CN115745401A - Silicon nitride ceramic encapsulated oxygen-nitrogen glass and preparation method and application thereof - Google Patents
Silicon nitride ceramic encapsulated oxygen-nitrogen glass and preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 138
- 239000000919 ceramic Substances 0.000 title claims abstract description 104
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 86
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 29
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- 239000000203 mixture Substances 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 17
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- 238000007873 sieving Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
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- 239000002994 raw material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001513 hot isostatic pressing Methods 0.000 description 16
- 239000011148 porous material Substances 0.000 description 11
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Abstract
The invention relates to silicon nitride ceramic encapsulated oxygen-nitrogen glass and a preparation method and application thereof. The composition of the oxynitride glass contains Y 2 O 3 ‑Al 2 O 3 ‑SiO 2 -AlN; wherein Y is 2 O 3 36.6-43.7 wt% of Al 2 O 3 The content of (A) is 24.8-29.6 wt%, siO 2 The content of (A) is 17.7-22.1 wt%, and the content of AlN is 4.6-20.9 wt%.
Description
Technical Field
The invention relates to silicon nitride ceramic encapsulated oxygen-nitrogen glass and a preparation method and application thereof, belonging to the field of preparation of silicon nitride ceramics.
Background
The silicon nitride ceramic has the advantages of low density, good mechanical property, high temperature resistance, wear resistance, corrosion resistance, electric insulation, non-magnetic conductivity and the like, can be used as a bearing ball to completely cover the application field of precise and above-medium-speed all-steel bearing balls, and can be used in working environments which cannot be met by traditional metal balls, such as high-speed, high-low temperature, vacuum, insulation, non-magnetic conductivity, instant non-lubrication and the like. But silicon nitride is a strong covalent bond material and sintering is very difficult. Due to the special columnar crystal morphology of the silicon nitride ceramics, holes are easily formed by the mutual staggered lap joint of crystal grains. Even when the liquid-phase sintering aid is added, there are regions where the liquid phase is not sufficiently filled or the liquid phase volatilizes, and residual pores are formed. These residual pores will become short plates during service, causing the silicon nitride ceramic to fail. In order to sufficiently eliminate these pores, an effective method is to subject the silicon nitride ceramic to hot isostatic pressing. However, when the silicon nitride ceramic obtained by gas pressure sintering is subjected to hot isostatic pressing, the pores on the surface of the silicon nitride ceramic provide passages for the diffusion of high-pressure gas, so that the high-pressure gas enters the interior of the ceramic, and the ceramic matrix cracks or pores in the interior of the ceramic cannot be compressed or discharged under the action of the external high gas pressure.
Disclosure of Invention
Therefore, the invention provides silicon nitride ceramic-encapsulated oxynitrided glass, a preparation method and application thereof.
In a first aspect, the present invention provides a silicon nitride ceramic encapsulating oxy-nitride glass, the composition of which comprises Y 2 O 3 -Al 2 O 3 -SiO 2 -AlN; wherein Y is 2 O 3 The content of (B) is 36.6-43.7 wt%, al 2 O 3 The content of (A) is 24.8-29.6 wt%, siO 2 The content of the AlN is 17.7-22.1 wt%, and the content of the AlN is 4.6-20.9 wt%.
Preferably, the bending strength of the oxynitride glass is 123.3 to 170.9MPa; the Vickers hardness of the oxygen-nitrogen glass is 9.7-11.3 GPa; the fracture toughness of the oxygen-nitrogen glass is 1.2-1.7 MPa-m 1/2 。
In a second aspect, the invention provides an oxynitride glass powder for encapsulating silicon nitride ceramics, wherein the composition of the oxynitride glass powder comprises Y 2 O 3 -Al 2 O 3 -SiO 2 -AlN; it is provided withMiddle Y 2 O 3 36.6-43.7 wt% of Al 2 O 3 The content of (B) is 24.8-29.6 wt%, siO 2 The content of the AlN is 17.7 to 22.1 weight percent, and the content of the AlN is 4.6 to 20.9 weight percent; preferably, the oxynitride glass powder has a particle size of 40 to 325 mesh.
The inventors first considered: in order to maximize the effect of hot isostatic pressing, it is necessary to close the open pores on the surface of the silicon nitride ceramic to prevent the high-pressure gas from diffusing into the ceramic. One method of effectively closing surface pores is to glass encapsulate silicon nitride ceramics. However, due to the high creep temperature of the silicon nitride ceramic, the softening temperature of the encapsulating glass adapted thereto should be high enough and have good wettability with the silicon nitride ceramic so as to adhere firmly to the surface of the silicon nitride ceramic.
Therefore, the present inventors have creatively used Y 2 O 3 、Al 2 O 3 、SiO 2 AlN is used as a raw material, and a glass component which has moderate viscosity, good wettability with silicon nitride ceramics and temperature matching with the hot isostatic pressing temperature of the silicon nitride ceramics is obtained through component regulation. The invention optimizes the components of the oxynitride glass to adapt to the hot isostatic pressing process and obtain better effect of promoting densification. And then, a glass encapsulating layer with proper thickness is formed on the surface of the silicon nitride ceramic through the control of an encapsulating process, so that the performance of the silicon nitride ceramic is promoted to be improved in the hot isostatic pressing process.
In a third aspect, the invention provides a method for preparing a silicon nitride ceramic-encapsulated oxynitride glass, which comprises the following steps:
will Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Mixing the powder with AlN powder to obtain mixed powder;
and putting the mixed powder into a crucible, and placing the crucible in a sintering furnace for glass melting to obtain the oxygen-nitrogen glass.
In a fourth aspect, the invention provides a method for preparing silicon nitride ceramic encapsulated oxygen-nitrogen glass powder, comprising the following steps: will Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Mixing the powder with AlN powder to obtain mixed powder；
Putting the mixed powder into a crucible, and placing the crucible in a sintering furnace for glass melting to obtain oxygen-nitrogen glass;
and crushing the oxynitride glass to obtain oxynitride glass powder.
Preferably, the mixing method comprises the following steps: with Y 2 O 3 、Al 2 O 3 、SiO 2 And AlN as raw material, and solvent as solvent to prepare slurry. Then ZrO 2 The ball is used as a grinding medium, and the mixed powder is obtained by ball milling, drying and sieving.
Preferably, the rotation speed of the ball milling is 200-400 rpm, and the ball milling time is 3-6 hours; the solvent is deionized water or/and an organic solvent; the organic solvent is at least one selected from alcohol, terpineol and dimethyl sulfoxide.
Preferably, the glass melting temperature is 1500-1700 ℃, the time is 2-3 hours, and the atmosphere is Ar or N 2 。
In a fifth aspect, the invention provides a silicon nitride ceramic encapsulation method, completely burying silicon nitride ceramic in oxynitride glass powder for silicon nitride ceramic encapsulation, placing in a sintering furnace for glass encapsulation, and forming a glass encapsulation layer on the surface of the silicon nitride ceramic; preferably, the temperature of the glass encapsulation is 1400-1600 ℃, the time is 10-30 minutes, and the atmosphere is N 2 。
In a sixth aspect, the present invention provides a modified silicon nitride ceramic comprising: silicon nitride ceramics and a glass encapsulating layer formed on the surface of the silicon nitride ceramics; the composition of the glass encapsulating layer comprises Y 2 O 3 -Al 2 O 3 -SiO 2 -AlN; wherein Y is 2 O 3 36.6-43.7 wt% of Al 2 O 3 The content of (A) is 24.8-29.6 wt%, siO 2 The content of (A) is 17.7-22.1 wt%, and the content of AlN is 4.6-20.9 wt%; preferably, the thickness of the glass encapsulation layer is 9.7 to 28.6 μm.
In a seventh aspect, the present invention provides a post-hot isostatic pressing method for modified silicon nitride ceramic, where the post-hot isostatic pressing is performed on the modified silicon nitride ceramic to promote performance improvement of the silicon nitride ceramic, and parameters of the post-hot isostatic pressing include: the temperature of the heat treatment is 1650 ℃ to 1650 ℃, the time is 2 hours and the air pressure is 160MPa.
Has the beneficial effects that:
in the invention, the oxynitride glass is used as a glass encapsulating layer, so that the glass and Si can be reinforced 3 N 4 Interface bonding force of ceramics; alN is used as a nitrogen source, so that the solid solubility of N atoms in the glass can be improved, nitrogen-oxygen bonds are increased, and the strength of the glass is improved; by adopting the powder embedding mode, a compact glass encapsulating layer can be formed on the surface of the silicon nitride ceramic, and Si can be fully eliminated through hot isostatic pressing post-treatment 3 N 4 Residual pores in the ceramic further increase Si 3 N 4 Strength of the ceramic, and obtaining Si with excellent comprehensive performance 3 N 4 And (3) ceramic.
Drawings
FIG. 1 is a topographical view of a polished surface of the oxynitride glass prepared in example 1;
FIG. 2 is a phase analysis diagram of an oxynitride glass obtained in example 4;
FIG. 3 is a graph of the morphology of the silicon nitride ceramic encapsulation interface prepared in example 5.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention.
In the present disclosure, the composition of the oxynitride glass or glass powder for encapsulating silicon nitride ceramic is Y 2 O 3 -Al 2 O 3 -SiO 2 AlN, in amorphous form.
In an alternative embodiment, Y 2 O 3 36.6-43.7 wt% of Al 2 O 3 The content of (B) is 24.8-29.6 wt%, siO 2 The content of the AlN is 17.7-22.1 wt%, and the content of the AlN is 4.6-20.9 wt%.
In the invention, the oxynitride glass or glass powder for encapsulating the silicon nitride ceramic has the characteristics of high melting point and adjustable physical and chemical properties, is found in the intergranular phase of the silicon nitride ceramic, has better wettability with the silicon nitride ceramic, and is an ideal glass system for encapsulating the silicon nitride ceramic.
The following is an exemplary description of the preparation of the silicon nitride ceramic encapsulating oxy-nitrogen glass (or powder).
Will Y 2 O 3 、Al 2 O 3 、SiO 2 And proportioning the mixture and AlN according to a proportion, and carrying out ball milling and mixing uniformly to obtain slurry. And drying and sieving the slurry to obtain mixed powder. As an example, with Y 2 O 3 、Al 2 O 3 、SiO 2 And AlN as raw material, alcohol as solvent, preparing the raw materials into slurry with certain solid content, and ZrO 2 Ball milling, drying and sieving to obtain mixed powder.
And putting the mixed powder into a crucible, and placing the crucible in a sintering furnace for glass melting. The glass melting temperature is 1500-1700 ℃, the time is 2-3 hours, and the atmosphere is Ar or N 2 。
And crushing the glass blocks obtained by melting into glass powder. Wherein the grain diameter of the glass powder is 40-325 meshes.
In the present invention, Y is 2 O 3 、Al 2 O 3 、SiO 2 And AlN is used as a raw material, the raw material is melted and crushed into glass powder, and the silicon nitride ceramic is embedded to realize glass encapsulation, so that the glass encapsulating layer is obtained. Preferably, the glass encapsulation layer has a thickness of 9.7 to 28.6 μm. The method can realize the rapid batch glass encapsulation of the silicon nitride ceramics, has better sealing performance and is suitable for the hot isostatic pressing treatment of the silicon nitride ceramics.
As an example of encapsulation, si is used 3 N 4 Embedding the ceramic into oxygen-nitrogen glass powder, placing in a sintering furnace, carrying out glass encapsulation in nitrogen atmosphere, heating to 1400-1700 ℃ (preferably 1400-1600 ℃), keeping the temperature for 10-30min, and cooling with the furnace. Thus obtaining the silicon nitride ceramic encapsulated by the oxynitride glass.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Preparation example of silicon nitride ceramics
Si in the invention 3 N 4 The preparation method of the ceramic comprises the following steps:
s1, weighing 94g of Si 3 N 4 ，3g Al 2 O 3 And 3g of Y 2 O 3 A total of 100g;
s2, preparing the mixed powder in the step S1 into slurry with certain solid content, and carrying out planetary ball milling for 4 hours at the rotating speed of 300rpm;
s3, drying and grinding the slurry obtained in the step S2, sieving the slurry by a 100-mesh sieve, performing dry pressing preforming under the pressure of 20MPa, and performing cold isostatic pressing forming under the pressure of 200 MPa;
s4, putting the ceramic biscuit obtained in the step S3 into a BN (boron nitride) mold, putting the ceramic biscuit into an air pressure sintering furnace, and filling N 2 Sintering at 1760 ℃ and 2MPa for 60 minutes as protective gas to obtain the silicon nitride ceramic for glass encapsulation, wherein the relative density is 94.7 percent, the bending strength is 803.5 +/-15.2 MPa, and the fracture toughness is 6.8 +/-0.11 MPa.m 1/2 Si with Vickers hardness of 14.3 + -0.04 GPa 3 N 4 A ceramic.
Example 1
An oxygen-nitrogen glass for encapsulating silicon nitride ceramics and a preparation method thereof comprise the following steps:
s1, weighing 36.6g of Y 2 O 3 ，24.8g Al 2 O 3 ，17.7g SiO 2 And 20.9g AlN for a total of 100g;
s2, preparing the mixed powder in the step S1 into slurry with certain solid content, performing ball milling for 6 hours at the speed of 200rpm, and drying and sieving to obtain mixed powder;
s3, mixing the mixed powder obtained in the step S2 with N 2 Melting at 1700 ℃ for 3 hours in atmosphere to obtain the product with the bending strength of 165.3MPa and the fracture toughness of 1.5 MPa.m 1/2 Oxygen having a Vickers hardness of 9.9GPaNitrogen glass, namely crushing the glass and sieving the glass by a 60-mesh sieve to obtain glass powder;
and S4, completely burying the silicon nitride ceramic in the glass powder, and treating the silicon nitride ceramic in a sintering furnace at 1600 ℃ for 10min to form a glass encapsulating layer with the thickness of 28.6 microns on the surface of the silicon nitride ceramic.
As a result of observing the polished surface of the oxynitride glass obtained in the present embodiment, as shown in fig. 1, it can be seen that the oxynitride glass has very high denseness, and a small amount of dendrites are present in the matrix, which is advantageous for enhancing the strength of the glass matrix.
Example 2
An oxygen-nitrogen glass for encapsulating silicon nitride ceramics and a preparation method thereof comprise the following steps:
s1, weighing 43.7g of Y 2 O 3 ，29.6g Al 2 O 3 ，22.10g SiO 2 And 4.6g AlN for a total of 100g;
s2, preparing the mixed powder in the step S1 into slurry with a certain solid content, carrying out ball milling for 3 hours at the speed of 300rpm, drying and sieving to obtain mixed powder;
s3, mixing the mixed powder obtained in the step S2 with N 2 Melting at 1700 ℃ for 2.5 hours in atmosphere to obtain the alloy with the bending strength of 130.5MPa and the fracture toughness of 1.3 MPa.m 1/2 Oxygen-nitrogen glass with Vickers hardness of 10.1GPa, and glass powder is obtained after the glass is crushed and sieved by a 60-mesh sieve;
and S4, completely burying the silicon nitride ceramic in the glass powder, and treating the silicon nitride ceramic in a sintering furnace at 1400 ℃ for 30min to form a glass encapsulating layer with the thickness of 9.7 mu m on the surface of the silicon nitride ceramic.
Example 3
An oxygen-nitrogen glass for encapsulating silicon nitride ceramics and a preparation method thereof comprise the following steps:
s1, weighing 39.8g of Y 2 O 3 ，26.30g Al 2 O 3 ，19.50g SiO 2 And 14.4g AlN for a total of 100g;
s2, preparing the mixed powder in the step S1 into slurry with a certain solid content, carrying out ball milling for 4 hours at the speed of 350rpm, drying and sieving to obtain mixed powder;
s3, mixing the mixed powder obtained in the step S2 with N 2 Under the condition of atmosphere,the bending strength is 170.9MPa and the fracture toughness is 1.7 MPa.m after being melted at 1650 ℃ for 2.5 hours 1/2 Oxygen-nitrogen glass with the Vickers hardness of 11.3GPa is crushed and sieved by a 60-mesh sieve to obtain glass powder;
s4, completely burying the silicon nitride ceramic in the glass powder, and placing the glass powder in a sintering furnace to be treated for 20min at 1550 ℃, so as to form a glass encapsulating layer with the thickness of 24.3 mu m on the surface of the silicon nitride ceramic.
Example 4
An oxygen-nitrogen glass for encapsulating silicon nitride ceramics and a preparation method thereof comprise the following steps:
s1, weighing 40.2g of Y 2 O 3 ，25.50g Al 2 O 3 ，21.60g SiO 2 And 12.7g AlN for a total of 100g;
s2, preparing the mixed powder in the step S1 into slurry with certain solid content, performing ball milling for 6 hours at the speed of 300rpm, and drying and sieving to obtain mixed powder;
s3, mixing the mixed powder obtained in the step S2 with N 2 Melting at 1500 deg.C for 2.5 hr under atmosphere to obtain a product with bending strength of 123.3MPa and fracture toughness of 1.2 MPa-m 1/2 Crushing oxygen-nitrogen glass with the Vickers hardness of 9.7GPa, and sieving the glass with a 60-mesh sieve to obtain glass powder;
and S4, completely burying the silicon nitride ceramic in the glass powder, and treating the silicon nitride ceramic in a sintering furnace at 1500 ℃ for 15min to form a glass encapsulating layer with the thickness of 18.3 mu m on the surface of the silicon nitride ceramic.
The phase of the oxynitride glass obtained in this example 4 was analyzed, and the result is shown in fig. 2, where the overall spectrum shows an amorphous steamed bread peak, indicating that the oxynitride glass exists mainly in an amorphous form.
Example 5
An oxygen-nitrogen glass for encapsulating silicon nitride ceramics and a preparation method thereof comprise the following steps:
s1, weighing 37.2g of Y 2 O 3 ，28.80g Al 2 O 3 ，20.70g SiO 2 And 13.3g AlN for a total of 100g;
s2, preparing the mixed powder in the step S1 into slurry with certain solid content, performing ball milling for 4 hours at the speed of 400rpm, and drying and sieving to obtain mixed powder;
s3, mixing the mixed powder obtained in the step S2 with N 2 Under the atmosphere, the alloy can be melted for 2 hours at 1600 ℃ to obtain the alloy with the bending strength of 161.4MPa and the fracture toughness of 1.6 MPa.m 1/2 Oxygen-nitrogen glass with Vickers hardness of 10.6GPa, and glass powder is obtained after the glass is crushed and sieved by a 60-mesh sieve;
s4, completely burying the silicon nitride ceramic in the glass powder, and treating the silicon nitride ceramic in a sintering furnace at 1450 ℃ for 10min to form a glass encapsulating layer with the thickness of 15.5 mu m on the surface of the silicon nitride ceramic.
As a result of observing the oxynitride glass-encapsulated silicon nitride ceramic obtained in example 5, as shown in FIG. 3, it can be seen that some pores are present in the silicon nitride ceramic after the gas pressure sintering, and measures are required to eliminate the pores. By adopting the technical route of the embodiment, a 15.5-micron-thickness glass encapsulating layer can be formed on the surface of the silicon nitride ceramic, and the diffusion of high-pressure gas to the interior of the ceramic in the hot isostatic pressing process is prevented.
Comparative example 1
The composition of the oxynitride glass powder in comparative example 1 was: 40.2g Y 2 O 3 ，25.50g Al 2 O 3 ，25.60g SiO 2 And 7.7g AlN totaled 100g. The experimental parameters of the preparation were identical to those of example 4. Due to SiO 2 High content, low melting point of glass, boiling and volatilizing when melting at 1600 deg.C, and SiO 2 High content, low glass strength, bending strength of 67.3MPa, and fracture toughness of 0.9 MPa-m 1/2 The Vickers hardness was 7.6GPa. When the glass powder is used for encapsulating silicon nitride ceramics, the formed glass encapsulating layer is thin and is about 3.1 mu m.
Comparative example 2
The composition of the oxynitride glass powder in comparative example 2 was: 36.6g of Y 2 O 3 ，24.8g Al 2 O 3 ，12.7g SiO 2 And 25.9g AlN for a total of 100g. The experimental parameters of the preparation were identical to those of example 1. Because the AlN content is high and the melting point of the glass is high, the glass does not present a glass state when being melted at 1600 ℃, and the glass powder cannot be prepared and the silicon nitride ceramic cannot be encapsulated.
Example 6
Silicon nitride ceramics, glass-encapsulated layer silicon nitride ceramics prepared in examples 1 to 5 and comparative examples 1 to 2 were respectively subjected to hot isostatic pressing, and their mechanical properties were measured and compared. Wherein the parameters of the hot isostatic pressing treatment comprise: the temperature of the heat treatment is 1650 ℃, the time is 2 hours, and the air pressure is 160MPa.
Table 1 shows the performance parameters of the silicon nitride ceramics:
| flexural Strength (MPa) | Fracture toughness (MPa. M) 1/2 ) | Vickers hardness (GPa) | |
| Raw sample | 803.5±15.2 | 6.8±0.11 | 14.3±0.04 |
| Original sample + HIP | 881.5±19.2 | 6.7±0.15 | 14.3±0.06 |
| EXAMPLE 1 hip | 951.5±23.3 | 7.7±0.11 | 14.6±0.03 |
| EXAMPLE 2 hip + | 1021.5±38.9 | 8.2±0.14 | 14.7±0.05 |
| EXAMPLE 3 hip | 1071.6±22.3 | 8.6±0.12 | 14.6±0.03 |
| EXAMPLE 4 hip | 1101.9±24.3 | 8.8±0.21 | 14.8±0.01 |
| EXAMPLE 5 hip | 1199.2±33.6 | 9.7±0.11 | 14.9±0.02 |
| Comparative example 1 hip | 921.8±28.5 | 7.3±0.19 | 14.2±0.03 |
| Comparative example 2 hip | 867.7±19.8 | 7.4±0.22 | 14.3±0.02 |
* HIP stands for hot isostatic pressing.
As can be seen from the above 8 cases, the present invention employs Y 2 O 3 -Al 2 O 3 -SiO 2 AlN oxynitride glass as an encapsulating layer, which can reinforce the glass and Si 3 N 4 Interface bonding force of ceramics; alN is used as a nitrogen source, so that the solid solubility of N atoms in the glass can be improved, nitrogen-oxygen bonds are increased, and the strength of the glass is improved; by adopting the powder embedding mode, a compact glass encapsulating layer can be formed on the surface of the silicon nitride ceramic, and Si can be fully eliminated through hot isostatic pressing post-treatment 3 N 4 Residual pores in the ceramic further increase Si 3 N 4 Strength of the ceramic, and obtaining Si with excellent comprehensive performance 3 N 4 A ceramic.
Finally, it is necessary to mention that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adjustments made by those skilled in the art based on the above descriptions of the present invention are included in the scope of the present invention.
Claims (10)
1. An oxynitride glass for encapsulating silicon nitride ceramic, wherein the oxynitride glass has a composition comprising Y 2 O 3 -Al 2 O 3 -SiO 2 -AlN; wherein Y is 2 O 3 The content of (B) is 36.6-43.7 wt%, al 2 O 3 The content of (B) is 24.8-29.6 wt%, siO 2 The content of the AlN is 17.7-22.1 wt%, and the content of the AlN is 4.6-20.9 wt%.
2. The silicon nitride ceramic encapsulating oxy-nitride glass according to claim 1, wherein the oxynitride glass has a flexural strength of 123.3 to 170.9MPa; the Vickers hardness of the oxygen-nitrogen glass is 9.7-11.3 GPa; the oxynitride glass has a fracture toughness of 1.2 to 1.7MPa m 1/2 。
3. The oxygen-nitrogen glass powder for encapsulating the silicon nitride ceramic is characterized by comprising Y 2 O 3 -Al 2 O 3 -SiO 2 -AlN; wherein Y is 2 O 3 36.6-43.7 wt% of Al 2 O 3 Is 24.8E29.6wt％，SiO 2 The content of the AlN is 17.7 to 22.1 weight percent, and the content of the AlN is 4.6 to 20.9 weight percent; preferably, the oxynitride glass powder has a particle size of 40 to 325 mesh.
4. A method for producing an oxynitride glass for encapsulating silicon nitride ceramic according to claim 1, comprising:
will Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Mixing the powder with AlN powder to obtain mixed powder;
and putting the mixed powder into a crucible, and placing the crucible into a sintering furnace for glass melting to obtain the oxynitride glass.
5. A method for preparing the silicon nitride ceramic-encapsulated oxynitrided glass powder according to claim 3, comprising:
will Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Mixing the powder with AlN powder to obtain mixed powder;
putting the mixed powder into a crucible, and placing the crucible into a sintering furnace for glass melting to obtain oxygen-nitrogen glass;
and crushing the oxynitride glass to obtain oxynitride glass powder.
6. The method of manufacturing according to claim 4 or 5, wherein the method of mixing comprises: with Y 2 O 3 、Al 2 O 3 、SiO 2 And AlN as raw materials, and taking a solvent as a solvent to prepare slurry; then ZrO 2 The ball is used as a grinding medium, and the mixed powder is obtained by ball milling, drying and sieving.
7. The preparation method of claim 6, wherein the rotation speed of the ball mill is 200-400 rpm, and the ball milling time is 3-6 hours; the solvent is deionized water or/and an organic solvent; the organic solvent is at least one selected from alcohol, terpineol and dimethyl sulfoxide.
8. The method according to claim 4 or 5, wherein the glass is melted at 1500 to 1700 ℃ for 2 to 3 hours in Ar or N atmosphere 2 。
9. A silicon nitride ceramic encapsulation method is characterized in that the silicon nitride ceramic is completely buried in the silicon nitride ceramic encapsulation oxygen-nitrogen glass powder body of claim 3 and placed in a sintering furnace for glass encapsulation, and a glass encapsulation layer is formed on the surface of the silicon nitride ceramic; preferably, the temperature of the glass envelope is 1400-1600 ℃, the time is 10-30 minutes, and the atmosphere is N 2 。
10. A modified silicon nitride ceramic, comprising: silicon nitride ceramics and a glass encapsulating layer formed on the surface of the silicon nitride ceramics; the composition of the glass encapsulation layer comprises Y 2 O 3 -Al 2 O 3 -SiO 2 -AlN; wherein Y is 2 O 3 36.6-43.7 wt% of Al 2 O 3 The content of (B) is 24.8-29.6 wt%, siO 2 The content of the AlN is 17.7 to 22.1 weight percent, and the content of the AlN is 4.6 to 20.9 weight percent; preferably, the thickness of the glass encapsulation layer is 9.7 to 28.6 μm.
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