CN116872573A - Heat insulation and bearing integrated material and preparation method and application thereof - Google Patents

Heat insulation and bearing integrated material and preparation method and application thereof Download PDF

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CN116872573A
CN116872573A CN202310649088.9A CN202310649088A CN116872573A CN 116872573 A CN116872573 A CN 116872573A CN 202310649088 A CN202310649088 A CN 202310649088A CN 116872573 A CN116872573 A CN 116872573A
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ceramic
metal
layer
composite material
slurry
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CN116872573B (en
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索进平
程佳昕
蔡基利
胡逸飞
王恒
徐昂
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D18/00Pressure casting; Vacuum casting
    • B22D18/02Pressure casting making use of mechanical pressure devices, e.g. cast-forging
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B64AIRCRAFT; AVIATION; COSMONAUTICS
    • B64GCOSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
    • B64G1/00Cosmonautic vehicles
    • B64G1/22Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
    • B64G1/52Protection, safety or emergency devices; Survival aids
    • B64G1/58Thermal protection, e.g. heat shields
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • C22C1/1073Infiltration or casting under mechanical pressure, e.g. squeeze casting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/304Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00Vehicles
    • B32B2605/18Aircraft

Abstract

The invention belongs to the technical field related to aircraft protection structures, and discloses a heat-insulating bearing integrated material, a preparation method and application thereof, wherein the integrated material comprises self-repairing Al arranged from top to bottom 2 O 3 A ceramic protective layer, a ceramic-metal co-continuous composite material structural layer and a metal connecting layer; the ceramic metal is co-continuously compoundedThe material structure layer comprises a gradient porous ceramic skeleton and a TiAl alloy matrix phase filled in the gradient porous ceramic skeleton. The invention contains gradient co-continuous ceramic-metal composite material, and realizes the integrated design and preparation of the heat-proof and heat-insulating structure and the bearing structure.

Description

Heat insulation and bearing integrated material and preparation method and application thereof
Technical Field
The invention belongs to the technical field related to aircraft protection structures, and particularly relates to a heat insulation bearing integrated material, a preparation method and application thereof.
Background
In the high-speed flight process of the high Mach number (Ma not less than 4) aircraft, the aircraft needs to face a severe pneumatic heating environment, the surface temperature of the aircraft can reach more than 1500 ℃, and the environment brings great challenges to a thermal protection system and a bearing structure of the aircraft: on the one hand, severe pneumatic heating causes a decrease in the elastic modulus and strength limit of the material, resulting in a decrease in the load-bearing capacity of the material; on the other hand, the material forms larger thermal gradient due to different thermal resistances, generates larger thermal stress, is overlapped with the flight aerodynamic load effect, and affects the stability of the structure; furthermore, the aircraft structure generates excessive deformation under the double effects of high-temperature thermal stress and aerodynamic force, so that the aerodynamic shape of the structure is damaged, and the safety and reliability of the aircraft are seriously affected. Therefore, the structural thermal protection problem of hypersonic aircrafts is one of the bottleneck problems restricting their development.
In conventional designs, the thermal protection material and the load-bearing structure of the spacecraft are developed in separate designs. The single thermal protection layer does not have bearing capacity, and needs to keep the integrity of the thermal protection layer, so that the weight of the aircraft is increased, and the defects of low structural efficiency, poor bonding connection maintainability, reduced mechanical property and the like are caused, so that the aircraft has great potential safety hazard. With the continuous progress of technology, an integrated design technology integrating heat protection, heat insulation and structural bearing functions has become one of key technologies for manufacturing various aerospace vehicles.
However, integrating the thermal protection function with the load bearing function must overcome the contradiction between the two functions in a single material: materials with strong bearing capacity, particularly metal materials, generally have good heat conducting capacity, which is unfavorable for heat protection of the structure, while light heat insulating materials such as ceramic materials have excellent heat insulating performance, but have poor mechanical performance and cannot bear the load. The current research on the structural heat protection integrated design mainly aims at optimizing and regulating the contradiction. For example, the united states aerospace agency has proposed in 2006 a corrugated sandwich structure integrated thermal protection system, the structure consisting of a high temperature titanium alloy upper panel, titanium alloy corrugated structural webs and an aluminum alloy lower panel, and filling the structural void with alumina fiber insulation material, the inclined web structure being capable of withstanding higher in-plane and aerodynamic loads, while the alumina fibers to some extent block and dissipate the high temperatures of the surface. But the ripple web in this structure is stronger to the heat transfer ability of structure inside, and the thermal short circuit effect is too high promptly, is unfavorable for the thermal-insulated design of structure. How to design a composite structure, the bearing capacity of the metal material and the heat insulation capacity of the ceramic material are better combined, which is the focus of the current integrated research of aircraft protection, so that the development of corresponding ceramic-metal composite technology, especially the design technology and the industrialized preparation technology of the ceramic-metal co-continuous composite structure, is needed in the art.
As disclosed in patent CN102102720B, a ceramic-metal co-continuous composite material and a preparation method thereof are disclosed, the method comprises the steps of preparing silicon carbide foam ceramic by a polymer pyrolysis method, and then injecting molten copper alloy into a foam ceramic skeleton by an extrusion casting method to obtain the ceramic-metal composite material. However, the pore structure of the foam ceramic prepared by the method is difficult to control, random, irregular or closed pore structures inevitably appear, the mechanical strength of the porous ceramic is reduced, the process repeatability is low, the controllability is poor, the space structure optimization design of the ceramic-metal composite material is greatly limited, and in addition, great pressure is required to be applied in the extrusion casting process, so that the structural integrity of the porous ceramic body is difficult to ensure.
As another example, patent CN115533080a discloses a method for preparing a gradient ceramic-metal composite armor, where a method of melt infiltration combined with hot isostatic pressing is used to fill a metal melt into a porous ceramic core plate formed by additive manufacturing, to promote further densification of the ceramic and metal, thereby preparing the composite armor. The ceramic-metal composite material prepared by the method has higher density and better performance, but has higher requirements on equipment, needs to build a high-temperature and high-pressure device, has complex process, needs to prepare an alloy ingot from metal firstly in the preparation process, and then heats the alloy ingot to a certain temperature higher than the melting point of the alloy ingot, so that the metal melt and the porous ceramic surface have better wettability, the infiltration process is slower, the production efficiency is low, the cost is higher, and the large-scale preparation of the ceramic-metal co-continuous composite material is limited.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a heat-insulating bearing integrated material, a preparation method and application thereof, wherein the heat-insulating bearing integrated material contains a gradient co-continuous ceramic-metal composite material, and realizes the integrated design and preparation of a heat-insulating structure and a bearing structure.
To achieve the above object, according to one aspect of the present invention, there is provided an insulating and load-bearing integrated material comprising self-repairing Al disposed from top to bottom 2 O 3 A ceramic protective layer, a ceramic-metal co-continuous composite material structural layer and a metal connecting layer; the ceramic-metal co-continuous composite material structure layer comprises a gradient porous ceramic skeleton and a TiAl alloy matrix phase filled in the gradient porous ceramic skeleton.
Further, the ceramic-metal co-continuous composite structural layer comprises a ceramic material and a metal material, wherein the ceramic material is Al 2 O 3 、ZrO 2 Or any of SiC; the metal material is TiAl alloy, and the atomic ratio of Ti to Al is any one of 6:4, 5:5 or 4:6.
Further, the gradient porous ceramic skeleton is of a Diamond three-period minimum curved surface structure with a porosity gradient, wherein the volume fraction of a ceramic phase in an upper panel is 50% -70%, the volume fraction of a metal phase in a lower panel is 30% -50%, and the volume fraction of the metal phase in the lower panel is 50% -70%.
Further, the self-repairingComposite Al 2 O 3 The ceramic protective layer is formed by reacting TiAl alloy in the ceramic-metal co-continuous composite material structural layer through an atmosphere treatment process.
Further, the material of the metal connecting layer is TiAl alloy with the same component as that in the ceramic-metal co-continuous composite material structural layer.
The invention also provides a preparation method of the heat insulation bearing integrated material, which comprises the following steps:
(1) Preparing a porous ceramic prefabricated framework and metal slurry;
(2) Placing the porous ceramic prefabricated framework in a hot die casting die to be preheated together, pouring the metal slurry into the die, applying pressure to the metal slurry by utilizing a pneumatic punching machine to enable the metal slurry to be filled and compacted in the porous ceramic prefabricated framework, and obtaining a solid porous ceramic metal co-continuous blank after cooling;
(3) Placing the porous ceramic-metal co-continuous blank in a tube furnace for degreasing treatment to remove organic components in the blank, and then obtaining a ceramic-metal continuous composite material layer through a sintering process; at the moment, metal connecting layers are formed on two opposite surfaces of the ceramic-metal continuous composite material layer;
(4) The obtained ceramic-metal continuous composite material layer is placed in an atmosphere tube furnace to be subjected to nitriding and oxidizing treatment so that one surface of the ceramic-metal continuous composite material layer forms a layer of self-repairing Al 2 O 3 And (5) a ceramic protective layer, so as to obtain the integrated material.
Further, in the step (1), a three-dimensional model with completely communicated pores is constructed by adopting Al 2 O 3 、ZrO 2 Or any ceramic powder in SiC is used as a molding raw material, and the three-dimensional model is molded by photo-curing 3D printing, so that the ceramic prefabricated framework with the gradient porous structure is obtained.
Further, the porous structure is a Diamond-type structure, the total porosity is preferably 50%, wherein the upper panel porosity is preferably 30% -50%, and the lower panel porosity is preferably 50% -70%; the photo-curing 3D printing parameters are as follows: the exposure power density was 7mw/cm 2 Exposure time is 10s, slice layerThe thickness was 30um.
Further, evenly mixing paraffin, beeswax and stearic acid according to a certain component proportion, heating to a molten state, preheating TiAl alloy powder, adding the preheated TiAl alloy powder into molten wax slurry, and preparing metal slurry through stirring and degassing; in the step (2), the heating temperature of the metal slurry is 120-150 ℃, and the heating temperature of the ceramic prefabricated framework and the die is 60-80 ℃; the working pressure of the pneumatic punching machine is 0.2-0.4 MPa, the pressure maintaining time is 20-40 s, and the cooling temperature is 20-30 ℃.
The invention also provides application of the heat insulation bearing integrated material in an aerospace vehicle structure.
In general, compared with the prior art, the heat insulation bearing integrated material and the preparation method and application thereof have the following advantages:
1. compared with the existing laminated structure, antinode plate structure or honeycomb structure, the light heat insulation bearing integrated material provided by the invention has the advantage that in the aspect of structural bearing, the strength and rigidity of the composite material can be effectively improved due to continuous penetration of ceramic; meanwhile, because the metal phases are continuously distributed, the stress is transferred when the composite material is stressed, so that the stress of the composite material is uniform, and the stress concentration is avoided, thereby the composite material has better structural bearing capacity and impact resistance.
2. In the aspect of heat insulation and prevention functions, the Diamond-type minimum curved surface co-continuous structure can effectively reduce the thermal stress in the composite material, improve the high-temperature performance, and the composite material of the structure also has lower equivalent heat conductivity coefficient according to the numerical simulation result; in addition, al formed on the surface of the composite material by atmosphere treatment 2 O 3 The ceramic protective layer has low heat conductivity coefficient, can be self-repaired in a high-temperature low-oxygen environment, and continuously reacts to form new Al 2 O 3 The ceramic layer further improves the heat-proof and heat-insulating performance of the material, thereby ensuring the stability of the aircraft heat protection integrated system.
3. The preparation method provided by the invention adopts photo-curing 3D printing, has high molding precision and high resolution, provides technical support for precisely preparing the curved-surface structural porous ceramic, fully exerts the advantage of strong designability of the 3D printing technology, can precisely control structural parameters such as pore shape, porosity, pore diameter and the like, is beneficial to systematic research on the structural-performance relationship of the ceramic-metal co-continuous composite material, and lays a foundation for preferentially preparing the composite material capable of simultaneously meeting structural bearing and heat insulation indexes.
4. The preparation method provided by the invention is different from the existing solution infiltration method, fully utilizes the good fluidity of paraffin and other organic substances in a molten state and the characteristics of cooling and solidification, and completes the processes of filling and forming under the condition of slightly higher than room temperature.
5. The metal slurry for preparing the composite material has better fluidity and stability, can complete the complete filling of the metal phase in the porous ceramic prefabricated framework by using smaller pneumatic pressure, and has simple technical process and better molding effect.
Drawings
FIG. 1 is a schematic view of a heat insulating and load bearing integrated material according to the present invention;
FIG. 2 is a schematic structural diagram of a Diamond type gradient porous ceramic skeleton provided by the embodiment of the invention;
FIG. 3 is a flow chart of a method of preparing the thermally insulating load-bearing integrated material of FIG. 1;
FIG. 4 is a graph of compressive stress as a function of compressive strain for a sample provided by the present invention;
fig. 5 (a), (b), (c), and (d) are stress and temperature profiles, respectively, of a ceramic skeleton filled with titanium aluminide alloy and a ceramic skeleton with pores filled with titanium aluminide alloy;
fig. 6 (a) and (b) are temperature distribution diagrams of the heat insulation and bearing integrated material and the sandwich structure provided by the invention, respectively.
The same reference numbers are used throughout the drawings to reference like elements or structures, wherein: 1-self-repairing Al 2 O 3 The ceramic protective layer, the 2-gradient porous ceramic framework, the 3-TiAl alloy matrix phase and the 4-TiAl metal connecting layer.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a heat-insulating bearing integrated material, which comprises self-repairing Al arranged from top to bottom 2 O 3 A ceramic protective layer, a ceramic-metal co-continuous composite material structural layer and a metal connecting layer; the ceramic-metal co-continuous composite material structure layer comprises a gradient porous ceramic skeleton and a TiAl alloy matrix phase filled in the gradient porous ceramic skeleton.
The ceramic-metal co-continuous composite material structure layer comprises a ceramic material and a metal material, wherein the ceramic material is Al 2 O 3 、ZrO 2 Or any of SiC; the metal material is TiAl alloy, and the atomic ratio of Ti to Al is any one of 6:4, 5:5 or 4:6.
The gradient porous ceramic skeleton is a Diamond-type three-period minimum curved surface structure with a porosity gradient, wherein the volume fraction of a ceramic phase in an upper panel is 50% -70%, the volume fraction of a metal phase is 30% -50%, the volume fraction of the ceramic phase in a lower panel is 30% -50%, and the volume fraction of the metal phase is 50% -70%.
The self-repairing Al 2 O 3 The ceramic protective layer is formed by atmosphere treatment of TiAl alloy in the ceramic-metal co-continuous composite material structural layerThe self-repairing agent is generated by the process reaction and has a self-repairing function in a high-temperature environment.
The metal connecting layer is TiAl alloy with the same component as the ceramic-metal co-continuous composite material structural layer and is used for being connected with the aircraft body part.
The invention also provides a preparation method of the heat insulation bearing integrated material, which mainly comprises the following steps:
step one, preparing a porous ceramic prefabricated framework and metal slurry.
Specifically, a three-dimensional model with completely communicated pores is designed and constructed by adopting Al 2 O 3 、ZrO 2 Or any ceramic powder in SiC is used as a molding raw material, and the three-dimensional model is molded by photo-curing 3D printing, so that the ceramic prefabricated framework with the gradient porous structure is obtained. Wherein the porous structure is of a Diamond type structure, the total porosity is preferably 50%, the upper panel porosity is preferably 30% -50%, and the lower panel porosity is preferably 50% -70%; the photo-curing 3D printing parameters are as follows: the exposure power density was 7mw/cm 2 The exposure time was 10s and the slice thickness was 30um.
Uniformly mixing paraffin, beeswax and stearic acid according to a certain component proportion, heating to a molten state, preheating TiAl alloy powder, adding the preheated TiAl alloy powder into molten wax slurry, stirring and degassing to prepare slurry with good fluidity and stability. Wherein paraffin is used as a binder, beeswax is used as a plasticizer, stearic acid is used as a surfactant, and the mass ratio of the paraffin to the stearic acid is preferably 20:4:1; heating and uniformly stirring the mixture in a stainless steel crucible, wherein the heating temperature is 120-150 ℃, and the organic components account for 10-20% of the total mass percentage of the metal slurry; the metal powder is TiAl alloy powder, the atomic ratio of Ti to Al is any one of 6:4, 5:5 or 4:6, the preheating temperature is 60-80 ℃, and the total mass percentage of the metal powder in the metal slurry is preferably 80-90%; the degassing mode is vacuum degassing, and the vacuum drying box is pumped to a set vacuum degree and maintained for 15-30 min. The viscosity of the prepared metal slurry is less than 0.1 Pa.s.
And secondly, placing the porous ceramic prefabricated framework in a hot die casting die to preheat together, pouring the metal slurry into the die, applying pressure to the metal slurry by utilizing a pneumatic punching machine to enable the metal slurry to be filled and compacted in the porous ceramic prefabricated framework, and obtaining a solid porous ceramic metal co-continuous blank after cooling.
Wherein the heating temperature of the metal slurry is 120-150 ℃, and the heating temperature of the ceramic prefabricated framework and the die is 60-80 ℃; the working pressure of the pneumatic punching machine is 0.2-0.4 MPa, the pressure maintaining time is 20-40 s, and the cooling temperature is 20-30 ℃.
Step three, placing the porous ceramic-metal co-continuous blank body in a tube furnace for degreasing treatment to remove organic components in the blank body, and then obtaining a ceramic-metal continuous composite material layer through a sintering process; at this time, metal connecting layers are formed on two opposite surfaces of the ceramic-metal continuous composite material layer.
The degreasing treatment process is formulated according to a thermogravimetric analysis result curve, the temperature is raised to 200 ℃ from room temperature, and the temperature is kept for 1 to 2 hours; heating to 400 ℃ again, and preserving heat for 2-4 hours, wherein the atmosphere is one of Ar gas or vacuum; the sintering process is as follows: the sintering atmosphere is one of Ar gas or vacuum, the heating rate is 5 ℃/min-10 ℃/min, the sintering temperature is 1300 ℃ -1400 ℃, and the heat preservation time is 2 h-3 h.
Step four, placing the obtained ceramic-metal continuous composite material layer in an atmosphere tube furnace for nitriding and oxidizing treatment so as to form a layer of self-repairing Al on one surface of the ceramic-metal continuous composite material layer 2 O 3 And (5) a ceramic protective layer, so as to obtain the integrated material.
The nitriding treatment process is preferably as follows: NH (NH) 3 Nitriding under atmosphere at 900 ℃ for 2 hours; the oxidation treatment process is preferably as follows: 5% O 2 Oxidizing with 95% Ar under mixed atmosphere at 800 ℃ for 0.5h.
The invention also provides application of the heat insulation bearing integrated material in an aerospace vehicle structure.
The invention is described in further detail below with respect to a few specific examples.
Example 1
A light heat insulation bearing integrated material with gradient function composite structure, the structure of which is shown in figure 1, the material is made of self-repairing Al 2 O 3 The ceramic protection layer, the ceramic-metal co-continuous composite material structure layer and the metal connecting layer.
In the ceramic-metal co-continuous composite material structural layer, the ceramic material is Al 2 O 3 、ZrO 2 Or any of SiC; the metal material is TiAl alloy, and the atomic ratio of Ti to Al is any one of 6:4, 5:5 or 4:6. The ceramic skeleton of the ceramic-metal co-continuous composite material structural layer is preferably a Diamond-type three-period minimum curved surface structure with a porosity gradient, wherein the volume fraction of the ceramic phase of the upper panel is preferably 50-70%, and the volume fraction of the metal phase is 30-50%; the lower panel preferably has a ceramic phase volume fraction of 30-50% and a metal phase volume fraction of 50-70%. The self-repairing Al 2 O 3 The ceramic protective layer is formed by reacting TiAl alloy in the ceramic-metal co-continuous structural layer through a preferable atmosphere treatment process, and has a self-repairing function in a high-temperature environment. The metal connecting layer is made of TiAl alloy with the same component as that in the ceramic-metal co-continuous structural layer and is used for being connected with the aircraft body part.
The structure of the porous ceramic skeleton in the ceramic-metal co-continuous composite material structural layer is shown in figure 2, and the porous ceramic skeleton has the characteristics of regularity, uniformity, smoothness and continuity, and is not easy to generate stress concentration when stressed, so that the material has higher bearing capacity; the metal phase fills the vacant part of the structure, is uniform, smooth and continuous, and the ceramic phase and the metal phase which are continuously distributed respectively provide higher strength, rigidity, failure strain and fracture toughness, so that the material has higher structural bearing capacity and better impact resistance. Meanwhile, the Diamond-type minimum curved surface co-continuous structure can effectively reduce the thermal stress in the composite material, improves the high-temperature performance, and has lower equivalent heat conductivity coefficient.
As shown in fig. 3, a preparation method of the heat insulation and bearing integrated material comprises the following preparation steps:
(1) Preparing a porous ceramic prefabricated framework: designing and constructing a three-dimensional model of a porous structure with completely communicated pores, wherein Al is adopted 2 O 3 、ZrO 2 Or any ceramic powder in SiC is used as a molding raw material, and the three-dimensional model is molded by photo-curing 3D printing, so that the ceramic prefabricated framework with the gradient porous structure is obtained.
(2) Preparation of metal slurry: uniformly mixing paraffin, beeswax and stearic acid according to a certain component proportion, heating to a molten state, preheating TiAl alloy powder, adding the preheated TiAl alloy powder into molten wax slurry, stirring and degassing to prepare slurry with good fluidity and stability.
(3) Hot pressing and injection molding: and (3) placing the ceramic prefabricated framework into a hot die casting die to be preheated together, pouring metal slurry into the die, applying pressure to the metal slurry by utilizing a pneumatic punching machine to enable the metal slurry to be filled in the ceramic prefabricated framework tightly, and cooling to obtain a solid ceramic-metal co-continuous blank. And metal connecting layers are formed on two surfaces of the ceramic-metal co-continuous green body.
(4) Degreasing and sintering: and (3) placing the ceramic-metal co-continuous blank body in a tube furnace for degreasing treatment to remove organic components in the blank body, and then obtaining the ceramic-metal co-continuous composite material through a sintering process.
(5) Surface atmosphere treatment: the prepared ceramic-metal composite material is placed in an atmosphere tube furnace for nitriding and oxidizing treatment, wherein one metal connecting layer forms a layer of Al 2 O 3 And a ceramic protective layer.
Example 2
A preparation method of a heat-insulating bearing integrated material comprises the following preparation steps:
(1) Firstly, constructing a Diamond-type porous ceramic structure model by adopting modeling software MATLAB, wherein the total porosity is preferably 50%, and the porosities of the upper panel and the lower panel are both 50%; siC is used as a raw material, and the porous ceramic skeleton is rapidly formed by photo-curing 3D printing.
(2) Respectively weighing a certain amount of paraffin, beeswax and stearic acid, wherein the mass ratio of the paraffin to the beeswax is 20:4:1, placing the paraffin, the beeswax and the stearic acid in a stainless steel crucible, heating to be molten, stirring uniformly by using a glass rod, weighing a certain amount of TiAl alloy powder with the atomic ratio of Ti to Al of 4:6, preheating, adding the TiAl alloy powder into the molten paraffin, wherein the preheating temperature is 60 ℃, the organic component accounts for 20% by mass, and the TiAl alloy powder accounts for 80% by mass; fully stirring until a suspension slurry with better fluidity and stability is formed, wherein the viscosity of the suspension slurry is less than 0.1 Pa.s; transferring the slurry into a vacuum drying oven, wherein the set temperature of the vacuum drying oven is 120 ℃, opening a vacuum pump until the vacuum degree reaches 200Pa, and taking out after maintaining the pressure for 15 min.
(3) And (3) putting the prepared porous ceramic skeleton into a mould to be heated together, wherein the heating temperature is 60 ℃, injecting the prepared metal slurry into the mould, setting the working pressure of a pneumatic punching machine to be 0.2MPa, keeping the pressure for 20s, filling the metal slurry into the ceramic prefabricated skeleton by using the pneumatic pressure to be compact, naturally cooling to 20 ℃, and demoulding after the slurry is cooled and solidified to obtain a solid ceramic-metal co-continuous blank.
(4) Placing the prepared green body into an atmosphere tube furnace, vacuumizing, introducing Ar gas as a protective atmosphere, heating from room temperature to 200 ℃ at a heating rate of 1 ℃/min, and preserving heat for 2 hours; heating to 400 ℃ again, and preserving heat for 2 hours to remove organic components in the blank; and heating to 1300 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling along with a furnace to obtain the SiC/TiAl alloy co-continuous structure composite material with the ceramic phase accounting for 50% of the volume percentage.
(5) Placing the prepared SiC/TiAl alloy co-continuous composite material into an atmosphere tube furnace, vacuumizing, and introducing NH 3 Heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and nitriding the surface of the material; after cooling, vacuumizing again, introducing 5% O 2 Mixing with 95% Ar, heating to 800 deg.C at a heating rate of 5 deg.C/min, maintaining for 0.5 hr, oxidizing the surface of the material to form a layer of Al on the surface 2 O 3 A ceramic protective layer; finally obtain the product from Al 2 O 3 The light heat insulation bearing integrated material consists of a ceramic protective layer, a ceramic-metal co-continuous composite material layer and a metal connecting layer.
Example 3
A preparation method of a heat insulation bearing integrated material with a gradient functional composite structure comprises the following preparation steps:
(1) Firstly, constructing a Diamond type porous ceramic structure model by using modeling software MATLAB, wherein the total porosity is preferably 50%, the upper panel porosity is preferably 40%, and the lower panel porosity is preferably 60%; with ZrO 2 As a raw material, a porous ceramic skeleton is rapidly formed by photo-curing 3D printing.
(2) Respectively weighing a certain amount of paraffin, beeswax and stearic acid, wherein the mass ratio of the paraffin to the beeswax is 20:4:1, placing the paraffin, the beeswax and the stearic acid in a stainless steel crucible, heating to be molten, stirring uniformly by using a glass rod, weighing a certain amount of TiAl alloy powder with the atomic ratio of Ti to Al of 5:5, preheating, adding the TiAl alloy powder into the molten paraffin, wherein the preheating temperature is 70 ℃, the mass percentage of organic components is 15%, and the mass percentage of the TiAl alloy powder is 85%; fully stirring until a suspension slurry with better fluidity and stability is formed, wherein the viscosity of the suspension slurry is less than 0.1 Pa.s; transferring the slurry into a vacuum drying oven, setting the temperature of the vacuum drying oven to 140 ℃, opening a vacuum pump until the vacuum degree reaches 200Pa, maintaining the pressure for 20min, and taking out.
(3) And (3) putting the prepared porous ceramic skeleton into a mould to be heated together, wherein the heating temperature is 70 ℃, injecting the prepared metal slurry into the mould, setting the working pressure of a pneumatic punching machine to be 0.3MPa, keeping the pressure for 30s, filling the metal slurry into the ceramic prefabricated skeleton by using the pneumatic pressure to be compact, naturally cooling to 25 ℃, and demoulding after the slurry is cooled and solidified to obtain a solid ceramic-metal co-continuous blank.
(4) Placing the prepared green body into an atmosphere tube furnace, vacuumizing, introducing Ar gas as a protective atmosphere, heating from room temperature to 200 ℃ at a heating rate of 1 ℃/min, and preserving heat for 1h; heating to 400 ℃ again, and preserving heat for 3 hours to remove organic components in the blank; heating to 1350 ℃ again at a heating rate of 8 ℃/min, preserving heat for 2.5h, and cooling along with the furnace to obtain the ZrO with gradient structure 2 A TiAl alloy co-continuous structure composite material.
(5) The ZrO to be produced 2 Placing the TiAl alloy co-continuous composite material into an atmosphere tube furnace, vacuumizing, and introducing NH 3 Heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and nitriding the surface of the material; after cooling, vacuumizing again, introducing 5% O 2 Mixing with 95% Ar, heating to 800 deg.C at a heating rate of 5 deg.C/min, maintaining for 0.5 hr, oxidizing the surface of the material to form a layer of Al on the surface 2 O 3 A ceramic protective layer; finally obtain the product from Al 2 O 3 The light heat insulation bearing integrated material consists of a ceramic protective layer, a gradient ceramic metal co-continuous composite material layer and a metal connecting layer.
Example 4
A preparation method of a heat insulation bearing integrated material with a gradient functional composite structure comprises the following preparation steps:
(1) Firstly, constructing a Diamond type porous ceramic structure model by using modeling software MATLAB, wherein the total porosity is preferably 50%, the upper panel porosity is preferably 30%, and the lower panel porosity is preferably 70%; with Al 2 O 3 As a raw material, a porous ceramic skeleton is rapidly formed by photo-curing 3D printing.
(2) Respectively weighing a certain amount of paraffin, beeswax and stearic acid, wherein the mass ratio of the paraffin to the beeswax is 20:4:1, placing the paraffin, the beeswax and the stearic acid in a stainless steel crucible, heating to be molten, stirring uniformly by using a glass rod, weighing a certain amount of TiAl alloy powder with the atomic ratio of Ti to Al of 6:4, preheating, adding the TiAl alloy powder into the molten paraffin, wherein the preheating temperature is 80 ℃, the organic component accounts for 10% of the mass ratio, and the TiAl alloy powder accounts for 90% of the mass ratio; fully stirring until a suspension slurry with better fluidity and stability is formed, wherein the viscosity of the suspension slurry is less than 0.1 Pa.s; transferring the slurry into a vacuum drying oven, setting the temperature of the vacuum drying oven to be 150 ℃, opening a vacuum pump until the vacuum degree reaches 200Pa, maintaining the pressure for 30min, and taking out.
(3) And (3) putting the prepared porous ceramic skeleton into a mould to be heated together, wherein the heating temperature is 80 ℃, injecting the prepared metal slurry into the mould, setting the working pressure of a pneumatic punching machine to be 0.4MPa, keeping the pressure for 40s, filling the metal slurry into the ceramic prefabricated skeleton by using the pneumatic pressure to be compact, naturally cooling to 30 ℃, and demoulding after the slurry is cooled and solidified to obtain a solid ceramic-metal co-continuous blank.
(4) Placing the prepared green body into an atmosphere tube furnace, vacuumizing, introducing Ar gas as a protective atmosphere, heating from room temperature to 200 ℃ at a heating rate of 1 ℃/min, and preserving heat for 1h; heating to 400 ℃ again, and preserving heat for 4 hours to remove organic components in the blank; heating to 1400 ℃ at a heating rate of 10 ℃/min, preserving heat for 3 hours, and cooling along with the furnace to obtain the Al with the gradient structure 2 O 3 A TiAl alloy co-continuous structure composite material.
(5) Al to be prepared 2 O 3 Placing the TiAl alloy co-continuous composite material into an atmosphere tube furnace, vacuumizing, and introducing NH 3 Heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and nitriding the surface of the material; after cooling, vacuumizing again, introducing 5% O 2 Mixing with 95% Ar, heating to 800 deg.C at a heating rate of 5 deg.C/min, maintaining for 0.5 hr, oxidizing the surface of the material to form a layer of Al on the surface 2 O 3 A ceramic protective layer; finally obtain the product from Al 2 O 3 The light heat insulation bearing integrated material consists of a ceramic protective layer, a gradient ceramic metal co-continuous composite material layer and a metal connecting layer.
Please refer to fig. 4, which is a graph showing a change of compressive stress with compressive strain, wherein the preparation conditions of the sample are as follows: the porous ceramic skeleton in step (1) had a porosity of 70%, and the sintering temperature in step (4) was 1450℃for 2 hours, with the other conditions being the same as in example 4.
Referring to fig. 5, the continuous pores of the porous ceramic skeleton are filled with the TiAl alloy phase, so that the thermal conductivity of the material is improved, and the temperature is distributed more uniformly in the ceramic skeleton, thereby reducing the thermal stress and improving the impact resistance.
The comparison of the material obtained by the invention with the prior sandwich structure is shown in fig. 6 and table 1 in detail.
Table 1, results of comparison of properties of the materials obtained according to the invention with the prior art sandwich constructions
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. The utility model provides a thermal-insulated integration material that bears which characterized in that:
the integrated material comprises self-repairing Al arranged from top to bottom 2 O 3 A ceramic protective layer, a ceramic-metal co-continuous composite material structural layer and a metal connecting layer; the ceramic-metal co-continuous composite material structure layer comprises a gradient porous ceramic skeleton and a TiAl alloy matrix phase filled in the gradient porous ceramic skeleton.
2. The thermally insulating load-bearing integrated material of claim 1, wherein: the ceramic-metal co-continuous composite material structure layer comprises a ceramic material and a metal material, wherein the ceramic material is Al 2 O 3 、ZrO 2 Or any of SiC; the metal material is TiAl alloy, and the atomic ratio of Ti to Al is any one of 6:4, 5:5 or 4:6.
3. The thermally insulating load-bearing integrated material of claim 1, wherein: the gradient porous ceramic skeleton is a Diamond-type three-period minimum curved surface structure with a porosity gradient, wherein the volume fraction of a ceramic phase in an upper panel is 50% -70%, the volume fraction of a metal phase is 30% -50%, the volume fraction of the ceramic phase in a lower panel is 30% -50%, and the volume fraction of the metal phase is 50% -70%.
4. The insulation of claim 1Bear integration material, its characterized in that: the self-repairing Al 2 O 3 The ceramic protective layer is formed by reacting TiAl alloy in the ceramic-metal co-continuous composite material structural layer through an atmosphere treatment process.
5. The thermally insulating load-bearing integrated material of claim 1, wherein: the material of the metal connecting layer is TiAl alloy with the same component as that in the ceramic-metal co-continuous composite material structural layer.
6. A method of making an insulation load bearing integrated material as claimed in any one of claims 1 to 5, comprising the steps of:
(1) Preparing a porous ceramic prefabricated framework and metal slurry;
(2) Placing the porous ceramic prefabricated framework in a hot die casting die to be preheated together, pouring the metal slurry into the die, applying pressure to the metal slurry by utilizing a pneumatic punching machine to enable the metal slurry to be filled and compacted in the porous ceramic prefabricated framework, and obtaining a solid porous ceramic metal co-continuous blank after cooling;
(3) Placing the porous ceramic-metal co-continuous blank in a tube furnace for degreasing treatment to remove organic components in the blank, and then obtaining a ceramic-metal continuous composite material layer through a sintering process; at the moment, metal connecting layers are formed on two opposite surfaces of the ceramic-metal continuous composite material layer;
(4) The obtained ceramic-metal continuous composite material layer is placed in an atmosphere tube furnace to be subjected to nitriding and oxidizing treatment so that one surface of the ceramic-metal continuous composite material layer forms a layer of self-repairing Al 2 O 3 And (5) a ceramic protective layer, so as to obtain the integrated material.
7. The method for preparing the heat insulation and bearing integrated material according to claim 6, wherein the method comprises the following steps: in the step (1), a three-dimensional model with completely communicated pores is constructed by adopting Al 2 O 3 、ZrO 2 Or any one of the ceramic powder in SiC is used as a molding raw material, and the three-dimensional model is molded by photo-curing 3D printing, thereby obtaining the ladder-shaped ceramic powderCeramic prefabricated framework with porous structure.
8. The method for preparing the heat insulation and bearing integrated material according to claim 6, wherein the method comprises the following steps: the porous structure is a Diamond structure, the total porosity is 50%, wherein the upper panel porosity is 30% -50%, and the lower panel porosity is 50% -70%; the photo-curing 3D printing parameters are as follows: the exposure power density was 7mw/cm 2 The exposure time was 10s and the slice thickness was 30um.
9. The method for preparing the heat insulation and bearing integrated material according to claim 6, wherein the method comprises the following steps: uniformly mixing paraffin, beeswax and stearic acid according to a certain component proportion, heating to a molten state, preheating TiAl alloy powder, adding the preheated TiAl alloy powder into molten wax slurry, and stirring and degassing to prepare metal slurry; in the step (2), the heating temperature of the metal slurry is 120-150 ℃, and the heating temperature of the ceramic prefabricated framework and the die is 60-80 ℃; the working pressure of the pneumatic punching machine is 0.2-0.4 MPa, the pressure maintaining time is 20-40 s, and the cooling temperature is 20-30 ℃.
10. Use of an insulation load bearing integrated material as claimed in any one of claims 1 to 8 in an aerospace vehicle structure.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6322897B1 (en) * 1997-05-28 2001-11-27 Siemens Aktiengesellschaft Metal-ceramic gradient material, product made from a metal-ceramic gradient material and process for producing a metal-ceramic gradient material
JP2004002130A (en) * 2002-04-22 2004-01-08 National Institute Of Advanced Industrial & Technology Ceramic porous body and its forming process
CN102775673A (en) * 2012-06-26 2012-11-14 北京科技大学 Preparation and application methods of thermoplastic adhesive for powder microinjection molding
CN104099557A (en) * 2014-07-21 2014-10-15 兰州理工大学 Preparation method of zero-defect porous ceramic/Ti-Al alloy composite membrane
CN106270512A (en) * 2016-09-01 2017-01-04 中国地质大学(武汉) 3D prints support slurry, metal paste and the Method of printing of metal labyrinth
CN109516788A (en) * 2018-11-07 2019-03-26 三峡大学 A kind of copper/alumina composite material preparation method based on diamond curved surface
CN113071158A (en) * 2021-04-12 2021-07-06 中国航空制造技术研究院 Composite armor protection structure and preparation method thereof
CN114619719A (en) * 2022-03-15 2022-06-14 江苏新扬新材料股份有限公司 Heat-insulation high-pressure-resistance heat protection structure and preparation method thereof
CN115028473A (en) * 2022-05-06 2022-09-09 深圳市吉迩技术有限公司 Method for preparing porous ceramic coated with metal coating and aerosol generating device
CN115507703A (en) * 2022-10-14 2022-12-23 盐城工学院 Continuous functional gradient ceramic/metal bionic composite armor and preparation method thereof
CN115533080A (en) * 2022-09-26 2022-12-30 华中科技大学 Preparation method of porous ceramic reinforced metal composite armor with gradient porosity

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6322897B1 (en) * 1997-05-28 2001-11-27 Siemens Aktiengesellschaft Metal-ceramic gradient material, product made from a metal-ceramic gradient material and process for producing a metal-ceramic gradient material
JP2004002130A (en) * 2002-04-22 2004-01-08 National Institute Of Advanced Industrial & Technology Ceramic porous body and its forming process
CN102775673A (en) * 2012-06-26 2012-11-14 北京科技大学 Preparation and application methods of thermoplastic adhesive for powder microinjection molding
CN104099557A (en) * 2014-07-21 2014-10-15 兰州理工大学 Preparation method of zero-defect porous ceramic/Ti-Al alloy composite membrane
CN106270512A (en) * 2016-09-01 2017-01-04 中国地质大学(武汉) 3D prints support slurry, metal paste and the Method of printing of metal labyrinth
CN109516788A (en) * 2018-11-07 2019-03-26 三峡大学 A kind of copper/alumina composite material preparation method based on diamond curved surface
CN113071158A (en) * 2021-04-12 2021-07-06 中国航空制造技术研究院 Composite armor protection structure and preparation method thereof
CN114619719A (en) * 2022-03-15 2022-06-14 江苏新扬新材料股份有限公司 Heat-insulation high-pressure-resistance heat protection structure and preparation method thereof
CN115028473A (en) * 2022-05-06 2022-09-09 深圳市吉迩技术有限公司 Method for preparing porous ceramic coated with metal coating and aerosol generating device
CN115533080A (en) * 2022-09-26 2022-12-30 华中科技大学 Preparation method of porous ceramic reinforced metal composite armor with gradient porosity
CN115507703A (en) * 2022-10-14 2022-12-23 盐城工学院 Continuous functional gradient ceramic/metal bionic composite armor and preparation method thereof

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