on 500X SEM image (area %) Diamond content in layer 2 (middle) by Image analysis on 500X SEM image (area %) Diamond content in layer 3 (next to substrate) by Image analysis on 500X SEM image (area %) Thickness of diamond layer 1 ( ⁇ m) Thickness of diamond layer 2 ( ⁇ m) Thickness of diamond layer 3 ( ⁇ m) Q
  • Table 7 shows the properties of the inserts post HPHT sintering.
  • Table 7 Composite of material post HPHT sintering Sample Number of entities/grains in image Magnification of SEM-image (X) % of diamond entities that contain pores and/ or defects and /or cracks that are filled with constituents of the cemented carbide A (invention) 40 200 48 B (invention) 21 370 52 F (invention) 85 140 60 R (layer 3) (benchmark) 60 1000 7
  • Table 7 shows that the benchmark comparison, R, has a much lower percentage of diamond entities that contain pores and/ or defects and /or cracks that are filled with constituents of the cemented carbide and thus falls outside of the scope of the claims.
  • Figures 1a and 1b show SEM images at x140 and x450 magnification respectively of the structure of sample F, wherein there is a high percentage of diamond entities that contain pores and/ or defects and /or cracks that are filled with constituents of the cemented carbide. This can be compared to figure 3 that is an SEM image of sample R, which has a much lower percentage of diamond entities that contain pores and/ or defects and /or cracks that are filled with constituents of the cemented carbide.
  • Table 8 shows further comparative samples.
  • the samples shown in this table are produced by conventional sintered at a temperature of 1410 °C in vacuum and applying an argon pressure at 60 bars at maximum temperature.
  • Table 8 Composition of cemented carbide samples used for comparison.
  • Table 9 shows example of the hardness and fracture toughness of the sintered SCCGs and cemented carbides.
  • Table 9 Hardness and toughness properties Sample Average grain size of the metal carbide( WC) ( ⁇ m) Nominal binder content in SCCG HV20 K1C 3 (MPa/m) SCCG-1 0.75 1 13 Co, 0.56 Cr 1380 17.08 3 SCCG-2 1.2 1 12.0 Co 1300 18.30 3 SCCG-5 1.1 1 8 Co, 0.8 Cr 1560 11.74 3 SCCG-4 2.8 1 11 Co, 1.11 Cr 1350 12.84 3 S 1.72 2 6.0 Co 1450 11.2 4 T 1.4 1 8 Co, 0.8 Cr 1520 12.0 3 U 5.02 2 11 Co, 1.11 Cr 1060 13.3 4 1 By Jeffries 2 D50 by EBSD 3 K1C from Palmqvist indents using Shettys formula and 30 kg load 4 K1C from SEVNB
  • Table 9 shows that all the SCCGs have a K1C > 10 mPa/m and that the hardness and toughness of the sintered SCCG and cemented carbides can be controlled by their composition. It was not possible to measure the hardness and toughness of the composite materials comprising the diamond and the high hardness would break the measuring equipment.
  • the samples were ground, lapped and ion polished until the cemented carbide matrix and the diamond entities are in the same height level and thereafter SEM images was taken about 100 microns from the top of the dome (surface) and about 100 microns above the substrate.
  • the images were analyzed with ImageJ program from Fiji. The scale in the images was set in the program prior to the image analysis.
  • the area of interest was set to be the carbide matrix and the diamond entities was regarded as background.
  • the threshold was set so that the diamonds entities that contained no CC constituents were black and the diamond entities that contained CC constituents also contained white areas or spots. The same threshold was used on both images.
  • the samples tested in an abrasion wear test wherein the sample tips are worn against a rotating granite log counter surface in a turning operation.
  • the test parameters used were as follows: 100 N load applied to each insert, granite log rpm ⁇ 190, log diameter ranging from 130 to 150 mm, and a horizontal feed rate of 0.339 mm/rev. As much of the length of the log (max 300 mm) was used in each test to remove that difference in composition in the rock have a significant impact on the results. If large piece broke out from the log this area was avoided and therefore the length in some tests were shorter than 300 mm.
  • the sliding distance varied due to the difference in diameter and length of the part of the rock that could be used but were around 330-460 m and the mass loss versus sliding distance was approximately linear between the three samples of each grade that was tested.
  • the sample was cooled by a continuous flow of water. Each sample was carefully cleaned and weighed prior to and after the test. Mass loss of one sample per material was evaluated, the sample volume loss for each of the tested materials was calculated from the measured mass loss and sample density, the results are presented in table 11.
  • Table 11 shows that the inventive samples have a lower wear rate that the comparative samples and similar wear to the benchmark examples even though they been produced with lower diamond content and consequently at lower cost. Moreover, the mismatch in CTE (thermal expansion coefficient) of the diamond containing layer in the invention compared to the cemented carbide base portion is significantly reduced with a lower diamond content and with separated diamond entities. Thus, the need for a layered structure with lower diamond composition towards the carbide base is removed.
  • the insert compression test method involves compressing a drill bit insert between two planeparallel hard counter surfaces, at a constant displacement rate, until the failure of the insert.
  • a test fixture based on the ISO 4506:2017 (E) standard "Hardmetals - Compression test” was used, with cemented carbide anvils grade H6F from Hyperion having a hardness exceeding 2000 HV, while the test method itself was adapted to toughness testing of rock drill inserts.
  • the fixture was fitted onto an Instron 5989 test frame.
  • the loading axis was identical with the axis of rotational symmetry of the inserts.
  • the counter surfaces of the fixture fulfilled the degree of parallelism required in the ISO 4506:2017 (E) standard, i.e. a maximum deviation of 0.5 ⁇ m / mm.
  • the tested inserts were loaded at a constant rate of crosshead displacement equal to 0.6 mm / min until failure, while recording the load-displacement curve.
  • the compliance of the test rig and test fixture was subtracted from the measured load-displacement curve before test evaluation.
  • One diamond composite inserts was tested but at least three cemented carbide inserts per run.
  • the counter surfaces were inspected for damage before each test. Insert failure was defined to take place when the measured load suddenly dropped by at least 1000 N.
  • each sample was analyzed in the same way where a plane parallel section was cut from an insert using EDM cutting and mechanically polished. Thereafter, the samples were ion-polished using the flat mode until the diamonds and the cemented carbide were on the same height level after approximately 200-300 min at 6V and 20 min at 2V with 4° sample angle.
  • the post-processing was performed using AztecCrystal 2.2 software. For diamond map wild spike removal and zero solution removal down to 5 neighbours with 10 iterations per step. Additional Pseudo-symmetry rotations was removed, of axis [111] with an angle of 60 degrees (allowed deviating angle 5 degrees). Diamond-diamond boundaries were defined as having a misorientation angle larger than 10 degrees and boundaries was closed. Boarder grains were excluded. Smallest grain was defined as having size of 50 pixels in area. For WC auto-cleaning was used with an addition of Pseudo-symmetry rotations removal of axis [0001] with and angle of 30 degrees (allowed deviating angle 5 degrees).
  • WC-WC boundaries were defined as having a misorientation angle larger than 3 degrees and boundaries was closed. Boarder grains were excluded. Smallest grain was defined as having size of 13 pixels in area.
  • Table 14 EBSD results Sample Area d50 grain size of diamond by EBSD Area d10 grain size of diamonds by EBSD Area d90 grain size of diamond by EBSD % of the diamond entities comprising a plurality of crystals having a two or more different orientations wherein different orientations is defined as two or diamonds crystals having diamond to diamond bonding with at least 10 degrees difference in orientation by EBSD G (inventive) 30.72 12.2 45.1 54 F (inventive) 48.3 25.9 62.0 52 R -layer 3 (benchmark) 10.0 6.5 13.2 14

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JPH08109431A (ja) * 1994-10-11 1996-04-30 Read:Kk 硬質合金を結合材とするダイヤモンド燒結体及びその製造方法
EP1028171A1 (de) * 1995-11-15 2000-08-16 Sumitomo Electric Industries, Ltd. Überhartes Verbundmaterial
EP1231288A1 (de) * 1999-10-29 2002-08-14 Sumitomo Electric Industries, Ltd. Kompositmaterial mit ultraharten partikeln
WO2009128034A1 (en) 2008-04-15 2009-10-22 Element Six (Production) (Pty) Ltd Super-hand enhanced hard-metals
US7647992B2 (en) 2000-03-09 2010-01-19 Smith International, Inc. Polycrystalline diamond carbide composites
US20110226532A1 (en) * 2008-10-21 2011-09-22 Cornelis Roelof Jonker Insert for an attack tool, method for making same and tools incorporating same
US20130213721A1 (en) * 2010-06-16 2013-08-22 Element Six Abrasives, S.A. Superhard cutter

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08109431A (ja) * 1994-10-11 1996-04-30 Read:Kk 硬質合金を結合材とするダイヤモンド燒結体及びその製造方法
EP1028171A1 (de) * 1995-11-15 2000-08-16 Sumitomo Electric Industries, Ltd. Überhartes Verbundmaterial
EP1231288A1 (de) * 1999-10-29 2002-08-14 Sumitomo Electric Industries, Ltd. Kompositmaterial mit ultraharten partikeln
US7647992B2 (en) 2000-03-09 2010-01-19 Smith International, Inc. Polycrystalline diamond carbide composites
WO2009128034A1 (en) 2008-04-15 2009-10-22 Element Six (Production) (Pty) Ltd Super-hand enhanced hard-metals
US20110020163A1 (en) * 2008-04-15 2011-01-27 Roger William Nigel Nilen Super-Hard Enhanced Hard Metals
US20110226532A1 (en) * 2008-10-21 2011-09-22 Cornelis Roelof Jonker Insert for an attack tool, method for making same and tools incorporating same
US20130213721A1 (en) * 2010-06-16 2013-08-22 Element Six Abrasives, S.A. Superhard cutter

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Title
YEHIA H M ET AL: "Effect of diamond additions on the microstructure, physical and mechanical properties of WC- TiC- Co/Ni Nano-composite", INTERNATIONAL JOURNAL OF REFRACTORY METALS AND HARD MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 71, 22 November 2017 (2017-11-22), pages 198 - 205, XP085328405, ISSN: 0263-4368, DOI: 10.1016/J.IJRMHM.2017.11.018 *

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