CN114180987A - Method for preparing hierarchical porous ceramic by photocuring and forming of photosensitive emulsion/foam - Google Patents
Method for preparing hierarchical porous ceramic by photocuring and forming of photosensitive emulsion/foam Download PDFInfo
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Abstract
The invention belongs to the field of porous ceramic materials, and relates to a method for preparing hierarchical porous ceramic by photocuring and forming of photosensitive emulsion/foam, which comprises the following steps: adding deionized water into ceramic powder and/or ceramic powder oxide sol nanoparticles, and preparing ceramic slurry with uniformly dispersed ceramic particles by ultrasonic and ball milling; adding a photosensitive monomer and a photoinitiator into the ceramic slurry, adding a surface modifier for surface hydrophobic modification, and fully stirring and mixing to obtain stable photosensitive particle stable emulsion/foam with photosensitive characteristics, wherein an oil phase is required to be introduced for emulsion preparation; and (3) applying the photosensitive particle stable emulsion/foam to photocuring forming of parts with complex shapes on 3D printing equipment, and drying, degreasing and sintering to obtain the hierarchical porous ceramic with a porous structure as a framework. The method provides a novel paste source for the photocuring 3D printing technology, and introduces a micron-scale or nano-scale hole structure into a 3D printing forming framework.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a method for preparing hierarchical porous ceramic by photocuring and forming of photosensitive emulsion/foam.
Background
The introduction of the porous structure into the ceramic material can endow the material with the advantages of low volume density, high specific surface area, low thermal conductivity, low dielectric constant, excellent specific strength and the like, and the porous ceramic material has wide application prospects in the fields of gas/liquid filtration, catalyst carriers, biological scaffolds, heat exchangers, supercapacitors, sensors and the like by combining the characteristics of corrosion resistance, high temperature resistance, high strength, high hardness and the like of the ceramic material.
The processes currently commonly used to prepare porous materials include: the method comprises an organic foam impregnation method, a pore-forming agent adding method, a direct foaming method, a freeze drying method and the like, but the processes can not form parts with complex shapes and can not meet the personalized customization requirements. The methods such as an organic foam impregnation method, a pore-forming agent adding method and the like can cause cracking of a ceramic framework in the cracking process of the template, so that the strength of the material is reduced; the direct foaming method and the freeze drying method also have the problems of large shrinkage rate, low strength and the like.
The photocuring forming technology slices through 3D modeling, and then endows designability of the shape of the ceramic material with slurry in a layer-by-layer accumulation mode, and has the advantages of high forming precision, excellent surface quality, raw material saving, short production period and the like. At present, the photocuring forming technology is mostly used for preparing ceramic parts with compact skeleton structures, and is limited by forming precision, and the method is difficult to prepare products with complex internal porous structures.
The raw materials of the photocuring forming technology can be divided into two types: one is resin-based light-cured ceramic, the ceramic slurry usually adopts acrylic ester as a photosensitive monomer, a corresponding photoinitiator is added into the acrylic ester, and then ceramic powder and the photosensitive monomer are directly mixed to prepare photosensitive ceramic suspension. Chinese patent CN110156375A, adding a dispersant into photosensitive resin such as 1, 6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA), stirring and mixing uniformly, then gradually adding alumina powder into the photosensitive resin, and then removing gas in the photosensitive ceramic slurry by adding a defoaming agent, vacuumizing and the like to obtain the final alumina ceramic slurry. Chinese patent CN113501719A uses hydroxyethyl methacrylate (HEMA), 2-phenoxyethyl acrylate (PHEA), 1, 6-hexanediol diacrylate (HDDA) and the like as photosensitive monomers, and adds silicon nitride powder to fully stir and completely disperse in photosensitive resin, and then adds photoinitiator, sintering aid, dispersant and the like to mix uniformly to prepare photosensitive ceramic suspension. The slurry is mainly used for printing compact ceramics, and the slurry is easy to settle in the placement process, so that the components of printed products are not uniform.
The other is water-based light-cured ceramic, and the ceramic slurry replaces an acrylate photosensitive monomer with a water-soluble photosensitive monomer. Chinese patents CN107382312A and CN109485433A select acrylamide as a photosensitive monomer and add N, N' -methylene bisacrylamide to prepare a photosensitive aqueous solution, then add nano-scale or submicron-scale ceramic powder into the photosensitive aqueous solution in batches, and then add additives such as a dispersant, a photoinitiator, a defoaming agent and the like to stir uniformly to obtain the required ceramic slurry. Such processes are also commonly used for printing dense ceramics, and while such slurries may be left for extended periods of time without settling, such processes result in greenware having low strength.
Chinese patent CN109180175A discloses a biological ceramic slurry for photocuring 3D printing and a preparation method thereof, a bone tissue engineering scaffold and application thereof. Taking beta-tricalcium phosphate powder as a main raw material, adding a small amount of lithium stone-making nano powder, and carrying out ball milling and mixing to obtain a solid phase; and mixing the photosensitive resin, the photoinitiator and the dispersant to obtain a liquid phase. Adding the solid phase into the liquid phase, mechanically stirring to obtain a biological ceramic slurry, and preparing the biological ceramic slurry into the bone tissue engineering scaffold by photocuring 3D printing, high-temperature degreasing and high-temperature sintering. Although the porosity is as high as more than 70 percent and the pore channels are communicated in three dimensions, the porosity is derived from the design of a model used for 3D printing, and the diameter of the pores is larger and is more than 500 mu m.
Chinese patent CN109095917A discloses a preparation method of bioactive porous hydroxyapatite/barium titanate composite ceramic based on 3D printing. Barium titanate powder and hydroxyapatite powder are used as main raw materials, the barium titanate powder and the hydroxyapatite powder are mixed with photosensitive resin, additives such as a dispersing agent, a binder, a photoinitiator and the like are added into the mixture, and the mixture is stirred and ball-milled to obtain photosensitive ceramic slurry. After a porous structure is designed through three-dimensional modeling software, the slurry is applied to a ceramic finished product formed by digital light processing 3D printing equipment. The finished product pores are designed by three-dimensional modeling software, and the surface is still in a compact structure.
Chinese patent CN108069704A discloses a preparation method of ceramic slurry for 3D printing, which comprises the steps of firstly preparing ceramic powder slurry using water as a solvent, then adding water-soluble photosensitive monomer, one or more emulsifiers, weak flocculant, sintering aid and photoinitiator into the slurry, ball-milling, standing, and then carrying out high-speed shearing emulsification under the condition of introducing gas to obtain emulsified ceramic powder slurry. The invention selects water-based photosensitive substances without adding oil phase, adopts the modes of emulsification, flocculation and ventilation by introducing pores, and has more added auxiliaries and complex process.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing hierarchical porous ceramic by photocuring and forming of photosensitive emulsion/foam, which can provide a novel paste source for photocuring 3D printing technology, and introduces a micron-scale or nano-scale pore structure into a 3D printing and forming skeleton structure to prepare ceramic parts with complex shapes and fine hierarchical porous structures, and has considerable application prospects in the fields of catalyst carriers, biomedical materials, filtering materials, light heat insulation materials and the like.
The invention is realized by the following technical scheme:
a method of photocuring formation of a photosensitive emulsion/foam to produce a hierarchical porous ceramic, the method comprising:
adding deionized water into ceramic powder and/or ceramic powder oxide sol nanoparticles, and preparing ceramic slurry with uniformly dispersed ceramic particles by ultrasonic and ball milling;
adding a photosensitive monomer and a photoinitiator into the ceramic slurry, then adding a certain amount of surface modifier to perform surface hydrophobic modification on ceramic particles, and fully stirring and mixing to prepare stable photosensitive particle stable emulsion/foam with photosensitive characteristics; wherein, the preparation of the photosensitive particle stable emulsion needs to introduce an oil phase,
and applying the photosensitive particle stable emulsion/foam to a photocuring forming 3D printing device to form parts with complex shapes, and drying, degreasing and sintering to obtain the hierarchical porous ceramic with a porous structure.
Further, the ceramic powder is inorganic non-metallic material powder, and comprises one or more of oxide ceramic powder and non-oxide ceramic powder; the oxide ceramic powder and the non-oxide ceramic powder specifically include: alumina, silicon oxide, zirconia, titanium dioxide, hydroxyapatite, beta-tricalcium phosphate, silicon nitride, silicon carbide, fly ash, coal gangue, kaolin, metallurgical slag, secondary aluminum ash, waste glass and tailings;
the ceramic powder oxide sol nano-particles are prepared by adopting the ceramic powder; specifically, the sol comprises one or more of aluminum sol, silica sol, zirconium sol and titanium sol.
Further, ceramic powder and/or ceramic powder oxide sol nanoparticles are mixed with deionized water, and then the mixture is subjected to ball milling and ultrasonic treatment to obtain uniformly dispersed ceramic slurry, wherein the solid phase mass fraction of the ceramic slurry is 5-85%.
Further, the preparation method of the photosensitive particle stable emulsion is one of the following three methods:
(1) adding a photosensitive oil phase monomer and a photoinitiator into the ceramic slurry, stirring until the photoinitiator is completely dissolved in the photosensitive oil phase monomer, adding a surface modifier in the mixing process to perform hydrophobic modification on ceramic particles, fully stirring and mixing to obtain a photosensitive particle stable emulsion, wherein the stirring time is 10min-24 h;
(2) adding a water-soluble photosensitive monomer, a cross-linking agent and a photoinitiator into the ceramic slurry to obtain a photosensitive water-based suspension, adding an oil phase with a single component for mixing, then adding a surface modifier for hydrophobic modification, and stirring to obtain a photosensitive particle stable emulsion, wherein the stirring time is 10min-24 h;
(3) adding a water-soluble photosensitive monomer, a cross-linking agent and a photoinitiator into the ceramic slurry to obtain a photosensitive water-based suspension, mixing a photosensitive oil-phase monomer, the photoinitiator and the photosensitive water-based suspension, then adding a surface modifier for hydrophobic modification, and stirring to obtain a photosensitive particle stable emulsion, wherein the stirring time is 10min-24 h;
the preparation method of the photosensitive particle stable foam specifically comprises the following steps: adding a water-soluble photosensitive monomer, a cross-linking agent and a photoinitiator into the ceramic slurry, uniformly mixing and completely dissolving to obtain a photosensitive water-based suspension, fully stirring and foaming the photosensitive water-based suspension, adding a surface modifier for hydrophobic modification in the foaming process, and stirring and foaming until stable photosensitive particle stable foam is formed. Stirring for 10min-24 h;
in the preparation process of the emulsion, ceramic particles exist in a water-oil two-phase interface, so that the emulsion stably exists and oil-water separation does not occur; in the foam preparation process, the modified ceramic particles are stably adsorbed on a gas/liquid interface, so that unstable phenomena such as liquid drainage, bubble disproportionation or combination and the like of the foam are avoided. Because the water phase or the oil phase in the emulsion and the water phase in the foam contain photosensitive monomers, after the irradiation of light with specific wavelength, the photosensitive monomers generate cross-linking polymerization reaction to enable the ceramic particles wrapped in the photosensitive monomers to be solidified and formed, the water or the oil volatilizes after the emulsion is dried to leave holes on the original position to form a porous structure, and the position of the gas phase in the foam is the source of the holes. After photocuring and forming, the ceramic parts with complex shapes and fine hierarchical pore structures can be obtained, wherein the hierarchical pore structures are derived from the pore structures designed by a 3D printing model and micron-scale or even nano-scale holes formed by removing a template in photosensitive particle stable emulsion/foam.
The photosensitive substance used for preparing the photosensitive particle stable emulsion is present in the water phase and/or the oil phase; the photosensitive substance used for preparing the photosensitive particle-stabilized foam exists in an aqueous phase;
in the photosensitive particle stable emulsion/foam, the photoinitiator accounts for 0.1-10% of the total mass of the photosensitive monomer (photosensitive oil phase monomer or water-soluble photosensitive monomer); in the photosensitive particle stable emulsion, the water phase accounts for 5-95% of the total mass of the photosensitive particle stable emulsion.
Furthermore, the characteristics of photocuring require that the ceramic slurry has photosensitive characteristics, and the added photosensitive monomers comprise water-soluble photosensitive monomers and photosensitive oil-phase monomers;
the water-soluble photosensitive monomer comprises acrylamide, methacrylamide and hydroxymethyl acrylamide, and one or more of N, N' -methylene bisacrylamide and ethylene glycol dimethacrylate is/are added as a cross-linking agent when the water-soluble photosensitive monomer is adopted;
the water-soluble photosensitive monomer is added in an amount of 5-30 wt% of the photosensitive aqueous suspension, and the cross-linking agent is added in an amount of 0.1-6 wt% of the photosensitive aqueous suspension;
the photosensitive oil phase monomers include: 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), Epoxy Acrylate (EA), hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), Tripropylene Glycol Diacrylate (TGD), polyethylene glycol diacrylate (PEGDA), urethane acrylate (PUA), tripropylene glycol diacrylate (TPGDA), 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexanecarboxylate (UVR-6105), polyether acrylate (PEAAM), ditrimethylolpropane acrylate (Di-TMPTA), 2-phenoxyethyl acrylate (PHEA);
the photoinitiator is one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), 4-dimethylaminobenzoic acid ethyl Ester (EPD), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (907), diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate (UVI-6976), 4-phenyl Benzophenone (BPZ), Benzophenone (BP), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (2959) One or more kinds;
the oil phase of the single component is one or more of n-octane, n-hexane, n-decane, corn oil, sunflower seed oil, toluene and styrene.
Further, a hydrophobic modifier is added into the ceramic slurry to modify the surface of the ceramic particles, and then the surface modifier is completely adsorbed on the surfaces of the particles through stirring; the surfactant includes: one or more of propionic acid, butyric acid, valeric acid, caproic acid, hexylamine, sodium dodecyl sulfate, sodium butane sulfonate, sodium heptane sulfonate, sodium dodecyl benzene sulfonate, cocamidopropyl betaine, hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, propyl gallate, octyl gallate, triton, tween 20, tween 40 and tween 80;
the addition amount of the surface modifier accounts for 0.05-20% of the total mass of the photosensitive particle stable emulsion/foam.
Further, the prepared stable emulsion/foam of photosensitive particles is used as a feed material to be applied to photocuring forming 3D printing equipment to prepare a part blank with a complex shape, and the photocuring forming process parameters are as follows: the ultraviolet light irradiation wavelength is as follows: 365-405 nm, a scanning speed of 500-2The curing time is 0.5s-15 min.
Furthermore, the temperature of the printed parts is 20-95 ℃ in the drying process, and the printed parts are kept stand for 10min-7 d.
Further, the heating rate is 0.01-10 ℃/min in the degreasing process, the degreasing temperature is 400-; the heating rate is 0.1-20 ℃/min in the high-temperature sintering process, the sintering temperature is 500-2000 ℃, and the temperature is kept for 5min-48 h.
Further, the porosity of the prepared hierarchical pore ceramic is 10% -99%; the air holes of the hierarchical hole structure comprise millimeter-scale hole structures designed by 3D printing and micron-scale and nanometer-scale holes introduced by photosensitive particle stable emulsion/foam; wherein, the photosensitive particles stabilize micron-sized or nano-sized holes introduced by the emulsion/foam, and the aperture range is 5nm-200 μm; the aperture range of the 3D printing design hole structure is 0.2-20 mm. The hierarchical porous ceramic has excellent performances of high specific surface area, high strength and the like.
When preparing the photosensitive particle stable emulsion/foam, the key point is to form stable emulsion/foam, in the process of preparing the photosensitive particle stable emulsion, the ceramic particles are used as the stabilizer of water phase and oil phase when the water phase and the oil phase are stirred and mixed, so that the emulsion exists stably, and oil-water separation and particle sedimentation do not occur; in the process of preparing the photosensitive particle stable foam, when the water phase and the air phase are mixed, the particles are stably adsorbed on a gas/liquid interface, so that the foam is not subjected to liquid drainage, bubble disproportionation or combination. The photo-curable polymer and the non-photosensitive aqueous phase/oil phase in the emulsion are dried and degreased to remove the photo-curable polymer and the non-photosensitive aqueous phase/oil phase, leaving holes in the original positions, and the position of the gas phase in the foam is the source of the holes.
The invention has the beneficial technical effects that:
one or more ceramic powders with different particle sizes can be used as raw materials to prepare the photosensitive particle stable emulsion/foam. Stabilizing the emulsion for photosensitive particles: the photosensitive monomer can only exist in the water phase, can only exist in the oil phase, and can also exist in both the water phase and the oil phase; foam stabilization for photosensitive particles: the photosensitive monomer is present in the aqueous phase. The invention not only widens the variety of raw materials for preparing the light-cured ceramic slurry, but also prepares the cream-shaped emulsion/foam, and removes the template after drying and degreasing to obtain the porous structure. In addition, the pore structure characteristics such as porosity, pore size and the like can be regulated and controlled through the hydrophobicity degree of the particle surface, the solid phase content, the water-oil ratio and the stirring speed.
The emulsion/foam with stable photosensitive particles has good stability, can be kept still for more than one month, and solves the problem that the particles in the existing photocuring ceramic slurry are easy to settle. The prepared photosensitive particle stable emulsion/foam paste can be used as a feed for photocuring forming, and hierarchical porous ceramics with different sizes and apertures can be formed by designing a three-dimensional model. The hierarchical porous material effectively integrates the performance advantages brought by various porous structures, so that the material has excellent performances of high permeability, high specific surface area, good mechanical property, low volume density and the like, the function maximization of the material in the same volume level and different scale porous structures is realized, and the hierarchical porous material has wide application prospects in the aspects of biomedical materials, filtering materials, catalyst carriers and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
Example 1
Adding alumina sol and silica sol powder into deionized water, and preparing uniformly dispersed ceramic slurry by ball milling and ultrasonic treatment, wherein the ceramic powder accounts for 25 wt% of the total amount of the ceramic slurry. Taking HDDA as a photosensitive oil phase monomer, adding a photoinitiator 819 into the HDDA, wherein the content of the photoinitiator is 1.5 wt% of that of the photosensitive oil phase monomer, and stirring the oil phase mixed solution on a magnetic stirrer for 30min until the photoinitiator is completely dissolved in the photosensitive monomer.
And fully stirring and mixing the ceramic slurry and the photosensitive oil phase mixed solution for 3 hours, wherein the water phase accounts for 40 wt% of the total amount of the water phase and the oil phase. During the mixing process, valeric acid is added to hydrophobically modify alumina sol and silica sol, and the addition amount of the valeric acid is 2.36 wt% of the total amount of the water phase and the oil phase. After the water-oil phase forms a stable emulsion, the emulsion is used for preparing a part with a customized shape on a photocuring forming printer. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 405nm, a scanning speed of 2000mm/s, a slice thickness of 30 μm, and an exposure intensity of 50mJ/cm2The curing time was 40 s.
Standing and drying the obtained parts at 20 ℃ for 1d, and then sintering the parts in a box furnace, wherein the heating rate is 0.25 ℃/min in the degreasing process, the degreasing temperature is 600 ℃, and the heat preservation time is 2 h; the heating rate is 2 ℃/min in the high-temperature sintering process, the sintering temperature is 1400 ℃, and the temperature is kept for 2 h. The prepared porous material has uniform pore distribution, the average pore diameter is 38 mu m,the porosity is 60 percent, and the volume density is 0.80g/cm3The multi-level pore ceramic component.
Example 2
Adding hydroxyapatite powder into deionized water, and performing ball milling and ultrasonic treatment to obtain uniformly dispersed ceramic slurry, wherein the ceramic powder accounts for 10 wt% of the total amount of the ceramic slurry. Taking HDDA and TMPTA as photosensitive oil phase monomers, wherein the mass ratio of the two photosensitive monomers is HDDA: TMPTA =2:1, adding a photoinitiator TPO into the mixture, wherein the content of the photoinitiator accounts for 0.1 wt% of the total amount of the oily photosensitive monomers HDDA and TMPTA, and placing the oil phase mixed solution on a magnetic stirrer to stir for 60min until the photoinitiator is completely dissolved in the photosensitive monomers.
And fully stirring and mixing the ceramic slurry and the photosensitive oil phase mixed solution for 10min, wherein the water phase accounts for 20 wt% of the total amount of the water phase and the oil phase. Adding tween 80 to hydrophobically modify the hydroxyapatite in the mixing process, wherein the adding amount of the tween 80 is 0.05 wt% of the total amount of the water phase and the oil phase. After the water-oil phase forms a stable emulsion, the emulsion is used for preparing a part with a customized shape on a photocuring forming printer. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 405nm, a scanning speed of 500mm/s, a slice thickness of 20 μm, and an exposure intensity of 10mJ/cm2The curing time was 0.5 s.
Standing and drying the obtained parts at 40 ℃ for 1h, and then sintering the parts in a box furnace, wherein the heating rate is 0.01 ℃/min in the degreasing process, the degreasing temperature is 500 ℃, and the heat preservation time is 10 h; the heating rate is 0.1 ℃/min in the high-temperature sintering process, the sintering temperature is 900 ℃, and the temperature is kept for 20 h. The obtained product has uniform pore distribution, average pore diameter of 200 μm, porosity of 99%, and volume density of 0.05g/cm3The multi-level pore ceramic component.
Example 3
Adding kaolin and aluminum ash into deionized water, and preparing uniformly dispersed ceramic slurry by ball milling and ultrasonic treatment, wherein the ceramic powder accounts for 50 wt% of the total amount of the ceramic slurry. Adding acrylamide, N, N '-methylene bisacrylamide and a photoinitiator 1173 into the ceramic slurry, uniformly mixing and completely dissolving to obtain the photosensitive water-based suspension, wherein the content of the acrylamide is 20 wt% of that of the photosensitive water-based suspension, the content of the N, N' -methylene bisacrylamide is 2 wt% of that of the photosensitive water-based suspension, and the addition amount of the 1173 is 1 wt% of that of the acrylamide. N-octane was chosen as the oil phase.
And fully stirring and mixing the photosensitive ceramic water-based suspension and n-octane for 48 hours, wherein the water phase accounts for 70 wt% of the total amount of the water phase and the oil phase. Sodium heptanesulfonate and sodium dodecyl sulfate are added in the mixing process to carry out hydrophobic modification on kaolin and aluminum ash, and the total addition amount of the sodium heptanesulfonate and the sodium dodecyl sulfate is 4.0wt.% of the total amount of the water phase and the oil phase. After the water-oil phase forms a stable emulsion, the emulsion is used for preparing a part with a customized shape on a photocuring forming printer. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 365nm, a scanning speed of 1000mm/s, a slice thickness of 40 μm, and an exposure intensity of 300mJ/cm2The curing time was 10 min.
Standing and drying the obtained parts at 25 ℃ for 3h, and then sintering the parts in a box furnace, wherein the heating rate is 10 ℃ per min in the degreasing process, the degreasing temperature is 600 ℃, and the heat preservation time is 3 h; the heating rate is 20 ℃/min in the high-temperature sintering process, the sintering temperature is 1300 ℃, and the temperature is kept for 10 h. The obtained product has uniform pore distribution, pore diameter of 5 μm, porosity of 50%, and volume density of 0.90g/cm3The multi-level pore ceramic component.
Example 4
Adding silicon nitride into deionized water, and preparing uniformly dispersed ceramic slurry by ball milling and ultrasonic treatment, wherein the ceramic powder accounts for 55 wt% of the total amount of the ceramic slurry. Adding methacrylamide, ethylene glycol dimethacrylate and a photoinitiator BPZ into the ceramic slurry, uniformly mixing and completely dissolving to obtain a photosensitive water-based suspension, wherein the content of the methacrylamide is 30 wt% of the photosensitive water-based suspension, the content of the ethylene glycol dimethacrylate is 6 wt% of the photosensitive water-based suspension, and the addition amount of the BPZ is 1.5 wt% of the acrylamide content. Toluene was chosen as the oil phase.
And fully stirring and mixing the photosensitive ceramic water-based suspension and toluene for 24 hours, wherein the water phase accounts for 40 wt% of the total amount of the water phase and the oil phase. Cetyl ammonium chloride is added in the mixing processThe silicon nitride particles are subjected to hydrophobic modification, and the addition amount of the hexadecyl ammonium chloride is 8 wt% of the total amount of the water phase and the oil phase. After the water-oil phase forms a stable emulsion, the emulsion is used for preparing a part with a customized shape on a photocuring forming printer. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 395nm, scanning speed of 1500mm/s, slice thickness of 30 μm, and exposure intensity of 100mJ/cm2The curing time was 15 min.
Standing and drying the obtained parts at 60 ℃ for 1d, and then sintering the parts in a box furnace, wherein the heating rate is 2 ℃ per min in the degreasing process, the degreasing temperature is 950 ℃, and the heat preservation time is 2 hours; the heating rate is 5 ℃/min in the high-temperature sintering process, the sintering temperature is 1800 ℃, and the temperature is kept for 3 h. The obtained product has uniform pore distribution, average pore diameter of 10 μm, porosity of 66%, and volume density of 0.54g/cm3The multi-level pore ceramic component.
Example 5
Adding silicon carbide powder into deionized water, and preparing uniformly dispersed ceramic slurry by ball milling and ultrasonic treatment, wherein the ceramic powder accounts for 85 wt% of the total amount of the ceramic slurry. Adding acrylamide, N-N '-methylene bisacrylamide and a photoinitiator 1173 into the ceramic slurry, uniformly mixing and completely dissolving to obtain the photosensitive water-based suspension, wherein the acrylamide content is 20 wt% of the photosensitive water-based suspension, the N, N' -methylene bisacrylamide content is 1.2 wt% of the photosensitive water-based suspension, and the addition amount of 1173 is 1 wt% of the acrylamide content. Selecting PEAAM as a photosensitive oil phase monomer, adding a photoinitiator UVI-6976 into the oil phase monomer, wherein the content of the photoinitiator accounts for 1.0 wt% of that of the oily photosensitive monomer PEAAM, and stirring the oil phase mixed solution on a magnetic stirrer for 30min until the photoinitiator is completely dissolved in the photosensitive monomer.
And fully stirring and mixing the photosensitive water-based suspension and the photosensitive oil-phase mixed solution for 30min, wherein the water phase accounts for 20 wt% of the total amount of the water phase and the oil phase. During the mixing process, sodium dodecyl sulfate is added to carry out hydrophobic modification on the silicon carbide, and the addition amount of the sodium dodecyl sulfate is 10 wt% of the total amount of the water phase and the oil phase. After the water-oil two-phase emulsion is formed into stable emulsion, it can be used on the light-curing forming printer to make the part with customized shapeAnd (3) a component. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 405nm, a scanning speed of 5000mm/s, a slice thickness of 300 μm, an exposure intensity of 200mJ/cm2The curing time was 20 s.
Standing and drying the obtained parts at 95 ℃ for 10h, and then sintering the parts in a box furnace, wherein the heating rate is 2 ℃ per min in the degreasing process, the degreasing temperature is 650 ℃, and the heat preservation time is 2 h; the heating rate is 5 ℃/min in the high-temperature sintering process, the sintering temperature is 2000 ℃, and the temperature is kept for 3 h. The obtained product has uniform pore distribution, average pore diameter of 50 μm, porosity of 75%, and volume density of 0.55g/cm3The multi-level pore ceramic component.
Example 6
Adding titanium sol powder into deionized water, and preparing uniformly dispersed ceramic slurry by ball milling and ultrasonic treatment, wherein the ceramic powder accounts for 5 wt% of the total amount of the ceramic slurry. Adding acrylamide, N, N '-methylene bisacrylamide and a photoinitiator BP into the ceramic slurry, uniformly mixing and completely dissolving to obtain the photosensitive water-based suspension, wherein the acrylamide content is 5 wt% of the photosensitive water-based suspension, the N, N' -methylene bisacrylamide content is 0.5 wt% of the photosensitive water-based suspension, and the addition amount of the BP is 1 wt% of the acrylamide content.
Fully stirring and foaming the photosensitive water-based suspension, adding propyl gallate to perform hydrophobic modification on the titanium sol in the foaming process, wherein the addition amount of the propyl gallate is 0.3 wt% of the total amount of the photosensitive water-based suspension, and the total stirring time is 10 hours. After the stable photosensitive foam is formed, it is used on a photocuring forming printer to produce custom-shaped parts. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 365nm, a scanning speed of 2500mm/s, a slice thickness of 100 μm, and an exposure intensity of 40mJ/cm2The curing time was 40 s.
And standing and drying the obtained parts at 30 ℃ for 3d, and then sintering the parts in a box type furnace, wherein the heating rate is 1 ℃/min in the high-temperature sintering process, the sintering temperature is 800 ℃, and the temperature is kept for 12 h. The obtained product has uniform pore distribution, average pore diameter of 25 μm, porosity of 98%, and volume density of 0.08g/cm3Multi-level hole ceramic parts。
Example 7
Adding coal gangue powder and alumina sol into deionized water, wherein the mass ratio of the two ceramic powders is as follows: alumina sol =3:1, and uniformly dispersed ceramic slurry is prepared by ball milling and ultrasonic treatment, wherein the ceramic powder accounts for 60 wt% of the total amount of the ceramic slurry. Adding hydroxymethyl acrylamide, ethylene glycol dimethacrylate and a photoinitiator 2959 into the ceramic slurry, uniformly mixing and completely dissolving to obtain the photosensitive water-based suspension, wherein the content of the hydroxymethyl acrylamide is 15 wt% of the photosensitive water-based suspension, the content of the ethylene glycol dimethacrylate is 1.5 wt% of the photosensitive water-based suspension, and the addition amount of 2959 is 2 wt% of the content of the hydroxymethyl acrylamide.
Fully stirring and foaming the photosensitive water-based suspension, adding sodium dodecyl sulfate to perform hydrophobic modification on coal gangue powder and aluminum sol particles in the foaming process, wherein the addition amount of the sodium dodecyl sulfate is 1.6 wt% of the total amount of the photosensitive water-based suspension, and the total stirring time is 5 hours. After the stable photosensitive foam is formed, it is used on a photocuring forming printer to produce custom-shaped parts. The parameters of the photocuring forming process are as follows: the ultraviolet light irradiation wavelength is as follows: 375nm, a scanning speed of 4000mm/s, a slice thickness of 150 μm, an exposure intensity of 80mJ/cm2The curing time was 2 min.
And standing and drying the obtained parts at 70 ℃ for 10min, then sintering the parts in a box type furnace, wherein the heating rate in the high-temperature sintering process is 5 ℃/min, the sintering temperature is 1550 ℃, and keeping the temperature for 4 h. Sintering to obtain the product with uniform pore distribution, average pore diameter of 10 μm, porosity of 55%, and volume density of 0.65g/cm3The multi-level pore ceramic component.
The method provided by the invention uses the hydrophobization modified ceramic particles as the interface stabilizer of the emulsion/foam, has the advantages of excellent stability and uniform and controllable pore structure, and the pores of the product skeleton can be derived from volatilization of a water phase or an oil phase in the emulsion or gas phase in the foam stabilized by the particles. In consideration of the requirement of preparing the ceramic product with the hierarchical pore structure by the photocuring forming technology, the invention provides that ceramic particles subjected to surface hydrophobic modification treatment are used as interface stabilizing substances of particle stabilizing emulsion/foam, photosensitive water phase or oil phase is introduced, the stable photosensitive particle stabilizing emulsion/foam is prepared by mechanical stirring treatment, then the stable photosensitive particle stabilizing emulsion/foam is cured and formed by photopolymerization, a blank with a porous skeleton structure is obtained by volatilization of the water phase/oil phase in the drying process and removal of a polymer in the degreasing process, and finally the hierarchical pore ceramic material with a complex shape and a fine structure is prepared by high-temperature sintering. The photosensitive particle stable emulsion/foam is used as a feed of a photocuring forming technology, can be applied to producing ceramic parts with a porous skeleton structure, and can widen the application range of porous materials in the fields of biology, environment, medicine, energy, national defense and the like while improving the comprehensive performance of products by virtue of the hierarchical pore structure.
Wherein, in the preparation process of the emulsion, the modified ceramic particles exist in an oil/water two-phase interface, so that the emulsion stably exists without phase separation; in the foam preparation process, the modified ceramic particles are stably adsorbed on a gas/liquid interface, so that unstable phenomena such as liquid drainage, bubble disproportionation or combination and the like of the foam are avoided. Because the water phase or oil phase in the emulsion and the water phase in the foam contain photosensitive monomers, after the irradiation of light with specific wavelength, the photosensitive monomers generate cross-linking polymerization reaction to enable the ceramic particles wrapped in the photosensitive monomers to be solidified and formed, the water phase or oil phase which does not contain photosensitive components volatilizes after the emulsion is dried to form a porous structure, and the position of the gas phase in the foam is the pore source. The invention provides a novel paste source for the photocuring 3D printing technology, introduces a micron-scale or nano-scale hole structure into a 3D printing forming skeleton structure, prepares ceramic parts with complex shapes and fine multi-level hole structures, and has considerable application prospect in the fields of catalyst carriers, biomedical materials, filtering materials, light heat insulation materials and the like.
Claims (10)
1. A method for preparing hierarchical porous ceramics by photocuring and forming of photosensitive emulsion/foam, which is characterized by comprising the following steps:
adding deionized water into ceramic powder and/or ceramic powder oxide sol nanoparticles, and preparing ceramic slurry with uniformly dispersed ceramic particles by ultrasonic and ball milling;
adding a photosensitive monomer and a photoinitiator into the ceramic slurry, then adding a certain amount of surface modifier to perform surface hydrophobic modification on ceramic particles, and fully stirring and mixing to prepare stable photosensitive particle stable emulsion/foam with photosensitive characteristics; wherein, the preparation of the photosensitive particle stable emulsion needs to introduce an oil phase;
and applying the photosensitive particle stable emulsion/foam to a photocuring forming 3D printing device to form parts with complex shapes, and drying, degreasing and sintering to obtain the hierarchical porous ceramic with a porous structure.
2. The method for preparing the hierarchical porous ceramic by photocuring and forming of the photosensitive emulsion/foam according to claim 1, wherein the ceramic powder is inorganic non-metallic material powder and comprises one or more of oxide ceramic powder and non-oxide ceramic powder; the oxide ceramic powder and the non-oxide ceramic powder specifically include: alumina, silicon oxide, zirconia, titanium dioxide, hydroxyapatite, beta-tricalcium phosphate, silicon nitride, silicon carbide, fly ash, coal gangue, kaolin, metallurgical slag, secondary aluminum ash, waste glass and tailings;
the ceramic powder oxide sol nano-particles comprise one or more of aluminum sol, silica sol, zirconium sol and titanium sol.
3. The method for preparing the hierarchical porous ceramic by photocuring forming of the photosensitive emulsion/foam as claimed in claim 1, wherein ceramic powder and/or ceramic powder oxide sol nanoparticles are mixed with deionized water, and then are subjected to ball milling and ultrasonic preparation to obtain uniformly dispersed ceramic slurry, wherein the solid phase mass fraction of the ceramic slurry is 5% -85%.
4. The method for preparing hierarchical porous ceramics according to claim 1, wherein the photosensitive particle-stabilized emulsion is prepared by one of the following three methods:
(1) adding a photosensitive oil phase monomer and a photoinitiator into the ceramic slurry, stirring until the photoinitiator is completely dissolved in the photosensitive oil phase monomer, adding a surface modifier in the mixing process to perform hydrophobic modification on ceramic particles, fully stirring and mixing to obtain a photosensitive particle stable emulsion, wherein the stirring time is 10min-24 h;
(2) adding a water-soluble photosensitive monomer, a cross-linking agent and a photoinitiator into the ceramic slurry to obtain a photosensitive water-based suspension, adding an oil phase with a single component for mixing, then adding a surface modifier for hydrophobic modification, and stirring to obtain a photosensitive particle stable emulsion, wherein the stirring time is 10min-24 h;
(3) adding a water-soluble photosensitive monomer, a cross-linking agent and a photoinitiator into the ceramic slurry to obtain a photosensitive water-based suspension, mixing a photosensitive oil-phase monomer, the photoinitiator and the photosensitive water-based suspension, then adding a surface modifier for hydrophobic modification, and stirring to obtain a photosensitive particle stable emulsion, wherein the stirring time is 10min-24 h;
the preparation method of the photosensitive particle stable foam specifically comprises the following steps: adding a water-soluble photosensitive monomer, a cross-linking agent and a photoinitiator into the ceramic slurry, uniformly mixing and completely dissolving to obtain a photosensitive water-based suspension, fully stirring and foaming the photosensitive water-based suspension, adding a surface modifier in the foaming process to perform hydrophobic modification, stirring and foaming until stable photosensitive particle stable foam is formed, wherein the stirring time is 10min-24 h;
wherein the photosensitive substance used for preparing the photosensitive particle-stabilized emulsion is present in the aqueous phase and/or the oil phase; the photosensitive substance used for preparing the photosensitive particle-stabilized foam exists in an aqueous phase;
in the photosensitive particle stable emulsion/foam, the photoinitiator accounts for 0.1 to 10 percent of the total mass of the photosensitive monomer; in the photosensitive particle stable emulsion, the water phase accounts for 5-95% of the total mass of the photosensitive particle stable emulsion.
5. The method for preparing hierarchical porous ceramic by photo-curing and forming of photosensitive emulsion/foam according to claim 1 or 4, wherein the photosensitive monomer comprises a water-soluble photosensitive monomer and a photosensitive oil-phase monomer;
the water-soluble photosensitive monomer comprises acrylamide, methacrylamide and hydroxymethyl acrylamide, and one or more of N, N' -methylene bisacrylamide and ethylene glycol dimethacrylate are added as a cross-linking agent when the water-soluble photosensitive monomer is adopted;
the water-soluble photosensitive monomer is added in an amount of 5-30 wt% of the photosensitive aqueous suspension, and the cross-linking agent is added in an amount of 0.1-6 wt% of the photosensitive aqueous suspension;
the photosensitive oil phase monomer comprises: 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, epoxy acrylate, hydroxyethyl methacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, urethane acrylate, tripropylene glycol diacrylate, 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, polyether acrylate, ditrimethylolpropane acrylate, 2-phenoxyethyl acrylate;
the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 4-ethyl dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate, 4-phenyl benzophenone, benzophenone and one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone;
the oil phase of the single component is one or more of n-octane, n-hexane, n-decane, corn oil, sunflower seed oil, toluene and styrene.
6. The method for preparing hierarchical porous ceramic by photocuring and forming of photosensitive emulsion/foam according to claim 1, wherein the surfactant comprises: one or more of propionic acid, butyric acid, valeric acid, caproic acid, hexylamine, sodium dodecyl sulfate, sodium butane sulfonate, sodium heptane sulfonate, sodium dodecyl benzene sulfonate, cocamidopropyl betaine, hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, propyl gallate, octyl gallate, triton, tween 20, tween 40 and tween 80;
the addition amount of the surface modifier accounts for 0.05-20% of the total mass of the photosensitive particle stable emulsion/foam.
7. The method for preparing the hierarchical porous ceramic by the photocuring forming of the photosensitive emulsion/foam as claimed in claim 1, wherein the prepared photosensitive particle-stabilized emulsion/foam is used as a feed for a photocuring forming 3D printing device to prepare a part blank with a complex shape, and the photocuring forming process parameters are as follows: the ultraviolet light irradiation wavelength is as follows: 365-405 nm, a scanning speed of 500-2The curing time is 0.5s-15 min.
8. The method for preparing the hierarchical porous ceramic by photocuring and forming of the photosensitive emulsion/foam as claimed in claim 1, wherein the temperature of the printed part is 20-95 ℃ during drying, and the printed part is kept for 10min-7 d.
9. The method for preparing a hierarchical porous ceramic by photocuring and forming of a photosensitive emulsion/foam as claimed in claim 1, wherein the temperature rise rate is 0.01-10 ℃/min in the degreasing process, the degreasing temperature is 400-950 ℃, and the heat preservation time is 5min-48 h; the heating rate is 0.1-20 ℃/min in the high-temperature sintering process, the sintering temperature is 500-2000 ℃, and the temperature is kept for 5min-48 h.
10. The method for preparing the hierarchical porous ceramic by photocuring and forming of the photosensitive emulsion/foam according to claim 1, wherein the porosity of the prepared hierarchical porous ceramic is 10% -99%; the air holes of the hierarchical hole structure comprise millimeter-scale hole structures designed by 3D printing and micron-scale and nanometer-scale holes introduced by photosensitive particle stable emulsion/foam; wherein, the photosensitive particles stabilize micron-sized or nano-sized holes introduced by the emulsion/foam, and the aperture range is 5nm-200 μm; the aperture range of the 3D printing design hole structure is 0.2-20 mm.
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