CN102807357B - Block aerogel composite material and preparation method thereof - Google Patents
Block aerogel composite material and preparation method thereof Download PDFInfo
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- CN102807357B CN102807357B CN201210244730.7A CN201210244730A CN102807357B CN 102807357 B CN102807357 B CN 102807357B CN 201210244730 A CN201210244730 A CN 201210244730A CN 102807357 B CN102807357 B CN 102807357B
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Abstract
The invention discloses a block aerogel composite material and a preparation method thereof. The block aerogel composite material consists of reticular cellulose nano fiber skeletons and sol in a combining way, wherein the porosity of the aerogel composite material is 80-99.5 percent, the density is 0.015-0.680g/cm<3>, the BET specific surface area is 150-1200m<2>/g, the coefficient of heat conductivity is 0.015-0.045Wm<-1>k<-1> and the modulus of elasticity is 0.5-150MPa. The block aerogel composite material provided by the embodiment of the invention has the advantages that since the material consists of the reticular cellulose nano fiber skeletons and the sol in the combining way, the mechanical property of the block aerogel composite material can be obviously improved, the heat conductivity is low, the density is small and the specific surface area is large; and besides, the equipment cost can be decreased by adopting a relatively low and safe freeze-drying method to replace the traditional supercritical drying method.
Description
Technical field
The present invention relates to technical field of composite materials, more specifically, the present invention relates to a kind of block aerogel composite and preparation method thereof.
Background technology
Aerogel is a kind ofly with gas, replace the liquid in gel and do not change in essence the network structure of gel itself or the special gel of volume, is the dried product of hydrogel or organogel.It has the features such as nano level vesicular structure and high porosity, be at present known to one of the solid material of density minimum.Due to aerogel, to have specific surface area large, the feature such as porosity is high, and density is low, and thermal conductivity is low, so it is at super insulation body, and high energy physics, effective catalyst and support of the catalyst, there is huge application potential the aspects such as energy storage material.Meanwhile, the density that block aerogel is ultralow and the specific surface area of superelevation make it in the performance that improves metal oxide device, gas and biosensor, and battery, the aspects such as heterogeneous catalysis and advanced low-k materials show good application prospect.
In aerogel preparation process, for fear of the subsiding of its inner skeleton structure, all adopt traditionally the method for supercritical drying.Although supercutical fluid can effectively be eliminated the fluid of capillary force and avoid the contraction of gel skeleton in drying process, the expensive and dangerous large-scale production and application that greatly limit aerogel material of supercritical drying as a kind of.Lyophilize is owing to there not being curved liquid surface in its drying process, and can avoid well subsiding of aerogel skeleton, be a kind of can be for the Perfected process of large-scale production and application.But the fluid before lyophilize in porous skeleton structure solidifies caused stress can be made to cause the cracked of aerogel, is difficult to obtain bulk aerogel.In addition, intrinsic fragility and the poor mechanical property of aerogel material also limited the application of aerogel material in some fields.
The Chinese patent that grant number is CN 1244397C provides a kind of method of producing rapidly aerogel product, adopts and passes through supercritical CO
2rather than the CO of liquid
2inject preheated with precharge to basic for super critical condition or on reactor and the solvent in wet gel carry out the mode of quick exchange of solvent.Preferably to supercritical CO
2adopt pressure pulse to strengthen exchange of solvent.But the energy consumption of the method also significantly strengthens, complicated operation, and the dangerous feature high, that cost is high of supercritical drying itself does not improve.
The Chinese patent that publication number is CN 101973752A provides a kind of glass fibre to strengthen silicon dioxide silica aerogel composite material and preparation method thereof.But the precursor material more complicated that the method is used, and need to carry out necessary pre-treatment to glass fibre, and the dry strictly control of drying conditions of normal temperature and pressure, to actual production, cause certain restriction.
Publication number is that the Chinese patent of CN 100386260C discloses the preparation method that a kind of brucite fiber strengthens aerosil lagging material.It is raw materials that the method be take process water glass or silicon sol and natural brucite staple fibre.But to the dispersion of brucite fiber and more loaded down with trivial details to forming solvent exchange and hydrophobic treatment process that gel carries out, limited to a certain extent practical application.
Publication number provides a kind of preparation method of silicon dioxide silica aerogel composite material of doped with aramid fibre for the Chinese patent of CN 101823867A, the method is used silicon source and alcoholic solvent mixed preparing silicon sol, mix again aramid fiber and tensio-active agent, standing after its gel, again through aging and solvent replacing, under normal pressure, classification is dried, and obtains the silicon dioxide silica aerogel composite material of required doped with aramid fibre.But the method requires that aramid fiber is had to good dispersion, also will add tensio-active agent, and before constant pressure and dry, need to carry out loaded down with trivial details solvent exchange.
United States Patent (USP) discloses in No. 2002/0094426 a kind of aerogel material that strengthens structure that combines is provided, and this strengthens specifically spandex fiber bat of structure.Aerogel is formed to precursor liquids and pour in bat, then supercritical drying forms aerogel, thereby forms aerogel film.Yet, remain here and adopt high, the dangerous large supercritical process of cost to carry out treatment gel, and material therefor shortage plasticity-and formability, so practical application is subject to certain restrictions.
United States Patent (USP) the 5th, provides a kind of by the aerogel powder method of preparing continuous sample glued together in 786, No. 059.Specifically aerogel particle is sprayed in the conjugate fiber material of two kinds of firm polymer formation that are connected with higher and lesser temps melting zone.When being heated to lower melt temperature, when being cross-linked with each other, fabric fibre also combines with aerogel particle.But the mixture hardness ratio of gained is larger, under the effect of external force particle can be broken or and fiber separation, so aerogel fragment can come off from fabric.
Prior art is in the urgent need to obtaining the block aerogel material of excellent performance, and can prepare with low cost the method for the block aerogel material of these excellent performances.
Summary of the invention
The present invention is intended at least one of solve the problems of the technologies described above.
For this reason, one object of the present invention is to propose a kind of have higher porosity, mechanical property is strong and Young's modulus is large block aerogel composite.
According to the aerogel composite of the embodiment of the present invention, by reticulated cellulose nanofiber skeleton and colloidal sol, be composited, wherein, the porosity of described aerogel composite is 80～99.5%, density is 0.015～0.680g/cm
3, BET specific surface area is 150～1200m
2/ g, thermal conductivity is 0.018～0.04 Wm
-1k
-1, Young's modulus is 0.5～150MPa.
According to the aerogel composite of the embodiment of the present invention, owing to being composited by reticulated cellulose nanofiber skeleton and colloidal sol, therefore can significantly improve the mechanical property of aerogel composite, obtain the aerogel composite of lower thermal conductivity, low density, high-specific surface area, in addition, can also adopt relatively inexpensive, safe drying means to replace traditional supercritical drying drying method and reduce preparation cost.
Another object of the present invention is to propose a kind of method for the preparation of block aerogel composite, said method comprising the steps of: reticulated cellulose nanofiber skeleton a) is provided; B) provide colloidal sol; C) described reticulated cellulose nanofiber skeleton is reacted and obtains mixture with described colloidal sol; And d) described mixture is carried out to lyophilize, obtain block aerogel composite product.
In addition, the method for the preparation of aerogel composite according to the above embodiment of the present invention, can also have following additional technical characterictic:
According to one embodiment of present invention, described lyophilize comprises: described mixture is placed in and is preheated to the trimethyl carbinol of 50～100 ℃ or the aqueous solution of the trimethyl carbinol carries out solvent exchange reaction, after question response 2～72h, reacted mixture is carried out to lyophilize at 0～-50 ℃, obtain described aerogel composite.
According to one embodiment of present invention, in described step a), with cellulose aquagel, prepare described reticulated cellulose nanofiber skeleton, described step a) comprises:
A-1) described cellulose aquagel is placed in to alkali aqueous solution, at 80～100 ℃, reacts 4～24h;
A-2) cellulose aquagel after reaction 4～24h is placed in to deionized water, at 60～100 ℃, reacts 2～36h;
A-3) by reaction, the cellulose aquagel after 2～36h is placed in and is preheated to the trimethyl carbinol of 50～100 ℃ or the aqueous solution of the trimethyl carbinol carries out solvent exchange reaction, after reaction 2～20h, by reacted cellulose aquagel lyophilize, obtain described reticulated cellulose nanofiber skeleton.
According to one embodiment of present invention, described step c) specifically comprises:
C-1) described cellulose nano-fibrous skeleton is immersed in described colloidal sol, until described cellulose nano-fibrous skeleton through shrinking, after swelling is returned original volume again by its taking-up;
C-2) the cellulose nano-fibrous skeleton after taking out is placed in to alcohol atmosphere gel aging, obtains the mixture of cellulose nano-fibrous skeleton and colloidal sol.
According to one embodiment of present invention, also comprise the steps:
E) described aerogel composite is carried out in atmosphere of inert gases to charing, obtain the aerogel composite of charing.
According to one embodiment of present invention, described colloidal sol is silicon dioxide gel, metal oxide sol or organism colloidal sol.
According to one embodiment of present invention, described colloidal sol is silicon dioxide gel, described step b) comprises: after silica precursor sol body, alcohol and water are mixed, add an acidic catalyst and stir, after presoma hydrolysis finishes, add again basic catalyst and stir, obtaining described silicon dioxide gel.
According to one embodiment of present invention, described colloidal sol is organism colloidal sol, described step b) comprising: after organism sol precursor is mixed in water, add basic catalyst and stir, obtaining described organism colloidal sol.
According to one embodiment of present invention, described colloidal sol is metal oxide sol, and described step b) comprises: after metal oxide sol presoma is mixed with alcohol, water, add an acidic catalyst and stir, obtaining described metal oxide sol.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 is the method flow schematic diagram for the preparation of block aerogel composite according to the embodiment of the present invention;
Fig. 2 is according to the structural representation under the scanning electronic microscope of the aerosil of the embodiment of the present invention;
Fig. 3 is according to structural representation under the reticulated cellulose nanofiber skeleton scanning electronic microscope of the embodiment of the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
If no special instructions, the implication of the scientific and technical terminology in this specification sheets is identical with the general implication of understanding of those skilled in the art, but if any conflict, with the definition in this specification sheets, is as the criterion.
In specification sheets and claims, use relate to group component, processing condition all should be understood by " approximately " and modify as all numerical value of temperature of reaction and time etc. in all scenario.The all scopes that relate to same composition or character include end points, and this end points can combine independently.Because these scopes are continuous, so they are included in each numerical value between minimum value and maximum value.It will also be appreciated that any numerical range expection that the application quotes comprises all subranges within the scope of this.
First, describe according to the block aerogel composite described in the embodiment of the present invention in conjunction with the embodiments.
According to one embodiment of present invention, described block aerogel composite is composited by reticulated cellulose nanofiber skeleton and colloidal sol.
Source about described reticulated cellulose nanofiber skeleton is not particularly limited, and described reticulated cellulose nanofiber skeleton can be for being purchased or synthetic preparing.Preferably, according to one embodiment of present invention, described reticulated cellulose nanofiber skeleton adopts cellulose aquagel to prepare gained, and the source of cellulose aquagel comprises the hydrogel that microorganism fermentation produces, but is not limited to this.
According to one embodiment of present invention, the mass percent of described cellulose nano-fibrous skeleton can be in very wide in range range, for example, for being greater than 0wt% to being less than 100wt%.In actual applications, can adjust as required.Preferably, the mass percent of described cellulose nano-fibrous skeleton is 0.0001wt% to 99.9wt%.More preferably, the mass percent of described cellulose nano-fibrous skeleton is 0.001wt% to 95wt%.Most preferably, the mass percent of described cellulose nano-fibrous skeleton is 0.01wt% to 90wt%.
About described colloidal sol type, it will be appreciated that, the colloidal sol type adopting depends on the aerogel that final expectation obtains.
At present, aerogel can be divided into according to its composition: the charcoal-aero gel that inorganic aerogels, organic aerogel and organic aerogel charing obtain.
The inorganic aerogels of having developed has: unit oxide silica aerogel has SiO
2, Al
2o
3, B
2o
3, MoO
2, MgO, ZrO
2, SnO
2, WO
3, Nb
2o
5, Cr
2o
3deng; Binary or multivariant oxide aerogel have Al
2o
3/ SiO
2, B
2o
3/ SiO
2, P
2o
5/ SiO
2, Nb
2o
5/ SiO
2, Dy
2o
3/ SiO
2, Er
2o
3/ SiO
2, Lu
2o
3/ Al
2o
3, CuO/Al
2o
3, NiO/Al
2o
3, PbO/Al
2o
3, Cr
2o
3/ AI
2o
3, Fe
2o
3/ Al
2o
3, FeO
3/ SiO
2, Li
2o/B
2o
3, CuO/ZnO/ZrO
2; Metal-aerogel mixing material as high performance catalyst has Cu/Al
2o
3, Ni/AI
2o
3, Pd/Al
2o
3, Al/Fe
2o
3; High temperature superconducting materia YBa
2cu
3o
7-x; Superfine metal, ceramic powder etc.
Organic aerogel has resorcinol-formaldehyde (RF), carbamide (MF), phenolic resin coating-formaldehyde (PF), mixture cresol-formaldehyde (JF), polymeric polyisocyanate (PUR), Phloroglucinol monomethyl ether-formaldehyde (P-F), etc.Organic aerogel is compared and is had strong infrared absorption with inorganic aerogels (as aerosil), makes organic aerogel have lower radiant heat conductance.
The block aerogel composite colloidal sol used according to the present invention, can adopt any colloidal sol that can obtain above-mentioned aerogel, and the colloidal sol preferably adopting is silicon dioxide gel, metal oxide sol and organism colloidal sol.
According to one embodiment of present invention, the porosity of described block aerogel composite is 80～99.5%.In one embodiment, the porosity of described block aerogel composite is 85～98%.In another embodiment, the porosity of described block aerogel composite is 90～96%.In another embodiment, the porosity of described block aerogel composite is 93～95%.
According to one embodiment of present invention, the density of described block aerogel composite is 0.015～0.680g/cm
3, in one embodiment, the density of described block aerogel composite is 0.05～0.50g/cm
3.In another embodiment, the density of described block aerogel composite is 0.10～0.35g/cm
3.In another embodiment, the density of described block aerogel composite is 0.10～0.30g/cm
3.In another embodiment, the density of described block aerogel composite is 0.15～0.20g/cm
3.
According to one embodiment of present invention, the BET specific surface area of described block aerogel composite is 150～1200m
2/ g.In one embodiment, the BET specific surface area of described block aerogel composite is 200～1000m
2/ g.In another embodiment, the BET specific surface area of described block aerogel composite is 500～900m
2/ g.In another embodiment, the BET specific surface area of described block aerogel composite is 550～850m
2/ g.In another embodiment, the BET specific surface area of described block aerogel composite is 650～800m
2/ g.
According to one embodiment of present invention, the thermal conductivity of described block aerogel composite is 0.015～0.045Wm
-1k
-1.In one embodiment, the thermal conductivity of described block aerogel composite is 0.018～0.040Wm
-1k
-1.The thermal conductivity of described block aerogel composite is 0.020～0.035Wm in another embodiment
-1k
-1.In another embodiment, the thermal conductivity of described block aerogel composite is 0.025～0.030Wm
-1k
-1.
According to one embodiment of present invention, the Young's modulus of described block aerogel composite is 0.5～150MPa.In one embodiment, the Young's modulus of described block aerogel composite is 10～120MPa.In another embodiment, the Young's modulus of described block aerogel composite is 20～100MPa.In another embodiment, the Young's modulus of described block aerogel composite is 30～80MPa.
According to one embodiment of present invention, the mean pore size of described block aerogel composite is 1～100 nanometer.In one embodiment, the mean pore size of described block aerogel composite is 10～80 nanometers.In another embodiment, the mean pore size of described block aerogel composite is 20～50 nanometers.In another embodiment, the mean pore size of described block aerogel composite is 30～40 nanometers.
According to one embodiment of present invention, the pore volume of described block aerogel composite is 0.5～29.6cm
2/ g.In one embodiment, the pore volume of described block aerogel composite is 1.0～25.0cm
2/ g.In another embodiment, the pore volume of described block aerogel composite is 2.0～20.0cm
2/ g.In another embodiment, the pore volume of described block aerogel composite is 5.0～15.0cm
2/ g.
Material of the present invention is the aerogel block body of bulk.According to one embodiment of present invention, the size range of described block aerogel composite can reach 2000*1000*80mm.In one embodiment, material of the present invention is of a size of 1500*800*50mm.In another embodiment, material of the present invention is of a size of 1000*600*40mm.In another embodiment, material of the present invention is of a size of 600*500*30mm.In another embodiment, material of the present invention is of a size of 500*400*20mm.
Below with reference to Fig. 1, describe according to the flow process of the method for the preparation of block aerogel composite of the embodiment of the present invention.
Concrete, according to the method for the preparation of aerogel composite of the embodiment of the present invention, can comprise the following steps:
A) provide reticulated cellulose nanofiber skeleton;
B) provide colloidal sol;
C) described reticulated cellulose nanofiber skeleton is reacted and obtains mixture with described colloidal sol;
D) described mixture is carried out to lyophilize, obtain block aerogel composite product.
Thus, by cryodesiccated method, replace traditional supercritical drying drying method and prepare aerogel composite, reduced preparation cost, and reaction conditions requires lower, improve the security of producing, reduced the restriction of actual production, can carry out fairly large production.
According to the method for the preparation of block aerogel composite of the present invention, described reticulated cellulose nanofiber skeleton can be for being purchased or synthetic preparing.Preferably, according to one embodiment of present invention, described reticulated cellulose nanofiber skeleton adopts cellulose aquagel to prepare gained.
With cellulose aquagel, preparing reticulated cellulose nanofiber skeleton can comprise:
1) described cellulose aquagel being placed in to alkali aqueous solution reacts.
Alkali aqueous solution for using in reaction, it will be appreciated that, the selection of described alkali aqueous solution is not particularly limited, so long as have the solution of hydroxide ion.For example, operable alkali aqueous solution comprises the aqueous solution of alkali metal hydroxide and the aqueous solution of alkaline earth metal hydroxides.Be preferably the NaOH aqueous solution.The concentration of alkali aqueous solution is generally 2～20wt%, is preferably 8%～15wt%, more preferably 5%～10wt%.
Reaction is carried out conventionally at 60～120 ℃, preferably at 70～110 ℃, carries out, and more preferably at 80～100 ℃, carries out, and most preferably at 85～95 ℃, carries out.According to one embodiment of present invention, reaction is carried out at 90 ℃.Reaction times is generally 3～30h, is preferably 4～24h, and more preferably 8～20h, most preferably is 10～15h.
2) cellulose aquagel of above-mentioned reaction being placed in to deionized water reacts.This reaction is carried out at suitable temperature, and temperature of reaction is generally 60～110 ℃, is preferably 70～100 ℃, more preferably 80～90 ℃.Treatment time is generally 2～36h, is preferably 5～25h, more preferably 10～15h.
3) above-mentioned reacted cellulose aquagel is placed in to organic solvent and carries out solvent exchange reaction.In this step, with the organic solvent that surface tension is little, replace the water in gel.
In principle, can use and meet the following organic solvent requiring: under normal temperature, be liquid, zero pour is near 0 ℃ or more than 0 ℃; During gas-solid balance, system has higher saturation vapour pressure to guarantee that solid state crystallization distils fast with respect to glassware for drinking water, and the steam distilling out is easy to again be caught by cold-trap (50 ℃) simultaneously; For cryodesiccated solvent, before and after solidification and crystallization, there is no obvious volume change; And need to there is lower toxicity and lower cost.According to one embodiment of present invention, the organic solvent of use is the aqueous solution of the trimethyl carbinol or the trimethyl carbinol.
When adopting the aqueous solution of the trimethyl carbinol, conventionally use the mixing solutions of the trimethyl carbinol and deionized water.It will be appreciated that, for the volume ratio of the trimethyl carbinol and deionized water, be not particularly limited.According to one embodiment of present invention, the volume ratio of normally used deionized water and the trimethyl carbinol is (0～3): 1.In one embodiment, the volume ratio of deionized water and the trimethyl carbinol is (1～2): 1.In another embodiment, the volume ratio of deionized water and the trimethyl carbinol is 3:2.
In solvent exchange reaction process, can change as required replacement(metathesis)reaction solvent used, changing number of times can be 1～5 time, is preferably 2～4 times.
Particularly, in solvent exchange reaction, the cellulose aquagel of processing is placed in and is preheated to 50～100 ℃, be preferably 60～90 ℃, more preferably in the aqueous solution of the trimethyl carbinol of 70～80 ℃ or the trimethyl carbinol, carry out solvent exchange.The time of solvent exchange can be 2～24h, is preferably 5～20h, more preferably 10～15h.
4) cellulose aquagel above-mentioned solvent exchange being reacted carries out lyophilize, obtains reticulated cellulose nanofiber skeleton standby.
In addition, in step a), for the source of used cellulose aquagel, be not particularly limited, for example, can ferment after gained gel or plant cellulose dissolve and separate out gained gel for microorganism.When described cellulose aquagel is while separating out gained gel after plant cellulose dissolves, in preparing the process of the cellulose nano-fibrous skeleton of shape, can reduce the treating processes of alkali aqueous solution and deionized water, only described cellulose aquagel need to be placed in and be preheated to the trimethyl carbinol of 50～100 ℃ and the mixing solutions of deionized water carries out solvent exchange reaction 2～20h, by reacted cellulose aquagel lyophilize, obtain described reticulated cellulose nanofiber skeleton.
Particularly, according to one embodiment of present invention, step a) provides the method for reticulated cellulose nanofiber skeleton to comprise:
A-1) described cellulose aquagel is placed in to alkali aqueous solution, at 80～100 ℃, reacts 4～24h;
A-2) cellulose aquagel after reaction 4～24h is placed in to deionized water, at 60～100 ℃, reacts 2～36h;
A-3) by reaction, the cellulose aquagel after 2～36h is placed in and is preheated to the trimethyl carbinol of 50～100 ℃ or the aqueous solution of the trimethyl carbinol carries out solvent exchange reaction, after reaction 2～20h, by reacted cellulose aquagel lyophilize, obtain described reticulated cellulose nanofiber skeleton, as shown in Figure 3.
According to the method for the preparation of block aerogel composite of the present invention, next provide colloidal sol.About described colloidal sol, it will be appreciated that, described colloidal sol has multiple choices, can use in principle any colloidal sol that obtains existing dissimilar aerogel.Preferably, described colloidal sol can comprise silicon dioxide gel, organosol, and metal oxide sol, or comprise any two or three formed mixed sols system in above-mentioned three kinds of colloidal sols simultaneously.
When described colloidal sol is silicon dioxide gel, its preparation process specifically can comprise: after silica precursor sol body, alcohol and water are mixed, add an acidic catalyst and stir, after presoma hydrolysis finishes, then add basic catalyst and stir, obtaining silicon dioxide gel.
It will be appreciated that, the material using in described silicon dioxide gel preparation process is not particularly limited, described silica precursor sol body comprises tetraethoxy, methyl silicate, methyl tetraethoxy, methyl methyl silicate or silicic acid propyl ester, preferred tetraethoxy, described alcohol comprises methyl alcohol, ethanol, propyl alcohol or Virahol, preferred alcohol, described an acidic catalyst comprises hydrochloric acid, oxalic acid, sulfuric acid, hydrofluoric acid or nitric acid, preferred hydrochloric acid, and described basic catalyst comprises ammoniacal liquor, sodium hydroxide, sodium carbonate, preferably ammoniacal liquor.
Further, described silica precursor sol body: water: alcohol: an acidic catalyst: the mol ratio of basic catalyst is 1:(1～27): (3～30): (0.0005～0.005): (0.0005～0.01), be preferably 1:(2～20): (5～25): (0.001～0.005): (0.0025～0.008), more preferably 1:(5～15): (8～20): (0.015～0.004): (0.002～0.006).
According to one embodiment of present invention, the silica precursor sol body adopting is tetraethoxy, and alcohol is ethanol, an acidic catalyst acetic acid, and basic catalyst is ammoniacal liquor.
When described colloidal sol is organism colloidal sol, its preparation process specifically can comprise: after organism sol precursor is mixed in water, add basic catalyst and stir, obtaining described organism colloidal sol.
It will be appreciated that, the material using in described organism colloidal sol preparation process is not particularly limited, described organism sol precursor comprises Resorcinol and formaldehyde, Phloroglucinol and formaldehyde, trimeric cyanamide and formaldehyde, mixture cresol and formaldehyde, polymeric polyisocyanate, poly-N hydroxymethyl acrylamide and Resorcinol, resol and formaldehyde, resol and furfural, preferred Resorcinol and formaldehyde, 2, 4-resorcylic acid and formaldehyde, meta-cresol and formaldehyde, described basic catalyst is sodium carbonate, ammoniacal liquor, sodium hydroxide or sodium bicarbonate, preferred sodium carbonate, solvent for use is water or ethanol, preferably water.
In the preparation of organism colloidal sol, those skilled in the art can select or regulate according to practical situation the ratio of each component, thereby obtain the organosol of expectation.
According to one embodiment of present invention, the organism sol precursor adopting is Resorcinol and formaldehyde, basic catalyst is sodium carbonate, Resorcinol wherein: formaldehyde: water: the mol ratio of sodium carbonate can be 1:1.5～2.5:50～1500:0.001～0.1, be preferably 1:1.8～2.2:50～1000:0.002～0.1, be preferably 1:1.8～2.0:150～500:0.005～0.05.
When described colloidal sol is metal oxide sol, its concrete operation step can comprise: after metal oxide sol presoma is mixed with alcohol, water, add an acidic catalyst and stir, obtaining described metal oxide sol.
It will be appreciated that, the material using in described metal oxide sol preparation process is not particularly limited, and described organism sol precursor comprises butyl (tetra) titanate, titanium chloride, iron(ic) chloride, iron nitrate, zirconium chloride, zirconium nitrate, tin chloride, nitric acid tin, aluminum chloride, Tributyl aluminate, aluminum isopropylate, aluminum nitrate, preferred butyl (tetra) titanate, described alcohol comprises ethanol, methyl alcohol, propyl alcohol, Virahol, preferred alcohol, described an acidic catalyst comprises acetic acid, hydrochloric acid, nitric acid, sulfuric acid, preferably acetic acid.
According to one embodiment of present invention, the metal oxide sol presoma adopting is butyl (tetra) titanate, and alcohol is ethanol, and an acidic catalyst is acetic acid.Butyl (tetra) titanate wherein: ethanol: water: the mol ratio of acetic acid is 1:1～20:1～16:0.8～5.5, is preferably 1:8～18:2～8:1.3～2.5, more preferably 1:5～15:3～5:1.5～2.0.
According to the method for the preparation of block aerogel composite of the present invention, step c) is that the above-mentioned reticulated cellulose nanofiber skeleton providing is reacted with colloidal sol, obtains mixture.Particularly, step c) can comprise:
C-1) cellulose nano-fibrous skeleton is immersed in colloidal sol, until described cellulose nano-fibrous skeleton through shrinking, after swelling is returned original volume again by its taking-up;
C-2) the cellulose nano-fibrous skeleton after taking out is placed in to alcohol atmosphere gel aging, obtains the mixture of cellulose nano-fibrous skeleton and colloidal sol.
About material related in step c) and reaction conditions, be not particularly limited step c-2) in the alcohol that uses can be methyl alcohol, ethanol, propyl alcohol or butanols.According to one embodiment of present invention, this alcohol is preferably ethanol.
Step c-2) aging described in is to continue at a certain temperature to carry out for some time.According to one embodiment of present invention, aging temperature can be 20～80 ℃, is preferably 30～60 ℃, more preferably 40～50 ℃.Digestion time can be 1～24h, preferably 2～18h, more preferably 5～15h.
According to the method for the preparation of block aerogel composite of the present invention, finally carry out step d) mixture is carried out to lyophilize, thereby obtain aerogel composite of the present invention.This step comprises solvent exchange and two steps of lyophilize.
In solvent exchange, according to one embodiment of present invention, use the mixing solutions of the trimethyl carbinol or the trimethyl carbinol and deionized water.Volume ratio about the described trimethyl carbinol and deionized water is not particularly limited, and preferably, the volume ratio of described deionized water and the described trimethyl carbinol is (0～3): 1.
About cryodesiccated method, it will be appreciated that, the equipment using in freezing dry process is not particularly limited, can be for example conventional freezing or heating installation, as long as can reach the needed temperature of reaction.
Particularly, according to one embodiment of present invention, the operation of step d) specifically can comprise:
The mixture that step c) is obtained is placed in and is preheated to the trimethyl carbinol of 50～100 ℃ and the mixing solutions of deionized water carries out solvent exchange reaction, after question response 2～72h, reacted mixture is carried out to lyophilize at 0～-50 ℃, obtain described aerogel composite, as shown in Figure 2.
In addition, in order further to improve the mechanical property of described aerogel composite, according to one embodiment of present invention, also the aerogel composite after lyophilize can be carried out in atmosphere of inert gases to charing, obtain the aerogel composite of charing.
The selection of described rare gas element is not particularly limited, and preferably, described rare gas element can be nitrogen.
Therefore, according to one embodiment of present invention, the method for the preparation of block aerogel composite of the present invention can also comprise the steps:
E) described aerogel composite is carried out in atmosphere of inert gases to charing, to obtain the aerogel composite of charing.
According to the method for the preparation of block aerogel composite of the present invention, can obtain the aerogel block body of bulk.It will be appreciated that, the size of the aerogel material that present method is prepared is not particularly limited, as long as have corresponding mould and reaction vessel can prepare the composite aerogel of arbitrary shape and size.
According to the method for the preparation of block aerogel composite of the present invention, the size range of the aerogel composite finally obtaining can reach 2000*1000*80mm.In one embodiment, the aerogel composite that method of the present invention obtains is of a size of 1500*800*50mm.In another embodiment, the aerogel composite that method of the present invention obtains is of a size of 1000*600*40mm.In another embodiment, the aerogel composite that method of the present invention obtains is of a size of 600*500*30mm.In another embodiment, the aerogel composite that method of the present invention obtains is of a size of 500*400*20mm.
The method that the present invention prepares aerogel composite adopts relatively inexpensive, safe drying means to replace traditional supercritical drying drying method, reduced the preparation cost of aerogel composite, obtain large-sized block materials, further expanded the application of aerogel composite.
Aerogel composite of the present invention can, for lagging material, optical material, electrode materials, semiconductor material, magneticsubstance etc., have great application potential in fields such as aviation, the energy, information, environmental protection, medicine, agricultural chemicals, metallurgy, building, fire protection flame retarding and scientific experiments.Particularly, aerogel composite of the present invention is suitable as lagging material and applies at building field, comprises the thermal insulation layer that is applied to material of construction.
Embodiment
Below in conjunction with specific embodiment, describe according to aerogel composite of the present invention.
Embodiment 1
The seed culture fluid of cultured acetobacter xylinum bacterial classification is in advance inoculated in 12L acetobacter xylinum fermentation culture with 10% inoculum size, and fully vibration, is statically placed in and in 30 ℃ of constant temperature, cultivates 15 days to obtain cellulose aquagel.Wherein acetobacter xylinum fermentation culture contains glucose 2%, peptone 0.5%, and yeast powder 0.5%, five water Sodium phosphate dibasic 0.27%, citric acid-hydrate 0.115%, pH is 6.0, and high-temperature sterilization 20min.
The cellulose aquagel that microorganism fermentation is come is placed in 90 ℃ of processing 10h of the NaOH aqueous solution of 5%, be placed in again 85 ℃ of deionized waters and process 15h, change during this time deionized water 3 times, 60 ℃ of the trimethyl carbinol that is 1:1 by volume ratio again and the mixed solutions of deionized water carry out solvent exchange 10h, change during this time mixed solution 2 times, lyophilize to sample complete drying obtains netted micro organism cellulose skeleton (cellulose aerogels).
In 20L deionized water, add 1.1kg Resorcinol, 0.6kg formaldehyde and 50gNaCO
3, after stirring, the Mierocrystalline cellulose network skeleton preparing is placed in to this organosol, treat that Mierocrystalline cellulose block has swelling to return original volume afterwards by its taking-up through shrinking.Treat that Resorcinol and formaldehyde gel are to be placed on aging 4h in 50 ℃ of baking ovens, then to put into volume ratio be that 50 ℃ of the trimethyl carbinol of 1:1 and the mixed solutions of deionized water carry out solvent exchange 15h, during change mixed solution 4 times.The gel that solvent exchange is crossed is placed in refrigerator-20 ℃ freezing 14h, then lyophilize is to sample complete drying, obtains complete and intensity and remarkable organic (RF) composite aerogel material strengthening of snappiness.Its significant parameter is shown in Table 1.
The significant parameter of the composite aerogel that table 1 prepares according to embodiment 1
Embodiment 2
The seed culture fluid of cultured acetobacter xylinum bacterial classification is in advance inoculated in 10L acetobacter xylinum fermentation culture with 12% inoculum size, and fully vibration, is statically placed in and in 30 ℃ of constant temperature, cultivates 20 days to obtain cellulose aquagel.Wherein acetobacter xylinum fermentation culture contains glucose 4%, peptone 0.8%, and yeast powder 0.5%, five water Sodium phosphate dibasic 0.35%, citric acid-hydrate 0.115%, pH is 6.2, and high-temperature sterilization 20min.
The cellulose aquagel that microorganism fermentation is come is placed in 90 ℃ of processing 8h of the NaOH aqueous solution of 6%, be placed in again 85 ℃ of deionized waters and process 15h, change during this time deionized water 3 times, 58 ℃ of the trimethyl carbinol that is 1:1 by volume ratio again and the mixed solutions of deionized water carry out solvent exchange 10h, change during this time mixed solution 2 times, lyophilize to sample complete drying obtains netted micro organism cellulose skeleton (cellulose aerogels).
In 5.5L ethanol, splash into 3L butyl (tetra) titanate, 1L deionized water, the acetic acid of 0.816L is uniformly mixed and obtains TiO
2colloidal sol.The Mierocrystalline cellulose network skeleton preparing is placed in to this TiO
2colloidal sol in, treat that Mierocrystalline cellulose block has swelling to return after original volume its taking-up through shrinking.Treat TiO
2gel to be to be placed on aging 4h in 50 ℃ of baking ovens, then to put into volume ratio be that 60 ℃ of the trimethyl carbinol of 1:1 and the mixed solutions of deionized water carry out solvent exchange 20h, during change mixed solution 4 times.The gel that solvent exchange is crossed is placed in refrigerator-20 ℃ freezing 10h, then lyophilize is to sample complete drying, obtains complete and pliable and tough titanium dioxide composite aerogel material.Its significant parameter is shown in Table 2.
The significant parameter of the composite aerogel that table 2 prepares according to embodiment 2
Embodiment 3
The seed culture fluid of cultured acetobacter xylinum bacterial classification is in advance inoculated in 15L acetobacter xylinum fermentation culture with 12% inoculum size, and fully vibration, is statically placed in and in 30 ℃ of constant temperature, cultivates 12 days to obtain cellulose aquagel.Wherein acetobacter xylinum fermentation culture contains glucose 3%, peptone 0.6%, and yeast powder 0.5%, five water Sodium phosphate dibasic 0.29%, citric acid-hydrate 0.125%, pH is 6.0, and high-temperature sterilization 20min.
The cellulose aquagel that microorganism fermentation is come is placed in 90 ℃ of processing 12h of the NaOH aqueous solution of 4%, be placed in again 80 ℃ of deionized waters and process 20h, change during this time deionized water 4 times, 60 ℃ of the trimethyl carbinol that is 2:3 by volume ratio again and the mixed solutions of deionized water carry out solvent exchange 12h, change during this time mixed solution 2 times, lyophilize to sample complete drying obtains netted micro organism cellulose skeleton (cellulose aerogels).
Respectively get tetraethoxy 6L, deionized water 2L, adds the hydrochloric acid of 0.16L 1% after ethanol 9.2L mixes, and stirs the ammoniacal liquor that adds 0.55L 0.1M after 1h, obtains silicon dioxide gel.The cellulose aerogels preparing is before immersed in to this sol system, treats that Mierocrystalline cellulose block has swelling to return original volume afterwards by its taking-up through shrinking.Treat that silica dioxide gel is to be placed on aging 3h in 50 ℃ of baking ovens, then to put into volume ratio be that 60 ℃ of the trimethyl carbinol of 2:3 and the mixed solutions of deionized water carry out solvent exchange 12h, during change mixed solution 3 times.The gel that solvent exchange is crossed is placed in refrigerator-20 ℃ freezing 12h, then lyophilize is to sample complete drying, obtains complete and intensity and the remarkable silicon dioxide composite aerogel material strengthening of toughness.Its significant parameter is shown in Table 3.
The significant parameter of the composite aerogel that table 3 prepares according to embodiment 3
Embodiment 4
Plant cellulose is separated out again to the trimethyl carbinol that formed gel is 1:1 by volume ratio and deionized water 50 ℃ of mixed solutions through dissolving carry out solvent exchange 14h, change during this time mixed solution 3 times, lyophilize to sample complete drying obtains netted plant cellulose skeleton (cellulose aerogels).
Respectively get tetraethoxy 3L, deionized water 1.8L, adds the hydrochloric acid of 0.19L 1% after ethanol 9.2L mixes, and stirs the ammoniacal liquor that adds 0.8L 0.1M after 1h, obtains silicon dioxide gel.The cellulose aerogels preparing is before immersed in to this sol system, treats that Mierocrystalline cellulose block has swelling to return original volume afterwards by its taking-up through shrinking.Treat that silica dioxide gel is to be placed on aging 4h in 50 ℃ of baking ovens, then to put into volume ratio be that 50 ℃ of the trimethyl carbinol of 1:1 and the mixed solutions of deionized water carry out solvent exchange 15h, during change mixed solution 4 times.The gel that solvent exchange is crossed is placed in refrigerator-20 ℃ freezing 14h, then lyophilize is to sample complete drying, obtains complete and intensity and the remarkable silicon dioxide composite aerogel material strengthening of toughness.Its significant parameter is shown in Table 4.
The significant parameter of the composite aerogel that table 4 prepares according to embodiment 4
Embodiment 5
By method described in embodiment 1, prepare organic (RF) composite aerogel material, this matrix material is placed in to 900 ℃ of nitrogen atmospheres and processes 5h, after charing, form carbon aerogel material.Its significant parameter is shown in Table 5.
The significant parameter of the carbon aerogel material that table 5 prepares according to embodiment 5
Comparative example 1
Respectively get tetraethoxy 6mL, deionized water 2mL, adds the hydrochloric acid of 0.16mL1% after ethanol 9.2mL mixes, and stirs the ammoniacal liquor that adds 0.55mL0.1M after 1h, obtains silicon dioxide gel.Get this silicon dioxide gel 5mL and be placed in cylindrical die.Treat that silica dioxide gel is to be placed on aging 3h in 50 ℃ of baking ovens, then to put into volume ratio be that 60 ℃ of the trimethyl carbinol of 2:3 and the mixed solutions of deionized water carry out solvent exchange 12h, during change mixed solution 3 times.The gel that solvent exchange is crossed is placed in refrigerator-20 ℃ freezing 12h, then lyophilize is to sample complete drying, obtains the cracked serious and higher simple aerosil of fragility.Its significant parameter is shown in Table 6.
The significant parameter of the aerogel material that table 6 prepares according to comparative example 1
In above-mentioned all embodiment and comparative example, resulting aerogel sample all adopts U.S. Merck & Co., Inc instrument (Gemini V, Micromeritics) measurement the specific area under liquid nitrogen temperature, pore volume and pore size distribution, the thermal conductivity instrument (C-Therm TCi thermal conductivity analyzer) of employing C-Therm company carries out the mensuration of thermal conductivity, adopt block quality to determine density with the ratio of measured volume, adopt the universal electrical material-testing machine (Instron3365) of Instron company to measure Young's modulus, porosity is obtained by following formula:
Wherein ρ, ρ
sand ρ
cbe respectively the apparent density of aerogel material, the skeletal density of pure aerogel (aerosil, metal oxide aerogel, organic aerogel), the skeletal density of pure cellulose aerogel, ω
sand ω
cbe respectively non-cellulose (silicon-dioxide, metal oxide or organism) and cellulosic massfraction.
From the result of above-described embodiment, can see, aerogel composite of the present invention is owing to being composited by reticulated cellulose nanofiber skeleton and colloidal sol, significantly improve the mechanical property of aerogel composite, obtained the aerogel composite of lower thermal conductivity, low density, high-specific surface area.With respect to not having and the compound aerogel of Mierocrystalline cellulose can only prepare for powder through lyophilize, the aerogel material of compound cellulose prepared by present method can obtain large-sized block materials through lyophilize, and this huge advantage is that aerogel material has been paved road in the practical application of more areas.
In addition, the present invention replaces traditional supercritical drying drying method by cryodesiccated method and prepares aerogel composite, has reduced preparation cost, and reaction conditions requires lower, improve the security of producing, reduced the restriction of actual production, can carry out fairly large production.
In the description of this specification sheets, the description of reference term " embodiment ", " a kind of embodiment " etc. means to be contained at least one embodiment of the present invention or embodiment in conjunction with specific features, structure, material or the feature of this embodiment or embodiment description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or embodiment.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or embodiment.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (8)
1. for the preparation of a method for block aerogel composite, it is characterized in that, comprise the following steps:
A) provide reticulated cellulose nanofiber skeleton;
B) provide colloidal sol;
C) described reticulated cellulose nanofiber skeleton is reacted and obtains mixture with described colloidal sol; With
D) described mixture is carried out to lyophilize, obtains described block aerogel composite,
Described lyophilize comprises:
Described mixture is placed in and is preheated to the trimethyl carbinol of 50～100 ℃ or the aqueous solution of the trimethyl carbinol carries out solvent exchange reaction, after question response 2～72h, reacted mixture is carried out to lyophilize at 0～-50 ℃, obtain described aerogel composite, in described step a), with cellulose aquagel, prepare described reticulated cellulose nanofiber skeleton, described step a) comprises:
A-1) described cellulose aquagel is placed in to alkali aqueous solution, at 80～100 ℃, reacts 4～24h;
A-2) cellulose aquagel after reaction 4～24h is placed in to deionized water, at 60～100 ℃, reacts 2～36h;
A-3) by reaction, the cellulose aquagel after 2～36h is placed in and is preheated to the trimethyl carbinol of 50～100 ℃ or the aqueous solution of the trimethyl carbinol carries out solvent exchange reaction, after reaction 2～20h, by reacted cellulose aquagel lyophilize, obtain described reticulated cellulose nanofiber skeleton.
2. the method for the preparation of block aerogel composite according to claim 1, is characterized in that, described step c) specifically comprises:
C-1) described cellulose nano-fibrous skeleton is immersed in described colloidal sol, until described cellulose nano-fibrous skeleton through shrinking, after swelling is returned original volume again by its taking-up;
C-2) the cellulose nano-fibrous skeleton after taking out is placed in to alcohol atmosphere gel aging, obtains the mixture of cellulose nano-fibrous skeleton and colloidal sol.
3. the method for the preparation of block aerogel composite according to claim 1, is characterized in that, also comprises the steps:
E) described aerogel composite is carried out in atmosphere of inert gases to charing, obtain the aerogel composite of charing.
4. the method for the preparation of block aerogel composite according to claim 1, is characterized in that, described colloidal sol is silicon dioxide gel, metal oxide sol or organism colloidal sol.
5. the method for the preparation of block aerogel composite according to claim 4, it is characterized in that, described colloidal sol is silicon dioxide gel, described step b) comprises: after silica precursor sol body, alcohol and water are mixed, add an acidic catalyst and stir, after presoma hydrolysis finishes, add again basic catalyst and stir, obtaining described silicon dioxide gel.
6. the method for the preparation of block aerogel composite according to claim 4, it is characterized in that, described colloidal sol is organism colloidal sol, described step b) comprising: after organism sol precursor is mixed in water, add basic catalyst and stir, obtaining described organism colloidal sol.
7. the method for the preparation of block aerogel composite according to claim 4, it is characterized in that, described colloidal sol is metal oxide sol, described step b) comprises: after metal oxide sol presoma is mixed with alcohol, water, add an acidic catalyst and stir, obtaining described metal oxide sol.
8. a block aerogel composite of preparing according to the method for the preparation of block aerogel composite described in any one in claim 1-7, it is characterized in that, described aerogel composite is composited by reticulated cellulose nanofiber skeleton and colloidal sol, wherein, the porosity of described aerogel composite is 80～99.5%, and density is 0.015～0.680 g/cm
3, BET specific surface area is 150～1200 m
2/ g, thermal conductivity is 0.015～0.045 W m
-1k
-1, Young's modulus is 0.5～150 MPa.
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