CN113896542A - Ceramic material with strong fracture toughness, preparation method and application thereof - Google Patents

Ceramic material with strong fracture toughness, preparation method and application thereof Download PDF

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CN113896542A
CN113896542A CN202111294921.XA CN202111294921A CN113896542A CN 113896542 A CN113896542 A CN 113896542A CN 202111294921 A CN202111294921 A CN 202111294921A CN 113896542 A CN113896542 A CN 113896542A
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ceramic material
fracture toughness
sio
nano
powder
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陈照强
张帅
肖光春
许崇海
衣明东
张静婕
崔昊
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Qilu University of Technology
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Abstract

The invention belongs to the technical field of ceramic material preparation, and relates to a ceramic material with strong fracture toughness, a preparation method and application thereof, wherein the ceramic material comprises the following components in parts by weight: according to the volume percentage of each raw material component: alpha-Si3N4 55‑75％，TiC 5‑15％，ZrSi20-15% of nano h-BN @ SiO2 0‑15％，Al2O3 3‑7％，Y2O35-7%, wherein, the nano h-BN @ SiO2Is not 0. h-BN @ SiO through nano core-shell structure2And the material and a base material form an in-crystal structure, so that the fracture toughness is greatly improved.

Description

Ceramic material with strong fracture toughness, preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic material preparation, and relates to a ceramic material with strong fracture toughness, a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Dry cutting has become a research hotspot of the current cutting machining technology. Since no cutting fluid is involved in dry cutting, the environmental pollution and the cost of cutting are much less than those of cutting fluid. Although the dry cutting has the advantages, the friction coefficient between the workpiece material and the cutter is obviously increased in the dry cutting, the cutting temperature is higher, the cutter is worn quickly, and the service life and the cutting processing quality of the cutter are further influenced. Therefore, the wear resistance and lubricity of the cutting tool are required to be high in dry cutting. The self-repairing ceramic tool and the self-lubricating ceramic tool are researched by a scholart aiming at the problems, and the ceramic tool has self-repairing or self-lubricating capacity through reasonable design of material components of the ceramic tool.
The inventor finds that improving the self-repairing or self-lubricating capability of the ceramic cutter has a better effect on improving the ceramic material. However, the ceramic material still has poor fracture toughness, which is not favorable for prolonging the service life of the ceramic material. In order to improve the fracture toughness of the ceramic material, some patents improve the toughness by controlling the sintering treatment of the ceramic material and regulating and controlling the sintering conditions, but the adjustment of the fracture toughness of the ceramic material by the method is limited. In some technologies, the toughness of the ceramic is improved by adding graphene or silicon oxide, but the methods are not only complex in preparation process, but also have limited improvement on the fracture toughness of the ceramic material, and even affect other properties of the ceramic material. Therefore, how to further improve the fracture toughness of the ceramic material is crucial.
Disclosure of Invention
In order to solve the defects of the prior art, the inventionThe invention provides a ceramic material with strong fracture toughness, a preparation method and application thereof, and h-BN @ SiO of a nano core-shell structure is prepared2And the material and a base material form an in-crystal structure, so that the fracture toughness is greatly improved.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, a high fracture toughness ceramic material comprises: according to the volume percentage of each raw material component: alpha-Si3N4 55-75％，TiC 5-15％，ZrSi20-15% of nano h-BN @ SiO2 0-15％，Al2O3 3-7％，Y2O35-7%, wherein, the nano h-BN @ SiO2Is not 0.
In a second aspect of the present invention, a method for preparing a ceramic material with high fracture toughness comprises:
(1) respectively weighing alpha-Si according to the component proportion of the ceramic material3N4、TiC、ZrSi2、Al2O3And Y2O3Powder, namely adding a dispersing agent and absolute ethyl alcohol into each component respectively, and stirring and dispersing to prepare a suspension; then, mixing the suspensions of the components to obtain a complex phase suspension;
(2) ball-milling the complex phase suspension in the step (1) in an inert atmosphere; after ball milling for 40-50h, weighing nano h-BN @ SiO according to the component proportion2In the nanometer h-BN @ SiO2Adding a dispersing agent, and pouring into a ball milling device for continuous ball milling for 3-6 h; and after the ball milling is finished, drying to obtain mixed powder.
(3) And (3) putting the mixed powder in the step (2) into an SPS sintering furnace for spark plasma sintering.
In the third aspect of the invention, the ceramic material obtained by any one of the preparation methods has the bending strength of 750-820MPa, the hardness of 13-16GPa and the fracture toughness of 8.00-8.73 MPa-m1/2。
In a fourth aspect of the present invention, any of the ceramic materials with high fracture toughness and/or the preparation method of the ceramic materials with high fracture toughness is applied to the preparation of a cutting tool.
One or more embodiments of the present invention have the following advantageous effects:
(1) by nano h-BN @ SiO2And ZrSi2The synergistic effect of the repairing agents can improve the cutting performance of the ceramic material.
(2) And the nano h-BN @ SiO with the core-shell structure2The nano h-BN and the base material form an in-crystal structure in the SPS sintering process, so that the fracture toughness of the ceramic material is greatly improved.
(3) The ceramic material obtained by the invention not only can greatly improve the fracture toughness of the ceramic material, but also can keep higher bending strength, and the nano h-BN @ SiO is added2And ZrSi2The ceramic cutting tool material crack sample is recovered to 99 percent of the strength of the smooth sample, and only ZrSi is added2The flexural strength of the ceramic material cracked sample was only restored to 92% of the smooth sample.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1: SEM image of the section of the ceramic material of example 2;
FIG. 2: the ceramic material is in a crack shape without heat treatment;
FIG. 3: the crack morphology of the ceramic material after the heat treatment at 800 ℃ in example 2;
FIG. 4: XRD detection of the ceramic material of example 2;
FIG. 5: the distribution of Zr, Si and O elements at the cracks of the ceramic material in example 2 is shown.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
At present, the fracture toughness of the ceramic cutter material still cannot meet the industrial requirement, and meanwhile, the existing method for improving the fracture toughness is complex and high in cost, and the improvement on the fracture toughness is limited. In particular, some methods fail to achieve both high flexural strength and high hardness while increasing fracture toughness. Therefore, the invention provides a ceramic material with strong fracture toughness, a preparation method and application thereof.
In one or more embodiments of the present invention, a high fracture toughness ceramic material comprises: according to the volume percentage of each raw material component: alpha-Si3N4 55-75％，TiC 5-15％，ZrSi20-15% of nano h-BN @ SiO2 0-15％，Al2O3 3-7％，Y2O35-7%, wherein, the nano h-BN @ SiO2Is not 0.
In one aspect, ZrSi is present during the air heat treatment2And SiO2Nano h-BN @ SiO with damaged shell2ZrO formed by reaction with oxygen2、SiO2、B2O3The crack can be repaired, the strength of the material is recovered, the healing strength is high, and the time is short; on the other hand, the nano h-BN and the base material form an in-crystal structure in the SPS sintering process, so that the fracture toughness of the ceramic material is greatly improved.
The inventor finds that only nano h-BN can form an intragranular type with a matrix material, and the method plays a very key role in improving the fracture toughness. However, when h-BN is in the order of micrometers, it is impossible to form an intragranular form with the substrate.
Further, the ceramic material with strong fracture toughness comprises: according to the volume percentage of each raw material component: alpha-Si3N4 57-72％，TiC 10％，ZrSi 210% of nano h-BN @ SiO2 0-15％，Al2O3 3％，Y2O35%, nano h-BN @ SiO2Is not 0. The ceramic material obtained by the composition has the optimal strength, hardness and fracture toughness.
Specifically, the nano h-BN @ SiO2The preparation method comprises the following steps:
adding the nano h-BN particles and polyvinylpyrrolidone into absolute ethyl alcohol to prepare suspension, and stirring and dispersing; heating at 30-50 deg.C, adding distilled water and ammonia water, mixing, stirring, and slowly adding ethyl orthosilicate; performing centrifugal separation after aging to obtain colloid; adding n-butanol solution into the colloid, and performing azeotropic drying.
The method can obtain h-BN @ SiO of the nano core-shell structure2The addition of the titanium-based alloy into a matrix material can improve the fracture toughness of the ceramic material. Nano h-BN @ SiO2Is a coating type structural material, and forms a layer of SiO on the surface of nano h-BN by using a non-uniform nucleation method2The shell avoids the adverse effect on the mechanical property of the ceramic cutter material caused by directly adding the nano h-BN. With SiO2The coating layer can drive the nano h-BN to be uniformly distributed in the basal body of the ceramic cutter in the SPS sintering process, and the performance of the ceramic cutter material is improved.
In one or more embodiments of the present invention, a method for preparing a ceramic material with high fracture toughness comprises:
(1) respectively weighing alpha-Si according to the component proportion of the ceramic material3N4、TiC、ZrSi2、Al2O3And Y2O3Powder, namely adding a dispersing agent and absolute ethyl alcohol into each component respectively, and stirring and dispersing to prepare a suspension; then, mixing the suspensions of the components to obtain a complex phase suspension;
(2) ball-milling the complex phase suspension in the step (1) in an inert atmosphere; after ball milling for 40-50h, pressWeighing nano h-BN @ SiO according to component proportion2In the nanometer h-BN @ SiO2Adding a dispersing agent, and pouring into a ball milling device for continuous ball milling for 3-6 h; and after the ball milling is finished, drying to obtain mixed powder.
(3) And (3) putting the mixed powder in the step (2) into an SPS sintering furnace for spark plasma sintering.
By the method, the synergistic cooperation effect among the components can be fully exerted, the formation of an in-crystal form is facilitated, and the properties of fracture toughness, compressive strength, hardness and the like are facilitated to be improved.
In the step (1), the dispersant is selected from polyvinylpyrrolidone, polyethylene glycol and sodium tripolyphosphate, and preferably polyethylene glycol 4000. The polyethylene glycol 4000 dispersant particles can cover the ceramic material powder particles to generate a steric hindrance effect, and the covering effect of the steric hindrance effect reduces the potential, so that a good particle dispersing effect is achieved.
In the step (1), the alpha-Si3N4The average particle size of the powder is 0.5-1 μm; the average grain diameter of the TiC powder is 0.5-1 mu m; ZrSi2The average particle size of the powder is 1-3 μm; nano h-BN @ SiO2The average grain diameter is 0.1-0.5 μm; al (Al)2O3The average particle size of the powder is 0.5-2 μm; y is2O3The average particle diameter of the powder is 0.1-0.5 μm. Controlling the particle size has a certain promoting effect on obtaining a uniform and stable structure.
In the step (2), during ball milling, the ball: the mass ratio of the materials is 8-15: 0.5-3; preferably 10: 1.
in the step (3), the SPS sintering temperature is 1500-2000 ℃, and the SPS sintering temperature is 1700 ℃ preferably; or, the heat preservation time is 5-20min, preferably 10 min; alternatively, the axial pressure is 20 to 40MPa, preferably 30 MPa.
In one or more embodiments of the invention, the ceramic material obtained by any one of the preparation methods has the bending strength of 750-820MPa, the hardness of 13-16GPa and the fracture toughness of 8.00-8.73 MPa-m1/2。
In one or more embodiments of the present invention, any of the ceramic materials with strong fracture toughness and/or any of the methods for preparing the ceramic materials with strong fracture toughness and/or the use of the ceramic materials in the preparation of cutting tools are provided.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
In the raw material composition of each example, α -Si3N4The average particle size of the powder is 0.5-1 μm; the average grain diameter of the TiC powder is 0.5-1 mu m; ZrSi2The average particle size of the powder is 1-3 μm; nano h-BN @ SiO2The particle is self-made, and the average particle size is 0.1-0.5 mu m; al (Al)2O3The average particle size of the powder is 0.5-2 μm; y is2O3The average particle diameter of the powder is 0.1-0.5 μm.
Example 1
The preparation method of ceramic material with strong fracture toughness is characterized by that its raw material component volume percentage is alpha-Si3N4 67％，TiC 10％，ZrSi 210% of nano h-BN @ SiO2 5％，Al2O3 3％，Y2O3 5％。
Wherein, the nano h-BN @ SiO2The specific preparation process comprises the following steps: (1) weighing a proper amount of h-BN particles and polyvinylpyrrolidone (PVP) and adding absolute ethyl alcohol to prepare suspension with a certain concentration, and then ultrasonically dispersing the suspension for 30min while mechanically stirring to ensure that the nano h-BN has good dispersibility in the solution.
(2) And weighing a proper amount of tetraethoxysilane solution, ammonia water and distilled water according to the amount of the h-BN particles. Adding the ethyl orthosilicate solution into a separating funnel, diluting with a certain amount of alcohol, and fully shaking to fully mix the ethyl orthosilicate and the absolute ethyl alcohol.
(3) And (3) placing the mechanically stirred and ultrasonically dispersed h-BN suspension into a heat collection type magnetic stirrer, wherein the temperature of the heat collection type magnetic stirrer is set to be 40 ℃, adding the distilled water and the ammonia water in the step (2), and fully mixing the distilled water and the ammonia water to create alkaline and water conditions for hydrolysis of the tetraethoxysilane.
(4) And (4) slowly adding tetraethoxysilane into the mixed solution in the step (3) by using a separating funnel, and controlling the titration rate to be 0.4 ml/min.
(5) After titration is finished, the colloid in the step (4) is aged for 6 hours, then the colloid is placed into a high-speed centrifuge for centrifugation and cleaning, the rotation speed of the centrifuge is 6500r/min, the centrifugation time is 6min, the centrifuged supernatant is poured out, distilled water is added for continuing centrifugation and cleaning, and the centrifugation and cleaning are carried out for 5 times.
(6) According to the weight ratio of distilled water: n-butanol 6: 4, weighing the two solutions, then introducing the colloid after centrifugal cleaning in the step (5) into a mixed solution of distilled water and n-butanol, mechanically stirring and ultrasonically dispersing for 40 min. And finally, the obtained product is placed in a heat collection type magnetic stirrer (the temperature of the heat collection type magnetic stirrer is set to be 98 ℃) to carry out azeotropic drying.
Respectively weighing Si according to the component proportion of the ceramic cutter material3N4、TiC、ZrSi2、Al2O3And Y2O3And (3) respectively adding a proper amount of polyethylene glycol 4000 dispersant into the powder, and adding absolute ethyl alcohol, mechanically stirring and ultrasonically dispersing for 30 min. The dispersed solution was then mixed and stirred continuously with ultrasound for 30 min. Then pouring the suspension after ultrasonic stirring into a ball milling tank, and mixing the suspension according to the weight ratio of balls: the materials are mixed at a ratio of 10:1, and nitrogen is filled as protective atmosphere for ball milling for 44 h. To avoid nano h-BN @ SiO in the mechanical ball milling process2The shell of the particle is damaged, so the h-BN @ SiO is weighed according to the component proportion after ball milling for 44 hours2Adding a dispersing agent into the particles, ultrasonically stirring for 50min, pouring the mixture into a ball milling tank, and continuously ball-milling for 4 h. After the ball milling is finished, putting the ball-milled complex phase suspension into a vacuum drying oven, and carrying out vacuum drying at the temperature of 110 ℃/24 h. And finally, sieving the dried powder in a 100-mesh sieve, and then loading the powder into a graphite grinding tool to perform spark plasma sintering, wherein the sintering temperature is 1700 ℃, the heat preservation time is 10min, and the axial pressure is 30 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test of the material shows that the bending strength of the material is 782MPa, the hardness is 15.32GPa, and the fracture toughness is 8.52 MPa.m1/2. Prefabricating on the surface of a cutter by using a Vickers hardness tester300-. Carrying out heat treatment on the crack sample in a high-temperature air furnace, wherein the heat treatment temperature is 800 ℃, and the heat preservation time is 60 min; the heat-treated crack sample is subjected to room temperature bending strength test, the strength of the sample is increased from 213MPa when cracks occur to 773MPa, and the strength of the sample is recovered to 98% of that of a smooth sample.
Example 2
The preparation method of ceramic material with strong fracture toughness is characterized by that its raw material component volume percentage is alpha-Si3N4 62％，TiC 10％，ZrSi 210% of nano h-BN @ SiO 2 10％，Al2O3 3％，Y2O3 5％。
Wherein, the nano h-BN @ SiO2The specific preparation process comprises the following steps: (1) weighing a proper amount of h-BN particles and polyvinylpyrrolidone (PVP) and adding absolute ethyl alcohol to prepare suspension with a certain concentration, and then ultrasonically dispersing the suspension for 30min while mechanically stirring to ensure that the nano h-BN has good dispersibility in the solution.
(2) And weighing a proper amount of tetraethoxysilane solution, ammonia water and distilled water according to the amount of the h-BN particles. Adding the ethyl orthosilicate solution into a separating funnel, diluting with a certain amount of alcohol, and fully shaking to fully mix the ethyl orthosilicate and the absolute ethyl alcohol.
(3) And (3) placing the mechanically stirred and ultrasonically dispersed h-BN suspension into a heat collection type magnetic stirrer, wherein the temperature of the heat collection type magnetic stirrer is set to be 40 ℃, adding the distilled water and the ammonia water in the step (2), and fully mixing the distilled water and the ammonia water to create alkaline and water conditions for hydrolysis of the tetraethoxysilane.
(4) And (4) slowly adding tetraethoxysilane into the mixed solution in the step (3) by using a separating funnel, and controlling the titration rate to be 0.4 ml/min.
(5) After titration is finished, the colloid in the step (4) is aged for 6 hours, then the colloid is placed into a high-speed centrifuge for centrifugation and cleaning, the rotation speed of the centrifuge is 6500r/min, the centrifugation time is 6min, the centrifuged supernatant is poured out, distilled water is added for continuing centrifugation and cleaning, and the centrifugation and cleaning are carried out for 5 times.
(6) According to the weight ratio of distilled water: n-butanol 6: 4, weighing the two solutions, then introducing the colloid after centrifugal cleaning in the step (5) into a mixed solution of distilled water and n-butanol, mechanically stirring and ultrasonically dispersing for 40 min. And finally, the obtained product is placed in a heat collection type magnetic stirrer (the temperature of the heat collection type magnetic stirrer is set to be 98 ℃) to carry out azeotropic drying.
Respectively weighing Si according to the component proportion of the ceramic cutter material3N4、TiC、ZrSi2、Al2O3And Y2O3And (3) respectively adding a proper amount of polyethylene glycol 4000 dispersant into the powder, and adding absolute ethyl alcohol, mechanically stirring and ultrasonically dispersing for 30 min. The dispersed solution was then mixed and stirred continuously with ultrasound for 30 min. Then pouring the suspension after ultrasonic stirring into a ball milling tank, and mixing the suspension according to the weight ratio of balls: the materials are mixed at a ratio of 10:1, and nitrogen is filled as protective atmosphere for ball milling for 44 h. To avoid h-BN @ SiO in the mechanical ball milling process2The shell of the particle is damaged, so the h-BN @ SiO is weighed according to the component proportion after ball milling for 44 hours2Adding a dispersing agent into the particles, ultrasonically stirring for 50min, pouring the mixture into a ball milling tank, and continuously ball-milling for 4 h. After the ball milling is finished, putting the ball-milled complex phase suspension into a vacuum drying oven, and carrying out vacuum drying at the temperature of 110 ℃/24 h. And finally, sieving the dried powder in a 100-mesh sieve, and then loading the powder into a graphite grinding tool to perform spark plasma sintering, wherein the sintering temperature is 1500 ℃, the heat preservation time is 20min, and the axial pressure is 40 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 702MPa, the hardness is 15.21GPa, and the fracture toughness is 8.73 MPa.m1/2。
As in fig. 1, 10 vol.% of nano h-BN @ SiO was added2Si of (2)3N4/TiC/ZrSi2/h-BN@SiO2The nano h-BN with a flaky structure is obviously present in the ceramic material, and part of the nano h-BN forms an intracrystalline structure (white square box). At the same time because of SiO2The outer shell can play a role in binding h-BN in spark plasma sintering, so that the h-BN can be uniformly distributed in the fracture surface without obvious clusterAnd (4) polymerizing.
300-350 mu m cracks are prefabricated on the surface of the cutter by using a Vickers hardness tester. Carrying out heat treatment on the crack sample in a high-temperature air furnace, wherein the heat treatment temperature is 800 ℃, and the heat preservation time is 60 min; the heat-treated crack sample is subjected to room temperature bending strength test, the strength of the sample is increased from 205MPa when cracks occur to 698MPa, and the strength of the sample is recovered to 99% of that of a smooth sample. Compared to the ceramic material without heat treatment (fig. 2), the crack surface morphology after heat treatment is shown in fig. 3, and the crack is found to be substantially healed. EDS analysis revealed that the distribution of Zr, Si, and O elements at the cracks is due to ZrSi as shown in FIG. 42TiO formed by oxidation2And SiO2The cracks are repaired. And the XRD map of FIG. 5 also demonstrates ZrO2And SiO2Is present.
Comparative example 1:
the only difference from example 2 is that: without addition of nano h-BN @ SiO 2 10％。
The ceramic material prepared in this comparative example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 627MPa, the hardness is 15.91GPa, and the fracture toughness is 5.68 MPa.m1/2。
Comparative example 2:
the only difference from example 2 is that: the added is micron-sized h-BN @ SiO 2 10％。
Wherein, the micron h-BN @ SiO2The specific preparation process comprises the following steps: (1) weighing a proper amount of h-BN particles and polyvinylpyrrolidone (PVP) and adding absolute ethyl alcohol to prepare suspension with a certain concentration, and then carrying out ultrasonic dispersion on the suspension for 15min while mechanically stirring.
(2) And weighing a proper amount of tetraethoxysilane solution, ammonia water and distilled water according to the amount of the h-BN particles. Adding the ethyl orthosilicate solution into a separating funnel, diluting with a certain amount of alcohol, and fully shaking to fully mix the ethyl orthosilicate and the absolute ethyl alcohol.
(3) And (3) placing the mechanically stirred and ultrasonically dispersed h-BN suspension into a heat collection type magnetic stirrer, wherein the temperature of the heat collection type magnetic stirrer is set to be 50 ℃, adding the distilled water and the ammonia water in the step (2), and fully mixing the distilled water and the ammonia water to create alkaline and water conditions for hydrolysis of the tetraethoxysilane.
(4) And (4) slowly adding ethyl orthosilicate into the mixed solution in the step (3) by using a separating funnel, and controlling the titration rate to be 1 ml/min.
(5) After titration is finished, the colloid in the step (4) is aged for 6 hours, then the colloid is placed into a high-speed centrifuge for centrifugation and cleaning, the rotation speed of the centrifuge is 6500r/min, the centrifugation time is 6min, the centrifuged supernatant is poured out, absolute ethyl alcohol is added, the centrifugation and cleaning are continuously carried out, and the centrifugation and cleaning are carried out for 5 times.
(6) Putting the mixed solution after centrifugal cleaning into a vacuum drying oven, adjusting the temperature to 70 ℃, and drying for 18 h. Grinding the dried particles to obtain the micron h-BN @ SiO2And (3) granules.
The ceramic material prepared in this comparative example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 580MPa, the hardness is 15.06GPa, and the fracture toughness is 4.18 MPa.m1/2。
And (4) analyzing results: due to the addition of micron-sized h-BN @ SiO2In the sintering process, an in-crystal structure cannot be formed, the pinning effect of the nano particles is lacked, and the mechanical property, particularly the fracture toughness, of the ceramic material is low.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. High fracture toughnessThe ceramic material of (2), characterized by comprising: according to the volume percentage of each raw material component: alpha-Si3N4 55-75％，TiC 5-15％，ZrSi20-15% of nano h-BN @ SiO2 0-15％，Al2O33-7％，Y2O35-7%, wherein, the nano h-BN @ SiO2Is not 0.
2. The ceramic material with high fracture toughness of claim 1, wherein the ceramic material comprises: according to the volume percentage of each raw material component: alpha-Si3N4 57-72％，TiC 10％，ZrSi210% of nano h-BN @ SiO2 0-15％，Al2O33％，Y2O35%, nano h-BN @ SiO2Is not 0.
3. The ceramic material with high fracture toughness of claim 1, wherein the nano h-BN @ SiO2The preparation method comprises the following steps:
adding the nano h-BN particles and polyvinylpyrrolidone into absolute ethyl alcohol to prepare suspension, and stirring and dispersing; heating at 30-50 deg.C, adding distilled water and ammonia water, mixing, stirring, and slowly adding ethyl orthosilicate; performing centrifugal separation after aging to obtain colloid; adding n-butanol solution into the colloid, and performing azeotropic drying.
4. A preparation method of a ceramic material with strong fracture toughness is characterized by comprising the following steps:
(1) respectively weighing alpha-Si according to the component proportion of the ceramic material3N4、TiC、ZrSi2、Al2O3And Y2O3Powder, namely adding a dispersing agent and absolute ethyl alcohol into each component respectively, and stirring and dispersing to prepare a suspension; then, mixing the suspensions of the components to obtain a complex phase suspension;
(2) ball-milling the complex phase suspension in the step (1) in an inert atmosphere; after ball milling for 40-50h, weighing nano h-BN @ SiO according to the component proportion2In the nanometer h-BN @ SiO2Adding inPouring the dispersing agent into a ball milling device to continuously perform ball milling for 3-6 h; and after the ball milling is finished, drying to obtain mixed powder.
(3) And (3) putting the mixed powder in the step (2) into an SPS sintering furnace for spark plasma sintering.
5. The method for preparing a ceramic material with high fracture toughness as claimed in claim 4, wherein in step (1), said dispersant is selected from polyvinylpyrrolidone, polyethylene glycol, and sodium tripolyphosphate, preferably polyethylene glycol 4000.
6. The method for preparing a ceramic material with high fracture toughness as claimed in claim 4, wherein, in step (1), said α -Si is added3N4The average particle size of the powder is 0.5-1 μm; the average grain diameter of the TiC powder is 0.5-1 mu m; ZrSi2The average particle size of the powder is 1-3 μm; h-BN @ SiO2The average grain diameter is 0.1-0.5 μm; al (Al)2O3The average particle size of the powder is 0.5-2 μm; y is2O3The average particle diameter of the powder is 0.1-0.5 μm.
7. The method for preparing a ceramic material with high fracture toughness according to claim 4, wherein in the step (2), when ball milling is performed, the ratio of the ball: the mass ratio of the materials is 8-15: 0.5-3; preferably 10: 1.
8. the method for preparing a ceramic material with high fracture toughness as claimed in claim 4, wherein in the step (3), the SPS sintering temperature is 1500-2000 ℃, preferably 1700 ℃; or, the heat preservation time is 5-20min, preferably 10 min; alternatively, the axial pressure is 20 to 40MPa, preferably 30 MPa.
9. The ceramic material obtained by the preparation method as set forth in any one of claims 4 to 8, wherein the ceramic material has a flexural strength of 750-820MPa, a hardness of 13-16GPa, and a fracture toughness of 8.00-8.73 MPa-m1/2。
10. A method of producing a high fracture toughness ceramic material according to any one of claims 1 to 3 and/or a high fracture toughness ceramic material according to any one of claims 4 to 8 and/or the use of a ceramic material according to claim 9 for the production of a cutting tool.
CN202111294921.XA 2021-11-03 2021-11-03 Ceramic material with strong fracture toughness, preparation method and application thereof Pending CN113896542A (en)

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CN1131937A (en) * 1994-08-09 1996-09-25 株式会社丰田中央研究所 Composite material and production method therefor
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