CN115611273B - Porous framework with multi-radial microstructure and preparation method and application thereof - Google Patents
Porous framework with multi-radial microstructure and preparation method and application thereof Download PDFInfo
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- CN115611273B CN115611273B CN202211082582.3A CN202211082582A CN115611273B CN 115611273 B CN115611273 B CN 115611273B CN 202211082582 A CN202211082582 A CN 202211082582A CN 115611273 B CN115611273 B CN 115611273B
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- porous
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- 239000013354 porous framework Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 238000011282 treatment Methods 0.000 claims abstract description 55
- 239000000945 filler Substances 0.000 claims abstract description 52
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 238000007710 freezing Methods 0.000 claims abstract description 27
- 230000008014 freezing Effects 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005520 cutting process Methods 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000005498 polishing Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 54
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
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- 239000007788 liquid Substances 0.000 claims description 11
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- 238000000498 ball milling Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000005057 refrigeration Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
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- 238000005303 weighing Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000011231 conductive filler Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
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- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
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- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound 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 2
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- 230000006835 compression Effects 0.000 abstract description 13
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 45
- 229910021389 graphene Inorganic materials 0.000 description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 229910052742 iron Inorganic materials 0.000 description 21
- 239000002042 Silver nanowire Substances 0.000 description 20
- 238000012546 transfer Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052582 BN Inorganic materials 0.000 description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000002609 medium Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 4
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- 229910052786 argon Inorganic materials 0.000 description 3
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- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 238000005266 casting Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012595 freezing medium Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0605—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances by sublimating
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Structural Engineering (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
A porous skeleton with multi-radial microstructure, a preparation method and application thereof belong to the technical field of porous materials. The preparation method of the porous framework comprises the following steps: mixing the filler, the binder and water to obtain a filler mixture; pre-placing the multi-radial orientation forming device into a low-temperature refrigerating medium, adding the filler mixture into the multi-radial orientation forming device, performing freezing treatment to form a frozen mixture, and performing freeze drying treatment to obtain a porous skeleton precursor; sintering heat treatment is carried out to obtain a porous framework; cutting and polishing to remove the convex part below the bottom, thus obtaining the porous skeleton with multi-radial microstructure. The porous skeleton has a vivid multi-radial microstructure, ensures an ordered three-dimensional transmission network, simultaneously remarkably improves the compression resilience performance of the structure, and can be used as a heat-conducting filler and an adsorption medium. The invention has the advantages of wide application range, simple preparation process, controllable preparation structure, relatively mild reaction conditions and high yield.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a porous framework with a multi-radial microstructure, and a preparation method and application thereof.
Background
The porous skeleton has low density, high specific surface area, high aperture ratio and other features, and may be used widely in adsorption separation, heat insulation, heat conduction, energy storage, biological tissue and other fields. The microstructure including microstructure morphology, skeleton orientation, pore size distribution, size and other parameters have great influence on the final performance of the porous skeleton, so that the design and control of the microstructure of the porous skeleton are very important.
Freezing casting, also known as ice template method, is a widely used technique that has been widely used to make various porous materials from ceramics, metals, polymers, biological macromolecules and carbon materials. By freezing the mixture containing the filler, the ice crystals solidify along a temperature gradient on the filler side, during which process the ice crystals are able to redistribute the filler locations, effectively forming the desired porous microstructure. Traditional freeze casting mainly yields two structures: vertically oriented (low filler content) and cellular (high filler content) microstructures. Both of the above structures have significant disadvantages:
(1) Vertically oriented structures have an oriented microstructure in the axial direction, and are generally limited by their own anisotropy. Many application scenarios require isotropic porous frameworks, which not only need to exhibit good mass transfer performance in the axial direction, but also ensure the regularity of the mass transfer channels in the radial direction.
(2) The number of interfaces in the honeycomb structure is large, and mass transfer channels are blocked, resulting in poor mass transfer performance. The adjacent interfaces at the nodes form mechanical coupling, and once the microstructure is subjected to external force, the microstructure is easy to collapse and the compression resilience is poor.
The porous skeleton with the multi-radial microstructure overcomes the problems, improves the mechanical strength and compression resilience under the condition of guaranteeing an isotropic mass transfer channel, and meets the complex requirements of the existing application scene on the performance of the porous skeleton. Therefore, the invention has very important significance and application prospect in a simple, rapid and universal method for preparing the porous framework with the multi-radial microstructure.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a general method for preparing the porous framework with the multi-radial microstructure, which provides a new thought for optimizing the microstructure of the porous framework and the technical process of the traditional ice template method and solves the technical bottleneck at present. The porous skeleton prepared by the method has a vivid multi-radial microstructure, ensures an ordered three-dimensional transmission network, and simultaneously remarkably improves the compression resilience performance of the structure, and can be used as a heat conduction filler and an adsorption medium. The invention has the advantages of wide application material range, simple preparation process, controllable preparation structure, relatively mild reaction condition and high yield, and has good application prospect in various fields.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in one aspect, the present invention provides a method for preparing a porous scaffold having a multi-radial microstructure, comprising the steps of:
(1) Weighing filler and water, optionally weighing binder, and mixing to obtain filler mixture; if there is a strong interaction force, such as hydrogen bonding, between the fillers, no binder is needed.
(2) Taking a multi-radial orientation forming device, putting the multi-radial orientation forming device into a low-temperature refrigerating medium in advance, filling the filler mixture obtained in the step (1) into the multi-radial orientation forming device, performing freezing treatment to form a frozen mixture, and performing freeze drying treatment on the frozen mixture to obtain a porous skeleton precursor;
(3) And (3) optionally sintering the porous skeleton precursor obtained in the step (2) to obtain a porous skeleton, and cutting and polishing to obtain the porous skeleton with the radial microstructure. The sintering process is performed according to the application scenario of the porous skeleton. If the porous skeleton requires good compression resilience, the porous skeleton does not need sintering treatment; if a good mass transfer behaviour is required for the porous skeleton, a sintering process is required.
In the preparation method, the filler in the step (1) is any substance which does not react with water at normal temperature; preferably, the filler is one or more of boron nitride, silicon carbide, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, graphene, carbon nanotubes, diamond, silver nanoparticles and copper nanowires; more preferably, the appearance of the filler is granular, linear or flaky, and the size of the filler is 10 nm-500 mu m; the mass ratio of the filler to the water to the binder is 1: 4-100: 0 to 0.3.
The binder comprises polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose; the binder has the following functions: (1) The adhesive can effectively increase the viscosity of the filler mixture and slow down the sedimentation speed of the filler, so that the frozen product has a uniform microstructure; (2) The adhesive can effectively improve the mechanical property of the porous framework and endow the porous framework with good compression rebound resilience; (3) The binder is selected to ensure that the porous framework does not collapse in the subsequent heat sintering treatment process. Preferably, if there is a strong interaction force between the fillers, such as hydrogen bonding, no binder is needed.
The modes of mixing treatment include ultrasonic, mechanical stirring and planetary ball milling. When the filler content or binder content is low, the viscosity of the mixture is low and a uniformly dispersed mixture of filler can be prepared using ultrasound, mechanical stirring or a combination thereof. When the filler content or the binder content is high, the viscosity of the mixture is high, and conventional ultrasonic or mechanical stirring cannot uniformly disperse the filler, so that planetary ball milling equipment is required to prepare the mixture.
In the preparation method, the multi-radial orientation forming device in the step (2) mainly comprises a metal cylinder ring, a porous polymer round gasket, a solid metal cylinder and an aluminum foil adhesive tape. The bottom of the metal cylinder ring is sealed by an aluminum foil tape, the porous polymer circular gasket is placed at the bottom of the metal cylinder ring and is in close contact with the aluminum foil tape, and the solid metal cylinder is placed in the hole of the porous polymer circular gasket. The metal cylinder ring and the solid metal cylinder have good heat conduction performance, and can form radial temperature gradient after being contacted with a low-temperature refrigeration medium, so that ice crystals are promoted to grow along the periphery of the cylinder ring to the center of the cylinder ring and along the center of the metal cylinder to the periphery. The aluminum foil tape has good heat conduction performance, can form an axial temperature gradient after being contacted with a low-temperature refrigeration medium, and is easy to detach.
According to the preparation method, the diameter of the porous polymer circular gasket is equal to the inner diameter of the metal cylinder ring, the diameter of the hole in the porous polymer circular gasket is equal to the diameter of the solid metal cylinder, and the height of the solid metal cylinder is larger than that of the metal cylinder ring;
The length ratio of the inner diameter to the height of the metal cylindrical ring is 0.1-10: 1, the length ratio of the outer diameter to the inner diameter of the metal cylindrical ring is 1.01-1.5: 1, a step of;
The length ratio (m) of the hole diameter (D) of the polymer circular gasket to the inner diameter (D) of the metal cylinder ring is 0.05-0.95: 1, a step of; preferably, the length ratio (m) of the hole diameter of the polymer circular gasket to the inner diameter of the metal cylindrical ring is 0.1-0.5: 1, a step of; the ratio of the pore diameter of the polymeric circular shim to the length of the inner diameter of the metal cylindrical ring determines the structural anisotropy ratio of the three-dimensional skeleton and the number of radial microstructures. Each hole in the polymer spacer corresponds to a radial microstructure. Thus, the smaller the length ratio (m), the greater the upper limit of the number of holes in the polymer gasket and the number of metal cylinders, and the greater the upper limit of the number of radial microstructures, and the greater the regulatory capability on the microstructures.
The holes in the polymer circular gasket are arranged in a central symmetry manner, and the number of the holes is n=1+2x, wherein x is less than or equal to 160; preferably, x is less than or equal to 40; the length ratio (m) determines the upper limit of the number of pores, and the pore size and the number of pores determine the specific microscopic morphology of the three-dimensional skeleton. The increase of the n value is beneficial to compression retraction elastic energy and capillary adsorption capacity; the effect of the increase of the n value on the heat conduction capacity is not a single trend, and a critical value exists under specific conditions, and the heat conduction capacity is enhanced to the greatest extent at the critical value.
The nearest distance s between adjacent holes in the polymer circular gasket is defined as the distance between the centers of two holes, s is more than or equal to 2d, wherein d is the diameter of the hole in the polymer circular gasket. Sufficient growth of ice crystals in the radial direction can be ensured, making the three-dimensional skeleton structure more isotropic.
The metal materials of the metal cylinder ring and the solid metal cylinder are any metal substance or alloy composed of a plurality of metal substances which do not react with water at normal temperature; preferably, the metal materials of the metal cylindrical ring and the solid metal cylinder comprise steel, copper alloy, tin-nickel-copper alloy, silver, gold, aluminum, iron, zinc alloy, tin and lead;
The polymer in the porous polymer circular gasket is any polymer which does not react with water at normal temperature; preferably, the polymer in the porous polymeric circular gasket comprises epoxy, polyurethane, phenolic, unsaturated polyester, amino, polyethylene, polypropylene, polyvinyl chloride, polystyrene or polysiloxane. The polymer gasket has two functions: (1) The polymer has low heat conduction and poor heat transfer effect, prevents the formation of axial temperature gradient and promotes the growth of ice crystals mainly in the radial direction; (2) The polymer shim was perforated to hold the solid metal cylinder in a vertical orientation and was in contact with the aluminum foil tape.
The preparation method comprises the following specific operations of the porous skeleton precursor obtained in the step (2): taking a multi-radial orientation forming device, putting the multi-radial orientation forming device into a low-temperature refrigerating medium in advance, filling a filler mixture into the multi-radial orientation forming device, performing freezing treatment, taking out a solid metal cylinder in the multi-radial orientation forming device, adding the filler mixture into the multi-radial orientation forming device again, performing freezing treatment to form a frozen mixture, and performing freeze drying treatment to obtain the porous skeleton precursor. In the first freezing treatment process, the metal cylinder ring and the solid metal cylinder simultaneously induce radial temperature gradient to promote the radial growth of ice crystals. In the second freezing treatment process, after the solid metal cylinder is taken out, the filler mixture is poured into the cavity left by the metal cylinder, and the aluminum foil tape is contacted with the freezing medium to induce an axial temperature gradient so as to promote the axial growth of ice crystals. The frozen product has smooth surface on one side and salient points on the surface on the other side, and the salient points correspond to the fixing parts of the metal cylinder in the polymer gasket.
The low-temperature refrigeration medium is at least one of dry ice, liquid nitrogen or liquid helium;
the freezing treatment is to drop the filler mixture into a multi-radial orientation forming device and indirectly contact the filler mixture with a low-temperature refrigeration medium, so that a continuous self-assembly forming process is initiated; the water in the mixture forms ice crystals along the temperature gradient, which squeeze the filler during growth, thereby forming the filler into a three-dimensional skeleton with a specific microstructure.
The freeze-drying treatment is to put the frozen mixture into a freeze dryer to sublimate the ice.
The sintering treatment conditions in the step (3) are as follows: performing first sintering under the inert gas atmosphere at the temperature of 200-450 ℃ for 1-8 h; the sintering process removes the binder through a thermal cracking process and ensures that the porous framework does not collapse. And after the completion, performing second sintering under the atmosphere of mixed gas or inert gas of hydrogen and nitrogen at the temperature of 450-2500 ℃ for 1-12 h. The mixed atmosphere of hydrogen and nitrogen is directed to a metal with relatively high activity, which is oxidized to some extent when placed in air or during the first sintering process, and the oxidized metal can be reduced by sintering with hydrogen. Inert atmospheres are directed to materials with higher chemical stability. Preferably, the inert gas is at least one of helium, nitrogen and argon.
The cutting and polishing treatment comprises the step of treating the lateral salient points of the porous framework by using a linear cutting machine and a polishing machine.
In a second aspect, the present invention provides a porous scaffold having a multi-radial microstructure, obtainable by any of the preparation methods described herein.
In a third aspect, the present invention provides the use of the porous scaffold with multi-radial microstructures as a thermally conductive filler and an adsorption medium.
Compared with the prior art, the invention has the following beneficial effects:
1. Compared with the structure prepared by the traditional ice template method, the porous skeleton with the multi-radial microstructure has more regular and straight-through radial and axial mass transfer channels, thereby showing good mass transfer performance. In addition, the heat conductive filler in the porous skeleton of the present invention has a three-dimensional skeleton structure, and exhibits better compression resilience in the axial direction. As the heat conducting filler, the heat conductivity of the compound in the radial direction and the axial direction can be effectively improved, and the heat conducting filler can be applied to the thermal interface material industry as a good high heat conducting filler framework. As an adsorption medium, the straight-through mass transfer channel provides better capillary force and can adsorb target substances faster.
2. According to the preparation method of the porous framework with the multi-radial microstructure, provided by the invention, the filler, the binder and the water are mixed to form the uniform filler mixture, and the filler mixture is subjected to freezing treatment, freeze drying, sintering heat treatment and polishing, so that the preparation method is wide in applicable material range, controllable in porous framework size, simple in preparation process and relatively mild in reaction condition, the technical bottlenecks of narrow applicable material range and complex preparation process of the conventional common method are effectively solved, and the application prospect of the porous framework in various fields is widened.
Drawings
FIG. 1 is a flow chart of a general method for preparing a porous skeleton with multiple radial microstructures;
FIG. 2 is a schematic diagram illustrating the dimensions of a multi-radial orientation molding apparatus according to the present invention;
FIG. 3 is a schematic structural view of a porous skeleton with multiple radial microstructures according to the present invention;
FIG. 4 is a schematic diagram of the structures of the products prepared in comparative examples 1 and 2.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The method specifically comprises the following implementation steps:
a general method for preparing a porous skeleton with multiple radial microstructures, the process steps of which are shown in fig. 1, comprises the following steps:
S01, mixing the filler, the binder and water to obtain a filler mixture.
S02, sealing the bottom of a metal cylindrical ring by using an aluminum foil adhesive tape, placing a porous polymer gasket in the metal cylindrical ring, pushing down to the bottom, closely contacting with the aluminum foil adhesive tape, and inserting a solid metal cylinder into a hole of the polymer gasket to obtain a multi-radial orientation forming device, wherein a size explanatory diagram of the multi-radial orientation forming device is shown in figure 2; pre-placing the multi-radial orientation forming device into a low-temperature refrigerating medium, adding the filler mixture into the multi-radial orientation forming device, and performing freezing treatment to form a frozen mixture; taking out the solid metal cylinder, adding the filler mixture into the multi-radial orientation molding device again, and performing freezing treatment to form a frozen mixture; and (3) performing freeze drying treatment on the frozen mixture to obtain the porous skeleton precursor.
S03, carrying out sintering heat treatment on the porous framework precursor, and firstly, carrying out pre-sintering treatment at a lower temperature under an inert atmosphere to thermally crack the binder; and then carrying out high-temperature heat treatment under the mixed gas of hydrogen and nitrogen or inert atmosphere to form cross-linking of the filler, thereby obtaining the porous framework.
S04, cutting and polishing the porous framework to obtain the porous framework with the multi-radial microstructure.
Based on the general method for preparing porous frameworks with multi-radial microstructures described above, the following examples of the present invention also provide specific porous framework materials.
Example 1:
the preparation process of the graphene oxide porous skeleton with the multi-radial microstructure comprises the following specific steps:
s11, graphene oxide sheets with the sheet diameter of 50 mu m and the thickness of 400nm are mixed with water according to the mass ratio of 0.008:1, performing ball milling in a planetary ball mill after mixing to obtain a uniform graphene oxide mixture, wherein the solid content is 8mg/mL;
S12, sealing the bottom of an iron cylindrical ring by using an aluminum foil adhesive tape (the inner diameter of the iron cylindrical ring is 30mm, the outer diameter of the iron cylindrical ring is 35mm, and the height of the iron cylindrical ring is 40 mm), placing resin gaskets (m=0.2, n=7, holes are arranged in a central symmetry manner, s=10 mm) with Kong Huanyang, placing the resin gaskets inside the iron cylindrical ring, pushing the resin gaskets down to the bottom, tightly contacting with the aluminum foil adhesive tape, and inserting a solid iron cylinder into the holes of the epoxy resin gaskets; pre-placing a forming device into liquid nitrogen, adding the graphene oxide mixture into the forming device, and performing freezing treatment to form a frozen mixture; taking out the solid iron cylinder, adding the graphene oxide mixture into a forming device again, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the graphene oxide porous skeleton precursor.
S13, not performing sintering treatment.
S14, cutting the salient points on one side of the graphene oxide porous framework by using a cutting tool, and polishing the cut surface by using sand paper to obtain the graphene oxide porous framework with the multi-radial microstructure. The three-dimensional structure of the graphene oxide porous skeleton is shown in fig. 3.
The graphene oxide porous skeleton of this example 1 shows good compression resilience, and after 15 compression cycles at 50% strain, the plastic deformation of the skeleton is 1.3%, and the mechanical strength is attenuated by 4%. The regular isotropic mass transfer channels also ensure the capillary force action of the framework on the solvent. The graphene oxide porous skeleton is placed into chloroform solvent, taken out and weighed, and the adsorption capacity to chloroform is calculated to be 240g/g (namely, 1g of graphene oxide porous skeleton can adsorb 240g of chloroform). Compared with the porous skeleton prepared by the traditional ice template method, the graphene oxide porous skeleton with the multi-radial microstructure has more regular isotropic mass transfer channels. The presence of multiple radial microstructures can more effectively tolerate large elastic deformations while preventing structural damage or collapse.
Example 2:
the preparation process of the porous boron nitride sheet skeleton with the multi-radial microstructure comprises the following specific steps:
S21, boron nitride tablets with the diameter of 100 microns and the thickness of 1 micron, carboxymethyl cellulose and water are mixed according to the mass ratio of 1:0.05:5, ball milling is carried out in a planetary ball mill after mixing, so as to obtain a uniform boron nitride sheet mixture;
S22, sealing the bottom of a copper cylinder ring by using an aluminum foil adhesive tape (the inner diameter of the copper cylinder ring is 25.4mm, the outer diameter of the copper cylinder ring is 30mm, and the height of the copper cylinder ring is 35 mm), placing polysiloxane gaskets with holes (m=0.15, n=13, and the holes are arranged in a central symmetry manner, s=5 mm) in the copper cylinder ring, pushing the copper cylinder ring down to the bottom, tightly contacting with the aluminum foil adhesive tape, and inserting a solid copper cylinder into the holes of the polysiloxane gaskets; pre-placing the forming device into liquid nitrogen, adding the boron nitride sheet mixture into the forming device, and performing freezing treatment to form a frozen mixture; taking out the solid copper cylinder, adding the boron nitride sheet mixture into a forming device again, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the boron nitride porous skeleton precursor.
S23, carrying out two-stage sintering treatment on the boron nitride porous skeleton precursor: the first sintering heat treatment temperature is 350 ℃, the sintering atmosphere is helium, and the sintering time is 3 hours; the second sintering temperature is 1900 ℃, the sintering atmosphere is nitrogen, and the sintering time is 10 hours.
S24, cutting the salient points on one side of the boron nitride porous framework by using linear cutting equipment, and polishing the cut surface by using polishing equipment to obtain the boron nitride porous framework with the multi-radial microstructure.
The thermal conductivities of the composite material of the boron nitride porous skeleton filled with epoxy resin with the multi-radial microstructure of the present example 2 measured in the radial and axial directions were 6.3W/mK and 6.8W/mK, respectively. Compared with the porous skeleton prepared by the traditional ice template method, the porous skeleton of boron nitride with multi-radial microstructure has an isotropic heat conduction network and more regular mass transfer channels.
Example 3:
the preparation process of the silver nanowire porous skeleton with the multi-radial microstructure comprises the following specific steps:
S31, silver nanowires with the length of 30 mu m and the diameter of 300nm, polyvinylpyrrolidone and water are mixed according to the mass ratio of 1:0.1:20, stirring in a magnetic stirrer after mixing to obtain a uniform silver nanowire mixture;
S32, sealing the bottom of an aluminum cylindrical ring by using an aluminum foil adhesive tape (the inner diameter of the aluminum cylindrical ring is 50mm, the outer diameter of the aluminum cylindrical ring is 55mm, and the height of the aluminum cylindrical ring is 40 mm), placing a phenolic resin gasket with holes (m=0.15, n=7, the holes are arranged in a central symmetry manner, s=5 mm) in the copper cylindrical ring, pushing the copper cylindrical ring down to the bottom, tightly contacting with the aluminum foil adhesive tape, and inserting a solid aluminum cylinder into the holes of the phenolic resin gasket; pre-placing a forming device into liquid nitrogen, adding the silver nanowire mixture into the forming device, and performing freezing treatment to form a frozen mixture; taking out the solid aluminum cylinder, adding the silver nanowire mixture into a forming device again, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the silver nanowire porous skeleton precursor.
S33, carrying out two-stage sintering treatment on the silver nanowire porous skeleton precursor: the first sintering heat treatment temperature is 380 ℃, the sintering atmosphere is argon, and the sintering time is 2 hours; the second sintering temperature is 1500 ℃, the sintering atmosphere is hydrogen/nitrogen mixed gas, and the sintering time is 5h.
S34, cutting the salient points on one side of the silver nanowire porous framework by using linear cutting equipment, and polishing the cut surface by using polishing equipment to obtain the silver nanowire porous framework with the multi-radial microstructure.
The thermal conductivities of the composite material of the silver nanowire porous skeleton filled with epoxy resin with the multi-radial microstructure of the present example 3 measured in the radial and axial directions were 36.2W/mK and 34.7W/mK, respectively.
Example 4:
the preparation process of the graphene oxide porous framework comprises the following specific steps:
D31. graphene oxide sheets with the sheet diameter size of 50 mu m and the thickness of 400nm and water are mixed according to the mass ratio of 0.008:1, performing ball milling in a planetary ball mill after mixing to obtain a uniform graphene oxide mixture, wherein the solid content is 8mg/mL;
D32. Sealing the bottom of an iron cylindrical ring by using an aluminum foil adhesive tape (the inner diameter of the iron cylindrical ring is 30mm, the outer diameter of the iron cylindrical ring is 35mm, and the height of the iron cylindrical ring is 40 mm), placing resin gaskets (m=0.1, n=13, holes are arranged in a central symmetry manner, s=6 mm) with Kong Huanyang, putting the resin gaskets inside the iron cylindrical ring, pushing the resin gaskets down to the bottom, tightly contacting with the aluminum foil adhesive tape, and inserting solid iron cylinders into the holes of the epoxy resin gaskets; pre-placing a forming device into liquid nitrogen, adding the graphene oxide mixture into the forming device, and performing freezing treatment to form a frozen mixture; taking out the solid iron cylinder, adding the graphene oxide mixture into a forming device again, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the graphene oxide porous skeleton precursor.
D33. No sintering treatment is performed.
D34. cutting the salient points on one side of the graphene oxide porous framework by using a cutting tool, and polishing the cut surface by using sand paper to obtain the graphene oxide porous framework with the multi-radial microstructure.
The graphene oxide porous skeleton is subjected to 15 times of compression cycles under 50% strain, and then is subjected to plastic deformation to be 0.7%, and the mechanical strength is attenuated by 3.3%. The regular isotropic mass transfer channels also ensure the capillary force action of the framework on the solvent. The graphene oxide porous skeleton is placed into chloroform solvent, taken out and weighed, and the adsorption capacity to chloroform is calculated to be 260g/g (namely, 1g of graphene oxide porous skeleton can adsorb 260g of chloroform).
Example 5:
The preparation process of the silver nanowire porous framework comprises the following specific steps:
D41. Silver nanowires with the length of 30 mu m and the diameter of 300nm, polyvinylpyrrolidone and water are mixed according to the mass ratio of 1:0.1:20, stirring in a magnetic stirrer after mixing to obtain a uniform silver nanowire mixture;
D42. Sealing the bottom of an aluminum cylindrical ring by using an aluminum foil adhesive tape (the inner diameter of the aluminum cylindrical ring is 50mm, the outer diameter of the aluminum cylindrical ring is 55mm, and the height of the aluminum cylindrical ring is 40 mm), placing a phenolic resin gasket with holes (m=0.15, n=5, holes are arranged in a central symmetry manner, s=12.5 mm) in the copper cylindrical ring, pushing the copper cylindrical ring down to the bottom, tightly contacting with the aluminum foil adhesive tape, and inserting a solid aluminum cylinder into the holes of the phenolic resin gasket; pre-placing a forming device into liquid nitrogen, adding the silver nanowire mixture into the forming device, and performing freezing treatment to form a frozen mixture; taking out the solid aluminum cylinder, adding the silver nanowire mixture into a forming device again, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the silver nanowire porous skeleton precursor.
D43. carrying out two-stage sintering treatment on the silver nanowire porous skeleton precursor: the first sintering heat treatment temperature is 380 ℃, the sintering atmosphere is argon, and the sintering time is 2 hours; the second sintering temperature is 1500 ℃, the sintering atmosphere is hydrogen/nitrogen mixed gas, and the sintering time is 5h.
D44. And cutting the convex points on one side of the silver nanowire porous framework by using linear cutting equipment, and polishing the cut surface by using polishing equipment to obtain the silver nanowire porous framework with the multi-radial microstructure.
The thermal conductivities of the composite material with the silver nanowire porous skeleton filled with the epoxy resin and the multi-radial microstructure measured in the radial direction and the axial direction are 39.4W/mK and 36.2W/mK respectively.
Comparative example 1:
the preparation method of the graphene oxide porous framework by using the traditional ice template method process comprises the following specific steps:
D11. graphene oxide sheets with the sheet diameter size of 50 mu m and the thickness of 400nm and water are mixed according to the mass ratio of 0.008:1, performing ball milling in a planetary ball mill after mixing to obtain a uniform graphene oxide mixture, wherein the solid content is 8mg/mL;
D12. Sealing the bottom of a polyvinyl chloride ring by using an aluminum foil tape (the inner diameter of the polyvinyl chloride ring is 30mm, the outer diameter of the polyvinyl chloride ring is 35mm, and the height of the polyvinyl chloride ring is 40 mm), pre-placing the polyvinyl chloride ring into liquid nitrogen, adding the graphene oxide mixture into the polyvinyl chloride ring, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the graphene oxide porous framework.
D13. no sintering treatment is performed.
D14. Without the need for cutting and grinding processes.
The three-dimensional structure of the graphene oxide porous skeleton obtained in comparative example 1 is shown in fig. 4a, and after the graphene oxide porous skeleton in comparative example 1 is subjected to 15 compression cycles under 50% strain, the plastic deformation of the skeleton is 9%, and the mechanical strength is attenuated by 15%. The graphene oxide porous skeleton is placed into a chloroform solvent, taken out and weighed, and the adsorption capacity of the graphene oxide porous skeleton to chloroform is calculated to be 105g/g (namely, 105g of chloroform can be adsorbed by 1g of graphene oxide porous skeleton).
Comparative example 2:
The preparation method of the graphene oxide porous framework by using a double-orientation ice template method comprises the following specific steps:
D21. Graphene oxide sheets with the sheet diameter size of 50 mu m and the thickness of 400nm and water are mixed according to the mass ratio of 0.008:1, performing ball milling in a planetary ball mill after mixing to obtain a uniform graphene oxide mixture, wherein the solid content is 8mg/mL;
D22. Sealing the bottom of an iron cylindrical ring by using an aluminum foil tape (the inner diameter of the iron cylindrical ring is 30mm, the outer diameter of the iron cylindrical ring is 35mm, and the height of the iron cylindrical ring is 40 mm), pre-placing the iron cylindrical ring into liquid nitrogen, adding the graphene oxide mixture into the iron cylindrical ring, and performing freezing treatment to form a frozen mixture; and performing freeze drying treatment on the frozen mixture to obtain the graphene oxide porous framework.
D23. no sintering treatment is performed.
D24. without the need for cutting and grinding processes.
The three-dimensional structure of the graphene oxide porous skeleton obtained in comparative example 2 is shown in fig. 4b, and after the graphene oxide porous skeleton in comparative example 2 is subjected to 15 compression cycles under 50% strain, the plastic deformation of the skeleton is 4%, and the mechanical strength is attenuated by 9%. The graphene oxide porous skeleton is placed into chloroform solvent, taken out and weighed, and the adsorption capacity to chloroform is calculated to be 195g/g (namely, 195g of chloroform can be adsorbed by 1g of graphene oxide porous skeleton).
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. The preparation method of the porous framework with the multi-radial microstructure is characterized by comprising the following steps of:
(1) Weighing filler and water, weighing binder, and mixing to obtain filler mixture;
(2) Taking a multi-radial orientation forming device, putting the multi-radial orientation forming device into a low-temperature refrigerating medium in advance, filling a filler mixture into the multi-radial orientation forming device, performing freezing treatment, taking out a solid metal cylinder in the multi-radial orientation forming device, adding the filler mixture into the multi-radial orientation forming device again, performing freezing treatment to form a frozen mixture, and performing freeze drying treatment to obtain a porous skeleton precursor;
The multi-radial orientation forming device mainly comprises a metal cylindrical ring, a porous polymer circular gasket, a solid metal cylinder and an aluminum foil adhesive tape, wherein the bottom of the metal cylindrical ring is sealed by the aluminum foil adhesive tape;
(3) And (3) sintering the porous skeleton precursor obtained in the step (2) to obtain a porous skeleton, and cutting and polishing to obtain the porous skeleton with the radial microstructure.
2. The method according to claim 1, wherein the filler in the step (1) is any substance which does not chemically react with water at normal temperature;
the binder comprises polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose; the mode of mixing treatment comprises ultrasonic, mechanical stirring and planetary ball milling; the mass ratio of the filler to the water to the binder is 1: 4-100: 0 to 0.3.
3. The method of manufacturing according to claim 1, wherein the diameter of the perforated polymeric circular gasket is equal to the inner diameter of the metal cylindrical ring, the diameter of the holes in the perforated polymeric circular gasket is equal to the diameter of the solid metal cylinder, and the height of the solid metal cylinder is greater than the height of the metal cylindrical ring;
The length ratio of the inner diameter to the height of the metal cylindrical ring is 0.1-10: 1, the length ratio of the outer diameter to the inner diameter of the metal cylindrical ring is 1.01-1.5: 1, a step of;
The length ratio of the hole diameter of the polymer circular gasket to the inner diameter of the metal cylinder ring is 0.05-0.95: 1, a step of;
The holes in the polymer circular gasket are arranged in a central symmetry manner, wherein the number of the holes is n=1+2x, and x is less than or equal to 160;
The nearest distance s between adjacent holes in the polymer circular gasket is defined as the distance between the centers of two holes, s is more than or equal to 2d, wherein d is the diameter of the hole in the polymer circular gasket.
4. The method of claim 1, wherein the ratio of the hole diameter of the polymeric circular gasket to the inner diameter of the metal cylindrical ring is 0.1 to 0.5:1, a step of;
The holes in the polymer circular gasket are arranged in a central symmetry manner, wherein the number of the holes is n=1+2x, and x is less than or equal to 40.
5. The preparation method according to claim 1, wherein the metal material of the metal cylinder ring and the solid metal cylinder is an alloy composed of any metal substance or a plurality of metal substances which do not chemically react with water at normal temperature;
The polymer in the circular porous polymer gasket is any polymer which does not react with water at normal temperature.
6. The method of claim 1, wherein the cryogenic refrigeration medium is at least one of dry ice, liquid nitrogen, or liquid helium;
The freezing treatment is to drop the filler mixture into a multi-radial orientation forming device and indirectly contact the filler mixture with a low-temperature refrigeration medium, so that a continuous self-assembly forming process is initiated;
The freeze-drying treatment is to put the frozen mixture into a freeze dryer to sublimate the ice.
7. The method according to claim 1, wherein the sintering treatment in the step (3) is performed under the following conditions: performing first sintering under the inert gas atmosphere at the temperature of 200-450 ℃ for 1-8 h; after the completion, performing second sintering under the atmosphere of mixed gas or inert gas of hydrogen and nitrogen at the temperature of 450-2500 ℃ for 1-12 h;
The cutting and polishing treatment comprises the step of treating the lateral salient points of the porous framework by using a linear cutting machine and a polishing machine.
8. A porous scaffold having a multi-radial microstructure, characterized by being obtained by the production method according to any one of claims 1 to 7.
9. Use of a porous scaffold with multi-radial microstructures as defined in claim 8 as a thermally conductive filler and an adsorption medium.
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| WO2011121571A1 (en) * | 2010-04-01 | 2011-10-06 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Microreactor comprising a porous ceramic material |
| CN102826855A (en) * | 2012-06-21 | 2012-12-19 | 清华大学 | Preparation method of porous ceramic pipe with gradient through hole structure |
| CN104945005A (en) * | 2015-06-25 | 2015-09-30 | 西安理工大学 | Porous material with central symmetry structure and method for preparing the same |
| CN106075591A (en) * | 2016-07-12 | 2016-11-09 | 东华大学 | A kind of enhancing lamella composite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011121571A1 (en) * | 2010-04-01 | 2011-10-06 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Microreactor comprising a porous ceramic material |
| CN102826855A (en) * | 2012-06-21 | 2012-12-19 | 清华大学 | Preparation method of porous ceramic pipe with gradient through hole structure |
| CN104945005A (en) * | 2015-06-25 | 2015-09-30 | 西安理工大学 | Porous material with central symmetry structure and method for preparing the same |
| CN106075591A (en) * | 2016-07-12 | 2016-11-09 | 东华大学 | A kind of enhancing lamella composite and preparation method thereof |
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