CN114890425A - Elastic silicon carbide nanowire aerogel with multilevel structure and 3D printing preparation method and application thereof - Google Patents
Elastic silicon carbide nanowire aerogel with multilevel structure and 3D printing preparation method and application thereof Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 86
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000010146 3D printing Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 81
- 239000004917 carbon fiber Substances 0.000 claims abstract description 81
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- -1 polysiloxane Polymers 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- 238000005336 cracking Methods 0.000 claims abstract description 11
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 238000007639 printing Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000002070 nanowire Substances 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 26
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
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- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical group OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229920013818 hydroxypropyl guar gum Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000000919 ceramic Substances 0.000 abstract description 15
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000011049 filling Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
- C01B32/977—Preparation from organic compounds containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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- B33Y80/00—Products made by additive manufacturing
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Abstract
The invention discloses an elastic silicon carbide nanowire aerogel with a multilevel structure, and a 3D printing preparation method and application thereof, and belongs to the technical field of ceramic aerogel preparation. The method comprises the following steps: preparing carbon fiber water-based 3D printing ink; printing a carbon fiber-based structure; after heat treatment and polysiloxane sol impregnation, obtaining polysiloxane sol/3D printing carbon fiber base structure; cracking in argon atmosphere to obtain a 3D printed carbon fiber/silicon carbide nanowire hybrid structure; and performing heat treatment to obtain the elastic silicon carbide nanowire aerogel with the multilevel structure. The method adjusts the macro and micro structures of the elastic silicon carbide nanowire aerogel through 3D printing, and shows good flexibility in adjusting the mechanical strength and heat conduction of the aerogel. The prepared elastic silicon carbide nanowire aerogel with the three-dimensional complex multilevel structure is suitable for heat management devices, lightweight structural members, high-temperature filters, catalyst carriers, electrode diaphragms and other related potential applications.
Description
Technical Field
The invention belongs to the technical field of ceramic aerogel preparation, and particularly relates to elastic silicon carbide nanowire aerogel with a multilevel structure, and a 3D printing preparation method and application thereof.
Background
Elastic ceramic aerogel composed of one-dimensional ceramic nanowires or two-dimensional nanosheets is attractive due to its ultra-light weight, ultra-high porosity, ultra-low thermal conductivity, excellent thermal stability and simultaneously recoverable deformability, and has wide application prospects in the fields of heat insulation, catalysis, filtration, aerospace and the like. To date, a number of methods have been employed to prepare elastic ceramic aerogels, such as freeze casting and supercritical drying, chemical vapor deposition, and template assisted conversion. Freeze casting is a common method for preparing porous structure ceramic aerogel, and is a general strategy for arranging the microstructure in a controllable manner, and by adjusting the concentration of suspension and the freezing condition, super-elastic SiC nanowires and silicon dioxide nanofiber aerogel with different densities and well-arranged microstructures can be prepared. The chemical vapor deposition is a simple and convenient method, and can be used for preparing the high-flexibility paper-shaped SiC nanowire aerogel, and the paper-shaped SiC nanowire aerogel can realize reversible compressibility, crack insensitivity and even reversible stretching. The template-assisted conversion method is an efficient and extensible method, and can be used for preparing elastic SiC nanowire aerogel with simple macroscopic geometric shapes. Despite the numerous manufacturing methods available, the production of emerging elastic ceramic aerogels currently faces challenges such as poor processability, difficulty in obtaining complex shapes suitable for practical applications, and difficulty in precisely tailoring microstructure and mechanical properties.
Three-dimensional (3D) printing provides a solution to the manufacture of aerogels with rather complex macro and micro structures. 3D printing can build materials with engineered structures with high precision and speed, facilitating the customization of the macro, geometric and micro structure of aerogels. Direct ink writing is an extrusion-based 3D printing method that can be used to make closed and open porous structures with pore size accuracies from millimeters to micrometers. For example, by organizing a hierarchical load-bearing network composed of emulsified/foamed ceramic ink, the mechanical efficiency of the porous structure can be increased even at high porosities of 94%. The microstructure, geometry, and especially mechanical properties of the porous ceramic can also be customized by direct foam writing. It has been reported that silica aerogel objects are produced by direct ink writing, which enables highly accurate tailored thermal insulation applications. Furthermore, the addition of functional nanoparticle manganese dioxide in the ink allows tunable functionality such as gas pumping and volatile organic compound degradation.
However, since the types of ink materials available for direct ink writing are very limited and most are brittle, 3D printing technology is currently limited to the preparation of brittle ceramic aerogels, but the 3D printing preparation of elastic ceramic aerogels is still difficult to achieve, especially elastic aerogels of complex structure.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the present invention aims to provide an elastic silicon carbide nanowire aerogel with a multilevel structure and a 3D printing preparation method thereof, which can adjust the macro and micro structures of the elastic silicon carbide nanowire aerogel through 3D printing, can realize the preparation of the elastic aerogel with a complex structure, and show good flexibility in adjusting the mechanical strength and the thermal conductivity of the aerogel.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a 3D printing preparation method of elastic silicon carbide nanowire aerogel with a multilevel structure, which comprises the following steps:
1) preparing carbon fiber water-based 3D printing ink;
2) printing the carbon fiber-based structure by using carbon fiber water-based 3D printing ink;
3) carrying out heat treatment on the 3D printed carbon fiber-based structure, and soaking polysiloxane sol to obtain polysiloxane sol/3D printed carbon fiber-based structure;
4) in an argon atmosphere, carrying out cracking treatment on the polysiloxane sol/3D printing carbon fiber base structure to obtain a 3D printing carbon fiber/silicon carbide nanowire hybrid structure;
5) and (3) carrying out heat treatment on the 3D printed carbon fiber/silicon carbide nanowire hybrid structure to obtain the elastic silicon carbide nanowire aerogel with the multilevel structure.
Further, the carbon fiber water-based 3D printing ink in the step 1) is composed of chopped carbon fibers, a solvent, a thickening agent, gas-phase nano-silica and a pore-forming agent.
Preferably, in step 1), the carbon fiber water-based 3D printing ink is prepared, and the preparation of the raw materials comprises the following steps: 3 to 28 percent of chopped carbon fiber, 4 to 12 percent of gas phase nano silicon dioxide, 2 to 10 percent of pore forming agent, 1.5 to 2.5 percent of thickening agent and 47.5 to 89.5 percent of solvent.
More preferably, the length of the chopped carbon fiber is 100-250 μm; the size of the gas phase nano silicon dioxide is 7-40 nm and 100m 2 /g<Specific surface area<400m 2 (ii)/g; the pore-forming agent is selected from polystyrene microspheres, polymethyl methacrylate microspheres, wood powder and the like, and the size of the pore-forming agent is 5-80 mu m; the thickening agent is selected from hydroxypropyl methyl cellulose, guar gum, xanthan gum and the like; the solvent is water.
Further preferably, the water is deionized water.
Preferably, when the carbon fiber water-based 3D printing ink is prepared, the chopped carbon fibers and the pore-forming agent are added into the solvent, high-speed stirring is carried out for 5-30 minutes at the rotating speed of 7000-18000 r/min, finally the thickening agent and the gas-phase nano-silica are added, and mechanical stirring is carried out for 1-4 hours at the rotating speed of 1000-3000 r/min.
Further preferably, the high-speed stirring treatment selects a high-speed dispersion homogenizer.
Preferably, in step 2), the carbon fiber-based structure is printed with a direct ink writing 3D printer: the control of the shape, the structure, the size, the pore shape and the pore size of the carbon fiber-based structure is realized by writing a G code; the 3D printing speed is 5-25 mm/s, and the printing size is larger than 10 mm.
Preferably, in the step 3), the heat treatment temperature is 400-600 ℃, the heat treatment time is 0.5-3.5 hours, and the heat treatment atmosphere is air; the amount of the carbon fiber-based structure after heat treatment dipped in polysiloxane sol accounts for 1-15% of the mass of the carbon fiber-based structure, and the dipping treatment time is 0.5-2 h; the polysiloxane sol consists of 6.1-23.8 wt% of siloxane, 7.4-28.5 wt% of water and 47.7-86.5 wt% of absolute ethyl alcohol.
Preferably, in the step 4), the cracking temperature is 1300-1600 ℃, and the treatment time is 1-3 h.
Further preferably, the cracking temperature is 1550 ℃.
Preferably, in the step 5), the heat treatment is carried out at 700-800 ℃ for 1-4 h in an air atmosphere.
The invention also discloses the elastic silicon carbide nanowire aerogel with the multilevel structure prepared by the 3D printing preparation method, wherein the elastic silicon carbide nanowire aerogel with the multilevel structure has a multilevel structure spanning the macroscopic scale and the microscopic scale, and the preparation method comprises the following steps:
microscopically, silicon carbide nanowires (primary structures) with the diameter of 20-700 nm form nanowire columns (secondary structures) with the diameter of 400-600 mu m, and the elastic silicon carbide nanowire aerogel (tertiary structures) with the macroscopic size of more than 10mm and complex shapes are formed by horizontally arranging and vertically laminating the nanowire columns.
The invention further discloses application of the elastic silicon carbide nanowire aerogel with the multilevel structure in preparation of heat management devices, lightweight structural members, high-temperature filters, catalyst carriers or electrode diaphragms.
Compared with the prior art, the invention has the following beneficial effects:
according to the 3D printing preparation method of the multilevel-structure elastic silicon carbide nanowire aerogel disclosed by the invention, the carbon fiber water-based 3D printing ink is prepared at first, which is a key factor for finally preparing the elastic ceramic aerogel, and the elastic ceramic aerogel is formed by self-assembling in the 3D-printed carbon fiber-based structure, so that the structure and the performance of the final aerogel are determined by the 3D-printed carbon fiber-based structure.
Furthermore, the method disclosed by the invention can realize accurate regulation and control of the overall complex macrostructure, size, pore shape, pore size and the like of the silicon carbide nanowire aerogel by writing a G code. The density of the silicon carbide nanowire aerogel is controlled by adjusting the components of the carbon fiber water-based 3D printing ink and the concentration of the impregnated polysiloxane sol.
The silicon carbide nanowire aerogel prepared by the method microscopically consists of silicon carbide nanowires to form nanowire columns, and the elastic silicon carbide nanowire aerogel with a complicated macroscopic shape is finally formed by the horizontal arrangement and the vertical lamination of the nanowire columns. The flexible silicon carbide nanowires that can be bent are the essential reason for achieving the mechanical elasticity of the ceramic aerogel. The prepared silicon carbide nanowire aerogel has a complex multistage macroscopic and microscopic structure, and has good and adjustable mechanical property and heat-insulating property.
The elastic SiC nanowire aerogel prepared by 3D printing has potential application value in the fields of heat management devices, lightweight structural members, high-temperature filters, catalyst carriers, electrode diaphragms and the like.
Drawings
Fig. 1 is a macro-morphology of a multi-stage elastic SiC nanowire aerogel prepared by 3D printing in embodiment 1 of the present invention;
fig. 2 is a microscopic morphology of the elastic SiC nanowire aerogel with the multilevel structure prepared by 3D printing in example 1 of the present invention;
fig. 3 is an XRD spectrogram of the elastic SiC nanowire aerogel with a multilevel structure prepared by 3D printing in example 2 of the present invention;
fig. 4 is a compressive stress-strain curve of the elastic SiC nanowire aerogel with a multilevel structure prepared by 3D printing according to example 4 of the present invention;
fig. 5 shows the thermal conductivity of the elastic SiC nanowire aerogel with a multilevel structure prepared by 3D printing in example 5 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
This embodiment realizes carrying out accurate regulation and control to macrostructure, size, pore shape, the pore size of multistage structure elasticity carborundum nanowire aerogel through compiling 3D and printing G code route, and concrete step is as follows:
1) adding 5 wt% of chopped carbon fiber and 2 wt% of polystyrene microspheres into deionized water, stirring for 15 minutes by using a high-speed dispersion homogenizer at the rotating speed of 10000 revolutions per minute, adding 1.5 wt% of hydroxypropyl methyl cellulose, finally adding 4 wt% of fumed silica, and continuing to mechanically stir for 3 hours at the rotating speed of 1500 revolutions per minute to obtain the carbon fiber water-based 3D printing ink.
2) 3D modeling is carried out by adopting 3DS MAX software, the design of a macroscopic structure and size is realized through modeling, and an STL file is exported. The STL file is sliced by adopting ULTIMAKER CURA software, the shape of pores of a 3D printing structure, such as square pores, triangular pores and hexagonal pores, is regulated and controlled by changing filling patterns in the slicing process, the size of the pores is changed by regulating and controlling filling density, the higher the filling rate is, the smaller the pores are, the smaller the filling rate is, and the larger the pores are. And obtaining a G code after slicing, and then leading in a direct ink writing 3D printer to print the carbon fiber-based structure. The structural dimension of the design of the embodiment is 30mm multiplied by 25mm, the pore shape is square, the pore size is 2mm multiplied by 2mm, and the filling rate is 60%.
3) The 3D printed carbon fiber based structure was naturally dried and then treated at 400 ℃ for 3.5 hours in an air atmosphere. Then, 5 wt% of the siloxane sol was impregnated and finally dried in an oven at 80 ℃ overnight.
4) And (3) cracking the polysiloxane sol/3D printing carbon fiber base structure for 3 hours at 1300 ℃ in an argon atmosphere to obtain the 3D printing carbon fiber/silicon carbide nanowire hybrid structure.
5) And (3) carrying out heat treatment on the 3D-printed carbon fiber/silicon carbide nanowire hybrid structure at 800 ℃ for 1 hour in an air atmosphere to obtain the 3D-printed elastic silicon carbide nanowire aerogel with the multilevel structure.
Example 2
The density of the multilevel-structure elastic silicon carbide nanowire aerogel is regulated and controlled by adjusting the components of the carbon fiber water-based 3D printing ink, and the method comprises the following specific steps:
1) adding 28 wt% of chopped carbon fiber and 10 wt% of polystyrene microspheres into deionized water, stirring for 30 minutes by using a high-speed dispersion homogenizer at the rotating speed of 8000 revolutions per minute, adding 2.5 wt% of xanthan gum, finally adding 12 wt% of fumed silica, and continuing to mechanically stir for 1 hour at the rotating speed of 3000 revolutions per minute to obtain the carbon fiber water-based 3D printing ink.
2) 3D modeling is carried out by adopting 3DS MAX software, the structure is a cube, the size is 30mm multiplied by 30mm, and an STL file is exported. And (3) slicing the STL file by adopting ULTIMAKER CURA software, wherein the shape of a pore is square, the size of the pore is 2mm multiplied by 2mm, and the filling rate is 80%. And obtaining a G code after slicing, and then leading in a direct ink writing 3D printer to print the carbon fiber-based structure.
3) The 3D printed carbon fiber based structure was dried naturally for 4 hours, dried in an oven at 80 ℃ for 4 hours, and then treated in an air atmosphere at 600 ℃ for 1 hour. Then, a 5 wt% siloxane sol was impregnated and finally dried in an oven at 80 ℃ overnight.
4) And (3) cracking the polysiloxane sol/3D printing carbon fiber base structure for 2.5 hours at 1400 ℃ in an argon atmosphere to obtain the 3D printing carbon fiber/silicon carbide nanowire hybrid structure.
5) And (3) carrying out heat treatment on the 3D-printed carbon fiber/silicon carbide nanowire hybrid structure for 2 hours at 750 ℃ in an air atmosphere to obtain the 3D-printed elastic silicon carbide nanowire aerogel with the multilevel structure.
Example 3
The embodiment regulates and controls the density of the elastic silicon carbide nanowire aerogel with the multilevel structure by adjusting the mass ratio of the impregnated polysiloxane sol with the 3D printed carbon fiber-based structure, and comprises the following specific steps:
1) adding 15 wt% of chopped carbon fibers and 8 wt% of wood powder into deionized water, stirring for 5 minutes by using a high-speed dispersion homogenizer at the rotating speed of 18000 r/min, adding 2 wt% of hydroxypropyl methyl cellulose, finally adding 10 wt% of fumed nano silicon dioxide, and continuing mechanically stirring for 4 hours at the rotating speed of 2000 r/min to obtain the carbon fiber water-based 3D printing ink.
2) 3D modeling is carried out by adopting 3DS MAX software, the structure is a cube, the size is 30mm multiplied by 30mm, and an STL file is exported. And (3) slicing the STL file by adopting ULTIMAKER CURA software, wherein the shape of a pore is square, the size of the pore is 2mm multiplied by 2mm, and the filling rate is 80%. Obtain the G code after the section, import direct ink afterwards and write 3D printer and print carbon fiber base structure.
3) The 3D printed carbon fiber based structure was dried naturally and then treated in an air atmosphere at 500 ℃ for 2 hours. Then, 1 wt%, 5 wt%, 10 wt%, 15 wt% of the siloxane sol was impregnated, respectively, and finally dried in an oven at 100 ℃ overnight.
4) And (3) cracking the polysiloxane sol/3D printing carbon fiber base structure at 1500 ℃ for 2.5 hours in an argon atmosphere to obtain the 3D printing carbon fiber/silicon carbide nanowire hybrid structure.
5) And (3) carrying out heat treatment on the 3D-printed carbon fiber/silicon carbide nanowire hybrid structure at 700 ℃ in an air atmosphere for 3 hours to obtain the 3D-printed elastic silicon carbide nanowire aerogel with the multilevel structure.
Example 4
This embodiment adjusts its mechanical strength through 3D printing the structure regulation and control of hierarchical structure carborundum nanowire aerogel, and concrete step is as follows:
1) adding 15 wt% of chopped carbon fiber and 8 wt% of polymethyl methacrylate microspheres into deionized water, stirring for 30 minutes by using a high-speed dispersion homogenizer at the rotating speed of 7000 r/min, adding 2 wt% of hydroxypropyl methylcellulose, finally adding 10 wt% of fumed silica, and continuing to mechanically stir for 3 hours at the rotating speed of 2500 r/min to obtain the carbon fiber water-based 3D printing ink.
2) 3D modeling is carried out by adopting 3DS MAX software, the structure is a cube, the size is 30mm multiplied by 30mm, and an STL file is exported. And (3) slicing the STL file by adopting ULTIMAKER CURA software, and setting three pore shapes, namely a square shape, a triangular shape and a hexagonal shape, wherein the filling rate is 85 percent. And obtaining a G code after slicing, and then leading in a direct ink writing 3D printer to print the carbon fiber-based structure.
3) The 3D printed carbon fiber based structure was naturally dried and then treated in an air atmosphere at 500 ℃ for 2 hours. Then, 10 wt% of the siloxane sol was impregnated and finally dried in an oven at 100 ℃ overnight.
4) And (3) cracking the polysiloxane sol/3D printed carbon fiber-based structure for 1 hour at 1600 ℃ in an argon atmosphere to obtain the 3D printed carbon fiber/silicon carbide nanowire hybrid structure.
5) And (3) carrying out heat treatment on the 3D-printed carbon fiber/silicon carbide nanowire hybrid structure at 700 ℃ in an air atmosphere for 3 hours to obtain the 3D-printed elastic silicon carbide nanowire aerogel with the multilevel structure.
Example 5
This embodiment is through the heat conduction action of the whole density regulation and control aerogel of 3D printing adjustment hierarchical structure carborundum nanowire aerogel, and concrete step is as follows:
1) adding 15 wt% of chopped carbon fibers and 8 wt% of polystyrene microspheres into deionized water, stirring for 20 minutes by using a high-speed dispersion homogenizer at the rotating speed of 10000 revolutions per minute, adding 2 wt% of guar gum, finally adding 10 wt% of fumed nano silicon dioxide, and continuing to mechanically stir for 2.5 hours at the rotating speed of 2500 revolutions per minute to obtain the carbon fiber water-based 3D printing ink.
2) 3D modeling is carried out by adopting 3DS MAX software, the structure is a cube, the size is 25mm multiplied by 25mm, and an STL file is exported. And (3) slicing the STL file by adopting ULTIMAKER CURA software, and setting the shape of the pore as a square and the filling rate as 100% for complete filling. And obtaining a G code after slicing, and then leading in a direct ink writing 3D printer to print the carbon fiber-based structure.
3) The 3D printed carbon fiber based structure was naturally dried and then treated at 550 ℃ for 1 hour in an air atmosphere. Then, 5 wt%, 10 wt%, 15 wt% of the siloxane sol was impregnated, respectively, and finally dried in an oven at 100 ℃ overnight.
4) And (3) cracking the polysiloxane sol/3D printed carbon fiber base structure for 3 hours at 1550 ℃ in an argon atmosphere to obtain the 3D printed carbon fiber/silicon carbide nanowire hybrid structure.
5) And (3) carrying out heat treatment on the 3D printed carbon fiber/silicon carbide nanowire hybrid structure for 2 hours at 750 ℃ in an air atmosphere to obtain the 3D printed elastic silicon carbide nanowire aerogel with the multilevel structure.
The structural characterization and performance test results of the elastic silicon carbide nanowire aerogel with the multilevel structure prepared by the embodiment of the invention are as follows:
referring to FIG. 1, the SiC nanowire aerogel having a multilevel structure of 30mm × 30mm × 25mm in size, which was prepared in example 1, had a density of 28.5mg/cm 3 The SiC aerogel can stand at the tip of a leaf, and the low density of the SiC nanowire aerogel is reflected.
Referring to fig. 2, in order to obtain a scanning electron microscope photomicrograph of the elastic SiC nanowire aerogel with a multilevel structure prepared in example 1, it can be seen that the silicon carbide aerogel prepared by 3D printing is composed of silicon carbide nanowires, and the diameters of the nanowires are about 20 to 700 nm.
Referring to fig. 3, an XRD spectrum of the silicon carbide nanowire aerogel with a multilevel structure prepared in example 2 shows that the silicon carbide aerogel prepared by the method of the present invention is 3C — SiC, and exhibits a small-layer dislocation peak (SF) around 33.4 °.
Referring to fig. 4, as to the stress-strain curve of the SiC aerogel with a multilevel structure prepared by 3D printing in example 4, it can be seen that the aerogel has a recovery capability of 8% when compressed to 10% strain, shows compressibility, and overcomes the brittleness of the conventional ceramic aerogel.
Referring to fig. 5, which is a density-thermal conductivity relationship diagram at room temperature of the multi-stage SiC aerogel prepared in example 5, the thermal conductivity is 0.046-0.054W/m · k, and increases with increasing density, so that the SiC aerogel has good thermal insulation performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A3D printing preparation method of elastic silicon carbide nanowire aerogel with a multilevel structure is characterized by comprising the following steps:
1) preparing carbon fiber water-based 3D printing ink;
2) printing a carbon fiber-based structure by using carbon fiber water-based 3D printing ink;
3) carrying out heat treatment on the 3D printed carbon fiber-based structure, and soaking polysiloxane sol to obtain polysiloxane sol/3D printed carbon fiber-based structure;
4) in an argon atmosphere, carrying out cracking treatment on the polysiloxane sol/3D printing carbon fiber base structure to obtain a 3D printing carbon fiber/silicon carbide nanowire hybrid structure;
5) and (3) carrying out heat treatment on the 3D printed carbon fiber/silicon carbide nanowire hybrid structure to obtain the elastic silicon carbide nanowire aerogel with the multilevel structure.
2. The 3D printing preparation method of the multilevel structure elastic silicon carbide nanowire aerogel according to claim 1, wherein in the step 1), carbon fiber water-based 3D printing ink is prepared, and the preparation method comprises the following steps of: 3 to 28 percent of chopped carbon fiber, 4 to 12 percent of gas phase nano silicon dioxide, 2 to 10 percent of pore forming agent, 1.5 to 2.5 percent of thickening agent and 47.5 to 89.5 percent of solvent.
3. The 3D printing preparation method of the multilevel-structure elastic silicon carbide nanowire aerogel according to claim 2, wherein the length of the chopped carbon fiber is 100-250 μm; the size of the gas phase nano silicon dioxide is 7-40 nm and 100m 2 /g<Specific surface area<400m 2 (ii)/g; the pore-forming agent is selected from polystyrene microspheres, polymethyl methacrylate microspheres or wood powder, and the size is 5-80 μm; the thickener is selected from hydroxypropyl methylcellulose, guar gum or xanthan gum; the solvent is water.
4. The 3D printing preparation method of the multilevel-structure elastic silicon carbide nanowire aerogel according to claim 2, characterized in that when preparing the carbon fiber water-based 3D printing ink, chopped carbon fibers and a pore-forming agent are added into a solvent, the mixture is stirred at a high speed at a rotating speed of 7000-18000 r/min for 5-30 minutes, finally, a thickening agent and gas-phase nano-silica are added, and the mechanical stirring is continued at a rotating speed of 1000-3000 r/min for 1-4 hours.
5. The 3D printing preparation method of the multilevel structure elastic silicon carbide nanowire aerogel according to claim 1, wherein in the step 2), a carbon fiber-based structure is printed by a direct ink writing 3D printer: the control of the shape, the structure, the size, the pore shape and the pore size of the carbon fiber-based structure is realized by writing a G code; the 3D printing speed is 5-25 mm/s, and the printing size is larger than 10 mm.
6. The 3D printing preparation method of the multilevel-structure elastic silicon carbide nanowire aerogel according to claim 1, wherein in the step 3), the heat treatment temperature is 400-600 ℃, the heat treatment time is 0.5-3.5 h, and the heat treatment atmosphere is air; the amount of the carbon fiber-based structure after heat treatment dipped in polysiloxane sol accounts for 1-15% of the mass of the carbon fiber-based structure, and the dipping treatment time is 0.5-2 h; the polysiloxane sol comprises 6.1-23.8% of siloxane, 7.4-28.5% of water and 47.7-86.5% of absolute ethyl alcohol by mass percent.
7. The 3D printing preparation method of the multilevel-structure elastic silicon carbide nanowire aerogel according to claim 1, wherein in the step 4), the cracking temperature is 1300-1600 ℃, and the treatment time is 1-3 h.
8. The 3D printing preparation method of the multilevel-structure elastic silicon carbide nanowire aerogel according to claim 1, wherein in the step 5), the heat treatment is carried out at 700-800 ℃ for 1-4 h in an air atmosphere.
9. The elastic silicon carbide nanowire aerogel with the multilevel structure prepared by the 3D printing preparation method of any one of claims 1 to 8 is characterized in that the elastic silicon carbide nanowire aerogel with the multilevel structure has a multilevel structure spanning macroscopic and microscopic scales, wherein:
microscopically, the silicon carbide nanowires with the diameter of 20-700 nm form nanowire columns with the diameter of 400-600 mu m, and the elastic silicon carbide nanowire aerogel with the macroscopic size of more than 10mm and a complex shape is formed by horizontally arranging and vertically laminating the nanowire columns.
10. Use of the multi-stage structure elastic silicon carbide nanowire aerogel of claim 9 in the preparation of heat management devices, lightweight structural members, high temperature filters, catalyst supports or electrode separators.
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