Manganese steel reinforced with titanium boride and titanium carbide, and method of manufacturing the same

Abstract

A composite material comprising: at least one reinforcing zone comprising Titanium carbide (TiC) and Titanium boride (TiB2) and a manganese steel matrix; a manganese steel zone that surrounds each of the reinforcing zones; and an interface layer positioned between each of the reinforcing zones and the manganese steel zone characterized in that: the average grain size of both the TiC and the TiB2 particles in each of the reinforcing zone(s) is between 6-20 µm.

Description

TECHNICAL FIELD

[0001] The present invention relates to a composite material based on reinforced manganese steel and a method for making the same.BACKGROUND

[0002] A particular category of wear resistant steels is typically referred to as manganese steel or Hatfield steel. These materials are suitable for applications where a high toughness and a moderate abrasion resistance are required including for example use as wear parts for crushers that are subjected to strong abrasion and dynamic surface pressures due to the rock crushing action. Abrasion results when the rock material contacts the wear part and strips-off material from the wear part surface. Additionally, the surface of the wear part is subjected to significantly high surface pressures that cause wear part fatigue and breakage.

[0003] Manganese or Hadfield steel is typically characterised by having an amount of manganese, usually above 11% by weight. However, the problem with manganese steel is that it is typically too ductile for wear parts in modern crushers that are subject to extreme operating conditions, meaning the at the lifetime of the wear parts is reduced and the maintenance costs are increased. Therefore, the problem to be solved is to provide a manganese steel with enhanced wear resistance.

[0004] A known solution is to reinforce at least part of the manganese steel with particles having an increased hardness. WO20200222662 discloses a composite material, however the problem with this material is that is not provide an optimal balance between wear resistance and impact resistance and an even more significant problem is that there is poor bonding between the reinforcing particle and the manganese steel matrix and poor bonding between reinforced and non-reinforced zones, which leads to reduced wear resistance and premature failure of the wear parts. Therefore, the problem to be solved to provide a composite material that can be used for wear parts having an optimal balance between wear resistance and impact resistance, wherein there is improved bonding between the reinforcing particles and the manganese matrix and the bonding between the reinforced and non-reinforced zones in order to reduce defects and cracking that would lead to premature failure of the wear parts.

[0005] Yunhong Liang et al.: "Fabrication of bionic composite material using self propagating hightemperature synthesis in the Cu-Ti-B4C system during steel casting", Journal of Asian Ceramic Societies, vol. I , no. 4, 13 November 2013 (2013-11 -13), pages 339-345, XP093161134, ISSN: 21 87-0764, DOI: 10.1 01 6 / j.jascer.201 3.10.004 and Yunhong Liang et al.: "Effect of Cu content in Cu-Ti-B4C system on fabricating TiC / TiB2 particulates locally reinforced steel matrix composites", Materials and Design, vol. 40, 23 March 2012 (2012-03-23), pages 64-69, XP093161 136, ISSN: 0261-3069, DOI: 10.1 016 / j.matdes.2012.03.023 both disclose reinforced steel.DEFINITIONS

[0006] A "catalysis" is a metal powder or mixture of metal powders which during the reaction in the self-propagating high temperature synthesis (SHS) undergo melting and form a matrix of the composite zone. The fundamental role of catalysis is to reduce the amount of dissipated energy in the SHS process.

[0007] A "compact" is a densified powder composition.SUMMARY OF INVENTION

[0008] It is an objective of this invention to provide a novel and improved composite material for wear parts. The objective is achieved by providing a composite material according to claim 1.

[0009] Advantageously, this produces a composite material that has both increased wear resistance and structural integrity. Therefore, when the material is used on areas of wear parts that are highly exposed to wear the lifetime of the parts is increased. If the average grain size of the TiB 2 and TiC grains is too large, then the composite material will be too brittle. If the average grain size of the TiC and TiB 2 grains in too small the wear resistance will be reduced. The combination of the TiB 2 with the TiC is particularly advantageous because it provides higher hardness in the reinforcing zones leading to highly wear resistant material. Further, the combination of the rectangular shaped TiB 2 with the round shaped TiC particles is particularly advantageous in providing a solid, robust reinforcing zone that is able to stop crack propagation. Hence, it enhances the toughness mechanism of the composite. Further, this composition results in good bonding between the manganese steel zone and each of the reinforcing zones and consequently the structural integrity of the composite material is improved, meaning that the lifetime of the wear parts that the materials is used in is increased. Furthermore, compared to using WC in the reinforcing there are no issues with eta-phase formation and compared to using NbC in the reinforcing zone using TiB 2 and TiC is cheaper.

[0010] In an example embodiment, the average grain size of TiB 2 particles in each of the reinforcing zone(s) is between 6-20 µm, preferably 8-19 µm, more preferably between 12-15 µm. Advantageously, this combination results in high mechanical and wear resistance properties, for example if the grain size is too high then the material will become more brittle and if the grain size is too high then the material will become more brittle and if the grain size is too low then the toughness is reduced. In other words, it provides an optimal balance between hardness and toughness.

[0011] In an example embodiment, the average grain size of TiC particles in each of the reinforcing zone(s) is between 6-10 µm, preferably 7-10 µm, more preferably between 8-9-µm. Advantageously, this combination results in high mechanical and wear resistance properties, for example if the grain size is too high then the material will become more brittle and if the grain size is too low then the toughness is reduced. In other words, it provides an optimal balance between hardness and toughness.

[0012] In the present invention, the composite material comprises a total of between 40-90 wt% of TiB 2 and TiC in each of the reinforcing zones. Preferably between 60-90 wt%, even more preferably between 70-90 wt%. Advantageously, this provides the optimal balance between wear resistance and impact resistance. If the wt% of TiB 2 and TiC in each of the reinforcing zones in too high the composite material will be too brittle and more prone to failure. If the wt% of the TiB 2 and TiC in each of the reinforcing zones is too low, then composite material will have low hardness and therefore it will not have sufficient wear resistance.

[0013] In an example embodiment, the wt% of TiB 2 in each of the reinforcing zones 4 is between 6-20, preferably between 8-19, more preferably between 12-15.

[0014] In an example embodiment, the wt% of TiC in each of the reinforcing zones 4 is between 1-10, preferably between 5-10, more preferably between 8-9.

[0015] In the present invention, the composition of the manganese steel in manganese steel zone has the chemical composition by weight of: carbon: 0.5 to 2.0%; manganese: 11 to 22%; silicon: 0.2 to 1.0%; chromium: 1 to 2%; nickel: up to 0.6%; molybdenum: up to 0.5%; and a balance of Iron. Advantageously, this steel composition is characterized by the addition of micro-alloying elements such as chromium, nickel and molybdenum in good amounts which induce high yield strength and high hardness resulting in increase in wear resistance of manganese steel.

[0016] In the present invention, the Vickers hardness of the reinforcing zones is between 700-1700 HV1 and the hardness of the manganese steel zone is between 200 - 320 HV1 before work hardening. Advantageously, the increased hardness in the reinforcing zones leads to a more wear resistant material.

[0017] In the present invention, the interface layer is free of defects. Advantageously, the absence of any defects in the interface layer means that there is good bonding between the manganese steel zone and each of the reinforcing zones and consequently the structural integrity of the composite material is improved, meaning that the lifetime of the wear parts that the materials is used in is increased. Further, the absence of the presence of any pores is an indication that the composition has the ability to absorb the excess heat and gases from the SHS process and so therefore signifies that the synthesis reaction has been successful.

[0018] In the present invention, the wettability between the TiB 2 and TiC particles and the manganese steel in the reinforcing zone (s) is >99%, preferably >99.5%, even more preferably >99.9%. Advantageously, good wettability induces an excellent bonding between the composite zone and manganese steel preventing defects such as pores and cracks to form and consequently the wear resistance increases.

[0019] In an example embodiment, the each of the reinforcing zones has a volume of between 30-75 cm 3< . Advantageously, this size provides the optimal balance between wear resistance and impact resistance.

[0020] In an example embodiment, at least 95 % of the TiB 2 and TiC particles in the reinforcing zones have a rectangular shape and round shapes respectively. Advantageously, the mixture of rectangular shape and round shapes of TiB 2 and TiC particles respectively will contribute to crack deflection and stop crack propagation increasing the ductility and high wear resistance of the reinforcing zone.

[0021] In an example embodiment, the distance between two neighbouring reinforcing zones is between 1-5 mm, preferably between 1-3 mm, more preferably between 1-2 mm. Advantageously, this provides the optimal balance between wear resistance and impact resistance. If the reinforcing zones are spaced too far apart then the wear resistance will not be high enough. If the reinforcing zones are spaced to close together then the impact resistance will not be high enough.

[0022] Another aspect of the present invention relates to a wear part comprising the composite material as described hereinbefore or hereinafter. Advantageously, the presence of the reinforcing zones within the manganese zone will improve the wear resistance and therefore the lifetime of the wear parts which in turn increases profitability.

[0023] Another aspect of the present invention relates to a method of producing the composite material according to claim 6. The powders are preferably compacted at a pressure between 575 and 625 MPa.

[0024] Advantageously, if this pressing pressure is used the compacts have a low density which enables the manganese steel to more easily infiltrate between the TiB 2 and TiC particles and consequently results in improved bonding between the TiB 2 and TiC particles and the manganese steel. Further it avoids the creation of defects which would lead to premature failure of the wear parts that the composite material is used in.

[0025] Preferably, the catalysis is selected from Fe, Mn, Ni, Mo, Cr, W, Al, or a mixture thereof.

[0026] Advantageously, the addition of a catalysis in a specific amount will contribute to a strong stabilization to austenite phase within the microstructure in addition to good mechanical properties and high wear resistance. The catalysis addition will also act as a grain growth inhibitor which results in a fine microstructure.BRIEF DECRSIPTION OF DRAWINGS

[0027] Figure 1: Shows a line drawing of the composition of the composite material. Figure 2: Shows an SEM image taken of the reinforced zone with low magnification on the left and high magnification on the right. Figure 3: Shows an SEM image taken of the interface layer with low magnification on the left and high magnification on the right. Figure 4: Shows an SEM image of the composite material. Figure 5: Shows a perspective drawing of a wear part. Figure 6: Shows an SEM image of comparative sample B having pores in the interface layer. Figure 7: Shows an SEM image of comparative sample F having pores in the reinforced zone. DETAILED DESCRIPTION

[0028] Figure 1 shows a composite material 2 comprising at least one reinforcing zone 4 comprising TiB 2 and TiC particles; and a manganese steel matrix; a manganese steel zone 6 that surrounds each of the reinforcing zones 4; and an interface layer 8 positioned between each of the reinforcing zones 4 and the manganese steel zone 6. In each of the reinforcing zones, the TiB 2 and TiC particles act to reinforce the manganese steel matrix.

[0029] The average grain size of the TiB 2 and TiC particles in each of the reinforcing zone(s) (4) is between 6-20 µm, preferably between 8-18 µm, most preferably between 10-15µm.

[0030] In an example embodiment, the average grain size of the TiB 2 particles in each of the reinforcing zone(s) (4) is between 6-20 µm, preferably between 8-19 µm, most preferably between 12-15µm.

[0031] In an example embodiment, the average grain size of the TiC particles in each of the reinforcing zone(s) (4) is between 6-10 µm, preferably between 7-10 µm, most preferably between 8-9-µm. The average grain size of the TiB 2 and TiC particles is measured by Scanning Electron Microscopy (SEM) analysis where several and different areas from the samples were analysed and particle sizes were measured. The magnification was selected such that there were at least 50 grains in the image to be measured Then, the average particle size was calculated.

[0032] Each interface layer 8 comprises TiB 2 and TiC particles and manganese steel and can be distinguished from the reinforcing zones 4 as the shape and size of the TiB 2 and TiC particles are different. The interface layer(s) 8 can be distinguished from the reinforcing zone(s) 4 can either: comparing the geometry and / or comparing the average grain size. If the geometry is being compared, the reinforcing zone(s) 4 comprise >90% TiB 2 and TiC particles having a rectangular shape and round shapes respectively whereas the interface layer(s) 8 comprise <5% a rectangular shape and round shapes respectively. A TiB 2 is considered to have a rectangular geometry if the particles have 4 sharp edges and TiC particles are considered to have round geometry if the grains have no sharp edges. If the grain size is being compared the average TiB 2 and TiC particles size of in the interface layer(s) 8 is at least 5% less than the average TiB 2 and TiC particles size on the reinforcing zone(s) 4.

[0033] Figure 2 shows a Scanning Electron microscope image using MIRA3 TESCAN equipment. A secondary electron detector (SE) with a high voltage of 15 KV and a working distance of 9 mm configuration were used. SEM image of the TiB 2 and TiC particles in the reinforcing zone 4. Figure 3 shows an SEM image of the TiB 2 and TiC particles in the interface layer 8. The different TiB 2 and TiC particles geometry and size can clearly be seen when comparing these two figures.

[0034] In the present invention, the total wt% of TiB 2 and TiC particles in each of the reinforcing zones 4 is between 40-90 %, preferably between 60-90 %, more preferably between 70-90%,

[0035] In an example embodiment the wt% of TiB 2 in each of the reinforcing zones 4 is between 6-20, preferably between 8-19, more preferably between 12-5.

[0036] In an example embodiment the wt% of TiC in each of the reinforcing zones 4 is between 6-10, preferably between 7-10, more preferably between 8-9. In the present invention, the composition of the manganese steel in manganese steel zone 6 has the chemical composition by weight of: carbon: 0.5 to 2.0%; manganese: 11 to 22%; silicon: 0.2 to 1.0%; chromium: 1 to 2%; nickel: up to 0.6%, molybdenum: up to 0.5% and a balance of Fe.

[0037] In an example embodiment, the chemical composition of the manganese steel in each of the reinforcing zones 4 has the chemical composition by weight of: 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % P.

[0038] In the present invention, the hardness of the reinforcing zones 4 is between 700-1700HV1, preferably between 750-900 HV1. The hardness of the manganese steel zone 6 is between 200 - 320 HV1.

[0039] Hardness is measured using Vickers hardness mapping on polished samples using a 1 kg load and a holding time of 15 seconds. A micro-hardness tester, Matsuzawa, model MXT was used. Hardness measurement profiles are performed starting from the non-reinforce zone, moving to the interface layer and then to the reinforced zone.

[0040] In the present invention, the interface layer 8 is free of defects. Defects are considered to be cracks or pores.

[0041] In the present invention, the wettability between the TiB 2 and TiC particles and the manganese steel in the reinforcing zones 4 is >99%, preferably >99.5%, more preferably >99.9%, most preferably 100%. Wettability is measured by a Scanning Electron Microscope representing the contact area and the bonding between the TiB 2 and TiC particles in each of the reinforcing zones 4 and the manganese steel.

[0042] In an example embodiment each of the reinforcing zones 4 has a volume of between 30-75 cm 3< . For example, but not limited to the reinforcing zone(s) 4 could have a length of between 100-200 mm, preferably between 100-150 mm, a width of between 20-30 mm, preferably between 20-25 mm and a thickness between 15-30 mm, preferably between 15-25 mm.

[0043] In an example embodiment >90%, preferably >95%, preferably >98%, more preferably >99% of the TiB 2 and TiC particles in each of the reinforcing zones 4 have a have a rectangular shape and round shape respectively. Preferably, the TiB 2 and TiC particles are uniformly distributed in the manganese steel in the reinforcing zone(s). To calculate the percentage of the TiB 2 grains having a rectangular and the percentage TiC grains having a round shape a SEM fracture surface image is taken, then the number of grains having the rectangular geometry, the number of grains having a round geometry and the total number of grains is counted. The percentage of rectangular grains can then by calculated from "(number of grains having rectangular geometry / total number of grains) x 100". The percentage of round grains can then by calculated from "(number of grains having round geometry / total number of grains) x 100". The magnification of the SEM fracture surface image should be set such that the total number of grains in the image is at least 50 for good statistics.

[0044] In an example embodiment, there are a plurality of reinforcing zones 4 with its interface zone 8 and the distance between two neighbouring reinforcing zones 4 with its interface layer 8 is between 1-5 mm, preferably between 1-3 mm, more preferably between 1-2 mm.

[0045] Figure 5 shows an example of a wear part 14 comprising the composite material 2 as described hereinabove or hereinafter. For example, the wear part 2 could be, but not limited to, a cone crusher or a stationary jaw crusher or a mobile jaw crusher that is configured to crush material or other material / rock processing unit. The reinforcing zone(s) 4 are positions on the wear parts 14 in the locations that are most subjected to high wear, for example on a crushing zone 18 of a cone crusher 16.

[0046] The method for producing the composite material 2 as described hereinbefore or hereinafter comprising the steps of: a) mixing together 40-80 wt% Titanium (Ti), 20-60 wt% Boron carbide (B 4 C) and 0-30 wt % catalysis powders; b) compacting the mixed powders together to form at least one compact using a compacting with a pressure 550 - 650 MPa, preferably between 500-650 MPa, more preferably between 550-650 MPa; c) positioning and optionally fixing at least one compact into the interior of a mold; d) pouring molten casting manganese steel into the mold to surround the at least one compact to initiate a self-propagating high temperature synthesis (SHS) reaction to produce a cast; e) heat treating the cast; and then f) quenching the cast.

[0047] Preferably, the cast is treated at a temperature of between 1400-1500°C, the cast is quenched using water. Preferably, the catalysis is selected from Fe, Co, Ni, Mo, Cr, W, Al, or a mixture thereof. Carbon could be added in the form of graphite, amorphous graphite, a carbonaceous material or mixtures thereof. The compacts could for example be held in place using me a metallic fixation system to hold them in place during casting.EXAMPLES Example 1- Samples

[0048] Sample A is a comparative sample of non-reinforced manganese steel having the composition 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % P.

[0049] Samples B-H are samples of composite materials produced by mixing together powders of titanium, boron carbide, and a catalysis powder. The compacting the mixed powders to form compacts which were then positioned in a mold and then molten manganese steel having a composition of 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % was poured into the mold to surround the compacts which initiated a SHS reaction, the cast was then heat treated at a temperature of 1450 °C and then quenching with water. Table 1 shows a summary of the reinforced samples: Table 1: Summary of samplesSampleCompacting pressure used (MPa)Average TiB 2 and TiC particles size in reinforced zone (µm)TiB 2 and TiC content in reinforced zone (wt%)Wettability (%)A (comparative)----B (comparative)600257060C (inventive)6001585100D (inventive)6001290100E (inventive)6001090100F ((inventive)6001580100G (comparative)50055060H (comparative)5001.54570

[0050] It can be seen if the compacting pressure is not high enough then the wettability is reduced.Example 2 - Hardness

[0051] Vickers hardness was measured by a micro-hardness tester, Matsuzawa, model MXT using 1 kgf and a holding time of 15 seconds. Hardness measurement profiles are performed starting from the non-reinforce zone, moving to the interface layer and then to the reinforced zone.

[0052] The hardness measurement results are shown in Table 2 below: Table 2: Hardness measurementSampleHardness in manganese steel zone (HV1)Hardness in Interface layerHardness in reinforced zoneA (comparative)250--B (comparative)280300700C (inventive)300401922D (inventive)320427875E (inventive)320463745F (inventive)310440821G-(comparative)280350710H (comparative)290300725

[0053] It can be seen that the inventive samples have an increased hardness in reinforced zones compared to the comparative samples.Example 3 - Wear test

[0054] Wear was tested using a standard wear test using a lab jaw crusher. The wear test procedure consists on using fixed amount of rocks from 1 Ton up to 4 Ton of rocks. Four plates, two stationary and two moving, were placed inside the jaw crusher. Reference plates were also mounted in both positions. The reference plates are based on Weldox type of material.

[0055] The calculation of wear is based on the difference in volume loss of the test plates compared to the reference plates. All plates were weighed before and after wear test. Then volume loss is calculated using the density of 7.85 g / cm 3< and 7.6 g / cm 3< for the reference and test plates respectively. The total wear ratio (WR) is calculated according to ASTM G81-97a(2013).

[0056] The wear test results are shown in table 3 below: Table 3: Wear test resultsSampleWear ratio rateA0.35B0.20

[0057] It can be seen that the wear rate for the inventive sample is lower than the comparative benchmark sample.Example 4 - Defects

[0058] Table 4: DefectsSampleDefects in the reinforced zoneDefects in the interface layerA (comparative)-B (comparative)crackscracksC (inventive)nonenoneD (inventive)nonenoneE (inventive)nonenoneF (comparative)poresPores and cracksG (inventive)nonenoneH (inventive)nonenone

[0059] Defects were assessed by using Scanning Electron microscopy analysis where cracks and pores are identified. It can be seen that the inventive samples are free of defects. It can be seen that the comparative sample contains pores and cracks. Figure 6 shows the pores in the interface layer in sample B and figure 7 shows pores in the reinforced zone in sample F, whereas figure 4 shows the absence of any pores from sample C.

Examples

example 1 -

Example 1- Samples

[0048]Sample A is a comparative sample of non-reinforced manganese steel having the composition 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % P.

[0049]Samples B-H are samples of composite materials produced by mixing together powders of titanium, boron carbide, and a catalysis powder. The compacting the mixed powders to form compacts which were then positioned in a mold and then molten manganese steel having a composition of 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % was poured into the mold to surround the compacts which initiated a SHS reaction, the cast was then heat treated at a temperature of 1450 °C and then quenching with water. Table 1 shows a summary of the reinforced samples:

Table 1: Summary of samples

SampleCompacting pressure used (MPa)Average TiB 2 and TiC particles size in reinforced zone (µm)TiB 2 and TiC content in reinforced zone (wt%)Wettability (%)

A (comparative)----

B (comparative)600257060

C (invent...

example 2-hardness

Example 2 - Hardness

[0051]Vickers hardness was measured by a micro-hardness tester, Matsuzawa, model MXT using 1 kgf and a holding time of 15 seconds. Hardness measurement profiles are performed starting from the non-reinforce zone, moving to the interface layer and then to the reinforced zone.

[0052]The hardness measurement results are shown in Table 2 below:

Table 2: Hardness measurement

SampleHardness in manganese steel zone (HV1)Hardness in Interface layerHardness in reinforced zone

A (comparative)250--

B (comparative)280300700

C (inventive)300401922

D (inventive)320427875

E (inventive)320463745

F (inventive)310440821

G-(comparative)280350710

H (comparative)290300725

[0053]It can be seen that the inventive samples have an increased hardness in reinforced zones compared to the comparative samples.

example 4 -

Example 4 - Defects

[0058]

Table 4: Defects

SampleDefects in the reinforced zoneDefects in the interface layer

A (comparative)-

B (comparative)crackscracks

C (inventive)nonenone

D (inventive)nonenone

E (inventive)nonenone

F (comparative)poresPores and cracks

G (inventive)nonenone

H (inventive)nonenone

[0059]Defects were assessed by using Scanning Electron microscopy analysis where cracks and pores are identified. It can be seen that the inventive samples are free of defects. It can be seen that the comparative sample contains pores and cracks. Figure 6 shows the pores in the interface layer in sample B and figure 7 shows pores in the reinforced zone in sample F, whereas figure 4 shows the absence of any pores from sample C.

TECHNICAL FIELD

[0001] The present invention relates to a composite material based on reinforced manganese steel and a method for making the same.BACKGROUND

[0002] A particular category of wear resistant steels is typically referred to as manganese steel or Hatfield steel. These materials are suitable for applications where a high toughness and a moderate abrasion resistance are required including for example use as wear parts for crushers that are subjected to strong abrasion and dynamic surface pressures due to the rock crushing action. Abrasion results when the rock material contacts the wear part and strips-off material from the wear part surface. Additionally, the surface of the wear part is subjected to significantly high surface pressures that cause wear part fatigue and breakage.

[0003] Manganese or Hadfield steel is typically characterised by having an amount of manganese, usually above 11% by weight. However, the problem with manganese steel is that it is typically too ductile for wear parts in modern crushers that are subject to extreme operating conditions, meaning the at the lifetime of the wear parts is reduced and the maintenance costs are increased. Therefore, the problem to be solved is to provide a manganese steel with enhanced wear resistance.

[0004] A known solution is to reinforce at least part of the manganese steel with particles having an increased hardness. WO20200222662 discloses a composite material, however the problem with this material is that is not provide an optimal balance between wear resistance and impact resistance and an even more significant problem is that there is poor bonding between the reinforcing particle and the manganese steel matrix and poor bonding between reinforced and non-reinforced zones, which leads to reduced wear resistance and premature failure of the wear parts. Therefore, the problem to be solved to provide a composite material that can be used for wear parts having an optimal balance between wear resistance and impact resistance, wherein there is improved bonding between the reinforcing particles and the manganese matrix and the bonding between the reinforced and non-reinforced zones in order to reduce defects and cracking that would lead to premature failure of the wear parts.

[0005] Yunhong Liang et al.: "Fabrication of bionic composite material using self propagating hightemperature synthesis in the Cu-Ti-B4C system during steel casting", Journal of Asian Ceramic Societies, vol. I , no. 4, 13 November 2013 (2013-11 -13), pages 339-345, XP093161134, ISSN: 21 87-0764, DOI: 10.1 01 6 / j.jascer.201 3.10.004 and Yunhong Liang et al.: "Effect of Cu content in Cu-Ti-B4C system on fabricating TiC / TiB2 particulates locally reinforced steel matrix composites", Materials and Design, vol. 40, 23 March 2012 (2012-03-23), pages 64-69, XP093161 136, ISSN: 0261-3069, DOI: 10.1 016 / j.matdes.2012.03.023 both disclose reinforced steel.DEFINITIONS

[0006] A "catalysis" is a metal powder or mixture of metal powders which during the reaction in the self-propagating high temperature synthesis (SHS) undergo melting and form a matrix of the composite zone. The fundamental role of catalysis is to reduce the amount of dissipated energy in the SHS process.

[0007] A "compact" is a densified powder composition.SUMMARY OF INVENTION

[0008] It is an objective of this invention to provide a novel and improved composite material for wear parts. The objective is achieved by providing a composite material according to claim 1.

[0009] Advantageously, this produces a composite material that has both increased wear resistance and structural integrity. Therefore, when the material is used on areas of wear parts that are highly exposed to wear the lifetime of the parts is increased. If the average grain size of the TiB 2 and TiC grains is too large, then the composite material will be too brittle. If the average grain size of the TiC and TiB 2 grains in too small the wear resistance will be reduced. The combination of the TiB 2 with the TiC is particularly advantageous because it provides higher hardness in the reinforcing zones leading to highly wear resistant material. Further, the combination of the rectangular shaped TiB 2 with the round shaped TiC particles is particularly advantageous in providing a solid, robust reinforcing zone that is able to stop crack propagation. Hence, it enhances the toughness mechanism of the composite. Further, this composition results in good bonding between the manganese steel zone and each of the reinforcing zones and consequently the structural integrity of the composite material is improved, meaning that the lifetime of the wear parts that the materials is used in is increased. Furthermore, compared to using WC in the reinforcing there are no issues with eta-phase formation and compared to using NbC in the reinforcing zone using TiB 2 and TiC is cheaper.

[0010] In an example embodiment, the average grain size of TiB 2 particles in each of the reinforcing zone(s) is between 6-20 µm, preferably 8-19 µm, more preferably between 12-15 µm. Advantageously, this combination results in high mechanical and wear resistance properties, for example if the grain size is too high then the material will become more brittle and if the grain size is too high then the material will become more brittle and if the grain size is too low then the toughness is reduced. In other words, it provides an optimal balance between hardness and toughness.

[0011] In an example embodiment, the average grain size of TiC particles in each of the reinforcing zone(s) is between 6-10 µm, preferably 7-10 µm, more preferably between 8-9-µm. Advantageously, this combination results in high mechanical and wear resistance properties, for example if the grain size is too high then the material will become more brittle and if the grain size is too low then the toughness is reduced. In other words, it provides an optimal balance between hardness and toughness.

[0012] In the present invention, the composite material comprises a total of between 40-90 wt% of TiB 2 and TiC in each of the reinforcing zones. Preferably between 60-90 wt%, even more preferably between 70-90 wt%. Advantageously, this provides the optimal balance between wear resistance and impact resistance. If the wt% of TiB 2 and TiC in each of the reinforcing zones in too high the composite material will be too brittle and more prone to failure. If the wt% of the TiB 2 and TiC in each of the reinforcing zones is too low, then composite material will have low hardness and therefore it will not have sufficient wear resistance.

[0013] In an example embodiment, the wt% of TiB 2 in each of the reinforcing zones 4 is between 6-20, preferably between 8-19, more preferably between 12-15.

[0014] In an example embodiment, the wt% of TiC in each of the reinforcing zones 4 is between 1-10, preferably between 5-10, more preferably between 8-9.

[0015] In the present invention, the composition of the manganese steel in manganese steel zone has the chemical composition by weight of: carbon: 0.5 to 2.0%; manganese: 11 to 22%; silicon: 0.2 to 1.0%; chromium: 1 to 2%; nickel: up to 0.6%; molybdenum: up to 0.5%; and a balance of Iron. Advantageously, this steel composition is characterized by the addition of micro-alloying elements such as chromium, nickel and molybdenum in good amounts which induce high yield strength and high hardness resulting in increase in wear resistance of manganese steel.

[0016] In the present invention, the Vickers hardness of the reinforcing zones is between 700-1700 HV1 and the hardness of the manganese steel zone is between 200 - 320 HV1 before work hardening. Advantageously, the increased hardness in the reinforcing zones leads to a more wear resistant material.

[0017] In the present invention, the interface layer is free of defects. Advantageously, the absence of any defects in the interface layer means that there is good bonding between the manganese steel zone and each of the reinforcing zones and consequently the structural integrity of the composite material is improved, meaning that the lifetime of the wear parts that the materials is used in is increased. Further, the absence of the presence of any pores is an indication that the composition has the ability to absorb the excess heat and gases from the SHS process and so therefore signifies that the synthesis reaction has been successful.

[0018] In the present invention, the wettability between the TiB 2 and TiC particles and the manganese steel in the reinforcing zone (s) is >99%, preferably >99.5%, even more preferably >99.9%. Advantageously, good wettability induces an excellent bonding between the composite zone and manganese steel preventing defects such as pores and cracks to form and consequently the wear resistance increases.

[0019] In an example embodiment, the each of the reinforcing zones has a volume of between 30-75 cm 3< . Advantageously, this size provides the optimal balance between wear resistance and impact resistance.

[0020] In an example embodiment, at least 95 % of the TiB 2 and TiC particles in the reinforcing zones have a rectangular shape and round shapes respectively. Advantageously, the mixture of rectangular shape and round shapes of TiB 2 and TiC particles respectively will contribute to crack deflection and stop crack propagation increasing the ductility and high wear resistance of the reinforcing zone.

[0021] In an example embodiment, the distance between two neighbouring reinforcing zones is between 1-5 mm, preferably between 1-3 mm, more preferably between 1-2 mm. Advantageously, this provides the optimal balance between wear resistance and impact resistance. If the reinforcing zones are spaced too far apart then the wear resistance will not be high enough. If the reinforcing zones are spaced to close together then the impact resistance will not be high enough.

[0022] Another aspect of the present invention relates to a wear part comprising the composite material as described hereinbefore or hereinafter. Advantageously, the presence of the reinforcing zones within the manganese zone will improve the wear resistance and therefore the lifetime of the wear parts which in turn increases profitability.

[0023] Another aspect of the present invention relates to a method of producing the composite material according to claim 6. The powders are preferably compacted at a pressure between 575 and 625 MPa.

[0024] Advantageously, if this pressing pressure is used the compacts have a low density which enables the manganese steel to more easily infiltrate between the TiB 2 and TiC particles and consequently results in improved bonding between the TiB 2 and TiC particles and the manganese steel. Further it avoids the creation of defects which would lead to premature failure of the wear parts that the composite material is used in.

[0025] Preferably, the catalysis is selected from Fe, Mn, Ni, Mo, Cr, W, Al, or a mixture thereof.

[0026] Advantageously, the addition of a catalysis in a specific amount will contribute to a strong stabilization to austenite phase within the microstructure in addition to good mechanical properties and high wear resistance. The catalysis addition will also act as a grain growth inhibitor which results in a fine microstructure.BRIEF DECRSIPTION OF DRAWINGS

[0027] Figure 1: Shows a line drawing of the composition of the composite material. Figure 2: Shows an SEM image taken of the reinforced zone with low magnification on the left and high magnification on the right. Figure 3: Shows an SEM image taken of the interface layer with low magnification on the left and high magnification on the right. Figure 4: Shows an SEM image of the composite material. Figure 5: Shows a perspective drawing of a wear part. Figure 6: Shows an SEM image of comparative sample B having pores in the interface layer. Figure 7: Shows an SEM image of comparative sample F having pores in the reinforced zone. DETAILED DESCRIPTION

[0028] Figure 1 shows a composite material 2 comprising at least one reinforcing zone 4 comprising TiB 2 and TiC particles; and a manganese steel matrix; a manganese steel zone 6 that surrounds each of the reinforcing zones 4; and an interface layer 8 positioned between each of the reinforcing zones 4 and the manganese steel zone 6. In each of the reinforcing zones, the TiB 2 and TiC particles act to reinforce the manganese steel matrix.

[0029] The average grain size of the TiB 2 and TiC particles in each of the reinforcing zone(s) (4) is between 6-20 µm, preferably between 8-18 µm, most preferably between 10-15µm.

[0030] In an example embodiment, the average grain size of the TiB 2 particles in each of the reinforcing zone(s) (4) is between 6-20 µm, preferably between 8-19 µm, most preferably between 12-15µm.

[0031] In an example embodiment, the average grain size of the TiC particles in each of the reinforcing zone(s) (4) is between 6-10 µm, preferably between 7-10 µm, most preferably between 8-9-µm. The average grain size of the TiB 2 and TiC particles is measured by Scanning Electron Microscopy (SEM) analysis where several and different areas from the samples were analysed and particle sizes were measured. The magnification was selected such that there were at least 50 grains in the image to be measured Then, the average particle size was calculated.

[0032] Each interface layer 8 comprises TiB 2 and TiC particles and manganese steel and can be distinguished from the reinforcing zones 4 as the shape and size of the TiB 2 and TiC particles are different. The interface layer(s) 8 can be distinguished from the reinforcing zone(s) 4 can either: comparing the geometry and / or comparing the average grain size. If the geometry is being compared, the reinforcing zone(s) 4 comprise >90% TiB 2 and TiC particles having a rectangular shape and round shapes respectively whereas the interface layer(s) 8 comprise <5% a rectangular shape and round shapes respectively. A TiB 2 is considered to have a rectangular geometry if the particles have 4 sharp edges and TiC particles are considered to have round geometry if the grains have no sharp edges. If the grain size is being compared the average TiB 2 and TiC particles size of in the interface layer(s) 8 is at least 5% less than the average TiB 2 and TiC particles size on the reinforcing zone(s) 4.

[0033] Figure 2 shows a Scanning Electron microscope image using MIRA3 TESCAN equipment. A secondary electron detector (SE) with a high voltage of 15 KV and a working distance of 9 mm configuration were used. SEM image of the TiB 2 and TiC particles in the reinforcing zone 4. Figure 3 shows an SEM image of the TiB 2 and TiC particles in the interface layer 8. The different TiB 2 and TiC particles geometry and size can clearly be seen when comparing these two figures.

[0034] In the present invention, the total wt% of TiB 2 and TiC particles in each of the reinforcing zones 4 is between 40-90 %, preferably between 60-90 %, more preferably between 70-90%,

[0035] In an example embodiment the wt% of TiB 2 in each of the reinforcing zones 4 is between 6-20, preferably between 8-19, more preferably between 12-5.

[0036] In an example embodiment the wt% of TiC in each of the reinforcing zones 4 is between 6-10, preferably between 7-10, more preferably between 8-9. In the present invention, the composition of the manganese steel in manganese steel zone 6 has the chemical composition by weight of: carbon: 0.5 to 2.0%; manganese: 11 to 22%; silicon: 0.2 to 1.0%; chromium: 1 to 2%; nickel: up to 0.6%, molybdenum: up to 0.5% and a balance of Fe.

[0037] In an example embodiment, the chemical composition of the manganese steel in each of the reinforcing zones 4 has the chemical composition by weight of: 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % P.

[0038] In the present invention, the hardness of the reinforcing zones 4 is between 700-1700HV1, preferably between 750-900 HV1. The hardness of the manganese steel zone 6 is between 200 - 320 HV1.

[0039] Hardness is measured using Vickers hardness mapping on polished samples using a 1 kg load and a holding time of 15 seconds. A micro-hardness tester, Matsuzawa, model MXT was used. Hardness measurement profiles are performed starting from the non-reinforce zone, moving to the interface layer and then to the reinforced zone.

[0040] In the present invention, the interface layer 8 is free of defects. Defects are considered to be cracks or pores.

[0041] In the present invention, the wettability between the TiB 2 and TiC particles and the manganese steel in the reinforcing zones 4 is >99%, preferably >99.5%, more preferably >99.9%, most preferably 100%. Wettability is measured by a Scanning Electron Microscope representing the contact area and the bonding between the TiB 2 and TiC particles in each of the reinforcing zones 4 and the manganese steel.

[0042] In an example embodiment each of the reinforcing zones 4 has a volume of between 30-75 cm 3< . For example, but not limited to the reinforcing zone(s) 4 could have a length of between 100-200 mm, preferably between 100-150 mm, a width of between 20-30 mm, preferably between 20-25 mm and a thickness between 15-30 mm, preferably between 15-25 mm.

[0043] In an example embodiment >90%, preferably >95%, preferably >98%, more preferably >99% of the TiB 2 and TiC particles in each of the reinforcing zones 4 have a have a rectangular shape and round shape respectively. Preferably, the TiB 2 and TiC particles are uniformly distributed in the manganese steel in the reinforcing zone(s). To calculate the percentage of the TiB 2 grains having a rectangular and the percentage TiC grains having a round shape a SEM fracture surface image is taken, then the number of grains having the rectangular geometry, the number of grains having a round geometry and the total number of grains is counted. The percentage of rectangular grains can then by calculated from "(number of grains having rectangular geometry / total number of grains) x 100". The percentage of round grains can then by calculated from "(number of grains having round geometry / total number of grains) x 100". The magnification of the SEM fracture surface image should be set such that the total number of grains in the image is at least 50 for good statistics.

[0044] In an example embodiment, there are a plurality of reinforcing zones 4 with its interface zone 8 and the distance between two neighbouring reinforcing zones 4 with its interface layer 8 is between 1-5 mm, preferably between 1-3 mm, more preferably between 1-2 mm.

[0045] Figure 5 shows an example of a wear part 14 comprising the composite material 2 as described hereinabove or hereinafter. For example, the wear part 2 could be, but not limited to, a cone crusher or a stationary jaw crusher or a mobile jaw crusher that is configured to crush material or other material / rock processing unit. The reinforcing zone(s) 4 are positions on the wear parts 14 in the locations that are most subjected to high wear, for example on a crushing zone 18 of a cone crusher 16.

[0046] The method for producing the composite material 2 as described hereinbefore or hereinafter comprising the steps of: a) mixing together 40-80 wt% Titanium (Ti), 20-60 wt% Boron carbide (B 4 C) and 0-30 wt % catalysis powders; b) compacting the mixed powders together to form at least one compact using a compacting with a pressure 550 - 650 MPa, preferably between 500-650 MPa, more preferably between 550-650 MPa; c) positioning and optionally fixing at least one compact into the interior of a mold; d) pouring molten casting manganese steel into the mold to surround the at least one compact to initiate a self-propagating high temperature synthesis (SHS) reaction to produce a cast; e) heat treating the cast; and then f) quenching the cast.

[0047] Preferably, the cast is treated at a temperature of between 1400-1500°C, the cast is quenched using water. Preferably, the catalysis is selected from Fe, Co, Ni, Mo, Cr, W, Al, or a mixture thereof. Carbon could be added in the form of graphite, amorphous graphite, a carbonaceous material or mixtures thereof. The compacts could for example be held in place using me a metallic fixation system to hold them in place during casting.EXAMPLES Example 1- Samples

[0048] Sample A is a comparative sample of non-reinforced manganese steel having the composition 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % P.

[0049] Samples B-H are samples of composite materials produced by mixing together powders of titanium, boron carbide, and a catalysis powder. The compacting the mixed powders to form compacts which were then positioned in a mold and then molten manganese steel having a composition of 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % was poured into the mold to surround the compacts which initiated a SHS reaction, the cast was then heat treated at a temperature of 1450 °C and then quenching with water. Table 1 shows a summary of the reinforced samples: Table 1: Summary of samplesSampleCompacting pressure used (MPa)Average TiB 2 and TiC particles size in reinforced zone (µm)TiB 2 and TiC content in reinforced zone (wt%)Wettability (%)A (comparative)----B (comparative)600257060C (inventive)6001585100D (inventive)6001290100E (inventive)6001090100F ((inventive)6001580100G (comparative)50055060H (comparative)5001.54570

[0050] It can be seen if the compacting pressure is not high enough then the wettability is reduced.Example 2 - Hardness

[0051] Vickers hardness was measured by a micro-hardness tester, Matsuzawa, model MXT using 1 kgf and a holding time of 15 seconds. Hardness measurement profiles are performed starting from the non-reinforce zone, moving to the interface layer and then to the reinforced zone.

[0052] The hardness measurement results are shown in Table 2 below: Table 2: Hardness measurementSampleHardness in manganese steel zone (HV1)Hardness in Interface layerHardness in reinforced zoneA (comparative)250--B (comparative)280300700C (inventive)300401922D (inventive)320427875E (inventive)320463745F (inventive)310440821G-(comparative)280350710H (comparative)290300725

[0053] It can be seen that the inventive samples have an increased hardness in reinforced zones compared to the comparative samples.Example 3 - Wear test

[0054] Wear was tested using a standard wear test using a lab jaw crusher. The wear test procedure consists on using fixed amount of rocks from 1 Ton up to 4 Ton of rocks. Four plates, two stationary and two moving, were placed inside the jaw crusher. Reference plates were also mounted in both positions. The reference plates are based on Weldox type of material.

[0055] The calculation of wear is based on the difference in volume loss of the test plates compared to the reference plates. All plates were weighed before and after wear test. Then volume loss is calculated using the density of 7.85 g / cm 3< and 7.6 g / cm 3< for the reference and test plates respectively. The total wear ratio (WR) is calculated according to ASTM G81-97a(2013).

[0056] The wear test results are shown in table 3 below: Table 3: Wear test resultsSampleWear ratio rateA0.35B0.20

[0057] It can be seen that the wear rate for the inventive sample is lower than the comparative benchmark sample.Example 4 - Defects

[0058] Table 4: DefectsSampleDefects in the reinforced zoneDefects in the interface layerA (comparative)-B (comparative)crackscracksC (inventive)nonenoneD (inventive)nonenoneE (inventive)nonenoneF (comparative)poresPores and cracksG (inventive)nonenoneH (inventive)nonenone

[0059] Defects were assessed by using Scanning Electron microscopy analysis where cracks and pores are identified. It can be seen that the inventive samples are free of defects. It can be seen that the comparative sample contains pores and cracks. Figure 6 shows the pores in the interface layer in sample B and figure 7 shows pores in the reinforced zone in sample F, whereas figure 4 shows the absence of any pores from sample C.

Examples

example 1 -

Example 1- Samples

[0048]Sample A is a comparative sample of non-reinforced manganese steel having the composition 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % P.

[0049]Samples B-H are samples of composite materials produced by mixing together powders of titanium, boron carbide, and a catalysis powder. The compacting the mixed powders to form compacts which were then positioned in a mold and then molten manganese steel having a composition of 1-1.5 %C, 11-14 % Mn, 0.4-0.8 % Si, 1.3-2.0 % Cr, 0.6 % Ni, 0.065 % was poured into the mold to surround the compacts which initiated a SHS reaction, the cast was then heat treated at a temperature of 1450 °C and then quenching with water. Table 1 shows a summary of the reinforced samples:

Table 1: Summary of samples

SampleCompacting pressure used (MPa)Average TiB 2 and TiC particles size in reinforced zone (µm)TiB 2 and TiC content in reinforced zone (wt%)Wettability (%)

A (comparative)----

B (comparative)600257060

C (invent...

example 2-hardness

Example 2 - Hardness

[0051]Vickers hardness was measured by a micro-hardness tester, Matsuzawa, model MXT using 1 kgf and a holding time of 15 seconds. Hardness measurement profiles are performed starting from the non-reinforce zone, moving to the interface layer and then to the reinforced zone.

[0052]The hardness measurement results are shown in Table 2 below:

Table 2: Hardness measurement

SampleHardness in manganese steel zone (HV1)Hardness in Interface layerHardness in reinforced zone

A (comparative)250--

B (comparative)280300700

C (inventive)300401922

D (inventive)320427875

E (inventive)320463745

F (inventive)310440821

G-(comparative)280350710

H (comparative)290300725

[0053]It can be seen that the inventive samples have an increased hardness in reinforced zones compared to the comparative samples.

example 4 -

Example 4 - Defects

[0058]

Table 4: Defects

SampleDefects in the reinforced zoneDefects in the interface layer

A (comparative)-

B (comparative)crackscracks

C (inventive)nonenone

D (inventive)nonenone

E (inventive)nonenone

F (comparative)poresPores and cracks

G (inventive)nonenone

H (inventive)nonenone

[0059]Defects were assessed by using Scanning Electron microscopy analysis where cracks and pores are identified. It can be seen that the inventive samples are free of defects. It can be seen that the comparative sample contains pores and cracks. Figure 6 shows the pores in the interface layer in sample B and figure 7 shows pores in the reinforced zone in sample F, whereas figure 4 shows the absence of any pores from sample C.

Claims

1. A composite material (2) comprising: at least one reinforcing zone (4) comprising Titanium carbides (TiC) and Titanium borides (TiB2) and a manganese steel matrix; wherein the total weight % (wt%) of TiC and TiB2 in each of the reinforcing zones (4) is between 40-90; a manganese steel zone (6) that surrounds each of the reinforcing zones (4); wherein the composition of the manganese steel in manganese steel zone (6) has the chemical composition by weight of: carbon: 0.5 to 2.0%; manganese: 11 to 22%; silicon: 0.2 to 1.0%; chromium: 1 to 2%; nickel: up to 0.6%; molybdenum: up to 0.5%; and a balance of iron; and an interface layer (8) positioned between each of the reinforcing zones (4) and the manganese steel zone (6); wherein the hardness of the reinforcing zones (4) is between 700-1700 HV1 and the hardness of the manganese steel zone (6) is between 200 - 320 HV1 before work hardening; wherein the average grain size of both the TiC and the TiB2 particles in each of the reinforcing zone(s) (4) is between 6-20 µm is measured by Scanning Electron Microscopy (SEM); wherein the interface layer (8) is free of defects wherein defects are considered to be cracks or pores, wherein defects are assessed by using Scanning Electron microscopy analysis; and wherein wettability between the TiC and TiB2 particles and the manganese steel in the reinforcing zones (4) is >90% wherein wettability is measured using SEM.

2. The composite material (2) according to claim 1 wherein the average grain size of the TiC particles in each of the reinforcing zone(s) (4) is between 6-10 µm.

3. The composite material (2) according to any of the previous claims wherein each of the reinforcing zones has a volume of between 30-75 cm3.

4. The composite material (2) according to any of the previous claims wherein at least 90% of the TiC particles have a round shape and at least 90% of the TiB2 particles have a rectangular shape.

5. A crusher wear part (14) comprising the composite material (2) according to any of claims 1-4.

6. A method of producing the composite material (2) according to any of claims 1-4 comprising the steps of: a) mixing together 40-80 wt% Titanium (Ti),20-60 wt% Boron carbide (B4C) and 0-30 wt % catalysis powders; b) compacting the mixed powders together to form at least one compacts (20); c) positioning and optionally fixing at least one compact (20) into the interior of a mold (22); d) pouring molten casting manganese steel (24) into the mold (22) to surround the at least one compact (20) to initiate a self-propagating high temperature synthesis (SHS) reaction to produce a cast (26); e) heat treating the cast (26) f) quenching the cast (26), wherein in step b) the powders are compacting with a pressure of between 550-650 MPa.

7. The method according to claim 6 wherein the catalysis is selected from iron, cobalt, nickel, molybdenum, chromium, tungsten, aluminum, or a mixture thereof.

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