CN117070819B - A Ti(C,N)-based cermet cutting tool material, its preparation method and application - Google Patents
A Ti(C,N)-based cermet cutting tool material, its preparation method and applicationInfo
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- CN117070819B CN117070819B CN202311079848.3A CN202311079848A CN117070819B CN 117070819 B CN117070819 B CN 117070819B CN 202311079848 A CN202311079848 A CN 202311079848A CN 117070819 B CN117070819 B CN 117070819B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22C29/04—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a Ti (C, N) -based metal ceramic cutter material, a preparation method and application thereof, wherein the material comprises at least one of ① titanium carbonitride, nitride and carbide with the mass fraction of more than 45% and one of tungsten carbide with the mass fraction of more than 55%, ② weighing various raw materials according to a proportion, mixing, carrying out alcohol wet milling, spray granulation, compression molding and argon micro-pressure sintering, and ③ preparing a metal ceramic cutter through a post-treatment process. The metal ceramic comprises two hard phase particles of a black core-gray ring structure and a white core-gray ring structure, has typical mixed crystal structure characteristics, and generates a Ti (C, N) fine crystal layer with the thickness of 2-20 mu m on the surface of a substrate, so that the surface hardness is greatly improved, the wear resistance, the high temperature resistance and the impact resistance of the material are obviously improved, and the cutting life of a cutter is prolonged by 3-5 times.
Description
Technical Field
The invention belongs to the technical field of metal ceramics, and particularly relates to a Ti (C, N) -based metal ceramic cutter material, and a preparation method and application thereof.
Background
With the rapid development of modern material technology, various novel difficult-to-process materials are widely applied to the fields of aerospace, rail transit, energy power and the like, and the development of cutting tool materials in the directions of long service life, high efficiency and high precision is also required.
Ti (C, N) -based cermet is used as a new hard cutting tool material, and has not only high hardness and high wear resistance of ceramic phase, but also strength and toughness of metal phase. Compared with the traditional WC-Co hard alloy, the Ti (C, N) -based metal ceramic has more excellent red hardness and high-temperature oxidation resistance, can be used for dry high-speed cutting, has high processing efficiency and good surface quality, and is particularly suitable for the finish/semi-finish machining of materials such as iron castings, steel pieces, high-temperature alloys and the like.
However, ti (C, N) -based cermets are large in brittleness, insufficient in toughness while obtaining high hardness, and a chipping phenomenon frequently occurs in a cutting process of a tool, resulting in a limited range of application thereof. In order to improve the impact toughness of the metal ceramic material, the content of the binding phase is often required to be improved, but the hardness is also reduced, the wear resistance is reduced, and the processing life of the cutter is shortened. For many years, related technicians have sought a preparation method capable of strengthening and toughening metal ceramics, but the preparation method is broken through, and most of technical schemes proposed in patent papers are difficult to apply to actual production.
The related art discloses a TiCN-based metal ceramic with a gradient structure prepared by a low-pressure nitriding sintering method, however, 10 mbar-300 mbar nitrogen is introduced to change the balance nitrogen partial pressure in a sintering furnace, the nitriding reaction process is difficult to control, the variation of matrix components from outside to inside is large, and the stability fluctuation of a cutter is easy to be caused.
The related art also discloses a method for preparing the cobalt-free titanium-based metal ceramic with the surface fine grain functional gradient by combining negative pressure nitriding and negative pressure carburizing, but the preparation process is complex in control process, and the CH 4 gas is introduced at high temperature, so that the potential safety hazard is high, and the safety production requirement is not met.
Therefore, the invention provides a preparation method of the Ti (C, N) -based metal ceramic cutter material with the surface fine-grain reinforced mixed-grain structure, and the matrix can have excellent wear resistance and impact resistance through special component design and argon micro-pressure sintering technology, so that the universality of the cutter is obviously improved.
Disclosure of Invention
The invention provides a Ti (C, N) -based cermet cutter material, which aims at solving at least one scheme in the prior art.
The invention also provides a preparation method of the Ti (C, N) -based metal ceramic cutter material.
The invention also provides application of the Ti (C, N) -based metal ceramic cutter material.
Specifically, the first aspect of the invention provides a Ti (C, N) -based cermet cutter material, which comprises the following preparation raw materials in percentage by mass:
42.2-58.6% of titanium source, 11.5-25.5% of tungsten source and 13.3-19.2% of metal powder;
The titanium source is at least one of titanium carbonitride, titanium nitride and titanium carbon compound;
The tungsten source is tungsten carbon compound;
the metal powder is cobalt powder or nickel powder.
According to one of the technical schemes of the cutter material, the cutter material has at least the following beneficial effects:
According to the invention, a titanium source and a tungsten source are matched, the component design can enable two hard phase particles to be generated in a metal ceramic tissue, one is a black core-gray ring structure particle taking coarse Ti-rich carbon nitride particles as cores, the other is a white core-gray ring structure particle taking fine W-rich carbides as cores, the toughness of a matrix can be improved, and the other can play roles of dispersion strengthening and reinforcing and toughening.
On the one hand, as the sintering temperature increases, a large amount of coarse Ti-rich carbonitride particles are not completely dissolved and remain as nucleation sites, while the alloy components dissolved in the binder phase precipitate around them to form a (Ti, W.) (C, N) annular phase;
On the other hand, because the content of fine W-rich carbide particles is high, exceeding the dissolution limit in the binder phase, most of the particles do not dissolve completely to form nucleation sites, so that other alloy components also form (Ti, W.) (C, N) annular phases around them by a dissolution-precipitation mechanism.
In addition, the toughness and the impact resistance of the material can be further improved by adopting the Co/Ni composite binding phase.
The preparation raw material of the invention not only can enable the matrix to have higher toughness and impact resistance, but also can enable the surface of the matrix to obtain higher hardness and wear resistance, and the cutting life of the cutter is improved by 3-5 times.
According to some embodiments of the invention, the Ti (C, N) -based cermet tool material comprises black core-gray ring structured hard phase particles and white core-gray ring structured hard phase particles;
the black core in the black core-gray ring structure particles is Ti-rich carbonitride;
the gray ring structural phase in the black core-gray ring structural particles is an A (C, N) solid solution;
the A comprises at least one of titanium and tungsten;
The equivalent particle diameter of the black core-gray ring structural particles is 0.6-3.0 mu m;
The white core part in the Bai Xin-gray ring structure particle is a carbide rich in W;
the gray ring structural phase in the Bai Xin-gray ring structural particles is B (C, N) solid solution;
The B comprises at least one of titanium and tungsten;
The equivalent particle diameter of Bai Xin-gray ring structural particles is 0.4-1.5 mu m;
a fine crystal layer with the thickness of 2-20 mu m is generated on the surface of the Ti (C, N) matrix;
The hard phase particles of the fine crystal layer are Ti (C, N), and the equivalent particle diameter is 0.3-1.8 mu m.
According to some embodiments of the invention, the gray ring structural phase in the black core-gray ring structural particles is a (Ti, W, ta, mo, W) (C, N) solid solution.
According to some embodiments of the invention, the gray ring structural phase in the Bai Xin-gray ring structural particles is a (Ti, W, ta, mo, W) (C, N) solid solution.
According to some embodiments of the invention, the starting material for preparing the Ti (C, N) -based cermet tool material further comprises a transition metal carbide.
According to some embodiments of the invention, the transition metal carbide comprises at least one of a tantalum carbon compound, a niobium carbon compound, a molybdenum carbon compound, a zirconium carbon compound, a vanadium carbon compound, and a chromium carbon compound.
The invention can obviously improve the high-temperature red hardness and the high-temperature wear resistance of the matrix by adding a proper amount of carbide such as Ta, nb, zr and the like.
According to some embodiments of the invention, the transition metal carbide has a particle size of 1.0 μm to 4.0 μm.
According to some embodiments of the invention, the titanium source comprises more than 45% titanium by mass.
According to some embodiments of the invention, the tungsten source comprises more than 55% tungsten by mass.
According to some embodiments of the invention, the particle size of the titanium source is 1.5 μm to 3.5 μm.
According to some embodiments of the invention, the tungsten source has a particle size of 0.5 μm to 1.5 μm.
The second aspect of the invention discloses a preparation method of the Ti (C, N) -based metal ceramic cutter material, which comprises the following steps:
s1, mixing the preparation raw materials to prepare a mixture;
S2, pressing and forming the mixture to obtain a pressed blank;
S3, de-esterifying the pressed compact and sintering;
The sintering is performed by vacuum sintering, first argon micro-pressure sintering and second argon micro-pressure sintering;
the temperature of the first argon micro-pressure sintering is 1460-1520 ℃;
the temperature of the second argon micro-pressure sintering is 1250-1350 ℃.
According to some embodiments of the invention, the mixing comprises ball milling, sieving, and spray granulation.
According to some embodiments of the invention, the ball mill mixing is performed in a drum ball mill.
According to some embodiments of the invention, the ball-material ratio of the ball-milling mixture is 6:1-10:1.
According to some embodiments of the invention, the rotational speed of the ball-milled mixture is 30 rpm-50 rpm.
According to some embodiments of the invention, the time of ball milling and mixing is 24-48 hours.
According to some embodiments of the invention, the pressure of the press forming is 200mpa to 300mpa.
According to some embodiments of the invention, the temperature of the de-esterification is 400 ℃ to 600 ℃.
According to some embodiments of the invention, the time for the de-esterification is 1h to 2h.
According to some embodiments of the invention, the vacuum sintering temperature is 1100 ℃ to 1200 ℃.
According to some embodiments of the invention, the vacuum sintering has a vacuum level of less than 5Pa.
According to some embodiments of the invention, the time of vacuum sintering is 3-6 hours.
According to some embodiments of the invention, the argon pressure of the first argon micro-pressure sintering and the argon pressure of the second micro-pressure sintering are each independently selected from 10mbar to 500mbar.
According to some embodiments of the invention, the time of the first argon micro-pressure sintering is 0.5h to 1.5h.
According to some embodiments of the invention, the second argon micropressure sintering is performed for 1-8 hours.
According to some embodiments of the invention, the argon micro-pressure sintering is performed for the second time and then cooled to below 800 ℃, and the cooling rate is 25-35 ℃ per minute.
According to some embodiments of the invention, the argon pressure of the first argon micro-pressure sintering is 10mbar to 500mbar.
According to some embodiments of the invention, the argon flow of the first argon micro-pressure sintering is 3L/min-18L/min.
According to some embodiments of the invention, the argon pressure of the second micro-pressure sintering is 10mbar to 500mbar.
According to some embodiments of the invention, the argon flow of the first argon micro-pressure sintering is 3L/min-18L/min.
According to some embodiments of the present invention, the method of preparing a Ti (C, N) -based cermet tool material comprises the steps of:
s01, weighing preparation raw materials and paraffin according to a proportion, and then performing ball milling mixing, screening and spray granulation to obtain a mixture;
s02, pressing and forming the mixture obtained in the step S01 under the pressure of 200-300 MPa to obtain a pressed blank;
S03, sintering the pressed compact obtained in the step S02 in a de-esterification/sintering integrated furnace, wherein the sintering process comprises the following steps:
Firstly, heating to 400-600 ℃, and performing positive pressure de-esterification of hydrogen on the pressed compact for 1-2 hours;
Then continuously heating the de-esterified compact to 1100-1200 ℃, wherein the stage is vacuum sintering, the vacuum degree is lower than 5Pa, and the heat preservation time is 3-6 h;
then heating to 1460-1520 ℃, wherein the argon micro-pressure sintering is performed at the stage, and the heat preservation time is 0.5-1.5 h;
Then cooling to 1250-1350 ℃, wherein the stage is argon micro-pressure sintering, and the heat preservation time is 1-8 hours;
and finally, cooling the workpiece with a cooling rate of 25-35 ℃ per minute to below 800 ℃ and cooling the workpiece with a furnace to obtain the Ti (C, N) -based metal ceramic cutter material with the surface fine-grain reinforced mixed crystal structure.
Performing positive pressure de-esterification of hydrogen at 400-600 ℃ and preserving heat for 1-2 hours to remove paraffin wax forming agent in the pressed compact completely and avoid carbon residue in the sintered compact;
Vacuum sintering is carried out at 1100-1200 ℃ and heat preservation is carried out for 3-6 hours, so that hard phase particles are pre-coarsened by solid diffusion, and pores in the sintering body are in an open pore state, thereby inhibiting the growth and development of the particles in the subsequent liquid phase sintering process;
Argon micro-pressure sintering is carried out at 1460 ℃ to 1520 ℃ and the heat preservation time is 0.5h to 1.5h, so that the sintered body obtains higher density, argon partial pressure can prevent nitrogen molecules from escaping, nitrogen atoms or nitrogen molecules are promoted to diffuse to a surface layer area through openings to be enriched, and the nitrogen atoms or nitrogen molecules react with Ti and C atoms to generate Ti (C, N) fine crystal layers in situ;
Argon micro-pressure sintering is carried out at 1250-1350 ℃ for 2-4 hours, so that the sintered body is completely densified, and meanwhile, hard phase particles are prevented from roughening, and then, the growth and thickening of the Ti (C, N) fine crystal layer on the surface are further promoted.
The cooling stage is carried out at a cooling rate of 25-35 ℃ per minute to below 800 ℃ so as to inhibit the precipitation of alloy elements and the growth of annular phases, so that the substrate maintains the characteristic at high temperature.
The third aspect of the invention discloses the application of the Ti (C, N) -based metal ceramic tool material in preparing a cutting tool.
According to the invention, through specific component design, the cermet can obtain hard phase particles with two different shapes and sizes, the toughening of the matrix is realized, and in addition, a Ti (C, N) fine crystal layer can be generated on the surface of the matrix through an argon micro-pressure sintering technology, so that the surface hardness and the wear resistance are obviously improved.
The Ti (C, N) -based metal ceramic cutter material with the surface fine-grain reinforced mixed crystal structure prepared by the invention can meet continuous strong wear-resistant processing working conditions, can be applied to intermittent impact-resistant processing working conditions, and improves the cutting life of the cutter by 3-5 times.
The invention has no special requirement on production equipment, has simple process control process and is beneficial to industrial popularization and application.
Drawings
The present invention is further described below with reference to the accompanying drawings for the convenience of understanding by those skilled in the art.
Fig. 1 is an SEM image of Ti (C, N) -based cermet tool materials with a surface fine-grained reinforced mixed crystal structure prepared in example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment is a metal ceramic cutter material, which comprises the following preparation raw materials in percentage by mass:
57.2% of Ti-C-N powder with the mass fraction of 75.5%, 2.5 μm of powder particle size, 18.5% of tungsten carbide powder with the mass fraction of 98.2% of W, 0.8 μm of powder particle size, 14.0% of Co+Ni powder, 2.0 μm of powder particle size, 5.6% of TaC powder, 2.5 μm of powder particle size, 3.6% of Mo 2 C powder, 3.5 μm of powder particle size, 1.1% of VC powder and 1.5 μm of powder particle size.
The preparation method of the metal ceramic cutter material in the embodiment comprises the following steps:
S1, adding paraffin accounting for 2.5% of the total mass of the raw materials into titanium carbonitride powder, tungsten carbide powder, co+Ni powder, taC powder, mo 2 C powder and VC powder, and then placing into a roller ball mill for mixing, wherein the ball milling medium is ethanol, the ball material ratio is 8:1, the rotating speed of the ball mill is 35r/min, and the ball milling time is 36h.
After being evenly mixed, the slurry is taken out and sieved by a 200-mesh sieve, and then spray drying is carried out to obtain a mixture;
S2, pressing and forming the mixture prepared in the step S1 under 260MPa pressure to obtain a pressed compact with a certain size and shape;
S3, sintering the pressed compact obtained in the step S2 in a de-esterification/sintering integrated furnace, wherein the specific sintering process is as follows:
Firstly, heating to 500 ℃ to perform positive pressure de-esterification of hydrogen on the pressed compact, wherein the heating rate is 1 ℃ per minute, and preserving heat for 0.5h;
Then heating to 1200 ℃ for vacuum sintering, wherein the vacuum degree is lower than 5Pa, the heating rate is 5 ℃ per minute, and the temperature is kept for 4 hours;
Then heating to 1500 ℃ for argon micro-pressure sintering, wherein the argon flow is 8L/min, the argon pressure is 150mbar, the heating rate is 7 ℃/min, and the temperature is kept for 1h;
then cooling to 1300 ℃ for argon micro-pressure sintering, wherein the argon flow is 10L/min, the argon pressure is 300mbar, the cooling rate is 10 ℃/min, and the temperature is kept for 3 hours;
and finally, cooling to below 800 ℃ at a cooling rate of 35 ℃ per minute, and then cooling along with a furnace to obtain the Ti (C, N) -based metal ceramic cutter material with the surface fine-grain reinforced mixed crystal structure.
An SEM image of the Ti (C, N) -based cermet tool material prepared in this example is shown in fig. 1. As can be seen from FIG. 1, the microstructure contains hard phase particles with a black core/gray ring structure with an equivalent particle diameter of 0.8-2.5 μm, wherein the black core is Ti-rich carbonitride, the gray ring structure phase is (Ti, W, ta, mo, W) (C, N) solid solution, and white core/gray ring structure hard phase particles with an equivalent particle diameter of 0.6-1.5 μm, the white core is W-rich carbide, the gray ring structure phase is (Ti, W, ta, mo, W) (C, N) solid solution, and a Ti (C, N) fine crystal layer with a thickness of 6 μm is formed on the surface layer of the matrix, and the equivalent particle diameter is 0.3-1.8 μm.
The mechanical property detection is carried out on the material obtained in the embodiment, the hardness of the prepared metal ceramic material is HRA93.5, the fracture toughness is 9.9 MPa.m 1/2, and the bending strength is 2480MPa.
Comparative example 1
The raw material proportion of the comparison product is consistent with that of the example 1, the preparation method is characterized in that vacuum atmosphere is adopted in the sintering process, argon is filled into the mixture at the final sintering temperature of 1500 ℃ for argon micro-pressure sintering, the heat preservation time is 1h, and the metal ceramic cutter material is obtained after cooling.
Cutting performance tests were conducted on the materials obtained in example 1 and comparative example 1, and a TNMG160408-FG cutter of ISO standard was prepared, the cut material was 45 steel, the cutting speed was 240m/min, the cutting depth was 0.5mm, the cutting feed was 0.2mm/rev, and the comparative test was conducted with the conventional cutter under the same processing parameters, and the flank wear Vb was required to be less than 0.2mm, the surface roughness Ra was less than 3.2 μm, and the test results were shown in Table 1. From the test results, the cutting life of the tool prepared by the method of this example can be improved by 3.5 times.
Table 1 results of tool cutting test in this example
Example 2
The embodiment is a metal ceramic cutter material, which comprises the following preparation raw materials in percentage by mass:
48.5% of Ti-C-N powder with the mass fraction of 66.2%, 3.2 mu m of powder particle size, 24.2% of tungsten carbide powder with the mass fraction of 85.5% of W, 1.4 mu m of powder particle size, 15.5% of Co+Ni powder, 1.3 mu m of powder particle size, 6.1% of NbC powder, 2.0 mu m of powder particle size, 5.0% of Mo 2 C powder, 1.4 mu m of powder particle size, 0.7% of ZrC powder and 2.2 mu m of powder particle size.
The preparation method of the metal ceramic cutter material in the embodiment comprises the following steps:
S1, adding paraffin accounting for 2.5% of the total mass of the raw materials into titanium carbonitride powder, tungsten carbide powder, co+Ni powder, nbC powder, mo 2 C powder and ZrC powder, placing into a roller ball mill for mixing, wherein the ball milling medium is ethanol, the ball material ratio is 6:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 48 hours.
After being evenly mixed, the slurry is taken out and sieved by a 200-mesh sieve, and then spray drying is carried out to obtain a mixture;
S2, pressing and forming the mixture prepared in the step S1 under 300MPa pressure to obtain a pressed compact with a certain size and shape;
S3, sintering the pressed compact obtained in the step S2 in a de-esterification/sintering integrated furnace, wherein the specific sintering process is as follows:
firstly, heating to 400 ℃, performing positive pressure de-esterification of hydrogen on the pressed compact, wherein the heating rate is 1 ℃ per minute, and preserving heat for 2 hours;
then heating to 1100 ℃ for vacuum sintering, wherein the vacuum degree is lower than 5Pa, the heating rate is 5 ℃ per minute, and the temperature is kept for 6 hours;
then heating to 1520 ℃ for argon micro-pressure sintering, wherein the argon flow is 3L/min, the argon pressure is 100mbar, the heating rate is 7 ℃/min, and the temperature is kept for 0.5h;
Then cooling to 1250 ℃ for argon micro-pressure sintering, wherein the argon flow is 12L/min, the argon pressure is 240mbar, the cooling rate is 10 ℃/min, and the temperature is kept for 6 hours;
and finally, cooling to below 800 ℃ at the cooling rate of 30 ℃ per min, and then cooling along with a furnace to obtain the Ti (C, N) -based metal ceramic cutter material with the surface fine-grain reinforced mixed crystal structure.
As a result of examining the microstructure and mechanical properties of the cermet obtained in this example, it was found that a Ti (C, N) fine grain layer having a thickness of 10 μm was formed on the surface layer of the matrix, and the material had a hardness of HRA93.0, a fracture toughness of 10.3 MPa.m 1/2 and a flexural strength of 2643MPa.
Example 3
The embodiment is a metal ceramic cutter material, which comprises the following preparation raw materials in percentage by mass:
The mass fraction of Ti is 52.6% of titanium carbonitride powder with the mass fraction of 70.5%, the particle size of the powder is 2.0 mu m, the mass fraction of W is 14.5% of tungsten carbide powder with the mass fraction of 95.6%, the particle size of the powder is 1.0 mu m, the mass fraction of Co+Ni powder is 18.9%, the particle size of the powder is 1.6 mu m, the particle size of TaC powder is 3.3%, the particle size of the powder is 1.9 mu m, the particle size of NbC powder is 4.9%, the particle size of the powder is 2.0 mu m, the particle size of Mo 2.2%, the particle size of the powder is 3.0 mu m, the particle size of Cr 3C2 powder is 0.6%, and the particle size of the powder is 1.7 mu m.
The preparation method of the metal ceramic cutter material in the embodiment comprises the following steps:
S1, adding paraffin accounting for 2.5% of the total mass of the raw materials into titanium carbonitride powder, tungsten carbide powder, co+Ni powder, taC powder, nbC powder, mo 2 C powder and Cr 3C2 powder, placing into a roller ball mill for mixing, wherein the ball milling medium is ethanol, the ball material ratio is 6:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 48 hours.
After being evenly mixed, the slurry is taken out and sieved by a 200-mesh sieve, and then spray drying is carried out to obtain a mixture;
s2, pressing and forming the mixture prepared in the step S1 under 220MPa pressure to obtain a pressed compact with a certain size and shape;
S3, sintering the pressed compact obtained in the step S2 in a de-esterification/sintering integrated furnace, wherein the specific sintering process is as follows:
firstly, heating to 600 ℃, performing positive pressure de-esterification of hydrogen on the pressed compact, wherein the heating rate is 1 ℃ per minute, and preserving heat for 1h;
then heating to 1160 ℃ for vacuum sintering, wherein the vacuum degree is lower than 5Pa, the heating rate is 5 ℃ per minute, and the temperature is kept for 5 hours;
Then heating to 1460 ℃ for argon micro-pressure sintering, wherein the argon flow is 14L/min, the argon pressure is 350mbar, the heating rate is 7 ℃/min, and the temperature is kept for 1.5h;
Then cooling to 1350 ℃ for argon micro-pressure sintering, wherein the argon flow is 4L/min, the argon pressure is 100mbar, the cooling rate is 10 ℃/min, and the temperature is kept for 8 hours;
finally, the cooling rate is reduced to below 800 ℃ at 25 ℃ per minute, and then the surface fine-grain reinforced mixed crystal structure Ti (C, N) -based metal ceramic cutter material is obtained after cooling along with a furnace.
As a result of examining the microstructure and mechanical properties of the cermet obtained in this example, it was found that a fine grain layer of Ti (C, N) was formed on the surface layer of the matrix at a thickness of 16. Mu.m, and the material had a hardness of HRA93.8, a fracture toughness of 9.2 MPa.m 1/2 and a flexural strength of 2288MPa.
In summary, the present invention adopts coarse Ti-containing carbonitride or nitride powder and fine W-containing carbide powder to match, and the composition has the advantages of being capable of forming two hard phase particles in the metal ceramic structure, one being black core-gray ring structure particles with coarse Ti-rich carbonitride particles as cores, and the other being white core-gray ring structure particles with fine W-rich carbide as cores, the former being capable of achieving high toughness of the matrix, and the latter being capable of achieving dispersion strengthening and reinforcing effects. The formation mechanism of the two hard phase particles is that, on the one hand, as the sintering temperature increases, a large amount of coarse Ti-rich carbonitride particles are not completely dissolved and remain as nucleation sites, while the alloy components dissolved in the binder phase are precipitated around them to form (Ti, W.) (C, N) annular phases, and on the other hand, as the content of fine W-rich carbide particles is high, the dissolution limit of the binder phase is exceeded, and most of the particles are not completely dissolved to form nucleation sites, so that other alloy components are also formed around them by the dissolution-precipitation mechanism to form (Ti, W.) (C, N) annular phases. In addition, the addition of a proper amount of Ta, nb, zr and the like can obviously improve the high-temperature red hardness and the high-temperature wear resistance of the matrix, and the adoption of the Co/Ni composite binding phase can further improve the toughness and the impact resistance of the material.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
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| US4778521A (en) * | 1986-02-20 | 1988-10-18 | Hitachi Metals, Ltd. | Tough cermet and process for producing the same |
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| EP0819776B1 (en) * | 1996-07-18 | 2001-04-04 | Mitsubishi Materials Corporation | Cutting blade made of titanium carbonitride-type cermet, and cutting blade made of coated cermet |
| CN101302595A (en) * | 2008-07-08 | 2008-11-12 | 湖南科技大学 | High wear-resistant Ti(C,N)-based cermet tool and its preparation |
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