CN112743080B - Method for preparing Ti (C, N) -based metal ceramic cutter material with high heat resistance through in-situ integration - Google Patents
Method for preparing Ti (C, N) -based metal ceramic cutter material with high heat resistance through in-situ integration Download PDFInfo
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- 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
Abstract
A method for preparing Ti (C, N) -based metal ceramic cutter material with high heat resistance by in-situ integration belongs to the technical field of new metal ceramic materials. The method comprises the following steps: 1) Preparation of nanocrystalline Al x CoCrFeNiTi high-entropy alloy binding phase powder; 2) The raw materials are proportioned and mixed to prepare the Ti (C, N) -TiB 2 ‑Al x A CoCrFeNiTi cermet mixture; 3) Preparing a cutter mixed green body; 4) And (3) placing the cutter mixed green body into an atmosphere sintering furnace to be sintered into a cutter sample. The Ti (C, N) -based composite cermet material prepared by the method of the invention has Ti (C, N) and TiB 2 The double-core-ring structure is compact and uniform in grain structure distribution, can be used for high-efficiency processing of high-strength and other difficult-to-cut materials, and realizes industrial application of the cutter.
Description
Technical Field
The invention belongs to the technical field of new metal ceramic materials, and particularly relates to an in-situ integrated preparation method of Ti (C, N) -TiB used in severe environments such as high temperature and high speed for cutting high-strength structural steel 2 -Al x A method for preparing a CoCrFeNiTi metal ceramic cutter material.
Background
In recent years, the aviation industry and the heavy machinery manufacturing industry in China have rapidly developed, and the development is turned to independent innovation from purely relying on foreign technologies, and the development is changed from purely relying on purchasing to independent design and manufacturing. As an important part in the manufacturing process, the material is required to have high reliability, good toughness and matching property and certain corrosion resistance. High-strength steels such as 15-5PH martensitic precipitation hardening stainless steel, 1Cr18Ni9Ti stainless steel, 69111 stainless steel and the like have excellent mechanical properties and corrosion resistance under normal temperature and high temperature conditions, and are paid attention to the development of main beams, mechanical parts and the like of a machine body. However, high-strength steel, as a typical difficult-to-machine material, is prone to poor cutting performance such as large cutting force, high cutting temperature, severe work hardening phenomenon, severe tool wear, and the like during machining, and directly affects the machining cost and efficiency of enterprises. In order to meet the cutting requirements of high-strength steel, matched cutter materials are urgently needed.
The cutter material capable of realizing high-strength steel processing mainly comprises coating hard alloy and Al 2 O 3 Ceramics and Ti (C, N) -based cermets. The coating hard alloy generally selects TiN and diamond-like carbon as coating materials, and the coating materials are mainly utilized to reduce diffusion and chemical reaction between a cutter and a workpiece, so that the abrasion and damage of the blade are delayed to a certain degree. The method is limited by lower binding force between the coating and the base material and larger internal stress, has deviation of thermal stability, is easy to cause the coating to be peeled off, and is not suitable for high-efficiency processing of stainless steel. Al (Al) 2 O 3 The ceramic has high hardness, wear resistance and strong chemical stability, is slightly bonded with a workpiece material, is not easy to generate accumulated scraps, is limited by a ceramic ionic bond combination mode with low strength and large brittleness, and is not suitable for the finish machining of stainless steel. Compared with the prior art, the Ti (C, N) -based metal ceramic integrates the advantages of a metal binding phase (high toughness) and a ceramic phase (high hardness), and obtains ideal comprehensive performance. The Ti (C, N) -based cermet not only has high hardness, wear resistance, red hardness, excellent chemical stability and extremely low friction coefficient with metal, but also has certain toughness and strengthAnd (4) degree. The high-temperature hardness of Ti (C, N) -based cermet is obviously higher than that of high-speed steel and WC-Co hard alloy, the fracture toughness is obviously higher than that of superhard material and ceramic, and a vacuum area between a hard alloy cutter and a ceramic cutter is compensated in the range of processing materials. However, ti (C, N) -based cermet has a contradiction between toughness and heat resistance, i.e., an increase in toughness lowers the heat resistance of the material. The traditional metal ceramics all adopt Ni/Co as a binder phase, and when high-strength steel is cut, the high temperature is caused by difficult cutting property. At high temperature, the bonding phase mainly takes dislocation climbing, the slippage system is increased, and even creep damage is generated, so that the strength of the metal bonding phase is rapidly reduced (commonly called softening), the toughness and the wear resistance of the metal ceramic are weakened, and the phenomena of peeling and even micro tipping easily occur in the service process. Therefore, having high heat resistance and good toughness is a key to the development of high strength steel cutting using Ti (C, N) -based cermets.
In order to improve the requirement of low heat resistance of Ti (C, N) -based cermets, researchers have conducted a great deal of research in attempting to improve the heat resistance of cermets by reducing the binder phase content, adding rare earth elements, and using high-entropy alloys as the binder phase. For example, in Chinese patent No. ZL201711080421.X, ti (C, N) -based cermet is obtained by atmosphere sintering with low Co content as binder phase. Although the heat resistance of the cermet can be improved, the toughness of the cermet is lowered, and the cermet is liable to fail quickly during cutting. In Chinese patent No. 201810822205.6, ti (C, N) -based cermet with high thermal shock resistance and cutting performance is obtained by vacuum/pressure sintering by using rare earth elements NbC, VC and the like as additives, but the improvement of heat resistance is limited.
The Ti (C, N) -based cermet is prepared by adopting a high-entropy alloy consisting of Cr, ni, fe, co, al, cu, zr and Mo as a binder phase and sintering in vacuum/atmosphere according to Chinese patent number 201810611621.1. By means of the high lattice distortion and the delayed diffusion effect of the high-entropy alloy, the heat resistance of the metal ceramic is greatly improved. However, the melting point of the high-entropy alloy is higher (more than 1400 ℃), and in order to obtain higher compactness, the traditional preparation process needs higher sintering temperature and heat preservation time, so that Ti (C, N) grains grow seriously, and finally, the abnormal growth of Ti (C, N) grains is reducedMechanical properties of the cermet. Therefore, researchers consider adopting a new preparation method, and try to achieve the purpose of inhibiting abnormal growth of crystal grains by reducing the sintering temperature and the sintering time, and further improve the toughness of the metal ceramic. For example, chinese patent No. 201811106938.6, coNiFeCuMn is adopted x The high-entropy alloy is a binding phase, and the Ti (C, N) -based metal ceramic is prepared by microwave sintering. Peng et al (Y PengZJ Peng, XY Ren, ceramics International, 2012) produced ultrafine grained Ti (C, N) -based cermets by spark plasma sintering. Although the microwave sintering and spark plasma sintering can improve the toughness of the cermet, the resultant cermet has a low degree of densification, which is liable to cause chipping. Therefore, the invention adopts the reaction hot-pressing integrated sintering technology to prepare the Ti (C, N) -based cermet with the high-entropy alloy as the binder phase by means of Al x The heat resistance of the CoCrFeNiTi high-entropy alloy is improved, and the high compactness and the grain uniformity formed by reaction hot pressing are cooperated to improve the comprehensive performance of the metal ceramic.
Disclosure of Invention
Aiming at the defects in the prior art and overcoming the problem of contradiction between heat resistance and strength and toughness, the invention aims to design and provide a preparation method of a high-entropy alloy strengthening and toughening Ti (C, N) -based cermet material.
A method for preparing a Ti (C, N) -based metal ceramic cutter material with high heat resistance in situ integrally is characterized by comprising the following steps:
1) Preparation of nanocrystalline Al x CoCrFeNiTi high-entropy alloy binding phase powder;
2) The raw materials are proportioned and mixed to prepare Ti (C, N) -TiB 2 -Al x A CoCrFeNiTi cermet mixture;
3) Preparing a cutter mixed green body;
4) And (3) placing the cutter mixed green body into an atmosphere sintering furnace to be sintered into a cutter sample.
One heightThe method for preparing the Ti (C, N) -based metal ceramic cutting tool material by heat resistance in-situ integration is characterized in that the step 1) specifically comprises the following steps: according to atomic percent Al: co: cr: fe: ni: ti =0.3-1:1:1:1:1:1, weighing raw material powder, mixing, adding n-heptane accounting for 5-10wt% of the total weight of the raw materials, performing mechanical alloying planetary ball milling, and performing ultrasonic vibration screening after the ball milling is finished to prepare nanocrystalline Al x And introducing Ar of 0.05MPa into the CoCrFeNiTi high-entropy alloy binding phase powder for protection for later use.
The method for preparing the Ti (C, N) -based cermet cutter material with high heat resistance in situ integrally is characterized in that a ball milling medium is a hard alloy ball, the ball-material ratio is 1 to 10, the ball milling rotation speed is 250-350r/min, the ball milling time is 24-48h, the machine is stopped once every 5h, the machine is stopped for 30min, and the mesh number of the ultrasonic vibration sieve is 270 meshes.
The method for preparing the Ti (C, N) -based metal ceramic cutting tool material with high heat resistance in situ integration is characterized in that the step 2) specifically comprises the following steps: weighing 50-58 wt% of Ti and B 4 C14~20wt%，BN5~10wt%，WC2~8%，Mo 2 C 2~8wt%，TaC2~8wt%，Al x Placing the CoCrFeNiTi high-entropy alloy in a V-shaped mixer at 8-15wt%, adding paraffin liquid accounting for 2-5 wt% of the total weight of the raw materials and absolute ethyl alcohol accounting for 25-30wt%, mixing, drying, and granulating in a granulator to obtain the Ti (C, N) -TiB 2 -Al x A CoCrFeNiTi cermet mixture.
The method for preparing the Ti (C, N) -based metal ceramic cutter material with high heat resistance through in-situ integration is characterized in that the stirring speed of a mixer is 300-400r/min, the ball-to-material ratio is 1.
The method for preparing the Ti (C, N) -based metal ceramic cutting tool material with high heat resistance in situ integration is characterized in that the step 3) specifically comprises the following steps: ti (C, N) -TiB prepared in the step 2) 2 -Al x Placing the CoCrFeNiTi metal ceramic mixture on a hydraulic forming machine to be pressed into a green body, and placing the green body on a pressHeating the mixture in an atmosphere sintering furnace to 200 to 300 ℃, preserving heat for 1 to 2h, and introducing 30 to 45L/hN into the furnace 2 And preparing the cutter mixed green body.
The method for preparing the Ti (C, N) -based metal ceramic cutter material with high heat resistance through in-situ integration is characterized in that the hydroforming mode is cold isostatic pressing, and the pressure is 150 to 200MPa.
The method for preparing the Ti (C, N) -based metal ceramic cutting tool material with high heat resistance in situ integration is characterized in that the step 4) specifically comprises the following steps: and (3) placing the cutter mixed green compact in an atmosphere sintering furnace, heating to 1350-1400 ℃, preserving heat for 0.5-1h, and cooling to obtain a cutter sample.
The method for preparing the Ti (C, N) -based metal ceramic cutter material with high heat resistance in situ integration is characterized in that the atmospheric pressure in the atmosphere sintering furnace is 2-5 MPa, and the atmosphere is N 2 Or Ar, the heating is: rapidly heating to 1100-1150 ℃ at a speed of 10-20 ℃/min, preserving heat for 10-20min, slowly heating to 1350-1400 ℃ at a speed of 5-10 ℃/min, and cooling: cooling along with the furnace at 14000 to 1000 ℃, and starting a heat dissipation fan of a hearth to cool quickly at the temperature of below 1000 ℃.
The invention has the following beneficial effects: (1) The method for preparing the Ti (C, N) -based metal ceramic cutting tool material with high heat resistance and in-situ integration can prepare and obtain a Ti (C, N) -based composite metal ceramic material with good comprehensive performance and excellent heat resistance; the Scanning Electron Microscope (SEM) analysis of the material can find that the material obtained by the invention has Ti (C, N) and TiB 2 The double 'core-ring' structure is compact and the crystal grain structure is uniformly distributed.
(2) According to the method for preparing the Ti (C, N) -based metal ceramic cutter material with high heat resistance in situ integration, the prepared material has the room temperature hardness of 20.5-22.5 GPa, the bending strength of 950-1300 MPa and the fracture toughness of 8-10 MPa.m 1/2 At 1000 ℃, the hardness is more than or equal to 10GPa, the bending strength is more than or equal to 700MPa, and the fracture toughness is more than or equal to 6 MPa.m 1/2 And can be used for high-efficiency processing of high-strength and other difficult-to-cut materials.
(3) The method for preparing the Ti (C, N) -based metal ceramic cutter material with high heat resistance in situ in an integrated manner has the possibility of preparing cutters in an industrialized batch manner, and realizes industrialized application of the cutters.
Drawings
FIG. 1 is a TEM image of AlCoCrFeNiTi high-entropy alloy powder prepared by mechanical alloying in example 1 of the present invention;
FIG. 2 shows Ti (C, N) -TiB of example 1 of the present invention 2 -SEM picture of AlCoCrFeNiTi cermet wherein (a) polished face, (b) fracture;
FIG. 3 shows Al in example 2 of the present invention 0.3 TEM image of CoCrFeNiTi high-entropy alloy powder;
FIG. 4 shows Ti (C, N) -TiB of example 2 of the present invention 2 -Al 0.3 Scanning electron micrograph of CoCrFeNiTi cermet: (a) a polishing surface; (b) a fracture.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1:
a method for preparing a Ti (C, N) -based metal ceramic cutter material with high heat resistance by in-situ integration comprises the following steps:
the method comprises the following steps: preparing nanocrystalline AlCoCrFeNiTi high-entropy alloy powder: weighing various raw material powders according to the atomic percentage of Al: co: cr: fe: ni: ti =1:1:1:1:1:1; and (2) performing mechanical planetary ball milling on the weighed raw materials, wherein the ball milling medium is hard alloy balls, the ball-material ratio is 1. And adding 5wt% of n-heptane as a process control agent in the ball milling process, stopping the machine every 5 hours, and stopping the machine for 30min. In addition, ar gas of 0.05MPa is introduced for protection after the powder is canned. After the ball milling is finished, sieving the mixture in a 270-mesh sieve.
Step two: proportioning and mixing reaction raw materials; the reaction raw materials comprise the following components in percentage by weight: ti50 wt%, B 4 17wt% of C, 8wt% of BN, 5wt% of WC and Mo 2 5wt% of C, 5wt% of TaC and 10wt% of AlCoCrFeNiTi high-entropy alloy. And (3) placing the weighed mixed powder into a V-shaped mixer, stirring at the rotating speed of 300r/min, and adding paraffin liquid accounting for 2wt% of the total weight and paraffin liquid accounting for 125wt% of absolute ethyl alcohol, wherein the absolute ethyl alcohol is used as a mixing medium, and the mixing time is 24 hours. Mixing and granulating in a granulator after the mixture is dried, and drying at 90 ℃ to obtain Ti (C, N) -TiB 2 -AlCoCrFeNiTi cermet mix.
Step three: preparing a cutter green body: hydraulically pressing at 150MPa cold isostatic pressure to obtain corresponding cutter blank, heating to 250 deg.C in an atmosphere sintering furnace, maintaining for 2 hr, and introducing 30L/hr N 2 (ii) a The cold isostatic pressing can reduce the problem of uneven density caused by uneven stress of a common hydraulic press, and the cutter material prepared by using the cold isostatic pressing has even density and no pore defect because the laminated crack is possibly generated by overlarge pressure.
Step four: placing the cutter green body after prepressing in N 2 In an atmosphere hot pressing sintering furnace, raising the furnace temperature to 1350 ℃ in stages and preserving the heat for 1h: 20 ℃/min at 300 to 1150 ℃; and (3) heat preservation: keeping the temperature at 1150 ℃ for 20min; 10 ℃/min at 1150 to 1350 ℃. After sintering, the Ti (C, N) -TiB is obtained by quickly cooling to room temperature 2 -AlCoCrFeNiTi cermet cutter material.
In the process, an atmosphere hot-pressing sintering process is adopted, and the raw materials of the metal ceramic material can completely react and promote high compactness and grain uniformity in the reaction hot-pressing process by virtue of atmosphere pressure, fast/slow temperature rise and fast cooling, so that the Ti (C, N) -based composite metal ceramic material with good comprehensive performance is obtained.
By reasonably proportioning the components of the reaction raw materials and carrying out a hot-pressing sintering process, the good comprehensive performance of the Ti (C, N) -based metal ceramic material can be controlled, and the heat resistance and the obdurability are excellent; the strength, hardness and toughness of the material are improved through fine grain strengthening effect, the heat resistance is improved by means of high lattice distortion and delayed diffusion effect of the high-entropy alloy, the high compactness and grain uniformity formed by hot pressing are improved, and the toughness and heat resistance of the composite metal ceramic cutter material are comprehensively improved.
And (3) carrying out mechanical property test on the sample prepared by the reaction hot pressing sintering: the room temperature hardness is 21.5GPa; the bending strength is 1157MPa; the fracture toughness is 8.9 MPa.m 1/2 At 1000 ℃, the hardness is 11.2GPa, the bending strength is 816MPa, and the fracture toughness is6.8MPa·m 1/2 . TEM image of AlCoCrFeNiTi high-entropy alloy powder prepared by mechanical alloying shows that the powder has a nanocrystalline structure, as shown in figure 1. When a sample prepared by reactive hot pressing sintering is observed under a Scanning Electron Microscope (SEM), as shown in figure 2, the obtained material is found to have a Ti (C, N) and TiB2 double 'core-ring' structure, and is compact and uniform in structural distribution.
Example 2:
a method for preparing a Ti (C, N) -based metal ceramic cutter material with high heat resistance by in-situ integration comprises the following steps:
the method comprises the following steps: nanocrystalline Al 0.3 Preparing CoCrFeNiTi high-entropy alloy powder: weighing various raw material powders according to the atomic percentage of Al: co: cr: fe: ni: ti =0.3:1:1:1:1:1; and (2) performing mechanical planetary ball milling on the weighed raw materials, wherein the ball milling medium is hard alloy balls, the ball-material ratio is 1. Adding 10wt% of n-heptane as a process control agent in the ball milling process, stopping the machine every 5h, and stopping the machine for 30min. In addition, ar gas of 0.05MPa is introduced for protection after the powder is canned. After the ball milling is finished, sieving the mixture in a 270-mesh sieve.
Step two: proportioning and mixing reaction raw materials; the reaction raw materials comprise the following components in percentage by weight: ti 55wt%, B 4 18wt% of C, 8wt% of BN, 4wt% of WC and Mo 2 C4 wt%, taC 3wt%, al 0.3 The CoCrFeNiTi high-entropy alloy accounts for 8wt%. And (2) placing the weighed mixed powder in a V-shaped mixer, stirring at the rotation speed of 400r/min, and adding paraffin liquid accounting for 2wt% of the total weight and absolute ethyl alcohol accounting for 25wt% of the total weight in a ball-material ratio of 1. Mixing and granulating in a granulator after the mixture is dried, and drying at 90 ℃ to obtain Ti (C, N) -TiB 2 - Al 0.3 A CoCrFeNiTi cermet mixture;
step three: preparing a cutter green body: hydraulically pressing at 200MPa cold isostatic pressure to obtain corresponding cutter blank, heating to 300 deg.C in an atmosphere sintering furnace, maintaining for 1 hr, introducing 40L/hr N into the furnace 2 。
Step four: placing the cutter green body after prepressing in N 2 In an atmosphere hot-pressing sintering furnace, raising the furnace temperature to 1400 ℃ in stages and preserving the temperature for 0.5h: 15 ℃/min at 300 to 1100 ℃; and (3) heat preservation: keeping the temperature at 1100 ℃ for 10min;1150 to 1400 ℃ at 5 ℃/min. After sintering, the Ti (C, N) -TiB is obtained by fast cooling to room temperature 2 -Al 0.3 A CoCrFeNiTi metal ceramic cutter material.
And (3) carrying out mechanical property test on the sample prepared by the reaction hot pressing sintering: the room temperature hardness is 22.1GPa; bending strength is 1036MPa; the fracture toughness is 8.4 MPa.m 1/2 At 1000 ℃, the hardness is 11.9GPa, the bending strength is 743MPa, and the fracture toughness is 6.1 MPa.m 1/2 。
Al prepared by mechanical alloying 0.3 TEM image of CoCrFeNiTi high-entropy alloy powder shows that the powder has a nanocrystalline structure, as shown in FIG. 3. When a sample prepared by reactive hot press sintering was observed under a Scanning Electron Microscope (SEM), as shown in FIG. 4, the obtained material was found to exhibit Ti (C, N) and TiB 2 The structure of the double 'core-ring' structure is compact, but has a certain amount of abnormally grown grains.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (3)
1. A method for preparing a Ti (C, N) -based metal ceramic cutter material with high heat resistance in situ integrally is characterized by comprising the following steps:
1) Preparation of nanocrystalline Al x CoCrFeNiTi high-entropy alloy binder phase powder, wherein nanocrystalline Al x X in the CoCrFeNiTi high-entropy alloy binding phase powder is 0.3-1:
according to atomic percent Al: co: cr: fe: ni: ti =0.3-1:1:1:1:1:1, weighing raw material powder, mixing, adding n-heptane accounting for 5-10wt% of the total weight of the raw materials, performing mechanical alloying planetary ball milling, and performing ultrasonic vibration screening after the ball milling is finished to prepare nanocrystalline Al x CoCrFeNiTi high-entropy alloy binder phase powderFinally, introducing Ar of 0.05MPa for protection for later use;
2) The raw materials are proportioned and mixed to prepare Ti (C, N) -TiB 2 -Al x The CoCrFeNiTi cermet mixture comprises the following components:
weighing 50-58 wt% of raw materials Ti and B according to the weight percentage 4 C14~20wt%，BN5~10wt%，WC2~8%，Mo 2 C 2~8wt%，TaC2~8wt%，Al x Placing the CoCrFeNiTi high-entropy alloy in a V-shaped mixer at 8-15wt%, adding paraffin liquid accounting for 2-5 wt% of the total weight of the raw materials and absolute ethyl alcohol accounting for 25-30wt%, mixing, drying, and granulating in a granulator to obtain the Ti (C, N) -TiB 2 -Al x A CoCrFeNiTi cermet mixture;
3) Preparing a cutter mixed green body:
ti (C, N) -TiB prepared in the step 2) 2 -Al x Placing the CoCrFeNiTi metal ceramic mixture on a hydraulic forming machine to be pressed into a green body, wherein the hydraulic forming mode is cold isostatic pressing forming, the pressure is 150 to 200Mpa, the green body is placed in an atmosphere sintering furnace to be heated to 200 to 300 ℃ and insulated for 1 to 2h, and 30 to 45L/hN is introduced into the furnace 2 Preparing a cutter mixed green body;
4) And (3) placing the cutter mixed green body into an atmosphere sintering furnace to be sintered into a cutter sample:
heating the cutter mixed green blank to 1350-1400 ℃ in an atmosphere sintering furnace, keeping the temperature for 0.5-1h, and cooling to obtain a cutter sample, wherein the atmosphere pressure in the atmosphere sintering furnace is 2-5 MPa, and the atmosphere is N 2 Or Ar, wherein the heating to 1350-1400 ℃ is as follows: rapidly heating to 1100-1150 ℃ at a speed of 10-20 ℃/min, preserving heat for 10-20min, slowly heating to 1350-1400 ℃ at a speed of 5-10 ℃/min, and cooling: cooling along with a furnace at 1400 to 1000 ℃, and starting a hearth heat dissipation fan for quick cooling below 1000 ℃.
2. The method for preparing the Ti (C, N) -based cermet cutter material with high heat resistance in situ integrally as claimed in claim 1, wherein the ball milling medium is cemented carbide balls, the ball-to-material ratio is 1:10, the ball milling rotation speed is 250-350r/min, the ball milling time is 24-48h, the machine is stopped once every 5h, the machine is stopped for 30min, and the sieve mesh number of the ultrasonic vibration sieve is 270 meshes.
3. The method for preparing the Ti (C, N) -based cermet cutter material with high heat resistance through in-situ integration as claimed in claim 1, wherein the stirring speed of a V-shaped mixer is 300 to 400r/min, the ball-feed ratio is 1.
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| US4769070A (en) * | 1986-09-05 | 1988-09-06 | Sumitomo Electric Industries, Ltd. | High toughness cermet and a process for the production of the same |
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