CN115724681A - 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 using three-dimensional modeling software; carrying out photocuring 3D printing and molding on a resin template with a regular structure; preparing silicon carbide ceramic slurry, and carrying out ball milling and aging; injecting ceramic slurry into the mold with the resin template, degassing, compacting and curing to obtain a porous silicon carbide ceramic blank; and (3) the green body is densified through the processes of pyrolysis, reaction sintering and the like to obtain the porous silicon carbide ceramic with a regular pore structure. The porous silicon carbide ceramic has a macroscopically regular pore structure, high volume fraction, good geometric dimension precision and higher density, and overcomes the problem of mechanical property deterioration caused by triangular holes left by template removal in the conventional template slurry hanging method for preparing porous foam.
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 valued in 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 the open-cell foam template material in slurry, inherits the random structure of the foam template, presents a random structure with low repeatability and long-range disorder in a macroscopic view, and has morphological defects, so that the porous ceramic material has uncertainty of mechanical and physical properties.
The 3D printing (or incremental manufacturing, additive manufacturing) technology is a technology for manufacturing a solid part by a material layer-by-layer accumulation method through three-dimensional modeling based on the principle of discrete material layer-by-layer accumulation molding, and is also a systematic and comprehensive technology combining multiple fields of computers, materials, machinery, and the like. According to different base materials used by the 3D printing technology, the method can be divided into a metal material, a high polymer material, a ceramic material and a composite material 3D printing technology; according to different forming principles, the method can be divided into selective laser sintering, three-dimensional photocuring printing technology, direct ink-jet printing, wire extrusion type 3D printing technology and the like. Compared with the traditional manufacturing technology, the 3D printing technology has the advantages of raw material saving, capability of realizing near-net-shape forming, capability of manufacturing materials with complex shapes and difficult processing, flexible and controllable design and production space and the like.
The Chinese patent with application publication number CN 107032798A discloses a preparation method of a porous ceramic material based on photocuring rapid prototyping, which comprises the steps of preparing a photocuring resin prepolymer, an active diluent, a surface modifier, ceramic powder, a pore-forming agent, a photoinitiator and other raw materials into porous ceramic slurry, then placing the ceramic slurry into photocuring 3D printing equipment for prototyping to obtain a green body, and finally degreasing and sintering the green body to obtain the porous ceramic material.
The Chinese patent with application publication number CN 108101574A discloses a method for preparing a ceramic porous piece through 3D printing and the ceramic porous piece, wherein the method comprises the steps of filling ceramic paste prepared from ceramic powder, a binder, a defoaming agent, a solvent and other raw materials into a bin of a desktop 3D printer for printing to prepare a blank of the ceramic porous piece; then placing the blank in a carbon dioxide atmosphere to gradually dry and polymerize for solidification; and finally, placing the solidified ceramic porous member blank in an air furnace to carry out integrated degreasing-sintering treatment to obtain the required ceramic porous member.
The technology for preparing the ceramic material by directly utilizing 3D printing mainly comprises the steps of preparing ceramic powder and an auxiliary agent into slurry, printing a ceramic blank by the 3D printing technology, and carrying out degreasing, sintering and other processes to realize the molding of the ceramic material. Although the advantages of the 3D printing technology are partially exerted, the material prepared by 3D printing of the ceramic slurry is generally rough, has low density, is not sintered completely in the material, is easy to have preparation defects remained, and has poor dimensional accuracy.
The Chinese patent with the application publication number of CN 201811321262.2 discloses a preparation method of porous silicon carbide ceramic based on a P curved surface, the method combines 3D printing and slip casting processes, and Al is added into slurry 2 O 3 And Y 2 O 3 Sintering the mixture into a hole by liquid phase sinteringThe porosity of the porous ceramic material with a regular structure is 80-95%. However, the liquid phase sintering method is liable to cause large shrinkage deformation of the green body during sintering, which is not favorable for controlling the precise 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, which combine the advantages of high precision of a template prepared by a photocuring 3D printing technology, extremely small shrinkage rate and high densification degree of a reaction sintering technology product, and solve the problems of low designability of a material structure, large sintering shrinkage, poor dimensional precision, low density, low mechanical property, low preparation efficiency and the like in the prior art.
The technical scheme of the invention is as follows:
a preparation method of porous silicon carbide ceramic with a regular pore structure comprises the following steps:
step 1, constructing a polyhedron periodically stacked in space or a geometric figure with a regular pore structure based on a triple-period minimum curved surface by using three-dimensional modeling software; utilizing photocuring 3D printing to form a resin template with a regular structure, carefully cleaning residual resin on the surface, and then carrying out secondary curing to obtain an occupation resin template;
step 2, preparing matrix ceramic slurry, performing ball milling dispersion and aging, pouring the matrix ceramic slurry into a mold in which the resin template obtained in the step 1 is placed, and performing degassing, compacting and curing 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 carrying out heat treatment under the inert gas protection or vacuum condition, wherein the heating rate is 1-10 ℃/min, the temperature is 600-1500 ℃, the heat preservation time is 10-300 min, so as to degrease and remove the resin template obtained in the step 1, and obtain a porous silicon carbide ceramic preform with the regular pore structure;
step 4, based on the prefabricated body obtained in the step 3, realizing densification in a high-temperature reaction sintering mode under the protective atmosphere or vacuum condition, wherein the temperature is 900-2500 ℃, and the heat preservation time is 10 min-6 h, so as to obtain the porous silicon carbide ceramic material with a regular pore structure; wherein the protective atmosphere is one or two of argon and nitrogen;
and 5, performing one or more than two of the following post-treatment operations on the porous silicon carbide ceramic material with the regular pore structure 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.
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:
according to the mass portion, 50 to 1000 portions of silicon carbide ceramic powder, 50 to 1000 portions of reaction phase, 0 to 500 portions of pore-forming agent, 50 to 500 portions of cross-linking agent and 50 to 1000 portions of solvent; the addition amount of the curing agent is 0 to 0.2 time of the mass of the cross-linking 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 dispersion 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 procedure of the matrix ceramic slurry is selected from one of the following methods: (a) Adopting a normal pressure heating and curing method, heating at 50-300 ℃, heating at a rate of 0.1-10 ℃/min, and keeping the temperature until the cross-linking agent is cured to obtain a ceramic green body; (b) And (2) 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 slurry, and the ceramic green body is obtained after the cross-linking agent is cured after heat preservation.
According to the preparation method of the porous silicon carbide ceramic with the regular pore structure, a reaction phase is a carbon source, a cross-linking agent is phenolic resin, a curing agent is p-toluenesulfonic acid, a solvent is ethanol, a pore-forming agent is silicon powder, and a dispersing agent comprises one or more than two of polycarboxylic acid ammonium salt, polyacrylic acid ammonium salt, stearic acid amide and carboxymethyl cellulose.
The preparation method of the porous silicon carbide ceramic material with the regular pore structure comprises a three-dimensional continuous supporting framework (a) with a regular periodic structure and a three-dimensional communicating channel hole (b) complementary with the spatial topological structure of the supporting framework, wherein:
the supporting framework (a) is a single-phase silicon carbide ceramic material or a complex-phase ceramic material consisting 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 nanometer and/or micron-sized pore diameters;
the aperture size range of pores contained in the supporting framework (a) is 1 nm-100 mu m, and the porosity p of the body of the supporting framework (a) is 0 and p is less than or equal to 70 percent.
In the preparation method of the porous silicon carbide ceramic with the regular pore structure, the basic unit of the regular pore structure comprises but is not limited to polyhedron or geometry based on triple period minimum curved surface.
In the preparation method of the porous silicon carbide ceramic with the regular pore structure, the basic unit of the regular pore structure of the polyhedron comprises but is not limited to one or the combination of more than two of hexahedrons, octahedrons, tetradecahedrons and rhombic dodecahedrons.
The preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the following basic units of the regular pore structure based on the triple-period minimum curved surface geometry, but is not limited to the following steps: one or a combination of more than two of Gyroid, diamond, iWP and Neovius.
The preparation method of the porous silicon carbide ceramic with the regular pore structure has the advantages that the size of the basic unit of the regular pore structure is 1-10 mm.
The porous silicon carbide ceramic with the regular pore structure is applied to any one of the following fields: the device comprises a separation material, a filter material, a catalytic carrier material, a micro-reactor, a micro-heat exchange material, a composite material reinforcement, a sound absorption/noise reduction material, a wave absorption material, a fluid distribution material, a rectification filler, a material for reaction fractionation, a material for reaction rectification and a fixed valve in a fractionating/rectifying tower.
The design idea of the invention is as follows:
the invention utilizes three-dimensional modeling software to construct geometrical figures with regular pore structures, such as polyhedrons periodically stacked in space or geometrical bodies based on triple-period minimum curved surfaces; carrying out photocuring 3D printing and molding on a resin template with a regular structure; preparing silicon carbide ceramic slurry, and performing ball milling and aging; injecting ceramic slurry into the mold with the resin template, degassing, compacting and curing to obtain a porous silicon carbide ceramic blank; and (3) the green body is densified through the processes of pyrolysis, reaction sintering and the like to obtain the porous silicon carbide ceramic with a regular pore structure.
The invention provides a targeted preparation process for the construction and regulation of the pore structure of the porous silicon carbide ceramic material with the regular pore structure, prepares the porous resin template with the regular pore structure by utilizing the photocuring 3D printing technology which has high efficiency, low cost, excellent precision and easy realization, and prepares the porous silicon carbide ceramic material with the regular pore structure and high dimensional precision by combining a reaction sintering process. Meanwhile, the porous silicon carbide ceramic material with the regular pore structure is macroscopically constructed by a regular and periodic three-dimensional continuous support framework and three-dimensional continuous channel holes with complementary topological structures in space, the regular pore structure such as periodically stacked polyhedrons in space or a geometric body based on a triple periodic minimum curved surface is realized, and meanwhile, the support framework has high volume fraction and two types of pores of macroscopic three-dimensional communication holes with adjustable and controllable sizes and three-dimensional continuous micron and/or nanometer pores in the support framework, and 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 preparation precision of the photocuring 3D printing technology, extremely small shrinkage rate and high densification degree of a reaction sintering technology product, overcomes the defects of large product shrinkage, difficult control of precision, easy change and even damage of a topological structure and the like of a liquid phase sintering method, realizes high-efficiency preparation of the three-dimensional communicated porous silicon carbide ceramic material with the regular pore structure, high dimensional precision and high volume fraction, and lays a foundation for application of the ceramic material.
2. The porous silicon carbide ceramic material with the regular pore structure has regular macroscopic supporting frameworks and pore structures, such as polyhedral structures periodically stacked in space or geometric structures based on triple-period minimum curved surfaces.
3. In the porous silicon carbide ceramic material with the regular pore structure, the supporting framework occupies a higher volume fraction, and has good geometric dimension precision and higher density.
4. The macroscopic three-dimensional communicated channel hole (b) and the pore size containing the nanometer-grade and/or micron-grade pore diameter in the supporting framework (a) of the porous silicon carbide ceramic material with the regular pore structure can be regulated and controlled.
5. The porous silicon carbide ceramic material with the regular pore structure solves the problem of mechanical property deterioration caused by triangular holes left by template removal in the traditional template slurry hanging method for preparing porous foam silicon carbide ceramic; compared with the common porous foam silicon carbide ceramic with a random structure, the regular pore structure and the solid structure enable the stress at the node of the material to be more uniform, the whole body to be more stable, and the mechanical property to be better.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a flow chart of a preparation process of the porous silicon carbide ceramic material with a regular pore structure according to the present invention.
2 (a) -2 (b) are the macro-topography of the space occupying porous template material with regular pore structure according to the present invention.
Fig. 3 (a) -3 (b) are macroscopic morphologies of the porous silicon carbide ceramic material with regular pore structure according to the present invention.
Fig. 4 (a) -4 (b) are enlarged partial appearances of the porous silicon carbide ceramic material with regular pore structure according to the present invention.
FIG. 5 shows the fracture morphology of the porous silicon carbide ceramic material with a regular pore structure and a porous supporting skeleton according to the present invention.
FIG. 6 shows the fracture morphology of the porous silicon carbide ceramic material with a dense supporting skeleton and a regular pore structure according to the present invention.
Detailed Description
In the specific implementation process, the preparation method of the porous silicon carbide ceramic with the regular pore structure comprises the following steps:
(1) And (3) a regular geometric structure construction procedure: firstly, constructing geometrical figures with regular pore structures, such as polyhedrons periodically stacked in space or geometrical bodies based on triple-period minimum curved surfaces by utilizing three-dimensional modeling software; and secondly, forming a resin template with a regular structure by utilizing photocuring 3D printing, carefully cleaning residual resin on the surface, and performing secondary curing to obtain the resin template for occupying space, which has proper strength and toughness.
(2) Preparing base ceramic slurry: in the working procedure, 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, reaction phases such as a carbon source or a silicon source and the like, 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 multilevel gradation method and is used for improving the solid phase content and enhancing the mechanical property of the silicon carbide ceramic, wherein the volume fraction of the solid phase is controlled to be more than 50 percent; uniformly mixing all the powder and the additive, performing ball milling dispersion for 30-300 min, and aging for 4-48 h, wherein the viscosity of the obtained slurry is controlled within 1 Pa.s.
(3) The preparation process of the porous silicon carbide ceramic material preform comprises the following steps: firstly, the resin template for occupying space obtained in the step (1) is placed in a mould. And (3) pouring the prepared slurry obtained in the step (2) into the mold, degassing, tapping 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) A normal pressure heating and curing method is adopted, the heating temperature is 50-300 ℃, the heating rate is 0.1-10 ℃/min, and the ceramic green body is obtained after the cross-linking agent is cured after heat preservation; (b) 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 slurry, and the ceramic green body is obtained after the cross-linking agent is cured after heat preservation. And finally, drying the obtained porous silicon carbide ceramic green body with the regular pore structure, and then carrying out heat treatment under the inert gas protection or vacuum condition, wherein the heating rate is 1-10 ℃/min, the temperature is 600-1500 ℃, the heat preservation time is 10-300 min, so as to degrease and remove the resin template for occupying, and obtain the porous silicon carbide ceramic preform with the regular pore structure.
(4) Reaction sintering and forming: performing high-temperature sintering molding on the preform obtained in the step (3) to realize densification, wherein the sintering molding adopts a reaction sintering process, and the high-temperature reaction sintering is performed under a protective atmosphere, a reaction gas atmosphere or a vacuum condition to realize densification; 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 selected from one or two of high-purity argon protection and high-purity nitrogen protection.
(5) And a post-treatment process: subjecting the material obtained in step (4) to one or more of the following operations: washing with deionized water, washing with absolute ethyl alcohol, washing with acetone, washing with an acid solution, washing with an alkali solution, roasting in air, and roasting in a pure oxygen atmosphere to obtain the porous silicon carbide ceramic part with the regular pore structure.
The invention provides a porous silicon carbide ceramic material with a regular pore structure, which is composed of a three-dimensional continuous supporting framework (a) with a regular periodic structure and a three-dimensional communicating pore canal (b) complementary with the spatial topological structure of the supporting framework. Wherein, the supporting framework (a) is a single-phase silicon carbide ceramic material or a complex-phase ceramic material consisting of silicon carbide and silicon. The porosity p of the body of the supporting framework (a) is 0 but less than or equal to 70 percent, and the body of the supporting framework (a) is of a compact structure or a porous structure. The body of the porous structure supporting framework (a) contains pores with nano-scale and/or micro-scale pore diameters, and the pore diameter size range of the pores is 1 nm-100 mu m. The material of the supporting framework (a) body can be homogeneous or inhomogeneous, 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 basic unit of regular pore structure of the supporting skeleton (a) includes, but is not limited to, polyhedrons such as hexahedrons, octahedrons, tetradecahedrons, rhombic dodecahedrons, etc., and geometric bodies such as Gyroid, diamond, iWP, neoovius, etc., which are based on the minimum surface of triple cycle.
As shown in fig. 1, the preparation process of the porous silicon carbide ceramic material with a regular pore structure of the present invention is as follows:
the method comprises the steps of constructing a geometric figure by adopting three-dimensional modeling software, preparing porous resin with a regular pore structure as a template material (the framework configuration, the unit cell size and the volume fraction reach a preset design value) by adopting a photocuring 3D printing technology, preparing matrix silicon carbide ceramic slurry, performing ball milling dispersion and aging, pouring the slurry into a mold with a resin template, and constructing a porous silicon carbide ceramic material support framework green body with the regular pore structure by filling three-dimensional communicated meshes of an occupied template material → drying, degreasing and removing the occupied porous material template to obtain a porous silicon carbide ceramic material molding prefabricated body with the regular pore structure → densification by high-temperature reaction sintering molding, thereby obtaining the porous silicon carbide ceramic material with the regular pore structure → post-treatment (selected)'. According to a specific process for preparing a porous silicon carbide ceramic material with a regular pore structure, the following examples are listed:
example 1
In this embodiment, the preparation process of the porous silicon carbide ceramic material with the tetrakaidecahedron regular pore structure is as follows:
(1) Preparation of fourteen-surface porous template material for occupying space: and (3) drawing a basic unit with a tetrakaidecahedron structure, a unit cell size of 3mm and a volume fraction of 50% by using 3D drawing software, obtaining a topological structure which is complementary with the tetrakaidecahedron in space by using Boolean operation, and respectively carrying out array in the X direction, the Y direction and the Z direction to obtain a geometric figure before printing. And performing step-by-step 3D printing manufacturing by using a photocuring 3D printer and photosensitive resin at a resolution ratio of 0.025mm on a Z axis, and cleaning the printed occupied resin template by using isopropanol and performing secondary curing for later use.
(2) Preparing a porous silicon carbide material supporting framework (a) green slurry: silicon carbide powder (average particle size of 7 μm), carbon powder (average particle size of 5 μm, reaction phase), silicon powder (average particle size of 3.5 μm, pore-forming agent), phenolic resin (cross-linking agent), p-toluenesulfonic acid (curing agent) and ethanol are mixed according to the proportion of 50-1000 g: 50-1000 g:0 to 500g: 50-500 g: (0-0.2) times of the mass of the phenolic resin: 50-1000 mL (500g in this embodiment 100g.
(3) Preparing a porous silicon carbide material green body: namely the construction of the green body of the supporting skeleton (a). Placing the space-occupying template in the step (2) in a mold with similar size, completely filling the green slurry in the step (2) into macroscopic three-dimensional communicated meshes of the space-occupying resin template material in the step (1), drying at 80-150 ℃ after degassing and jolt ramming, semi-curing for 30 minutes-10 days (drying at 100 ℃ and semi-curing for 4 hours in the embodiment), and finally completely curing at 150-300 ℃ (200 ℃ in the embodiment) to complete construction of the green support framework (a) so as to obtain the porous silicon carbide ceramic material green body with the tetradecahedron regular pore structure.
(4) Removing the occupied resin template material: and (2) removing the occupied resin template material from the green blank material under the protection of high-purity argon (the volume fraction of the argon is more than or equal to 99.999%) or other inert gases, wherein the heating rate is 1-10 ℃/min, the treatment temperature is 600-1500 ℃, and 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 adopted), so that the porous silicon carbide ceramic material forming preform with the tetrakaidecahedron regular pore structure is prepared.
(5) Reaction sintering and forming: and (2) sintering the formed preform and a proper amount of pre-arranged additional silicon source (the mass of the silicon source is 60 percent of the mass of the preform) at high temperature of 1450-2500 ℃ for 10 min-6 h under the protection of high-purity argon gas or vacuum (in the embodiment, the temperature is 1600 ℃, and the heat preservation time is 1 h) to prepare the porous silicon carbide ceramic material with the tetrakaidecahedron regular pore structure.
(6) Post-treatment (optional): subjecting the sample obtained in step (5) to one or more of the following operations: washing with deionized water, washing with absolute ethyl alcohol, washing with acetone, washing with an acid solution, washing with an alkali solution, roasting in air, and roasting in a pure oxygen atmosphere to obtain the porous silicon carbide ceramic material with a tetrakaidecahedron regular pore structure.
The structure of the porous material is macroscopically constructed by a fourteen-surface-body supporting framework network which is three-dimensionally continuous and regularly arranged, the unit cell size is 3mm, and the macroscopic porosity is 50%. Wherein the chemical composition of the supporting framework mainly comprises silicon carbide, and the supporting framework comprises pores with the pore diameters from nano-scale to micron-scale, and the average pore diameter is 3.5 mu m. The average compression strength of the porous silicon carbide material is 52.7MPa, the average bending strength is 16.5MPa, and the total porosity (the sum of the pores containing three-dimensional communicating pores and the pores with the diameters from nano-scale to micro-scale in the supporting framework) is 55%.
Example 2
In this embodiment, the preparation process of the porous silicon carbide ceramic material with the dense support framework having the tetrakaidecahedron regular pore structure is as follows:
the difference from the embodiment 1 is that the molding process in the step (5) is: the shaped precursor was placed in a vacuum sintering furnace, and an excess amount (mass: 100% of the mass of the preform) of silicon particles having an average particle size of 5mm was uniformly placed on a sample of the shaped preform. The temperature is 1450-2500 ℃, and the heat preservation time is 10 min-6 h (in the embodiment, the temperature is 1650 ℃, and the heat preservation time is 2 h). The obtained porous silicon carbide ceramic material is macroscopically constructed by a fourteen-surface-body support framework network which is three-dimensionally continuous and regularly arranged and three-dimensionally communicated regular channel holes, and the unit cell size is 3mm. Wherein, the supporting framework is a compact structure, and the chemical composition mainly comprises 82.7wt% of silicon carbide and 17.3wt% of silicon; the average compression 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 a regular pore dense support framework having a complementary structure with a tetrakaidecahedron is as follows:
the difference from example 2 is that the process for preparing the space occupying porous template material in step (1) comprises the following steps: basic units with a tetrakaidecahedron structure, a unit cell size of 5mm and a volume fraction of 30% were drawn using 3D mapping software. The obtained porous silicon carbide ceramic material is macroscopically constructed by a support skeleton network which is three-dimensionally continuous and regularly arranged and has a space complementary structure with the tetradecahedron and three-dimensionally communicated regular channel holes of the tetradecahedron structure, and the unit cell size is 5mm. Wherein, the supporting framework is a compact structure, and the chemical composition mainly comprises 83.2wt% of silicon carbide and 16.8wt% of silicon; the average compression 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 porous silicon carbide ceramic material with the dense support framework and the regular pore structure with the Gyroid triple period minimum curved surface is as follows:
the difference from the embodiment 2 is that, in the step (1), the 3D drawing software is used to draw the geometric figure with the Gyroid structure, and the surface equation is as follows:
cos(x)·sin(y)+cos(y)·sin(z)+cos(z)·sin(x)＝0
the single cell is divided into two complementary parts with the same topological structure by the curved surface, the volume fractions of the parts are both 50%, and one of the parts is taken as an occupying template structure. The obtained porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous supporting framework network with Gyroid triple period minimum curved surface characteristics 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 a compact structure. The average compression 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 framework silicon carbide ceramic material with the iWP triple-period minimum curved surface regular pore structure is as follows:
the difference from the embodiment 2 is that the step (1) is: and drawing a geometric figure with an iWP structure by using 3D drawing software, wherein 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, the volume fractions of the two complementary topological structures are 50%, the structure of a solid occupying eight corner points and the center of the square unit cell is marked as an N type, and the complementary topological structure is marked as a P type. Taking an N-type structure as an occupying template structure. The obtained porous silicon carbide ceramic material is macroscopically constructed by a P-type three-dimensional continuous supporting framework network with iWP triple-period minimum curved surface characteristics and N-type three-dimensional communicated channel holes, the unit cell size is 3mm, and the macroscopic porosity is 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 a compact structure. The average compression 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 framework silicon carbide ceramic material with the Diamond triple period minimum curved surface regular pore structure is as follows:
the difference from the embodiment 2 is that the step (1) is: drawing a geometric figure with a Diamond structure by using 3D drawing software, wherein the 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 parts are both 50%, and one part is taken as an occupying template structure. The obtained porous silicon carbide ceramic material is macroscopically constructed by a three-dimensional continuous supporting skeleton network with a Diamond 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 a compact structure. The average compression 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), it can be seen from the macro-morphology of the space-occupying porous template material with regular pore structure that the shape of the porous template material manufactured by the photocuring 3D printing method can be freely designed, and the size can be directly and flexibly controlled.
As shown in fig. 3 (a) -3 (b), it can be seen from the macro topography of the porous silicon carbide ceramic material with regular pore structure, the porous silicon carbide ceramic material is constructed by a regular three-dimensional continuous support skeleton and regular three-dimensional connected channel pores.
As shown in fig. 4 (a) -4 (b), it can be seen from the local enlarged morphology of the porous silicon carbide ceramic material with regular pore structure that the porous silicon carbide ceramic material has high geometric accuracy, prominent details and good shape reproducibility to the placeholder porous template.
As shown in fig. 5, it can be seen from the fracture morphology of the porous silicon carbide ceramic material with a regular pore structure and a porous support skeleton, that the support skeleton of the porous silicon carbide ceramic material contains a large amount of micron-sized pores, and is formed by sintering a large amount of particles corresponding to the constituent materials.
As shown in fig. 6, as can be seen 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 embodiment result shows that the porous silicon carbide ceramic material with the regular pore structure is constructed by a macrostructure which is provided with a regular three-dimensional continuous supporting framework and regularly three-dimensionally communicated channel holes. Preparing a resin material with a regular pore structure as an occupying template by a photocuring 3D printing method, and obtaining a porous silicon carbide ceramic material forming prefabricated body with a regular pore structure by a preparation process represented by 'filling three-dimensional communicated pores of the occupying template material with slurry → removing the occupying template material → pretreating'. And preparing the porous silicon carbide ceramic material with high dimensional precision through a reaction sintering molding process and a post-treatment process. The technology has simple process and small equipment investment; the technical scheme combining the 3D printing technology and the reactive sintering overcomes the defects of large product shrinkage, difficult control of precision, easy change and even damage of a topological structure and the like in a 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 material has regular macroscopic supporting frameworks and pore structures such as a polyhedral structure periodically stacked in space or a geometric structure based on a triple-period minimum curved surface, and has good structural designability; (2) The composite material has relatively high volume fraction (namely relatively low porosity), good geometric dimension precision and high compactness; (3) The supporting framework can contain pores with nano-scale and/or micro-scale pore diameters, and the pore diameter size can be regulated and controlled; (4) The problem of mechanical property deterioration caused by triangular holes left in the porous foamed ceramics prepared by a traditional template slurry hanging method due to template removal is solved, and compared with the common porous foamed silicon carbide ceramics with a random structure, the regular pore structure and the solid structure enable the stress at the material node to be more uniform, the whole structure is more stable, and the mechanical property is better. The porous silicon carbide ceramic with the regular pore structure is used in any one of the following fields: the device comprises a separation material, a filter material, a catalytic carrier material, a micro-reactor, a micro-heat exchange material, a composite material reinforcement, a sound absorption/noise reduction material, a wave absorption material, a fluid distribution material, a rectification filler, a material for reaction fractionation, a material for reaction rectification and a fixed valve in a fractionating/rectifying tower.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.
Claims (10)
1. A preparation method of porous silicon carbide ceramic with a regular pore structure is characterized by comprising the following steps:
step 1, constructing a polyhedron periodically stacked in space or a geometric figure with a regular pore structure based on a triple-period minimum curved surface by using three-dimensional modeling software; utilizing photocuring 3D printing to form a resin template with a regular structure, carefully cleaning residual resin on the surface, and then carrying out secondary curing to obtain an occupation resin template;
step 2, preparing matrix ceramic slurry, performing ball milling dispersion and aging, pouring the matrix ceramic slurry into a mold in which the resin template obtained in the step 1 is placed, and performing degassing, compacting and curing 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 carrying out heat treatment under the inert gas protection or vacuum condition, wherein the heating rate is 1-10 ℃/min, the temperature is 600-1500 ℃, the heat preservation time is 10-300 min, so as to degrease and remove the resin template obtained in the step 1, and obtain a 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 the 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 of argon and nitrogen;
and 5, performing one or more than two of the following post-treatment operations on the porous silicon carbide ceramic material with the regular pore structure 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.
2. The method for preparing porous silicon carbide ceramic with regular pore structure according to claim 1, wherein in step 2, the base 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:
according to the mass parts, 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 time of the mass of the cross-linking agent, and the addition amount of the dispersing agent is 0.01 to 0.1 percent of the mass of the total slurry.
3. The method for preparing porous silicon carbide ceramic with regular pore structure according to claim 2, wherein the volume fraction of solid phase of matrix ceramic slurry is controlled to be more than 50%, the ball milling dispersion 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 procedure of the matrix ceramic slurry is selected from one of the following methods: (a) A normal pressure heating and curing method is adopted, the heating temperature is 50-300 ℃, the heating rate is 0.1-10 ℃/min, and the ceramic green body is obtained after the cross-linking agent is cured after heat preservation; (b) And (2) 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 slurry, and the ceramic green body is obtained after the cross-linking agent is cured after heat preservation.
4. The method for preparing porous silicon carbide ceramic with regular pore structure as claimed in claim 2, wherein the reaction phase is carbon source, the cross-linking agent is phenolic resin, the curing agent is p-toluenesulfonic acid, the solvent is ethanol, the pore-forming agent is silicon powder, and the dispersing agent includes but is not limited to one or more of ammonium polycarboxylates, ammonium polyacrylates, stearamides and carboxymethylcellulose.
5. The method for preparing porous silicon carbide ceramic with regular pore structure according to claim 1, wherein the porous silicon carbide ceramic material is composed of a support skeleton (a) with three-dimensional continuity and regular periodic structure and three-dimensional communication channel holes (b) complementary to spatial topology thereof, wherein:
the supporting framework (a) is a single-phase silicon carbide ceramic material or a complex-phase ceramic material consisting 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 nano-scale and/or micro-scale pore diameters;
the aperture size of pores contained in the supporting framework (a) ranges from 1nm to 100 mu m, and the porosity p of the body of the supporting framework (a) is 0 but p is less than or equal to 70 percent.
6. The method for preparing porous silicon carbide ceramic with regular pore structure according to claim 1, wherein the basic unit of regular pore structure includes but is not limited to polyhedron or geometry based on triple period minimum curve.
7. The method for preparing a porous silicon carbide ceramic having a regular pore structure according to claim 6, wherein the basic unit of the regular pore structure of the polyhedron includes, but is not limited to, one or a combination of two or more of hexahedron, octahedron, tetradecahedron, and rhombohedral.
8. The method for preparing porous silicon carbide ceramic with regular pore structure according to claim 6, wherein the regular pore structure basic unit based on the triple-period minimum curved geometry includes but is not limited to: one or a combination of more than two of Gyroid, diamond, iWP and Neovius.
9. The method for preparing a porous silicon carbide ceramic having a regular pore structure according to claim 1, wherein the regular pore structure has a basic unit size of 1 to 10mm.
10. Use of a porous silicon carbide ceramic with a regular pore structure according to any one of claims 1 to 9, wherein the porous silicon carbide ceramic with a regular pore structure is used in any one of the following fields: separating material, filtering material, catalytic carrier material, micro-reactor, micro-heat exchange material, composite material reinforcement, sound absorption/noise reduction material, wave absorption material, fluid distribution material, rectification filler, material for reaction fractionation, material for reaction rectification and fixed valve in the fractionating/rectifying tower.
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