US20130292612A1 - Electrode for electric-discharge surface treatment and method for forming electrode for electric-discharge surface treatment - Google Patents

Electrode for electric-discharge surface treatment and method for forming electrode for electric-discharge surface treatment Download PDF

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US20130292612A1
US20130292612A1 US13/701,643 US201113701643A US2013292612A1 US 20130292612 A1 US20130292612 A1 US 20130292612A1 US 201113701643 A US201113701643 A US 201113701643A US 2013292612 A1 US2013292612 A1 US 2013292612A1
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electrode
powder
electric
tic
coating
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US13/701,643
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Nobuyuki Sumi
Akihiro Goto
Hiroyuki Teramoto
Yusuke Yasunaga
Yoshikazu Nakano
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Mitsubishi Electric Corp
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Mitsubishi Electric Corp
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00Coating not provided for in groups C23C2/00 - C23C24/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40Making wire or rods for soldering or welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23HWORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H1/00Electrical discharge machining, i.e. removing metal with a series of rapidly recurring electrical discharges between an electrode and a workpiece in the presence of a fluid dielectric
    • B23H1/04Electrodes specially adapted therefor or their manufacture

Definitions

  • the present invention relates to an electric-discharge surface treatment in which pulsed electric discharge is generated between an electrode and a base material by using a green compact, which is formed by compressing a powder of a hard material, as the electrode, and by using energy of the electric discharge, a coating including an electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of the base material.
  • JP-A-2005-21355 discloses a surface treating method for a dense and relatively thick coating (the order of 100 ⁇ m or greater) which needs strength and lubricity under a high-temperature environment.
  • This technology is a method of forming a dense and strong coating with high adhesion between powder materials by making an electrode contain 1.5 wt % to 5.0 wt % of Si or 1.0 wt % to 4.5 wt % of B such that Si or B absorbs oxygen atoms in the coating and thus the unnecessary oxygen atoms are removed from the coating.
  • electric-discharge surface treated surfaces have hardness of 1700 HV to 2500 HV, and are very hard. However, their surface roughness is slightly large as 6 ⁇ mRz to 12 ⁇ mRz. For this reason, for a purpose in which good surface roughness is necessary, it is required to form a smoother hard coating.
  • Patent Document 1 International Publication No. W001/005545
  • Patent Document 2 JP-A-2005-21355
  • the present invention is made in view of the above-mentioned problem, and an object of the present invention is to provide an electric-discharge surface treatment method capable of forming a smooth and high-hardness coating.
  • An electrode for electric-discharge surface treatment of the present invention which is used in the electric-discharge surface treatment in which pulsed electric discharge is generated between the electrode and a base material in a machining fluid or in the air by using a green compact, which is formed by compressing powder of an electrode material, as the electrode, and by using energy of the electric discharge, a coating including the electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of a base material, wherein a mixture of Si powder having an average particle diameter of not less than 0.3 ⁇ m and not more than 10 ⁇ m and hard material powder having an average particle diameter of not less than 0.3 ⁇ m and not more than 10 ⁇ m is used as the electrode material.
  • FIG. 1 is a characteristic diagram illustrating a relation between a mixing ratio of Si in an electrode and a coating surface roughness.
  • FIG. 2 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a coating hardness.
  • FIG. 3 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a Si concentration of a coating.
  • FIG. 4 is a SEM photograph of a TiC coating which is a comparative example for a first embodiment.
  • FIG. 5 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 6 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 7 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 8 is a SEM photograph of a Si coating surface which is a comparative example for the first embodiment.
  • FIG. 9 is a SEM photograph of crushed and mixed powder.
  • FIG. 10 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 11 is a SEM photograph of the crushed and mixed powder.
  • FIG. 12 shows a measurement result of a particle size distribution for the crushed and mixed powder.
  • FIG. 13 shows a measurement result of an X-ray diffraction pattern from a direction of the Si-mixed TiC coating surface.
  • FIG. 14 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a concentration of Ti in the coating.
  • FIG. 15 is a view illustrating a coating forming mechanism.
  • FIG. 16 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and an erosion resistance.
  • FIG. 18 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a corrosion resistance.
  • FIG. 19 shows an observation result for a surface state of a coating after being immersed in aqua regia for one hour.
  • FIG. 20 is a view illustrating a relation between the mixing ratio (weight ratio) of Si in the electrode and each property of a coating.
  • Electrodes for electric-discharge surface treatment are made of mixed powders of TiC and Si prepared by mixing TiC powder and Si powder at slightly different ratios, and a voltage is applied between the electrode and a workpiece (base material) and electric discharge is generated, whereby a coating is formed on the base material.
  • FIG. 1 is a view illustrating a relation between a mixing ratio (wt %) of Si in an electrode and a surface roughness of a coating.
  • FIG. 2 is a view illustrating a relation between the mixing ratio (wt %) of Si in the electrode and the hardness of the coating.
  • a method of measuring the surface roughness used in the present embodiment is as follows. The measurement was made by using a Form Talysurf made by Taylor Hobson as a measuring apparatus, a standard stylus, a measurement length of 4.8 mm, a high-band cutoff length of 0.8 mm, a band width ratio of 100:1, and a Gaussian filter as a filter type. The measured values were based on JIS B0601:2001.
  • the amount of Si is a value measured from the surface direction of the coating by an energy dispersive X-ray spectrometry method (EDX), and measurement conditions are an acceleration voltage of 15.0 kV, and an illumination current of 1.0 nA.
  • EDX energy dispersive X-ray spectrometry method
  • electrodes having different mixing ratios for example, an electrode in which a mixing ratio of the TiC powder to the Si powder is 8:2 is referred to as a “TiC+Si (8:2) electrode” and an electrode in which a mixing ratio of the TiC powder to the Si powder is 5:5 referred to as a “TiC+Si (5:5) electrode”.
  • FIGS. 4 to 8 show the SEM observation results of surfaces which are treated with a TiC electrode as a comparative example, the TiC+Si (8:2) electrode, a TiC+Si (7:3) electrode, the TiC+Si (5:5) electrode and an Si electrode as a comparative example.
  • Si has a coefficient of viscosity (0.94 mN ⁇ s/m 2 ) smaller than those of other metals. Therefore, if Si is mixed, when an electrode material being melted by electric discharge moves onto a base material and coagulates, since the concentration of Si of the melted portion increases, as a result, the coefficient of viscosity of the melted portion is reduced and the electrode material coagulates while spreading flat. Therefore, it can be considered that swells are reduced.
  • an average particle diameter of raw powder configuring the electrode for the electric-discharge surface treatment according to the present embodiment refers to a particle diameter (D50) at an integration value 50% in a particle size distribution which is obtained by a laser diffraction and scattering particle size analyzer (“MT3000” manufactured by Microtrack).
  • the TiC powder which is a hard material having an average particle diameter of 5 ⁇ m or an average particle diameter of 1.3 ⁇ m and the Si powder having an average particle diameter of 5 ⁇ m are used and mixed to prepare the electrode for the electric-discharge surface treatment.
  • the TiC powder and the Si powder it is only necessary to select the TiC powder and the Si powder to be in the range of an average particle diameter of not less than 0.3 ⁇ m and not more than 10 ⁇ m.
  • each electrode material is separately crushed using a ball mill and then mixed or both electrode materials are mixed while simultaneously crushing both electrode materials using the ball mill.
  • raw powder which configures the electrode for the electric-discharge surface treatment or the powder (crushed and mixed powder) after being crushed and mixed are selected in the range of the average particle diameter of not less than 0.3 ⁇ m and not more than 10 ⁇ m.
  • the reason for selecting the average particle diameter of not less than 0.3 ⁇ m is because it was apparent from the experiment of the present inventors that a good coating cannot be obtained at the average particle diameter of less than 0.3 ⁇ m.
  • the coating has a rough surface (surface roughness Rz: 9 ⁇ m) as in the FIG. 10 .
  • the average particle diameter of the raw powder or the crushed and mixed powder is preferably not less than 0.3 ⁇ m, more preferably not less than 0.6 ⁇ m, further preferably not less than 1 ⁇ m.
  • the reason for selecting the average particle diameter of not more than 10 ⁇ m is because, when the average particle diameter of more than 10 ⁇ m, a short-circuit between the poles is more likely to occur during the electric-discharge surface treatment and thus a stable electric discharge is less likely to occur and also a convex portion is formed on the coating surface starting from the short-circuit point and thus a good coating cannot be obtained. Therefore, the average particle diameter is preferably not more than 10 ⁇ m, more preferably not more than 7 ⁇ m, further preferably not more than 5 ⁇ m.
  • the range of the average particle diameter of not more than 10 ⁇ m refers to a condition where the powder having the particle diameter of not less than 20 ⁇ m is preferably not more than 5 vol %, more preferably not more than 3 vol %, further preferably not more than 1 vol %.
  • FIGS. 11 and 12 respectively show a SEM photograph and a measurement result of a particle size distribution for the crushed and mixed powder in a condition where the weight ratio of the TiC powder and Si powder is 8:2 and the powder having the particle diameter of not less than 20 ⁇ m is not more than 1%.
  • the average particle diameter (D50) is 3.577 ⁇ m and the powder having the particle diameter of less than 20 ⁇ m is 99.76 vol %, that is, the powder having the particle diameter of not less than 20 ⁇ m is 0.24 vol %.
  • This crushed and mixed powder is used to produce the electrode and then the electric-discharge surface treatment using the electrode is implemented. As a result, a good coating equivalent to FIG. 5 (surface treated with TiC+Si (8:2) electrode) can be obtained.
  • the TiC+Si electrode prepared by mixing the TiC powder and the Si powder while varying the mixing ratio thereof little by little is considered. From the result of X-ray diffraction measurement for the coating treated with the electrodes for the electric-discharge surface treatment which have respectively different mixing ratio, it was found that the diffraction peak of TiC is confirmed and it was seen that the TiC at the time of the electrode material exists as TiC in the coating even after the electric-discharge surface treatment. The diffraction peak of an elementary substance of Ti is not confirmed.
  • FIG. 13 shows XRD diffraction measurement result of the coatings formed by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode and the TiC+Si (5:5) electrode, as examples.
  • FIG. 14 shows a relation between the mixing ratio of Si in the electrode and the concentration of Ti in the coating.
  • the mixing ratio of Si in the electrode increases, that is, the mixing ratio of TiC in the electrode decreases, the concentration of Ti in the coating is reduced. Since a peak of the elementary substance of Ti is not shown from the XRD diffraction measurement results, it can be considered that, even though a portion of TiC of an electrode may be decomposed during the electric-discharge surface treatment, most of TiC exists intactly in the coating.
  • the mixing ratio of Si in the electrode increases, that is, the mixing ratio of TiC in the electrode reduces, the concentration of TiC in the coating also relatively reduces.
  • the element Si exists at several to several tens wt % at the treated surfaces like in the above-mentioned quantitative analysis, as the results of the X-ray diffraction measurement, it was not possible to confirm the diffraction peaks of crystals of Si at all coatings. Therefore, it can be considered that the elementary substance Si forms an alloy together with the components of the base material, or is in an amorphous state.
  • the erosion resistance of each of the coatings treated by the TiC+Si electrodes formed by mixing the TiC powder and the Si powder at slightly different ratios is evaluated.
  • the base material is SUS630 (H1075).
  • the erosion resistance is evaluated by hitting the coatings with waterjet. It is generally said that the erosion resistance has a strong correlation with the hardness. Meanwhile, it has been known that the erosion resistance has many points which cannot be explained only by the hardness, and is influenced by the characteristics of surfaces as a factor other than the hardness, and the erosion resistance of a smooth surface is higher than that of a rough surface.
  • FIG. 12 is a view illustrating a relation between the mixing ratio of Si in the electrode and the erosion resistance.
  • FIG. 17 shows results of observation of the surface states of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode and the TiC+Si (5:5) electrode after injection of waterjet of 80 MPa for one hour, as examples.
  • FIG. 13 also shows results of observation of only the base material, the coating by the TiC electrode, and the coating by the Si electrode for comparison. At the base material without any coating, damage had occurred, and even at the treated surface by the TiC electrode, damage had occurred. Meanwhile, at all of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode, and the TiC+Si (5:5) electrode, damage had not occurred.
  • the corrosion resistance of each of the coatings was evaluated.
  • the base material was SUS 316.
  • the coatings treated by the electrodes formed by mixing Si at 5 wt % or greater in TiC has high corrosion resistance.
  • Si was contained at about 5 wt %, a few defects existed at the surface, and thus a variation in the evaluation was seen. Therefore, if the mixing ratio of Si further increases, it is possible to give a sufficient effect when the mixing ratio of Si is 10 wt % or greater, and it is more preferable to mix Si at 20 wt % or greater.
  • the mixing ratio of Si was 20 wt % or greater, high corrosion resistance was obtained without a variation in the evaluation.
  • FIG. 18 schematically shows a relation between the mixing ratio of Si in the electrode and the corrosion resistance.
  • FIG. 19 shows results of observation of the surface states of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode, and the TiC+Si (5:5) electrode after dipping in aqua regia serving as a corrosion solution for one hour, as examples.
  • FIG. 19 also shows results of observation of the base material without any coating, the coating by the TiC electrode, and the coating by the Si electrode for comparison.
  • the base material without any coatings greatly corroded, and the surface treated by the TiC electrode also corroded. Meanwhile, at all of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode, and the TiC+Si (5:5) electrode, corrosion had not occurred.
  • the surface roughness is at the same degree as that of the coating by the TiC electrode, and sufficient erosion resistance, corrosion resistance, and oxidation resistance are not obtained. Also, when the mixing ratio of Si is 60 wt % or greater, the hardness is at the same degree as that of the coating by the Si electrode is obtained, and the other characteristics also are at the same degrees as those of the coating by the Si electrode. Particularly, the surface roughness is deteriorated.
  • the concentrations of Si, TiC, and a base material (Fe) of a coating which is obtained by treating carbon steel S45C by TiC+Si electrodes formed by mixing the Si powder at slightly different ratios in the TiC powder, are as shown in FIG. 21 .
  • the concentrations of Si, TiC, and the base material component (Fe) of a smooth coating with high hardness, high erosion resistance, high corrosion resistance, and high oxidation resistance formed on carbon steel S45C by electrodes containing Si at the mixing ratio of 5 wt % to 60 wt % were in ranges of 1 wt % to 11 wt %, 10 wt % to 75 wt %, and 20 wt % to 90 wt %, respectively.
  • the mixing ratio of TiC to Si has been defined.
  • the density of TiC is 4.93 g/cm 3 and the density of Si is 2.3 g/cm 3
  • the volume ratio of TiC to Si is 90 vol % (volume percent):10 vol %
  • the weight ratio of TiC to Si is 40 wt %:60 wt %
  • the volume ratio of TiC to Si is 25 vol %:75 vol %.
  • Si is mixed at 10 vol % to 75 vol % in another hard material, it is possible to form a smooth coating having high hardness, high erosion resistance, high corrosion resistance, and high oxidation resistance.
  • Si has been used as a material to be mixed.
  • metal powder having a small coefficient of viscosity is mixed, it is possible to obtain the same effects.
  • a material having a small coefficient of viscosity such as K, Li, Na, Ge, Ca, Mg, Al, P, Bi, Sn, or In, may also be used.
  • the TiC powder and the Si powder are mixed at a predetermined weight ratio.
  • a powder containing TiC and Si at a predetermined ratio in advance may be used to form an electrode for electric-discharge surface treatment. This case is more preferable since it is possible to uniformly mix TiC and Si.
  • the Fe-base material is used as the base material.
  • the base material is a Ni-base alloy or a Co alloy of heat-resistant alloys, it is possible to obtain the same effects.
  • the coating by the TiC electrode has surface roughness higher than that in the case where the base material is Fe-based.
  • a TiC+Si electrode is used, it is possible to obtain the same effects.
  • JP-A-556-51543 As an invention in which Si is added to an electrode material, there is JP-A-556-51543. However, this is an invention regarding an electrode for general electric discharge machining, is for increasing a machining speed, and is an invention in a field different from the present invention in which a hard material coating is formed, and Si is mixed such that the coating becomes smooth, whereby a coefficient of viscosity is reduced.
  • JP-A-2005-21355 is for establishing a surface treatment method for a dense and relatively thick coating (made of a metal material in the order of 100 ⁇ m or greater) with no vacancy which needs a strength and lubricity in a high temperature environment, and discloses an electrode for electric-discharge surface treatment containing 1.0 wt % to 4.5 wt % of B (boron) or 1.5 wt % to 5.0 wt % of Si (silicon) as an electrode material for absorbing oxygen atoms.
  • the present invention is for establishing a surface treatment method of a smooth and high-hardness coating of a hard material having a thickness 5 ⁇ m to 20 ⁇ m, and uses a weight ratio of mixed Si of 5 wt % to 60 wt %. Therefore, the present invention is an invention in a field different from JP-A-2005-21355.
  • the electrode for electric-discharge surface treatment according to the present invention can be appropriately used for electric-discharge surface treatment work on metal molds, steam turbines, and the like.

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Abstract

An electrode for electric-discharge surface treatment, which is used in the electric-discharge surface treatment in which pulsed electric discharge is generated between the electrode and a base material in a machining fluid or in the air by using a green compact, which is formed by compressing powder of an electrode material, as the electrode, and by using energy of the electric discharge, a coating including the electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of a base material, wherein a mixture of Si powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm and hard material powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm is used as the electrode material.

Description

    TECHNICAL FIELD
  • The present invention relates to an electric-discharge surface treatment in which pulsed electric discharge is generated between an electrode and a base material by using a green compact, which is formed by compressing a powder of a hard material, as the electrode, and by using energy of the electric discharge, a coating including an electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of the base material.
  • BACKGROUND ART
  • International publication No. WO 01/005545 discloses a practical electrode for electric-discharge surface treatment and a forming method thereof. This technology is a method of forming a practical electrode for the electric-discharge surface treatment which has a proper strength and safety and easily crumbles. In this method, TiC powder which is metal carbide powder and TiH2 which is metal hydride powder are mixed, are compressed, and are heat-treated such that hydrogen is released from the TiH2 powder, whereby Ti powder is prepared.
  • JP-A-2005-21355 discloses a surface treating method for a dense and relatively thick coating (the order of 100 μm or greater) which needs strength and lubricity under a high-temperature environment. This technology is a method of forming a dense and strong coating with high adhesion between powder materials by making an electrode contain 1.5 wt % to 5.0 wt % of Si or 1.0 wt % to 4.5 wt % of B such that Si or B absorbs oxygen atoms in the coating and thus the unnecessary oxygen atoms are removed from the coating.
  • As a result of the electric-discharge surface treatment using the electrode for electric-discharge surface treatment as described above, the lives of press molds, a turret punch presses, cutting tools, and the like, have extended.
  • Meanwhile, electric-discharge surface treated surfaces have hardness of 1700 HV to 2500 HV, and are very hard. However, their surface roughness is slightly large as 6 μmRz to 12 μmRz. For this reason, for a purpose in which good surface roughness is necessary, it is required to form a smoother hard coating.
  • CITATION LIST Patent Document
  • Patent Document 1: International Publication No. W001/005545
  • Patent Document 2: JP-A-2005-21355
  • DISCLOSURE OF THE INVENTION Problems That the Invention Is To Solve
  • The present invention is made in view of the above-mentioned problem, and an object of the present invention is to provide an electric-discharge surface treatment method capable of forming a smooth and high-hardness coating.
  • Means For Solving the Problems
  • An electrode for electric-discharge surface treatment of the present invention, which is used in the electric-discharge surface treatment in which pulsed electric discharge is generated between the electrode and a base material in a machining fluid or in the air by using a green compact, which is formed by compressing powder of an electrode material, as the electrode, and by using energy of the electric discharge, a coating including the electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of a base material, wherein a mixture of Si powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm and hard material powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm is used as the electrode material.
  • Advantage of the Invention
  • According to the present invention, it is possible to form a smooth and high-hardness coating.
  • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a characteristic diagram illustrating a relation between a mixing ratio of Si in an electrode and a coating surface roughness.
  • FIG. 2 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a coating hardness.
  • FIG. 3 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a Si concentration of a coating.
  • FIG. 4 is a SEM photograph of a TiC coating which is a comparative example for a first embodiment.
  • FIG. 5 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 6 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 7 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 8 is a SEM photograph of a Si coating surface which is a comparative example for the first embodiment.
  • FIG. 9 is a SEM photograph of crushed and mixed powder.
  • FIG. 10 is a SEM photograph of a Si-mixed TiC coating surface.
  • FIG. 11 is a SEM photograph of the crushed and mixed powder.
  • FIG. 12 shows a measurement result of a particle size distribution for the crushed and mixed powder.
  • FIG. 13 shows a measurement result of an X-ray diffraction pattern from a direction of the Si-mixed TiC coating surface.
  • FIG. 14 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a concentration of Ti in the coating.
  • FIG. 15 is a view illustrating a coating forming mechanism.
  • FIG. 16 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and an erosion resistance.
  • FIG. 17 shows an observation result for a surface state of a coating after a water-jet injection.
  • FIG. 18 is a characteristic diagram illustrating a relation between the mixing ratio of Si in the electrode and a corrosion resistance.
  • FIG. 19 shows an observation result for a surface state of a coating after being immersed in aqua regia for one hour.
  • FIG. 20 is a view illustrating a relation between the mixing ratio (weight ratio) of Si in the electrode and each property of a coating.
  • FIG. 21 is a view illustrating a relation between the mixing ratio of Si into the electrode and each component concentration of a coating.
  • MODE FOR CARRYING OUT THE INVENTION
  • Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.
  • First Embodiment
  • The present embodiment will be described using TiC powder as powder of a hard material. Electrodes for electric-discharge surface treatment are made of mixed powders of TiC and Si prepared by mixing TiC powder and Si powder at slightly different ratios, and a voltage is applied between the electrode and a workpiece (base material) and electric discharge is generated, whereby a coating is formed on the base material.
  • FIG. 1 is a view illustrating a relation between a mixing ratio (wt %) of Si in an electrode and a surface roughness of a coating. As results of measurement of the surface roughness of coatings obtained by treating carbon steel S45C by the electrodes of TiC and Si formed while changing the mixing ratio of the Si powder to the TiC powder, as the mixing ratio of Si in the electrode increases, the surface roughness of the coating is reduced. In the present embodiment, the surface roughness of the coating changes within a range of 2 μmRz to 6 μmRz.
  • FIG. 2 is a view illustrating a relation between the mixing ratio (wt %) of Si in the electrode and the hardness of the coating. As the results of measurement of the hardness of coatings obtained by treating carbon steel S45C by the electrodes of TiC and Si formed while changing the mixing ratio of the Si powder to the TiC powder little by little, when the mixing ratio of Si is 60 wt % or less, as the mixing ratio of Si in the electrode increases, the hardness of the coating is reduced. Meanwhile, when the mixing ratio of Si is not less than 60 wt %, the hardness of the coating dies not change so much. In the present embodiment, the hardness of the coating changes within a range of 800 HV to 1700 HV.
  • As shown in FIG. 1, since the surface roughness of the coating gradually reduces as the mixing ratio of Si in the electrode increases, it is possible to arbitrarily control the surface roughness of the coating between 2 μmRz to 6 μmRz by using an electrode obtained by arbitrarily changing the weight ratio of Si in the electrode. Also, as shown in FIG. 2, since the hardness of the coating is gradually reduced as the mixing ratio of Si in the electrode increases, it is possible to arbitrarily control the hardness of the coating between 800 HV to 1700 HV by arbitrarily changing the weight percent of Si in the electrode.
  • Here, a method of measuring the surface roughness used in the present embodiment is as follows. The measurement was made by using a Form Talysurf made by Taylor Hobson as a measuring apparatus, a standard stylus, a measurement length of 4.8 mm, a high-band cutoff length of 0.8 mm, a band width ratio of 100:1, and a Gaussian filter as a filter type. The measured values were based on JIS B0601:2001.
  • The measurement of the hardness of the coating was performed from the surface direction of the coating, and a measured load was 10 gf. A measuring apparatus is a micro hardness tester made by Shimadzu Corporation.
  • As results of measurement of the Si concentrations of coatings, which are obtained by treating carbon steel S45C by the electrodes of TiC and Si formed while changing the mixed ratio of the Si powder to the TiC powder, a relation between the weight ratio of Si in the electrodes and the Si concentrations of the coatings is as shown in FIG. 3. As the weight percent of Si in the electrode increases, the Si concentration of the coating also increases.
  • Here, the amount of Si is a value measured from the surface direction of the coating by an energy dispersive X-ray spectrometry method (EDX), and measurement conditions are an acceleration voltage of 15.0 kV, and an illumination current of 1.0 nA.
  • As described above, as the mixing ratio of Si in the electrode increases, the concentration of Si contained in the coating increases, and therefore, it can be considered that the surface roughness of the coating is reduced. In order to examine this mechanism, surfaces of the coatings was observed with an SEM. As a result, it was observed that as the concentration of Si increases, defects such as cracks was reduced at the coatings, and a swell of each electric discharge trace was reduced.
  • Hereinafter, electrodes having different mixing ratios (weight ratios), for example, an electrode in which a mixing ratio of the TiC powder to the Si powder is 8:2 is referred to as a “TiC+Si (8:2) electrode” and an electrode in which a mixing ratio of the TiC powder to the Si powder is 5:5 referred to as a “TiC+Si (5:5) electrode”.
  • As an example, FIGS. 4 to 8 show the SEM observation results of surfaces which are treated with a TiC electrode as a comparative example, the TiC+Si (8:2) electrode, a TiC+Si (7:3) electrode, the TiC+Si (5:5) electrode and an Si electrode as a comparative example.
  • It can be observed that in the surface treated with the TiC electrode, defects such as cracks are increased and swells of each electric discharge traces becomes larger, in the surfaces treated with the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode and the TiC+Si (5:5) electrode, in this order, defects such as cracks are decreased and the swells of each electric discharge trace becomes smaller, and in the surface treated with the Si electrode, defects such as cracks are not observed and the swells of each electric discharge trace becomes very small.
  • Here, a mechanism of the swells of each electric discharge trace reducing due to the concentrations of Si contained in the coatings increasing is considered as follows. Si has a coefficient of viscosity (0.94 mN·s/m2) smaller than those of other metals. Therefore, if Si is mixed, when an electrode material being melted by electric discharge moves onto a base material and coagulates, since the concentration of Si of the melted portion increases, as a result, the coefficient of viscosity of the melted portion is reduced and the electrode material coagulates while spreading flat. Therefore, it can be considered that swells are reduced.
  • Next, a particle diameter of raw powder used for forming the electrode is described.
  • Here, an average particle diameter of raw powder configuring the electrode for the electric-discharge surface treatment according to the present embodiment refers to a particle diameter (D50) at an integration value 50% in a particle size distribution which is obtained by a laser diffraction and scattering particle size analyzer (“MT3000” manufactured by Microtrack).
  • In the present embodiment, the TiC powder which is a hard material having an average particle diameter of 5 μm or an average particle diameter of 1.3 μm and the Si powder having an average particle diameter of 5 μm are used and mixed to prepare the electrode for the electric-discharge surface treatment. However, it is only necessary to select the TiC powder and the Si powder to be in the range of an average particle diameter of not less than 0.3 μm and not more than 10 μm.
  • With respect to the electrode manufacturing, it is considered that each electrode material is separately crushed using a ball mill and then mixed or both electrode materials are mixed while simultaneously crushing both electrode materials using the ball mill. In both cases, it is only necessary that raw powder which configures the electrode for the electric-discharge surface treatment or the powder (crushed and mixed powder) after being crushed and mixed are selected in the range of the average particle diameter of not less than 0.3 μm and not more than 10 μm.
  • The reason for selecting the average particle diameter of not less than 0.3 μm is because it was apparent from the experiment of the present inventors that a good coating cannot be obtained at the average particle diameter of less than 0.3 μm.
  • For example, in a case where the TiC+Si electrode is produced using the crushed and mixed powder having the average particle diameter of less than 0.3 μm as in the SEM photograph of FIG. 9, as the electric-discharge surface treatment is carried out, the coating has a rough surface (surface roughness Rz: 9 μm) as in the FIG. 10. This is probably because the sticking between the powders becomes strong due to the sintering and the electrode becomes too strong and thus the electrode material does not transfer well to the base material during the electric-discharge surface treatment. Therefore, the average particle diameter of the raw powder or the crushed and mixed powder is preferably not less than 0.3 μm, more preferably not less than 0.6 μm, further preferably not less than 1 μm.
  • On the contrary, the reason for selecting the average particle diameter of not more than 10 μm is because, when the average particle diameter of more than 10 μm, a short-circuit between the poles is more likely to occur during the electric-discharge surface treatment and thus a stable electric discharge is less likely to occur and also a convex portion is formed on the coating surface starting from the short-circuit point and thus a good coating cannot be obtained. Therefore, the average particle diameter is preferably not more than 10 μm, more preferably not more than 7 μm, further preferably not more than 5 μm.
  • Specifically, the range of the average particle diameter of not more than 10 μm refers to a condition where the powder having the particle diameter of not less than 20 μm is preferably not more than 5 vol %, more preferably not more than 3 vol %, further preferably not more than 1 vol %.
  • The reason is because, when a lot of powder having the particle diameter of not less than 20 μm is contained, a short-circuit between the poles is more likely to occur through the powder having the particle diameter of not less than 20 μm during the electric-discharge surface treatment and thus a stable electric discharge is less likely to occur and also a convex portion is formed on the coating surface starting from the short-circuit point and thus a good coating cannot be obtained.
  • FIGS. 11 and 12 respectively show a SEM photograph and a measurement result of a particle size distribution for the crushed and mixed powder in a condition where the weight ratio of the TiC powder and Si powder is 8:2 and the powder having the particle diameter of not less than 20 μm is not more than 1%. As illustrated in FIGS. 11 and 12, it is clearly shown that the average particle diameter (D50) is 3.577 μm and the powder having the particle diameter of less than 20 μm is 99.76 vol %, that is, the powder having the particle diameter of not less than 20 μm is 0.24 vol %. This crushed and mixed powder is used to produce the electrode and then the electric-discharge surface treatment using the electrode is implemented. As a result, a good coating equivalent to FIG. 5 (surface treated with TiC+Si (8:2) electrode) can be obtained.
  • Next, the TiC+Si electrode prepared by mixing the TiC powder and the Si powder while varying the mixing ratio thereof little by little is considered. From the result of X-ray diffraction measurement for the coating treated with the electrodes for the electric-discharge surface treatment which have respectively different mixing ratio, it was found that the diffraction peak of TiC is confirmed and it was seen that the TiC at the time of the electrode material exists as TiC in the coating even after the electric-discharge surface treatment. The diffraction peak of an elementary substance of Ti is not confirmed. FIG. 13 shows XRD diffraction measurement result of the coatings formed by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode and the TiC+Si (5:5) electrode, as examples.
  • Meanwhile, as the mixing ratio of Si in the electrode increases, that is, the mixing ratio of TiC in the electrode decreases, integral intensities of all of the diffraction peaks of TiC of the coatings are also reduced. FIG. 14 shows a relation between the mixing ratio of Si in the electrode and the concentration of Ti in the coating. As the mixing ratio of Si in the electrode increases, that is, the mixing ratio of TiC in the electrode decreases, the concentration of Ti in the coating is reduced. Since a peak of the elementary substance of Ti is not shown from the XRD diffraction measurement results, it can be considered that, even though a portion of TiC of an electrode may be decomposed during the electric-discharge surface treatment, most of TiC exists intactly in the coating. As described above, it can be inferred that if the mixing ratio of Si in the electrode increases, that is, the mixing ratio of TiC in the electrode reduces, the concentration of TiC in the coating also relatively reduces.
  • As described above, it can be considered that if the mixing ratio of Si in the electrode increases, the concentration of hard TiC in the coating reduces, and thus, the hardness of the coating reduces.
  • Meanwhile, although the element Si exists at several to several tens wt % at the treated surfaces like in the above-mentioned quantitative analysis, as the results of the X-ray diffraction measurement, it was not possible to confirm the diffraction peaks of crystals of Si at all coatings. Therefore, it can be considered that the elementary substance Si forms an alloy together with the components of the base material, or is in an amorphous state.
  • Effects obtained by mixing Si in the electrode and increasing the concentration of Si in the coating are summarized as shown in FIG. 15. When the mixing ratio of Si in the electrode is small, at the portion (the coating) having melted by the electric-discharge surface treatment, there are many defects such as cracks and a swell of each electric discharge trace is large. Meanwhile, as the mixing ratio of Si increases, defects such as cracks are reduced, and a swell of each electric discharge trace is reduced. Also, regarding the coating, it can be inferred that the elementary substance of Si and the components of the base material form an alloy or are in an amorphous state, and it is inferred that TiC spreads therein. A portion of the coating spreads to a position lower than the height of the base material. The coating including the spread portion is about 5 μm to 20 μm.
  • Next, the erosion resistance of each of the coatings treated by the TiC+Si electrodes formed by mixing the TiC powder and the Si powder at slightly different ratios is evaluated. In the evaluation, the base material is SUS630 (H1075). The erosion resistance is evaluated by hitting the coatings with waterjet. It is generally said that the erosion resistance has a strong correlation with the hardness. Meanwhile, it has been known that the erosion resistance has many points which cannot be explained only by the hardness, and is influenced by the characteristics of surfaces as a factor other than the hardness, and the erosion resistance of a smooth surface is higher than that of a rough surface. Although it has been known that high erosion resistance is obtained at the coating treated by the Si electrode, as results of this evaluation, an improvement in the erosion resistance began to appear at the coatings treated by the electrodes formed by mixing no less than 5 wt % of Si in TiC. When Si was contained at about 5 wt %, some defects existed at the surface, and thus a variation was seen in the evaluation. Therefore, it was found out that if the mixing ratio of Si is further increased, it is possible to give a sufficient effect when the mixing ratio of Si is 10 wt % or greater, and it is more preferable to mix Si at 20 wt % or greater. In a case of mixing Si at 20 wt % or greater, the coating has high erosion resistance without a variation in the evaluation. FIG. 12 is a view illustrating a relation between the mixing ratio of Si in the electrode and the erosion resistance.
  • It is thought that the coating has high erosion resistance as described above due to combined effects of the following points.
      • Since the coating is amorphous, it is difficult for breaking to occur from particle boundaries.
      • Since TiC spreads, the hardness is high.
      • Since Si is mixed, the coating is smooth.
  • FIG. 17 shows results of observation of the surface states of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode and the TiC+Si (5:5) electrode after injection of waterjet of 80 MPa for one hour, as examples. FIG. 13 also shows results of observation of only the base material, the coating by the TiC electrode, and the coating by the Si electrode for comparison. At the base material without any coating, damage had occurred, and even at the treated surface by the TiC electrode, damage had occurred. Meanwhile, at all of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode, and the TiC+Si (5:5) electrode, damage had not occurred.
  • Next, the corrosion resistance of each of the coatings was evaluated. In this evaluation, the base material was SUS 316. Although it is known that high corrosion resistance is obtained at the coating treated by the Si electrode, the coatings treated by the electrodes formed by mixing Si at 5 wt % or greater in TiC has high corrosion resistance. When Si was contained at about 5 wt %, a few defects existed at the surface, and thus a variation in the evaluation was seen. Therefore, if the mixing ratio of Si further increases, it is possible to give a sufficient effect when the mixing ratio of Si is 10 wt % or greater, and it is more preferable to mix Si at 20 wt % or greater. When the mixing ratio of Si was 20 wt % or greater, high corrosion resistance was obtained without a variation in the evaluation. FIG. 18 schematically shows a relation between the mixing ratio of Si in the electrode and the corrosion resistance.
  • It is thought that the coating has high corrosion resistance as described above due to combined effects of the following points.
      • Since the coating is amorphous, it is difficult for breaking to occur from particle boundaries.
      • Since Si is mixed, defects such as cracks are few.
  • FIG. 19 shows results of observation of the surface states of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode, and the TiC+Si (5:5) electrode after dipping in aqua regia serving as a corrosion solution for one hour, as examples. FIG. 19 also shows results of observation of the base material without any coating, the coating by the TiC electrode, and the coating by the Si electrode for comparison. The base material without any coatings greatly corroded, and the surface treated by the TiC electrode also corroded. Meanwhile, at all of the coatings treated by the TiC+Si (8:2) electrode, the TiC+Si (7:3) electrode, and the TiC+Si (5:5) electrode, corrosion had not occurred.
  • From the results obtained until now, if the mixing ratio (weight ratio) of Si in the electrode for electric-discharge surface treatment is taken on a horizontal axis, and the characteristics (the surface roughness, the hardness, the erosion resistance, the corrosion resistance, and the oxidation resistance) of the coating obtained by treatment by the electrode are taken on a vertical axis, graphs as shown in FIG. 21 are obtained. That is, when the mixing ratio of Si is 5 wt % to 60 wt %, it is possible to form a smooth coating having high hardness, high erosion resistance, high corrosion resistance, and high oxidation resistance. When the mixing ratio of Si is 5 wt % or less, the surface roughness is at the same degree as that of the coating by the TiC electrode, and sufficient erosion resistance, corrosion resistance, and oxidation resistance are not obtained. Also, when the mixing ratio of Si is 60 wt % or greater, the hardness is at the same degree as that of the coating by the Si electrode is obtained, and the other characteristics also are at the same degrees as those of the coating by the Si electrode. Particularly, the surface roughness is deteriorated.
  • From results of element concentration measurement and X-ray diffraction by the EDX, the concentrations of Si, TiC, and a base material (Fe) of a coating, which is obtained by treating carbon steel S45C by TiC+Si electrodes formed by mixing the Si powder at slightly different ratios in the TiC powder, are as shown in FIG. 21.
  • As described above, the concentrations of Si, TiC, and the base material component (Fe) of a smooth coating with high hardness, high erosion resistance, high corrosion resistance, and high oxidation resistance formed on carbon steel S45C by electrodes containing Si at the mixing ratio of 5 wt % to 60 wt % were in ranges of 1 wt % to 11 wt %, 10 wt % to 75 wt %, and 20 wt % to 90 wt %, respectively.
  • In the present embodiment, the case of mixing Si in TiC has been described. However, since good characteristics are obtained due to the above-mentioned reasons, instead of TiC, other hard materials, for example, metals such as W and Mo, and ceramics such as carbides including WC, VC, Cr3C2, MoC, SiC, and TaC may also be used. Also, nitrides such as TiN and SiN and oxides such as Al2O3 may also be used. In a case of using an insulator, by sufficiently mixing Si so as to ensure electrical conductivity, it is possible to obtain the same effects.
  • In a case where another material and Si was mixed within the same volume ratio range as that in the case of TiC and Si, the same effects were obtained. In the present embodiment, the mixing ratio of TiC to Si has been defined. However, since the density of TiC is 4.93 g/cm3 and the density of Si is 2.3 g/cm3, if the volume ratio is calculated by dividing weights by the densities, for example, when the weight ratio of TiC to Si is 95 wt %:5 wt %, the volume ratio of TiC to Si is 90 vol % (volume percent):10 vol %, and when the weight ratio of TiC to Si is 40 wt %:60 wt %, the volume ratio of TiC to Si is 25 vol %:75 vol %. In other words, if Si is mixed at 10 vol % to 75 vol % in another hard material, it is possible to form a smooth coating having high hardness, high erosion resistance, high corrosion resistance, and high oxidation resistance.
  • Also, in the present embodiment, Si has been used as a material to be mixed. However, even when metal powder having a small coefficient of viscosity is mixed, it is possible to obtain the same effects. Instead of Si, a material having a small coefficient of viscosity, such as K, Li, Na, Ge, Ca, Mg, Al, P, Bi, Sn, or In, may also be used.
  • In the present embodiment, the TiC powder and the Si powder are mixed at a predetermined weight ratio. However, a powder containing TiC and Si at a predetermined ratio in advance may be used to form an electrode for electric-discharge surface treatment. This case is more preferable since it is possible to uniformly mix TiC and Si.
  • In the present embodiment, the Fe-base material is used as the base material. However, even if other materials are used, it is possible to obtain the same effects. For example, even if the base material is a Ni-base alloy or a Co alloy of heat-resistant alloys, it is possible to obtain the same effects. Also, in a case where the base material is Al or Cu, the coating by the TiC electrode has surface roughness higher than that in the case where the base material is Fe-based. However, if a TiC+Si electrode is used, it is possible to obtain the same effects.
  • As an invention in which Si is added to an electrode material, there is JP-A-556-51543. However, this is an invention regarding an electrode for general electric discharge machining, is for increasing a machining speed, and is an invention in a field different from the present invention in which a hard material coating is formed, and Si is mixed such that the coating becomes smooth, whereby a coefficient of viscosity is reduced.
  • JP-A-2005-21355 is for establishing a surface treatment method for a dense and relatively thick coating (made of a metal material in the order of 100 μm or greater) with no vacancy which needs a strength and lubricity in a high temperature environment, and discloses an electrode for electric-discharge surface treatment containing 1.0 wt % to 4.5 wt % of B (boron) or 1.5 wt % to 5.0 wt % of Si (silicon) as an electrode material for absorbing oxygen atoms. However, the present invention is for establishing a surface treatment method of a smooth and high-hardness coating of a hard material having a thickness 5 μm to 20 μm, and uses a weight ratio of mixed Si of 5 wt % to 60 wt %. Therefore, the present invention is an invention in a field different from JP-A-2005-21355.
  • INDUSTRIAL APPLICABILITY
  • The electrode for electric-discharge surface treatment according to the present invention can be appropriately used for electric-discharge surface treatment work on metal molds, steam turbines, and the like.

Claims (8)

1. An electrode for electric-discharge surface treatment, which is used in the electric-discharge surface treatment in which pulsed electric discharge is generated between the electrode and a base material in a machining fluid or in the air by using a green compact, which is formed by compressing powder of an electrode material, as the electrode, and by using energy of the electric discharge, a coating including the electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of a base material,
wherein a mixture of Si powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm and hard material powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm is used as the electrode material.
2. The electrode for electric-discharge surface treatment according to claim 1,
wherein powder, which includes not more than 5 vol % of powder having a particle diameter of not less than 20 μm, is selected as the hard material and the Si powder which have the average particle diameter of not more than 10 μm.
3. The electrode for electric-discharge surface treatment according to claim 2,
wherein powder, which includes not more than 3 vol % of powder having a particle diameter of not less than 20 μm, is selected as the hard material and the Si powder which have the average particle diameter of not more than 10 μm.
4. The electrode for electric-discharge surface treatment according to claim 1,
wherein the Si powder is mixed to the electrode for electric-discharge surface treatment by 10 to 75 vol %.
5. A method for forming an electrode for electric-discharge surface treatment, which is used in the electric-discharge surface treatment in which pulsed electric discharge is generated between the electrode and a base material in a machining fluid or in the air by using a green compact, which is formed by compressing powder of an electrode material, as the electrode, and by using energy of the electric discharge, a coating including the electrode material or a reaction product of the electrode material reacted by the electric discharge energy is formed on a surface of a base material,
wherein Si powder is mixed to hard material powder while being crushed to obtain a mixed and crushed powder having an average particle diameter of not less than 0.3 μm and not more than 10 μm, and the mixed and crushed powder is compressed to form the electrode material.
6. The method for forming the electrode for electric-discharge surface treatment according to claim 5,
wherein crushing is performed to the hard material and the Si powder which have the average particle diameter of not more than 10 μm until a percentage of powder having a particle diameter of not less than 20 μm is not more than 5 vol %.
7. The method for forming the electrode for electric-discharge surface treatment according to claim 6,
wherein crushing is performed to the hard material and the Si powder which have the average particle diameter of not more than 10 μm until a percentage of powder having a particle diameter of not less than 20 μm is not more than 3 vol %.
8. The method for forming the electrode for electric-discharge surface treatment according to claim 5,
wherein the Si powder is mixed to the hard material powder by 10 to 75 vol %.
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