CN110064347A - Porous aerogel and its preparation method and application based on bionical vascular bundle micro-structure - Google Patents
Porous aerogel and its preparation method and application based on bionical vascular bundle micro-structure Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- 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
- B01J20/28047—Gels
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Abstract
The present invention relates to aerogel material technical fields, and in particular to a kind of porous aerogel and its preparation method and application based on bionical vascular bundle micro-structure.The preparation method of porous aerogel provided by the invention based on bionical vascular bundle micro-structure, using the freezing casting method of forming by inorganic nano-fiber, organic high molecular polymer is prepared into porous aerogel, it has " layer-trestle-layer " structure assembled by fiber trestle and compatible encapsulating layer, " layer-trestle-layer " structure is ordered three-dimensional porous network structure, include vascular bundle cross, longitudinal section biomimetic features, it can provide high-permeability microchannel, with excellent bionical hydrophobic performance and high oil absorption ability, it can be applied to the adsorbing separation of oil product in oil water mixture；Meanwhile also there is the porous aerogel excellent resistance to mechanical to squeeze fatigue behaviour, and after removal drives deformation load, can restore automatically to initial configuration, can use as elastic material.
Description
Technical field
The present invention relates to aerogel material technical fields, and in particular to a kind of porous gas based on bionical vascular bundle micro-structure
Gel and its preparation method and application.
Background technique
By evolving for a long time, biomaterial often show optimization Multi-scale model and light, electricity, magnetic, heat,
Many excellent properties of power etc., such as high-strength light, automatically cleaning, intelligent response, environmental suitability, self-healing and self-replacation
Function etc., these are all the excellent properties that people are dreamed of in designing and preparing new material.Therefore, mimic biology material
Design feature and functional characteristic and develop the extensive concern that biomimetic material causes researchers.But develop bionical material
Material will not only simulate the structure feature of biomaterial, more simulate its specific function.
In emerging field of nanometer material technology, aerogel material is as a kind of based on across scale and Bionic Design thought construction
The porous globality solid matter of grade, have excellent extending buckling mechanical structure, this unique solid-state skeletal support and
The high-permeability nanoporous network structure of gaseous medium out-phase filling composition makes its usually porosity with higher and soft bullet
Property.But the pore structure of existing aerogel material is mostly unordered type, and compared with order type structure, the suction of disordered structure assembly
Echoing mechanical extrusion performance has largely uncontrollability.Therefore, there is an urgent need to obtain from the biosystem of the Nature
Inspiration is taken, to design the biomimetic porous aeroge of order type structure and structure-controllable.
Summary of the invention
The purpose of the present invention is to provide a kind of porous aerogels and preparation method thereof based on bionical vascular bundle micro-structure
And application, porous aerogel provided by the invention have " layer-trestle-layer " structure, have excellent bionical hydrophobic performance, high suction
Oily ability and excellent resistance to mechanical squeeze fatigue behaviour.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of porous aerogel based on bionical vascular bundle micro-structure, including following step
It is rapid:
Inorganic nano-fiber, organic high molecular polymer and solvent are mixed, mixed slurry is obtained；
The mixed slurry is placed in mold, the mold for being contained with mixed slurry is placed in substrate, is then carried out cold
Freeze casting and forming, obtains the porous aerogel based on bionical vascular bundle micro-structure.
Preferably, the diameter of the inorganic nano-fiber is 10~120nm, and length is 50nm~500 μm.
Preferably, the weight average molecular weight of the organic high molecular polymer be 1200~500000, the degree of polymerization be 10~
1000000。
Preferably, the concentration of inorganic nano-fiber is 5~30mg/mL, organic high molecular polymer in the mixed slurry
Concentration be 5~50mg/mL.
Preferably, the material of the mold includes metal, quartz glass or organic silicon rubber；The wall thickness of the mold is
0.1~0.8cm.
Preferably, the material of the substrate includes dimethyl silicone polymer, cyclomethicone, amino silicone, poly- first
Base phenyl siloxane, polysiloxane polyether copolymer or polystyrene；The substrate with a thickness of 10 μm~10cm.
Preferably, the molding temperature of the freezing casting is -20~-50 DEG C, and the time is 30s~0.5h.
The present invention provides preparation method described in above-mentioned technical proposal be prepared based on bionical vascular bundle micro-structure
Porous aerogel has " layer-trestle-layer " structure assembled by fiber trestle and compatible encapsulating layer, wherein the fiber
Trestle is formed by inorganic nano-fiber, and the compatible encapsulating layer is formed by organic high molecular polymer.
Preferably, the density of the porous aerogel based on bionical vascular bundle micro-structure is 14.21~35.58mg/
cm3。
The present invention provides the porous aerogels described in above-mentioned technical proposal based on bionical vascular bundle micro-structure as absorption
The application of separation material or elastic material.
The present invention provides a kind of preparation methods of porous aerogel based on bionical vascular bundle micro-structure, including following step
It is rapid: inorganic nano-fiber, organic high molecular polymer and solvent being mixed, mixed slurry is obtained；The mixed slurry is placed in
In mold, the mold for being contained with mixed slurry is placed in substrate, then carries out freezing casting molding, is obtained based on bionical dimension pipe
The porous aerogel of beam micro-structure.The present invention utilizes the freezing casting method of forming by inorganic nano-fiber, organic high molecular polymer
It is prepared into porous aerogel, structure is (wherein, with " layer-trestle-layer " assembled by fiber trestle and compatible encapsulating layer
The fiber trestle is formed by inorganic nano-fiber, and the compatible encapsulating layer is formed by organic high molecular polymer), " layer-
Trestle-layer " structure is ordered three-dimensional porous network structure, horizontal, the longitudinal section biomimetic features comprising vascular bundle, it is possible to provide high-permeability
Microchannel has excellent bionical hydrophobic performance and high oil absorption ability, can be applied to the absorption of oil product in oil water mixture
Separation；Meanwhile also there is the porous aerogel excellent resistance to mechanical to squeeze fatigue behaviour, and drive deformation load in removal
Afterwards, it can restore automatically to initial configuration, can be used as elastic material.The experimental result of embodiment shows that the present invention mentions
The porous aerogel of confession is 74.2~99.9g/g to the adsorption capacity of variety classes oil product, can bear compression strain be 30%~
90%, elasticity modulus is 0.1425~0.5921kPa, is all larger than 90 ° with the interfacial contact angle of water droplet.
In addition, the preparation method raw material of porous aerogel provided by the invention is easy to get, simple process, production cost are low, it can
Control property is strong；The features such as material and size by control mold and substrate, can regulate and control the pore mode during freezing casting,
That realizes the controllable regulation of the bionical pore structure of micro-scale in final gained porous aerogel and macro-scale pattern can modulation
Property.
Detailed description of the invention
Fig. 1 is the flow chart of porous aerogel of the present invention preparation based on bionical vascular bundle micro-structure；
Fig. 2 is the scanning electron microscope diagram of porous aerogel prepared by embodiment 1；
Fig. 3 is the scanning electron microscope diagram of porous aerogel prepared by embodiment 3；
Fig. 4 is that porous aerogel prepared by embodiment 3 strains scanning electron microscope diagram after extruding at one time 50%；
Fig. 5 is porous aerogel static surface contact angle figure prepared by embodiment 1；
Fig. 6 is porous aerogel static surface contact angle figure prepared by embodiment 2；
Fig. 7 is porous aerogel static surface contact angle figure prepared by embodiment 3；
Fig. 8 is copper nano-wire-polyvinyl alcohol cellular aeroge compression stress strain curve figure prepared by embodiment 3.
Specific embodiment
The present invention provides a kind of preparation methods of porous aerogel based on bionical vascular bundle micro-structure, including following step
It is rapid:
Inorganic nano-fiber, organic high molecular polymer and solvent are mixed, mixed slurry is obtained；
The mixed slurry is placed in mold, the mold for being contained with mixed slurry is placed in substrate, is then carried out cold
Freeze casting and forming, obtains the porous aerogel based on bionical vascular bundle micro-structure.
Inorganic nano-fiber, organic high molecular polymer are prepared into porous airsetting using the freezing casting method of forming by the present invention
Glue, have assembled by fiber trestle and compatible encapsulating layer " layer-trestle-layer " structure (wherein, the fiber trestle by
Inorganic nano-fiber is formed, and the compatible encapsulating layer is formed by organic high molecular polymer), " layer-trestle-layer " structure is
Ordered three-dimensional porous network structure, horizontal, the longitudinal section biomimetic features comprising vascular bundle, it is possible to provide high-permeability microchannel has
Excellent bionical hydrophobic performance and high oil absorption ability, can be applied to the adsorbing separation of oil product in oil water mixture；Meanwhile it is described
Also there is porous aerogel excellent resistance to mechanical to squeeze fatigue behaviour, and after removal drives deformation load, can restore automatically
To initial configuration, can be used as elastic material.
The present invention mixes inorganic nano-fiber, organic high molecular polymer and solvent, obtains mixed slurry.
In the present invention, the diameter of the inorganic nano-fiber is preferably 10~120nm, more preferably 20~80nm；It is long
Degree preferably 50nm~500 μm, more preferably 10~100 μm.In the present invention, the inorganic nano-fiber preferably includes copper and receives
Rice noodles, silver nanowires, stannum nanowire, niobium nano wire, indium nano wire, silicon nanowires, cupric oxide nano line, silver oxide nanowire,
In tin oxide nano-wire, niobium oxide nano wire, indium oxide nano thread, silicon carbide nanometer line, platinum cobalt nanowire and platinum nickel nano wire
One or more, more preferably copper nano-wire or silver nanowires.
In the present invention, the weight average molecular weight of the organic high molecular polymer is preferably 1200~500000, more preferably
It is 10000~100000；The degree of polymerization is preferably 10~1000000, and more preferably 5000~30000.In the present invention, described to have
Machine high molecular polymer preferably includes polyvinyl alcohol, polyethylene glycol, chitosan, sodium alginate, chitin (i.e. chitin), sulfuric acid
Chondroitin, polyacrylamide, polymethyl methacrylate, polystyrene-acrylonitrile copolymer and Polybutadiene-acrylonitrile copolymerization
One or more of object, more preferably sodium alginate or polyvinyl alcohol.
Required inorganic nano-fiber and organic high molecular polymer obtain specific group when the present invention is for preparing porous aerogel
Not special restriction is closed, specifically, such as preparing porous aerogel using copper nano-wire and sodium alginate as raw material, with copper nano-wire
With polyvinyl alcohol be raw material prepare porous aerogel, porous aerogel is prepared by raw material of silver nanowires and sodium alginate or
Porous aerogel is prepared using silver nanowires and polyvinyl alcohol as raw material.
In the present invention, the solvent preferably includes water and organic solvent；The organic solvent preferably include benzene, toluene,
One or more of methylene chloride, n,N-Dimethylformamide and dimethyl sulfoxide, more preferably n,N-Dimethylformamide.
In the present invention, the volume ratio of the water and organic solvent is preferably (3~10): (0.5~4), more preferably (5~8): (1~
3)。
In the present invention, the concentration of inorganic nano-fiber is preferably 5~30mg/mL in the mixed slurry, and more preferably 5
~22.1mg/mL；The concentration of organic high molecular polymer is preferably 5~50mg/mL, more preferably 5~38.9mg/mL.This hair
The bright dosage by controlling inorganic nano-fiber and organic high molecular polymer guarantees there is " layer-stack in gained porous aerogel
Frame-layer " structure；If organic high molecular polymer dosage is very few, can not form to obtain aeroge through subsequent freezing casting；Such as
Fruit organic high molecular polymer dosage is excessive, although aeroge can be obtained, aeroge internal gutter is closo, does not have
There is " layer-trestle-layer " structure.
The present invention mixes the inorganic nano-fiber, organic high molecular polymer and solvent not special restriction,
Each component can sufficiently be dissolved, be dispersed.In the present invention, the inorganic nano-fiber, organic high molecular polymer and
Solvent mixing preferably carries out under agitation, and the revolving speed of the stirring is preferably 300~500rpm.In the embodiment of the present invention
In, specifically organic high molecular polymer solution is mixed with inorganic nano-fiber aqueous dispersions；The organic polymer polymerization
Solvent is preferably water and organic solvent in object solution, and the present invention is fine for the organic high molecular polymer solution and inorganic nano
The not special restriction of the proportion of the concentration and the two of tieing up aqueous dispersions, it is organic in gained mixed slurry after both guarantees mixing
The concentration of high molecular polymer and inorganic nano-fiber meets above-mentioned requirements.
After obtaining mixed slurry, the mixed slurry is placed in mold by the present invention, will be contained with the mold of mixed slurry
It is placed in substrate, then carries out freezing casting molding, obtain the porous aerogel based on bionical vascular bundle micro-structure.
In the present invention, the material of the mold preferably includes metal, quartz glass or organic silicon rubber, and the metal is excellent
Choosing includes aluminium, copper or iron；The wall thickness of the mold is preferably 0.1~0.8cm, more preferably 0.2~0.4cm.The present invention for
The shape of the mold does not have special restriction, selects suitable shape according to actual needs；In the present invention, the mould
Tool is preferably hollow square body, hollow cuboid or hollow cylinder.Material, the size and shape that the present invention passes through control mold
Etc. features, can regulate and control the pore mode during freezing casting, realize that micro-scale is bionical in final gained porous aerogel
The controllable regulation and the adjustable denaturation of macro-scale pattern of pore structure.
In the present invention, the material of the substrate preferably includes dimethyl silicone polymer, cyclomethicone, amino silicone oxygen
Alkane, polymethylphenylsiloxane, polysiloxane polyether copolymer or polystyrene；The thickness of the substrate is preferably 10 μm~
10cm, more preferably 10 μm~1cm, further preferably 10~30 μm.Material and thickness of the present invention by control substrate, energy
Enough regulate and control the pore mode and pore rate during freezing casting, realizes that micro-scale is bionical in final gained porous aerogel
The controllable regulation of pore structure.
In the present invention, the molding temperature of the freezing casting be preferably -20~-50 DEG C, the time be preferably 30s~
0.5h.The present invention preferably passes through liquid nitrogen and provides the freezing casting molding temperature, as shown in Figure 1, being specifically in sheet metal
Substrate is placed above, mold is placed in substrate, mixed slurry is poured into mold, liquid then is placed below in sheet metal
Nitrogen, using liquid nitrogen control sheet metal temperature (the as molding temperature of freezing casting, and set temperature by armored temperature
Sensor detection), it realizes and freezing casting molding is carried out to mixed slurry in mold；In freezing casting forming process, macromolecule
Polymer is extruded stratification in ice crystal production process, and inorganic nano-fiber can then be overlapped on interlayer and form trestle, and final group
Dress forms " layer-trestle-layer " structure, obtains the porous aerogel with bionical vascular bundle micro-structure.The present invention is for the gold
The specific type for belonging to plate does not have special restriction, in an embodiment of the present invention, specifically uses copper sheet material；In the present invention
In, the thickness of the sheet metal is preferably 0.1~1cm, more preferably 0.25~0.6cm.
After completing the freezing casting molding, gained is preferably formed jelly entity and mold separation after dry and obtained by the present invention
To the porous aerogel based on bionical vascular bundle micro-structure.In the present invention, the drying is preferably freeze-dried；The freezing
Dry temperature is preferably -50 DEG C, and the time is preferably 48h.
The present invention provides preparation method described in above-mentioned technical proposal be prepared based on bionical vascular bundle micro-structure
Porous aerogel has " layer-trestle-layer " structure assembled by fiber trestle and compatible encapsulating layer, wherein the fiber
Trestle is formed by inorganic nano-fiber, and the length of the fiber trestle is preferably 10~150 μm；The compatible encapsulating layer is by organic
High molecular polymer is formed, and the thickness of the compatible encapsulating layer is preferably 0.5~12 μm.It in the present invention, can be according to corresponding original
The content of inorganic nano-fiber and organic high molecular polymer in the dosage control porous aerogel of material.
In the present invention, the density of the porous aerogel based on bionical vascular bundle micro-structure be 14.21~
35.58mg/cm3.The present invention passes through the dosage of control inorganic nano-fiber and organic high molecular polymer, the material of mold and substrate
The features such as matter and size realize the regulation of porous aerogel density, make it have excellent bionical hydrophobic performance, high oil absorption ability
Fatigue behaviour is squeezed with excellent resistance to mechanical.
The present invention provides the porous aerogels described in above-mentioned technical proposal based on bionical vascular bundle micro-structure as absorption
The application of separation material or elastic material.Porous aerogel provided by the invention based on bionical vascular bundle micro-structure has excellent
Resistance to mechanical squeeze fatigue behaviour, and after removal drives deformation load, can restore automatically to initial configuration, bullet can be used as
Property materials'use；Meanwhile also there is excellent bionical hydrophobic performance and high oil absorption ability, it can be applied to oily in oil water mixture
The adsorbing separation of product.In the present invention, the porous aerogel based on bionical vascular bundle micro-structure is as adsorption and separation material
When, application method preferably includes: the porous aerogel based on bionical vascular bundle micro-structure being placed in oil water mixture, the base
Oil product can be adsorbed in the porous aerogel of bionical vascular bundle micro-structure, to realize the separation of oil product and water phase；In the present invention,
The oil product preferably includes one or more of gasoline, kerosene, diesel oil, olive oil and peanut oil.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
Copper nano-wire based on bionical vascular bundle micro-structure-sodium alginate porous aerogel preparation, as shown in Figure 1, packet
Include following steps:
0.49g sodium alginate (weight average molecular weight 15000, the degree of polymerization 5000) solid particle is weighed in 30mL beaker
In, 10mLN is added thereto, 10mL deionized water is then added in dinethylformamide, mechanical under 500rpm speed conditions
12h is stirred, uniform sodium alginate soln is obtained；
Taking the copper nano-wire aqueous dispersions that 5mL concentration is 45mg/mL, (wherein, the diameter of copper nano-wire is 20nm, and length is
100 μm), separately take the above-mentioned sodium alginate soln of 7.5mL to be slowly added into copper nano-wire aqueous dispersions, in 300rpm speed conditions
Lower magnetic agitation 8h, obtains mixed slurry；
Dimethyl silicone polymer substrate (with a thickness of 0.01cm) is placed on clean face copper sheet material (with a thickness of 0.5cm),
Then placing mold in dimethyl silicone polymer substrate, (material is quartz glass, and shape is hollow square body, and wall thickness is
0.2cm), above-mentioned mixed slurry is poured into mold；Place liquid nitrogen under copper sheet face, using liquid nitrogen control copper sheet material reach-
20 DEG C (set temperature is detected by armored temperature sensor), after the molding of 5min freezing casting, gained is formed and is frozen in fact
Body and mold separation obtain receiving based on the copper of bionical vascular bundle micro-structure after freeze-drying (temperature is -50 DEG C, time 48h)
Rice noodles-sodium alginate porous aerogel.
Embodiment 2
The preparation of silver nanowires based on bionical vascular bundle micro-structure-sodium alginate porous aerogel, comprising the following steps:
1.4g sodium alginate (weight average molecular weight 25000, the degree of polymerization 10000) solid particle is weighed in 30mL beaker
In, 10mLN is added thereto, 10mL deionized water is then added in dinethylformamide, mechanical under 500rpm speed conditions
12h is stirred, uniform sodium alginate soln is obtained；
Taking the silver nanowires aqueous dispersions that 5mL concentration is 11mg/mL, (wherein, the diameter of silver nanowires is 30nm, and length is
100 μm), separately take the above-mentioned sodium alginate soln of 5mL to be slowly added into silver nanowires aqueous dispersions, under 300rpm speed conditions
Magnetic agitation 8h, obtains mixed slurry；
Dimethyl silicone polymer substrate (with a thickness of 0.01cm) is placed on clean face copper sheet material (with a thickness of 0.5cm),
Then placing mold in dimethyl silicone polymer substrate, (material is quartz glass, and shape is hollow square body, and wall thickness is
0.2cm), above-mentioned mixed slurry is poured into mold；Place liquid nitrogen under copper sheet face, using liquid nitrogen control copper sheet material reach-
30 DEG C (set temperature is detected by armored temperature sensor), after the molding of 2min freezing casting, gained is formed and is frozen in fact
Body and mold separation obtain the Yin Na based on bionical vascular bundle micro-structure after freeze-drying (temperature is -50 DEG C, time 48h)
Rice noodles-sodium alginate porous aerogel.
Embodiment 3
The preparation of copper nano-wire based on bionical vascular bundle micro-structure-polyvinyl alcohol cellular aeroge, comprising the following steps:
1.2g polyvinyl alcohol (weight average molecular weight 15000, the degree of polymerization 5000) solid particle is weighed in 50mL beaker,
20mLN is added thereto, 20mL deionized water is then added in dinethylformamide, and machinery stirs under 500rpm speed conditions
12h is mixed, uniform poly-vinyl alcohol solution is obtained；
Taking the copper nano-wire aqueous dispersions that 1.6mL concentration is 75mg/mL, (wherein, the diameter of copper nano-wire is 20nm, length
It is 100 μm), separately take the above-mentioned poly-vinyl alcohol solution of 7.5mL to be slowly added into copper nano-wire aqueous dispersions, in 300rpm revolving speed item
Magnetic agitation 8h under part, obtains mixed slurry；
Dimethyl silicone polymer substrate (with a thickness of 0.03cm) is placed on clean face copper sheet material (with a thickness of 0.6cm),
Then mold (material is silicon rubber, and shape is hollow square body, wall thickness 0.2cm) is placed in dimethyl silicone polymer substrate,
Above-mentioned mixed slurry is poured into mold；Liquid nitrogen is placed under copper sheet face, reaching -50 DEG C using liquid nitrogen control copper sheet material (should
Set temperature is detected by armored temperature sensor), after the molding of 30s freezing casting, gained is formed and freezes entity and mold
Separation obtains the poly- second of copper nano-wire-based on bionical vascular bundle micro-structure after freeze-drying (temperature is -50 DEG C, time 48h)
Enol porous aerogel.
Embodiment 4
The preparation of silver nanowires based on bionical vascular bundle micro-structure-polyvinyl alcohol cellular aeroge, comprising the following steps:
0.6g polyvinyl alcohol (weight average molecular weight 15000, the degree of polymerization 5000) solid particle is weighed in 50mL beaker,
20mLN is added thereto, 20mL deionized water is then added in dinethylformamide, and machinery stirs under 500rpm speed conditions
12h is mixed, uniform poly-vinyl alcohol solution is obtained；
Taking the silver nanowires aqueous dispersions that 5mL concentration is 56mg/mL, (wherein, the diameter of silver nanowires is 30nm, and length is
150 μm), separately take the above-mentioned poly-vinyl alcohol solution of 10mL to be slowly added into silver nanowires aqueous dispersions, in 300rpm speed conditions
Lower magnetic agitation 8h, obtains mixed slurry；
Dimethyl silicone polymer substrate (with a thickness of 0.01cm) is placed on clean face copper sheet material (with a thickness of 0.25cm),
Then placing mold in dimethyl silicone polymer substrate, (material is quartz glass, and shape is hollow square body, and wall thickness is
0.2cm), above-mentioned mixed slurry is poured into mold；Place liquid nitrogen under copper sheet face, using liquid nitrogen control copper sheet material reach-
50 DEG C (set temperature is detected by armored temperature sensor), after the molding of 1min freezing casting, gained is formed and is frozen in fact
Body and mold separation obtain the Yin Na based on bionical vascular bundle micro-structure after freeze-drying (temperature is -50 DEG C, time 48h)
Rice noodles-polyvinyl alcohol cellular aeroge.
The porous aerogel of Examples 1 to 4 preparation is characterized, specific as follows:
Fig. 2 is the scanning electron microscope diagram of porous aerogel prepared by embodiment 1, and Fig. 3 is the porous of the preparation of embodiment 3
The scanning electron microscope diagram of aeroge.By Fig. 2 and Fig. 3, it is found that layer-trestle-layer structure is in vertical distribution, shape is embedded in airsetting
In glue, sodium alginate or polyvinyl alcohol form compatible encapsulating layer (with a thickness of 0.5~12 μm), copper nanometer in aforementioned preparation process
Line forms fiber trestle (length is 10~30 μm), and effective structure joins each compatible encapsulating layer, and ultimately forming has " layer-trestle-layer "
The porous aerogel of structure.The scanning electron of porous aerogel prepared by porous aerogel and embodiment 4 prepared by embodiment 2 is aobvious
Micro mirror figure is similar with Fig. 2 and Fig. 3, it can be observed that porous aerogel has " layer-trestle-layer " structure.
Fig. 4 is that porous aerogel prepared by embodiment 3 strains scanning electron microscope diagram after extruding at one time 60%.By
It is found that after undergoing the extruding under the strained condition, copper nano-wire-polyvinyl alcohol cellular aeroge still is able to keep exclusive Fig. 4
" layer-trestle-layer " structure, show that there is " layer-trestle-layer " structure excellent resistance to mechanical to squeeze fatigue behaviour.Embodiment
1, porous aerogel prepared by embodiment 2 and embodiment 4 is in one time 60% strain scanning electron microscope diagram after extruding and Fig. 4
It is similar, after undergoing the extruding under the strained condition, it can be observed that porous aerogel still has " layer-trestle-layer " structure.
Fig. 5 is porous aerogel static surface contact angle figure prepared by embodiment 1, and Fig. 6 is porous gas prepared by embodiment 2
Gel static surface contact angle figure, Fig. 7 are that porous aerogel static surface contact angle figure prepared by embodiment 3 is (direct by instrument
Derived Contact-angle measurement result is light grey in current Fig. 5~7 and compared with the data of small type size, for the ease of more intuitively reading
Contact angular data has marked out corresponding porous aerogel static surface contact angle data in the upper left corner of Fig. 5~7).By Fig. 5~7
It is found that the porous aerogel of Examples 1 to 3 preparation all has preferable hydrophobic effect, contact angle is all larger than 90 °.
Table 1 is the density and Young's modulus data of the porous aerogel of Examples 1 to 4 preparation, as shown in Table 1, embodiment 1
The density of the porous aerogel of~4 preparations has adjustable denaturation (14.21~35.58mg/cm3), the corresponding Young's modulus of material
Also there is adjustable denaturation (0.1425~0.5921kPa)；And by adjusting inorganic nano-fiber and organic high molecular polymer
The regulation of porous aerogel density and Young's modulus may be implemented in the features such as the size of dosage, mold and substrate.
The density and Young's modulus data of the porous aerogel of 1 Examples 1 to 4 of table preparation
The performance of the porous aerogel of Examples 1 to 4 preparation is measured, specific as follows:
Porous aerogel 0.01g prepared by Examples 1 to 4 is respectively placed in 2mL to contain in the water body of oil product, it is oily in water body
The concentration of product is 500mg/mL, after adsorbing 5nin, with oil product (gasoline, coal in water body after infrared spectrometric oil detector measurement absorption
Oil, diesel oil, olive oil or peanut oil) concentration, be calculated porous aerogel oil product absorption numerical value, the results are shown in Table 2, table 2
Middle experimental example 1~4 respectively corresponds the performance test experiment of the porous aerogel of Examples 1 to 4 preparation；Oil product adsorption number in table 2
The calculation formula for being worth (g/g) is as follows:
Oil product adsorbs numerical value=(M1-M0)/M0；
Wherein, M1For the quality (g) of porous aerogel after adsorption experiment；M0For the quality of porous aerogel before adsorption experiment
(g), i.e. M0=0.01g.
The calculation formula of oil product separative efficiency (%) is as follows in water body:
Oil product separative efficiency=[(C in water body0-C1)/C0]/M0* 100%；
Wherein, C1For the concentration (mg/mL) of oil product in water body after adsorption experiment；C0For oil product in water body before adsorption experiment
Concentration (mg/mL), i.e. C0=500mg/mL；M0For the quality (g) of porous aerogel before adsorption experiment, i.e. M0=0.01g.
The adsorption performance data of the porous aerogel of 2 Examples 1 to 4 of table preparation
As shown in Table 2, the porous aerogel of Examples 1 to 4 preparation all has preferable adsorbing and removing energy to above-mentioned oil product
Power.
Fig. 8 is copper nano-wire-polyvinyl alcohol cellular aeroge compression stress strain curve figure prepared by embodiment 3.By
For Fig. 8 it is found that under 30%, 60% and 90% effects of strain, 3 curves are integrally in closed state, show that copper nano-wire-is poly-
There is vinyl alcohol porous aerogel preferable resistance to mechanical to squeeze fatigue behaviour.Embodiment 1, embodiment 2 and embodiment 4 are prepared more
The compression stress strain curve figure of hole aeroge is similar with Fig. 8, under 30%, 60% and 90% effects of strain, 3 curves
Whole is in closed state, shows that there is porous aerogel preferable resistance to mechanical to squeeze fatigue behaviour.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the porous aerogel based on bionical vascular bundle micro-structure, which comprises the following steps:
Inorganic nano-fiber, organic high molecular polymer and solvent are mixed, mixed slurry is obtained；
The mixed slurry is placed in mold, the mold for being contained with mixed slurry is placed in substrate, then carries out freezing casting
Type is caused, the porous aerogel based on bionical vascular bundle micro-structure is obtained.
2. preparation method according to claim 1, which is characterized in that the diameter of the inorganic nano-fiber be 10~
120nm, length are 50nm~500 μm.
3. preparation method according to claim 1, which is characterized in that the weight average molecular weight of the organic high molecular polymer
It is 1200~500000, the degree of polymerization is 10~1000000.
4. preparation method according to claim 1, which is characterized in that the concentration of inorganic nano-fiber in the mixed slurry
For 5~30mg/mL, the concentration of organic high molecular polymer is 5~50mg/mL.
5. preparation method according to claim 1, which is characterized in that the material of the mold includes metal, quartz glass
Or organic silicon rubber；The wall thickness of the mold is 0.1~0.8cm.
6. preparation method according to claim 1, which is characterized in that the material of the substrate includes polydimethylsiloxanes
Alkane, cyclomethicone, amino silicone, polymethylphenylsiloxane, polysiloxane polyether copolymer or polystyrene；It is described
Substrate with a thickness of 10 μm~10cm.
7. preparation method according to claim 1, which is characterized in that the molding temperature of freezing casting is -20~-50
DEG C, the time is 30s~0.5h.
8. the porous airsetting based on bionical vascular bundle micro-structure that any one of claim 1~7 preparation method is prepared
Glue, which is characterized in that there is " layer-trestle-layer " structure assembled by fiber trestle and compatible encapsulating layer, wherein described
Fiber trestle is formed by inorganic nano-fiber, and the compatible encapsulating layer is formed by organic high molecular polymer.
9. the porous aerogel according to claim 8 based on bionical vascular bundle micro-structure, which is characterized in that described to be based on
The density of the porous aerogel of bionical vascular bundle micro-structure is 14.21~35.58mg/cm3。
10. claim 8 or 9 porous aerogels based on bionical vascular bundle micro-structure are as adsorption and separation material or elasticity
The application of material.
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