CN114633468B - Method for preparing stereoscopic aramid aerogel by suspension 3D printing and application - Google Patents
Method for preparing stereoscopic aramid aerogel by suspension 3D printing and application Download PDFInfo
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- CN114633468B CN114633468B CN202011489351.5A CN202011489351A CN114633468B CN 114633468 B CN114633468 B CN 114633468B CN 202011489351 A CN202011489351 A CN 202011489351A CN 114633468 B CN114633468 B CN 114633468B
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- 239000004760 aramid Substances 0.000 title claims abstract description 188
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 188
- 238000010146 3D printing Methods 0.000 title claims abstract description 151
- 239000000725 suspension Substances 0.000 title claims abstract description 104
- 239000004964 aerogel Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000011159 matrix material Substances 0.000 claims abstract description 81
- 239000002121 nanofiber Substances 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 238000007639 printing Methods 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000013538 functional additive Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- -1 transition metal nitrides Chemical class 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 241000237858 Gastropoda Species 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 239000013535 sea water Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 2
- 241000984642 Cura Species 0.000 claims description 2
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002042 Silver nanowire Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000011960 computer-aided design Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical group O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- 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
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
Abstract
The invention discloses a method for preparing stereoscopic aramid aerogel by suspension 3D printing and application thereof. The preparation method comprises the following steps: uniformly mixing at least aramid nanofiber, a functional additive and a solvent to form an aramid nanofiber dispersion liquid and using the aramid nanofiber dispersion liquid as 3D printing ink; taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix; carrying out suspension 3D printing by using a direct-writing forming printing method under the auxiliary action of a suspension matrix to obtain a 3D printed stereoscopic aramid gel component, and stably placing the stereoscopic aramid gel component in the suspension matrix; and then carrying out solvent replacement and drying treatment to obtain the 3D printing stereoscopic aramid aerogel. The suspension 3D printing preparation method can print the stereoscopic aramid gel with any size and shape, has the advantages of low energy consumption, high printing precision and simple process, and the obtained 3D printing stereoscopic aramid aerogel has the advantages of ultralow density, large specific surface area, low heat conductivity, structural designability and wide application prospect.
Description
Technical Field
The invention relates to a 3D printing method, in particular to a 3D printing stereoscopic aramid aerogel, and a method for preparing the 3D printing stereoscopic aramid aerogel by a novel suspension 3D printing method and application thereof, belonging to the technical field of 3D printing and nano porous materials.
Background
3D printing technology, also known as additive manufacturing technology, is a rapid prototyping technology that starts to rise in the late 80 s of the 20 th century. According to the accurate design of an object by Computer Aided Design (CAD) or tomography (CT), the ink materials are accurately stacked in 3D, and the complex 3D components are printed layer by layer. Compared with the traditional manufacturing mode, the 3D printing technology not only can greatly reduce the production cost, but also breaks through the limitation of the traditional manufacturing technology on complex shapes. As one of the most subverted technologies in the future, 3D printing technology has attracted global attention, and has been widely used in the fields of medical treatment, aerospace, construction, automobiles, and the like.
The 3D printing technology mainly includes a fused deposition technology, an inkjet printing technology, a photo-curing molding technology, a selective laser sintering technology, a direct writing molding technology, and the like. Among these, the direct write molding technique is a squeeze-based 3D printing technique, i.e., layer-by-layer deposition of liquid ink material. The direct writing forming technology can be compatible with various materials, can print various materials at the same time, and has simple equipment, simple and convenient operation and lower cost.
Aerogel is the lightest solid material for world-wide genius records, and is also known as a new material for world-wide changes. The gel material is a gel material with a dispersion medium as gas, and consists of nano-porous which are formed by mutually accumulating colloid particles or high polymer molecules into a network structure. The aramid aerogel has the advantages of high porosity, low density, large specific surface area, good heat insulation performance, excellent mechanical performance, good heat stability, chemical corrosion resistance and the like, and has extremely high application potential in the fields of protective equipment, infrared stealth, heat insulation, motion protection and the like, and although the 3D printing aramid aerogel (with the publication number of CN 110982111A) is prepared by a freezing-direct writing printing method at present, the printing method has the following defects: (1) failure to print three-dimensional structures; (2) print height is limited; (3) The rheological property of the ink is required, namely the ink is required to have certain viscosity and modulus so that the ink can keep a certain shape after extrusion; (4) refrigeration systems are sometimes required, and the energy consumption is high. Therefore, the preparation of the aramid aerogel with a three-dimensional structure by adopting a 3D printing method with low energy consumption, high precision and unlimited size and shape still has serious challenges.
Based on the above, a novel 3D printing technology is developed to overcome the defects of the existing direct-writing forming technology, and the 3D printing stereoscopic aramid aerogel is prepared to meet the needs of practical application, so that the problem which needs to be solved urgently is solved.
Disclosure of Invention
The invention mainly aims to provide a 3D printing stereoscopic aramid aerogel and a method for preparing the 3D printing stereoscopic aramid aerogel by using a suspension 3D printing method, so as to overcome the defects in the existing 3D printing technology, realize self-support of the stereoscopic structural aramid aerogel and expand the application range of the 3D printing and the aramid aerogel.
It is still another object of the present invention to provide the use of the aforementioned 3D printed stereoscopic aramid aerogel.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for preparing a stereoscopic aramid aerogel by suspension 3D printing, which comprises the following steps:
uniformly mixing at least aramid nanofiber, a functional additive and a solvent to form an aramid nanofiber dispersion;
taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix;
through the auxiliary effect of the suspension matrix, the suspension 3D printing is carried out by taking the aramid nanofiber dispersion liquid as 3D printing ink by using a direct writing forming printing method, so that a 3D printed stereoscopic aramid gel component is obtained and is stably placed in the suspension matrix;
and then sequentially carrying out solvent replacement and drying treatment on the 3D printed stereoscopic aramid gel component to obtain the 3D printed stereoscopic aramid aerogel.
In some embodiments, the suspension matrix comprises a primary component and a solvent, preferably further comprising a secondary component.
In some embodiments, the primary component includes, but is not limited to, any one or a combination of two or more of cross-linked polyacrylic acid copolymer, polyacrylamide, polyvinyl alcohol, gelatin, sodium alginate, dimethacrylate-modified polyethylene glycol, silica, lithium magnesium silicate, and the like.
In some embodiments, the adjunct ingredients include, but are not limited to, any one or a combination of two or more of potassium hydroxide, sodium hydroxide, triethanolamine, sodium bicarbonate, ammonia water, calcium chloride, and the like.
Further, the solvent includes one or a combination of two or more of water, ethanol, acetic acid, dimethyl sulfoxide, polyethylene glycol, glycerol, nitrogen methyl pyrrolidone, acetone, and the like.
In some embodiments, the functional additives include, but are not limited to, any one or a combination of two or more of carbon nanotubes, graphene, transition metal nitrides or carbides, metals, silica particles, etc., that impart high electrical conductivity, high thermal conductivity/insulation, light absorption, electromagnetic shielding functions to the final product.
In some embodiments, the method specifically comprises: transferring the 3D printing ink into an injector of a 3D printer, and directly extruding the aramid nanofiber dispersion liquid into the suspension matrix according to a set path by using a direct-writing forming printing method under the auxiliary effect of the suspension matrix at normal temperature to finally obtain the 3D printing stereoscopic aramid gel member.
The embodiment of the invention also provides the 3D printing stereoscopic aramid aerogel prepared by the method, which has a stereoscopic structure and a hierarchical porous aramid nanofiber network structure, wherein the hierarchical porous aramid nanofiber network structure consists of micropores with the aperture below 2nm, mesopores with the aperture of 2-50 nm and macropores with the aperture of 50-10 cm, the 3D printing stereoscopic aramid aerogel has the porosity of 50-99.99% and the density of 0.1-1500 mg/cm 3 Specific surface area of 50-2500 m 2 Per gram, the pore volume is 0.1-15 cm 3 Per gram, the thermal conductivity is 0.025-0.06W/(m) . K)。
The embodiment of the invention also provides application of the 3D printing stereoscopic aramid aerogel in the fields of heat preservation and insulation, catalysis, separation/adsorption, sea water desalination or electromagnetic shielding and the like.
The embodiment of the invention also provides a method for preparing the three-dimensional aerogel by suspension 3D printing, which comprises the following steps:
uniformly mixing at least the nanofibers, the functional additives and the solvent to form nanofiber dispersion;
taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix;
through the auxiliary effect of the suspension matrix, the nanofiber dispersion liquid is used as 3D printing ink for suspension 3D printing by using a direct writing forming printing method, so that a 3D printed stereoscopic gel component is obtained and is stably placed in the suspension matrix;
and then sequentially carrying out solvent replacement and drying treatment on the 3D printed stereoscopic gel component to obtain the 3D printed stereoscopic aerogel.
Compared with the prior art, the invention has the advantages that:
(1) According to the method for preparing the stereoscopic aramid aerogel by suspension 3D printing, a refrigerating system is not needed, printing can be performed at room temperature, energy consumption is low, a suspension matrix is hardly sensitive to temperature, and a system can be used for stably printing;
(2) According to the method for preparing the stereoscopic aramid aerogel by suspension 3D printing, disclosed by the invention, as the ink is extruded out of the needle head, rapid gelation can occur, and the requirements on the viscosity and modulus of the ink are low while the high printing precision is ensured;
(3) The method for preparing the stereoscopic aramid aerogel by suspension 3D printing can print the stereoscopic aramid aerogel with any size and shape, has low energy consumption, high printing precision and simple process, and has universality on various materials;
(4) According to the method for preparing the stereoscopic aramid aerogel by suspension 3D printing, the aperture of the obtained 3D printing stereoscopic aramid aerogel is composed of micropores below 2nm, mesopores between 2 and 50nm and macropores between 50nm and 10cm, the porosity is 1 to 99.99%, the 3D printing stereoscopic aramid aerogel has a stereoscopic structure with large specific surface area, low heat conductivity, ultralow density and designability, can be used in the fields of heat preservation and insulation, catalysis, separation/adsorption, sea water desalination, electromagnetic shielding and the like, and greatly expands the application range of the 3D printing and the aramid aerogel.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic flow chart of preparing a stereoscopic aramid aerogel by suspension 3D printing in an exemplary embodiment of the invention;
FIGS. 2a and 2b are rheological graphs of the suspension matrix obtained in example 1 of the present invention.
FIGS. 3 a-3 c are microscope pictures of 3D printed single aramid hydrogel lines obtained in examples 2, 3, and 4, respectively, of the present invention;
FIG. 4 is an optical photograph of a snail shell type 3D printed stereoscopic aramid gel obtained in example 5 of the present invention;
FIG. 5 is an optical photograph of a hose type 3D printed stereoscopic aramid hydrogel obtained in example 6 of the present invention;
FIG. 6 is an optical photograph of a vase-type 3D printed stereoscopic aramid organogel obtained in example 7 of the present invention;
FIG. 7 is an optical photograph of a pipe-type 3D printed stereoscopic aramid organogel obtained in example 8 of the present invention;
FIG. 8 is an optical photograph of a disc-type 3D printed stereoscopic aramid aerogel obtained in example 9 of the present invention;
FIG. 9 is a surface topography of a 3D printed aramid aerogel obtained in example 10 of the present invention;
FIGS. 10a and 10b show optical photographs of the resulting 3D printed aramid aerogel of comparative example 1 without suspension matrix printing;
fig. 11 shows a surface topography of the resulting 3D printed aramid aerogel of comparative example 2 without silica particles added.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has made long-term researches and a great deal of practices, and has developed a method for preparing a stereoscopic aramid aerogel by suspension 3D printing for the first time, so as to expand the application range of 3D printing and aramid aerogel, and please refer to fig. 1, the method for preparing a stereoscopic aramid aerogel by suspension 3D printing mainly uses an aramid nanofiber dispersion formed by uniformly mixing aramid nanofibers, functional additives and solvents as 3D printing ink, uses a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix, and uses a direct writing forming printing method to suspend the dispersion ink at normal temperature, so as to obtain a 3D printing stereoscopic aramid aerogel by solvent replacement and specific drying technology.
The technical scheme, the implementation process, the principle and the like are further explained as follows.
The method for preparing the stereoscopic aramid aerogel by suspension 3D printing provided by one aspect of the embodiment of the invention comprises the following steps:
uniformly mixing at least aramid nanofiber, a functional additive and a solvent to form an aramid nanofiber dispersion;
taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix;
through the auxiliary effect of the suspension matrix, the suspension 3D printing is carried out by taking the aramid nanofiber dispersion liquid as 3D printing ink by using a direct writing forming printing method, so that a 3D printed stereoscopic aramid gel component is obtained and is stably placed in the suspension matrix;
and then sequentially carrying out solvent replacement and drying treatment on the 3D printed stereoscopic aramid gel component to obtain the 3D printed stereoscopic aramid aerogel.
In some preferred embodiments, the preparation method specifically includes:
uniformly mixing aramid nanofibers, a functional additive and a solvent to form an aramid nanofiber dispersion liquid which is used as 3D printing ink;
taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix;
slicing a model designed by software, and importing a path into a 3D printer;
at normal temperature, suspending 3D printing is carried out on the 3D printing ink by using a direct-writing forming printing method under the auxiliary action of the suspension matrix, so as to obtain a 3D printed stereoscopic aramid gel member;
after the 3D printed stereoscopic aramid gel component is stabilized in a suspension matrix for a period of time, solvent replacement is carried out;
and drying the 3D printing stereoscopic aramid gel subjected to solvent replacement to obtain the 3D printing stereoscopic aramid aerogel.
In some preferred embodiments, the suspension matrix comprises a main component and a solvent.
Further, the suspension matrix also includes an adjunct ingredient.
In some preferred embodiments, the main component of the suspension matrix includes any one or a combination of two or more of cross-linked polyacrylic acid copolymer, polyacrylamide, polyvinyl alcohol, gelatin, sodium alginate, dimethacrylate modified polyethylene glycol, silica, lithium magnesium silicate, etc., but is not limited thereto.
In some preferred embodiments, the auxiliary components of the suspension matrix include any one or a combination of two or more of potassium hydroxide, sodium hydroxide, triethanolamine, sodium bicarbonate, ammonia water, calcium chloride, etc., but are not limited thereto.
Further, the solvent of the suspension matrix includes one or a combination of two or more of water, ethanol, acetic acid, dimethyl sulfoxide, polyethylene glycol, glycerin, azamethylpyrrolidone, acetone, etc., but is not limited thereto.
Further, the concentration of the main component in the suspension matrix is 0.01 to 60wt%, preferably 0.5 to 30wt%.
In some preferred embodiments, the functional additives include, but are not limited to, any one or a combination of two or more of carbon nanotubes, graphene, transition metal nitrides or carbides, metals (e.g., gold particles, silver nanowires, etc.), silica particles, etc., to impart high electrical conductivity, high thermal conductivity/insulation, light absorption, electromagnetic shielding functions to the final product.
In some preferred embodiments, the 3D printing ink further comprises an auxiliary component.
Further, the diameter of the aramid nanofiber is 1 nm-10 mu m, and the length is 5 nm-1 mm.
Further, the solvent includes dimethylsulfoxide, but is not limited thereto.
Further, the main component of the 3D printing ink is an aramid nanofiber/dimethyl sulfoxide dispersion liquid, and the auxiliary component comprises any one or more than two of water, methanol, ethanol, acetone, n-hexane, azamethylpyrrolidone, potassium hydroxide, tert-butyl alcohol and the like, but is not limited thereto.
In some preferred embodiments, the concentration of the aramid nanofiber dispersion is 0.001 to 30wt%, preferably 0.01 to 15wt%.
In some preferred embodiments, the aramid nanofiber dispersion has a plateau storage modulus of 0.1 to 100MPa, a plateau loss modulus of 0.1 to 100MPa, a yield stress of 0.1 to 1000Pa, and a shear rate of 1s -1 Apparent viscosity at 25 ℃ of 0.01 to 1000Pa . s。
In some preferred embodiments, the method specifically comprises: after slicing the model of the software design, the path is imported into a 3D printer, wherein the modeling software used includes but is not limited to any one of AutoCAD, UG NX, solidworks, proE/Creo, etc., and the slicing software used includes but is not limited to any one of Cura, XBuilder, makerbot, simplify3D, slic3r, etc.
In some preferred embodiments, the preparation method specifically includes: transferring the 3D printing ink into an injector of a 3D printer, and directly extruding the aramid nanofiber dispersion liquid into the suspension matrix according to a set path by using a direct-writing forming printing method under the auxiliary effect of the suspension matrix at normal temperature to finally obtain the 3D printing stereoscopic aramid gel member.
In some embodiments, the preparation method of the 3D printing stereoscopic aramid aerogel is to place 3D printing ink in a storage bin of a 3D printer at normal temperature, and print 3D stereoscopic aramid gel with different structures by designing the structure of a computer and importing related programs.
Further, the inside diameter of the needle used for the 3D printing is 10 μm to 5mm, preferably 50 μm to 1500 μm.
Further, the printing speed adopted by the 3D printing is 10 mm/min-10000 mm/min, preferably 500 mm/min-5000 mm/min.
Further, the structure of the 3D printed stereoscopic aramid gel member includes any one or a combination of more than two of a pipeline, a ring, a pyramid, a sphere, an ellipsoid, a cuboid, a snail shell, a hose, a disc, a vase, and the like, but is not limited thereto.
In some preferred embodiments, the preparation method specifically includes: and at normal temperature, solvent replacement is carried out on the 3D printing stereoscopic aramid gel component by using a replacement solvent, so as to obtain the 3D printing stereoscopic aramid hydrogel or organic gel.
Further, the displacement solvent includes, but is not limited to, any one or a combination of two or more of pure water, saline, phosphate buffer, ethanol, acetone, t-butanol, and azamethylpyrrolidone, etc.
In some preferred embodiments, the preparation method specifically includes: and drying the 3D printing stereoscopic aramid hydrogel or the organic gel to obtain the 3D printing stereoscopic aramid aerogel.
In some preferred embodiments, the drying process includes freeze drying and/or supercritical fluid drying, etc., but is not limited thereto.
Further, the 3D printing stereoscopic aramid aerogel is prepared by freeze drying or supercritical drying the 3D printing stereoscopic aramid hydrogel or organic gel.
Further, the freeze-drying cold trap temperature is-100-25 ℃, the vacuum degree is less than 0.1kPa, and the time is 10 min-72 h.
Further, the supercritical fluid is dried for 1-48 hours, and the supercritical fluid used includes any one or more than two of supercritical carbon dioxide, supercritical methanol, supercritical ethanol and the like, but is not limited thereto.
Another aspect of the embodiment of the present invention also provides a 3D printed stereoscopic aramid aerogel prepared by the foregoing method, having a stereoscopic structure and having a hierarchical porous aramid nanofiber network structure composed of micropores having a pore diameter of 2nm or less, mesopores having a pore diameter of 2nm to 50nm, and macropores having a pore diameter of 50nm to 10cm, the 3D printed stereoscopic aramid aerogel having a porosity of 50 to 99.99% and a density of 0.1 to 1500mg/cm 3 Specific surface area of 50-2500 m 2 Per gram, the pore volume is 0.1-15 cm 3 Per g, a thermal conductivity of [ 0.025-0.06W/(m) . K)]。
Another aspect of the embodiment of the invention also provides application of the 3D printing stereoscopic aramid aerogel in the fields of heat preservation and insulation, catalysis, separation/adsorption, sea water desalination, electromagnetic shielding and the like.
In particular, in said applications, at least part of the components thereof employ the aforementioned 3D printed stereoscopic aramid aerogel.
Another aspect of the embodiment of the present invention also provides a method for preparing a stereoscopic aerogel by suspension 3D printing, which includes:
uniformly mixing at least the nanofibers, the functional additives and the solvent to form nanofiber dispersion;
taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix;
through the auxiliary effect of the suspension matrix, the nanofiber dispersion liquid is used as 3D printing ink for suspension 3D printing by using a direct writing forming printing method, so that a 3D printed stereoscopic gel component is obtained and is stably placed in the suspension matrix;
and then sequentially carrying out solvent replacement and drying treatment on the 3D printed stereoscopic gel component to obtain the 3D printed stereoscopic aerogel.
In some preferred embodiments, the preparation method specifically includes:
uniformly mixing a nano material, a functional additive and a solvent to form a dispersion liquid which is used as 3D printing ink;
taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix;
slicing a model designed by software, and importing a path into a 3D printer;
at normal temperature, suspending 3D printing is carried out on the dispersion liquid ink by using a direct-writing forming printing method under the auxiliary action of the suspension matrix, so as to obtain a 3D printed stereoscopic gel member;
after the 3D printed stereoscopic gel component is stabilized in a matrix for a period of time, solvent replacement is carried out;
and drying the 3D printing stereoscopic gel subjected to solvent replacement to obtain the 3D printing stereoscopic aerogel.
Further, the nanomaterial in the 3D printing ink includes any one or a combination of more than two of aramid nanofibers, graphene oxide, sodium alginate, polyethylene glycols, collagen and the like, but is not limited thereto.
Further, the functional additives in the 3D printing ink include, but are not limited to, any one or a combination of two or more of carbon nanotubes, graphene, transition metal nitrides or carbides, metals, silica particles, etc., so as to impart high electrical conductivity, high thermal conductivity/insulation, light absorption, electromagnetic shielding functions to the final product.
According to the method for preparing the stereoscopic aramid aerogel by suspension 3D printing, a refrigerating system is not needed, printing can be performed at room temperature, energy consumption is low, a suspension matrix is hardly sensitive to temperature, and a system can be used for stably printing.
According to the method for preparing the stereoscopic aramid aerogel by suspension 3D printing, disclosed by the invention, as the ink is extruded out of the needle head, rapid gelation can occur, and the requirements on the viscosity and the modulus of the ink are low while the high printing precision is ensured.
The method for preparing the stereoscopic aramid aerogel by suspension 3D printing can print the stereoscopic aramid aerogel with any size and shape, has low energy consumption, high printing precision and simple process, and has universality on various materials.
According to the method for preparing the stereoscopic aramid aerogel by suspension 3D printing, the aperture of the obtained 3D printing stereoscopic aramid aerogel is composed of micropores below 2nm, mesopores between 2 and 50nm and macropores between 50nm and 10cm, the porosity is 1 to 99.99%, the 3D printing stereoscopic aramid aerogel has a stereoscopic structure with large specific surface area, low heat conductivity, ultralow density and designability, can be used in the fields of heat preservation and insulation, catalysis, separation/adsorption, sea water desalination, electromagnetic shielding and the like, and greatly expands the application range of the 3D printing and the aramid aerogel.
In summary, by the above technical scheme, the method for preparing the stereoscopic aramid aerogel by suspension 3D printing provided by the invention uses an aramid nanofiber dispersion liquid formed by uniformly mixing aramid nanofibers, functional additives and solvents as 3D printing ink, uses a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix, and uses a direct writing forming printing method to carry out suspension 3D printing on the dispersion liquid ink at normal temperature, and then obtains the 3D printing stereoscopic aramid aerogel by solvent replacement and a specific drying technology. The 3D printing stereoscopic aramid aerogel can be used in the fields of heat preservation and insulation, catalysis, separation/adsorption, sea water desalination, electromagnetic shielding and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments, and those skilled in the art may adapt to the actual situation. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The test methods in the following examples, in which no specific conditions are noted, were all conducted under conventional conditions. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
(1) 30wt% aramid nanofiber/carbon nanotube/dimethyl sulfoxide/water mixed dispersion was used as 3D printing ink.
(2) 20wt% of silica was thoroughly mixed with polyethylene glycol to prepare a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a circular ring structure is designed through a computer, related programs are led in, a needle head with the inner diameter of 5mm is adopted, the printing speed is 5000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And after the 3D printing stereoscopic aramid gel is subjected to solvent replacement by water, freeze-drying at-100 ℃ for 72 hours to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 85% and a density of 50mg/cm 3 A specific surface area of 1500m 2 Per g, pore volume of 8cm 3 Per g, a thermal conductivity of 0.04W/(m) . K)。
Fig. 2a and 2b show the rheology curves of the suspension matrix obtained in step (2) of this example.
Example 2
(1) 1wt% aramid nanofiber/graphene/dimethyl sulfoxide/ethanol mixed dispersion was used as 3D printing ink.
(2) After 0.01wt% gelatin was fully swollen in water, it was used as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a spiral structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 800 mu m is adopted, the printing speed is 1000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And after the 3D printing stereoscopic aramid gel is subjected to solvent replacement by water, performing freeze drying at the temperature of 50 ℃ below zero for 10min to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 80% and a density of 500mg/cm 3 Specific surface area of 1200m 2 Per g, pore volume of2cm 3 Per g, a thermal conductivity of 0.045W/(m) . K)。
Fig. 3a is a microscopic image of a 3D printed single aramid hydrogel line obtained after solvent substitution with water in step (4) of this example.
Example 3
(1) 0.1wt% aramid nanofiber/graphene/dimethyl sulfoxide/potassium hydroxide mixed dispersion was used as 3D printing ink.
(2) 0.5wt% polyacrylamide was fully swollen in acetic acid as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a spiral structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 500 mu m is adopted, the printing speed is 3000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel by using a phosphate buffer solution, and performing freeze drying at the temperature of 50 ℃ below zero for 36 hours to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 80% and a density of 100mg/cm 3 Specific surface area of 1000m 2 Per g, pore volume of 1cm 3 Per g, a thermal conductivity of 0.047W/(m) . K)。
Fig. 3b is a microscopic image of a 3D printed single aramid hydrogel line obtained after solvent replacement with phosphate buffer in step (4) of this example.
Example 4
(1) 0.01wt% aramid nanofiber/transition metal nitride/dimethyl sulfoxide/n-hexane mixed dispersion was used as 3D printing ink.
(2) 10wt% polyvinyl alcohol was fully swollen in glycerol and used as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a spiral structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 310 mu m is adopted, the printing speed is 5000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel by using saline, and performing freeze drying at the temperature of minus 100 ℃ for 72 hours to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 95% and a density of 1mg/cm 3 Specific surface area of 2000m 2 Per g, pore volume of 12cm 3 /g, a thermal conductivity of 0.035W/(m) . K)。
Fig. 3c is a microscopic image of a 3D printed single aramid hydrogel line obtained after solvent substitution with brine in step (4) of this example.
Example 5
(1) 1wt% aramid nanofiber/gold particle/dimethyl sulfoxide/water mixed dispersion was used as 3D printing ink.
(2) 10wt% sodium alginate was fully swelled in dimethyl sulfoxide and used as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a snail shell structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 400 mu m is adopted, the printing speed is 2000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel by using ethanol, and drying for 24 hours by using supercritical carbon dioxide to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 65% and a density of 1000mg/cm 3 A specific surface area of 50m 2 Per g, pore volume of 0.1cm 3 Per gram, a thermal conductivity of 0.055W/(m) . K)。
Fig. 4 is an optical photograph of the snail shell type 3D printed stereoscopic aramid gel obtained in step (3) of the present example.
Example 6
(1) 15wt% aramid nanofiber/silver nanowire/dimethyl sulfoxide/ethanol mixed dispersion was used as 3D printing ink.
(2) 30wt% of silicon dioxide is fully dispersed in polyethylene glycol, a certain amount of ammonia water is added, and the mixture is uniformly mixed to be used as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a hose-type structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 10 mu m is adopted, the printing speed is 10mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And after the 3D printing stereoscopic aramid gel is subjected to solvent replacement by water, freeze-drying at-50 ℃ for 24 hours to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 75% and a density of 1200mg/cm 3 Specific surface area of 1000m 2 Per g, pore volume of 5cm 3 Per g, a thermal conductivity of 0.05W/(m) . K)。
FIG. 5 is an optical photograph of the hose type 3D printed stereoscopic aramid hydrogel obtained by the solvent substitution with water in the step (4) of this example.
Example 7
(1) 0.05wt% aramid nanofiber/silica particles/dimethyl sulfoxide/azamethylpyrrolidone mixed dispersion was used as 3D printing ink.
(2) 5wt% of lithium magnesium silicate was thoroughly dispersed in water, and a certain amount of sodium bicarbonate was added thereto, and uniformly mixed to prepare a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a vase-type structure is designed through a computer, related programs are led in, a needle head with the inner diameter of 330 mu m is adopted, the printing speed is 1000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel by using tertiary butanol, and performing freeze drying at 25 ℃ for 72 hours to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed stereoscopic aramid aerogel obtained in the embodiment has the porosity of 99.99% and the density of 0.1mg/cm 3 Specific surface area of 2500m 2 Per gram, pore volume of 15cm 3 Per g, a thermal conductivity of 0.025W/(m) . K)。
FIG. 6 is an optical photograph of a vase-type 3D-printed stereoscopic aramid organogel obtained by solvent-displacing t-butanol in step (4) of this example.
Example 8
(1) 0.5wt% aramid nanofiber/transition metal carbide/dimethyl sulfoxide/ethanol mixed dispersion was used as 3D printing ink.
(2) 20wt% of silica was well dispersed in polyethylene glycol and a certain amount of triethanolamine was added, and the mixture was homogeneously mixed to prepare a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a pipeline structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 810 mu m is adopted, the printing speed is 10000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel by using ethanol, and drying for 1h by using supercritical carbon dioxide to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 90% and a density of 10mg/cm 3 A specific surface area of 1800m 2 Per g, pore volume of 10cm 3 Per g, a thermal conductivity of 0.037W/(m) . K)。
FIG. 7 is an optical photograph of a pipe-type 3D-printed stereoscopic aramid organogel obtained by solvent-displacing with ethanol in the step (4) of this example.
Example 9
(1) 1wt% aramid nanofiber/silver nanowire/dimethyl sulfoxide/t-butyl alcohol methyl mixed dispersion was used as 3D printing ink.
(2) 1wt% of the crosslinked polyacrylic acid copolymer was sufficiently swelled in glycerin, and a certain amount of potassium hydroxide was added, and after mixing uniformly, it was used as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a disc-type structure is designed through a computer, related programs are led in, a needle head with the inner diameter of 810 mu m is adopted, the printing speed is 8000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel, and drying for 36h through supercritical carbon dioxide to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed aramid aerogel obtained in this example had a porosity of 50% and a density of 1500mg/cm 3 Specific surface area of 100m 2 Per g, pore volume of 0.1cm 3 Per gram, a thermal conductivity of 0.06W/(m) . K)。
Fig. 8 is an optical photograph of the disc type 3D printed stereoscopic aramid aerogel obtained in this example.
Example 10
(1) 0.001wt% aramid nanofiber/silica particles/dimethyl sulfoxide/potassium hydroxide mixed dispersion was used as 3D printing ink.
(2) 60wt% of the crosslinked polyacrylic acid copolymer is fully swelled in water, and a certain amount of sodium hydroxide is added to be uniformly mixed to be used as a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a cylindrical structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 330 mu m is adopted, the printing speed is 3000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel, and drying for 48 hours through supercritical methanol to obtain the 3D printing stereoscopic aramid aerogel.
The 3D printed stereoscopic aramid aerogel obtained in the embodiment has the porosity of 98% and the density of 100mg/cm 3 Specific surface area of 2000m 2 Per g, pore volume of 12cm 3 Per gram, a thermal conductivity of 0.03W/(m) . K)。
Fig. 9 is a surface topography of the 3D printed stereoscopic aramid aerogel obtained in this example.
Through the embodiments 1 to 10, it can be found that the suspension 3D printing preparation method obtained by the technical scheme of the invention has the advantages of being capable of printing any size and shape, low in energy consumption, high in printing precision, simple in process, and having excellent performances such as universality on various materials, and the obtained 3D printing stereoscopic aramid aerogel has a hierarchical porous structure, ultralow density, large specific surface area, low thermal conductivity, structural designability and the like.
In addition, the inventor also refers to examples 1-10 to perform experiments with other raw materials and conditions listed in the specification, and also prepare the 3D printing stereoscopic aramid aerogel with hierarchical porous structure, ultra-low density, large specific surface area, low thermal conductivity and structural designability. The suspension 3D printing method provided by the invention has the advantages of capability of printing any size and shape, low energy consumption, high printing precision, simple process, universality for various materials and the like.
Comparative example 1
(1) Taking 1wt% of aramid nanofiber/gold particle/dimethyl sulfoxide/water mixed dispersion as 3D printing ink;
(2) The ink is placed in a storage bin of a 3D printer, a firewood pile structure is designed through a computer, related programs are led in, a needle head with the inner diameter of 400 mu m is adopted, the printing speed is 2000mm/min, and the ink is directly printed on a substrate according to a set path at normal temperature.
(3) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel by using ethanol, and drying for 24 hours by using supercritical carbon dioxide to obtain the 3D printing aramid aerogel.
This comparative example differs from example 5 in that: no suspension matrix was used. The method of the comparative example cannot print out a three-dimensional snail shell-shaped structure, so that a firewood pile-type structure is adopted.
Fig. 10a and 10b are optical photographs of the 3D printed aramid aerogel of the firewood stack obtained in step (3) of this comparative example.
Comparative example 2
(1) Taking 0.001wt% of aramid nanofiber/dimethyl sulfoxide/potassium hydroxide mixed dispersion as 3D printing ink;
(2) 60wt% of the crosslinked polyacrylic acid copolymer was fully swelled in water, and a certain amount of potassium hydroxide was added, and the mixture was uniformly mixed to prepare a suspension matrix.
(3) The ink is placed in a storage bin of a 3D printer, a cylindrical structure is designed through a computer, a related program is led in, a needle head with the inner diameter of 330 mu m is adopted, the printing speed is 3000mm/min, and the ink is printed into a suspension matrix according to a set path at normal temperature.
(4) And (3) performing solvent replacement on the 3D printing stereoscopic aramid gel, and drying for 48 hours through supercritical methanol to obtain the 3D printing stereoscopic aramid aerogel.
Comparative example and realityExample 10 differs in that: no functional additive silica particles were added. The 3D printing aramid aerogel obtained in the comparative example has a porosity of 40% and a density of 1800mg/cm 3 Specific surface area of 30m 2 Per g, pore volume of 0.01cm 3 Per g, a thermal conductivity of 0.1W/(m) . K)。
Fig. 11 is a surface topography of the cylindrical 3D printed stereoscopic aramid aerogel obtained in step (4) of the present comparative example.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (13)
1. The method for preparing the stereoscopic aramid aerogel by suspension 3D printing is characterized by comprising the following steps of:
uniformly mixing at least aramid nanofibers, functional additives and a solvent to form an aramid nanofiber dispersion, wherein the functional additives are selected from any one or more than two of carbon nanotubes, graphene, transition metal nitrides or carbides, metals and silicon dioxide particles, the solvent is dimethyl sulfoxide, the concentration of the aramid nanofiber dispersion is 0.001-30wt%, the platform storage modulus of the aramid nanofiber dispersion is 0.1-100 MPa, the platform loss modulus is 0.1-100 MPa, the yield stress is 0.1-1000 Pa, and the shear rate is 1s -1 Apparent viscosity at 25 ℃ of 0.01-1000 Pa . s；
Taking a matrix with thixotropic property, shear thinning property and rapid solid-liquid conversion as a suspension matrix, wherein the suspension matrix comprises a main component and a solvent, wherein the main component is selected from any one or more than two of cross-linked polyacrylic acid copolymer, polyacrylamide, polyvinyl alcohol, gelatin, sodium alginate, dimethacrylate modified polyethylene glycol, silicon dioxide and magnesium lithium silicate, the solvent is selected from one or more than two of water, ethanol, acetic acid, dimethyl sulfoxide, polyethylene glycol, glycerol, azomethylpyrrolidone and acetone, and the concentration of the main component in the suspension matrix is 0.01-60 wt%;
through the auxiliary effect of the suspension matrix, the suspension 3D printing is carried out by taking the aramid nanofiber dispersion liquid as 3D printing ink by using a direct writing forming printing method, a 3D printed stereoscopic aramid gel component is obtained and is stably placed in the suspension matrix, wherein the inner diameter of a needle used for suspension 3D printing is 10 mu m-5 mm, and the printing speed used for suspension 3D printing is 10 mm/min-10000 mm/min;
and then sequentially carrying out solvent replacement and drying treatment on the 3D printed stereoscopic aramid gel component to obtain the 3D printed stereoscopic aramid aerogel.
2. The method according to claim 1, characterized in that: the suspension matrix also comprises auxiliary components, wherein the auxiliary components comprise any one or more than two of potassium hydroxide, sodium hydroxide, triethanolamine, sodium bicarbonate, ammonia water and calcium chloride.
3. The method according to claim 1, characterized in that: the concentration of the main component in the suspension matrix is 0.5-30wt%.
4. The method according to claim 1, characterized in that: the diameter of the aramid nanofiber is 1 nm-10 mu m, and the length of the aramid nanofiber is 5 nm-1 mm.
5. The method according to claim 1, characterized in that: the concentration of the aramid nanofiber dispersion liquid is 0.01-15 wt%.
6. The method according to claim 1, characterized in that: the 3D printing ink further comprises auxiliary components, wherein the auxiliary components comprise any one or more than two of water, methanol, ethanol, acetone, n-hexane, azomethylpyrrolidone, potassium hydroxide and tert-butyl methyl alcohol.
7. The method according to claim 1, characterized in that it comprises in particular: after slicing the model designed by the software, the path is imported into a 3D printer, wherein the adopted modeling software comprises any one of AutoCAD, UG NX and Solidworks, proE/Creo, and the adopted slicing software comprises any one of Cura, XBuilder, makerbot, simplify3D, slic3 r.
8. The method according to claim 7, characterized in that it comprises in particular: transferring the 3D printing ink into an injector of a 3D printer, and directly extruding the aramid nanofiber dispersion liquid into the suspension matrix according to a set path by using a direct-writing forming printing method under the auxiliary action of the suspension matrix at normal temperature to finally obtain the 3D printing stereoscopic aramid gel member, wherein the inner diameter of a needle adopted for 3D printing is 50-1500 mu m, and the printing speed adopted for 3D printing is 500 mm/min-5000 mm/min.
9. The method according to claim 8, wherein: the structure of the 3D printed stereoscopic aramid gel component comprises any one or more than two of a pipeline, a circular ring, a pyramid, a sphere, a cuboid, a snail shell, a disc and a vase.
10. The method according to claim 1, characterized in that it comprises in particular: at normal temperature, solvent replacement is carried out on the 3D printing stereoscopic aramid gel component by using a replacement solvent, so as to obtain 3D printing stereoscopic aramid hydrogel or organogel; the replacement solvent comprises any one or more than two of pure water, saline, phosphate buffer solution, ethanol, acetone, tertiary butanol and nitrogen methyl pyrrolidone.
11. The method according to claim 10, characterized in that it comprises in particular: drying the 3D printing stereoscopic aramid fiber hydrogel or the organic gel to obtain 3D printing stereoscopic aramid fiber aerogel;
and/or the drying treatment comprises freeze drying and/or supercritical fluid drying; the temperature of the freeze-dried cold trap is-100-25 ℃, the vacuum degree is less than 0.1kPa, and the time is 10 min-72 h; the supercritical fluid is dried for 1-48 h, and the supercritical fluid comprises any one or more than two of supercritical carbon dioxide, supercritical methanol and supercritical ethanol.
12. A 3D printed stereoscopic aramid aerogel prepared by the method of any one of claims 1-11 having a stereoscopic structure and having a hierarchical porous aramid nanofiber network structure consisting of pore sizesMicropores below 2nm, mesopores with the aperture of 2-50 nm and macropores with the aperture of 50-10 cm, wherein the 3D printing stereoscopic aramid aerogel has the porosity of 50-99.99% and the density of 0.1-1500 mg/cm 3 Specific surface area of 50-2500 m 2 Per gram, the pore volume is 0.1-15 cm 3 Per g, a thermal conductivity of 0.025 to 0.06W/(m) . K)。
13. The use of the 3D printed stereoscopic aramid aerogel of claim 12 in the fields of thermal insulation, catalysis, separation/adsorption, sea water desalination or electromagnetic shielding.
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