CN117886610A - High-hardness and high-strength high-entropy carbonitride ceramic composite cutter and preparation method and application thereof - Google Patents
High-hardness and high-strength high-entropy carbonitride ceramic composite cutter and preparation method and application thereof Download PDFInfo
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- CN117886610A CN117886610A CN202410048001.7A CN202410048001A CN117886610A CN 117886610 A CN117886610 A CN 117886610A CN 202410048001 A CN202410048001 A CN 202410048001A CN 117886610 A CN117886610 A CN 117886610A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000005219 brazing Methods 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910009043 WC-Co Inorganic materials 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 7
- 229910001141 Ductile iron Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 229910001060 Gray iron Inorganic materials 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 13
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of ceramic materials, and discloses a high-hardness and high-strength high-entropy carbonitride ceramic composite cutter, and a preparation method and application thereof. The high-entropy carbonitride ceramic composite cutter comprises high-entropy carbonitride ceramic (Ti 0.25Zr0.25Nb0.25Ta0.25)CxN1‑x, x is more than or equal to 0.5 and less than or equal to 0.9 and WC-Co hard alloy used as a cutter bar, wherein the ceramic composite cutter is prepared by mixing TiC, zrC, nbC, taC, tiN, zrN, nbN with TaN, performing spark plasma sintering at 1600-1800 ℃ in argon atmosphere to prepare the high-entropy carbonitride ceramic, coating CuSnTi brazing filler metal between the high-entropy carbonitride ceramic and the WC-Co hard alloy, and performing welding at 880-930 ℃.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a high-hardness and high-strength high-entropy carbonitride ceramic composite cutter, and a preparation method and application thereof.
Background
The high-entropy ceramic is a new material design theory which appears in recent years, is a hot spot in the field of material research, and the concept of the high-entropy ceramic is originally developed from high-entropy alloy. High entropy ceramics are generally multicomponent single phase solid solutions composed of four or more cations in equi-or near-equi-amounts. The high-entropy ceramic has high strength, hardness, excellent wear resistance, excellent high-temperature strength, good structural stability, good corrosion resistance and oxidation resistance compared with a single-phase substance composed of the high-entropy ceramic due to the special high-entropy effect. Due to the increase in components, the combined space for exploring and discovering new materials is greatly increased. The high-entropy ceramic has the advantages that the configuration of the ceramic system is increased due to the increase of components, so that the Gibbs free energy of the ceramic system is reduced, the ceramic system is more stable, and the performance shows excellent stability. In addition, as various atoms are randomly distributed in the lattice, the surrounding environment and occupation of each atom are different, so that more lattice distortion and defects exist in the lattice, the slippage is difficult, and the performance is improved.
Since the high-entropy ceramic has high hardness and high wear resistance, the high-entropy ceramic is expected to be used as a cutting tool for realizing high-speed and long-service life cutting of high-hardness and high-cutting temperature materials such as gray cast iron, spheroidal graphite cast iron and the like, and bonding materials are easy to occur. However, the high-entropy ceramic has the disadvantages of complex preparation process, high cost, low toughness and strength, and difficulty in directly manufacturing a cutter. There is a need to design and develop a suitable method for use with cutting tools.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the primary object of the invention is to provide a high-entropy carbonitride ceramic composite tool with high hardness and high strength, which is formed by welding high-entropy carbonitride ceramic with the composition of (Ti 0.25Zr0.25Nb0.25Ta0.25)CxN1-x (0.5-0.9) and WC-Co hard alloy, wherein the high-entropy carbonitride ceramic has good hardness and excellent frictional wear performance and physical and chemical stability, and has good cutting performance as a cutting part of the welding tool, and the WC-Co hard alloy tool bar has high strength, so that the tool has good chipping resistance and fracture resistance.
Another object of the present invention is to provide a method for producing the above-mentioned high-hardness and high-strength high-entropy carbonitride ceramic composite tool. The method is to weld the high-entropy carbonitride ceramic and WC-Co hard alloy together in a welding mode to prepare the high-entropy ceramic cutter with high hardness and high strength.
It is a further object of the present invention to provide the use of the high-hardness and high-strength high-entropy carbonitride ceramic composite tool as described above. The cutter can be used for high-speed cutting of gray cast iron and spheroidal graphite cast iron.
The aim of the invention is achieved by the following technical scheme:
The high-hardness and high-strength high-entropy carbonitride ceramic composite cutter comprises high-entropy carbonitride ceramic (Ti 0.25Zr0.25Nb0.25Ta0.25)CxN1-x, x is more than or equal to 0.5 and less than or equal to 0.9 and cutter bar WC-Co hard alloy) serving as a cutter head, wherein the ceramic composite cutter is prepared by mixing TiC, zrC, nbC, taC, tiN, zrN, nbN with TaN, performing spark plasma sintering at 1600-1800 in an argon atmosphere to prepare the high-entropy carbonitride ceramic, coating CuSnTi brazing filler metal between the high-entropy carbonitride ceramic and the WC-Co hard alloy, applying pressure of 200-300N in a vacuum environment, and performing brazing at 880-930 .
Preferably, the ceramic cutter has a Vickers hardness of 23-27 GPa, a fracture toughness of 4.0-6.0 MPa-m 1 /2 and a bending strength of 1200-1500 MPa.
Preferably, the grain sizes of TiC, zrC, nbC, taC, tiN, zrN, nbN and TaN powder are 0.8-4 m, and the purity is more than 99%.
Preferably, the solder is CuSnTi mm thick and 0.05-0.13 mm thick, and the welding mode is brazing, and the brazing process is to perform brazing in a vacuum environment so as to prevent oxidation, and apply pressure of 200-300N to ensure that high-quality welding is formed on the connecting surfaces.
Preferably, the temperature rising rate of the spark plasma sintering is 50-150 /min; the sintering time is 10-20 min; the temperature rising rate of the brazing furnace is 50-200 /min; the sintering time is 0.5-1 h.
The preparation method of the high-hardness and high-strength high-entropy carbonitride ceramic composite cutter comprises the following specific steps:
s1, taking absolute ethyl alcohol as a solvent, taking tungsten carbide as a ball milling medium, performing ball milling and mixing on micron-sized TiC, zrC, nbC, taC, tiN, zrN, nbN and TaN powder, and drying to obtain mixed powder;
S2, filling the mixed powder into a graphite mold, pressurizing under argon atmosphere for 30-50 MPa, and performing spark plasma sintering at 1600-1800 to obtain high-entropy carbonitride ceramic;
S3, coating CuSnTi brazing filler metal between the high-entropy carbonitride ceramic and the WC-Co hard alloy, drying for 1-2 hours at 80-100 , then filling the brazing filler metal into a die, and applying 200-300N pressure in a vacuum environment to braze at 880-930 to obtain the high-entropy ceramic composite cutter.
The high-hardness and high-strength high-entropy carbonitride ceramic composite tool is applied to high-speed cutting of gray cast iron or spheroidal graphite cast iron.
Compared with the prior art, the invention has the following beneficial effects:
1. The high-entropy carbonitride ceramic composite cutter is formed by welding high-entropy carbonitride ceramic with the composition of (Ti 0.25Zr0.25Nb0.25Ta0.25)CxN1-x (x is more than or equal to 0.5 and less than or equal to 0.9) and WC-Co hard alloy, wherein the high-entropy carbonitride ceramic has good hardness, excellent friction and wear performance and physical and chemical stability, and has good cutting performance as a cutting part of the welding cutter, and the WC-Co hard alloy cutter bar has high strength, so that the cutter has good chipping resistance and breakage resistance.
2. The invention introduces a key technology in the preparation of the high-entropy carbonitride ceramic composite tool, and realizes the high-quality welding of the high-entropy carbonitride ceramic and WC-Co hard alloy by adopting CuSnTi brazing filler metal in a vacuum environment. The execution of the step ensures the purity of the welding process, and ensures that the high-entropy ceramic is tightly combined with the hard alloy while the characteristics of the high-entropy ceramic are maintained, thereby providing a solid foundation for the durability and the performance of the cutter. Welding is performed in a vacuum environment, so that the influence of oxidization and other pollutants on welding joint is avoided, and the preparation process of the cutter is ensured to be purer and more reliable. This is especially critical for materials with high environmental requirements such as high-entropy carbonitride ceramics, and effectively improves the overall quality and stability of the cutter.
3. The preparation of the high-entropy carbonitride ceramic composite cutter not only improves the overall performance of the cutter, but also endows the cutter with wider application fields. The cutting machine has the advantages that the cutting machine is excellent in gray cast iron or nodular cast iron cutting, brings great convenience to the fields of industrial production and cutting processing, and can efficiently cope with the processing requirements of various materials, so that the production efficiency is improved, and the cost is reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of the high entropy carbonitride ceramic composite ceramic tool of the present invention.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1. Preparation
(1) Mixing TiC (purity 99.5wt.%, particle size 1 m), zrC (purity 99.5wt.%, particle size 1 m), nbC (purity 99.5wt.%, particle size 1 m), taC (purity 99wt.%, particle size 1 m), tiN (purity 99.5wt.%, particle size 1 m), zrN (purity 99.5wt.%, particle size 1 m), nbN (purity 1.5 wt.%, particle size 1 m), nbN (purity 99.5wt.%, particle size 1 m) and TaN (purity 99.5wt.%, particle size 1 m) in a molar ratio of 9:9:9:9:1:1:1 with a ball milling medium, performing planetary ball milling at a rotation speed of 200r/min for 3h, and drying and sieving to obtain mixed powder;
(2) Filling the mixed powder into a graphite mold, placing the graphite mold in a Spark Plasma (SPS) sintering furnace, axially pressurizing for 30MPa in an argon atmosphere, heating to 1600 at 100 /min, preserving heat for 10min, and naturally cooling to room temperature along with the furnace to obtain massive high-entropy carbonitride ceramic, wherein the chemical formula of the massive high-entropy carbonitride ceramic is (Ti 0.25Zr0.25Nb0.25Ta0.25)C0.9N0.1.
(3) And (3) coating CuSnTi solder with the thickness of 0.1mm between the high-entropy carbonitride ceramic and WC-Co hard alloy, drying for 1h, placing in a brazing furnace, applying 200N pressure in a vacuum environment, heating to 880 at 100 /min, preserving heat for 30min, and naturally cooling to room temperature to obtain the high-entropy carbonitride ceramic composite cutter.
2. Performance test: the high-entropy carbonitride ceramic composite tool had a Vickers hardness of 25GPa, a fracture toughness of 5.8 MPa-m 1/2, a bending strength of 1262MPa, and a cutting life of 1633s when used for cutting spheroidal graphite cast iron.
FIG. 1 is a schematic diagram of the structure of the high entropy carbonitride ceramic composite tool of the present invention. As can be seen from fig. 1, the high-entropy carbonitride ceramic composite tool is formed by welding high-entropy carbonitride ceramic serving as a tool bit and a cemented carbide of a tool bar WC-Co by CuSnTi brazing filler metal.
Example 2
The difference from example 1 is that: the axial pressure of the spark plasma sintering in the step (2) is 50MPa.
The high-entropy carbonitride ceramic composite tool obtained in the example had a Vickers hardness of 27GPa, a fracture toughness of 4.2 MPa.m 1/2, a flexural strength of 1463MPa and a cutting life of 1643s.
Example 3
The difference from example 1 is that: the time of the heat preservation in the step (2) is 20min.
The high-entropy carbonitride ceramic composite tool obtained in the example had a Vickers hardness of 26.2GPa, a fracture toughness of 5.2 MPa.m 1/2, a flexural strength of 1330MPa and a cutting life of 1595s.
Example 4
The difference from example 1 is that: the sintering temperature in step (2) was 930 .
The high-entropy carbonitride ceramic composite tool obtained in the example had a Vickers hardness of 26.8GPa, a fracture toughness of 4.3 MPa.m 1/2 and a cutting life of 1621s.
Example 5
The difference from example 1 is that: the time of the heat preservation in the step (3) is 1h.
The high-entropy carbonitride ceramic composite tool obtained in the example had a Vickers hardness of 26.5GPa, a fracture toughness of 4.8 MPa.m 1/2, a flexural strength of 1382MPa and a cutting life of 1574s.
Example 6
The difference from example 1 is that: the molar ratio in the step (1) is 1:1:1:1:1:1:1, and the chemical formula of the prepared high-entropy carbonitride ceramic is (Ti 0.25Zr0.25Nb0.25Ta0.25)C0.5N0.5).
The high-entropy carbonitride ceramic composite tool obtained in the embodiment has the Vickers hardness of 23.4GPa, the fracture toughness of 5.8 MPa-m 1/2, the bending strength of 1283MPa and the cutting life of 1584s.
In summary, the high-entropy carbonitride ceramic composite tool obtained by the invention has a Vickers hardness of 23-27 GPa, a fracture toughness of 4-6 MPa-m 1/2, a bending strength of 1200-1500 MPa, a cutting life of 1550s or more, and preferably 1550-1650 s.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A high-hardness and high-strength high-entropy carbonitride ceramic composite cutter is characterized by comprising high-entropy carbonitride ceramic (Ti 0.25Zr0.25Nb0.25Ta0.25)CxN1-x, x is more than or equal to 0.5 and less than or equal to 0.9 and a cutter bar WC-Co hard alloy) serving as a cutter head, wherein the ceramic composite cutter is prepared by mixing TiC, zrC, nbC, taC, tiN, zrN, nbN with TaN, performing spark plasma sintering at 1600-1800 in an argon atmosphere to prepare the high-entropy carbonitride ceramic, coating CuSnTi brazing filler metal between the high-entropy carbonitride ceramic and the WC-Co hard alloy, applying pressure of 200-300N in a vacuum environment, and performing brazing at 880-930 .
2. The high hardness and high strength high entropy carbonitride ceramic composite tool according to claim 1, wherein the grain size of TiC, zrC, nbC, taC, tiN, zrN, nbN and TaN are both 0.8-4 m, and the purity is greater than 99%.
3. The high-hardness and high-strength high-entropy carbonitride ceramic composite tool according to claim 1, wherein the ceramic composite tool has a vickers hardness of 23 to 27GPa, a fracture toughness of 4 to 6 MPa-m 1/2, and a flexural strength of 1200 to 1500MPa.
4. The high-hardness and high-strength high-entropy carbonitride ceramic composite tool according to claim 1, wherein the temperature rise rate of spark plasma sintering is 50-150 /min; the sintering time is 10-20 min; the temperature rising rate of the brazing is 50-200 /min; the brazing time is 0.5-1 h.
5. The high-hardness and high-strength high-entropy carbonitride ceramic composite tool according to claim 1, wherein the CuSnTi brazing filler metal has a thickness of 0.05 to 0.13mm.
6. The method for producing a high-hardness and high-strength high-entropy carbonitride ceramic composite tool according to any one of claims 1 to 5, comprising the specific steps of:
s1, performing ball milling and mixing on TiC, zrC, nbC, taC, tiN, zrN, nbN and TaN powder by taking absolute ethyl alcohol as a solvent and tungsten carbide as a ball milling medium, and drying to obtain mixed powder;
S2, filling the mixed powder into a graphite mold, pressurizing under argon atmosphere for 30-50 MPa, and performing spark plasma sintering at 1600-1800 to obtain high-entropy carbonitride ceramic;
S3, coating CuSnTi brazing filler metal between the high-entropy carbonitride ceramic and the WC-Co hard alloy, drying for 1-2 hours at 80-100 , then filling the brazing filler metal into a die, and applying 200-300N pressure in a vacuum environment to braze at 880-930 to obtain the high-entropy ceramic composite cutter.
7. The method for manufacturing a high-hardness and high-strength high-entropy carbonitride ceramic composite tool according to claim 6, wherein the drying time in step S3 is 1 to 2 hours.
8. Use of the high-hardness and high-strength high-entropy carbonitride ceramic composite tool according to any one of claims 1 to 5 for high-speed cutting of gray cast iron or ductile iron.
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