OA21468A - Cemented carbide insert for mining or cutting applications comprising gamma phase carbide - Google Patents

Abstract

A sintered cemented carbide insert for mining or cutting applications comprising: a mean WC grain size of between 0.8 - 18 µm; a binder phase in a weight between 4 -18 wt%; gamma phase with the cubic gamma phase precursors in a weight of between 0.8 -10 wt%; any unavoidable impurities and a balance of WC; and wherein the difference between the hardness at any point 0.3 mm from the surface of the insert and the hardness of the bulk is at least 25 HV3, wherein hardness is measured according to ISO EN6507 and a method of producing said cemented carbide.

Description

CEMENTED CARBIDE INSERT FOR MINING OR CUTTING APPLICATIONS COMPRISING GAMMA PHASE CARBIDE

TECHNICAL FIELD

The présent invention relates to a cemented Carbide insert for mining or cutting applications 5 containing gamma phase Carbide and a method of making said mining insert.

BACKGROUND

Cemented Carbide has a unique combination of high elastic modulus, high hardness, high compressive strength, high wear and abrasion résistance with a good level of toughness. Therefore, cemented Carbide is commonly used in products such as mining tools. Cemented Carbide comprises a hard métal phase and a binder phase. Typically, the cemented Carbide used for mining inserts using tungsten Carbide hard métal phase, with only very minor quantifies of other carbides that are présent as impurities ratherthan purposely added.

The use of gamma phase hard metals which includes cubic carbides and nitrides and carbonitrides of titanium, tantalum and niobium Carbide that together with hexagonal tungsten

Carbide form a mixed cubic Carbide (Mel, Me2, Me3)(C) or mixed cubic carbonitride (Mel, Me2, Me3)(C,N), so called gamma phases, are commonly used in cemented carbides used in the métal cutting industry as they provide the benefit of improved wear résistance and improved résistance towards plastic deformation. However, gamma phase hard metals are not currently used in cemented Carbide for mining inserts as it embrittles the Carbide, which when subjected to mining operations, such as a percussive drilling action, will resuit in the inserts prematurely cracking, therefore reducing the lifetime of the inserts.

DEFINITIONS

By cemented Carbide is herein meant a material that comprises at least 50 wt% WC, possibly other hard constituents common in the art of making cemented carbides and a metallic binder phase preferably selected from one or more of Fe, Co and Ni.

The term bulk is herein meant the cemented Carbide of the innermost part (centre) of the rock drill insert and for this disclosure is the zone having the lowest hardness.

The term green refers to a cemented Carbide mining insert produced by milling the hard phase component(s) and the binder together and then pressing the milled powder to form a compact cemented Carbide mining insert, which has not yet been sintered.

The term cubic carbides refers to the cubic carbides such as TaC, NbC, TiC that together with hexagonal WC will form a cubic gamma phase during sintering.

The term cubic nitrides refers to cubic nitride such as TiN that together with hexagonal WC will form a cubic gamma phase during sintering.

The term cubic carbonitrides refers to the cubic carbonitride such as Ti(C,N) that together with hexagonal WC will form a cubic gamma phase during sintering.

The term gamma phase refers to the mixed cubic carbides and carbonitrides formed and precipitated during sintering when cubic Carbide and/or nitride formers/precursors are added prior to the green forming step in higher amounts than can be dissolved in the binder in the sintered cemented Carbide body. Typical cubic gamma phase formers/precursors are for example Ta, Nb and Ti that together with W from the hexagonal WC form the cubic gamma phase for example, but not limited to, (Ta,Nb,W)(C), (Ta, Nb, Ti, W)(C,N). It is assumed that substantially ail added cubic carbides/nitrides/carbonitrides form gamma phase and the amount of these cubic gamma phase precursors in the sintered body is either calculated from the sum of the added cubic carbide/nitrides/carbonitrides or can be calculated backwards by analysingthe element concentration of Mel, Me2 including nitrogen in the sintered body and assume that ail Mel was added as MelC, where Mel is a métal that form cubic carbides as Ta or Nb. If nitrogen is présent some of the Me2 was added as Me2N or Me2(C,N) and Me2C, where Me2 is a métal that forms both cubic carbides, nitrides and mixtures thereof as Ti. The elemental analyses are preferably performed using an XRF-instrument equipped with a wavelength dispersive spectrometer on an oxidised and dissolved sintered material that for example is included into a light element (as boron) glass. The analysis and évaluation are performed using quantitative XRF-methods that are carefully calibrated within the range of the claims.

SUMMARY OF INVENTION

A cemented Carbide mining insert having improved wear résistance without increased brittleness has now been developed. Different aspects of the invention include a cemented Carbide mining insert, a rock drill bit body comprising one or more mounted cemented Carbide inserts, and a method of producing a cemented Carbide insert, which are characterized by what is stated in the independent claims. Various embodiments of the invention are disclosed in the dépendent claims.

According to a first aspect of the présent invention there is a sintered cemented Carbide insert for mining or cutting applications comprising: a mean WC grain size of between 0.8 -18 pm; a binder phase in a weight between 4 -18 wt%; gamma phase with the cubic gamma phase precursors in a weight of between 0.8 -10 wt%; any unavoidable impurities and a balance of WC; and wherein the différence between the hardness at 0.3 mm at any point from the surface of the insert and the hardness of the bulk is at least 25 HV3, wherein hardness is measured according to ISO EN6507 3:2005.

Advantageously, a cemented Carbide mining insert having improved wear résistance without increased brittleness is provided. Therefore, the lifetime of the insert is increased. Further, it makes it easier to be able to use recycled Carbide, that typically has higher gamma phase content that would be acceptable for cemented Carbide grades that are commonly used for used mining or cutting applications. A cemented Carbide insert should be considered to include any insert used for interaction with rock, for example inserts for percussive drilling, top hammer drilling, down-the-hole (DTH) drilling, protection inserts or cutting tools.

According to second aspect of the présent invention there is a method of producing a cemented Carbide insert, comprising the steps of:

a) providing a green cemented Carbide insert comprising between 0.8 -10 wt% cubic carbides and or carbonitrides and or nitrides, between 4-18 wt% binder, any unavoidable impurities and a balance of WC hard phase;

b) sintering the green Carbide mining insert to form a sintered cemented Carbide insert;

c) subjecting the sintered cemented Carbide insert to a high energy post-treatment.

Advantageously, this method produces cemented Carbide inserts having improved wear résistance without increased brittleness and therefore the inserts produced by this method hâve an increased lifetime.

According to a third aspect, there is provided a rock drill bit body comprising one or more mounted cemented Carbide inserts.

BRIEF DECRSIPTION OF DRAWINGS

Figure 1: Schematic drawing showing the positions on the insert where the hardness and toughness measurements were taken.

Figure 2. Schematic drawing of a top hammer bit with ballistic inserts with the diameter measuring points indicated.

DETAILED DESCRIPTION

The présent invention relates to a sintered cemented Carbide insert for mining or cutting applications comprising: a mean WC grain size of between 0.8 -18 pm; a binder phase in a weight between 4-18 wt%; gamma phase with the cubic gamma phase precursors in a weight of between 0.8 -10 wt%; any unavoidable impurities and a balance of WC; and wherein the différence between the hardness at 0.3 mm from any point of the surface of the insert and the hardness of the bulk is at least 25 HV3, when the hardness is measured according to ISO EN6507.

Preferably the sintered WC grain size is between 0.8 -16 pm, more preferably between 0.8 8 pm or 0.8 - 5 pm or 0.9 - 8 pm or 1.0 - 5 pm or 1.0 - 4.0 pm.

The mean WC grain size was evaluated using the Jeffries method described below, from at least two different micrographs for each material. An average value was then calculated from the mean grain size values obtained from the individual micrographs (for each material respectively). The procedure for the mean grain size évaluation using a modified Jeffries method was the following:

A rectangular frame of suitable size was selected within the SEM micrograph so as to contain a minimum of 300 WC grains. The grains inside the frame and those intersected by the frame are manually counted, and the mean grain size is obtained from équations (1-3):

M^scalemm^^ ³ = --------------— (i)

Lscale micro ^x (,w£%Co .

-1.308823529 X _fwt%Co ¹⁰⁰------Zw ^/oLO ₊₁ 3q₈₈23529 \ 100 (2)

¹⁵⁰⁰ X

KxLzXVOZQ/o WC (îi-l+^xIOO (3)

Where:

d = mean WC grain size (μηη)

Li, L₂ = length ofsides of the frame (mm)

M = magnificationLscale mm = measured length ofscale bar on micrograph in mm

Lscale micro ⁼ octual length ofscale bar with respect to magnification (pm) ni - no. grains fully within the frame n₂ = no. grains intersected byframe boundary wt%Co = known cobalt content in weight %.

Equation (2) is used to estimate the WC fraction based on the known Co content in the material. Equation (3) then yields the mean WC grain size from the ratio of the total WC area in the frame to the number of grains contained in it. Equation (3) also contains a correction factor compensating for the fact that in a random 2D section, not ail grains will be sectioned through their maximum diameter.

Preferably, the binder phase is between 4-18 wt% or 5 -15 wt% or 5 -12 wt% or 6 -12 wt% or 5 - 8 wt% and 10 -15 wt%.

For percussive applications as Top hammer (TH) and Down the Hole (DTH) the grain sizes are 15 préférable between 0.8 - 5 microns and the binder phase concentration is préférable between 4-8 wt% and the room température hardness is préférable between 1250 -1650 HV20.

For Rotary applications the grain size is préférable between 2- 8 microns and the binder phase content is préférable between 8-15 wt% and the room température hardness is between 1000 -1400 HV20.

For mechanical cutting applications the grain sizes are préférable between 6-18 microns and the binder phase content are between 6-18 wt% and the room température hardness is préférable between 800 -1200 HV20.

Preferably, the weight percent of gamma phase is less than 10 wt%, more preferably less than 8 wt% even more préférable less than 6 wt% or less than 4 wt% or less than 2 wt%.

Preferably, the weight percent of gamma phase is > 0.8 wt%, more preferably > 0.9 wt%, more préférable > 1.0 wt%, even more préférable > 1.1 wt%, even more preferably >1.2 wt%.

The gamma phase forming carbides or nitrides or carbonitrides added could be any of Ta, N b, Ti, Zr, Hf.

Preferably, the volume of gamma phase is evenly distributed throughout the insert.

Preferably, the gamma phase grains are smallerthan 10 microns, more préférable smaller than 5 microns, préférable smallerthan 4 microns most préférable smallerthan 3 microns.

The hardness of the cemented Carbide inserts is measured using Vickers hardness measurement. The cemented Carbide bodies are sectioned along the longitudinal axis and polished using standard procedures. The sectioning is done with a diamond dise cutter under flowing water.

In one embodiment the différence between the hardness at 0.3 mm depth at any point of the surface of the dôme of the rock drill insert and the minimum hardness of the bulk of the rock drill insert is at least 25 HV3 or at least 30 HV3 or at least 35 HV3, or at least 40 HV3. The average hardness at a certain depth is defined as the average of at least 10 measured, more préférable 20 hardness values atthe certain depth evenly distributed around the insert. The large différence in hardness between the surface of the rock drill insert and its interior is présent overthe whole surface and will therefore also reduce the risk of other types of failures during handling.

Preferably, the cemented carbide insert has a bulk hardness of not higher than 1700 HV3 or not higher than 1650 HV3, or not higher than 1600 HV3.

In one embodiment the top of the insert has a higher surface hardness than the cylindrical part and the bottom, but the bulk hardness is the same in the interior of the insert.

Preferably, the binder phase comprises at least 80wt% of one or more of cobalt, nickel, iron or a combination thereof.

Preferably the binder phase is Co and / or Ni, most preferably Co, even more preferably between 3 to 20 wt% Co. Optionally, the binder is a nickel chromium or nickel aluminium alloy.

The carbide mining insert may optionally also comprise a grain refîner compound in an amount of <20 wt% of the binder content. The grain refîner compound is suitably selected from the group of carbides, mixed carbides, carbonitrides or nitrides of vanadium, chromium, tantalum and niobium. With the remainder of the; carbide mining insert being made up of the one or more hardphase components.

The binder content may be constant throughout the insert or hâve a gradient from the surface to the bulk of the insert.

Preferably, the cubic precursors for gamma phase is tantalum carbide or niobium carbide or a mixture thereof. This is bénéficiai for the plastic deformation résistance at elevated température.

Préférable the amount of TaC+NbC= 0.8 -10 wt% or 1 - 8 wt% or 1 - 5 wt% or 1.2 - 5 wt% or 1.2 to 3 wt% or 1.5 - 6 wt%.

Preferably, the ratio of Ta / Nb in weight is 0.1 -100, more préférable 0.5 - 50, even more préférable 1 -10, most préférable 2-6.

Optionally, the cemented Carbide also comprises Cr in such an amount that the mass ratio Cr/Co in the bulk is 0.04 - 0.19. Preferably, the mass ratio Cr/Co in the cemented Carbide is 0.06 - 0.16, more preferably the mass ratio Cr/Co in the cemented Carbide is 0.07 - 0.15, most préférable the mass ratio Cr/Co in the cemented Carbide is 0.075 - 0.12. Advantageously, the presence of the chromium improves the plastic deformation of the cemented Carbide, this enables higher compressive stresses to be introduced into the Carbide when it is treated with a surface high energy post-treatment, such as tumbling or intensive shaking. This increase in compressive stress provides an apparent hardness increase which improves the wear résistance of the cemented Carbide, without reducing the toughness.

The mass ratio of the Cr/binder is calculated by dividing the weight percentage (wt%) of the Cr 15 added to powder blend by the wt% of the binder in the powder blend, wherein the weight percentages are based on the weight of that component compared to the total weight of the powder blend. To a great extent the Cr is dissolved into the binder phase, however there could be some amount, e.g. up to 3 mass%, of undissolved chromium Carbide in the cemented Carbide body. It may however be préférable to only add Cr up to the mass ratio of Cr/binder so that ail the Cr dissolved into the binder so that the sintered cemented Carbide body is free of undissolved chromium carbides.

The Cr is normally added to the powder blend in the form of Cr₃C₂ as this provides the highest proportion of Cr per gram of powder, although it should be understood that the Cr could be added to the powder blend using an alternative chromium Carbide such as or Cr₇C₃ or a chromium 25 nitride or even a oxide. The addition of the Cr also has the effect of improving the corrosion résistance of the cemented Carbide body. The presence of the Cr also makes the binder prone to transform from fcc to hep during drilling, this is bénéficiai for absorbing some of the energy generated in the drilling operation. The transformation will thereby harden the binder phase and reduce the wear of the button during use thereof. The presence of the Cr will increase the wear résistance of the cemented Carbide and increase its ability for deformation hardening. The combination of the Cr in the cemented Carbide powder and the application of the powder comprising a grain refîner compound and optionally a carbon-based grain growth promoter, to at least one portion of the surface of the compact produces a cemented Carbide body having a

Chemical and hardness gradient which produce a cemented Carbide mining insert with high wear résistance.

In one embodiment of the présent invention, the cemented Carbide comprises M7C3 carbides and / or M23C6 Carbide, and possibly also M₃C₂ carbides, where M is Cr and possibly one or more of W, Co and any other éléments added to the cemented Carbide. By that is herein meant that the M7C3 and / or M23C6 Carbide carbides should be clearly visible in a SEM (scanning électron microscope) image using backscattering at a magnification enough to detect particles of a size of 100 nm. In one embodiment of the présent invention, the cemented carbide comprises M7C3 carbides and / or M₂3C₆ carbides in an amount given by the ratio vol% (M7C3 carbides and / or M₂3C₆ carbide) / vol% Co. Suitably the ratio vol% (M7C3 carbides and / or M23C6 carbide) / vol% Co is between 0.01 to 0.5 preferably between 0.03 to 0.25. The vol% of M7C3 carbides and / or M23C6 carbide and the Co binder can be measured by EBSD or image analysis using a suitable software.

In one embodiment the cemented carbide is free from eta phase and graphite. If the binder phase consists of cobalt, the cemented carbide will be free from eta phase and graphite when the Com/Co ratio is 0.75 Com/Co^0.98. The metals used as binder phase in cemented carbides, like

Co, Ni, and Fe are ferromagnetic. The saturation magnetization is the maximum possible magnetization of ferromagnetic material, characterized by parallel orientation of ail magnetic moments inside the material. A Foerster KOERZIMAT 1.096 is used to détermine the magnetic saturation (Corn) dipole moment jS and the derived weight spécifie saturation magnetization oS (4πσ) of the inserts. The Co content is then measured with XRF (X-ray fluorescence) using a Malvern Panalytical Axios Max Advanced instrument. The Com/%Co range that is between eta phase and graphite formation is affected by changing the binder composition, such as by adding Cr, Fe, Ni etc.

The solubility of W in the binder phase is directly related to the carbon content. The amount of W in the binder increases with decreasing carbon content until the limit for eta phase formation is reached. If the carbon content would decrease even lower, the solubility of W in the binder will not increase further. In some cemented carbide grades where it is bénéficiai to obtain a high amount of W dissolved in the binder, the carbon content has been kept low but above the limit for eta phase formation.

In one embodiment, the fracture toughness différence (Delta K1C) between 0.5 mm below the surface and the bulk is at least 1.5, more preferably at least 1.8, even préférable at least 2.0, most préférable at least 2.2 MPa*m . The fracture toughness K1C is measured using 5-10 Vickers indentations, 30 kg load and calculated using Shetty's formula.

Figure 1 shows the positions where the indentations were placed for delta K1C and delta HV3 measurements. On the left side of the sectioned and polished sample HV30 indentations were placed 0.5 mm from the surface 10 (unfilled diamonds) and in the bulk 20 (black diamonds). On the right side of the sample HV3 was measured 0.3 mm from the surface 30 (black filled diamonds), 1 mm from the surface 40 (grey diamonds) and in the bulk 50 (light grey diamonds).

In one embodiment, there is a rock drill bit body comprising one or more mounted cemented Carbide inserts as described hereinabove or hereinbelow.

According to one embodiment, the cemented Carbide inserts are mounted in a rock drill bit body of a top-hammer (TH) device or a down-the-hole (DTH) drilling device or a rotary drilling device or a cutting dise device. The rotary drilling device may be an oil and gas rotary cutter device. The invention also relates to a rock drill or cutting device, in particular a top-hammer device, or a downthe-hole drilling device, or a rotary drilling device, or a.cutting dise device as well as the use of a cemented Carbide insert according to the invention in such a device.

Another aspect of the présent disclosure relates to the use of the cemented Carbide mining insert as described hereinbefore or hereinafter for rock drilling or oil and gas drilling.

Another aspect of the présent invention is a method of producing a cemented Carbide insert according to any of daims 1-7, comprising the steps of:

a) providing a green cemented Carbide insert comprising between 0.8-10 wt% cubic carbides and or carbonitrides and or nitrides, between 4-18 wt% binder, any unavoidable impurities and a balance of WC hard phase;

b) sintering the green Carbide mining insert to form a sintered cemented Carbide insert;

c) subjecting the sintered cemented Carbide insert to a high energy post-treatment.

High energy post-treatment (HET) is considered to be a process wherein a post -treatment a homogenous cemented Carbide mining insert has been deformation hardened such that ÛHV3% > 9.72 - 0.00543*HV3buik, wherein the AHV3% is the percentage différence between the HV3 measurement at 0.3 mm from the surface compared the HV3 measurement in the bulk. HET could also be understood to mean a post- treatment process that induces a hardness différence between 0.3 mm from the surface and the bulk of at least 20 HV3. HET could also be understood to mean that there is both a hardness and toughness increase induced from the surface to the bulk without changing the Chemical composition or the WC grain size near the surface (0.3 mm below) or in the bulk.

To introduce higher levels of compressive stresses into the cemented Carbide mining insert, a high energy shaking or tumbling process may be used. There are many different possible process set ups that could be used to introduce HET, including the type of equipment, the volume of media added (if any), the treatment time and the process set up, e.g. RPM for a centrifugal tumbler or shaking equipment etc. Therefore, the most appropriate way to define HET is in terms of any process set up that introduces a spécifie degree of deformation hardening in a homogenous cemented Carbide mining insert consisting of WC-Co, having a mass of about 20g. In the présent disclosure, HET is defined as a post-treatment process that would introduce a hardness change, measured using HV3, after post-treatment (AHV3%) of at least:

AHV3% = 9.72 - 0.00543*HV3bulk (équation 1)

Wherein:

AHV3% = 100*(HV30.3mm - HV3bulk)/HV3bulk (équation 2)

HV3buik is an average of at least 10 indentation points measured in the innermost (centre) of the cemented Carbide mining insert and HV3o.3mm is an average of at least 10 indentation points at 0.3mm below the tumbled surface of the cemented Carbide mining insert. This is based on the measurements being made on a cemented Carbide mining insert having homogenous properties. By homogeneous properties we mean that post sintering the hardness different is no more than 1% from the surface zone to the bulk zone. The HET-parameters used to achieve the deformation hardening described in équations (1) and (2) on a homogenous cemented Carbide mining insert would be applied to cemented Carbide bodies having a gradient property.

HET may typically be performed using centrifugal tumbling in an ERBA 120, having a dise size of about 600 mm, run at about 200 RPM if the tumbling operation is either performed without media or with media that is larger in size than the inserts being tumbled, or at about 300 RPM if the media used is smaller in size than the inserts being tumbled; using a Rosier tumbler, having a dise size of about 350 mm, at about 280 RPM if the tumbling operation is either performed without media or with media that is larger in size than the inserts being tumbled, or at about 320 RPM if the media used is smaller in size than the inserts being tumbled. Typically, the parts are tumbled for at least 40-80 minutes. Using a commercially available paint shaker of trademark Corob™ Evoshake500 with a maximum load of 40 kg and a maximum shaking frequency of 65 Hz corresponding to 600 rpm. One insert up to the maximum load of the machine of inserts are placed in a plastic sealed containers being cylindrical or square in shape optional together with almost spherical cemented Carbide media of a hardness around 1200-1600 Vickers of sizes ranges from 3 - 20 mm in diameter with a small amount of cooling liquid (water with an antioxidizing agent) added, such that ndt ail of the inserts are covered in cooling liquid. The filling degree in the plastic containers is préférable between 20-80 % ofthe volume, most préférable between 30-50 % ofthe container volume. The container is shaken for 5-30 min using the 100% of the shaking capacity of the machine (600 rpm), préférable between 5-15 min which corresponds to or above the compressive stress levels that can be obtained in the ERBA 120 using the parameters above. Softer ramping steps can be applied by lower the rpm; this is bénéficiai if the inserts is prone to breaking. During the shaking process the inserts and the cooling liquid are heated up to about 70-90 degrees C.

In one embodiment, the high energy post treatment is conducted at an elevated température of or above 100°C, preferably at a température of or above 200°C, more preferably at a température of between 200°C and 450°C. The advantage the elevated process température is that an increased toughness ofthe Carbide and hence the collisions do not resuit in defects such as micro cracks, large cracks or edge chipping. The higher level of compressive stress in combination with decreased collision defects will improve the fatigue résistance and fracture toughness ofthe mining insert and consequently increase the lifetime ofthe insert. Further advantages ofthis method arethat insert geometries, such as those with a sharp bottom radius, which were previously prone to excessive damage to the corners and therefore low yields, can now be tumbled without causing edge damage. This opens the possibility to develop mining insert products with different geometries, which were previously not suitable for HET. The method also makes it possible to use cemented Carbide compositions that would hâve previously been too brittle for mining applications. The ability to introduce higher levels of compressive stress means that the toughness of the mining inserts is increased to an acceptable level and thus mining inserts having a higher hardness can be used which is bénéficiai for increasing the wear résistance of the mining inserts.

In one embodiment ofthe présent invention the mining insert is subjected to a surface hardening treatment at a température of between 150-250°C, preferably at a température of between 175-225°C.

In one embodiment ofthe présent invention the mining insert is subjected to a surface hardening treatment at a température of between 300-600°C, preferably at a température of between 350-550°C, more preferably of between 450-550°C.

The température is measured on the mining insert using any suitable method for measuring température. Preferably, an infrared température measurement device is used.

The effect of the surface hardening treatment at elevated températures is enhanced if the process is done in dry conditions. By dry conditions it is meant that no liquid is added to the process. Without being bound by this theory, it is thought that, if liquid is introduced to the process, it will keep the parts at room température. Further, the inclusion of the liquid will reduce the degree of the impact between the parts being HET-treated. Liquid prevents the internai friction and collision heat to increase the température in the collision points. If no liquid is used, then the température atthe collision points gets high resulting in a highertoughness ofthe material subjected to the collision points.

Alternatively, the tumbler could be pressurized to a pressure that prevents water from boilingso that it would be possible to conduct the high température HET-treated in wet conditions.

The HET process could be conducted in the presence or absence of media depending on the geometry and material composition of the mining inserts being tumbled. If it is decided to add media, the type and ratio of media to inserts is selected to suit the geometry and material composition ofthe mining inserts being HET-processed.

Optionally, ail or part ofthe heat is generated by friction between the inserts and any media added in the HET process.

In one embodiment the inserts can be heated in a separate step prior to the surface hardening 20 process step. Several methods can be used to create the elevated température ofthe mining insert, such as induction heating, résistance heating, hot air heating, flame heating, pre-heating on a hot surface, in an oven or furnace or using laser heating.

In one embodiment, the mining inserts are kept heated during the surface hardening process. For example, using an induction coil.

In one embodiment, ail or part ofthe heat is generated by the friction between the inserts and any media added in the HET- process. Advantageously, this removes débris and oxides, for example iron oxide, that are deposited on the insert surfaces from the inside ofthe process container. The second surface hardening process performed at room température could be performed in wet conditions, which will aid in removing dirt and dust from the mining inserts being treated which reduces health hazards.

In one embodiment, after the mining inserts hâve been subjected to the surface hardening process at an elevated température, the mining inserts are subjected to a second surface hardening process at room température.

In one embodiment, second surface hardening process is high energy tumbling.

In one embodiment, the high energy post-treatment is conducted by a bi-directional shaking process.

In one embodiment the main movement of the bi-directional shaking process is in the vertical direction and the minor movement is in the horizontal direction.

In one embodiment the bi-directional shaking process is conducted at 400-700 rpm for between 5-30 minutes. Preferably at between 500-600 rpm. Preferably for between 5-15 minutes.

EXAMPLES

Example 1-Samples

Table 1 shows the summary of the samples tested, including their compositions and surface hardening treatment. WC content is the balance in the example below.

Sample	Co Wt %	Cr Wt°/o	TiC Wt%	TiN Wt%	TaC Wt%	NbC Wt%	Sinter ed WC grain size (pm)	Bulk hardnes s HV20	Post sintering treatment
A (comparative)	6.0	-		-	-	-	1.91	1470	None
B (comparative)	6.0	-	-		-	-	1.91	1470	5 min HET
C (comparative)	6.0	-		-	-	-	1.91	. 1470	10 min HET
D (comparative)	7.6			-	1.20	0.32	1.08	1490	none
E (invention)	7.6		-	-	1.20	0.32	1.08	1490	5 min HET
F (invention)	7.6		-	-	1.20	0.32	1.08	1490	10 min HET

G (invention)	7.6		-	-	1.20	0.32	1.08	1490	HOT H ET 20 min
H (comparative)	7.2	-	1.90	0.40	2.90	0.49	1.53	1530	none
1 (invention)	7.2	-	1.90	0.40	2.90	0.49	1.53	1530	5 min HET
J (invention)	7.2	-	1.90	0.40	2.90	0.49	1.53	1530	10 min HET
K (comparative)	7.0	0.7			-	-	1.36	1480	none
L (comparative)	7.0	0.7	-	-	-	-	1.36	1480	5 min HET
M (comparative)	7.0	0.7	-	-	-	-	1.36	1480	10 min HET
N (comparative)	7.0	0.7	-	-	1.10	0.30	1.41	1541 HV3	none
0 (invention)	7.0	0.7	-	-	1.10	0.30	1.41	1541 HV3	5 min HET
P (comparative)	6.3	0.63	-	-	1.00	0.20	-	1556 HV3	none
Q (invention)	6.3	0.63	-	-	1.00	0.20	-	1556 HV3	5 min HET
R (comparative)	9.0	0.9	-		-	-	0.5	1740	10 min HET
S (comparative)	7	1.05	-	-	-		1.40	1535	5 min HET

Table 1: Summary of samples

AH cemented Carbide inserts were produced using a WC powder grain size measured as FSSS was before milling between 2 and 18 pm. The WC and Co powders were milled in a bail mill in wet conditions, using éthanol, with an addition of 2 wt% polyethylene glycol (PEG 3400) as organic binder (pressing agent) and cemented Carbide milling bodies. After milling, the mixture was spraydried in N2-atmosphere and then uniaxially pressed into GT7S100A mining inserts having a size of about 10 mm in outer diameter (OD) and about 16-20 mm in height with a weight of approximately 17g each with a spherical dôme (cutting edge) on the top. The samples were then sintered using Sinter-HIP in 55 bar Ar-pressure at 1410°C for 1 hour and then ground on the cylindrical part.

The samples that were HET were treated using a commercially available paint shaker of trademark Corob™ Evoshake500 with a maximum load of 40 kg and a maximum shaking frequency of 65 Hz (600 rpm). 20 inserts were placed in a plastic bucket height= 12 cm OD= 10 cm together with 3 kg 7 mm almost spherical cemented Carbide media of a hardness around 1600Vickers and 1 dl of water with an antioxidizing agent was added. The filling degree was about 40%. The bucket was shaken for 5 min using the 100% of the shaking capacity of the machine. Three softer ramping steps were also applied 30 s at 25%, 30 s at 50% and 30 s at 75% of the maximum shaking capacity. After 5 min at max frequency 10 inserts were removed (5 min HET) and then the same program was restarted for an additional 5 min at max frequency (10 min HET).

Some inserts were treated at 300 °C in a so called HOT HET treatment using the paint shaker of trademark Corob™ Simple Shake 90 with a maximum load of 40 kg and a maximum shaking frequency of 65 Hz (600 rpm). The hot shaking method was conducted at a frequency of 5 Hz. About 800 grams or 50 pièces of inserts and 3.75 kg Carbide media (7mm ballsj where placed in a cylindrical Steel container with inner diameter of 10.4 cm and inner height of 12.4 cm filling it up to 1/3 to 2/3 of the height, préférable around 1/2. The Steel cylinder with the mining insert were heated with media in a furnace to an elevated température of 300°C, the mining inserts were held at the target température for 120 minutes. After heating, the Steel cylinder was transferred straight into the paint shaker and immediately shook for 2 times 5 minutes using a program without ramping. The transfer time between the furnace until the shaker started was less than 20 seconds. The media (7 mm baIls) was made of a cemented Carbide grade having a sintered HV20 of about 1600. The shaking was performed in dry conditions, i.e. no water was added to the shaking and the samples were heated to 300°C. For ail ru ns the inserts were left to cool down to room température before they were subjected to a final wet shaking operation for 2 x 5 min using plastic buckets as in previous description. None of the inventive samples had any edge damage after the post treatment process.

Example 2 - Insert Compression test

The insert compression test method involves compressing a drill bit insert between two plane-parallel 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 Hard metals - 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 déviation of 0.5 pm / mm. The tested inserts were loaded at a constant rate of crosshead displacement equal to 0.6 mm / min until failure, while recording the load5 displacement curve. The compliance of the test rig and test fixture was subtracted from the measured load-displacement curve before test évaluation. Three inserts were tested 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. Subséquent inspection of tested inserts confirmed that this in ail cases this coincided with the occurrence of a macroscopically visible crack. The material strength was characterized by means of the total absorbed deformation energy until fracture. The summary fracture energy (Ec), in Joules (J), required to crush the samples is shown in table 2 below:

Sample	Fracture energy Ec (J)
A (comparative)	3.0
B (comparative)	8.0
C (comparative)	8.6
D (comparative)	5.0
E (invention)	8.0
F (invention)	14.5
H (comparative)	8.2
1 (invention)	16.5
J (invention)	18.3
K (comparative)	5.3
L (comparative)	14.3
M (comparative)	16.2
N (comparative)	7.2
O (invention)	15.2
S (comparative)	12.0

Table 2: Fracture energy (J) required to crush the samples

Example 3 - Hardness measurements

The hardness of the cemented Carbide inserts is measured using Vickers hardness 3 kg at both 0.3 mm and 1.0 mm from the surface of the inserts and also in the bulk of the inserts. The hardness measurements are an average of 30 indentations. Table 3 shows a summary of the hardness measurements and table 4 shows a summary of the delta HV3 hardness values.

Run	HV3 at the surface of the 0.3 mm from the surface of the insert	HV3 at a depth of 1 mm from the surface ofthe insert	HV3 bulk hardness measurement
E (invention)	1553.2	1526.4	1508.4
G (invention)	1559.4	1529.7	1512.9
1 (invention)	1574.5	1564.3	1548.8
O (invention)	1592.5	157Ï.0	1551.2
Q. (invention)	1637.9	1614.4	1608.6

Table 3: Hardness measurements

Run	AHV3 (HV3 0.3 mm from the surface ofthe insert-HV3 bulk)	AHV3 (HV3 1 mm from the surface ofthe insertHV3 in the bulk)	AHV3 (HV3 0.3 mm from the surface- HV3 1 mm from the surface)
E (invention)	44.8	18.0	26.8
G (invention)	46.5	16.8	29.7
1 (invention)	25.7	15.5	10.2
O (invention)	41.3	19.8	21.5
Q (invention)	29.3	5.8	23.5

Table 4: Delta HV3 hardness values

Example 4 - Wear test

The samples tested in an abrasion wear test, wherein the sample tips are worn against a rotating granité log counter surface in a turning operation. The test parameters used were as follows: 100 N load applied to each insert, granité 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 différence in composition in the rock hâve 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 différence in diameter and length ofthe part ofthe rockthat 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 three samples 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 5.

Sample	Wear rate mm3/m sliding
B (comparative)	8.79xl04
E (invention)	3.86X10'4
1 (invention)	4.97X10’4
O (invention)	2.96X104
Q (invention)	3.03Χ10’4

Table 4: Wear rates

Example 5 - Fracture Toughness

Fracture toughness measurements were made according to ISO/DIS 28079 using 30 kg load on 10 mm in diameter spherical domed samples that had been subjected to a 5 min HET treatment. The samples were sectioned in half through the dôme area, mounted in bakélite, polished with diamond paste and the crack length and diameter of 10 indentations 0.5 mm below the surface evenly distributed around the insert and at least 0.75 mm apart. The diameter of the indentations and the length of the cracks were measured using light optical microscope and 200 X magnification. The K1C of each indentation was calculated using Shetty's formula K1C= A *square root(H)/(P/Sum of L), where H is the hardness in N/mm², P is the applied load in N, Sum of L is the sum of crack length in mm, A is a constant with value of 0.0028 and K1C is given in MPa*m⁰·⁵. The average K1C value calculated and reported as KlC_surface and the crack length and diameter of 5 indentations in the middle of the 10 mm inserts were measured and the average calculated and reported as KlC_bulk. The K1C measurement and Delta KIC-values are shown in table 5.

Sample	Average K1C _surface (MPa*m05)	Average K1C_ bulk (MPa*m0·5)	Delta K1C (MPa*m°·5)
E (invention)	16.3	11.8	4.5
1 (invention)	13.7	10.9	2.8
O (invention)	13.3	10.7	2.6
Q (invention)	14.5	11.4	3.1

Table 5: K1C measurements and Delta K1C calculations

For an untreated sample delta K1C is zéro or close to zéro or even a slightly négative value.

Example 6 - Field trial 1

Table 6 shows the results from a wet underground top hammer application test. Inserts with diameter 13 mm diameter 11 mm and with spherical shaped dôme geometries were tested. The inserts were manufactured according to the description in example 1. The outer diameter of ail inserts were ground. The HET-treatments of the inserts were performed according to the description in example 1 and the inserts were not pre-heated.

The different grades and treatments were mounted in Steel bits having eight 13 mm inserts on the periphery/gauge and three 11 mm inserts on the front. The bits were tested in an underground gold mine in the north of Sweden in a top hammer application. The rock conditions were classified as very hard and very abrasive. Before drilling started the maximum diameter of each bit was measured to be around 56 mm. Each bit was drilled until the inserts were too blunt and the pénétration rate went down. The maximum diameter of the bit was then measured again and the différence in diameter was evaluated as wearfrom drilling. Another important factor in determining the success of the inserts is the number of insert breakage(s). Both wear and breakage results are shown in table 6.

	No of holes	Total drilled meter (DM)	Diameter loss (mm)	Average diameter wearfrom drilling (mm/m)	Number of insert chipped or broken at the periphery/gauge (8 in total)	Number of inserts chipped at the front (3 in total)
F (invention)	4	18	0.70	0.039	0	0
DP65™ (comparative)	4	18	0.70	0.039	1	0
M (comparative)	4	16	0.75	0.047	0	0
R (comparative)	1	3.8	0.10	0.026	1	0

	Outside invention R*	>2	6.5	n/a	n/a	8	3
Table 6. Results	rom the percussive drilling field test using spherica	inserts

*continiied drilling with the same bit as in the row above

The results show clearly that the inventive samples hâve both has a good wear résistance and no insert chipping or breakages, which would hâve normally been expected for a gamma phase containing grade in a percussive drilling operation. By combining a gamma phase containing grade with a HET treatment the full potential of the material can be utilized, and the performance is better than the State of the art grade DP65™ in terms of résistance towards chipping/insert failure and still having the same high wear résistance. That the site is challenging to drill in is also seen since the sub-micron (WC) and chromium-containing grade R failed completely after only 6.3 m in operation and that the prior art chromium containing grade M wears more than the gamma phase containing grade of the présent invention.

Example 7 - Field trial 2

Table 7 shows results from a wet underground top hammer application test inserts with diameter 8 mm diameter and 10 mm and with semi-ballisticaI shaped dôme geometries. The inserts were manufactured according to the description in example 1. The outer diameter of ail inserts was ground. The HET-treatments of the inserts were performed according to the description in example 1 and the invention samples was HOTHET-treated according to the description in example 1.

The different grades and treatments were mounted in Steel bits having six 10 mm inserts on the periphery/gauge and three 8 mm inserts on the front. Four bits/variant were produced and tested in an underground construction site in Stockholm in Sweden in a top hammer application. The rock conditions were classified as hard and abrasive. Before starting the drilling, the maximum diameter of each bit was measured and to be around 51 mm. The drilling was started, and each bit was used until the inserts were too blunt rate went down. The meters drilled before the pénétration went down and the maximum diameter of the bit was then measured, and the différence in diameter divided by drilled meters was calculated, this provides a good measure on the wear résistance of the grade. In this test no insert failures were observed.

	No of bits	Total drilled meter (DM)	Average diameter wear from drilling (mm/m)	Numberof insert chipped or broken
G (invention)	4	354	0.088	0
A (comparative)	4	221	0.094	0
Table 7. Results	rom the percussive drilling field test using semi-ballistica	inserts

The results show clearly that the gamma phase containing grade G (invention) has a higher wear résistance and can drill significantly longer before it needs to be re-ground than the current benchmark percussive grade A. Importantly, no insert breakages occurred for the gamma phase containing HOTHET treated inserts.

Example 8 - Field trial 3

Table 8 shows the results from a dry (air cooled) surface top hammer application test. Inserts with diameter 7 mm diameter with ballistic shaped dôme geometries were tested. The inserts were manufactured according to the description in example 1. The outer diameter of ail inserts was ground. The HET-treatments of the inserts were performed according to the description in example 1 and the inserts were not pre-heated.

The different grades and treatments were mounted in Steel bits having six 7 mm inserts on the periphery/gauge. The two front inserts in this test does not contribute to the diameter wear and for ail bits they were in the reference grade XT49 (sample B). The bits were tested in a stone quarry in the south west of Sweden in a top hammer application. The rock conditions were classified as homogenous but very hard and very abrasive with a quartz content of about 50% and during drilling significantly amount of heat was generated. A rig with two hammers was used simultaneously which allowed a good comparison between the variants. Before drilling started the maximum diameter of each bit was measured on three positions (Dl, D2, D3) and was around 33 mm. Each bit was drilled until the inserts got a significant wear but only two were drilled to end of life (either loss of

pénétration rate or if insert failures occurred). Figure 2 shows a top hammer bit with ballistic inserts with the diameter measuring points indicated.

The maximum diameter of the bit was then measured again on ail three (if no failures) positions and the différence in diameter was evaluated as wear from drilling. Another important factor in determining the success of the inserts is the number of insert breakage(s). Both wear and breakage results are shown in table 8.

	No of holes	Total drilled meter (DM)	Diameter loss (mm)	Average diameter wear from drilling (mm/m)	Number of insert chipped or broken at the periphery/gauge (6 in total)
0 (invention)	~90	137.2a	0.655	0.0048	0
B (comparative)	~90	139.2b	0.992	0.0071	0
L (comparative)	~60	95.6	0.560	0.0059	0
S (comparative)	~110	168e	1.03	0.0061	0

Table 8. Results from the percussive drilling field test using ballistic inserts ^a'^b Run simultaneously one of the left hammers and one of the right hammers.

^x Run until end of life

The results show clearly that the inventive samples hâve both good wear résistance and no insert chipping or breakages, which would hâve normally been expected for a gamma phase containing grade in a percussive drilling operation and the wear résistance of a gamma phase (y)+Cr grade is even better than two high Cr-containing grades having the same binder content and similar room température hardness (HV20). By combining a gamma phase (y) + Cr containing grade with a

HET treatment the full potential of the material can be utilized, and the wear résistance is significantly betterthan the State of the art grade XT49™, despite that XT49 has a lower Co-content that would be bénéficiai in dry (air cooled) drilling since the heat generated is significantly higher than in a water cooled percussive drilling.

Example 9 - Field trial 4

Table 9 shows the results from a dry (air cooled) surface top hammer application test. Inserts with diameter 7 mm diameter with ballistic shaped dôme geometries were tested. The inserts were manufactured according to the description in example 1 and the inventive sample, I, had a gamma phase free zone of about 20 microns after sintering, which will wear off quickly during drilling or be ground away during the outer diameter grounding. The outer diameter of ail inserts was ground. The HET-treatments of the inserts were performed according to the description in example 1 and the inserts were not pre-heated.

The different grades and treatments were mounted in Steel bits having six 7 mm inserts on the periphery/gauge. The two front inserts in this test does not contribute to the diameter wear and for ail bits they were in the reference grade XT49 (sample B). The bits were tested in a stone quarry in the south west of Sweden in a top hammer application. The rock conditions were classified as homogenous but very hard and very abrasive with a quartz content of about 50% and during drilling significantly amount of heat was generated. A rig with two hammers was used simultaneously which allowed a good comparison between the variants. Before drilling started the maximum diameter of each bit was measured on three positions (Dl, D2, D3) and was around 33 mm. Each bit was drilled until the inserts got a significant wear. The maximum diameter of the bit was then measured again on ail three (if no failures) positions and the différence in diameter was evaluated as wear from drilling. Another important factor in determining the success of the inserts is the number of insert breakage(s). Both wear and breakage results are shown in table 9.

	No of	Total	Diameter	Average	Number of
	holes	drilled	loss (mm)	diameter	insert chipped
		meter		wear from	or broken at the
		(DM)		drilling	periphery/gauge
				(mm/m)	(6 in total)
1 (invention)	~30	51a	0.42	0.0082	0

B (comparative)	~30	51b	0.50	0.0099	0

Table 9. Results from the percussive drilling field test using ballistic inserts ^a-^b Run simultaneously one of the left hammers and one of the right hammers.

The results show that the inventive sample I, despite having a quite high gamma phase content also including Ti and nitrogen ((Ti, Ta, Nb, W)(C,N)) had enough toughness & strength from 5 the HET-treatment to be used in a percussive drilling application in a very sensitive ballistic insert geometry. Sample I also showed an improved wear résistance compared to the State of the art grade XT49™ (sample B), despite that XT49 has a lower Co-content that would be bénéficiai in dry (air cooled) drilling since the heat generated is significantly higher than in a water cooled percussive drilling.

Claims (13)

1. A sintered cemented Carbide insert for mining or cutting applications comprising: a mean WC grain size of between 0.8 -18 pm;

a binder phase in a weight between 4-18 wt%

5 gamma phase with the cubic gamma phase precursors in a weight of between 0.8 -10 wt%;

any unavoidable impurities and a balance of WC; and wherein the différence between the hardness at any point 0.3 mm from the surface of the insert and the hardness of the bulk is at least 25 HV3 when measured according to ISO EN6507 3:2005.

2. The insert according to claim 1, wherein the binder phase comprises at least 80 wt% of one or more of cobalt, nickel, iron or a combination thereof.

3. The insert according to claim 1 or claim 2 wherein the cubic gamma phase precursors is

15 tantalum Carbide or niobium Carbide or a mixture thereof.

4. The insert according to any of the previous claims wherein the cemented Carbide also comprises Cr in such an amount that the mass ratio Cr/Co in the bulk is 0.04-0.19.

20

5. The insert according to any of the previous claims wherein the cemented Carbide comprises

M7C3 carbides and / or M23C6 carbides and wherein the ratio vol% (M7C3 carbides and / or M23C6 Carbide) / vol% Co is between 0.01 to 0.5.

6. The insert according to any of the previous claims wherein the delta K1C fracture toughness

25 at 0.5 mm below the surface compared to the K1C in the bulk is at least 1.5 MPa*m°⁵ higher measured according to ISO/DIS 28079.

7. A rock drill bit body comprising one or more mounted cemented Carbide inserts according to any one of claims 1-6.

8. A method of producing a cemented Carbide insert according to any of claims 1-6, comprising the steps of:

. a) providing a green cemented carbide insert comprising between 0.8-10 wt% cubic carbides and or carbonitrides and or nitrides, between 4-18 wt% binder, any unavoidable impurities and a balance of WC hard phase;

b) sintering the green carbide mining insert to form a sintered cemented carbide insert;

c) subjecting the sintered cemented carbide insert to a high energy post-treatment process.

9. The method according to claim 8 wherein the high energy post-treatment is high energy tumbling.

10. The method according to claim 8 or 9, wherein the high energy post- treatment is conducted at an elevated température of or above 100°C.

11. The method according to claim 8, wherein the high energy post-treatment is conducted by a bi-directional shaking process.

12. The method according to claim 8 and 11 wherein the main movement is in the vertical direction and the minor movement is in the horizontal direction.

13. The method according to claim 8 and claim 11 wherein the treatment is conducted at between 400-700 rpm for 5-30 min.