CN110818428A - Preparation method of eutectic reinforced toughened silicon nitride ceramic - Google Patents

Preparation method of eutectic reinforced toughened silicon nitride ceramic Download PDF

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CN110818428A
CN110818428A CN201911221429.2A CN201911221429A CN110818428A CN 110818428 A CN110818428 A CN 110818428A CN 201911221429 A CN201911221429 A CN 201911221429A CN 110818428 A CN110818428 A CN 110818428A
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silicon nitride
sintering
ceramic
mixture
mold
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CN110818428B (en
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陈克新
张�杰
刘光华
崔巍
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Tsinghua University
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Abstract

The invention discloses a preparation method of eutectic reinforced and toughened silicon nitride ceramics, belonging to the technical field of ceramic preparation, wherein the method enables a silicon nitride material to form an α and β phase eutectic structure to obtain the silicon nitride reinforced and toughened ceramic, and the relative density of the ceramic>99% fracture toughness>10MPa·m1/2Vickers hardness>18GPa, bending strength>600 MPa. The method comprises the following steps: 1) mixing silicon nitride raw material and sintering aid according to a certain proportion, making the uniformly-mixed powder pass through Spark Plasma Sintering (SPS) process to obtain the relative density>99%, α phase content>90 percent of primary sintered body, and then carrying out air pressure sintering, thereby generating α/β eutectic structure, the silicon nitride ceramic prepared by the invention has the characteristics of high strength, good compactness, high temperature resistance and wear resistance, obviously improves the fracture toughness and plasticity, and can be widely applied to the field of special materials.

Description

Preparation method of eutectic reinforced toughened silicon nitride ceramic
Technical Field
The invention belongs to the technical field of ceramic preparation, relates to a preparation method of high-performance silicon nitride ceramic, and particularly relates to a process technology for preparing silicon nitride ceramic with α/β eutectic structures.
Background
The silicon nitride ceramic has a plurality of excellent performances such as low density, high heat conductivity coefficient, high hardness, good thermal stability and chemical stability, is a material with the most excellent comprehensive performance in a structural ceramic family, and is widely applied to the fields of ceramic engines, cutting tools, heat conducting substrates and the like. However, the inherent brittleness of ceramic materials limits the further application and popularization of silicon nitride.
Disclosure of Invention
The invention aims to provide a process method for preparing silicon nitride ceramics with α/β eutectic structures, so that the prepared silicon nitride ceramics have relative density>99% fracture toughness>10MPa·m1/2Vickers hardness>18GPa, bending strength>600MPa, and can bear 1-3% of strain without generating fracture.
The technical scheme of the invention is as follows. A preparation method of eutectic strengthening and toughening silicon nitride ceramics comprises the following steps:
(1) preparing raw materials: uniformly mixing the following components to obtain a mixture;
silicon nitride powder; 70 to 90 weight percent of the total weight of the alloy,
a sintering aid; 5 to 20 weight percent of the total weight of the mixture,
a phase transition inhibitor; 1 to 10 percent;
(2) performing discharge plasma sintering (SPS) on the mixture obtained in the step (1) to obtain a primary sintered body;
(3) and (3) carrying out air pressure sintering on the product obtained in the step (2) to obtain the silicon nitride ceramic with α/β eutectic structure.
According to one embodiment of the present invention, in the process, for example, the purity of the silicon nitride powder raw material in step (1) is >99 wt%, the average particle size of the silicon nitride powder is 0.5-2 μm, and the α phase content of the silicon nitride powder is 95 wt%.
According to one embodiment of the invention, in the method, for example, the sintering aid in step (1) is selected from Al2O3、MgO、SiO2、Y2O3、ZrO2、R2O3(R represents a rare earth element such as La, Lu, Yb, etc.), MgSiN2At least one of (1).
According to one embodiment of the present invention, in the method, for example, CaO is selected as the phase change inhibitor in step (1).
According to one embodiment of the present invention, in the method, for example, the mixing means in the step (1) includes sand milling, ball milling, and stirring milling.
According to an embodiment of the present invention, in the method, for example, the step (2) includes: drying the mixture obtained in the step (1), sieving the dried mixture by a 60-200-mesh sieve, distributing the mixture in an SPS (semi-solid phase sintering) mould, then placing the reaction mould in a point plasma sintering device, vacuumizing, pressurizing the raw materials, and simultaneously electrifying and heating for sintering; after the reaction is finished, circulating water is introduced for cooling; finally obtaining a primary sintering product; preferably, the sintering pressure range is 10-100MPa, the sintering temperature is 1500 ℃, and the heat preservation time is 5 min.
According to an embodiment of the present invention, in the method, for example, the method further includes step (3) after step (2): and (3) carrying out air pressure sintering on the primary sintered body obtained in the step (2), wherein the air pressure sintering step is carried out according to the following process: the primary sintered body is placed in a boron nitride crucible, the temperature is raised to 1500-minus-one 1700 ℃ in a sintering furnace at the speed of 5-10 ℃/min, the temperature is preserved for 0.5-1h, then the temperature is rapidly lowered to 900 ℃, the temperature is raised to 1500-minus-one 1700 ℃ at the speed of 20 ℃/min, and then the furnace is stopped from heating and cooling to the room temperature.
According to one embodiment of the present invention, in the method, for example, the sintering process in step (4) is accompanied by the oscillation of the pressure in the furnace during the rapid cooling process, wherein the pressure oscillation is in the range of 1-8 MPa.
According to one embodiment of the present invention, in the method, for example, the average particle size of the sintering aid in the step (1) is 300-500nm, and the purity is >99 wt%.
According to an embodiment of the present invention, in the method, for example, the mixing medium of step (1) is selected from one of water, methanol, and ethanol; the grinding ball is selected from one of silicon nitride grinding ball, zirconia grinding ball and agate grinding ball.
According to one embodiment of the invention, in the method, for example, the sand mixing in step (1), the grinding balls are preferably silicon nitride grinding balls, and the grinding ball size is <1 mm.
According to one embodiment of the invention, in the method, for example, the ball milling material in step (1), the milling balls are preferably silicon nitride milling balls, and the size of the milling balls is 3-10 mm.
According to one embodiment of the invention, in the method, for example, the mill mixture is stirred in step (1), and the grinding balls are preferably silicon nitride grinding balls, and the size of the grinding balls is 3-10 mm.
According to one embodiment of the invention, in the method, for example, the rotation speed of the mixing mode in the step (1) is 300-.
According to one embodiment of the present invention, in the method, for example, the relative density of the primary sintered body of the step (2) is > 99%, and the α phase content is > 90%.
According to one embodiment of the present invention, in the method, for example, the SPS sintering mold in step (2) is made of graphite, and preferably, the mold and the mixture are isolated by using carbon paper.
According to one embodiment of the present invention, in the method, for example, the temperature rise rate of the SPS sintering in the step (2) is 150-.
The embodiment of the invention also provides the silicon nitride ceramic prepared by the method, which is characterized in that the relative density of silicon nitride is>99% fracture toughness>10MPa·m1/2Vickers hardness>18GPa, bending strength>600MPa。
According to one embodiment of the invention, the fracture toughness of the silicon nitride ceramic with the α/β eutectic structure is improved by more than 50% compared with the ceramic without the eutectic structure, and the silicon nitride ceramic can bear 1-3% of strain without fracture.
The silicon nitride ceramic prepared by the invention has α/β eutectic structures, and has the outstanding advantages that:
1. under the condition of bearing load, the silicon nitride ceramic with α/β eutectic structure prepared by the method can absorb energy through the phase change of α phase to β phase, and simultaneously, the α phase can generate volume change after being converted to β phase, so that the stress concentration in the ceramic can be relieved through the phase change, and the performance of the silicon nitride ceramic is improved;
2. the silicon nitride ceramic with α/β eutectic structure is prepared, and the characteristic that the volume change is generated after α phase is converted to β phase is utilized, so that a new thought is provided for solving the problem of poor past plastic property of the ceramic, the brittleness problem of the silicon nitride is improved, and the silicon nitride can bear 1-3% of strain without breaking;
3. and energy is saved. The preparation temperature of the silicon nitride preparation method is 1500-1700 ℃, and the longest heat preservation time is only 1 h. Compared with the traditional process for preparing silicon nitride, the sintering temperature is reduced by 100-200 ℃, and the time is shortened by 5-10 h.
4. High production efficiency and is suitable for mass production.
Drawings
FIG. 1 is an XRD analysis pattern of the silicon nitride powder products used in examples 1-4 and comparative example 1;
FIG. 2 is an XRD analysis pattern of the primary sintered body in example 1;
FIG. 3 is a gas pressure sintering process schedule of example 1;
FIG. 4 is an XRD analysis pattern of the silicon nitride ceramic product of example 1;
FIG. 5 is a BSE analysis of the silicon nitride ceramic product of example 1;
FIG. 6 is an XRD analysis pattern of the silicon nitride ceramic product of example 2;
FIG. 7A gas pressure sintering process regime of example 2;
FIG. 8 is an XRD analysis pattern of the silicon nitride ceramic product of example 3;
FIG. 9 example 3 gas pressure sintering Process regime
FIG. 10 an XRD analysis pattern of the silicon nitride ceramic product of example 4; (80% a)
FIG. 11 is an XRD analysis pattern of the silicon nitride ceramic product of comparative example 1.
Detailed Description
The invention will be further explained with reference to the drawings and examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Herein, the bending strength test of the silicon nitride ceramic is tested according to the standard GB/T6569-.
Example 1
(1) Mixing materials: uniformly mixing the dried ceramic raw materials in proportion, and sieving the mixture by a 60-mesh sieve, wherein the ceramic raw materials consist of the following components:
silicon nitride powder: 90 percent;
sintering aid: 9 percent;
phase transition inhibitor: 1 percent;
the sintering aid consists of the following components:
Al2O3：60％；
Y2O3：40％；
(2) grinding: placing powder to be mixed in a sand mill, and mixing the following materials according to the weight percentage: ethanol ═ 1: 2 adding powder and ethanol, setting the sanding speed to 3000r/min, and sanding for 2 hours.
(3) And (2) sintering, namely filling the powder into an SPS mold, filling the mold into an SPS device, vacuumizing, heating to 1500 ℃ at the speed of 150 ℃/min, preserving heat for 5min under the pressure of 10MPa, cooling to room temperature along with the furnace after heating is stopped, taking out a sample, obtaining a primary sintered body, putting the primary sintered body into a boron nitride crucible, filling the primary sintered body into an air pressure sintering furnace, heating to 1500 ℃ at the speed of 5 ℃/min, preserving heat for 1h under the nitrogen pressure of 4MPa, quickly cooling to 900 ℃, simultaneously reducing the pressure to 1MPa, then heating to 1500 ℃ at the speed of 20 ℃/min, stopping heating, and cooling to room temperature along with the furnace.
The obtained ceramic had a content of α phases of 70%, a relative density of 99.3%, and a fracture toughness of 10.5MPa m1/2The Vickers hardness is 18.6Gpa, the bending strength is 642MPa, and the steel can bear the strain of 2.5% at most without fracture.
Example 2
(1) Mixing materials: uniformly mixing the dried ceramic raw materials in proportion, and sieving the mixture by a 100-mesh sieve, wherein the ceramic raw materials consist of the following components:
silicon nitride powder: 80 percent;
sintering aid: 15 percent;
phase transition inhibitor: 5 percent;
the sintering aid consists of the following components:
MgO：40％；
Y2O3：40％；
SiO2：20％
(2) grinding: placing powder to be mixed in a ball mill, and mixing the following materials according to the weight percentage: ethanol ═ 1: 2, adding powder and ethanol, setting the sanding speed at 300r/min, and ball-milling for 10 hours.
(3) And (2) sintering, namely filling the powder into an SPS mold, filling the mold into an SPS device, vacuumizing, heating to 1500 ℃ at the speed of 150 ℃/min, preserving heat at the pressure of 50MPa for 5min, cooling to room temperature along with the furnace after heating is stopped, taking out a sample to obtain a primary sintered body, putting the primary sintered body into a boron nitride crucible, filling the primary sintered body into an air pressure sintering furnace, heating to 1600 ℃ at the speed of 5 ℃/min, preserving heat at the nitrogen pressure of 6MPa for 1h, quickly cooling to 900 ℃, simultaneously reducing the pressure to 1MPa, heating to 1600 ℃ at the speed of 20 ℃/min, stopping heating, and cooling to room temperature along with the furnace.
The obtained ceramic had a content of α phases of 50%, a relative density of 99.4%, and a fracture toughness of 10.5MPa m1/2The Vickers hardness is 19.3Gpa, the bending strength is 745MPa, and the strain of 2% can be endured at the maximum without breaking.
Example 3
(1) Mixing materials: uniformly mixing the dried ceramic raw materials in proportion, and sieving the mixture by a 200-mesh sieve, wherein the ceramic raw materials consist of the following components:
silicon nitride powder: 70 percent;
sintering aid: 20 percent;
phase transition inhibitor: 10 percent;
the sintering aid consists of the following components:
La2O3：40％；
MgSiN2：40％；
ZrO2：20％
(2) grinding: placing powder to be mixed in a stirring mill, and mixing the following materials: water 1: 3, adding powder and ethanol, setting the sanding rotating speed to be 500r/min, and grinding for 5 hours.
(3) And (2) sintering, namely filling the powder into an SPS mold, filling the mold into an SPS device, vacuumizing, heating to 1500 ℃ at the speed of 200 ℃/min, preserving heat for 5min under the pressure of 100MPa, cooling to room temperature along with the furnace after heating is stopped, taking out a sample to obtain a primary sintered body, putting the primary sintered body into a boron nitride crucible, filling the primary sintered body into an air pressure sintering furnace, heating to 1700 ℃ at the speed of 10 ℃/min, preserving heat for 1h under the nitrogen pressure of 8MPa, quickly cooling to 900 ℃, simultaneously reducing the pressure to 1MPa, heating to 1700 ℃ at the speed of 20 ℃/min, stopping heating, and cooling to room temperature along with the furnace.
The obtained ceramic had an α phase content of 20%, a relative density of 99.5%, and a fracture toughness of 10.5MPa m1/2The Vickers hardness is 19.7Gpa, the bending strength is 874MPa, and the steel can bear the strain of 1% at most without fracture.
Example 4
(1) Mixing materials: uniformly mixing the dried ceramic raw materials in proportion, and sieving the mixture by a 200-mesh sieve, wherein the ceramic raw materials consist of the following components:
silicon nitride powder: 90 percent;
sintering aid: 9 percent;
phase transition inhibitor: 1 percent;
the sintering aid consists of the following components:
Al2O3：60％；
Y2O3：40％；
(2) grinding: placing powder to be mixed in a ball mill, and mixing the following materials according to the weight percentage: methanol 1: 2, adding powder and ethanol, setting the sanding speed at 300r/min, and ball-milling for 10 hours.
(3) And (2) sintering, namely filling the powder into an SPS mold, filling the mold into an SPS device, vacuumizing, heating to 1500 ℃ at the speed of 200 ℃/min, preserving heat for 5min under the pressure of 20MPa, cooling to room temperature along with the furnace after heating is stopped, taking out a sample to obtain a primary sintered body, putting the primary sintered body into a boron nitride crucible, filling the primary sintered body into an air pressure sintering furnace, heating to 1500 ℃ at the speed of 10 ℃/min, preserving heat for 1h under the nitrogen pressure of 4MPa, quickly cooling to 900 ℃, simultaneously reducing the pressure to 1MPa, heating to 1500 ℃ at the speed of 20 ℃/min, stopping heating, and cooling to room temperature along with the furnace.
The obtained ceramic had an α phase content of 80%, a relative density of 99.3%, and a fracture toughness of 10.5MPa m1/2The Vickers hardness is 18.3Gpa, the bending strength is 657MPa, and the steel can bear 3% strain at most without fracture.
Comparative example 1
(1) Mixing materials: uniformly mixing the dried ceramic raw materials in proportion, and sieving the mixture by a 200-mesh sieve, wherein the ceramic raw materials consist of the following components:
silicon nitride powder: 80 percent;
sintering aid: 20 percent;
the sintering aid consists of the following components:
La2O3：40％；
MgSiN2：40％；
ZrO2：20％
(2) grinding: placing powder to be mixed in a ball mill, and mixing the following materials according to the weight percentage: methanol 1: 2, adding powder and ethanol, setting the sanding speed at 300r/min, and ball-milling for 10 hours.
(3) And (3) sintering: pressing the mixed powder into a biscuit by using a mold, then placing the biscuit in a boron nitride crucible, then placing the biscuit in a gas pressure sintering furnace, heating the biscuit to 1700 ℃ at the speed of 10 ℃/min, preserving the heat for 1h under the nitrogen pressure of 1MPa, and cooling the biscuit to the room temperature along with the furnace after the heating is stopped.
The obtained ceramic had a content of α phases of 0%, a relative density of 99.5%, and a fracture toughness of 6.5MPa · m1/2The vickers hardness is 16.7Gpa, and the bending strength is 863MPa, and the steel sheet has no strain-bearing capability.
The results of example 2 were compared with those of comparative example 1, and the experimental conditions of example 2 were substantially the same as those of comparative example 2, except that 10% of the phase transition inhibitor was added during the mixing process in example 2, the sintering process according to the present invention was used in example 2, and the conventional silicon nitride sintering process was used in comparative example 1. From the test results, the fracture toughness of the final sintered product was as high as 6.5MPa · m of comparative example 11/2The pressure was increased to 10.5MPa · m of example 21/2The Vickers hardness is improved from 16.7Gpa of comparative example 1 to 19.7Gpa of example 2, particularly, the comparative example 1 does not have the capability of bearing strain, and the example 2 can bear 1% of strain at most without fracture.

Claims (10)

1. A preparation method of eutectic strengthening and toughening silicon nitride ceramics is characterized by comprising the following steps:
(1) preparing raw materials: uniformly mixing the following components to obtain a mixture;
silicon nitride powder; 70 to 90 weight percent of the total weight of the alloy,
a sintering aid; 5 to 20 weight percent of the total weight of the mixture,
a phase transition inhibitor; 1 to 10 percent;
(2) performing discharge plasma sintering on the mixture obtained in the step (1) to obtain a primary sintered body;
(3) and (3) carrying out air pressure sintering on the product obtained in the step (2) to obtain the silicon nitride ceramic with α/β eutectic structure.
2. The process according to claim 1, wherein the purity of the silicon nitride powder in step (1) is >99 wt%, the average particle size is 0.5-2 μm, and the α phase content of the silicon nitride powder is 95 wt%;
the sintering aid is selected from Al2O3、MgO、SiO2、Y2O3、ZrO2、R2O3、MgSiN2At least one of; wherein R represents a rare earth element; the average particle size of the sintering aid is 300-500nm, and the purity of the sintering aid>99wt％；
And the phase change inhibitor is CaO.
3. The method of claim 1, wherein the mixing of step (1) comprises sand, ball or agitator milling; the medium is selected from one of water, methanol and ethanol; the sanded grinding ball is selected from one of silicon nitride grinding balls, zirconium oxide grinding balls and agate grinding balls; the size of the grinding ball is less than 1 mm; the grinding ball for ball milling is a silicon nitride grinding ball, and the size of the grinding ball is 3-10 mm; the grinding ball of the stirring mill is a silicon nitride grinding ball, and the size of the grinding ball is 3-10 mm.
4. The method as claimed in claim 1, wherein the mixing in step (1) is performed at a rotation speed of 300-3000r/min for a mixing time of 2-10 h.
5. The method of claim 1, wherein step (2) comprises: drying the mixture obtained in the step (1), sieving the dried mixture by a 60-200-mesh sieve, loading the dried mixture into an SPS (spark plasma sintering) mold, then placing the reaction mold into a discharge plasma sintering device, vacuumizing the reaction mold, pressurizing the raw materials, and simultaneously electrifying and heating the reaction mold for sintering; after the reaction is finished, cooling the sample along with the furnace; cooling to obtain a primary sintered product; the sintering pressure range is 10-100MPa, the sintering temperature is 1500 ℃, and the heat preservation time is 5 min.
6. The method as claimed in claim 1, wherein the sintering in step (2) is performed at a temperature rise rate of 150-; the used mold is made of graphite material, and carbon paper is used for isolation between the mold and the mixture.
7. The method of claim 1, wherein the relative density of the primary sintered body of step (2) is > 99% and the α phase content is > 90%.
8. The method of claim 1, wherein step (3) comprises: placing the product obtained in the step (2) in a boron nitride crucible, heating to 1700 ℃ at the speed of 5-10 ℃/min in a sintering furnace, preserving heat for 0.5-1h, then rapidly cooling to 900 ℃, heating to 1700 ℃ at the speed of 20 ℃/min, and then stopping heating and cooling to room temperature along with the furnace; in the process of rapid cooling, the oscillation range of the pressure in the furnace is 1-8 MPa.
9. The silicon nitride ceramic prepared according to any one of claims 1 to 8, wherein the relative density of silicon nitride is>99% fracture toughness>10MPa·m1/2Vickers hardness>18GPa, bending strength>600MPa。
10. The silicon nitride ceramic according to claim 9, wherein the silicon nitride ceramic has an α/β eutectic structure, has a fracture toughness that is improved by 50% or more compared to a ceramic without the eutectic structure, and can withstand a strain of 1 to 3% without fracture.
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