CN115386759B - Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic cutter material and preparation method thereof - Google Patents

Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic cutter material and preparation method thereof Download PDF

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CN115386759B
CN115386759B CN202211032706.7A CN202211032706A CN115386759B CN 115386759 B CN115386759 B CN 115386759B CN 202211032706 A CN202211032706 A CN 202211032706A CN 115386759 B CN115386759 B CN 115386759B
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CN115386759A (en
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王东
薛超
邱博
郁红陶
汪庆华
万宏强
韩权利
闫正虎
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Xian Technological University
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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
    • 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
    • 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
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • 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
    • 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
    • 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
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
    • 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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Abstract

The invention discloses a Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic cutter material and preparation method thereof, and Ti (C) 7 ,N 3 ) TiB as matrix phase 2 And nano WC as reinforcing phase, and adding small amount of Ni, mo, VC and Cr 3 C 2 As an additive, the best preparation process and Ti (C) with the best comprehensive performance are obtained 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic tool material. The invention adopts the plasma sintering method to sinter, and overcomes the defects of insufficient high-temperature hardness and insufficient wear resistance of the traditional metal ceramic cutter. Prepared Ti (C) 7 ,N 3 )/TiB 2 The WC micro-nano composite metal ceramic cutter material has high density, uniform grain average size distribution, higher bending strength, fracture toughness and hardness, and can be widely applied to cutting processing of difficult-to-process materials such as stainless steel, ultra-high strength steel and the like.

Description

Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic cutter material and preparation method thereof
Technical Field
The invention relates to a cutting tool material, in particular to a Ti (C, N) -based micro-nano composite metal ceramic cutting tool material and a preparation method thereof.
Background
The Ti (C, N) -based cermet maintains the characteristics of high strength, high hardness, wear resistance, high temperature resistance, oxidation resistance, chemical stability and the like of the ceramic, has better metal toughness and plasticity, is a very important tool material and structural material, and has become one of the most potential cutting tool materials. However, the main problem of Ti (C, N) -based cermet tools is still insufficient hot hardness and insufficient wear resistance, limiting their application. Therefore, development of a cermet tool material with high hardness and high wear resistance is a research focus in the field of cutting tool materials.
The increase of the C content in Ti (C, N) can refine Ti (C, N) crystal grains, improve bending strength and hardness, and the increase of the N content can reduce material compactness, so that the comprehensive mechanical property of Ti (C, N) is better when the C content in Ti (C, N) is higher than the N content. Thus, the present invention selects Ti (C 7 ,N 3 ) As a matrix phase of the cutter material, the material is favorable for refining grains and improving the compactness of the material, thereby improving the hardness and the wear resistance of the material.
TiB 2 Has very high hardness (32 GPa-529 GPa) and high elastic modulus (529 GPa), has excellent thermoelectric performance and chemical stability, and is applied to the engineering fields of cutting tools, abrasive materials, impact-resistant armor and the like. Thus, the present invention selects TiB 2 As an additive phase, the hardness and wear resistance of Ti (C, N) -based cermet tool materials are further improved.
TiB 2 The hardness of the ceramic material can be remarkably improved, but the toughness is poor. While nano WC particles can not only inhibit TiB 2 The grains are enlarged, and the grain-along fracture and the extraction of the nano grains are easy to occur in the crack propagation, thereby improving the toughness of the material. Thus, the present invention selects nano WC particles as the additive phase.
Ni and Mo vs TiB 2 The wetting effect of (C) is far better than other metals, so that TiB can be obtained 2 Higher compactibility is obtained at relatively low sintering temperatures. VC and Cr 3 C 2 Can effectively inhibit the growth of crystal grains and improve the density. Therefore, the invention selects a small amount of NiMo, VC and Cr 3 C 2 As an additive.
TiB 2 Has higher melting point and hardness, and can cause difficult sintering. When hot pressing or hot isostatic pressing sintering is adopted, long-time sintering is required, coarse microstructure of a sample cannot be avoided, impurity phases can be generated at grain boundaries, and mechanical properties can be reduced. The spark plasma sintering technology directly introduces pulse current between powder particles under the condition of pressurization to realize heating sintering, and has the advantages of uniform heating process, low sintering temperature, rapid sintering, high production efficiency and the like, so that the probability of grain growth in the sintering process can be well reduced, the obtained microstructure is uniform and fine, and the spark plasma sintering technology is an in-situ cleaning mode for rapidly preparing densification products. Therefore, a plasma sintering technique is employed as Ti (C 7 ,N 3 )/TiB 2 The preparation method of the WC micro-nano composite metal ceramic cutter material is a reasonable choice, and the technical difficulty is the optimization of sintering temperature, heat preservation time and sintering pressure.
Disclosure of Invention
The invention aims to provide a micro-nano composite metal ceramic cutter material and a preparation method thereof, wherein Ti (C) with average grain diameter of 0.5 mu m is used as the cutter material 7 ,N 3 ) TiB with an average particle size of 0.5 μm as matrix phase 2 Nano WC with average grain diameter of 0.14 mu m is used as reinforcing phase, and small amount of Ni, mo, VC and Cr are added 3 C 2 As an additive, the best preparation process and Ti (C) with the best comprehensive performance are obtained 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic tool material.
The technical scheme adopted by the invention is as follows:
Ti(C 7 ,N 3 )/TiB 2 the preparation method of the WC micro-nano composite metal ceramic cutter material comprises the following steps:
step one: preparing nano WC powder into suspension, and mechanically stirring and ultrasonically dispersing;
step two: adding a dispersing agent into the WC powder suspension obtained in the first step, adjusting the pH value of the suspension, and carrying out mechanical stirring and ultrasonic dispersion to obtain a uniform, stable and well-dispersed nano WC powder suspension;
step three: ti (C) 7 ,N 3 )、TiB 2 Adding the powder and the sintering aid into the uniformly dispersed nano WC powder suspension obtained in the second step, mixing, mechanically stirring and performing ultrasonic dispersion to obtain uniformly mixed slurry;
step four: ball milling the uniformly mixed slurry obtained in the step three, drying in an electrothermal vacuum drying oven, cooling, and sieving by using a 120-mesh sieve to obtain uniform fine mixed powder;
step five: loading the mixed powder obtained in the step four into a graphite die, and tabletting and forming to obtain a ceramic green body;
step six: plasma sintering the formed ceramic green body to obtain Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic tool material.
In the first step, the suspension is nano WC powder suspension with the volume fraction of 2.0 percent by taking absolute ethyl alcohol as a medium, the mechanical stirring and ultrasonic dispersion time is 20min, and the average particle size of the nano WC powder is 0.14 mu m.
In the second step, the dispersing agent is polyethylene glycol PEG 4000, the adding amount is 1.5% of the mass of nano WC, ammonia water is used for adjusting the pH value of the suspension to 9.5-10, and the mechanical stirring and ultrasonic dispersing time is 30 min.
In the third step, mechanical stirring and ultrasonic dispersion are carried out for 20 min.
The sintering aid is Ni, mo, VC and Cr 3 C 2 Ni, mo, VC and Cr 3 C 2 2 parts by mass of each was added, and 8 parts by mass in total.
Said Ti (C) 7 ,N 3 ) The average particle diameter of (2) is 0.5 μm, and the amount added is 57 to 67 parts by mass.
The TiB is 2 The average particle diameter of the powder was 0.5. Mu.m, and the amount added was 20 parts by mass.
The average particle diameter of the nano WC powder is 0.14 mu m, and the addition amount is 5-15 parts by mass.
In the fourth step, the ball milling medium is ceramic balls, the ball-material ratio is 10:1, and the ball milling time is 48 and h.
In the fourth step, the drying conditions are as follows: drying 12h at 100deg.C.
In the fifth step, the dried mixed raw material is molded into a columnar shape with the diameter of 20 multiplied by 10 mm.
In the sixth step, the sintering process is as follows:
vacuum is maintained in sintering, and the pressure is maintained at 32Mpa;1200 o Before C, at 200 o Heating at C/min to 1200 deg.C o C, heat preservation and sintering for 1min; exceeding 1200 o Heating to 1500 ℃ at 100 ℃ per minute, and preserving heat and sintering for 30 minutes; 100 at the back o Water cooling to 1000 a/min o And C, finally cooling to room temperature along with the furnace.
Ti (C) prepared by the preparation method as described in any one of the above 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic tool material.
The invention has the following advantages:
the micro-nano composite metal ceramic cutter material of the invention uses Ti (C) 7 ,N 3 ) TiB as matrix phase 2 And nano WC as reinforcing phase, and adding small amount of Ni, mo, VC and Cr 3 C 2 As an additive, the ceramic cutting tool is sintered by a plasma sintering method, so that the defects of insufficient high-temperature hardness and insufficient wear resistance of the existing ceramic cutting tool are overcome.
In the micro-nano composite metal ceramic cutter material system, nano WC is mainly distributed in the grains and is used as a matrix phase Ti (C 7 ,N 3 ) Nucleating agent for promoting diffusion of (C, N) element, thereby refining Ti (C) 7 ,N 3 ) Grains, and can reduce the number of excessive C, N at the grain boundary, and reduce the kind of grain boundary phase. Micron TiB 2 Mainly distributed at the grain boundary to prevent the migration of the grain boundary and the abnormal growth of the matrix phase, and simultaneously improve the density of the grain boundary, thereby overcoming the defects of insufficient hardness and insufficient wear resistance of the traditional Ti (C, N) -based ceramic cutter.
Ti (C) prepared by the preparation process of the invention 7 ,N 3 )/TiB 2 WC micro-nanoThe composite metal ceramic cutter material has high compactness, uniform grain average size distribution, higher bending strength, fracture toughness and hardness, and can be widely applied to cutting processing of difficult-to-process materials such as stainless steel, ultra-high strength steel and the like.
Drawings
Fig. 1 is a micro-nano composite cermet tool material fracture SEM with different mass fraction nano WC added.
Fig. 2 shows a micro-nano composite cermet tool material surface crack propagation SEM with addition of 10 wt% nano WC.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Ti (C) according to the invention 7 ,N 3 )/TiB 2 Preparation method of WC micro-nano composite metal ceramic cutter is Ti (C 7 ,N 3 ) With TiB 2 And first binding attempts of nano WC. The regulation and control of nanoparticle dispersing process, ball milling process, sieving process and plasma sintering process is Ti (C) 7 ,N 3 )/TiB 2 And the WC micro-nano composite metal ceramic has few pores and uniform grain average size distribution. The compact and uniform grain structure provides possibility for the excellent comprehensive mechanical properties of the tool, so that the preparation method of the simple, efficient and high-performance micro-nano composite metal ceramic tool is obtained, and specifically comprises the following steps:
comparative example
Step one: the required mass was calculated from nano WC powder having an average particle diameter of 0.5 μm and a purity of 99% and 0 mass part as a starting material, and then weighed. Preparing a suspension with the volume fraction of 2.0% from the weighed raw materials by taking absolute ethyl alcohol as a medium, mechanically stirring and ultrasonically dispersing for 20min;
step two: adding polyethylene glycol PEG 4000 with the mass of 1.5 percent relative to the nano WC into the nano WC suspension, then adopting an ammonia water titration method to adjust the PH value of the prepared nano WC suspension to 9.5, and finally dispersing the suspension for 30min by using mechanical stirring and ultrasonic dispersion to obtain a uniform, stable and well-dispersed nano powder suspension;
step three: average particle diameters of 0.5 μm and purities of 99% [ A1 ]]2 parts by mass of Ti (C) 7 ,N 3 ) And 20 parts by mass of TiB 2 Adding the powder into a uniformly dispersed nano WC powder suspension, and adding 2 parts of Ni, mo, VC and Cr respectively 3 C 2 Mixing, namely preparing mixed slurry with the volume fraction of 2.0% relative to the mixed powder by taking absolute ethyl alcohol as a medium, and mechanically stirring and ultrasonically dispersing for 20min to obtain uniformly mixed slurry;
step four: pouring the uniformly mixed slurry into a mixing bucket, adding alumina balls, wherein the mass ratio of balls to materials is 10:1, ball milling 48 and h on a planetary ball mill, drying 12: 12h in a ZK-40 electric heating vacuum drying oven at 100 ℃, cooling after vacuum drying, and sieving the mixture by using a 120-mesh sieve to obtain uniform fine mixed powder;
step five: the dried mixed raw materials are put into a graphite die with the diameter of 20 mm, compacted on a tablet press under the pressure of 30 Mpa, and made into a columnar shape with the height of 10 mm.
Step six: and (3) placing the ceramic green body after tabletting and molding together with a graphite mold into a plasma vacuum sintering furnace, and sintering under the pressure of 32Mpa to obtain the micro-nano composite metal ceramic. 1200 in order to prevent the powder grain growth o Before C, at 200 o Heating up in C/min; up to 1200 o C, heat preservation and sintering for 1min to eliminate gaps; exceeding 1200 o After C, in order to obtain the ceramic with excellent comprehensive performance, the grains are required to be fully grown, so that the heating rate is reduced, the temperature is increased to 1500 ℃ at 100 ℃ per minute, and the temperature is kept for 30 minutes; finally at 100 o Water cooling to 1000 a/min o And C, cooling to room temperature along with the furnace to obtain a sample.
Example 1
Step one: the required mass was calculated from 5 parts by mass of nano WC powder having an average particle diameter of 0.5 μm and a purity of 99% as a starting material, and then weighed. Preparing a suspension with the volume fraction of 2.0% from the weighed raw materials by taking absolute ethyl alcohol as a medium, mechanically stirring and ultrasonically dispersing for 20min;
step two: adding polyethylene glycol PEG 4000 with the mass of 1.5 percent relative to the nano WC into the nano WC suspension, then adopting an ammonia water titration method to adjust the PH value of the prepared nano WC suspension to 9.5, and finally dispersing the suspension for 30min by using mechanical stirring and ultrasonic dispersion to obtain a uniform, stable and well-dispersed nano powder suspension;
step three: the average particle diameters were 0.5 μm and the purities were 99% respectively, and 67 parts by mass of Ti (C 7 ,N 3 ) And 20 parts by mass of TiB 2 Adding the powder into a uniformly dispersed nano WC powder suspension, and adding 2 parts of Ni, mo, VC and Cr respectively 3 C 2 Mixing, namely preparing mixed slurry with the volume fraction of 2.0% relative to the mixed powder by taking absolute ethyl alcohol as a medium, and mechanically stirring and ultrasonically dispersing for 20min to obtain uniformly mixed slurry;
step four: pouring the uniformly mixed slurry into a mixing bucket, adding alumina balls, wherein the mass ratio of balls to materials is 10:1, ball milling 48 and h on a planetary ball mill, drying 12: 12h in a ZK-40 electric heating vacuum drying oven at 100 ℃, cooling after vacuum drying, and sieving the mixture by using a 120-mesh sieve to obtain uniform fine mixed powder;
step five: the dried mixed raw materials are put into a graphite die with the diameter of 20 mm, compacted on a tablet press under the pressure of 30 Mpa, and made into a columnar shape with the height of 10 mm.
Step six: and (3) placing the ceramic green body after tabletting and molding together with a graphite mold into a plasma vacuum sintering furnace, and sintering under the pressure of 32Mpa to obtain the micro-nano composite metal ceramic. 1200 in order to prevent the powder grain growth o Before C, at 200 o Heating up in C/min; up to 1200 o C, heat preservation and sintering for 1min to eliminate gaps; exceeding 1200 o After C, in order to obtain the ceramic with excellent comprehensive performance, the grains are required to be fully grown, so that the heating rate is reduced, the temperature is increased to 1500 ℃ at 100 ℃ per minute, and the temperature is kept for 30 minutes; finally at 100 o Water cooling to 1000 a/min o And C, cooling to room temperature along with the furnace to obtain a sample.
Example 2
Step one: the required mass was calculated from 10 parts by mass of nano WC powder having an average particle diameter of 0.5 μm and a purity of 99% as a starting material, and then weighed. Preparing a suspension with the volume fraction of 2.0% from the weighed raw materials by taking absolute ethyl alcohol as a medium, mechanically stirring and ultrasonically dispersing for 20min;
step two: adding polyethylene glycol PEG 4000 with the mass of 1.5 percent relative to the nano WC into the nano WC suspension, then adopting an ammonia water titration method to adjust the PH value of the prepared nano WC suspension to 9.5, and finally dispersing the suspension for 30min by using mechanical stirring and ultrasonic dispersion to obtain a uniform, stable and well-dispersed nano powder suspension;
step three: the average particle diameters were 0.5 μm, the purities were 99%, and 62 parts by mass of Ti (C 7 ,N 3 ) And 20 parts by mass of TiB 2 Adding the powder into a uniformly dispersed nano WC powder suspension, and adding 2 parts of Ni, mo, VC and Cr respectively 3 C 2 Mixing, namely preparing mixed slurry with the volume fraction of 2.0% relative to the mixed powder by taking absolute ethyl alcohol as a medium, and mechanically stirring and ultrasonically dispersing for 20min to obtain uniformly mixed slurry;
step four: pouring the uniformly mixed slurry into a mixing bucket, adding alumina balls, wherein the mass ratio of balls to materials is 10:1, ball milling 48 and h on a planetary ball mill, drying 12: 12h in a ZK-40 electric heating vacuum drying oven at 100 ℃, cooling after vacuum drying, and sieving the mixture by using a 120-mesh sieve to obtain uniform fine mixed powder;
step five: the dried mixed raw materials are put into a graphite die with the diameter of 20 mm, compacted on a tablet press under the pressure of 30 Mpa, and made into a columnar shape with the height of 10 mm.
Step six: and (3) placing the ceramic green body after tabletting and molding together with a graphite mold into a plasma vacuum sintering furnace, and sintering under the pressure of 32Mpa to obtain the micro-nano composite metal ceramic. 1200 in order to prevent the powder grain growth o Before C, at 200 o Heating up in C/min; up to 1200 o C, heat preservation and sintering for 1min to eliminate gaps; exceeding 1200 o After C, in order to obtain healdsThe ceramic with excellent combination property needs to enable grains to fully grow, so that the heating rate is reduced, the temperature is increased to 1500 ℃ at 100 ℃ per minute, and the temperature is kept for 30 minutes; finally at 100 o Water cooling to 1000 a/min o And C, cooling to room temperature along with the furnace to obtain a sample.
Example 3
Step one: the required mass was calculated from 15 parts by mass of nano WC powder having an average particle diameter of 0.5 μm and a purity of 99% as a starting material, and then weighed. Preparing a suspension with the volume fraction of 2.0% from the weighed raw materials by taking absolute ethyl alcohol as a medium, mechanically stirring and ultrasonically dispersing for 20min;
step two: adding polyethylene glycol PEG 4000 with the mass of 1.5 percent relative to the nano WC into the nano WC suspension, then adopting an ammonia water titration method to adjust the PH value of the prepared nano WC suspension to 9.5, and finally dispersing the suspension for 30min by using mechanical stirring and ultrasonic dispersion to obtain a uniform, stable and well-dispersed nano powder suspension;
step three: the average particle diameters were 0.5 μm and the purities were 99%, 57 parts by mass of Ti (C 7 ,N 3 ) And 20 parts by mass of TiB 2 Adding the powder into a uniformly dispersed nano WC powder suspension, and adding 2 parts of Ni, mo, VC and Cr respectively 3 C 2 Mixing, namely preparing mixed slurry with the volume fraction of 2.0% relative to the mixed powder by taking absolute ethyl alcohol as a medium, and mechanically stirring and ultrasonically dispersing for 20min to obtain uniformly mixed slurry;
step four: pouring the uniformly mixed slurry into a mixing bucket, adding alumina balls, wherein the mass ratio of balls to materials is 10:1, ball milling 48 and h on a planetary ball mill, drying 12: 12h in a ZK-40 electric heating vacuum drying oven at 100 ℃, cooling after vacuum drying, and sieving the mixture by using a 120-mesh sieve to obtain uniform fine mixed powder;
step five: the dried mixed raw materials are put into a graphite die with the diameter of 20 mm, compacted on a tablet press under the pressure of 30 Mpa, and made into a columnar shape with the height of 10 mm.
Step six: the ceramic green body after tabletting and forming is combined with a graphite die IAnd putting the ceramic material into a plasma vacuum sintering furnace, and sintering the ceramic material under the pressure of 32Mpa to obtain the micro-nano composite metal ceramic. 1200 in order to prevent the powder grain growth o Before C, at 200 o Heating up in C/min; up to 1200 o C, heat preservation and sintering for 1min to eliminate gaps; exceeding 1200 o After C, in order to obtain the ceramic with excellent comprehensive performance, the grains are required to be fully grown, so that the heating rate is reduced, the temperature is increased to 1500 ℃ at 100 ℃ per minute, and the temperature is kept for 30 minutes; finally at 100 o Water cooling to 1000 a/min o And C, cooling to room temperature along with the furnace to obtain a sample.
FIG. 1 shows SEM of a micro-nano composite cermet added with nano WC of different mass fractions sintered at 1500℃for 20 min. In the figure, (a) 0 wt% nano WC is added for the comparative example; (b) adding 5 wt% nano WC for example 1; (c) adding 10 wt% nano WC for example 2; (d) is addition of 15 wt% nano WC for example 3.
When nano WC particles were not added, coarse grains were more in the microstructure, and a large number of pores were also observed (see fig. 1 (a)). When the mass fraction of the nano WC particles is 5%, although a certain amount of pores and coarse grains occur in the microstructure of the ceramic material, the grain size distribution is uneven and the density is not high, but the number of coarse grains is reduced (see fig. 1 (b)). When the mass fraction of the nano WC particles is increased to 10%, pores in the microstructure are fewer, coarse grains are hardly found, the grain size distribution is relatively uniform (see fig. 1 (c)), and the ceramic material can obtain higher density, which shows that the addition of the nano WC particles obviously improves the microstructure of the material. When the mass fraction of nano WC particles increases to 15%, pores in the material start to increase again due to the severe aggregation of nano particles, and more coarse grains are generated (see fig. 1 (d)).
Table 1 shows the mechanical properties of micro-nano composite cermet tool materials with different mass fractions of nanoparticles WC added. From the table, as the mass fraction of the nano WC particles increases, the mechanical property of the cutter material is firstly increased and then decreased, and when the mass fraction of WC is 10%, the comprehensive mechanical property of the cutter material is optimal, and the bending strength of the cutter material is1096.45 MPa, fracture toughness 9.85 MPa.m 1/2 The hardness was 20.50 GPa. Therefore, the addition of a proper amount of nano WC particles is beneficial to improving the comprehensive mechanical properties of the metal ceramic material.
Table 1 mechanical properties of micro-nano composite cermet tool materials with different mass fractions nano WC added.
Nano WC mass fraction (wt.%) Flexural Strength (MPa) Fracture toughness (MPa.m) 1/2 ) Hardness (GPa)
0 782.52 7.50 17.30
5 943.26 8.24 18.82
10 1096.45 9.85 20.50
15 890.48 7.92 18.15
Fig. 2 is a SEM of crack propagation on the surface of the material of example 2. As can be seen from fig. 2, both crystal-penetrating cracks and crystal-along cracks exist in the crack propagation, which indicates that the fracture mode of the prepared micro-nano composite metal ceramic cutter material is a mixed type of crystal-penetrating fracture and crystal-along fracture. When the crack encounters the reinforced phase particles TiB and the nano particles WC in the process of expansion, the crack stops expanding under the pinning effect of the reinforced phase (B) or the nano particles (A) distributed in the grain boundary and the grain boundary, and the crack can continue to expand along the grain boundary position with smaller bonding force, so that deflection occurs, energy can be released in the process, and a crack expansion path becomes tortuous to play a toughening effect.
Liu et al prepared Ti (C) by hot pressed sintering 5 ,N 5 )/TiB 2 WC composite cermet tool and studied micron TiB 2 And influence of WC on mechanical properties thereof (Liu. Novel Ti (C, N) -based composite cermet tool and high temperature flexural Strength study [ D ]]Jinan: university of shandong, 2015.). It has not been found that nano WC is used as a reinforcing phase, and a plasma sintering process is used for preparing Ti (C) 7 ,N 3 )/TiB 2 The invention relates to a study of WC micro-nano composite metal ceramic cutters, which is the first attempt. The components, process parameters and mechanical properties of our are compared with those of Liu et al, see Table 2.
Table 2 composition, process parameters and mechanical properties (Ti (C) 5 ,N 5 )/TiB 2 WC and Ti (C) 7 ,N 3 )/TiB 2 /WC)
Component, process parameters Mechanical properties Ti(C 5 ,N 5 )/TiB 2 WC (Liu etc) Ti(C 7 ,N 3 )/TiB 2 WC (example 2)
Main component 55 wt.% micrometer Ti (C) 5 ,N 5 ) 20. 20 wt.% microtib 2 15. 15 wt.% micrometers WC, 5 wt% micron Ni, 5 wt% micron Mo 62 wt.% micrometer Ti (C) 7 ,N 3 ) 20. 20 wt.% micron TiB 2 10 wt% nano WC, 2 wt% micro Ni, 2 wt.% Mo, 2 wt wt.% VC, 2 wt wt.% Cr 3 C 2
Sintering pressure 32 MPa 32 MPa
Sintering temperature 1550 ℃ 1500 ℃
Holding time 60 min 30 min
Flexural Strength 796 MPa 1096.45 MPa
Fracture toughness 6.4 MPa·m 1/2 9.85 MPa·m 1/2
Hardness of 19.2 GPa 20.50 GPa
By comparing the components, process parameters and mechanical properties in table 2, we consider that the main reasons for the high mechanical properties of the cermet tools of the present invention should be: (1) nano WC particles are added. The nano WC particles have the function of refining grains, and meanwhile, the phenomenon of pinning of the nano particles can deflect cracks in the expansion process, so that the fracture toughness of the nano WC particles is improved. And (2) adopting a plasma sintering process. On the one hand improve TiB 2 On the other hand, the sintering temperature is reduced, and the sintering time is short. Thereby reducing the probability of grain growth in the sintering process, avoiding coarse microstructure, ensuring uniform and fine microstructure and high density.
The content of the invention is not limited to the examples listed, and any equivalent transformation to the technical solution of the invention that a person skilled in the art can take on by reading the description of the invention is covered by the claims of the invention.

Claims (5)

1.Ti(C 7 ,N 3 )/TiB 2 The preparation method of the WC micro-nano composite metal ceramic cutter material is characterized by comprising the following steps of:
the method comprises the following steps:
step one: preparing nano WC powder into suspension, and mechanically stirring and ultrasonically dispersing;
step two: adding a dispersing agent into the WC powder suspension obtained in the first step, adjusting the pH value of the suspension, and carrying out mechanical stirring and ultrasonic dispersion to obtain a uniform, stable and well-dispersed nano WC powder suspension;
step three: ti (C) 7 ,N 3 )、TiB 2 Adding the powder and the sintering aid into the uniformly dispersed nano WC powder suspension obtained in the second step, mixing, mechanically stirring and performing ultrasonic dispersion to obtain uniformly mixed slurry;
step four: ball milling the uniformly mixed slurry obtained in the step three, drying in an electrothermal vacuum drying oven, cooling, and sieving by using a 120-mesh sieve to obtain uniform fine mixed powder;
step five: loading the mixed powder obtained in the step four into a graphite die, and tabletting and forming to obtain a ceramic green body;
step six: plasma sintering the formed ceramic green body to obtain Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic cutter material;
in the first step, the suspension is nano WC powder suspension with volume fraction of 2.0% by taking absolute ethyl alcohol as a medium, the mechanical stirring and ultrasonic dispersion time is 20min, and the average particle size of the nano WC powder is 0.14 mu m;
in the second step, the dispersing agent is polyethylene glycol PEG 4000, the adding amount is 1.5% of the mass of nano WC, ammonia water is used for adjusting the pH value of the suspension to 9.5-10, and the mechanical stirring and ultrasonic dispersing time is 30min;
in the third step, mechanical stirring and ultrasonic dispersion are carried out for 20min;
the sintering aid is Ni, mo, VC and Cr 3 C 2 Ni, mo, VC and Cr 3 C 2 2 parts by mass of each was added, and 8 parts by mass in total; said Ti (C) 7 ,N 3 ) The average particle diameter of (2) is 0.5 mu m, and the addition amount is 57-67 parts by mass; the TiB is 2 The average particle diameter of the powder was 0.5 μm, and the amount added was 20 parts by mass; the average grain diameter of the nano WC powder is 0.14 mu m, and the addition amount is 5-15 parts by mass;
in the sixth step, the sintering process is as follows:
vacuum is maintained in sintering, and the pressure is maintained at 32Mpa; heating at 200deg.C/min before 1200deg.C, and sintering at 1200deg.C for 1min; heating to 1500 ℃ at 100 ℃/min after exceeding 1200 ℃, and preserving heat and sintering for 30min; and then water-cooling to 1000 ℃ at 100 ℃/min, and finally cooling to room temperature along with the furnace.
2. Ti (C) according to claim 1 7 ,N 3 )/TiB 2 The preparation method of the WC micro-nano composite metal ceramic cutter material is characterized in that：
In the fourth step, the ball milling medium is ceramic balls, the ball-material ratio is 10:1, and the ball milling time is 48 hours.
3. Ti (C) according to claim 1 7 ,N 3 )/TiB 2 The preparation method of the WC micro-nano composite metal ceramic cutter material is characterized by comprising the following steps of:
in the fourth step, the drying conditions are as follows: drying at 100deg.C for 12 hr.
4. Ti (C) according to claim 1 7 ,N 3 )/TiB 2 The preparation method of the WC micro-nano composite metal ceramic cutter material is characterized by comprising the following steps of:
and fifthly, molding the dried mixed raw materials to prepare a columnar shape with the diameter of 20 multiplied by 10 mm.
5. A Ti (C) produced by the production method as claimed in any one of claims 1 to 4 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic tool material.
CN202211032706.7A 2022-08-26 2022-08-26 Ti (C) 7 ,N 3 )/TiB 2 WC micro-nano composite metal ceramic cutter material and preparation method thereof Active CN115386759B (en)

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