CN115724681B - Preparation method and application of porous silicon carbide ceramic with regular pore structure - Google Patents
Preparation method and application of porous silicon carbide ceramic with regular pore structure Download PDFInfo
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Abstract
The invention relates to the field of porous materials, in particular to a preparation method and application of porous silicon carbide ceramic with a regular pore structure. Constructing geometric figures with regular pore structures such as polyhedrons periodically stacked in space or geometric bodies based on triple-period minimum curved surfaces by utilizing three-dimensional modeling software; photo-curing 3D printing to form a resin template with a regular structure; preparing silicon carbide ceramic slurry, ball milling and ageing; injecting ceramic slurry into a mould with a resin template placed, degassing, compacting and solidifying to obtain a porous silicon carbide ceramic blank; densification is realized on the green body through the processes of pyrolysis, reaction sintering and the like, and the porous silicon carbide ceramic with a regular pore structure is obtained. The porous silicon carbide ceramic has a macroscopically regular pore structure, high volume fraction, good geometric dimension precision and higher density, and solves the problem of mechanical property degradation caused by residual triangular holes of the porous foam prepared by a traditional template slurry hanging method due to template removal.
Description
Technical Field
The invention relates to the field of porous materials, in particular to a preparation method and application of porous silicon carbide ceramic with a regular pore structure.
Background
The porous ceramic material with the three-dimensional communicated open-pore network structure has the advantages of excellent physical and chemical properties, light weight, adjustable porosity, high permeability and the like, and is gradually and widely paid attention to the application fields of chemical process reinforcement, composite materials and the like. However, the porous ceramic material with the traditional three-dimensional connected open-cell network structure is mostly obtained by a process of repeatedly dipping an open-cell foam template material in slurry, inherits the random structure of the foam template, macroscopically presents a random structure with low repeatability and long-range no procedure, and has morphological defects, so that the porous ceramic material has uncertainty of mechanical and physical properties.
The 3D printing (or increment manufacturing and additive manufacturing) technology refers to a technology for manufacturing solid parts by adopting a material layer-by-layer accumulation method through three-dimensional modeling based on the principle of discrete material layer-by-layer accumulation forming, and is also a systematic and comprehensive technology combining multiple fields of computers, materials, machinery and the like. According to the different base materials used in the 3D printing technology, the printing technology can be divided into metal materials, high polymer materials, ceramic materials and composite materials; according to different molding principles, the method can be further divided into selective laser sintering and three-dimensional photo-curing printing technologies, direct ink-jet printing, silk extrusion type 3D printing technologies and the like. Compared with the traditional manufacturing technology, the 3D printing technology has the advantages of saving raw materials, realizing near net forming, being capable of manufacturing materials with complex shapes and difficult processing, being flexible and controllable in design and production space and the like.
The Chinese patent application publication No. CN 107032798A discloses a preparation method of a porous ceramic material based on photo-curing rapid prototyping, which comprises the steps of preparing raw materials such as photo-curing resin prepolymer, reactive diluent, surface modifier, ceramic powder, pore-forming agent, photoinitiator and the like into porous ceramic slurry, then placing the ceramic slurry into photo-curing 3D printing equipment for prototyping to obtain a blank, and finally degreasing and sintering the blank to obtain the porous ceramic material.
The invention patent of China with the application publication number of CN 108101574A discloses a method for preparing a ceramic porous piece by 3D printing and the ceramic porous piece, wherein the method is to put ceramic paste prepared from raw materials such as ceramic powder, a binder, a defoaming agent, a solvent and the like into a bin of a desktop 3D printer for printing so as to prepare a ceramic porous piece blank; then placing the blank in a carbon dioxide atmosphere for gradual drying polymerization and curing; and finally, placing the cured ceramic porous piece blank in an air furnace for integrated degreasing-sintering treatment to obtain the required ceramic porous piece.
The technology for preparing the ceramic material directly by using 3D printing mainly comprises the steps of preparing ceramic powder and an auxiliary agent into slurry, printing out a ceramic blank body by using a 3D printing technology, degreasing, sintering and the like, and forming the ceramic material. Although the method exerts some of the advantages of the 3D printing technology, the material prepared by 3D printing of the ceramic slurry is generally rough, low in density, incomplete in sintering inside the material, easy to remain preparation defects, and poor in product dimensional accuracy.
The Chinese patent application publication No. CN 201811321262.2 discloses a preparation method of porous silicon carbide ceramic based on P curved surface, which combines 3D printing and slip casting processes by adding Al into the slurry 2 O 3 And Y 2 O 3 And sintering auxiliary agents, and preparing the porous ceramic material with the regular structure and the porosity of 80-95% in a liquid phase sintering mode. However, the liquid phase sintering mode is easy to cause the blank to generate larger shrinkage deformation in the sintering process, which is not beneficial to controlling the accurate size and detail characteristics of the material.
Disclosure of Invention
The invention aims to provide a preparation method and application of porous silicon carbide ceramic with a regular pore structure, and the preparation method and application of porous silicon carbide ceramic have the advantages of high template precision, extremely small shrinkage rate and high densification degree of a reaction sintering technology product by combining a photocuring 3D printing technology, and solve the problems of low structural designability, large sintering shrinkage, poor dimensional precision, low density, low mechanical property, low preparation efficiency and the like of materials in the prior art.
The technical scheme of the invention is as follows:
the preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the following steps:
step 1, constructing a geometrical figure with a regular pore structure of a periodically stacked polyhedron or a geometric body based on a triple period minimum curved surface in space by utilizing three-dimensional modeling software; forming a resin template with a regular structure by using photo-curing 3D printing, carefully cleaning resin remained on the surface, and then performing secondary curing to obtain a resin template for occupying space;
step 2, preparing matrix ceramic slurry, ball-milling, dispersing, aging, pouring into a mold in which the resin template obtained in the step 1 is placed, and carrying out degassing, compaction and solidification to obtain a porous silicon carbide ceramic green body with a regular pore structure;
step 3, fully drying the porous silicon carbide ceramic green body with the regular pore structure obtained in the step 2, and then performing heat treatment under the protection of inert gas or under the vacuum condition, wherein the heating rate is 1-10 ℃/min, the temperature is 600-1500 ℃, and the heat preservation time is 10-300 min so as to degrease and remove the resin template obtained in the step 1, thereby obtaining the porous silicon carbide ceramic preform with the regular pore structure;
step 4, based on the prefabricated body obtained in the step 3, densification is realized in a high-temperature reaction sintering mode under a protective atmosphere or vacuum condition, the temperature is 900-2500 ℃, and the heat preservation time is 10 min-6 h, so that the porous silicon carbide ceramic material with a regular pore structure is obtained; wherein the protective atmosphere is one or two selected from argon and nitrogen;
step 5, based on the porous silicon carbide ceramic material with the regular pore structure obtained in the step 4, performing one or more than two of the following post-treatment operations: deionized water cleaning, absolute ethyl alcohol cleaning, acetone cleaning, acid solution cleaning, alkali solution cleaning, roasting in air and roasting in pure oxygen atmosphere.
In the preparation method of the porous silicon carbide ceramic with the regular pore structure, in the step 2, the matrix ceramic slurry comprises silicon carbide ceramic powder, a reaction phase, a pore-forming agent, a cross-linking agent, a curing agent, a dispersing agent and a solvent; wherein:
50-1000 parts of silicon carbide ceramic powder, 50-1000 parts of reaction phase, 0-500 parts of pore-forming agent, 50-500 parts of cross-linking agent and 50-1000 parts of solvent; the addition amount of the curing agent is 0 to 0.2 times of the mass of the crosslinking agent, and the addition amount of the dispersing agent is 0.01 to 0.1 percent of the mass of the total slurry.
According to the preparation method of the porous silicon carbide ceramic with the regular pore structure, the solid phase volume fraction of the matrix ceramic slurry is controlled to be more than 50%, the ball milling and dispersing time of the matrix ceramic slurry is 30-300 min, the aging time is 4-48 h, and the viscosity is controlled to be within 1 Pa.s; the curing process of the matrix ceramic slurry is selected from one of the following methods: (a) Adopting a normal pressure heating curing method, heating at 50-300 ℃ and heating rate of 0.1-10 ℃/min, and preserving heat until the cross-linking agent is cured to obtain a ceramic green body; (b) The ceramic green body is obtained after the curing of the cross-linking agent by adopting a pressurizing and heating curing method, wherein the heating temperature is 50-300 ℃, the heating rate is 0.1-10 ℃/min, the pressurizing pressure is 50-150 bar, the pressurizing gas is protective gas which does not react with the used slurry, and the heat is preserved.
The preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the steps of taking a carbon source as a reaction phase, taking phenolic resin as a crosslinking agent, taking p-toluenesulfonic acid as a curing agent, taking ethanol as a solvent, taking silicon powder as a pore-forming agent, and taking one or more than two of ammonium polycarboxylate, ammonium polyacrylate, stearic acid amide and carboxymethyl cellulose as a dispersing agent.
The preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the steps of forming a three-dimensional continuous support framework (a) with a regular periodic structure and three-dimensional communication channel holes (b) complementary with the space topological structure of the support framework (a), wherein:
the supporting framework (a) is made of single-phase silicon carbide ceramic material or composite ceramic material composed of silicon carbide and silicon;
the supporting framework (a) is a compact structure or a porous structure, and the porous structure supporting framework (a) contains pores with nanoscale and/or microscale apertures;
the pore size of the pores contained in the supporting framework (a) ranges from 1nm to 100 mu m, and the porosity p of the supporting framework (a) body is less than or equal to 0<p percent and less than or equal to 70 percent.
The preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the following steps of enabling basic units of the regular pore structure to comprise, but not be limited to, polyhedrons or minimum curved surface geometries based on triple periods.
The regular pore structure basic unit of the polyhedron comprises one or more than two of hexahedron, octahedron, decatetrahedron and rhombic dodecahedron.
The preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the following steps of, but not limited to: gyroid, diamond, iWP, neovius, or a combination of two or more thereof.
The preparation method of the porous silicon carbide ceramic with the regular pore structure has the basic unit size of 1-10 mm.
The porous silicon carbide ceramic with the regular pore structure is applied to any one of the following fields: separating material, filtering material, catalytic carrier material, micro reactor, micro heat exchange material, composite material reinforcing body, sound absorbing/noise reducing material, wave absorbing material, fluid distributing material, rectifying stuffing, reaction fractionating material, reaction rectifying material and internal fixed valve of the separating/rectifying tower.
The design idea of the invention is as follows:
according to the method, a three-dimensional modeling software is utilized to construct geometric figures with regular pore structures, such as polyhedrons periodically stacked in space or geometric bodies based on triple-period minimum curved surfaces; photo-curing 3D printing to form a resin template with a regular structure; preparing silicon carbide ceramic slurry, ball milling and ageing; injecting ceramic slurry into a mould with a resin template placed, degassing, compacting and solidifying to obtain a porous silicon carbide ceramic blank; densification is realized on the green body through the processes of pyrolysis, reaction sintering and the like, and the porous silicon carbide ceramic with a regular pore structure is obtained.
The invention provides a targeted preparation process for constructing and regulating the pore structure of the porous silicon carbide ceramic material with a regular pore structure, the preparation method has the advantages of high utilization efficiency, low cost, excellent precision and easiness in realization, and the preparation method is used for preparing the porous resin template with the regular pore structure by combining the photo-curing 3D printing technology with the reactive sintering process to prepare the porous silicon carbide ceramic material with the regular pore structure and high dimensional precision. Meanwhile, the porous silicon carbide ceramic material with the regular pore structure is macroscopically constructed by a three-dimensional continuous supporting framework with a regular and periodic structure and three-dimensional continuous channel holes with a complementary topological structure in space, so that the regular pore structures such as periodically stacked polyhedrons in space or geometries based on triple periodic minimum curved surfaces are realized, and meanwhile, the supporting framework has high volume fraction and has two types of pores including macroscopic three-dimensional communication holes with adjustable size and three-dimensional continuous micro-scale and/or nano-scale pores in the supporting framework, which is also one of the main innovation points of the invention.
The invention has the following advantages and beneficial effects:
1. the preparation method of the porous silicon carbide ceramic with the regular pore structure combines the advantages of high template precision prepared by a photo-curing 3D printing technology, extremely small product shrinkage rate and high densification degree of a reaction sintering technology, overcomes the defects of large product shrinkage, difficult control of precision, easy change or even damage of a topological structure and the like in a liquid phase sintering method, realizes the high-efficiency preparation of the three-dimensional communicated open-pore porous silicon carbide ceramic material with the regular pore structure, high dimensional precision and high volume fraction, and lays a foundation for the application of the porous silicon carbide ceramic material.
2. The porous silicon carbide ceramic material with the regular pore structure has regular macroscopic support frameworks and pore structures such as a polyhedral structure periodically stacked in space or a geometric body structure based on a triple-period minimum curved surface.
3. In the porous silicon carbide ceramic material with the regular pore structure, the supporting framework occupies higher volume fraction, and has good geometric dimension precision and higher density.
4. The macroscopic three-dimensional communicated channel holes (b) and the supporting framework (a) of the porous silicon carbide ceramic material with the regular pore structure are adjustable in pore size of nanoscale and/or microscale pore diameter.
5. The porous silicon carbide ceramic material with the regular pore structure solves the problem of mechanical property degradation caused by triangular pores remained by template removal in the traditional template slurry coating method for preparing porous foam silicon carbide ceramic; compared with the porous foam silicon carbide ceramic with a general random structure, the regular pore structure and the solid structure enable the stress at the material nodes to be more uniform, the whole is more stable, and the mechanical property is better.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description of the embodiments or the drawings used in the description of the prior art will make a brief description; it will be apparent to those of ordinary skill in the art that the drawings in the following description are of some embodiments of the invention and that other drawings may be derived from them without undue effort.
FIG. 1 is a flow chart of a preparation process of the porous silicon carbide ceramic material with a regular pore structure.
Fig. 2 (a) -2 (b) show the macroscopic morphology of the porous template material with regular pore structure for occupation in the present invention.
Fig. 3 (a) -3 (b) show the macroscopic morphology of the porous silicon carbide ceramic material with regular pore structure according to the present invention.
Fig. 4 (a) -4 (b) are partial enlarged morphologies of the porous silicon carbide ceramic material with a regular pore structure according to the present invention.
FIG. 5 shows fracture morphology of a porous silicon carbide ceramic material with a regular pore structure and a porous supporting framework.
FIG. 6 shows fracture morphology of a porous silicon carbide ceramic material with a dense support framework and a regular pore structure according to the invention.
Detailed Description
In a specific implementation process, the preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the following steps:
(1) The construction procedure of the regular geometric structure: firstly, constructing geometric figures with regular pore structures such as polyhedrons periodically stacked in space or geometric bodies based on triple periodic minimum curved surfaces by utilizing three-dimensional modeling software; and secondly, forming a resin template with a regular structure by using photo-curing 3D printing, carefully cleaning resin remained on the surface, and then performing secondary curing to obtain the space-occupying resin template with proper strength and toughness.
(2) Preparing a matrix ceramic slurry: in the process, a reaction sintering silicon carbide slurry system is adopted, and the components of the reaction sintering silicon carbide slurry system comprise silicon carbide ceramic powder, a reaction phase such as a carbon source or a silicon source, a cross-linking agent, a curing agent, a pore-forming agent, a dispersing agent and a solvent; the matrix ceramic slurry is prepared by a particle multistage grading method and is used for improving the solid phase content and enhancing the mechanical property of silicon carbide ceramic, wherein the solid phase volume fraction is controlled to be more than 50%; and uniformly mixing all the powder and the additive, performing ball milling and dispersing for 30-300 min, and aging for 4-48 h, wherein the viscosity of the obtained slurry is controlled within 1 Pa.s.
(3) Preparing a porous silicon carbide ceramic material preform: first, the resin template for space occupation obtained in the step (1) is placed in a mold. And (2) pouring the prepared slurry obtained in the step (2) into the die, and carrying out degassing, compaction and curing to obtain a porous silicon carbide ceramic green body with a regular pore structure, wherein the slurry curing process is selected from one of the following methods: (a) Adopting a normal pressure heating curing method, heating at 50-300 ℃ and heating rate of 0.1-10 ℃/min, and preserving heat until the cross-linking agent is cured to obtain a ceramic green body; (b) The ceramic green body is obtained after the curing of the cross-linking agent by adopting a pressurizing and heating curing method, wherein the heating temperature is 50-300 ℃, the heating rate is 0.1-10 ℃/min, the pressurizing pressure is 50-150 bar, the pressurizing gas is protective gas which does not react with the used slurry, and the heat is preserved. And finally, drying the obtained porous silicon carbide ceramic green body with the regular pore structure, performing heat treatment under the protection of inert gas or under the vacuum condition, wherein the heating rate is 1-10 ℃/min, the temperature is 600-1500 ℃, and the heat preservation time is 10-300 min, so as to degrease and remove the resin template for occupying space, thereby obtaining the porous silicon carbide ceramic preform with the regular pore structure.
(4) And (3) a reaction sintering forming process: densification is realized based on the prefabricated body obtained in the step (3) through high-temperature sintering molding, wherein the sintering molding adopts a reaction sintering process, and the densification is realized through high-temperature reaction sintering under a protective atmosphere or a reaction gas atmosphere or a vacuum condition; sintering at 900-2500 deg.c for 10 min-6 hr to obtain porous silicon carbide ceramic material with regular pore structure; the protective atmosphere is one or two selected from high-purity argon protection and high-purity nitrogen protection.
(5) Post-treatment procedure: and (3) carrying out one or more than two of the following operations on the material obtained in the step (4): deionized water cleaning, absolute ethyl alcohol cleaning, acetone cleaning, acid solution cleaning, alkali solution cleaning, roasting in air and roasting in pure oxygen atmosphere, thereby preparing the porous silicon carbide ceramic piece with a regular pore structure.
The invention provides a porous silicon carbide ceramic material with a regular pore structure, which consists of a three-dimensional continuous support framework (a) with a regular periodic structure and three-dimensional communicating pore channels (b) complementary with the space topological structure. Wherein the supporting framework (a) is made of single-phase silicon carbide ceramic material or composite ceramic material composed of silicon carbide and silicon. The self-porosity p of the supporting framework (a) body is 0<p-70%, and the supporting framework (a) body is of a compact structure or a porous structure. The porous structure supporting framework (a) body contains pores with nanoscale and/or microscale pore diameters, and the pore diameter size of the pores ranges from 1nm to 100 mu m. The material of the supporting framework (a) body can be homogeneous or heterogeneous, the physical structure of the supporting framework (a) body can be isotropic or anisotropic, and the basic unit size of the pore structure of the supporting framework (a) is 1-10 mm. The regular pore structure basic units of the support framework (a) include, but are not limited to, polyhedrons such as hexahedrons, octahedrons, tetrahedrons, rhombohedral dodecahedron, etc., and geometries based on triple-period minimum curved surfaces such as Gyroid, diamond, iWP, neovius.
As shown in fig. 1, the preparation process of the porous silicon carbide ceramic material with the regular pore structure comprises the following steps:
the method comprises the steps of adopting three-dimensional modeling software to construct geometric figures, preparing porous resin with a regular pore structure by using a photocuring 3D printing technology as a template material (the skeleton configuration, the unit cell size and the volume fraction reach preset values), preparing matrix silicon carbide ceramic slurry, performing ball milling dispersion and aging, pouring the matrix silicon carbide ceramic slurry into a mould provided with a resin template, adopting three-dimensional communicated meshes filled with a space-occupying template material to construct a green body of a porous silicon carbide ceramic material supporting skeleton with the regular pore structure, drying, degreasing and removing the space-occupying porous material template to obtain a porous silicon carbide ceramic material molding preform with the regular pore structure, performing high-temperature reaction sintering molding to realize densification, and obtaining the porous silicon carbide ceramic material with the regular pore structure, and performing post-treatment (selection). According to the specific process for preparing the porous silicon carbide ceramic material with the regular pore structure, the following examples are listed:
example 1
In this embodiment, the preparation process of the porous silicon carbide ceramic material with a decahedron regular pore structure is as follows:
(1) Preparation of a porous template material for tetrahedron occupation: drawing basic units with a tetradecahedron structure, a unit cell size of 3mm and a volume fraction of 50% by using 3D drawing software, obtaining a topological structure complementary with the tetradecahedron in space by using Boolean operation, and respectively carrying out array in X, Y, Z directions to obtain a geometric figure before printing. And (3) performing stepping type 3D printing manufacture by using a photocuring 3D printer and photosensitive resin with the resolution of 0.025mm on a Z axis, and cleaning the printed space occupying resin template by isopropanol and performing secondary curing for later use.
(2) Preparing a green body slurry of a porous silicon carbide material supporting framework (a): silicon carbide powder (average particle size 7 μm), carbon powder (average particle size 5 μm, reaction phase), silicon powder (average particle size 3.5 μm, pore-forming agent), phenolic resin (cross-linking agent), p-toluenesulfonic acid (curing agent) and ethanol according to the proportion of 50-1000 g: 50-1000 g: 0-500 g: 50-500 g: (0-0.2) times of phenolic resin mass: 50-1000 mL (500 g:100g:150g:300g:30g:200mL in this example), fully ball-milling and mixing for 60min, aging for 8h, adding ammonium polyacrylate (dispersing agent) to be 0.01% of the total mass of the slurry, fully stirring and removing bubbles, and then preparing the porous silicon carbide material support skeleton (a) green slurry with high solid powder content.
(3) Preparing a porous silicon carbide material green body: i.e. the construction of the green body of the support skeleton (a). Placing the space occupying template in the step (2) in a mould with similar size, then completely filling the green body slurry in the step (2) into macroscopic three-dimensional communicated meshes of the space occupying resin template material in the step (1), drying and semi-curing for 30 minutes to 10 days at 80 to 150 ℃ after degassing and compaction (drying and semi-curing for 4 hours at 100 ℃ in the embodiment), and finally completely curing at 150 to 300 ℃ (200 ℃ in the embodiment), thus completing the construction of the green body of the supporting framework (a) and obtaining the porous silicon carbide ceramic material green body with a decahedron regular pore structure.
(4) Removing the space-occupying resin template material: the green body material is subjected to the removal operation of the occupying resin template material under the protection of high-purity argon (the argon volume fraction is more than or equal to 99.999%) or other inert gases, the heating rate is 1-10 ℃/min, the treatment temperature is 600-1500 ℃, the heat preservation time is 10-300 min (in the embodiment, the heating rate is 5 ℃/min, the treatment temperature is 700 ℃, the heat preservation time is 150min and the nitrogen protection is carried out), and the porous silicon carbide ceramic material molding preform with the tetrahedron regular pore structure is prepared.
(5) And (3) a reaction sintering forming process: sintering the formed preform and a proper amount of pre-arranged external silicon source (the mass of the preform is 60%) at high temperature under the protection of high-purity argon or under vacuum condition, wherein the temperature is 1450-2500 ℃, and the heat preservation time is 10 min-6 h (the temperature is 1600 ℃ in the embodiment, the heat preservation time is 1 h), so as to prepare the porous silicon carbide ceramic material with the regular pore structure of the tetratetrahedra.
(6) Post-treatment (optional): subjecting the sample obtained in step (5) to one or more of the following operations: deionized water cleaning, absolute ethyl alcohol cleaning, acetone cleaning, acid solution cleaning, alkali solution cleaning, roasting in air and roasting in pure oxygen atmosphere, and obtaining the porous silicon carbide ceramic material with the regular tetrahedral pore structure.
The porous material is macroscopically constructed by a three-dimensional continuous regular tetrahedral support skeleton network, the unit cell size is 3mm, and the macroscopic porosity is 50%. Wherein the chemical constitution of the supporting framework mainly comprises silicon carbide, contains pores with the diameters of nanometer level to micrometer level, and has the average pore diameter of 3.5 mu m. The average compressive strength of the porous silicon carbide material is 52.7MPa, the average bending strength is 16.5MPa, and the total porosity (the sum of pores containing three-dimensional communication holes and the pores from nano-scale to micro-scale in the supporting framework) is 55%.
Example 2
In this embodiment, the preparation process of the dense support skeleton porous silicon carbide ceramic material with a tetrahedron regular pore structure is as follows:
the difference from example 1 is that the molding process described in step (5) is: the shaped precursor was placed in a vacuum sintering furnace and an excess of silicon particles having an average particle size of 5mm (mass of 100% of the mass of the preform) were uniformly placed on the shaped preform sample. The temperature is 1450-2500 ℃, and the heat preservation time is 10 min-6 h (the temperature is 1650 ℃ in the embodiment, and the heat preservation time is 2 h). The porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous regular tetrahedral support skeleton network and three-dimensional communicated regular channel holes, and the unit cell size is 3mm. Wherein the supporting framework is of a compact structure, and the chemical composition mainly comprises 82.7wt% of silicon carbide and 17.3wt% of silicon; the average compressive strength of the porous silicon carbide material is 72.3MPa, the average bending strength is 21.7MPa, and the total porosity is 50%.
Example 3
In this embodiment, the preparation process of the porous silicon carbide ceramic material with the regular pore compact support framework with the structure complementary to the fourteen surface bodies is as follows:
the difference from example 2 is that the preparation process of the porous template material for space occupation in step (1) is as follows: basic units with a tetrahedron structure, a unit cell size of 5mm, and a volume fraction of 30% were drawn using 3D drawing software. The porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous and regular support skeleton network which is in space complementary structure with the fourteen surface bodies and three-dimensional communicated regular channel holes in the fourteen surface body structure, and the unit cell size is 5mm. Wherein the supporting framework is of a compact structure, and the chemical composition mainly comprises 83.2wt% of silicon carbide and 16.8wt% of silicon; the average compressive strength of the porous silicon carbide material is 92.4MPa, the average bending strength is 28.2MPa, and the total porosity is 30%.
Example 4
In this embodiment, the preparation process of the dense support skeleton porous silicon carbide ceramic material with the Gyroid triple-period minimum curved surface regular pore structure is as follows:
unlike example 2, step (1) draws a geometric figure having a Gyroid structure using 3D drawing software, and the curved surface equation thereof is:
cos(x)·sin(y)+cos(y)·sin(z)+cos(z)·sin(x)＝0
the curved surface divides the unit cell into two parts which are complementary and have the same topological structure, the volume fractions of the two parts are 50%, and one part is taken as a space occupying template structure. The porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous support skeleton network with a Gyroid triple period minimum curved surface characteristic and three-dimensional communicated channel holes, and the unit cell size is 3mm. The chemical composition of the three-dimensional continuous supporting framework mainly comprises silicon carbide and silicon, and the three-dimensional continuous supporting framework is of a compact structure. The average compressive strength of the porous silicon carbide material is 86.6MPa, the average bending strength is 22.0MPa, and the total porosity is 50%.
Example 5
In this embodiment, the preparation process of the porous support skeleton silicon carbide ceramic material with iWP triple-period minimum curved surface regular pore structure is as follows:
the difference from example 2 is that step (1) is: the geometry with iWP structure is drawn by 3D drawing software, and the curved surface equation is as follows:
(cos(x)·cos(y))+(cos(y)·cos(z))+(cos(z)·cos(x))-(cos(x)·cos(y)·cos(z))＝-0.15507
the curved surface divides the unit cell into two complementary topological structures, and the volume fractions of the two topological structures are 50%, wherein the structure of the entity occupying eight corner points and the center of the unit cell is denoted as N type, and the topological structure complementary to the structure is denoted as P type. Taking the N-type structure as a space occupying template structure. The porous silicon carbide ceramic material is macroscopically constructed by a P-type three-dimensional continuous support skeleton network with iWP triple-period minimum curved surface characteristics and N-type three-dimensional communicated channel holes, and has a unit cell size of 3mm and a macroporosity of 50%. The chemical composition of the three-dimensional continuous supporting framework mainly comprises silicon carbide and silicon, and the three-dimensional continuous supporting framework is of a compact structure. The average compressive strength of the porous silicon carbide material is 79.9MPa, the average bending strength is 20.2MPa, and the total porosity is 50%.
Example 6
In this embodiment, the preparation process of the porous support skeleton silicon carbide ceramic material with the Diamond triple-period minimum curved surface regular pore structure is as follows:
the difference from example 2 is that step (1) is: and drawing a geometric figure with a Diamond structure by using 3D drawing software, wherein a curved surface equation is as follows:
sin(x)·sin(y)·sin(z)+sin(x)·cos(y)·cos(z)+cos(x)·sin(y)·cos(z)+cos(x)·cos(y)·sin(z)＝0
the curved surface divides the unit cell into two parts which are complementary and have the same topological structure, the volume fractions of the two parts are 50%, and one part is taken as a space occupying template structure. The porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous support skeleton network with a Diamond triple period minimum curved surface characteristic and three-dimensional communicated passage holes, and the unit cell size is 3mm. The chemical composition of the three-dimensional continuous supporting framework mainly comprises silicon carbide and silicon, and the three-dimensional continuous supporting framework is of a compact structure. The average compressive strength of the porous silicon carbide ceramic material is 27.6MPa, the average bending strength is 26.9MPa, and the total porosity is 50%.
As shown in fig. 2 (a) -2 (b), from the macroscopic morphology of the porous template material for occupation with a regular pore structure, the shape of the porous template material manufactured by the photo-curing 3D printing method can be freely designed, and the size can be directly and flexibly controlled.
As shown in fig. 3 (a) -3 (b), from the macroscopic morphology of the porous silicon carbide ceramic material having a regular pore structure, the porous silicon carbide ceramic material is constructed of a porous ceramic material having a regular three-dimensional continuous support skeleton and regular three-dimensional connected channel holes.
As shown in fig. 4 (a) -4 (b), from the local enlarged morphology of the porous silicon carbide ceramic material with a regular pore structure, the porous silicon carbide ceramic material has high geometric accuracy, outstanding details and good shape reproducibility on the occupied porous template.
As shown in fig. 5, it can be seen from the fracture morphology of the porous silicon carbide ceramic material with the regular pore structure of the porous support skeleton, the support skeleton of the porous silicon carbide ceramic material contains a large number of micro-scale pores, and is formed by sintering a large number of particles corresponding to the constituent materials.
As shown in fig. 6, from the fracture morphology of the porous silicon carbide ceramic material with a dense support skeleton and a regular pore structure, the support skeleton of the porous silicon carbide ceramic material is a dense structure.
The results of the embodiment show that the porous silicon carbide ceramic material with the regular pore structure provided by the invention has a macroscopic structure which is formed by constructing a regular three-dimensional continuous support framework and regular three-dimensional communicated channel holes. The preparation method comprises the steps of preparing a resin material with a regular pore structure by a photocuring 3D printing method to serve as a space occupying template, and adopting a preparation process represented by 'slurry filling three-dimensional communicated pores of the space occupying template material → removing the space occupying template material → preprocessing', so as to obtain a porous silicon carbide ceramic material molding preform with the regular pore structure. The porous silicon carbide ceramic material with high dimensional accuracy is prepared through a reaction sintering molding process and a post-treatment process. The technology is simple in process and small in equipment investment; the technical scheme combining the 3D printing technology and the reaction sintering overcomes the defects of large product shrinkage, difficult control of precision, easy change and even damage of topological structure and the like in the liquid phase sintering method. The prepared porous silicon carbide ceramic material with the regular pore structure is a novel porous ceramic material, and has the innovation points that: (1) Compared with the traditional foam material, the foam material has regular macroscopic support frameworks and pore structures such as a polyhedral structure periodically stacked in space or a geometric body structure based on a triple periodic minimum curved surface, and has good structural designability; (2) Has relatively high volume fraction (i.e. relatively low porosity) and good geometric dimension precision and high compactness; (3) The supporting framework can contain pores with nanoscale and/or microscale pore diameters, and the pore size can be regulated and controlled; (4) The problem of mechanical property degradation caused by residual triangular holes of porous foam ceramics prepared by a traditional template slurry coating method due to template removal is solved, and compared with the porous foam silicon carbide ceramics with a general random structure, the porous foam silicon carbide ceramics with a regular pore structure and a solid structure enable stress at material nodes to be more uniform, the whole is more stable, and the mechanical property is better. Porous silicon carbide ceramics with regular pore structure are used in any of the following fields: separating material, filtering material, catalytic carrier material, micro reactor, micro heat exchange material, composite material reinforcing body, sound absorbing/noise reducing material, wave absorbing material, fluid distributing material, rectifying stuffing, reaction fractionating material, reaction rectifying material and internal fixed valve of the separating/rectifying tower.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, one skilled in the art may make modifications and equivalents to the specific embodiments of the present invention, and any modifications and equivalents not departing from the spirit and scope of the present invention are within the scope of the claims of the present invention.
Claims (2)
1. The preparation method of the porous silicon carbide ceramic with the regular pore structure is characterized by comprising the following steps of:
(1) Drawing basic units with a tetradecahedron structure, a unit cell size of 5mm and a volume fraction of 30% by using 3D drawing software, obtaining a topological structure complementary with the tetradecahedron in space by using Boolean operation, and respectively carrying out array in X, Y, Z directions to obtain a geometric figure before printing; step 3D printing manufacturing is carried out by using a photocuring 3D printer and photosensitive resin with the resolution of 0.025mm on a Z axis, and the printed space-occupying resin template is cleaned by isopropanol and then subjected to secondary curing for later use;
(2) Preparing a green body slurry of a porous silicon carbide material supporting framework (a): the silicon carbide powder with the average grain diameter of 7 mu m, reactive phase carbon powder with the average grain diameter of 5 mu m, pore-forming agent silicon powder with the average grain diameter of 3.5 mu m, cross-linking agent phenolic resin, curing agent p-toluenesulfonic acid and ethanol are mixed according to the proportion of 500g:100g:150g:300g:30g:200mL, fully ball-milling and mixing for 60min, aging for 8h, adding dispersant ammonium polyacrylate to be 0.01% of the total mass of the slurry, fully stirring and removing bubbles to prepare porous silicon carbide material supporting framework (a) green body slurry with high solid powder content;
(3) Preparing a porous silicon carbide material green body: namely, constructing a green body of the supporting framework (a); placing the occupation template in the step (2) in a mould with similar size, then completely filling the green body slurry in the step (2) into macroscopic three-dimensional communicated meshes of the occupation resin template material in the step (1), drying and semi-curing for 4 hours at 100 ℃ after degassing and compaction, and finally completely curing at 200 ℃ to complete the construction of the green body of the supporting framework (a) so as to obtain a porous silicon carbide ceramic material green body;
(4) Removing the space-occupying resin template material: removing the space occupying resin template material of the green body material under the protection of high-purity argon or other inert gases with the argon volume fraction of more than or equal to 99.999%, heating up at a rate of 5 ℃/min, treating at a temperature of 700 ℃ for 150min, and protecting with nitrogen to obtain a porous silicon carbide ceramic material molding preform;
(5) And (3) a reaction sintering forming process: sintering the formed preform and an externally added silicon source which is arranged in advance and has the mass of 60 percent of the mass of the preform at high temperature under the protection of high-purity argon or under the vacuum condition, and preserving the temperature at 1600 ℃ for 1h to obtain the porous silicon carbide ceramic material;
(6) Post-treatment: subjecting the sample obtained in step (5) to one or more of the following operations: deionized water cleaning, absolute ethyl alcohol cleaning, acetone cleaning, acid solution cleaning, alkali solution cleaning, roasting in air and roasting in pure oxygen atmosphere to prepare porous silicon carbide ceramic material;
the porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous and regular support skeleton network which is arranged regularly and has a space complementary structure with a fourteen-surface body and three-dimensional communicated regular channel holes of the fourteen-surface body structure, and the unit cell size is 5mm; wherein the supporting framework is of a compact structure, and the chemical composition mainly comprises 83.2wt% of silicon carbide and 16.8wt% of silicon; the average compressive strength of the porous silicon carbide material is 92.4MPa, the average bending strength is 28.2MPa, and the total porosity is 30%.
2. The preparation method of the porous silicon carbide ceramic with the regular pore structure is characterized by comprising the following steps of:
(1) Drawing a geometric figure with a Gyroid structure by using 3D drawing software, wherein a curved surface equation is as follows:
cos(x)·sin(y)+cos(y)·sin(z)+cos(z)·sin(x)＝0
the curved surface divides a unit cell into two parts which are complementary and have the same topological structure, the volume fractions of the two parts are 50%, and one part is taken as a space occupying template structure; step 3D printing manufacturing is carried out by using a photocuring 3D printer and photosensitive resin with the resolution of 0.025mm on a Z axis, and the printed space-occupying resin template is cleaned by isopropanol and then subjected to secondary curing for later use;
(2) Preparing a green body slurry of a porous silicon carbide material supporting framework (a): the silicon carbide powder with the average grain diameter of 7 mu m, reactive phase carbon powder with the average grain diameter of 5 mu m, pore-forming agent silicon powder with the average grain diameter of 3.5 mu m, cross-linking agent phenolic resin, curing agent p-toluenesulfonic acid and ethanol are mixed according to the proportion of 500g:100g:150g:300g:30g:200mL, fully ball-milling and mixing for 60min, aging for 8h, adding dispersant ammonium polyacrylate to be 0.01% of the total mass of the slurry, fully stirring and removing bubbles to prepare porous silicon carbide material supporting framework (a) green body slurry with high solid powder content;
(3) Preparing a porous silicon carbide material green body: namely, constructing a green body of the supporting framework (a); placing the occupation template in the step (2) in a mould with similar size, then completely filling the green body slurry in the step (2) into macroscopic three-dimensional communicated meshes of the occupation resin template material in the step (1), drying and semi-curing for 4 hours at 100 ℃ after degassing and compaction, and finally completely curing at 200 ℃ to complete the construction of the green body of the supporting framework (a) so as to obtain a porous silicon carbide ceramic material green body;
(4) Removing the space-occupying resin template material: removing the space occupying resin template material of the green body material under the protection of high-purity argon or other inert gases with the argon volume fraction of more than or equal to 99.999%, heating up at a rate of 5 ℃/min, treating at a temperature of 700 ℃ for 150min, and protecting with nitrogen to obtain a porous silicon carbide ceramic material molding preform;
(5) And (3) a reaction sintering forming process: sintering the formed preform and an externally added silicon source which is arranged in advance and has the mass of 60 percent of the mass of the preform at high temperature under the protection of high-purity argon or under the vacuum condition, and preserving the temperature at 1600 ℃ for 1h to obtain the porous silicon carbide ceramic material;
(6) Post-treatment: subjecting the sample obtained in step (5) to one or more of the following operations: deionized water cleaning, absolute ethyl alcohol cleaning, acetone cleaning, acid solution cleaning, alkali solution cleaning, roasting in air and roasting in pure oxygen atmosphere to prepare porous silicon carbide ceramic material;
the porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous support skeleton network with a Gyroid triple period minimum curved surface characteristic and three-dimensional communicated channel holes, and the unit cell size is 3mm; the chemical composition of the three-dimensional continuous supporting framework mainly comprises silicon carbide and silicon, and the three-dimensional continuous supporting framework is of a compact structure; the average compressive strength of the porous silicon carbide material is 86.6MPa, the average bending strength is 22.0MPa, and the total porosity is 50%.
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