CN108069725A - A kind of hollow foam material and its preparation method and application - Google Patents

A kind of hollow foam material and its preparation method and application Download PDF

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Publication number
CN108069725A
CN108069725A CN201611001541.1A CN201611001541A CN108069725A CN 108069725 A CN108069725 A CN 108069725A CN 201611001541 A CN201611001541 A CN 201611001541A CN 108069725 A CN108069725 A CN 108069725A
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tube wall
microchannel
hollow
acid
foam material
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CN108069725B (en
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张劲松
高勇
田冲
杨振明
杨晓丹
矫义来
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Priority to PCT/CN2017/109865 priority patent/WO2018086522A1/en
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Abstract

The present invention relates to field of porous materials, specifically a kind of hollow foam material and its preparation method and application.The hollow foam material is macroscopically being formed by the support frame network struction of three-dimensional communication, and support frame itself is the microchannel with hollow structure of three-dimensional communication, and microchannel tube wall is fine and close or is the hole containing nanoscale and/or micron order aperture.Utilize the macromolecule resin foamed material with three-dimensional networks structure, using structure design of the present invention and preparation method, the hollow foam material of obtained three-dimensional networks.The hollow foam material has the hole of size adjustable three types simultaneously：The perforate mesh of macroscopic three dimensional connection, the hollow microchannel of three-dimensional communication, the intrinsic nanoscale of microchannel tube wall and/or the hole in micron order aperture.The hollow foam material has this innovative structure characteristic of the hollow microchannel of three-dimensional communication, lays the foundation for its application.

Description

A kind of hollow foam material and its preparation method and application
Technical field
The present invention relates to foamed material field, the hollow foam material of specifically a kind of three-dimensional communication and its preparation side Method and application.
Background technology
Foamed material is a kind of special porous material, and geometry is characterized in using polygon closed-loop to be substantially single Member, the three-dimensional networks that each elementary cell is interconnected to form.The material of this class formation possess light weight, adjustable porosity, Many advantages, such as high permeability, mass transfer of the fluid in the mesh of its three-dimensional communication, momentum are transferred, heat transfer efficiency is equal It can effectively improve.Thus, strengthen field in chemical process, the preparation and application of foamed material are just gradually subject to widely Pay attention to.
However, it is obtained using the preparation method described in the patent of invention US3090094 based on K.Schwartzwalder Traditional foamed material, although hollow structure may be contained in its support frame, template in by its preparation process The limitation of structure, the pass shape and size size of the hollow hole of support frame cross section can not regulate and control.Which results in biographies The foamed material of system is when needing the distribution of finely regulating fluid or needs while regulating and controlling multiple fluid, existing conventional foam The open-celled structure of the three-dimensional communication of material will be difficult to realize.
Hollow material is a kind of material of inside containing particular cavity, and research hotspot is concentrated mainly on doughnut material at present Material, i.e. fiber axially have the chemical fibre of thin tube-like cavity.It is covered with micropore on doughnut tube wall, aperture is can retain substance Molecular weight form reach, molecular cut off is up to thousands of to hundreds of thousands.Therefore, by the component that doughnut is assembled into micro-filtration, super The fields such as filter, dialysis, gas separation, reverse osmosis and evaporating-osmosis device are widely studied and apply.
Although doughnut itself has lot of advantages, the device assembled by it is in actual application, fluid Flow regime mostly based on concurrent flow or cross-current, the transmission of substance is mainly limited by diffusion law, and mass-transfer efficiency is not high. On the other hand, doughnut main component is chemical fibre at present, therefore temperature in use is usually no more than 400 DEG C.Therefore, there is an urgent need for Research and development are a kind of to be had compared with high mass transfer efficiency and mechanical property, high temperature resistant, corrosion-resistant, oxidation resistant Novel hollow material.
The content of the invention
It is an object of the invention to provide a kind of structure designs of hollow foam material and its preparation method and application, solve The problems such as fluid mass-transfer efficiency is low in the prior art, material non-refractory, not anti-oxidant, poor corrosion resistance, poor mechanical property.
Hollow structure is creatively introduced into foamed material by the present invention, develops hollow foam material, it is made to have both bubble The three-dimensional networks open-celled structure of foam material and the thin tube-like cavity structure of hollow material.Meanwhile for hollow foam material Innovative pore structure propose targetedly preparation process, be one of main innovation point of the present invention.
The technical scheme is that：
A kind of hollow foam material of three-dimensional communication, the hollow foam material is macroscopically three-dimensional even by support frame (a) It passes to form perforate (b) network structure, wherein, support frame (a) itself has the microchannel (c) that size is controllable, hollow, should The cross section of microchannel (c) is nearly round shape or ellipticity.
The tube wall of the hollow microchannel (c) is porous structure tube wall or compact texture tube wall.
The porous structure tube wall body contains nanoscale and/or the hole in micron order aperture.
The material of the tube wall body can be homogenously or inhomogenously.
The physical arrangement or chemical constitution of the tube wall body can be isotropic or anisotropic.
The mesh size (d1) of the perforate (b) is 0.2mm~20mm.
The outer diameter (d2) of the hollow microchannel (c) be 0.1mm~10mm, internal diameter size (d3) for 0.02mm~ 9mm。
The range of aperture size for the hole that the porous tube wall contains is 0.1nm~100 μm, and the porosity p of tube wall is 0<p ≤ 70%.
The material of the hollow foam material is selected from following one or more：Metal, ceramics, macromolecule, carbon materials Material.
The metal material be selected from comprising Li, Na, K, Al, Ca, Sr, Mg, Ni, Fe, Cu, V, Cr, Mo, W, Mn, Co, Zn, Y, Zr, Nb, Ag, Pd, Ru, Rh, Au, Pt, Ta, lanthanide series metal, the metal simple-substance of actinide metals, the alloy comprising above-mentioned element, It is more than one or both of metal solid solution or intermetallic compound；
The ceramic material is selected from following one or more：(1) oxide and composite oxides：Al2O3、SiO2、 ZrO2、MgO、CaO、BeO、SrO、NiO、CuO、TiO2、V2O5、Fe3O、RuO2、WO3、ZnO、SnO2、CdO、Nb2O5、PbO、 Pb3O4、Bi2O3、MoO3、Cr2O3、Y2O3、MnO、MnO2、Mn2O3、Mn3O4、CoO、Co3O4、Co2O3, lanthanide oxide, actinium series oxygen Compound；Mullite (3Al2O3·2SiO2), aluminum-spinel (MgO3Al2O3), magnesia chrome spinel (MgOCr2O3), zirconium English Stone (ZrO2·SiO2), calcium orthosilicate (2CaOSiO2), forsterite (2MgOSiO2), perovskite composite oxide (CaTiO3Or the CaTiO of doping3、BaTiO3Or the BaTiO of doping3、LiNbO3Or the LiNbO of doping3、SrZrO3Or doping SrZrO3、LaMnO3Or the LaMnO of doping3, doping SrCoyFe-1-yO3-δ, 0 ＜ y ＜, 1,0 ＜ δ ＜ 3, the A La substitutedxA1- xCoyFe1-yO3-δ, wherein A=Sr, Ba, Ca, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ δ ＜ 3)；(2) carbide：Carborundum, zirconium carbide, Tungsten carbide, titanium carbide, boron carbide, ramet, vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide, cementite, manganess carbide；(3) nitrogenize Object：α-Si3N4、β-Si3N4、AlN、Si6-xAlxOxN8-x、BN；(4)Si；
The macromolecule material is selected from following one or more：(1) polyolefins：Polytetrafluoroethylene (PTFE) gathers inclined fluorine Ethylene, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polystyrene, polyacrylonitrile；(2) it is polyamide-based：Polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), poly- 11 lactams (PA11), nylon 612 (PA612), the poly- last of the ten Heavenly stems Two acyl decamethylene diamines (PA1010)；(3) polyesters：Polyurethane, polymethyl methacrylate, polyisocyanurate (PIR), poly- carbon Acid esters, polybutyl terapthalate (PBT), polyethylene terephthalate (PET)；(4) polyethers：Polyphenylene oxide, polyphenyl Thioether；
The carbon material material is selected from following one or more：Graphite, agraphitic carbon, graphene, diamond, activity Charcoal, ordered mesopore carbon, unordered mesoporous carbon, carbon fiber, carbon nanotubes, carbon micron tube.
The present invention also puts forward a kind of method for preparing above-mentioned hollow foam material, which includes the following steps：
(1) preparation section of template foamed material is sacrificed：First, using the high score subtree with three-dimensional networks structure For fat foamed material as original template material, the macromolecule resin foamed material is epoxy resin, phenolic resin, furans tree It is more than one or both of fat, polyurethane, polyester, polyethers；Secondly, to the network skeleton of the macromolecule resin foamed material Muscle carries out thickening processing, until skeleton muscle fineness reaches size 0.02mm~9mm needed for the internal diameter of hollow microchannel, thus It is made and sacrifices template foamed material；
(2) foamed material precast body preparation section：The process is selected from following one or more kinds of combinations：(a) match somebody with somebody Gained in step (1) is sacrificed template foamed material and is sufficiently submerged in the green layer slurry by tube wall green layer slurry in microchannel processed In, it then takes out, removes extra slurry and carry out semi-solid preparation after 80~150 DEG C；Xun Huan carries out above-mentioned " dipping sizing agent-removal Additional size-semi-solid preparation " operation is pre-designed value until the thickness of microchannel tube wall green layer reaches, finally by sample in 100 ~300 DEG C are fully cured, and foamed material precast body is made；(b) using galvanoplastic, the skeleton muscle table of template foamed material is being sacrificed Face builds microchannel tube wall green layer, and foamed material precast body is thus made；(c) using electroless plating method, template foam is being sacrificed Thus foamed material precast body is made in the skeleton muscle surface construction microchannel tube wall green layer of material；(d) solution etches are used Method, performs etching microchannel tube wall green layer processing, and structure is distributed with particular geometric configuration or particular chemicals Thus foamed material precast body is made in microchannel tube wall green layer；(e) particular crystal grown using hydro-thermal reaction method, structure Microchannel tube wall green layer is built, foamed material precast body is thus made；(f) using anodizing, to microchannel tube wall green compact Layer carries out anodized, the microchannel tube wall green compact that structure is distributed with particular geometric configuration or particular chemicals Thus foamed material precast body is made in layer；(g) using sol-gel method, microchannel tube wall green layer is built, bubble is thus made The prefabricated body of foam；(h) using Langmuir-Blodgett methods, film of the structure with Langmuir-Blodgett film features Layer green layer, is thus made foamed material precast body；(i) using physical vaporous deposition, microchannel tube wall green layer is built, by Foamed material precast body is made in this；(j) using chemical vapour deposition technique, microchannel tube wall green layer is built, foam is thus made Prefabricated body；
(3) removing step of template foamed material is sacrificed：By foamed material precast body obtained in step (2) in indifferent gas It is pyrolyzed under body protection, 1~10 DEG C/min of heating rate, 600~900 DEG C of pyrolysis temperature, 10~300min of soaking time is obtained The sample obtained is handled by one or both of following operation is above：Acid solution cleaning, aqueous slkali are cleaned, acetone cleans, It is roasted in washes of absolute alcohol, deionized water cleaning, air；Hollow foam material shaping presoma is made；
(4) molding procedure：The process is selected from following one or more kinds of combinations：It (a) will be obtained by step (3) Foamed material shaping presoma carries out high temperature sintering, 900~2500 DEG C of temperature, soaking time 10min~6h under protective atmosphere； The protective atmosphere is selected from high-purity argon gas protection, high-purity hydrogen protection, high pure nitrogen protection, high-purity hydrogen-argon-mixed protection, true It is more than one or both of empty condition；(b) forming operation is carried out using galvanoplastic；(c) shaping behaviour is carried out using electroless plating method Make；(d) forming operation is carried out using solution etches method；(e) forming operation is carried out using hydro-thermal reaction method；(f) anodic oxygen is used Change method carries out forming operation；(g) forming operation is carried out using sol-gel method；(h) using Langmuir-Blodgett methods into Row forming operation；(i) forming operation is carried out using physical vaporous deposition；(j) shaping behaviour is carried out using chemical vapour deposition technique Make；(k) electrified regulation completion forming operation is carried out using to sample application voltage；
(5) postprocessing working procedures：After the shaping that will be obtained in step (4) sample one or both of proceed as follows with On：It roasts in acid solution cleaning, aqueous slkali cleaning, acetone cleaning, washes of absolute alcohol, deionized water cleaning, air, thus makes Obtain the hollow foam material of three-dimensional communication.
Thickening processing in step (1) is selected from following one or more：Galvanoplastic thickening, electroless plating method thickening, Sol-gel method.
Thickening processing in step (1) carries out as follows：By principal component：Solvent=100g：The ratio of (50~200) g Example prepares thickening slurry, and original template material is immersed into thickening slurry, and Xun Huan impregnate-remove additional size-half admittedly Change operation reaches size 0.02mm~9mm needed for the internal diameter of hollow microchannel up to skeleton muscle fineness, wherein, thickening slurry Principal component be selected from more than one or both of following substance：Polyurethane, phenolic resin, epoxy resin, furane resins, poly- second Enol, polyvinyl butyral, isocyanates, modified isocyanate, carboxymethyl cellulose, cellulose acetate, starch, oxidation Aluminium, magnesia, silica, calcium oxide, di-iron trioxide, ferroso-ferric oxide, cobalt oxide, manganese oxide, copper oxide, zinc oxide, oxygen Change tin, nickel oxide, graphite, agraphitic carbon, graphene, diamond, activated carbon, ordered mesopore carbon, unordered mesoporous carbon, carbon fiber, Carbon nanotubes, carbon micron tube, sylvite, sodium salt, calcium salt, magnesium salts, aluminium salt, ferrous salt, molysite, mantoquita, manganese salt, nickel salt, zinc salt, ammonium Salt, tartrate, bisulfites, sulphite, thiosulfate, halide salts, sulfonated bodies salt, salicylate, benzoic acid Salt, acetate, phosphate, carbonate, bicarbonate, lactate, sulfate, nitrate, Li, Na, K, Al, Ca, Sr, Mg, Ni, Fe, Cu, V, Cr, Mo, W, Mn, Co, Zn, Y, Zr, Nb, Ag, Pd, Ru, Rh, Au, Pt, Ta, lanthanide series metal, the metal of actinide metals Simple substance, the alloy comprising above-mentioned element, metal solid solution or intermetallic compound；Solvent be selected from it is following it is one or two kinds of with On：Water, ethyl alcohol, acetone, ethylene glycol, hexamethylene, n-hexane, toluene, dimethylbenzene, tetrahydrofuran.
In step (2), the microchannel tube wall green layer slurry presses 50 by principal component powder, binding agent, curing agent, solvent ~500g：50~200g：(being more than 0 to 0.2) times binding agent quality：The proportioning of 1000mL is made through abundant ball mill mixing；
Wherein, principal component powder is selected from the one or more of metal, ceramics, macromolecule or carbon material；
The metal material be selected from comprising Li, Na, K, Al, Ca, Sr, Mg, Ni, Fe, Cu, V, Cr, Mo, W, Mn, Co, Zn, Y, Zr, Nb, Ag, Pd, Ru, Rh, Au, Pt, Ta, lanthanide series metal, the metal simple-substance of actinide metals, the alloy comprising above-mentioned element, It is more than one or both of metal solid solution or intermetallic compound；
The ceramic material is selected from following one or more：(1) oxide and composite oxides：Al2O3、SiO2、 ZrO2、MgO、CaO、BeO、SrO、NiO、CuO、TiO2、V2O5、Fe3O、RuO2、WO3、ZnO、SnO2、CdO、Nb2O5、PbO、 Pb3O4、Bi2O3、MoO3、Cr2O3、Y2O3、MnO、MnO2、Mn2O3、Mn3O4、CoO、Co3O4、Co2O3, lanthanide oxide, actinium series oxygen Compound；Mullite (3Al2O3·2SiO2), aluminum-spinel (MgO3Al2O3), magnesia chrome spinel (MgOCr2O3), zirconium English Stone (ZrO2·SiO2), calcium orthosilicate (2CaOSiO2), forsterite (2MgOSiO2), perovskite composite oxide (CaTiO3Or the CaTiO of doping3、BaTiO3Or the BaTiO of doping3、LiNbO3Or the LiNbO of doping3、SrZrO3Or doping SrZrO3、LaMnO3Or the LaMnO of doping3, doping SrCoyFe-1-yO3-δ, 0 ＜ y ＜, 1,0 ＜ δ ＜ 3, the A La substitutedxA1- xCoyFe1-yO3-δ, wherein A=Sr, Ba, Ca, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ δ ＜ 3)；(2) carbide：Carborundum, zirconium carbide, Tungsten carbide, titanium carbide, boron carbide, ramet, vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide, cementite, manganess carbide；(3) nitrogenize Object：α-Si3N4、β-Si3N4、AlN、Si6-xAlxOxN8-x、BN；(4)Si；
The macromolecule material is selected from following one or more：(1) polyolefins：Polytetrafluoroethylene (PTFE) gathers inclined fluorine Ethylene, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polystyrene, polyacrylonitrile；(2) it is polyamide-based：Polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), poly- 11 lactams (PA11), nylon 612 (PA612), the poly- last of the ten Heavenly stems Two acyl decamethylene diamines (PA1010)；(3) polyesters：Polyurethane, polymethyl methacrylate, polyisocyanurate (PIR), poly- carbon Acid esters, polybutyl terapthalate (PBT), polyethylene terephthalate (PET)；(4) polyethers：Polyphenylene oxide, polyphenyl Thioether；
The carbon material material is selected from following one or more：Graphite, agraphitic carbon, graphene, diamond, activity Charcoal, ordered mesopore carbon, unordered mesoporous carbon, carbon fiber, carbon nanotubes, carbon micron tube；
Binding agent for polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, chitosan, alginic acid, sodium alginate, It is epoxy resin, phenolic resin, furane resins, polyurethane, Polycarbosilane, polyborazine, polyborosiloxane, PVDF hollow fiber membrane, poly- The one or more of zirconium borosilicate azane；
Curing agent is formaldehyde, glutaraldehyde, terephthalylidene aldehyde, water-soluble amine-formaldehyde condensation products, dimethyl urea, front three Base melamine, dimethyl ethyl urea, sodium sulphate, zinc sulfate, boric acid, borax, silane-type cross-linking agent, bichromate, chromic nitrate, The complex compound of chromium, cuprammonium hydroxide, urea, melamine, phenol, polyisocyanate, diethy-aceto oxalate, dimethyl oxalate, the third two Alcohol, organic titanium, epoxychloropropane, chlorethanol, sodium tetraborate, N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide, Beta-cyclodextrin, N-isopropylacrylamide, acrylamide, acrylic acid, methyl methacrylate, vanillic aldehyde, Geniposide, glyoxal, Poly- (N- ethylene glycols)-acetaldehyde, polyacrylonitrile, succinic acid and its derivative, amion acetic acid, lysine, two isocyanatos oneself Alkane, trimellitic anhydride, bromo-decane, to triazobenzene formic acid, heparin, ethylene glycol diglycidylether, epichlorohydrine, Acetic acid, citric acid, formic acid, hydroxyacetic acid, lactic acid, hydroxysuccinic acid, propionic acid, aliphatic acid, sodium citrate, calcium chloride, poly- second two Alcohol, aliphatic diamine class substance, polyamines, aromatic polyamine class substance, dicyandiamide class substance, imidazoles substance, modification Amine substance, boron trifluoride and complex compound, Versamid, hexa, benzene sulfonyl chloride, paratoluensulfonyl chloride, sulphur Acetoacetic ester, mahogany acid, p-methyl benzenesulfonic acid, paratoluenesulfonic acid sodium salt, paraformaldehyde, sodium hydroxide, acetin, propylene carbonate Ester, methylolurea, sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, hexanedioic acid, benzene sulfonic acid, phthalic anhydride, maleic anhydride, 3,3 '-two chloro- 4,4 '-two It is more than one or both of aminodiphenylmethane, divinylbenzene；
Solvent is more than one or both of water, ethyl alcohol, acetone, ethylene glycol, toluene, dimethylbenzene.
Also containing pore creating material to regulate and control the hole of microchannel tube wall in microchannel tube wall green layer slurry described in step (2) Structure.The regulation and control are preferably a step：(1) pore creating material is selected from metal pore creating material, oxide pore creating material, macromolecule pore creating material, nothing Machine salt pore creating material, the one or more of carbon material pore creating material, the granular size of pore creating material is 1nm~100 μm, and pore creating material is Addition is the 0.001%~20% of microchannel tube wall green layer slurry gross mass；(2) used stage by stage, successively containing of the same race Or the microchannel tube wall green layer slurry of pore creating material not of the same race carries out " dipping sizing agent-removal additional size-semi-solid preparation " Xun Huan behaviour Make, form the foamed material precast body with homogenously or inhomogenously microchannel tube wall green layer.
The structure of microchannel tube wall green layer described in step (2) can be part have pore structure, uniform pores structure or Substantially non-porous gap structure.
The hole is removed hole by the operation of in step (3), (4), (5) one-step or two-step combination of the above, into And prepare the hollow foam material with compact texture microchannel tube wall.
Functional modification process is further included after step (5), that is, passes through galvanoplastic, electroless plating method, solution etches method, sun Pole oxidizing process, sol-gel method, hydro-thermal reaction method, steam phase inversion, Langmuir-Blodgett methods, physical vapour deposition (PVD) Method, the one or more of chemical vapour deposition technique are contained in itself to the outer wall surface of microchannel tube wall, internal face or tube wall Nano-pore or micron openings carry out functional modification.
The hollow foam material of the present invention can be applied to following any fields：Separation membrane, Reaction Separation material, filtering Material, extract and separate material, reaction, extraction separation material, catalytic support material, microreactor, micro- heat exchange material, composite material Reinforcement, electrode material, sound absorption/acoustic damping materials, heat-barrier material, fluid-distributing material, reaction fractionation material, reactive distillation are used Material, point/rectifying column in fix valve etc..
The invention has the advantages that and advantageous effect：
1st, hollow foam material of the present invention has the hole of three types：Macroscopic three dimensional connection mesh, three-dimensional are even Logical hollow microchannel, the micron in the tube wall of microchannel or/and nanoscale hole.The hollow foam material comprehensively utilizes polymorphic type Hole and multistage pore dimension are conducive to flow through the fluid in the hollow foam material and carry out mass transfer, momentum transmission and heat Amount is transferred.
2nd, the cross section of microchannel (c) of the present invention is nearly round shape or ellipticity, is conducive to that microchannel in uniform thickness is made Tube wall, and the structural stability of microchannel tube wall is improved.
3rd, compared with general foamed material, the introducing of hollow structure of the present invention is conducive to prepare new with special construction Type functional material and composite material.
4th, the hollow foam material of three-dimensional networks of the present invention has compared with high mass transfer efficiency and mechanical property, resistance to High temperature, it is corrosion-resistant, anti-oxidant the features such as.
5th, the technology of the present invention is simple for process, without complex device.Hollow foam material high temperature resistant, anti-oxidant, corrosion-resistant, tool There is preferable mechanical property.
6th, hollow foam material of the present invention is a kind of brand-new porous material, is with a wide range of applications, It can be applied to following numerous areas：Separation membrane, Reaction Separation material, filtering material, extract and separate material, reaction, extraction point From material, catalytic support material, microreactor, micro- heat exchange material, composite material reinforcement body, electrode material, sound absorption/noise reduction material Material, heat-barrier material, fluid-distributing material, reaction fractionation with material, reactive distillation with material, point/rectifying column in fix valve etc..
Description of the drawings
Fig. 1 is the macro morphology of the hollow foam material of the present invention with porous tube wall.
Fig. 2 is the partial enlargement pattern of the hollow foam material of the present invention with porous tube wall.
Fig. 3 is the hollow microchannel tube wall pattern of the hollow foam material of the present invention with porous tube wall.
Fig. 4 is the hollow microchannel tube wall microscopic appearance of the hollow foam material of the present invention with porous tube wall.
Fig. 5 is the macro morphology of the hollow foam material with fine and close tube wall of the present invention.
Fig. 6 is the partial enlargement pattern of the hollow foam material with fine and close tube wall of the present invention.
Fig. 7 is the hollow microchannel tube wall pattern of the hollow foam material with fine and close tube wall of the present invention.
Fig. 8 is the preparation technology flow chart of hollow foam material of the present invention.
Specific embodiment
As shown in figure 8, in the structure design of hollow foam material and its specific embodiment of preparation process, the present invention Slurry is prepared as base stock using main component and pore creating material powder, high molecular material, solvent, is handled with skeleton muscle by thickening Three-dimensional communication sacrifice template foamed material as mould material, using " dipping sizing agent-removal additional size-baking and curing-is in advance For the preparation process of representative, (" dipping sizing agent-removal additional size-drying is solid for processing-high temperature sintering shaping-post processing (selection) " Change " operation as structure skeleton muscle microchannel tube wall green layer, this, which is operated, can cycle progress until microchannel tube wall green layer Thickness reaches design load), according to the detailed process for preparing hollow foam material, it is listed below several embodiments：
Embodiment 1
The present embodiment preparation process is the preparation of the hollow foam carbofrax material of the microchannel tube wall with porous structure Technique：
(1) preparation of thickening slurry：Polyvinyl alcohol powder, epoxy resin, curing agent, ethyl alcohol are made through abundant ball mill mixing Thickening slurry, polyvinyl alcohol, epoxy resin, curing agent, the proportioning of ethyl alcohol are 50~500g：More than 0 to 500g：10~100g： 1000mL (per 1000mL solvents i.e. in slurry, be corresponding with 50~500g polyvinyl alcohol powder, more than 0 to 500g epoxy resin and The corresponding curing agent of 10~100g epoxy resin).
(2) preparation of microchannel tube wall green layer slurry：By sic powder (5 μm of average grain diameter), silica flour (average grain diameter 3.5 μm), phenolic resin, p-methyl benzenesulfonic acid (curing agent), ethyl alcohol by proportioning 50~500g：50~500g：50~200g：(it is more than 0 to 0.2) times phenolic resin quality：Microchannel tube wall green layer slurry is made through abundant ball mill mixing in 1000mL.
(3) preparation of template foamed material is sacrificed：Use average mesh size that there is three-dimensional networks structure for 3mm Polyurethane resin foamed material, thickening processing is carried out to the network skeleton muscle of polyurethane resin foamed material：By polyurethane tree Fat vacuole foam is immersed in the thickening slurry prepared by step (1), after removing slurry extra in foam formwork material mesh after taking-up, In 80~150 DEG C of semi-solid preparations.According to size needed for the internal diameter for the hollow microchannel for finally needing hollow foam material to be prepared (0.02mm~9mm) is required, cycle progress " leaching hanging material-except additional size-semi-solid preparation " operate several times until network skeleton The fineness of muscle, which reaches, is pre-designed 550 μm of value.
(4) prepared by foamed material precast body：That is the structure of the tube wall green layer of the hollow microchannel of three-dimensional networks.By net Network skeleton muscle fineness thickening to the three-dimensional communication for being pre-designed value sacrifice template foamed material cut out to required shape and Then size is sufficiently submerged in the microchannel tube wall green layer slurry of step (2) preparation, remove template foamed material mesh In after extra slurry, in 80~150 DEG C of semi-solid preparations.According to the requirement for the hollow micro-channel tubes wall thickness being pre-designed, " hanging Material-remove additional size-semi-solid preparation " operation can cycle progress several times, finally by the skeleton foam of acquisition in 200~300 DEG C It is fully cured, completes the structure of microchannel tube wall green layer, obtain precast body foamed material.
(5) removal of template foamed material is sacrificed：By precast body foamed material high-purity argon gas (argon gas volume fraction >= 99.999%) or under other inert gas shieldings carry out sacrificing template foamed material goes division operation, and 1~10 DEG C of heating rate/ Min, 600~900 DEG C, 10~300min of soaking time for the treatment of temperature, the sample of acquisition can be selected in proceeding as follows One or more kinds of method processing：Acid solution cleaning, aqueous slkali cleaning, acetone cleaning, washes of absolute alcohol, deionized water are clear It washes, roasting, completely drying in air, hollow foam material shaping presoma is made.
(6) molding procedure：Shaping presoma is subjected to high temperature sintering, temperature under high-purity argon gas protection or vacuum condition 900~2500 DEG C, soaking time 10min~6h.
(7) (selection) is post-processed：The sample obtained in step (6) one or both of is proceeded as follows with top Method processing：Acid solution cleaning, aqueous slkali cleaning, organic solvent (including but not limited to acetone, absolute ethyl alcohol) cleaning, deionized water It is calcined in cleaning, air under roasting, inert atmosphere protection, the hollow foam material of three-dimensional networks is made.This hollow foam Material is mainly made of carborundum, is formed in macroscopically its structure by the support frame network struction of three-dimensional communication, macroscopic three dimensional The average value for connecting the mesh size of perforate is 2.5mm.Network skeleton itself has the micro- logical of hollow structure for three-dimensional communication Road, the average-size of hollow microchannel internal diameter is 500 μm, and the average-size of outer diameter is 900 μm.The chemical component of microchannel tube wall Mainly comprising carborundum, microchannel tube wall contains nanoscale to the hole in micron order aperture, and average pore size is 5 μm, and porosity is 50%.
Embodiment 2
The present embodiment preparation process is the preparation of the hollow foam carbofrax material of the microchannel tube wall with compact texture Technique：The present embodiment difference from Example 1 is that the molding procedure described in step (6) is：Shaping presoma is placed in very In empty sintering furnace, drive the silicon powder particle that average particle size particle size is 3mm is uniformly placed on body sample before the forming.Vacuumized conditions Under, 900~2500 DEG C of temperature, soaking time 10min~6h.The hollow foam material obtained, macroscopic three dimensional connection perforate The average value of mesh size is 0.5mm.Support frame itself is the microchannel with hollow structure of three-dimensional communication, hollow micro- logical The average-size of road internal diameter is 250 μm, and the average-size of outer diameter is 550 μm.Microchannel tube wall be compact texture, chemical component Mainly include carborundum and silicon.
Embodiment 3
The present embodiment preparation process is the preparation of the hollow foam alumina material of the microchannel tube wall with porous structure Technique：The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane.In step (2), Microchannel tube wall green layer slurry forms：Alumina powder (5 μm of average grain diameter), phenolic resin, p-methyl benzenesulfonic acid (cure Agent), ethyl alcohol by proportioning 50~500g：50~200g：(being more than 0 to 0.2) times phenolic resin quality：1000mL.With average mesh Size is replaced the polyurethane resin foam that average pore size is 3mm in step (3) by the polyurethane resin foamed material of 5mm.Step (3) the skeleton muscle fineness of support frame, which reaches, in is pre-designed 600 μm of value.The hollow foam material obtained, macroscopic view three The average value of the mesh size of dimension connection perforate is 4mm.Support frame itself has the micro- logical of hollow structure for three-dimensional communication Road, the average-size of hollow microchannel internal diameter is 550 μm, and the average-size of outer diameter is 1000 μm.The chemical structure of microchannel tube wall Into mainly comprising aluminium oxide, microchannel tube wall contains nanoscale to the hole in micron order aperture, and average pore size is 4 μm, porosity For 70%.
Embodiment 4
The present embodiment preparation process is the preparation of the hollow foam alumina material of the microchannel tube wall with compact texture Technique：The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane.In step (2), Microchannel tube wall green layer slurry forms：Alumina powder (5 μm of average grain diameter), Aluminum sol (a (Al2O3·nH2O)· bHx·cH2O), water is by 50~500g of proportioning：50~500g：1000mL.Polyurethane resin using average mesh size as 5mm steeps Foam material replaces the polyurethane resin foam that average pore size is 3mm in step (3).The skeleton hypertrophy of tendon and muscle of support frame in step (3) Thin degree, which reaches, is pre-designed 1100 μm of value.The hollow foam material obtained, the mesh size of macroscopic three dimensional connection perforate Average value is 4mm.Support frame itself is the microchannel with hollow structure of three-dimensional communication, and hollow microchannel internal diameter is averaged Size is 1000 μm, and the average-size of outer diameter is 1600 μm.Microchannel tube wall is compact texture, and chemical component mainly includes oxygen Change aluminium.
Embodiment 5
The present embodiment preparation process is the preparation work of the hollow foam Sialon material of the microchannel tube wall with porous structure Skill：The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane, with average mesh ruler It is very little that the polyurethane resin foam that average pore size is 3mm in step (3) is replaced by the polyurethane resin foamed material of 8mm.Step (2) In, slurry composition is：Sic powder (5 μm of average grain diameter), silica flour (3.5 μm of average grain diameter), silica powder (1 μ of average grain diameter M), active oxidation aluminium powder (2 μm of average grain diameter), phenolic resin, p-methyl benzenesulfonic acid (curing agent), ethyl alcohol are by 50~500g of proportioning： 50~500g：50~500g：50~500g：50~200g：(being more than 0 to 0.2) times phenolic resin quality：1000mL.Step (3) The skeleton muscle fineness of middle support frame, which reaches, is pre-designed 2200 μm of value.By pretreated shaping forerunner in step (6) Body carries out high temperature sintering in high pure nitrogen atmosphere, and temperature is 1200~2500 DEG C, keeps the temperature 10min~6h.What is obtained is hollow Foamed material, the average value of the mesh size of macroscopic three dimensional connection perforate is 5mm.Support frame itself has for three-dimensional communication The microchannel of hollow structure, the average-size of hollow microchannel internal diameter is 2000 μm, and the average-size of outer diameter is 3000 μm.It is micro- logical The chemical component of road tube wall mainly includes Sialon (Si6-xAlxOxN8-x), and microchannel tube wall contains nanoscale to micron order aperture Hole, average pore size be 3 μm, porosity 30%.
Embodiment 6
The present embodiment preparation process is the hollow foam carbofrax material of the microchannel tube wall with asymmetric porous structure Preparation process：The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane, with flat Equal mesh size replaces the polyurethane resin that average pore size is 3mm in step (3) to steep by the polyurethane resin foamed material of 5mm Foam.In step (2), two kinds of slurries are prepared, the composition of wherein slurry A is：Sic powder (5 μm of average grain diameter), silica flour are (average 3.5 μm of grain size), phenolic resin, p-methyl benzenesulfonic acid (curing agent), ethyl alcohol by proportioning 50~500g：50~500g：50~200g： (being more than 0 to 0.2) times phenolic resin quality：1000mL.The composition of slurry B is：Sic powder (0.5 μm of average grain diameter), silicon Powder (0.5 μm of average grain diameter), phenolic resin, p-methyl benzenesulfonic acid (curing agent), ethyl alcohol are by 50~500g of proportioning：50~500g：50 ~200g：(being more than 0 to 0.2) times phenolic resin quality：1000mL.The skeleton muscle fineness of support frame reaches in step (3) To being pre-designed 600 μm of value.In step (4) in the building process of microchannel tube wall green layer, first with slurry A in step (2) Carry out " hanging material-except additional size-semi-solid preparation " operation circulation progress is several times；Slurry B " hang in recycle step (2) Slurry-except additional size-semi-solid preparation " operation circulation progress is several times.The hollow foam material obtained, macroscopic three dimensional connection are opened The average value of the mesh size in hole is 4mm.Support frame itself is the microchannel with hollow structure of three-dimensional communication, hollow micro- The average-size of channel internal diameter is 550 μm, and the average-size of outer diameter is 1000 μm.The chemical component of microchannel tube wall mainly includes Carborundum, and microchannel tube wall contains asymmetric nanoscale to hole (the i.e. hole of micro-channel tubes parietal layer in micron order aperture Structure is anisotropic), wherein be 4 μm by 200 μ m thick region average pore size of tube wall inner wall side, porosity 50%.Tube 25 μ m thick region average pore size of wall outer wall side is 1 μm, porosity 45%.
Embodiment 7
The present embodiment preparation process is the preparation of the hollow foam stainless steel material of the microchannel tube wall with porous structure Technique, the present embodiment difference from Example 1 are, the epoxy resin in step (1) are replaced with polyurethane, with average mesh Size is replaced the polyurethane resin foam that average pore size is 3mm in step (3) by the polyurethane resin foamed material of 5mm.Step (2) in, slurry composition is：It is 316L stainless steels powder (10~30 μm of particle size range), phenolic resin, polyvinyl butyral, solid Agent, ethyl alcohol are by 50~500g of proportioning：50~200g：50~200g：(being more than 0 to 0.2) times phenolic resin quality：1000mL. Support frame muscle fineness, which reaches, in step (3) is pre-designed 600 μm of value.The hollow foam material obtained, macroscopic three dimensional The average value for connecting the mesh size of perforate is 4mm.Support frame itself is the microchannel with hollow structure of three-dimensional communication, The average-size of hollow microchannel internal diameter is 550 μm, and the average-size of outer diameter is 1000 μm.The chemical component master of microchannel tube wall 316L stainless steels are included, microchannel tube wall contains nanoscale to the hole in micron order aperture, and average pore size is 5 μm, porosity For 50%.
Embodiment 8
The present embodiment preparation process is the preparation process of the hollow foam copper product of the microchannel tube wall with porous structure： The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane, with average mesh size The polyurethane resin foam that average pore size is 3mm in step (3) is replaced by the polyurethane resin foamed material of 6mm.Step (2) In, slurry composition is：Copper oxide powder (10~30 μm of particle size range), copper powder material (10~30 μm of particle size range), phenolic resin, Polyvinyl butyral, curing agent, ethyl alcohol are by 50~500g of proportioning：50~500g：50~200g：50~200g：(be more than 0 to 0.2) times phenolic resin quality：1000mL.Support frame muscle fineness, which reaches, in step (3) is pre-designed 600 μm of value.It is obtained The hollow foam material obtained, the average value of the mesh size of macroscopic three dimensional connection perforate is 5mm.Support frame itself connects to be three-dimensional The logical microchannel with hollow structure, the average-size of hollow microchannel internal diameter is 550 μm, and the average-size of outer diameter is 1000 μm.For the chemical component of microchannel tube wall mainly comprising copper, microchannel tube wall contains nanoscale to the hole in micron order aperture, average Aperture is 3 μm, porosity 40%.
Embodiment 9
The present embodiment preparation process is the preparation process of the hollow foam copper product of the microchannel tube wall with compact texture, Specially following key step：
(1) preparation of thickening slurry：Polyvinyl alcohol powder, epoxy resin, curing agent, ethyl alcohol are made through abundant ball mill mixing Thickening slurry, polyvinyl alcohol, epoxy resin, curing agent, the proportioning of ethyl alcohol are 50~500g：More than 0 to 500g：10~100g： 1000mL (per 1000mL solvents i.e. in slurry, be corresponding with 50~500g polyvinyl alcohol powder, more than 0 to 500g epoxy resin and The corresponding curing agent of 10~100g epoxy resin).
(2) preparation of microchannel tube wall green layer plating solution：According to main salt (copper sulphate, copper chloride, basic copper carbonate, winestone Sour copper, copper acetate) 10~100g/L；Complexing agent (sodium potassium tartrate tetrahydrate, sodium citrate, sodium gluconate, triethanolamine, four hydroxypropyls Base ethylenediamine, glycerine, Glycolic acid or EDETATE DISODIUM) 10~100g/L；Reducing agent (formaldehyde, hydrazine, boron hydride, dimethylamino Borine, sodium hypophosphite) 10~100g/L；Additive (stabilizer, accelerating agent, leveling agent or brightener) 10~50g/L；PH tune It saves agent (sodium hydroxide, sodium carbonate) 10~50g/L and prepares electroless copper aqueous solution.
(3) preparation of template foamed material is sacrificed：Use average mesh size that there is three-dimensional networks structure for 3mm Polyurethane resin foamed material, thickening processing is carried out to the network skeleton muscle of polyurethane resin foamed material：By polyurethane tree Fat vacuole foam is immersed in the thickening slurry prepared by step (1), after removing slurry extra in foam formwork material mesh after taking-up, In 80~150 DEG C of semi-solid preparations.According to size needed for the internal diameter for the hollow microchannel for finally needing hollow foam material to be prepared (0.02mm~9mm) is required, cycle progress " leaching hanging material-except additional size-semi-solid preparation " operate several times until network skeleton The fineness of muscle, which reaches, is pre-designed 550 μm of value.
(4) prepared by foamed material precast body：That is the structure of the tube wall green layer of the hollow microchannel of three-dimensional networks.By net Network skeleton muscle fineness thickening to the three-dimensional communication for being pre-designed value sacrifice template foamed material cut out to required shape and The sample of size is sufficiently submerged in 3~5min of processing in the stannous chloride solution of 30~50g/L, sample then is put into 0.5 1~2min is handled in the palladium chloride solution of~1g/L.The redundant solution in three-dimensional communication perforate is removed after taking-up, is put into step (2) in the microchannel tube wall green layer plating solution prepared, it is 11~13 to maintain pH value, and temperature is 20~100 DEG C of progress electroless coppers Operation.1~10h of electroless copper operating time is determined according to the requirement for the hollow micro-channel tubes wall thickness being pre-designed, finally will Sample takes out, is dry after cleaning, completes the structure of microchannel tube wall green layer, obtains precast body foamed material.
(5) removal of template foamed material is sacrificed：By precast body foamed material high-purity argon gas (argon gas volume fraction >= 99.999%) or under other inert gas shieldings carry out sacrificing template foamed material goes division operation, and 1~10 DEG C of heating rate/ Min, 650 DEG C, 10~300min of soaking time for the treatment of temperature, the sample of acquisition can select one kind in proceeding as follows or Two or more method processing：Acid solution cleaning, aqueous slkali cleaning, acetone cleaning, washes of absolute alcohol, deionized water cleaning, sky Hollow foam material shaping presoma is made in roasting, completely drying in gas.
(6) molding procedure：Shaping presoma is subjected to high temperature sintering, temperature under high-purity argon gas protection or vacuum condition 800~1050 DEG C, heating rate 0.5~2 DEG C/min, soaking time 10min~6h.
(7) (selection) is post-processed：The sample obtained in step (6) one or both of is proceeded as follows with top Method processing：Acid solution cleaning, aqueous slkali cleaning, organic solvent (including but not limited to acetone, absolute ethyl alcohol) cleaning, deionized water It is calcined in cleaning, air under roasting, inert atmosphere protection, the hollow foam material of three-dimensional networks is made.In being obtained Empty foamed material is formed in macroscopically its structure by the support frame network struction of three-dimensional communication, macroscopic three dimensional connection perforate The average value of mesh size is 2.5mm.Support frame itself is the microchannel with hollow structure of three-dimensional communication, hollow micro- logical The average-size of road internal diameter is 500 μm, and the average-size of outer diameter is 900 μm.Microchannel tube wall be compact texture, chemical component Mainly include copper.
Embodiment 10
The present embodiment preparation process is the preparation work of the hollow foam material of the microchannel tube wall with porous structural pipe wall Skill is specially following key step：
(1) preparation of thickening slurry：Active oxidation magnesium powder, polyurethane, curing agent, ethyl alcohol are made through abundant ball mill mixing Thickening slurry, active oxidation magnesium powder, polyurethane, curing agent, the proportioning of ethyl alcohol are 50~500g：More than 0 to 500g：10~ 100g：1000mL (per 1000mL ethyl alcohol i.e. in slurry, be corresponding with 50~500g active oxidations magnesium powder, more than 0 to 500g polyurethane Curing agent corresponding with 10~100g epoxy resin).
(2) preparation of microchannel tube wall green layer slurry：By polytetrafluoroethylene (PTFE) powder (10 μm of average grain diameter), polytetrafluoroethyl-ne Alkene lotion (solid content 60wt%), aqueous polyurethane are by 50~500g of proportioning：1000g：50~500g, through abundant ball mill mixing system Into microchannel tube wall green layer slurry.
(3) preparation of template foamed material is sacrificed：Use average mesh size that there is three-dimensional networks structure for 5mm Polyurethane resin foamed material, thickening processing is carried out to the network skeleton muscle of polyurethane resin foamed material：By polyurethane tree Fat vacuole foam is immersed in the thickening slurry prepared by step (1), after removing slurry extra in foam formwork material mesh after taking-up, In 80~150 DEG C of semi-solid preparations.According to size needed for the internal diameter for the hollow microchannel for finally needing hollow foam material to be prepared (0.02mm~9mm) is required, cycle progress " leaching hanging material-except additional size-semi-solid preparation " operate several times until network skeleton The fineness of muscle, which reaches, is pre-designed 450 μm of value.
(4) prepared by foamed material precast body：That is the structure of the tube wall green layer of the hollow microchannel of three-dimensional networks.By net Network skeleton muscle fineness thickening to the three-dimensional communication for being pre-designed value sacrifice template foamed material cut out to required shape and Then size is sufficiently submerged in the microchannel tube wall green layer slurry of step (2) preparation, remove template foamed material mesh In after extra slurry, in 80~100 DEG C of semi-solid preparations.According to the requirement for the hollow micro-channel tubes wall thickness being pre-designed, " hanging Material-remove additional size-semi-solid preparation " operation can cycle progress several times, finally by the skeleton foam of acquisition in 100~120 DEG C It is fully cured, completes the structure of microchannel tube wall green layer, obtain precast body foamed material.
(5) removal of template foamed material is sacrificed：Precast body foamed material is cleaned in acid solution, then deionized water is clear It washes, hollow foam material shaping presoma is made after drying completely.
(6) molding procedure：Shaping presoma is subjected to forming operation under high-purity argon gas protection, 120~300 DEG C of temperature, Soaking time 10min~6h.
(7) (selection) is post-processed：The sample obtained in step (6) one or both of is proceeded as follows with top Method processing：Acid solution cleaning, aqueous slkali cleaning, organic solvent (including but not limited to acetone, absolute ethyl alcohol) cleaning, deionized water It is calcined in cleaning, air under roasting, inert atmosphere protection, the hollow foam material of three-dimensional networks is made.In being obtained Empty foamed material is formed in macroscopically its structure by the support frame network struction of three-dimensional communication, macroscopic three dimensional connection perforate The average value of mesh size is 4mm.Support frame itself be three-dimensional communication the microchannel with hollow structure, hollow microchannel The average-size of internal diameter is 400 μm, and the average-size of outer diameter is 900 μm.The chemical component of microchannel tube wall mainly includes poly- four Vinyl fluoride, microchannel tube wall are porous structural pipe wall, and containing nanoscale to the hole in micron order aperture, average pore size is 5 μm, hole Gap rate is 50%.
Embodiment 11
The present embodiment preparation process is the preparation of the hollow foam polythene material of the microchannel tube wall with porous structure Technique is specially following key step：The present embodiment difference from Example 10 is that microchannel tube wall is given birth in step (2) The preparation of base layer slurry：Polyethylene powder (10 μm of average grain diameter), polyethylene emulsion (solid content 40%), aqueous polyurethane are pressed Match 50~500g：1000g：Microchannel tube wall green layer slurry is made through abundant ball mill mixing in 50~500g.With average mesh Size is replaced the polyurethane resin foam that average pore size is 5mm in step (3) by the polyurethane resin foamed material of 8mm.Step (3) the skeleton muscle fineness of support frame, which reaches, in is pre-designed 600 μm of value.Semi-solid preparation temperature is 50 DEG C in step (4), most Final curing temperature is 60 DEG C.In step (6), forming temperature is 70~220 DEG C, soaking time 5min~3h.What is obtained is hollow Foamed material, the average value of the mesh size of macroscopic three dimensional connection perforate is 6.5mm.Support frame itself is the tool of three-dimensional communication There is the microchannel of hollow structure, the average-size of hollow microchannel internal diameter is 550 μm, and the average-size of outer diameter is 1000 μm.It is micro- Passage tube wall is compact texture, and chemical component mainly includes polyethylene.
Embodiment 12
The present embodiment preparation process is the preparation process of the hollow foam carbon material of the microchannel tube wall with porous structure： The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane.It is micro- logical in step (2) Road tube wall green layer slurry forms：Activated carbon powder (5 μm of average grain diameter), phenolic resin, p-methyl benzenesulfonic acid (curing agent), second Alcohol is by 50~500g of proportioning：50~200g：(being more than 0 to 0.2) times phenolic resin quality：1000mL, through abundant ball mill mixing system Into microchannel tube wall green layer slurry.It replaces putting down in step (3) using average mesh size by the polyurethane resin foamed material of 5mm The polyurethane resin foam that equal aperture is 3mm.The skeleton muscle fineness of support frame, which reaches, in step (3) is pre-designed value 1100μm.The hollow foam material obtained, the average value of the mesh size of macroscopic three dimensional connection perforate is 4mm.Support frame Itself it is the microchannel with hollow structure of three-dimensional communication, the average-size of hollow microchannel internal diameter is 1000 μm, outer diameter Average-size is 1600 μm.For the chemical component of microchannel tube wall mainly comprising activated carbon and indefiniteness carbon, microchannel tube wall is more Hole structural pipe wall, containing Subnano-class to the hole in micron order aperture, average pore size is 1 μm, porosity 60%.
Embodiment 13
The present embodiment preparation process is the preparation work of the hollow foam graphite material of the microchannel tube wall with compact texture Skill：The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane.It is micro- in step (2) Passage tube wall green layer slurry forms：Activated carbon powder (5 μm of average grain diameter), phenolic resin, p-methyl benzenesulfonic acid (curing agent), Ethyl alcohol is by 50~500g of proportioning：50~200g：(being more than 0 to 0.2) times phenolic resin quality：1000mL, through abundant ball mill mixing Microchannel tube wall green layer slurry is made.It is replaced using average mesh size by the polyurethane resin foamed material of 5mm in step (3) Average pore size is the polyurethane resin foam of 3mm.The skeleton muscle fineness of support frame, which reaches, in step (3) is pre-designed value 800μm.Postprocessing working procedures in step (7) are：High temperature graphitization is carried out under an inert atmosphere to the sample prepared in step (6) Processing, 600 DEG C~3000 DEG C of temperature.The hollow foam material obtained, the mesh size of macroscopic three dimensional connection perforate are averaged It is worth for 4mm.Support frame itself be three-dimensional communication the microchannel with hollow structure, the average-size of hollow microchannel internal diameter For 600 μm, the average-size of outer diameter is 1200 μm.Microchannel tube wall is fine and close structural pipe wall, and chemical component mainly includes stone Ink.
Embodiment 14
The present embodiment preparation process is hollow foam aluminium/composite material of silicon carbide of the microchannel tube wall with compact texture Preparation process：The present embodiment difference from Example 1 is, the epoxy resin in step (1) is replaced with polyurethane.With flat Equal mesh size replaces the polyurethane resin that average pore size is 3mm in step (3) to steep by the polyurethane resin foamed material of 5mm Foam.The skeleton muscle fineness of support frame, which reaches, in step (3) is pre-designed 1000 μm of value.The postprocessing working procedures of step (7) In, the hollow foam carbofrax material to the microchannel tube wall with porous structure prepared in step (6), for its microchannel Wall section carries out localized hyperthermia's liquid phase aluminising operation, and aluminising temperature is 600 DEG C~1000 DEG C, time 1min~3h.It is obtained Hollow foam material, macroscopic three dimensional connection perforate mesh size average value be 4mm.Support frame itself is three-dimensional communication The microchannel with hollow structure, the average-size of hollow microchannel internal diameter is 800 μm, and the average-size of outer diameter is 1600 μ m.Microchannel tube wall is compact texture, and chemical component mainly includes carborundum and aluminium.
As shown in Figure 1, it can be seen that the hollow foam material from the macro morphology of the hollow foam material with porous tube wall Material has typical foam porosity, possesses macroscopical perforate network hole of three-dimensional communication.
As shown in Fig. 2, the partial enlargement pattern from the hollow foam material with porous tube wall can be seen that by support rib Frame (a) three-dimensional communication is to form perforate (b) network structure.Wherein, support frame (a) itself have size it is controllable, it is hollow Microchannel (c), the cross section of the microchannel (c) is nearly round shape or ellipticity.
As shown in figure 3, it can be seen that this from the hollow microchannel tube wall pattern of the hollow foam material with porous tube wall Microchannel tube wall is porous structure.
It as shown in figure 4, can from the hollow microchannel tube wall microscopic appearance of the hollow foam material with porous tube wall Go out, tube wall body is formed for micron particles, has pore structure between particle.
As shown in figure 5, it can be seen that the hollow foam material from the macro morphology of the hollow foam material with fine and close tube wall Material has typical foam porosity, possesses macroscopical perforate network hole of three-dimensional communication.
As shown in fig. 6, the partial enlargement pattern from the hollow foam material with fine and close tube wall can be seen that support frame Itself it is hollow microchannel.
As shown in fig. 7, from the hollow microchannel tube wall pattern of the hollow foam material with fine and close tube wall can be seen that Empty microchannel tube wall itself is compact texture.
Specific embodiment shows the hollow foam material of three-dimensional networks of the present invention, macrostructure three The support frame of connection is tieed up, support frame itself is the microchannel with hollow structure of three-dimensional communication, and microchannel tube wall includes There are nanoscale or/and the hole in micron order aperture.Made using the macromolecule resin foamed material with three-dimensional networks structure For original template material, the sacrifice template foamed material that skeleton hypertrophy of tendon and muscle carefully reaches setting value is made after carrying out thickening processing.It will sacrifice Mould material immersion after template foamed material is cut out is full and uniform mixed through ball milling by principal component powder, macromolecule resin, solvent The additional size in template in mesh is removed in tube wall green layer slurry in microchannel made of conjunction, after taking-up, drying cycles several Secondary " dipping-except slurry-drying " operation.Then hot setting obtains and original foam after being pyrolyzed pretreatment under protective atmosphere The foaming structure shaping presoma of the similar three-dimensional networks of shape.Through molding procedure, postprocessing working procedures, hollow foam is made Material.The technical matters is simple, without complex device.Prepared hollow foam material is novel foam porous material, is innovated Point is that it has the hole of three types simultaneously：The perforate network of macroscopic three dimensional connection, the hollow microchannel, micro- of three-dimensional communication Nanoscale or/and micron order hole in passage tube wall.It is the hollow foam material high temperature resistant, anti-oxidant, corrosion-resistant, have preferable Mechanical property.

Claims (20)

1. the hollow foam material of a kind of three-dimensional communication, which is characterized in that the hollow foam material is macroscopically by support frame (a) three-dimensional communication to be to form perforate (b) network structure, wherein, support frame (a) itself have size it is controllable, it is hollow micro- Passage (c), the cross section of the microchannel (c) is nearly round shape or ellipticity.
2. hollow foam material according to claim 1, which is characterized in that the tube wall of the hollow microchannel (c) is Porous structure tube wall or compact texture tube wall.
3. the hollow foam material according to foregoing any claim, which is characterized in that the porous structure tube wall body Hole containing nanoscale and/or micron order aperture.
4. the hollow foam material according to foregoing any claim, which is characterized in that the material of the tube wall body can For homogenously or inhomogenously.
5. the hollow foam material according to foregoing any claim, which is characterized in that the physics knot of the tube wall body Structure or chemical constitution can be isotropic or anisotropic.
6. the hollow foam material according to foregoing any claim, which is characterized in that the mesh size of the perforate (b) D1 is 0.2mm~20mm.
7. the hollow foam material according to foregoing any claim, which is characterized in that the hollow microchannel (c) Outer diameter d2 is 0.1mm~10mm, and internal diameter size d3 is 0.02mm~9mm.
8. the hollow foam material according to foregoing any claim, which is characterized in that the hole that the porous tube wall contains The range of aperture size of gap is 0.1nm~100 μm, and the porosity p of tube wall is 0<P≤70%.
9. the hollow foam material according to foregoing any claim, which is characterized in that the material of the hollow foam material Matter is selected from following one or more：Metal, ceramics, macromolecule, carbon material.
10. hollow foam material according to claim 9, which is characterized in that the metal material be selected from comprising Li, Na, K, Al, Ca, Sr, Mg, Ni, Fe, Cu, V, Cr, Mo, W, Mn, Co, Zn, Y, Zr, Nb, Ag, Pd, Ru, Rh, Au, Pt, Ta, group of the lanthanides gold Category, the metal simple-substance of actinide metals, the alloy comprising above-mentioned element, metal solid solution or one kind in intermetallic compound or two Kind or more；
The ceramic material is selected from following one or more：(1) oxide and composite oxides：Al2O3、SiO2、ZrO2、 MgO、CaO、BeO、SrO、NiO、CuO、TiO2、V2O5、Fe3O、RuO2、WO3、ZnO、SnO2、CdO、Nb2O5、PbO、Pb3O4、 Bi2O3、MoO3、Cr2O3、Y2O3、MnO、MnO2、Mn2O3、Mn3O4、CoO、Co3O4、Co2O3, lanthanide oxide, actinide oxide, Mullite 3Al2O3·2SiO2, aluminum-spinel MgO3Al2O3, magnesia chrome spinel MgOCr2O3, zircon ZrO2·SiO2、 Calcium orthosilicate 2CaOSiO2, forsterite 2MgOSiO2, perovskite composite oxide, perovskite composite oxide is CaTiO3Or the CaTiO of doping3、BaTiO3Or the BaTiO of doping3、LiNbO3Or the LiNbO of doping3、SrZrO3Or doping SrZrO3、LaMnO3Or the LaMnO of doping3, doping SrCoyFe1-yO3-δ, 0 ＜ y ＜, 1,0 ＜ δ ＜ 3, the A La substitutedxA1- xCoyFe1-yO3-δ, wherein A=Sr, Ba, Ca, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ δ ＜ 3；(2) carbide：Carborundum, zirconium carbide, carbon Change tungsten, titanium carbide, boron carbide, ramet, vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide, cementite, manganess carbide；(3) nitrogenize Object：α-Si3N4、β-Si3N4、AlN、Si6-xAlxOxN8-x、BN；(4)Si；
The macromolecule material is selected from following one or more：(1) polyolefins：Polytetrafluoroethylene (PTFE), Kynoar, Polyethylene, polypropylene, polystyrene, polyvinyl chloride, polystyrene, polyacrylonitrile；(2) it is polyamide-based：Polycaprolactam PA6, Polyhexamethylene sebacamide PA610, poly- 11 lactams PA11, nylon 612 PA612, nylon 1010 PA1010；(3) polyesters：Polyurethane, polymethyl methacrylate, polyisocyanurate, makrolon, poly terephthalic acid Dibutyl ester, polyethylene terephthalate；(4) polyethers：Polyphenylene oxide, polyphenylene sulfide；
The carbon material material is selected from following one or more：Graphite, agraphitic carbon, graphene, diamond, activated carbon, Ordered mesopore carbon, unordered mesoporous carbon, carbon fiber, carbon nanotubes, carbon micron tube.
11. such as the preparation method of claim 1~10 any one of them hollow foam material, which is characterized in that the preparation side Method includes the following steps：
(1) preparation section of template foamed material is sacrificed：First, steeped using the macromolecule resin with three-dimensional networks structure For foam material as original template material, the macromolecule resin foamed material is epoxy resin, phenolic resin, furane resins, poly- It is more than one or both of urethane, polyester, polyethers；Secondly, to the network skeleton muscle of the macromolecule resin foamed material into The processing of row thickening, until skeleton muscle fineness reaches size 0.02mm~9mm needed for the internal diameter of hollow microchannel, is thus made Sacrifice template foamed material；
(2) foamed material precast body preparation section：The process is selected from following one or more kinds of combinations：(a) prepare micro- Gained in step (1) is sacrificed template foamed material and is sufficiently submerged in into the green layer slurry by passage tube wall green layer slurry, with After take out, remove extra slurry after 80~150 DEG C carry out semi-solid preparations；Xun Huan carries out above-mentioned " the extra slurry of dipping sizing agent-removal Material-semi-solid preparation " operation is pre-designed value until the thickness of microchannel tube wall green layer reaches, finally by sample in 100~300 DEG C It is fully cured, foamed material precast body is made；(b) using galvanoplastic, the skeleton muscle surface construction of template foamed material is being sacrificed Thus foamed material precast body is made in microchannel tube wall green layer；(c) using electroless plating method, template foamed material is being sacrificed Thus foamed material precast body is made in skeleton muscle surface construction microchannel tube wall green layer；(d) using solution etches method, to micro- Passage tube wall green layer performs etching processing, the micro-channel tubes that structure is distributed with particular geometric configuration or particular chemicals Thus foamed material precast body is made in wall green layer；(e) particular crystal grown using hydro-thermal reaction method builds microchannel Thus foamed material precast body is made in tube wall green layer；(f) using anodizing, sun is carried out to microchannel tube wall green layer Pole oxidation processes, the microchannel tube wall green layer that structure is distributed with particular geometric configuration or particular chemicals, thus make Obtain foamed material precast body；(g) using sol-gel method, microchannel tube wall green layer is built, it is prefabricated that foamed material is thus made Body；(h) using Langmuir-Blodgett methods, structure has the film layer green layer of Langmuir-Blodgett film features, Thus foamed material precast body is made；(i) using physical vaporous deposition, microchannel tube wall green layer is built, bubble is thus made The prefabricated body of foam；(j) using chemical vapour deposition technique, microchannel tube wall green layer is built, it is prefabricated that foamed material is thus made Body；
(3) removing step of template foamed material is sacrificed：Foamed material precast body obtained in step (2) is protected in inert gas It is pyrolyzed under shield, 1~10 DEG C/min of heating rate, 600~900 DEG C, 10~300min of soaking time of pyrolysis temperature, acquisition Sample is handled by one or both of following operation is above：Acid solution cleaning, aqueous slkali cleaning, acetone clean, are anhydrous It is roasted in ethyl alcohol cleaning, deionized water cleaning, air；Hollow foam material shaping presoma is made；
(4) molding procedure：The process is selected from following one or more kinds of combinations：(a) by step (3) obtained by foam Material shaping presoma carries out high temperature sintering, 900~2500 DEG C of temperature, soaking time 10min~6h under protective atmosphere；It is described Protective atmosphere is selected from high-purity argon gas protection, high-purity hydrogen protection, high pure nitrogen protection, high-purity hydrogen-argon-mixed protection, vacuum item It is more than one or both of part；(b) forming operation is carried out using galvanoplastic；(c) forming operation is carried out using electroless plating method； (d) forming operation is carried out using solution etches method；(e) forming operation is carried out using hydro-thermal reaction method；(f) anodizing is used Carry out forming operation；(g) forming operation is carried out using sol-gel method；(h) using Langmuir-Blodgett methods carry out into Type operates；(i) forming operation is carried out using physical vaporous deposition；(j) forming operation is carried out using chemical vapour deposition technique； (k) electrified regulation completion forming operation is carried out using to sample application voltage；
(5) postprocessing working procedures：More than sample one or both of proceeds as follows after the shaping that will be obtained in step (4)： It roasts in acid solution cleaning, aqueous slkali cleaning, acetone cleaning, washes of absolute alcohol, deionized water cleaning, air, is thus made The hollow foam material of three-dimensional communication.
12. the preparation method of hollow foam material according to claim 11, which is characterized in that the thickening in step (1) Processing is selected from following one or more：Galvanoplastic thickening, electroless plating method thickening, sol-gel method.
13. according to the preparation method of the hollow foam material described in claim 11, which is characterized in that the thickening in step (1) Processing carries out as follows：By principal component：Solvent=100：The mass ratio of (50~200) prepares thickening slurry, will be initial Mould material is immersed into thickening slurry, and Xun Huan impregnate-remove additional size-semi-solid preparation operation until the thin journey of skeleton hypertrophy of tendon and muscle Degree reaches size 0.02mm~9mm needed for the internal diameter of hollow microchannel；Wherein, the principal component of thickening slurry is in following substance One or more：It is polyurethane, phenolic resin, epoxy resin, furane resins, polyvinyl alcohol, polyvinyl butyral, different Cyanate, modified isocyanate, carboxymethyl cellulose, cellulose acetate, starch, aluminium oxide, magnesia, silica, calcium oxide, It is di-iron trioxide, ferroso-ferric oxide, cobalt oxide, manganese oxide, copper oxide, zinc oxide, tin oxide, nickel oxide, graphite, unformed Carbon, graphene, diamond, activated carbon, ordered mesopore carbon, unordered mesoporous carbon, carbon fiber, carbon nanotubes, carbon micron tube, urea, Sylvite, sodium salt, calcium salt, magnesium salts, aluminium salt, ferrous salt, molysite, mantoquita, manganese salt, nickel salt, zinc salt, ammonium salt, tartrate, sulfurous acid Hydrogen salt, sulphite, thiosulfate, halide salts, sulfonated bodies salt, salicylate, benzoate, acetate, phosphate, carbon Hydrochlorate, bicarbonate, lactate, sulfate, nitrate, Li, Na, K, Al, Ca, Sr, Mg, Ni, Fe, Cu, V, Cr, Mo, W, Mn, Co, Zn, Y, Zr, Nb, Ag, Pd, Ru, Rh, Au, Pt, Ta, lanthanide series metal, actinide metals metal simple-substance, include above-mentioned element Alloy, metal solid solution or intermetallic compound；Solvent is selected from following one or more：Water, ethyl alcohol, acetone, second two Alcohol, hexamethylene, n-hexane, toluene, dimethylbenzene, tetrahydrofuran.
14. according to the preparation method described in claim 11~13 any claim, which is characterized in that described in step (2) Microchannel tube wall green layer slurry presses 50~500g by principal component powder, binding agent, curing agent, solvent：50~200g：(it is more than 0 To 0.2) times binding agent quality：The proportioning of 1000mL is made through abundant ball mill mixing；
Wherein, principal component powder is selected from the one or more of metal, ceramics, macromolecule or carbon material；
The metal material be selected from comprising Li, Na, K, Al, Ca, Sr, Mg, Ni, Fe, Cu, V, Cr, Mo, W, Mn, Co, Zn, Y, Zr, Nb, Ag, Pd, Ru, Rh, Au, Pt, Ta, lanthanide series metal, the metal simple-substance of actinide metals, the alloy comprising above-mentioned element, metal are solid It is more than one or both of solution or intermetallic compound；
The ceramic material is selected from following one or more：(1) oxide and composite oxides：Al2O3、SiO2、ZrO2、 MgO、CaO、BeO、SrO、NiO、CuO、TiO2、V2O5、Fe3O、RuO2、WO3、ZnO、SnO2、CdO、Nb2O5、PbO、Pb3O4、 Bi2O3、MoO3、Cr2O3、Y2O3、MnO、MnO2、Mn2O3、Mn3O4、CoO、Co3O4、Co2O3, lanthanide oxide, actinide oxide； Mullite (3Al2O3·2SiO2), aluminum-spinel (MgO3Al2O3), magnesia chrome spinel (MgOCr2O3), zircon (ZrO2·SiO2), calcium orthosilicate (2CaOSiO2), forsterite (2MgOSiO2), perovskite composite oxide (CaTiO3Or the CaTiO of doping3、BaTiO3Or the BaTiO of doping3、LiNbO3Or the LiNbO of doping3、SrZrO3Or doping SrZrO3、LaMnO3Or the LaMnO of doping3, doping SrCoyFe-1-yO3-δ, 0 ＜ y ＜, 1,0 ＜ δ ＜ 3, the A La substitutedxA1- xCoyFe1-yO3-δ, wherein A=Sr, Ba, Ca, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ δ ＜ 3)；(2) carbide：Carborundum, zirconium carbide, Tungsten carbide, titanium carbide, boron carbide, ramet, vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide, cementite, manganess carbide；(3) nitrogenize Object：α-Si3N4、β-Si3N4、AlN、Si6-xAlxOxN8-x、BN；(4)Si；
The macromolecule material is selected from following one or more：(1) polyolefins：Polytetrafluoroethylene (PTFE), Kynoar, Polyethylene, polypropylene, polystyrene, polyvinyl chloride, polystyrene, polyacrylonitrile；(2) it is polyamide-based：Polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), poly- 11 lactams (PA11), nylon 612 (PA612), the poly- last of the ten Heavenly stems Two acyl decamethylene diamines (PA1010)；(3) polyesters：Polyurethane, polymethyl methacrylate, polyisocyanurate, makrolon, Polybutyl terapthalate, polyethylene terephthalate (4) polyethers：Polyphenylene oxide, polyphenylene sulfide；
The carbon material material is selected from following one or more：Graphite, agraphitic carbon, graphene, diamond, activated carbon, Ordered mesopore carbon, unordered mesoporous carbon, carbon fiber, carbon nanotubes, carbon micron tube；
Binding agent is polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, chitosan, alginic acid, sodium alginate, epoxy Resin, phenolic resin, furane resins, polyurethane, Polycarbosilane, polyborazine, polyborosiloxane, PVDF hollow fiber membrane, poly- zirconium boron The one or more of silazane；
Curing agent is formaldehyde, glutaraldehyde, terephthalylidene aldehyde, water-soluble amine-formaldehyde condensation products, dimethyl urea, trimethyl three Poly cyanamid, dimethyl ethyl urea, sodium sulphate, zinc sulfate, boric acid, borax, silane-type cross-linking agent, bichromate, chromic nitrate, chromium Complex compound, cuprammonium hydroxide, melamine, phenol, polyisocyanate, diethy-aceto oxalate, dimethyl oxalate, propylene glycol, have urea Machine titanium, epoxychloropropane, chlorethanol, sodium tetraborate, N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide, β-ring paste Essence, N-isopropylacrylamide, acrylamide, acrylic acid, methyl methacrylate, vanillic aldehyde, Geniposide, glyoxal, poly- (N- second Allyl diglycol)-acetaldehyde, polyacrylonitrile, succinic acid and its derivative, amion acetic acid, lysine, two isocyanato hexanes, inclined benzene Front three acid anhydrides, bromo-decane, to triazobenzene formic acid, heparin, ethylene glycol diglycidylether, epichlorohydrine, acetic acid, lemon Lemon acid, formic acid, hydroxyacetic acid, lactic acid, hydroxysuccinic acid, propionic acid, aliphatic acid, sodium citrate, calcium chloride, polyethylene glycol, fat Diamines substance, polyamines, aromatic polyamine class substance, dicyandiamide class substance, imidazoles substance, modified amine object Matter, boron trifluoride and complex compound, Versamid, hexa, benzene sulfonyl chloride, paratoluensulfonyl chloride, ethyl-sulfate, Mahogany acid, p-methyl benzenesulfonic acid, paratoluenesulfonic acid sodium salt, paraformaldehyde, sodium hydroxide, acetin, propene carbonate, hydroxyl first Base urea, sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, hexanedioic acid, benzene sulfonic acid, phthalic anhydride, maleic anhydride, 3,3 '-two chloro- 4,4 '-diamino two It is more than one or both of phenylmethane, divinylbenzene；
Solvent is more than one or both of water, ethyl alcohol, acetone, ethylene glycol, toluene, dimethylbenzene.
15. according to the preparation method described in claim 11~14 any claim, which is characterized in that described in step (2) Also containing pore creating material to regulate and control the pore structure of microchannel tube wall in the tube wall green layer slurry of microchannel.
16. according to the preparation method described in claim 15, which is characterized in that the regulation and control are preferably a step：(1) pore creating material selects From metal pore creating material, oxide pore creating material, macromolecule pore creating material, inorganic salts pore creating material, carbon material pore creating material one or two More than, the granular size of pore creating material is 1nm~100 μm, and pore creating material is that addition is microchannel tube wall green layer slurry gross mass 0.001%~20%；(2) starched stage by stage, successively using the microchannel tube wall green layer containing pore creating material of the same race or not of the same race Material carries out " dipping sizing agent-removal additional size-semi-solid preparation " circulate operation, is formed and is given birth to homogenously or inhomogenously microchannel tube wall The foamed material precast body of base layer.
17. according to the preparation method described in claim 11~16 any claim, which is characterized in that described in step (2) The structure of microchannel tube wall green layer can be that part has pore structure, uniform pores structure or substantially non-porous gap structure.
18. according to hollow foam material described in claim 17 and preparation method thereof, which is characterized in that the hole passes through step Suddenly in (3), (4), (5) operation of one-step or two-step combination of the above is appointed to remove hole, and then prepared micro- with compact texture The hollow foam material of passage tube wall.
19. according to the preparation method of the hollow foam material described in claim 11~18 any claim, which is characterized in that Functional modification process is further included after step (5), that is, passes through galvanoplastic, electroless plating method, solution etches method, anodic oxidation Method, sol-gel method, hydro-thermal reaction method, steam phase inversion, Langmuir-Blodgett methods, physical vaporous deposition, change The one or more kinds of of vapour deposition process are learned contained in itself to the outer wall surface of microchannel tube wall, internal face or tube wall to receive Metre hole or micron openings carry out functional modification.
20. according to the preparation of foregoing any requirement of right 1~10 hollow foam material or any claim 11~19 The application of hollow foam material obtained by method, which is characterized in that the hollow foam material is used for following any fields：UF membrane Material, Reaction Separation material, filtering material, extract and separate material, reaction, extraction separation material, catalytic support material, micro- reaction It is device, micro- heat exchange material, composite material reinforcement body, electrode material, sound absorption/acoustic damping materials, heat-barrier material, fluid-distributing material, anti- Should be fractionated with material, reactive distillation with material, point/rectifying column in fix valve.
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