WO2016056487A1 - 高温耐酸化性のレアメタルフリー硬質焼結体およびその製造方法 - Google Patents
高温耐酸化性のレアメタルフリー硬質焼結体およびその製造方法 Download PDFInfo
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B22F3/14—Both compacting and sintering simultaneously
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
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- B22F2201/00—Treatment under specific atmosphere
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- B22F2201/00—Treatment under specific atmosphere
- B22F2201/20—Use of vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/10—Carbide
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/15—Carbonitride
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12049—Nonmetal component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12049—Nonmetal component
- Y10T428/12056—Entirely inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12063—Nonparticulate metal component
- Y10T428/1209—Plural particulate metal components
Definitions
- the present invention relates to a hard sintered material that is optimal for cutting tools such as throw-away tips, wear-resistant tools, corrosion-resistant parts, and high-temperature members. Specifically, it relates to an inexpensive hard sintered body with improved high-temperature oxidation resistance and hardness by uniformly dispersing fine aluminum oxide in a metal binder phase not containing a rare metal, and a method for producing the same. is there.
- cemented carbide with tungsten carbide powder sintered using cobalt or nickel have been widely used.
- this cemented carbide is used at a high temperature of 600 ° C. or higher in the atmosphere, oxidation proceeds rapidly, so this cemented carbide has to be used at a lower temperature.
- cutting and die processing at high temperatures are becoming necessary, and hard materials that can be used at higher temperatures are being demanded.
- tungsten mine which is a raw material for tungsten carbide
- tungsten is unevenly distributed in some areas, so tungsten is a rare metal with country risk.
- a cermet obtained by sintering titanium carbide powder or titanium carbonitride powder using cobalt, nickel or the like instead of tungsten carbide is used. Cermet has higher hardness and superior oxidation resistance compared to cemented carbide.
- Cobalt and nickel are also rare metals that are concerned about resource depletion.
- Cobalt is designated as a first-class chemical substance in the PRTR Law and a second-class chemical substance in the Occupational Safety and Health Law, and should not be used as much as possible from the viewpoint of cost and environmental integration.
- development of an inexpensive tool material that stably supplies resources and does not contain rare metals is desired.
- a cemented carbide having a binder phase composed of one or two of Fe and Al instead of cobalt is known (for example, Patent Document 1).
- binder phase of cermet having titanium carbide (TiC) or titanium carbonitride (TiCN) as a hard phase is replaced with an intermetallic compound such as iron aluminide from cobalt or nickel, a hard material containing no rare metal is obtained.
- the present invention has been made in view of the above-described problems, and does not use rare metals, has a bending strength that can be used as a tool, has excellent high-temperature oxidation resistance, has high hardness at high temperatures, and is inexpensive. It is an object to provide a hard sintered body and a method for producing the same.
- the hard sintered body of the present invention is a hard sintered body containing a binder phase of 8.8 to 34.4 mol%, the balance being a hard phase and inevitable impurities, and the binder phase is mainly composed of FeAl. Containing iron aluminide and alumina having a particle size of 1 ⁇ m or less dispersed in iron aluminide, and the hard phase is a carbide, nitride, carbonitride of group 4 metal, group 5 metal, and group 6 metal of the periodic table, And borides, and at least one selected from these solid solutions.
- the method for producing a hard sintered body of the present invention includes a bonded particle powder containing an iron aluminide powder made of at least one selected from FeAl 2 , Fe 2 Al 5 , and FeAl 3 , and a Group 4 metal in the periodic table
- a sintering step of sintering the mixed powder is a bonded particle powder containing an iron aluminide powder made of at least one selected from FeAl 2 , Fe 2 Al 5 , and FeAl 3 , and a Group 4 metal in the periodic table
- the cutting or wear-resistant tool of the present invention uses the hard sintered body of the present invention as a raw material.
- a hard sintered body having excellent high-temperature oxidation resistance and high hardness at high temperatures can be obtained at low cost.
- a hard sintered body of the present invention a method for producing the hard sintered body, and a tool using the hard sintered body as a raw material will be described in detail based on embodiments and examples with reference to tables and drawings. To do.
- duplication description is abbreviate
- ⁇ is described between two numerical values to represent a numerical range, the two numerical values are also included in the numerical range.
- the hard sintered body according to the embodiment of the present invention includes a binder phase, a hard phase, and inevitable impurities.
- the binder phase content in the hard sintered body is preferably 2.4 to 53 mol%. With this content, a hard sintered body having a balance of bending strength, high-temperature oxidation resistance, hardness, and fracture toughness can be obtained.
- the content of the binder phase in the hard sintered body is less than 2.4 mol%, the hardness increases, but the bending strength and high-temperature oxidation resistance are inferior.
- the content of the binder phase in the hard sintered body is more than 53 mol%, the hardness is inferior.
- the binder phase contains iron aluminide and alumina.
- Iron aluminide is mainly composed of FeAl.
- Alumina has a particle size of 1 ⁇ m or less and is dispersed in the iron aluminide.
- the hard phase is composed of at least one selected from carbides, nitrides, carbonitrides, borides, and solid solutions of Group 4 metals, Group 5 metals, and Group 6 metals of the periodic table.
- the Group 4 metals in the periodic table are Ti, Zr, and Hf
- the Group 5 metals are V, Nb, and Ta
- the Group 6 metals are Cr, Mo, and W.
- the hard phase is made of at least one selected from Ti carbide, nitride, carbonitride, boride, and solid solutions thereof, or at least one of tungsten carbide and solid solutions thereof.
- the binder phase is at least one selected from boron, silicon, chromium, niobium, and molybdenum (hereinafter “addition”). May also be included).
- additional By including an additive in the binder phase, densification due to improved sinterability, improvement in high temperature creep characteristics, and improvement in oxidation resistance can be expected.
- the content of the additive in the hard sintered body is preferably greater than 0 mol% and not greater than 25 mol%. This is because if the content of the additive in the hard sintered body is too large, it becomes a hindrance to sintering, and various characteristics of the hard sintered body deteriorate.
- the binder phase content in the hard sintered body is more preferably 8.8 to 34.4 mol%. With this content, a hard sintered body that is excellent in fracture toughness, bending strength, and high-temperature oxidation resistance while having high hardness can be obtained. When the content of the binder phase in the hard sintered body is small, the hardness increases, but the bending strength and high-temperature oxidation resistance are inferior. When the content of the binder phase in the hard sintered body is too large, the hardness is inferior.
- the alumina content in the binder phase is preferably 24.2 to 50.0 mol%.
- the aluminum content of iron aluminide in the binder phase is preferably 24.6 to 57.7. When the aluminum content is more than these ranges, the fracture toughness value is lowered, and when it is less, the high temperature oxidation resistance is lowered.
- the method for producing a hard sintered body of the present invention includes a mixing and grinding step and a sintering step.
- the mixing and pulverizing step the combined particle powder and the hard particle powder are mixed and pulverized to obtain a mixed powder.
- the binding particle powder is composed of at least one selected from iron and aluminide powder composed of iron and aluminum excessively present in relation to iron, for example, FeAl 2 , Fe 2 Al 5 , and FeAl 3.
- This iron aluminide powder is a binder phase material.
- the hard particle powder is composed of at least one powder selected from carbides, nitrides, carbonitrides, and borides of Group 4, Metal, and Group 6 metals of the Periodic Table.
- the hard particle powder is preferably made of at least one selected from Ti carbide, nitride, carbonitride, and boride, or tungsten carbide powder.
- the mixed powder obtained in the mixing and grinding process is sintered.
- Hard sintering having a binder phase containing iron aluminide containing Fe 3 Al or FeAl as a main component and alumina having a particle size of 1 ⁇ m or less dispersed in the iron aluminide through a mixing and grinding step and a sintering step
- the body is obtained.
- the hard sintered body does not use rare metals, and has a bending strength that can be used as a tool, and excellent high-temperature oxidation resistance and high-temperature hardness. It becomes an inexpensive hard material having
- the hard sintered body of the present embodiment is composed of a binder phase and a hard phase
- the raw material powder of the binder phase and the hard phase are homogeneously mixed in order to improve mechanical properties and the like.
- the refinement of crystals of the hard phase and the binder phase is effective for improving the hardness and the like, it is preferable to obtain a raw material powder by dry and wet mixing and grinding. Due to the refinement in the mixing and pulverizing step, a new surface is generated in each of the raw material powders of the binder phase and the hard phase, and oxygen molecules and the like adhere to the new surface. For this reason, if the finely pulverized mixed powder is exposed to the atmosphere, the mixed powder is surely oxidized although it is large or small.
- At least one selected from FeAl 2 , Fe 2 Al 5 , and FeAl 3 is used as the iron aluminide powder for the binder phase material instead of the conventional Fe 3 Al or FeAl.
- Oxygen adsorbed on the mixed powder refined by mixing and pulverization and aluminum in excess of iron in the iron aluminide are expressed by the following chemical reaction formulas (2) to (4) as the temperature rises during sintering.
- a binder phase mainly composed of aluminum oxide and healthy FeAl iron aluminide is obtained. This aluminum oxide becomes fine crystal grains and is dispersed in the binder phase.
- the hard sintered body of the present embodiment like conventional cemented carbides and cermets, is obtained by mixing, molding, and sintering iron aluminide powder and hard phase material powder that are binder phase materials. Can be manufactured.
- the mixing method of the binder particle powder that is the binder phase material and the hard particle powder that is the hard phase material may be dry or wet.
- the oxygen content of the mixed powder since the oxygen content of the mixed powder must be controlled, the relationship between the mixing and pulverization time and the amount of oxygen contained in the obtained mixed powder is obtained in advance by experiments or the like, and the target predetermined oxygen amount The mixture is pulverized and mixed until it becomes a mixed powder containing.
- the combined particle powder and the hard particle powder are mixed with an organic solvent until a mixed powder containing a predetermined amount of oxygen is obtained by a wet mixing and pulverizing machine such as a rolling ball mill, a planetary ball mill, or an attritor.
- the mixed powder can be obtained by wet mixing and pulverizing.
- a vacuum mill container or a mill container substituted with argon or nitrogen until a mixed powder containing a predetermined amount of oxygen is obtained by a dry mixing and grinding machine such as a rolling ball mill, a planetary ball mill, or an attritor
- the mixed powder can also be obtained by dry-mixing and grinding the bonded particle powder and the hard particle powder and then exposing to air.
- a mixed powder containing a predetermined amount of oxygen obtained by mixing and pulverizing the binding particle powder and the hard particle powder is filled in a mold, press-molded, and then sintered to be a hard sintered body.
- Manufacturing. Sintering is preferably performed in a vacuum atmosphere, an argon atmosphere, a nitrogen atmosphere, or a hydrogen atmosphere.
- a mixed powder containing a predetermined amount of oxygen obtained by mixing and pulverizing the binder particle powder and the hard particle powder is filled into a mold for a pressure-current sintering apparatus, and while pressing the mold, You may sinter in a vacuum atmosphere, argon atmosphere, nitrogen atmosphere, or hydrogen atmosphere by electric heating.
- these obtained sintered bodies may be subjected to HIP treatment as necessary.
- the binder phase of the hard sintered body of this embodiment manufactured in this way is a healthy FeAl phase in which fine aluminum oxide is dispersed. For this reason, in the high-temperature oxidation atmosphere, the surface of the hard sintered body that is in contact with the atmosphere of the FeAl phase is newly oxidized, and an aluminum oxide film is formed on the surface of the hard sintered body. This aluminum oxide film covers the surface of the hard sintered body and stops the diffusion of oxygen into the hard sintered body. For this reason, the hard sintered body of the present embodiment exhibits very high temperature oxidation resistance. Moreover, since aluminum oxide also contributes to improvement in hardness, the hard sintered body of the present embodiment has high hardness at high temperatures.
- a commercially available TiC powder having an average particle size of 1.7 ⁇ m (manufactured by Nippon Shin Metal Co., Ltd.), TiCN powder having an average particle size of 1.4 ⁇ m (manufactured by Nippon Shin Metals Co., Ltd., TiC 07 N 03 ), 73 ⁇ m WC powder (manufactured by Nippon Shin Metal Co., Ltd.), WC powder having an average particle diameter of 0.92 ⁇ m (manufactured by Allied Material Co., Ltd.), TiN powder having an average particle diameter of 1.3 ⁇ m (manufactured by Nippon Shin Metal Co., Ltd.), an average particle diameter of 10 ⁇ m FeAl powder (manufactured by Kyoritsu Materials Co., Ltd.
- the mixed powder of A1 to A23, B1, and B3 was wet mixed and pulverized using acetone as a solvent by a rolling ball mill.
- Wet mixing and grinding was performed for 120 hours for A5 and A14, 108 hours for A17 and A21, 48 hours for B1, and 72 hours for others.
- B2 dry mixed grinding was performed for 1 hour. And what was wet-mixed and pulverized dried powder to obtain mixed powder, and what was dry-mixed and pulverized obtained mixed powder as it was.
- each of the obtained mixed powders of A1 to A23, B2, and B3 was filled into a graphite mold.
- the graphite mold filled with the powder was placed in an energization pulse sintering furnace, and sintered at a temperature of 1150 ° C. to 1300 ° C. for 10 minutes to 20 minutes while applying a pressure of 40 MPa to the graphite mold.
- the mixed powder of B1 the mixed powder is filled in a mold, press molding is performed by applying a pressure of 100 MPa to the mold by a hand press, and then 2 at a temperature of 1415 ° C. using a vacuum sintering furnace. Time sintering was performed.
- H v is the Vickers hardness (GPa)
- P is indentation load (N)
- C is the average crack length ([mu] m).
- B1 (cermet) of Comparative Example is known as a material excellent in high temperature oxidation resistance.
- the cumulative oxidation increase of A2 to A4 is about 30-60%, and the cumulative oxidation increase of A10 is 25.4% or less.
- These samples have very good high temperature oxidation resistance. showed that.
- the oxidation increase (unit: g / m 2 ) was 3.3 for A10 and 4. for A17. 0, indicating excellent oxidation resistance.
- FIG. 1 is a cross-sectional observation (SEM) after a high-temperature oxidation test of a hard sintered body of A3, and an analysis result of energy dispersive X-ray spectroscopy measurement for each element (Ti, Fe, Al, O) Is shown). From the SEM image, it was found that an aluminum oxide film having a thickness of about 2 ⁇ m was formed on the surface of the iron aluminide of the binder phase by oxidation on the surface exposed to the atmosphere on the left side of the image.
- FIG. 2 shows X-ray diffraction patterns of the hard sintered bodies A3 and B2.
- FeAl 2 was used in A3, and FeAl and Al 2 O 3 were used in B3.
- 3 to 8 are SEM images when the hard sintered bodies of A2 to A5, A10, and B2 are observed at a magnification of 5000 times.
- a circle with a diameter of 1 ⁇ m is shown in the lower right.
- White dots in the figure are Al 2 O 3 .
- the outer diameter of each white spot is 1 ⁇ m or less in the A3 hard sintered body, whereas the white spot having an outer diameter of 1 ⁇ m or more in the B2 hard sintered body as shown in FIG. Was scattered.
- the particle size of the Al 2 O 3 powder that is the raw material of B2 is 0.3 ⁇ m, it is considered that in the hard sintered body of B2, the Al 2 O 3 powder is coarsened by aggregation or the like in the sintering process.
- the hardness (unit: kgf mm ⁇ 2 ) at a high temperature was measured for a sample with excellent high-temperature oxidation resistance test results.
- the hardness measurement was performed by a method based on JIS Z2244. That is, after heating each sample to 800 ° C. and waiting for the temperature to settle, the Vickers indenter was brought into contact with the sample surface and the temperature of the indenter was heated to the sample temperature, and then the test load of 10 kgf was 15 Measurement was performed with a second pressure reduction. After measuring several points, the temperature was lowered by 100 ° C. and the hardness was measured in the same manner as the previous time until the sample temperature reached 400 ° C. Table 4 and FIG. 9 show the measurement results.
- the high-temperature hardness of the hard sintered body of A1, which has few binder phases, the hard sintered bodies of A10 and A17, and the hard sintered body of A20 mainly composed of tungsten carbide is the same as that of B1 of the comparative example at all temperatures. It was higher than the hardness of the cermet. Moreover, at 600 degrees C or less, the hardness of the hard sintered body of A2 and A3 was higher than the hardness of cermet. Further, when comparing the hardness of the hard sintered bodies of A3 and B3 having the same amount of the binder phase, it was equivalent at 800 ° C., but at 700 ° C. or less, the hardness of the hard sintered body of A3 was B3.
- Table 5 shows the measured values of the oxygen amount of the hard sintered body of each sample and the theoretically calculated values of the composition of the hard sintered body and binder phase of each sample calculated from the blended composition of the mixed powder.
- the oxygen amount of the hard sintered body was measured using an oxygen / nitrogen analyzer (manufactured by LECO, TC-436).
- Oxygen of all oxygen in the hard sintered body during Al 2 O 3, from substance amount of Al 2 O 3 in the hard sintered body is 1/3 of the amount of substance of oxygen in the hard sintered body, MolAl 2 O 3, which is the amount of Al 2 O 3 contained in 100 g of the hard sintered body, MolAl 2 O 3 1/3 ⁇ (4.06 / AtmO) [mol] It is.
- MolTiC which is the amount of TiC contained in the hard sintered body 100g, is a value obtained by dividing the mass of TiC in the hard sintered body 100g by the formula amount AtmTiC of TiC.
- MolTiC 95.94 ⁇ 0.892 /(0.892 ⁇ AtmTiC+0.108 ⁇ AtmFeAl 2 ) [mol] It is.
- MolFeAl which is the amount of FeAl contained in 100 g of the hard sintered body is MolFeAl 2 which is the amount of FeAl 2 contained in the mixed powder 95.94 g.
- MolFeAl 95.94 ⁇ 0.108 /(0.892 ⁇ AtmTiC+0.108 ⁇ AtmFeAl 2 ) [mol] It is.
- the values of MolTiC, MolFeAl, and MolAl 2 O 3 calculated by the above formula were substituted into the above formula to calculate the TiC mole fraction, the FeAl mole fraction, and the Al 2 O 3 mole fraction.
- the Al mole fraction in the iron aluminide in the hard sintered body 100 g is the amount of Al in the iron aluminide in the hard sintered body 100 g.
- the Al mole fraction in the iron aluminide in the binder phase was calculated by substituting the value of MolAl @ FeAl calculated by the above formula and the value of MolFeAl 2 at the time of mixing powder into the above formula.
- the molar fraction of Al 2 O 3 in the binder phase in 100 g of the hard sintered body is the same as that of Al 2 O 3 contained in 100 g of the hard sintered body.
- the amount of substance MolAl 2 O 3 is the amount of iron aluminide contained in 100 g of the hard sintered body, that is, the amount of FeAl 2 contained in the mixed powder 95.94 g and the amount of Al 2 O contained in 100 g of the hard sintered body.
- Molar fraction of Al 2 O 3 in the binder phase MolAl 2 O 3 / (MolFeAl 2 + MolAl 2 O 3 ) It is.
- the molar fraction of Al 2 O 3 in the binder phase was calculated by substituting MolAl 2 O 3 calculated by the above formula and the value of MolFeAl 2 at the time of mixing powder into the above formula.
- compositions of the hard sintered bodies and binder phases of A3, A4, A10, A14, and B2 were calculated in the same manner. From the results of energy dispersive X-ray spectroscopy measurement shown in FIG. 1 and the X-ray diffraction pattern results shown in FIG. 2, it is considered that the actually measured oxygen is bonded to Al.
- the hard sintered body of the present invention can be used as a raw material for cutting tools, wear-resistant tools, corrosion-resistant members, high-temperature members and the like that have been used in cemented carbides and cermets. Specifically, it can be suitably used as a material for cutting tools and materials for wear-resistant tools such as processing of difficult-to-cut materials exposed to high temperatures and high-temperature forging.
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Abstract
Description
4FeAl+3O2→4Fe+2Al2O3 (1)
また、硬質粒子からプリフォームを形成し、FeAlを溶侵する複合材料の製法では、複合材料の緻密化が困難で、複合材料の硬度や抗折力が低くなるという問題があった。
本発明の硬質焼結体は、結合相が8.8~34.4mol%含有され、残部が硬質相および不可避不純物からなる硬質焼結体であって、結合相が、FeAlを主成分とする鉄アルミナイドと、鉄アルミナイド中に分散した粒径1μm以下のアルミナとを含有し、硬質相が、周期表の4族金属、5族金属、および6族金属の炭化物、窒化物、炭窒化物、およびホウ化物、ならびにこれらの固溶体の中から選ばれた少なくとも一種からなる。
4FeAl2+3O2→4FeAl+2Al2O3 (2)
4Fe2Al5+9O2→8FeAl2+2Al2O3+6O2
→8FeAl+6Al2O3 (3)
4FeAl3+6O2→4FeAl2+2Al2O3+3O2
→4FeAl+4Al2O3 (4)
すなわち、A3およびB2の構成相にTiC、FeAl、およびAl2O3が含まれ、FeAl2が含まれないことがわかった。このことから、本発明の硬質焼結体の製造方法により、A3において、FeAl2からFeAlおよびAl2O3が生成されたことが示された。
硬質焼結体100gに含まれる酸素の物質量であるMolOは、
MolO=4.06/AtmO〔mol〕
である。
MolAl2O3=1/3×(4.06/AtmO)〔mol〕
である。
硬質焼結体100g中のTiCの質量
=95.94×0.892×AtmTiC
/(0.892×AtmTiC+0.108×AtmFeAl2)〔g〕
である。
MolTiC
=95.94×0.892
/(0.892×AtmTiC+0.108×AtmFeAl2)〔mol〕
である。
MolFeAl
=95.94×0.108
/(0.892×AtmTiC+0.108×AtmFeAl2)〔mol〕
である。
硬質焼結体のTiCのモル分率
=MolTiC/(MolTiC+MolFeAl+MolAl2O3)
硬質焼結体のFeAlのモル分率
=MolFeAl/(MolTiC+MolFeAl+MolAl2O3)
硬質焼結体のAl2O3のモル分率
=MolAl2O3/(MolTiC+MolFeAl+MolAl2O3)
である。前述の式によって算出されたMolTiC、MolFeAl、MolAl2O3の値を上記式に代入して、TiCモル分率、FeAlモル分率、およびAl2O3モル分率を算出した。
MolAl@Al2O3=2×MolAl2O3〔mol〕
である。
硬質焼結体100gに含まれる鉄アルミナイド中のAlの物質量、すなわちAl2O3中のAlを除いた硬質焼結体100gに含まれるAlの物質量であるMolAl@FeAlは、混合粉末95.94gに含まれていたFeAl2中のAlの物質量であるMolAl@FeAl2を用いると、
MolAl@FeAl=2×MolAl@FeAl2-MolAl@Al2O3
=2×MolAl@FeAl2-2×MolAl2O3〔mol〕
である。ここで、MolAl@FeAl2=2×MolFeAl2〔mol〕であるから、前述の式によって算出されたMolAl2O3と混合粉末配合時のMolFeAl2の値を上記式に代入して、MolAl@FeAlを算出した。
結合相中の鉄アルミナイド中のAlモル分率
=MolAl@FeAl/(MolAl@FeAl+MolFeAl2)
である。前述の式によって算出されたMolAl@FeAlと混合粉末配合時のMolFeAl2の値を上記式に代入して、結合相中の鉄アルミナイド中のAlモル分率を算出した。
結合相中のAl2O3のモル分率
=MolAl2O3/(MolFeAl2+MolAl2O3)
である。前述の式によって算出されたMolAl2O3と混合粉末配合時のMolFeAl2の値を上記式に代入して、結合相中のAl2O3のモル分率を算出した。
Claims (17)
- 結合相が8.8~34.4mol%含有され、残部が硬質相および不可避不純物からなる硬質焼結体であって、
前記結合相が、FeAlを主成分とする鉄アルミナイドと、前記鉄アルミナイド中に分散した粒径1μm以下のアルミナとを含有し、
前記硬質相が、周期表の4族金属、5族金属、および6族金属の炭化物、窒化物、炭窒化物、およびホウ化物、ならびにこれらの固溶体の中から選ばれた少なくとも一種からなる硬質焼結体。 - 前記硬質相が、Tiの炭化物、窒化物、炭窒化物、およびホウ化物、ならびにこれらの固溶体の中から選ばれた少なくとも一種からなる請求項1に記載の硬質焼結体。
- 前記硬質相が、炭化タングステンおよびその固溶体の少なくとも一方からなる請求項1に記載の硬質焼結体。
- ボロン、シリコン、クロム、ニオブ、およびモリブテンの中から選ばれた少なくとも一種が、前記結合相にさらに含有される請求項1~3のいずれか1項に記載の硬質焼結体。
- 前記結合相中の前記アルミナの含有量が24.2~50.0mol%である請求項1~4のいずれか1項に記載の硬質焼結体。
- 前記結合相中の鉄アルミナイドのアルミニウムの含有量が24.6~57.7mol%である請求項1~5のいずれか1項に記載の硬質焼結体。
- FeAl2、Fe2Al5、およびFeAl3の中から選ばれた少なくとも一種からなる鉄アルミナイド粉末を含有する結合粒子粉末と、周期表の4族金属、5族金属、および6族金属の炭化物、窒化物、炭窒化物、およびホウ化物の中から選ばれた少なくとも一種からなる硬質粒子粉末とを、混合および粉砕して混合粉末を得る混合粉砕工程と、
前記混合粉末を焼結する焼結工程と、
を有する硬質焼結体の製造方法。 - 前記硬質粒子粉末が、Tiの炭化物、窒化物、炭窒化物、およびホウ化物の中から選ばれた少なくとも一種からなる請求項7に記載の硬質焼結体の製造方法。
- 前記硬質粒子粉末が、炭化タングステンからなる請求項7に記載の硬質焼結体の製造方法。
- 前記混合粉末中の前記鉄アルミナイド粉末の含有量が2.4~24.4mol%であり、前記混合粉末中の前記硬質粒子粉末の含有量が75.6~97.6mol%である請求項7~9のいずれか1項に記載の硬質焼結体の製造方法。
- ボロン、シリコン、クロム、ニオブ、およびモリブテンの中から選ばれた少なくとも一種の添加粉末が、前記結合粒子粉末にさらに含有される請求項7~10のいずれか1項に記載の硬質焼結体の製造方法。
- Fe、FeB、Fe3Al、およびFeAlの中から選ばれた少なくとも一種からなる鉄系粉末が、前記結合粒子粉末にさらに含有される請求項7~11のいずれか1項に記載の硬質焼結体の製造方法。
- 前記混合粉砕工程が、所定の酸素量を含有する前記混合粉末が得られるまで、前記結合粒子粉末と前記硬質粒子粉末とを有機溶媒を用いた湿式混合粉砕して前記混合粉末を得る過程を備える請求項7~12のいずれか1項に記載の硬質焼結体の製造方法。
- 前記混合粉砕工程が、所定の酸素量を含有する前記混合粉末が得られるまで、真空のミル容器内またはアルゴンもしくは窒素で置換したミル容器内で、前記結合粒子粉末と前記硬質粒子粉末とを乾式混合粉砕後、大気暴露して前記混合粉末を得る過程を備える請求項7~12のいずれか1項に記載の硬質焼結体の製造方法。
- 前記焼結工程が、前記混合粉末を加圧成形した後に、真空雰囲気、アルゴン雰囲気、または窒素雰囲気で焼結する過程を備える請求項13または14に記載の硬質焼結体の製造方法。
- 前記焼結工程が、前記混合粉末を加圧しながら、真空雰囲気、アルゴン雰囲気、または窒素雰囲気で焼結する過程を備える請求項13または14に記載の硬質焼結体の製造方法。
- 請求項1~6のいずれか1項に記載の硬質焼結体を原材料とする切削用または耐摩耗用の工具。
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