CN112047741A - Symmetric layered gradient composite material and preparation method and application thereof - Google Patents
Symmetric layered gradient composite material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 29
- 239000000919 ceramic Substances 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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Abstract
The invention relates to a symmetrical layered gradient composite material, a preparation method and application thereof, wherein the method adopts a plasma activation sintering process to prepare the molybdenum/silicon nitride/molybdenum symmetrical layered gradient composite material, the activation effect on powder particles before sintering is realized through the coupling effect of a temperature field, an electric field and a pressure field, the preparation of the gradient composite material is further completed at a lower sintering temperature within a shorter sintering time, and the molybdenum/silicon nitride/molybdenum symmetrical layered gradient composite material with high density, less impurity content and good interface combination is finally and rapidly prepared by combining the plasma activation sintering method and the gradient of the gradient composite material.
Description
Technical Field
The invention belongs to the technical field of ceramic matrix composite preparation, and particularly relates to a symmetrical layered gradient composite material as well as a preparation method and application thereof.
Background
At present stage, Si3N4Is an important component in the current new materials of engineering structures, has the characteristics of oxidation resistance, high temperature resistance, corrosion resistance and the like, but the ceramic material is hard and brittle and is difficult to machine, so the ceramic material is difficult to manufacture into components with complex shapes, such as Si3N4Such high hardness, high temperature resistant special materials can only be joined with other materials (especially metal materials) to produce structural members that meet the engineering requirements, and many joining methods have been studied for decades, including: reactive metal methods, hot-press diffusion bonding methods, transition liquid phase bonding methods, reaction-forming bonding methods, and the like.
The sealing technology is widely applied to the high and new technical fields of aerospace, nuclear power generation and the like, and the basic industrial fields of petroleum, chemical industry and the like, the research and development of a plurality of pieces of machinery equipment depend on the sealing technology, and the safety, the reliability and the durability of the operation of the machinery equipment are directly determined; at present, the sealing technology level in China can not meet the requirements of production development far away, the leakage problem of some key occasions is not solved completely, and therefore the sealing technology needs to be further deeply researched.
The high-temperature sealing technology in various industries at present mainly comprises a sealing structure between mechanical partsOrganic/inorganic material gaskets, sealants, metal/ceramic weld seals, flexible graphite technology, and the like. The high-temperature sealing technology is very important for the high-temperature battery, the good sealing technology can ensure the energy storage quality of the battery, avoid the consumption of air and water on key active materials of the battery, prolong the service life of the battery and reduce the operation cost of the battery. Si3N4Due to good high-temperature stability, sealing insulation property, corrosion resistance and other properties, the ceramic is an ideal material for long-acting sealing insulation of the high-temperature energy storage system. However, Si completed based on conventional techniques3N4The metallization of the ceramic surface has the obvious problem that the ceramic/metal phase interface can not realize long-term sealing in the severe service environment of the energy storage technology, and the research on the novel nitride ceramic surface metallization technology is urgently needed.
The functional gradient material is a functional material with regularly gradually changed composition, structure and performance, and has the advantages of strong designability and service in extreme environment. The proposal of the concept of 'gradient compounding' and the research result thereof show that: it provides another important way for human to find materials which can normally work under extreme severe service environments such as high temperature, large temperature gradient, large mechanical load and the like. The material formed by ceramic/metal gradient composite has the advantages that the internal interface disappears and the factor that the physical properties of the combined part are not matched is avoided, so that the material can bear extremely high temperature and huge mechanical load, and can repeatedly work for a long time under the environment of frequent thermal shock and great temperature difference load.
It can be seen that, starting from the concept and idea of "gradient compounding", Si is used3N4The gradient structure design of the metal on the ceramic surface ensures that each element is continuously and gradiently distributed in space, the internal interface disappears, the thermal stress generated by the difference of the thermal expansion coefficients of the raw materials is relieved, the effective connection of the ceramic and the metal can be realized, the stability of the gradient sealing material is obviously improved, and the service life of a high-temperature energy storage system is obviously prolonged.
Disclosure of Invention
In order to solve the bottleneck problems, the invention aims to provide a symmetrical layered gradient composite material, a preparation method and an application thereof.
The invention provides a symmetrical layered gradient composite material, and raw materials for preparing the composite material comprise micron-sized ceramic Si3N4And Mo;
the composite material is of a laminated structure; adding the Si3N4As an intermediate layer on said Si3N4Si with the same mass fraction is respectively arranged at the upper end and the lower end3N4And a Mo layer.
Preferably, the method comprises the following steps:
step 1: mixing: according to the gradient layer number, the gradient components and the component thickness of each layer, Mo powder and Si are mixed3N4Mixing the powder and the sintering aid to form a mixture;
step 2: die filling: stacking the circular sheet structure prepared from the mixture in a graphite mold, performing compression molding, respectively arranging upper and lower graphite pressure heads sprayed with a boron nitride separant at the upper and lower ends of the circular sheet structure, and nesting a graphite carbon felt on the outer surface of the graphite mold;
and step 3: and (3) sintering: and (3) placing the graphite mould in the step (2) into a plasma activated sintering furnace for sintering.
Preferably, the sintering aid in the step 1 is MgO or/and Y2O3。
Preferably, the number of gradient layers in the step 1 is 5-20.
Preferably, the sintering comprises the step of keeping the temperature at 1800 ℃ for 5-20min at the heating rate of 300 ℃/min of 100-.
Preferably, the step 3 of sintering the graphite mold of the step 2 in a plasma activated sintering furnace comprises:
putting the ceramic powder and the sintering aid into a ball mill for ball milling for 2-4h, and then putting into a drying oven for drying for 12h, wherein the drying temperature is 80 ℃;
putting the ceramic powder and the sintering aid of each gradient intermediate layer into a ball mill for ball milling for 0.5-2h, and then putting into a drying oven for drying for 12h, wherein the drying temperature is 80 ℃;
and stacking the dried gradient layers, the ceramic powder and the metal powder in a graphite mould with the diameter of 15-25mm in a layered manner, and prepressing and molding the gradient layers, the ceramic powder and the metal powder under the pressure of 5-10MPa by using a tablet press.
Preferably, the invention also discloses application of the symmetrical layered gradient composite material as a high-temperature sealing insulating material of a liquid metal battery.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional hot-pressing sintering or pressureless sintering process, the technology introduces an electric field on the basis of a temperature field and a pressure field, and can play a role in activating the plasma of raw materials, so that the molybdenum/silicon nitride/molybdenum symmetrical layered gradient composite material with high density, less impurity content and good interface combination can be quickly prepared at lower sintering temperature and shorter heat preservation time.
2. The invention provides a symmetrical layered gradient composite material and a preparation method and application thereof, wherein the ceramic surface metal gradient structural design is adopted, the internal interface disappears and the thermal stress generated by large difference of the ceramic/metal thermal expansion coefficients is relieved by continuously changing the composition and the structure of the ceramic/metal, so that the material has higher mechanical strength, the integral densification and the ceramic surface metallization of the material are realized, the ceramic/metal connection is facilitated, and the sealing property and the stability of the material are improved.
3. According to the symmetrical layered gradient composite material and the preparation method and application thereof provided by the invention, aiming at the severe service environment of a high-temperature battery, silicon nitride ceramics is selected as a sealing material, the material has good high-temperature stability under the high-temperature environment, high-melting-point and low-expansion Mo metal with the thermal expansion coefficient matched with that of the ceramics is preferably selected, and the metallization of the surface of the ceramics is effectively realized.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural view of a molybdenum/silicon nitride/molybdenum symmetric layered gradient composite material according to the present invention;
in the figure: a is 3 layers of gradient transition layer materials designed in example 3; b is 5 layers of gradient transition layer material designed in example 2; c is 9 layers of gradient transition layer material designed in example 1;
FIG. 2 is an axial cross-sectional SEM of a gradient structure according to the present invention;
FIG. 3 is an EPMA diagram of Mo element in axial section of the gradient structure of the present invention;
FIG. 4 is a diagram of the Si element EPMA of the gradient structure axial section of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIGS. 1 to 4, the present invention provides a symmetric layered gradient composite, wherein the raw material of the gradient composite comprises a ceramic material Si having a particle size in the micrometer scale3N4And a high-melting metal Mo;
the composite material is of a laminated structure; adding the Si3N4As an intermediate layer on said Si3N4Si with the same mass fraction is respectively arranged at the upper end and the lower end3N4And a Mo layer;
a method of making the symmetric layered gradient composite, the method comprising the steps of:
step 1, mixing: according to the designed gradient layer number, gradient components and component thickness of each layer, Mo powder and Si are mixed3N4Fully mixing the powder and the sintering aid to obtain a mixture required by each layer;
step 2, die filling: sequentially stacking the mixture required by each layer into a graphite mold according to the structural design of the step 1, pressing and molding, then installing upper and lower graphite pressure heads sprayed with a boron nitride release agent, and nesting a graphite carbon felt on the outer surface of the mold;
and 3, sintering: placing the graphite mold filled with the sample to be sintered in a spark plasma sintering furnace, completing prepressing and vacuumizing, then axially pressurizing and introducing direct current pulse current to rapidly heat up to the sintering temperature;
step 4, stripping: opening the hearth when the temperature of the sintering system is reduced to room temperature, wherein the sample obtained in the graphite mold is Mo/Si3N4the/Mo symmetrical layered gradient composite material.
The sintering aid is MgO or/and Y2O3；
Controlling the plasma activation sintering temperature to be 1400-1800 ℃, the temperature rise speed to be 100-300 ℃/min and the sintering pressure to be 20-50MPa, and finally obtaining the symmetrical layered gradient composite material with excellent performance.
In the method, the number of the gradient layers is 5-20, and the mass fraction difference of the ceramic powder of the adjacent gradient layers is 5-20%.
In the above method, the sintering of the graphite mold in step 2 in step 3 in a plasma activated sintering furnace includes:
putting the ceramic powder and the sintering aid into a ball mill for ball milling for 2-4h, and then putting into a drying oven for drying for 12h, wherein the drying temperature is 80 ℃;
putting the ceramic powder and the sintering aid of each gradient intermediate layer into a ball mill for ball milling for 0.5-2h, and then putting into a drying oven for drying for 12h, wherein the drying temperature is 80 ℃;
and stacking the dried gradient layers, the ceramic powder and the metal powder in a graphite mould with the diameter of 15-25mm in a layered manner, and prepressing and molding the gradient layers, the ceramic powder and the metal powder under the pressure of 5-10MPa by using a tablet press.
The invention also discloses application of the symmetrical layered gradient composite material as a high-temperature sealing insulating material of the liquid metal battery.
The invention relates to a symmetrical layered gradient composite material and a preparation method thereof, belonging to the technical field of ceramic matrix composite material preparation, wherein a molybdenum/silicon nitride/molybdenum symmetrical layered gradient composite material is prepared by adopting a plasma activation sintering method, the method realizes the activation effect on powder particles before sintering through the coupling effect of a temperature field, an electric field and a pressure field, and further can complete the preparation of the gradient composite material at lower sintering temperature and shorter sintering time;
in addition, the method has the advantages of high heating rate, low sintering temperature and short heat preservation time.
In addition, the raw materials used in the invention have wide sources, the preparation process is simple and quick, and the prepared symmetric layered gradient composite material has strong high-temperature stability, corrosion resistance and insulating sealing performance, and effectively realizes long-acting insulating sealing of the high-temperature battery.
Example 1
Weighing proper amount of Si3N4Ball-milling the powder for 4 hours by using a ball mill, and then drying the powder in a vacuum drying oven at 80 ℃ for 12 hours; according to Si3N4The powder and the Mo powder are respectively weighed according to the mass percentage of 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 and 9:1, and are ball-milled by a ball mill for 2 hours and then dried in a vacuum drying oven at 80 ℃ for 12 hours.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the proportion of 1:1:4, the model of the ball mill is Retsch PM100, the rotating speed of the ball mill is set to 300 r/min, and mixed powder with the particle size of 0.5-2 μm is obtained.
And (3) paving the mixed powder into a graphite mold with the inner diameter of 25mm layer by layer according to the structural schematic diagram shown in figure 1c, wherein the using amount of the middle ceramic layer is 2g, the using amount of each gradient layer is 0.5g, the using amount of metal Mo at two ends is 4g, and performing hot-pressing sintering after prepressing the sample under the pressure of 6MPa for 30 s.
Plasma activated sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1600 ℃, the heating rate is 200 ℃/min, the heat preservation time is 5min, the axial pressure is 30MPa, and Mo/Si is obtained after sintering3N4the/Mo symmetrical layered gradient composite material.
Example 2
Weighing proper amount of Si3N4Ball-milling the powder for 4 hours by using a ball mill, and then drying the powder in a vacuum drying oven at 80 ℃ for 12 hours; according to Si3N4The powder and the Mo powder are respectively weighed according to the mass percentage of 1:9, 3:7, 5:5, 7:3 and 9:1, and are ball-milled for 2 hours by a ball mill and then are dried for 12 hours in a vacuum drying oven at 80 ℃.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the proportion of 1:1:4, the model of the ball mill is Retsch PM100, the rotating speed of the ball mill is set to 300 r/min, and mixed powder with the particle size of 0.5-2 μm is obtained.
And (3) paving the mixed powder into a graphite mold with the inner diameter of 25mm layer by layer according to the structural schematic diagram shown in figure 1b, wherein the using amount of the middle ceramic layer is 2g, the using amount of each gradient layer is 1g, the using amount of metal Mo at two ends is 4g, and hot-pressing sintering is carried out after prepressing the sample under the pressure of 6MPa for 30 s.
Plasma activated sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1600 ℃, the heating rate is 200 ℃/min, the heat preservation time is 5min, the axial pressure is 30MPa, and Mo/Si is obtained after sintering3N4the/Mo symmetrical layered gradient composite material.
Example 3
Weighing proper amount of Si3N4Ball-milling the powder for 4 hours by using a ball mill, and then drying the powder in a vacuum drying oven at 80 ℃ for 12 hours; according to Si3N4The powder and the Mo powder are respectively weighed according to the mass percentage of 3:7, 5:5 and 7:3, and are ball-milled for 2 hours by a ball mill and then put into a vacuum drying oven at 80 DEG CAnd drying for 12 h.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the proportion of 1:1:4, the model of the ball mill is Retsch PM100, the rotating speed of the ball mill is set to 300 r/min, and mixed powder with the particle size of 0.5-2 μm is obtained.
And (3) paving the mixed powder into a graphite mold with the inner diameter of 25mm layer by layer according to the structural schematic diagram shown in fig. 1a, wherein the using amount of the middle ceramic layer is 2g, the using amount of each gradient layer is 1g, the using amount of metal Mo at two ends is 4g, and performing hot-pressing sintering after prepressing a sample under the pressure of 6MPa for 30 s.
Plasma activated sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1600 ℃, the heating rate is 200 ℃/min, the heat preservation time is 5min, the axial pressure is 30MPa, and Mo/Si is obtained after sintering3N4the/Mo symmetrical layered gradient composite material.
Example 4
Weighing proper amount of Si3N4Ball-milling the powder for 4 hours by using a ball mill, and then drying the powder in a vacuum drying oven at 80 ℃ for 12 hours; according to Si3N4The powder and the Mo powder are respectively weighed according to the mass percentage of 1:9, 3:7, 5:5, 7:3 and 9:1, and are ball-milled for 2 hours by a ball mill and then are dried for 12 hours in a vacuum drying oven at 80 ℃.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the proportion of 1:1:4, the model of the ball mill is Retsch PM100, the rotating speed of the ball mill is set to 300 r/min, and mixed powder with the particle size of 0.5-2 μm is obtained.
And (3) paving the mixed powder into a graphite mold with the inner diameter of 15mm layer by layer according to the structural schematic diagram shown in figure 1b, wherein the using amount of the middle ceramic layer is 2g, the using amount of each gradient layer is 1g, the using amount of metal Mo at two ends is 4g, and performing hot-pressing sintering after prepressing the sample under the pressure of 6MPa for 30 s.
Plasma activated sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1500 ℃, the heating rate is 100 ℃/min, the heat preservation time is 20min, the axial pressure is 50MPa, and the sintered junction is formedPost-beam obtaining of Mo/Si3N4the/Mo symmetrical layered gradient composite material.
Example 5
Weighing proper amount of Si3N4Ball-milling the powder for 4 hours by using a ball mill, and then drying the powder in a vacuum drying oven at 80 ℃ for 12 hours; according to Si3N4The powder and the Mo powder are respectively weighed according to the mass percentage of 1:9, 3:7, 5:5, 7:3 and 9:1, and are ball-milled for 2 hours by a ball mill and then are dried for 12 hours in a vacuum drying oven at 80 ℃.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the proportion of 1:1:4, the model of the ball mill is Retsch PM100, the rotating speed of the ball mill is set to 300 r/min, and mixed powder with the particle size of 0.5-2 μm is obtained.
And (3) paving the mixed powder into a graphite mould with the inner diameter of 25mm layer by layer according to the structural schematic diagram of the ceramic/metal gradient composite high-temperature packaging material shown in figure 1b, wherein the using amount of a middle ceramic layer is 4g, the using amount of each gradient layer is 2g, the using amount of metal Mo at two ends is 8g, and performing hot-pressing sintering after prepressing a sample for 30s under the pressure of 6 MPa.
Plasma activated sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1600 ℃, the heating rate is 200 ℃/min, the heat preservation time is 5min, the axial pressure is 30MPa, and Mo/Si is obtained after sintering3N4the/Mo symmetrical layered gradient composite material.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art will appreciate that various modifications and changes can be made to the present invention. Any modification, equivalent replacement, improvement or the like made within the spirit and principle of the present invention is included in the scope of the claims of the present invention filed as filed.
Claims (7)
1. The symmetric layered gradient composite material is characterized in that raw materials for preparing the composite material comprise micron-sized ceramic Si3N4And Mo;
the composite material isA laminated structure; adding the Si3N4As an intermediate layer on said Si3N4Si with the same mass fraction is respectively arranged at the upper end and the lower end3N4And a Mo layer.
2. A method of making a symmetric layered gradient composite as described in claim 1, comprising the steps of:
step 1: mixing: according to the gradient layer number, the gradient components and the component thickness of each layer, Mo powder and Si are mixed3N4Mixing the powder and the sintering aid to form a mixture;
step 2: die filling: stacking the circular sheet structure prepared from the mixture in a graphite mold, performing compression molding, respectively arranging upper and lower graphite pressure heads sprayed with a boron nitride separant at the upper and lower ends of the circular sheet structure, and nesting a graphite carbon felt on the outer surface of the graphite mold;
and step 3: and (3) sintering: and (3) placing the graphite mould in the step (2) into a plasma activated sintering furnace for sintering.
3. The method for preparing a symmetric layered gradient composite material according to claim 2, wherein the sintering aid in step 1 is MgO or/and Y2O3。
4. The method for preparing a symmetric layered gradient composite according to claim 2, wherein the number of gradient layers in step 1 is 5-20.
5. The method as claimed in claim 2, wherein the sintering comprises maintaining the temperature at 1800 ℃ at a temperature rise rate of 100-.
6. The method for preparing the symmetrical layered gradient composite material according to claim 2, wherein the step 3 of sintering the graphite mold of the step 2 in a plasma activated sintering furnace comprises the following steps:
putting the ceramic powder and the sintering aid into a ball mill for ball milling for 2-4h, and then putting into a drying oven for drying for 12h, wherein the drying temperature is 80 ℃;
putting the ceramic powder and the sintering aid of each gradient intermediate layer into a ball mill for ball milling for 0.5-2h, and then putting into a drying oven for drying for 12h, wherein the drying temperature is 80 ℃;
and stacking the dried gradient layers, the ceramic powder and the metal powder in a graphite mould with the diameter of 15-25mm in a layered manner, and prepressing and molding the gradient layers, the ceramic powder and the metal powder under the pressure of 5-10MPa by using a tablet press.
7. Use of the symmetric layered gradient composite of claim 1 as a high temperature sealing insulation material for liquid metal batteries.
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