CN110282958A - Nanocrystalline aerogel material of a kind of high temperature resistant abnormity and preparation method thereof - Google Patents
Nanocrystalline aerogel material of a kind of high temperature resistant abnormity and preparation method thereof Download PDFInfo
- Publication number
- CN110282958A CN110282958A CN201910630467.7A CN201910630467A CN110282958A CN 110282958 A CN110282958 A CN 110282958A CN 201910630467 A CN201910630467 A CN 201910630467A CN 110282958 A CN110282958 A CN 110282958A
- Authority
- CN
- China
- Prior art keywords
- abnormity
- nanocrystalline
- aerogel material
- solution
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Abstract
The present invention relates to nanocrystalline aerogel material of a kind of high temperature resistant abnormity and preparation method thereof, the methods are as follows: the nanocrystalline dispersion liquid of preparation abnormity；The nanocrystalline dispersion liquid of abnormity is uniformly mixed with assembling agent by stirring and ultrasonic treatment, the first solution of mixed phase is obtained；Then catalyst solution is added, carries out gelation reaction process by stirring and being ultrasonically treated, then through vacuum pump-down process, obtain gelation reaction liquid；Aging Step and drying steps are carried out again, obtain special-shaped nanocrystalline aerogel material；The nanocrystalline aerogel material of abnormity is post-processed in more than two different temperatures stages, the nanocrystalline aerogel material of high temperature resistant abnormity is made.The present invention carries out heat treatment process stage by stage to aerogel material in last handling process, realize aerogel material microstructure Strengthening and Toughening, so that the structural strength of aerogel material significantly improves, large specific surface area after realizing that high temperature resistance is good and being heat-treated, can effectively insulating the special-shaped nanocrystalline aerogel material of the high temperature resistant preparation.
Description
Technical field
The present invention relates to aeroge preparation technical field more particularly to a kind of high temperature resistant nanocrystalline aerogel material of abnormity and
Preparation method.
Background technique
Nanoporous aerogel (abbreviation aeroge) material is the gel rubber material that a kind of decentralized medium is gas, is by colloid
Particle or the high-polymer molecule mutually build up a kind of nanoporous solid material with network structure of composition, the material mesoporous
The size of gap is in nanometer scale.Its porosity is up to 80~99.8%, and the typical sizes of hole are 1~100nm, specific surface area
For 200~1000m2/ g, and density can be down to 3kg/m3, and room temperature thermal coefficient can be down to 0.012W/mk.Just because of this
A little features make aerogel material have very wide application potential in terms of calorifics, acoustics, optics, microelectronics, particle detection.Mesh
Before, it is still heat-insulated field using the widest field of aeroge, since the unique nanostructure of aeroge can effectively drop
Low convection current conduction, solid phase conduction and heat radiation.Verified aeroge is a kind of effective heat-barrier material in existing research, but
At present it has been reported that high temperature resistant aeroge material highest resistance to extreme temperature be no more than 1100 DEG C.
Existing high temperature resistant aeroge mainly has carbon aerogels, ceramic aerogel, aerosil, aluminium oxide airsetting
Glue and zirconia aerogels etc..Carbon aerogels and ceramic aerogel have good high temperature resistance, but its application exists
Certain limitation, i.e., only may be implemented 1400 DEG C or more thermal insulation applications under oxygen-free environment, and carbon aerogels and ceramic aerogel
Inoxidizability there are no effective methods to overcome.The oxide silica aerogels such as silica, aluminium oxide and zirconium oxide are at high temperature
Serious crystal transfer and sintering, which can occur, leads to structure collapses, causes nano particle to be grown up, hole reduction, to make aeroge
Specific surface area decline sharply, weaken its heat-proof quality significantly, heat-insulated failure.For the limitation of oxide silica aerogel, have
Correlative study has carried out the modifying process such as rare-earth oxide or multi-component doped, but its function and effect is limited.
Chinese patent application CN201810068117.1 discloses a kind of preparation method of high temperature resistant aeroge material, although
The aeroge of this method preparation has good high-temperature stability, and heat resisting temperature is 1000 DEG C or more, or even is resistant to 1300 DEG C
Above high temperature, but the aerogel material can still generate series of phase transitions at a high temperature of 1200 DEG C or more, so that it is in high temperature
Specific surface area after heat treatment is smaller, is no more than 100m2/ g, therefore the high temperature insulating performance of the aerogel material is not very
It is good.
With the development of science and technology, each field proposes higher want to the temperature tolerance and high temperature insulating performance of heat-barrier material
It asks, hence it is highly desirable to develop a kind of effective method, prepares the airsetting with energy effectively insulating under high temperature resistant and high temperature
Glue material.
Summary of the invention
In order to solve the technical problems existing in the prior art, that the present invention provides a kind of preparation processes is simple, material is resistance to
Under high-temperature behavior is good and high temperature can effectively insulating the nanocrystalline aerogel material of novel fire resistant abnormity and preparation method thereof.
The present invention provides a kind of preparation method of the nanocrystalline aerogel material of high temperature resistant abnormity, the side in first aspect
Method includes the following steps:
(1) alumina nano powder and acid solution are uniformly mixed with water, obtain mixed liquor, then set the mixed liquor
1~10h is reacted at 140~340 DEG C, obtains the nanocrystalline dispersion liquid of abnormity；
(2) the nanocrystalline dispersion liquid of abnormity that step (1) obtains successively is passed through with selected from the assembling agent of silicic acid and/or silica solution
Stirring and ultrasonic treatment are uniformly mixed, and obtain the first solution of mixed phase of the nanocrystalline self assembly of abnormity；
(3) catalyst solution is added into the first solution of mixed phase that step (2) obtains, it is then successively agitated and ultrasonic
Processing obtains the second solution of mixed phase to carry out gelation reaction process, then by second solution of mixed phase in temperature is 25
DEG C and vacuum degree be 0.1~0.5MPa under conditions of carry out vacuumizing 0.1~1h, obtain gelation reaction liquid；
(4) the gelation reaction liquid that step (3) obtains successively is subjected to Aging Step and drying steps, abnormity nanometer is made
Brilliant aerogel material；With
(5) the nanocrystalline aerogel material of abnormity for obtaining step (4) is after more than two different temperatures stages carry out
The nanocrystalline aerogel material of high temperature resistant abnormity is made in reason.
Preferably, it includes the post-processing of the first temperature stage, second that described two above different temperatures stages, which carry out post-processing,
Temperature stage post-processing and the post-processing of third temperature stage；The temperature of the first temperature stage post-processing is 200 DEG C~500
DEG C, the time of the first temperature stage post-processing is 0.1~12h；The temperature of second temperature stage post-processing is 600 DEG C~
800 DEG C, the time of second temperature stage post-processing is 0.1~5h；The temperature of third temperature stage post-processing is 900 DEG C~
1600 DEG C, the time of third temperature stage post-processing is 0.1~5h.
Preferably, before carrying out the second temperature stage post-processing and third temperature stage post-processing, first will
The nanocrystalline aerogel material of abnormity is cooled to room temperature.
Preferably, in step (2), time of the stirring is 0.5~5h, the time of the ultrasonic treatment is 20~
60min；And/or in step (3), time of the stirring is 0.5~5h, the time of the ultrasonic treatment is 10~
120min。
Preferably, in step (1): the concentration of the alumina nano powder contained in the mixed liquor is 0.0002~50g/
ML, and the partial size of the alumina nano powder contained in the mixed liquor is 10~200nm；The acid solution is that hydrochloric acid is molten
One of liquid, acetum and sulfuric acid solution are a variety of；And/or the concentration of the acid solution is 0.1~5mol/L, it is described
The dosage of acid solution is 1~200mL.
Preferably, the solid content of the assembling agent is 2~10%；The catalyst solution is ammonia spirit and/or fluorination
Ammonium salt solution；The concentration of the catalyst solution is 0.1~2mol/L；And/or the nanocrystalline dispersion liquid of the abnormity, the assembling agent
Mass ratio with the catalyst solution is (5~200): (0.1~50): (0.5~5).
Preferably, the Aging Step are as follows: by the gelation reaction liquid prior to 15~55 DEG C at 12~72h of aging, so
12~72h of aging at 50~90 DEG C afterwards.
Preferably, in carrying out the Aging Step, so that the humidity of the gelation reaction liquid is not less than 80%.
Preferably, the drying is supercritical drying or constant pressure and dry.
It is different that the present invention in second aspect provides high temperature resistant made from the preparation method as the present invention described in first aspect
The nanocrystalline aerogel material of shape.
The present invention at least has the following beneficial effects: compared with prior art
(1) it is different from other to prepare high temperature resistant aeroge heat-barrier material by doping vario-property mode by the present invention, proposes logical
The stable aerogel material of mode preparation structure of special-shaped nanocrystalline self-supporting is crossed for high temperature high efficiency thermal insulation applications, it is this to change
Feasibility is had more into method.
(2) present invention is used as aeroge matrix skeleton using abnormity is nanocrystalline, which has more designability
And controllability, this mode can prepare the different aerogel material of nano unit, have self-supporting effect, overcome biography
System sol-gel process prepares the uncontrollability of aerogel process, can be designed that the shapes such as similar nanometer sheet/nano wire are single
The aerogel material of member.
(3) present invention uses sial compounding ingredients for the basis composition of aeroge, and silica solution can coat aluminium oxide nano
Crystalline substance obtains the aerogel material of compounding ingredients after gelation and drying process, and after high-temperature process, compounding ingredients can
To form the mullite phase more resistant to warm phase, the temperature tolerance of material can effectively improve.
(4) the nanocrystalline aerogel material of high temperature resistant abnormity in the present invention, there are the process of nanocrystalline assembling and heat treatments
Process (last handling process), nanocrystalline package technique combination heat treatment process, the nanoparticle of high temperatures is assembled
Bonding realizes effectively assembling and fixing for oxide nanocrystalline, realizes the preparation of core-shell structure porous network aeroge；Nucleocapsid
Structure forms network frame at high temperature, can effectively inhibit growing up for subscale nanocrystal, improve nanostructure
Stability, can prevent material occur at high temperature further collapse and crystal transfer, improve the temperature tolerance of material.
(5) present invention can be avoided in preparation process and be made using organic solvent using water silica sol as bonding agent
At environmental pollution and waste.
(6) the method for the present invention preparation aerogel material under the premise of remaining less than the lower thermal conductivity of 0.030W/mk,
Also there is excellent high temperature resistance, 1400 DEG C in short-term of resistance to extreme temperature may be implemented.
(7) aerogel material of the method for the present invention preparation uses segmented heat treatment process, which slows down
The crystal transfer process of material avoids porous structure recurring structure in rapid contraction process and collapses, realizes airsetting glue material
Expect microstructure Strengthening and Toughening, is conducive to the formation of sial compound phase and nanometer skeleton is more firm, so that the structure of aerogel material
Intensity significantly improves, be advantageously implemented large specific surface area after high temperature resistance is good and high-temperature heat treatment, can effectively insulating institute
State the preparation of the nanocrystalline aerogel material of high temperature resistant abnormity.
(8) the method for the present invention need to stir and be ultrasonically treated by solution in the nanocrystalline self assembling process of abnormity so that
Silicic acid or silica solution are sufficiently mixed with alumina nanoparticles, and pass through the modes such as weak intermolecular interaction or chemical bond
It carries out assembly and connection and forms uniform mixed phase；Meanwhile it is molten that catalyst is added after the nanocrystalline self assembly of abnormity in the method for the present invention
Liquid carries out solution stabilization removal, and gelation reaction needs adequately to be stirred in the process, ultrasound is so that catalyst uniformly divides
It dissipates, and obtained the second solution of mixed phase needs to remove the bubble formed in whipping process by vacuum pump-down process, to guarantee
The aeroge of subsequent preparation is without macroporous structure, to guarantee that obtained high temperature resistance is good, high temperature flowering structure is firm, high-temperature heat treatment
Afterwards large specific surface area, can effectively insulating the nanocrystalline aerogel material of high temperature resistant abnormity.
(9) porosity of the nanocrystalline aerogel material of high temperature resistant abnormity of the method for the present invention preparation is 90% or more, hole ruler
Very little is 5~500nm, and the gel particle partial size of aeroge is 10~800nm, and specific surface area is 130~600m under high temperature2/ g, it is resistance to
Hot temperature is 1200 DEG C or more.
Detailed description of the invention
Fig. 1 is preparation flow figure of the invention.
Fig. 2 is the nanocrystalline SEM figure of abnormity using the preparation of different adsorbents.In figure: being (a) that sulfuric acid is prepared as adsorbent
Nano line cluster；(b) it is nanometer sheet cluster that acetic acid is prepared as adsorbent；(c) it is nanometer rods that hydrochloric acid is prepared as adsorbent.
Fig. 3 is the SEM figure of abnormity nanocrystalline aerogel material heat treatment front and back prepared by the embodiment of the present invention 1.In figure:
(a) it is SEM figure before abnormity nanocrystalline aerogel material heat treatment；It (b) is after the nanocrystalline aerogel material of abnormity is heat-treated
SEM figure.
Fig. 4 is macroscopical optical photograph of abnormity nanocrystalline aerogel material heat treatment front and back prepared by the embodiment of the present invention 1.
In figure: (a) being macroscopical optical photograph before abnormity nanocrystalline aerogel material heat treatment；It (b) is the nanocrystalline airsetting glue material of abnormity
Macroscopical optical photograph after material heat treatment.
Fig. 5 is the energy spectrum diagram of the nanocrystalline aerogel material of high temperature resistant abnormity prepared by the embodiment of the present invention 1.In figure: (a) Si
(b)Al(c)O。
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of the nanocrystalline aerogel material of high temperature resistant abnormity, the side in first aspect
Method includes the following steps:
(1) alumina nano powder and acid solution are uniformly mixed with water, obtain mixed liquor, then set the mixed liquor
In 140~340 DEG C (such as 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C,
240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C or 340 DEG C) under reaction 1~
10h (such as 1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5 or 10h), obtains abnormity
Nanocrystalline dispersion liquid；In the present invention, the alumina nano powder can for example aoxidize for γ phase alumina nano powder or hydroxyl
The alumina nano powders such as aluminum nano；In the mixed liquor, the partial size of the alumina nano powder single particle is for example 10
In the range of~200nm；In the present invention, during reacting 1~10h at the mixed liquor is placed in 140~340 DEG C, institute
Acid solution (such as hydrochloric acid, acetic acid, sulfuric acid etc.), which is stated, as catalyst (adsorbent) can be catalyzed nucleus in some crystal orientation orientation
Growth ultimately forms the special-shaped nanoparticle such as nanometer sheet, nanometer rods, nano wire (abnormity is nanocrystalline).
(2) by the nanocrystalline dispersion liquid of abnormity that step (1) obtains, (such as aqueous silicon is molten with silicic acid and/or silica solution is selected from
Glue) assembling agent it is successively agitated and ultrasonic treatment is uniformly mixed, obtain the first solution of mixed phase of the nanocrystalline self assembly of abnormity；
Abnormity according to the present invention is nanocrystalline to aim at high temperature resistance design, and special-shaped nanocrystalline self assembling process is needed by molten
Liquid stirring and ultrasonic treatment, this process are to be sufficiently mixed silicic acid or silica solution with alumina nanoparticles, and pass through weak
The modes such as intermolecular interaction or chemical bond carry out assembly and connection and form uniform mixed phase.
(3) catalyst solution (such as ammonium hydroxide or NH are added into the first solution of mixed phase that step (2) obtains4F solution),
Then successively agitated and ultrasonic treatment obtains the second solution of mixed phase to carry out gelation reaction process, then by the mixing
The second solution of phase temperature be 25 DEG C and vacuum degree be 0.1~0.5MPa (such as 0.1,0.15,0.2,0.25,0.3,0.35,
0.4,0.45 or 0.5MPa) under conditions of vacuumize 0.1~1h (such as 0.1,0.2,0.3,0.4,0.5,0.6,0.7,
0.8,0.9 or 1h), obtain gelation reaction liquid；In the present invention, after abnormity is nanocrystalline by self assembly, it is molten that catalyst is added
Liquid makes solution stabilization removal, carries out gel process, which also needs adequately to be stirred, ultrasound is so that catalyst is uniform
Dispersion；And obtained the second solution of mixed phase needs to remove the bubble formed in whipping process by vacuum pump-down process, to protect
The aeroge of subsequent preparation is demonstrate,proved without macroporous structure.
(4) the gelation reaction liquid that step (3) obtains successively is subjected to Aging Step and drying steps, abnormity nanometer is made
Brilliant aerogel material.
(5) the nanocrystalline aerogel material of abnormity for obtaining step (4) is after more than two different temperatures stages carry out
It manages (heat treatment), the nanocrystalline aerogel material of high temperature resistant abnormity (the nanocrystalline aerogel heat-insulating material of high temperature resistant abnormity) is made；This
Invention uses segmented heat treatment process, which has slowed down the crystal transfer process of material, avoided porous structure
Recurring structure collapses in rapid contraction process, realizes aerogel material microstructure Strengthening and Toughening, is conducive to sial compound phase
It is formed and nanometer skeleton is more firm, so that the structural strength of aerogel material significantly improves, be advantageously implemented high temperature resistance
Large specific surface area after good and high-temperature heat treatment, can effectively insulating the nanocrystalline aerogel material of high temperature resistant abnormity system
It is standby.
The present invention is under the collective effect of step of the present invention (1) to step (5) just to guarantee that high temperature resistance has been made
It gets well, high temperature flowering structure is firm, large specific surface area, the high temperature resistant abnormity nanometer of the present invention of energy effectively insulating after high-temperature heat treatment
Brilliant aerogel material, the missing of either step are unfavorable for that the nanocrystalline airsetting glue material of high temperature resistant abnormity of the present invention is made
Material.
The present invention can determine the heat treatment temperature of material, material is by some temperature according to the use temperature of aerogel material
Degree pretreatment after, unstable phase tends towards stability, and can further use in the present context, and heat treatment temperature is higher, material it is close
Spend it is bigger, specific surface area is smaller, and heat insulation can be reduced accordingly, thus according to the use condition of material can design temperature tolerance with
The corresponding relationship of heat-proof quality.
According to some preferred embodiments, it includes the first temperature that described two above different temperatures stages, which carry out post-processing,
Stage post-processing, the post-processing of second temperature stage and the post-processing of third temperature stage；The temperature of the first temperature stage post-processing
Degree is 200 DEG C~500 DEG C (such as 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C or 500 DEG C), the first temperature stage
The time of post-processing is 0.1~12h (such as 0.1,0.5,1,2,3,4,5,6,7,8,9,10,11 or 12h)；The second temperature
The temperature of stage post-processing is 600 DEG C~800 DEG C (such as 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C), second temperature rank
The time of section post-processing is 0.1~5h (such as 0.1,0.5,1,1.5,2,2.5,3,3.5,4,4.5 or 5h)；The third temperature
Stage post-processing temperature be 900 DEG C~1600 DEG C (such as 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C,
1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C or 1600 DEG C), third temperature stage
The time of post-processing is 0.1~5h (such as 0.1,0.5,1,1.5,2,2.5,3,3.5,4,4.5 or 5h)；In the present invention, institute
Stating more than two different temperatures stages carries out post-processing and preferably comprises first temperature stage post-processing, the second temperature
Stage post-processing and third temperature stage post-processing, this is because the nanocrystalline airsetting glue material of abnormity that step (4) is obtained
Expect first stage low-temperature treatment 0.1-12h at 200-500 DEG C, be conducive to make sial composite aerogel that dehydroxylation process occur,
Realize that sial composite aerogel first step skeleton is strong；After the progress of above-mentioned first stage step, sample is cooled to room temperature, and is carried out
Second stage is heat-treated 0.1~5h under conditions of 600~800 DEG C, is conducive to make the crystal form of compound silicon-aluminum sol that preliminary turn occur
Become；It is cooled to room temperature, carries out the phase III to sample in above-mentioned second stage step, be heat-treated under conditions of 900~1600 DEG C
0.1~5h is so conducive to obtain the strong nanocrystalline aerogel material of high temperature resistant abnormity of structural framework.
According to some preferred embodiments, the second temperature stage post-processing and the third temperature stage are being carried out
Before post-processing, the nanocrystalline aerogel material of abnormity is first cooled to room temperature (such as 20~30 DEG C)；In the present invention, institute
State post-processing can for example be carried out in Muffle furnace, heating rate for example can for 1~10 DEG C/min (such as 1,2,3,4,5,6,
7,8,9 or 10 DEG C/min), being cooled to room temperature can be for example cooled to room temperature by way of cooling down with furnace.
According to some preferred embodiments, in step (2), time of the stirring be 0.5~5h (such as 0.5,1,
1.5,2,2.5,3,3.5,4,4.5 or 5h), time of the ultrasonic treatment be 20~60min (such as 20,25,30,35,40,
45,50,55 or 60min)；And/or in step (3), time of the stirring be 0.5~5h (such as 0.5,1,1.5,2,
2.5,3,3.5,4,4.5 or 5h), time of the ultrasonic treatment be 10~120min (such as 10,20,30,40,50,60,70,
80,90,100,110 or 120min) it is preferably 20~60min.
According to some preferred embodiments, in step (1): the alumina nano powder contained in the mixed liquor it is dense
Degree be 0.0002~50g/mL (such as 0.0002,0.002,0.02,0.2,2,5,10,15,20,25,30,35,40,45 or
50g/mL), such as by alumina nano powders such as the γ phase alumina nano powder of 1-500g or aluminum oxyhydroxide nano powders it is dispersed in
In 10-5000mL aqueous solution, so that the concentration of the alumina nano powder contained in the mixed liquor is 0.0002~50g/mL；
And the partial size of the alumina nano powder contained in the mixed liquor is 10~200nm；The acid solution is hydrochloric acid solution, vinegar
One of acid solution and sulfuric acid solution are a variety of, and in the present invention, what is prepared when using sulfuric acid as adsorbent is nanometer
Line cluster abnormity is nanocrystalline, and what is prepared when using acetic acid as adsorbent is that nanometer sheet cluster abnormity is nanocrystalline, makees when using hydrochloric acid
It is that nanometer rods abnormity is nanocrystalline for what is prepared when adsorbent；And/or the concentration of the acid solution be 0.1~5mol/L (such as
0.1,0.5,1,1.5,2,2.5,3,3.5,4,4.5 or 5mol/L), the dosage of the acid solution be 1~200mL (such as 1,
5,10,20,30,40,50,60,70,80,90,100,120,140,160,180 or 200mL).In the present invention, it is preferred to for institute
The concentration of the alumina nano powder contained in mixed liquor is stated to receive for the aluminium oxide contained in 0.0002~50g/mL, the mixed liquor
The partial size of rice flour is 10~200nm, and the concentration of the acid solution is 0.1~5mol/L, the dosage of the acid solution
For 1~200mL, it so may further ensure that the nanocrystalline unit of abnormity according to the present invention with more designability and controllable
Property, so as to further design the airsetting for the high temperature resistance that the shapes such as similar nanometer sheet/nano wire/nanometer rods are unit
Glue material.
According to some preferred embodiments, the solid content of the assembling agent be 2~10% (mass percentages) (such as
2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%), such as the solid content of silicate solution is 2~10%；The catalysis
Agent solution be ammonia spirit and/or ammonium fluoride solution, it is further preferred that the catalyst solution be ammonium fluoride solution, this be because
It is weaker compared to the catalysis intensity of ammonium fluoride solution for ammonia spirit, it is easy to cause the aerogel material brittleness of preparation big, prepares
Process is easy to happen fritter and falls off；The concentration of the catalyst solution be 0.1~2mol/L (such as 0.1,0.5,1,1.2,1.4,
1.6,1.8 or 2mol/L)；And/or the mass ratio of the nanocrystalline dispersion liquid of the abnormity, the assembling agent and the catalyst solution
For (5~200): (0.1~50): (0.5~5)；In the present invention, the nanocrystalline dispersion liquid of the more preferably described abnormity, solid content
The mass ratio of the catalyst solution for being 0.1~2mol/L for 2~10% assembling agent and concentration is (5~200):
(0.1~50): (0.5~5), the nanocrystalline dispersion liquid of abnormity carry out gelation reaction process under this proportion and are more advantageous to
Catalyst solution makes solution stabilization removal, carries out gel process.
According to some preferred embodiments, the Aging Step are as follows: by the gelation reaction liquid prior to 15~55 DEG C
(such as 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C or 55 DEG C) be preferably aging 12 at 15~35 DEG C~
72h (such as 12,24,36,48,60 or 72h), then in 50~90 DEG C of (such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75
DEG C, 80 DEG C, 85 DEG C or 90 DEG C) under 12~72h of aging (such as 12,24,36,48,60 or 72h).
According to some preferred embodiments, in carrying out the Aging Step, so that the gelation reaction liquid is wet
Degree is not less than 80%.
According to some specific embodiments, the Aging Step are as follows: gelation reaction liquid sealing is placed on 15-
Aging 12-72h, overlaps network sufficiently at 35 DEG C, is subsequently placed under water bath aging 12-72h at 50-90 DEG C, wants at this time
Ask the humidity of the gelation reaction liquid 80% or more；Ageing process setting is to lead to structure in order to avoid gel is too fast not
Stablize, while guaranteeing gel reaction sufficiently to make skeleton overlap joint completely, structure is strong, to advantageously ensure that obtained specific surface area
Greatly, the small nanocrystalline aerogel material of high temperature resistant abnormity of linear shrinkage ratio；The humidity of ageing process requires to be in order to avoid solidifying
Glue dehydration excessively forms xerogel.
According to some preferred embodiments, in step (4), the drying is supercritical drying or constant pressure and dry；It is excellent
Choosing, the drying are supercritical drying, further, it is preferred that first carrying out solvent displacement step before carrying out the drying
Suddenly, specifically, gel such as after above-mentioned gelation reaction liquid aging carries out solvent displacement by ethyl alcohol, acetone and other organic solvent
Process, displacement 2-5 days, are replaced 2-5 times every time；More preferably using dehydrated alcohol as the supercritical drying of dried medium, with anhydrous
Ethyl alcohol includes: the silicon for successively obtaining gel reaction liquid after aging and solvent displacement as the supercritical drying of dried medium
The compound wet gel of aluminium is loaded in supercritical drying equipment and the supercritical drying equipment is placed in autoclave, in autoclave
Dehydrated alcohol is added and seals, makes 2~50MPa of pressure in autoclave, temperature is 0~50 DEG C, keeps the pressure and temperature
5~72h is spent, then the fluid generated in dehydrated alcohol and drying process is discharged, the nanocrystalline aerogel material of abnormity is made.
According to some specific embodiments, the preparation process of the nanocrystalline aerogel material of the high temperature resistant abnormity includes:
The preparation of S1, the nanocrystalline dispersion liquid of abnormity: using alumina nano powder as raw material, the γ phase alumina of 1-500g is received
The alumina nano powders such as rice flour or aluminum oxyhydroxide nano powder are dispersed in 10-5000mL aqueous solution, wherein the single grain of nano powder
The partial size of son is within the scope of 10-200nm；Select hydrochloric acid, acetic acid, sulfuric acid (1-200mL) of 0.1-5mol/L etc. as catalyst
It is added in the mixed liquor of above-mentioned alumina nanoparticles, mixed liquor is placed in polytetrafluoroethylene (PTFE) as in the reaction kettle of liner, it is close
Envelope, is placed at 240 ± 100 DEG C and reacts 1-10h, obtains the nanocrystalline dispersion liquid of abnormity；During this, catalyst can be catalyzed crystalline substance
Core ultimately forms the special-shaped nanoparticle such as nanometer sheet, nanometer rods, nano wire in some crystal orientation oriented growth.
S2, the nanocrystalline self assembling process of abnormity: the nanocrystalline dispersion liquid 5-200g and 0.1-50g of abnormity of above-mentioned preparation is consolidated
Content is that the assemblings agent such as silicic acid or the silica solution of 2-10% are sufficiently mixed, and ultrasound 20- after 0.5-5h is sufficiently stirred in magneton
60min obtains the first solution of mixed phase of the nanocrystalline self assembly of abnormity；This process is to fill silicic acid with alumina nanoparticles
Divide mixing, and carries out assembly and connection by modes such as weak intermolecular interactions or chemical bond and form uniform mixed phase.
S3, gelation reaction process: the ammonium hydroxide of 0.5-5g 0.1-2mol/L/ is added in above-mentioned the first solution of mixed phase
Or NH4The catalyst solutions such as F solution, magneton are sufficiently stirred ultrasound 20-60min after 0.5-5h, obtain the second solution of mixed phase；With
Afterwards, the second solution of mixed phase being placed at 25 DEG C, vacuum degree is to take out solution left standstill after vacuumizing 0.1-1h under 0.1-0.5MPa,
Obtain gelation reaction liquid；Abnormity it is nanocrystalline by self assembly after, catalyst, which is added, makes solution stabilization removal, carries out gel mistake
Journey, process needs are adequately stirred, ultrasound is so that catalyst is evenly dispersed；And the mixed liquor is needed by vacuum suction
Process removes the bubble formed in whipping process, to guarantee the aeroge of subsequent preparation without macroporous structure.
S4, ageing process: the sealing of above-mentioned gelation reaction liquid is placed on aging 12-72h at 15-35 DEG C, fills network
Divide overlap joint, is subsequently placed under water bath aging 12-72h at 50-90 DEG C, requires the humidity in beaker 80% or more at this time；
Ageing process setting is to lead to structural instability in order to avoid gel is too fast, while guaranteeing that gel reaction sufficiently overlaps skeleton
Completely, structure is strong；The humidity requirement of ageing process is in order to avoid gel dehydration excessively forms xerogel.
S5, drying process: aeroge prepared by the present invention can be by drying sides such as supercritical drying or constant pressure and dries
Formula is realized；It is preferred that supercritical drying process, gel after above-mentioned aging carry out solvent displacement by ethyl alcohol, acetone and other organic solvent
Process, displacement 2-5 days, are replaced 2-5 times every time；It is preferred that using dehydrated alcohol as the supercritical drying of dried medium；Preferably,
Supercritical drying using dehydrated alcohol as dried medium includes: to be loaded on sial compound wet gel in supercritical drying equipment simultaneously
The supercritical drying equipment is placed in autoclave, dehydrated alcohol is added in autoclave and is sealed, the pressure in autoclave is made
Power is 2~50MPa, and temperature is 0~50 DEG C, the 5~72h of pressure and temperature is kept, then by dehydrated alcohol and drying process
The fluid of middle generation is discharged, and the nanocrystalline aerogel material of abnormity is made.
S6, heat treatment process: by the nanocrystalline aerogel material first stage of abnormity made from step S5 at 200-500 DEG C
Low-temperature treatment 0.1-12h makes sial composite aerogel that dehydroxylation process occur, and realizes that sial composite aerogel first step skeleton is strong
It is strong；After above-mentioned steps progress, sample is cooled to room temperature, and carries out second stage, and heat treatment 0.1 under conditions of 600~800 DEG C~
5h makes the crystal form of compound silicon-aluminum sol that preliminary transformation occur；It is cooled to room temperature, carries out the phase III, 900 to sample in upper step
It is heat-treated 0.1~5h under conditions of~1600 DEG C, is finally cooled to room temperature with furnace, obtains the strong high temperature resistant abnormity of structural framework
Nanocrystalline aerogel material.
It is different that the present invention in second aspect provides high temperature resistant made from the preparation method as the present invention described in first aspect
The nanocrystalline aerogel material of shape.The porosity of the nanocrystalline aerogel material of high temperature resistant abnormity of the method for the present invention preparation 90% with
On, pore size is 5~500nm, and the gel particle partial size of aeroge is 10~800nm, under high temperature specific surface area be 130~
600m2/ g, heat resisting temperature are 1200 DEG C or more；In the present invention, pore size refers to the microcosmic knot of aerogel material whole interior
The average pore size of structure, gel particle partial size refer to the size of nanoparticle inside aerogel particle.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
The preparation of S1, the nanocrystalline dispersion liquid of abnormity: using alumina nano powder as raw material, by the alumina nano powder of 20g point
It is dispersed in 500mL aqueous solution, wherein the partial size of nano powder single particle is within the scope of 10-200nm；Select the hydrochloric acid of 2mol/L molten
Liquid 15mL is added in the mixed liquor of above-mentioned alumina nanoparticles as catalyst (adsorbent), and mixed liquor is placed in polytetrafluoroethyl-ne
As in the reaction kettle of liner, sealing is placed at 240 DEG C and reacts 3h alkene, obtains the nanocrystalline dispersion liquid of abnormity.
S2, the nanocrystalline self assembling process of abnormity: it is by the nanocrystalline dispersion liquid 30g of abnormity and 20g solid content of above-mentioned preparation
4% silicic acid is sufficiently mixed, and ultrasound 30min after 5h is sufficiently stirred in magneton, obtains the mixed phase of the nanocrystalline self assembly of abnormity
First solution.
S3, gelation reaction process: the NH that 2g concentration is 1mol/L/ is added in above-mentioned the first solution of mixed phase4F is molten
Liquid, magneton are sufficiently stirred ultrasound 30min after 0.5h, obtain the second solution of mixed phase；Then, the second solution of mixed phase is placed in 25
At DEG C, vacuum degree is to take out solution left standstill after vacuumizing 0.1h under 0.5MPa, obtains gelation reaction liquid.
S4, ageing process: being placed on aging 12h at 25 DEG C for the sealing of above-mentioned gelation reaction liquid, overlap network sufficiently,
It is subsequently placed at aging 72h at lower 60 DEG C of water bath, and makes the humidity in beaker 80% or more.
S5, drying process: by gel after above-mentioned gelation reaction liquid aging, solvent replacement process is carried out by ethyl alcohol, often
Secondary displacement 3 days, replaces 3 times, obtains sial wet gel, then carry out the supercritical drying using dehydrated alcohol as dried medium:
By the compound wet gel of sial loaded on being placed in autoclave in supercritical drying equipment and by the supercritical drying equipment, in high pressure
Dehydrated alcohol is added in kettle and seals, makes the pressure 25MPa in autoclave, temperature is 30 DEG C, keeps the pressure and temperature
For 24 hours, then the fluid generated in dehydrated alcohol and drying process is discharged, the nanocrystalline aerogel material of abnormity is made.
S6, heat treatment process (last handling process): by the nanocrystalline aerogel material first stage of abnormity made from step S5
The low-temperature treatment 5h at 300 DEG C makes sial composite aerogel that dehydroxylation process occur, and realizes sial composite aerogel first step bone
Frame is strong；After above-mentioned steps progress, sample is cooled to room temperature, and is carried out second stage, is heat-treated 3h under conditions of 600 DEG C, makes
Preliminary transformation occurs for the crystal form of compound silicon-aluminum sol；It is cooled to room temperature to sample in upper step, carries out the phase III, 1200 DEG C
Under the conditions of be heat-treated 1h, be finally cooled to room temperature with furnace, obtain the strong nanocrystalline airsetting glue material of high temperature resistant abnormity of structural framework
Material；The heating rate of the heat treatment process in above three stage is 3 DEG C/min.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in the present embodiment
The surface of nanocrystalline aerogel material falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
The density of the nanocrystalline aerogel material of high temperature resistant abnormity manufactured in the present embodiment is 0.15g/cm3, porosity is
92%, pore size is 100~130nm, and gel particle partial size is 100~130nm, specific surface area 328m2/ g (passes through this implementation
The specific surface area that example above three phase heat treatment is crossed), heat resisting temperature is 1200 DEG C, thermal conductivity 0.024W/mK.
In the present embodiment, with do not pass through abnormity made from the step S5 that crosses of the present embodiment above three phase heat treatment
Nanocrystalline aerogel material is compared, and the linear shrinkage ratio of the nanocrystalline aerogel material of the abnormity of high temperature resistant made from the present embodiment is
0.65%, heat resisting temperature be 1200 DEG C, special instruction, when under heat treatment temperature after Overheating Treatment, aerogel material
Linear shrinkage ratio greater than 10%, indicate that the heat resisting temperature of the aerogel material is less than the heat treatment temperature.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that: in the system of the nanocrystalline dispersion liquid of abnormity of step S1
During standby, using the acetum of 20mL 2mol/L as adsorbent.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in embodiment 2
The surface of nanocrystalline aerogel material falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that: in the system of the nanocrystalline dispersion liquid of abnormity of step S1
During standby, using the sulfuric acid solution of 20mL 2mol/L as adsorbent.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in embodiment 3
The surface of nanocrystalline aerogel material falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that: heat treatment process is changed to the first stage at 300 DEG C
Low-temperature treatment 5h, second stage are heat-treated 1h at 1200 DEG C, and the phase III is heat-treated 0.5h at 1400 DEG C；Three phases
The heating rate of heat treatment process is 4 DEG C/min, is cooled to room temperature with furnace after heat preservation 0.5h at 1400 DEG C of the phase III, makes
Obtain the nanocrystalline aerogel material of high temperature resistant abnormity.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in embodiment 4
The surface of nanocrystalline aerogel material falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that: in the nanocrystalline self assembling process of step S2 abnormity,
Silicic acid is not added, the amount of the silica solution of addition is 2.5g.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in embodiment 5
The surface of nanocrystalline aerogel material falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that: during step S3 gelation reaction, catalyst
Solution selects the ammonia spirit of 1mol/L to replace NH4F solution, additional amount 2g.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in embodiment 6
The surface of nanocrystalline aerogel material falls off without loss of gloss, without changing colour, having, and other performance index are as shown in table 1.
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that: the drying process of step S5 is dry using normal pressure
Dry process, in gelation reaction liquid successively after aging and solvent swap step, constant pressure and dry 144h.
Performance test, discovery high temperature resistant abnormity are thermally shielded to the nanocrystalline aerogel material of high temperature resistant abnormity in embodiment 7
The surface of nanocrystalline aerogel material falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
Embodiment 8
Embodiment 8 is substantially the same manner as Example 1, the difference is that: the ageing process of step S4 are as follows: by above-mentioned gelation
Reaction solution sealing is placed on 72h at 25 DEG C.
Performance test is thermally shielded to the nanocrystalline aerogel heat-insulating material of high temperature resistant abnormity in embodiment 8, finds high temperature resistant
The surface of the nanocrystalline aerogel material of abnormity falls off without loss of gloss, without discoloration, nothing, and other performance index are as shown in table 1.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that: in step S6 heat treatment process (last handling process)
In: the nanocrystalline aerogel material of abnormity made from step S5 be warming up to 1200 DEG C (heat treatment temperatures) with furnace, heating speed
Rate is 3 DEG C/min, is cooled to room temperature with furnace after heat preservation 1h (heat treatment time), and high temperature resistant aeroge material is made.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that: in step S3 gelation reaction process not to described
The second solution of mixed phase is evacuated process；In step S4 ageing process: after second solution of mixed phase sealing
It is placed in aging 12h at 25 DEG C, overlaps network sufficiently, is subsequently placed at aging 72h at lower 60 DEG C of water bath, and make in beaker
Humidity 80% or more.
Comparative example 3
1. prepared by colloidal sol
Methyl orthosilicate 160g and acetonitrile 160g are weighed in 500mL beaker, is sealed against with preservative film and carries out magnetic force
Stir 1min.After mixing, it is the hydrochloric acid 60g of 0.003mol/L as catalyst that concentration, which is added, which needs slowly to add
Enter, and passes through magnetic agitation 5min；Above-mentioned mixed liquor is added in the there-necked flask of 1000mL, heating and magnetic force under the conditions of 70 DEG C
Stirring, and with reflux 30min, obtain the first solution of silica sol presoma；It is molten toward obtained silica sol presoma first
The methyl orthosilicate of 160g is added in liquid, continues heating and magnetic agitation under the conditions of 70 DEG C, reacts 16h, obtain silica sol
(silicon dioxide gel).The silica sol is diluted, the solvent 300g that the silica sol contains is steamed, adds second
Nitrile 600g is uniformly mixed, the silica sol after being diluted, and refrigerate to the silica sol after the dilution spare.
2. nanocrystalline assembling process
3.7g alumina nano powder is dissolved in 34g acetonitrile, is stirred evenly, the first mixed liquor is obtained, then toward described
For silicon dioxide gel 8g after above-mentioned dilution is added in first mixed liquor as bonding agent, it is mixed to obtain second by ultrasonic disperse 20min
Liquid is closed, then the ammonium hydroxide 2g that concentration is 0.43mol/L is added into second mixed liquor, continues ultrasound 20min, is made with oxidation
The nanocrystalline aeroge wet gel for skeleton of object.
3. gelling and aging
Aeroge wet gel obtained is placed in mold, is stood for 24 hours, 48h in 60 DEG C of baking ovens is subsequently placed at, completes gelling
With the process of aging.
4. solvent is replaced
Above-mentioned complete in the ethyl alcohol for being put into 10 times of volumes after gelling is taken out with the gel after aging is subjected to solvent displacement,
The time of solvent displacement is 3 days, which is repeated 3 times.
5. aerogel material is made in supercritical drying.
6. heat treatment process
Above-mentioned aerogel material be warming up to 1200 DEG C (heat treatment temperatures) with furnace, heating rate is 10 DEG C/min,
It is cooled to room temperature with furnace after heat preservation 1h (heat treatment time), high temperature resistant aeroge material is made.
High temperature resistant aeroge material in the high temperature resistant nanocrystalline aerogel material of abnormity and comparative example 1~3 in Examples 1 to 8
The performance indicator of material is as shown in table 1.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of the nanocrystalline aerogel material of high temperature resistant abnormity, which is characterized in that the method includes walking as follows
It is rapid:
(1) alumina nano powder and acid solution are uniformly mixed with water, obtain mixed liquor, be then placed in the mixed liquor
1~10h is reacted at 140~340 DEG C, obtains the nanocrystalline dispersion liquid of abnormity；
(2) the nanocrystalline dispersion liquid of abnormity that step (1) obtains and the assembling agent that is selected from silicic acid and/or silica solution is successively agitated
It is uniformly mixed with ultrasonic treatment, obtains the first solution of mixed phase of the nanocrystalline self assembly of abnormity；
(3) catalyst solution is added into the first solution of mixed phase that step (2) obtains, then successively agitated and ultrasonic treatment
To carry out gelation reaction process, obtain the second solution of mixed phase, then by second solution of mixed phase temperature be 25 DEG C simultaneously
And vacuum degree obtains gelation reaction liquid to carry out vacuumizing 0.1~1h under conditions of 0.1~0.5MPa；
(4) the gelation reaction liquid that step (3) obtains successively is subjected to Aging Step and drying steps, the nanocrystalline gas of abnormity is made
Gel rubber material；With
(5) the nanocrystalline aerogel material of abnormity that step (4) obtains is post-processed in more than two different temperatures stages, is made
Obtain the nanocrystalline aerogel material of high temperature resistant abnormity.
2. preparation method according to claim 1, it is characterised in that:
It includes the post-processing of the first temperature stage, after the second temperature stage that described two above different temperatures stages, which carry out post-processing,
Reason and the post-processing of third temperature stage；
The temperature of the first temperature stage post-processing is 200 DEG C~500 DEG C, and the time of the first temperature stage post-processing is 0.1
~12h；
The temperature of the second temperature stage post-processing is 600 DEG C~800 DEG C, and the time of second temperature stage post-processing is 0.1
~5h；
The temperature of the third temperature stage post-processing is 900 DEG C~1600 DEG C, and the time of third temperature stage post-processing is 0.1
~5h.
3. preparation method according to claim 2, it is characterised in that:
Before carrying out the second temperature stage post-processing and third temperature stage post-processing, first by the special-shaped nanometer
Brilliant aerogel material is cooled to room temperature.
4. preparation method according to claim 1, it is characterised in that:
In step (2), the time of the stirring is 0.5~5h, and the time of the ultrasonic treatment is 20~60min；And/or
In step (3), the time of the stirring is 0.5~5h, and the time of the ultrasonic treatment is 10~120min.
5. preparation method according to any one of claims 1 to 4, which is characterized in that in step (1):
The concentration of the alumina nano powder contained in the mixed liquor is 0.0002~50g/mL, and is contained in the mixed liquor
Alumina nano powder partial size be 10~200nm；
The acid solution is one of hydrochloric acid solution, acetum and sulfuric acid solution or a variety of；And/or
The concentration of the acid solution is 0.1~5mol/L, and the dosage of the acid solution is 1~200mL.
6. preparation method according to any one of claims 1 to 4, it is characterised in that:
The solid content of the assembling agent is 2~10%；
The catalyst solution is ammonia spirit and/or ammonium fluoride solution；
The concentration of the catalyst solution is 0.1~2mol/L；And/or
The mass ratio of the nanocrystalline dispersion liquid of the abnormity, the assembling agent and the catalyst solution is (5~200): (0.1~
50): (0.5~5).
7. preparation method according to any one of claims 1 to 4, it is characterised in that:
The Aging Step are as follows: by the gelation reaction liquid prior to 15~55 DEG C at 12~72h of aging, then in 50~90 DEG C
12~72h of lower aging.
8. preparation method according to claim 7, it is characterised in that:
In carrying out the Aging Step, so that the humidity of the gelation reaction liquid is not less than 80%.
9. preparation method according to any one of claims 1 to 4, it is characterised in that:
The drying is supercritical drying or constant pressure and dry.
10. the nanocrystalline aerogel material of the abnormity of the high temperature resistant as made from claim 1 to 9 described in any item preparation methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910630467.7A CN110282958B (en) | 2019-07-12 | 2019-07-12 | High-temperature-resistant special-shaped nanocrystalline aerogel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910630467.7A CN110282958B (en) | 2019-07-12 | 2019-07-12 | High-temperature-resistant special-shaped nanocrystalline aerogel material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110282958A true CN110282958A (en) | 2019-09-27 |
| CN110282958B CN110282958B (en) | 2022-02-01 |
Family
ID=68022552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910630467.7A Active CN110282958B (en) | 2019-07-12 | 2019-07-12 | High-temperature-resistant special-shaped nanocrystalline aerogel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110282958B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252789A (en) * | 2020-01-18 | 2020-06-09 | 航天特种材料及工艺技术研究所 | High-temperature-resistant alumina nanocrystalline aerogel material and preparation method thereof |
| CN111848205A (en) * | 2020-07-13 | 2020-10-30 | 航天特种材料及工艺技术研究所 | Method for preparing high-temperature-resistant aerogel heat-insulating material by normal-pressure drying |
| CN111848140A (en) * | 2020-07-13 | 2020-10-30 | 航天特种材料及工艺技术研究所 | Alumina nanowire aerogel thermal insulation material and preparation method thereof |
| CN111925194A (en) * | 2020-08-18 | 2020-11-13 | 航天特种材料及工艺技术研究所 | High-temperature-resistant high-performance aerogel composite material and preparation method thereof |
| CN111943654A (en) * | 2020-08-18 | 2020-11-17 | 航天特种材料及工艺技术研究所 | High-temperature-resistant and radiation-resistant aerogel composite material and preparation method thereof |
| CN111943704A (en) * | 2020-08-18 | 2020-11-17 | 航天特种材料及工艺技术研究所 | Reusable high-temperature-resistant nanocrystalline aerogel material and preparation method thereof |
| CN112536004A (en) * | 2020-12-03 | 2021-03-23 | 航天特种材料及工艺技术研究所 | High-temperature-resistant elastic graphene aerogel material and preparation method thereof |
| CN114804816A (en) * | 2022-05-23 | 2022-07-29 | 航天特种材料及工艺技术研究所 | High-temperature-resistant high-toughness nanowire aerogel material and preparation method thereof |
| CN114853453A (en) * | 2022-05-27 | 2022-08-05 | 航天特种材料及工艺技术研究所 | Hydrophobic ceramic aerogel material with micro-nano structure and preparation method thereof |
| CN114853457A (en) * | 2022-06-02 | 2022-08-05 | 航天特种材料及工艺技术研究所 | Alumina-carbon composite nanofiber aerogel material and preparation method thereof |
| CN114920539A (en) * | 2022-05-23 | 2022-08-19 | 航天特种材料及工艺技术研究所 | High-toughness radiation-resistant aerogel heat-insulating material and preparation method thereof |
| CN115246745A (en) * | 2022-07-14 | 2022-10-28 | 航天特种材料及工艺技术研究所 | High-temperature-resistant composite component aerogel material and preparation method thereof |
| WO2022263623A1 (en) * | 2021-06-17 | 2022-12-22 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Method for producing a sintered ceramic foam |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863201A (en) * | 2012-08-31 | 2013-01-09 | 航天材料及工艺研究所 | Preparation method of low-density high-temperature-resistant SiO2-MxOy compound aerogel heat insulating material |
| CN103342537A (en) * | 2013-07-03 | 2013-10-09 | 同济大学 | Preparation method of high temperature-resistant alumina aerogel material |
| CN103754887A (en) * | 2013-12-25 | 2014-04-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Heat-resisting silica aerogel material and preparation method thereof |
| CN108249901A (en) * | 2018-01-24 | 2018-07-06 | 航天特种材料及工艺技术研究所 | A kind of preparation method of high temperature resistant aeroge material |
| CN108689679A (en) * | 2018-05-29 | 2018-10-23 | 南京工业大学 | A kind of preparation method of high temperature resistant gradient fiber composite aerogel heat-insulating material |
-
2019
- 2019-07-12 CN CN201910630467.7A patent/CN110282958B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863201A (en) * | 2012-08-31 | 2013-01-09 | 航天材料及工艺研究所 | Preparation method of low-density high-temperature-resistant SiO2-MxOy compound aerogel heat insulating material |
| CN103342537A (en) * | 2013-07-03 | 2013-10-09 | 同济大学 | Preparation method of high temperature-resistant alumina aerogel material |
| CN103754887A (en) * | 2013-12-25 | 2014-04-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Heat-resisting silica aerogel material and preparation method thereof |
| CN108249901A (en) * | 2018-01-24 | 2018-07-06 | 航天特种材料及工艺技术研究所 | A kind of preparation method of high temperature resistant aeroge material |
| CN108689679A (en) * | 2018-05-29 | 2018-10-23 | 南京工业大学 | A kind of preparation method of high temperature resistant gradient fiber composite aerogel heat-insulating material |
Non-Patent Citations (1)
| Title |
|---|
| 高庆福等: "氧化铝气凝胶复合材料的制备与隔热性能", 《国防科技大学学报》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252789A (en) * | 2020-01-18 | 2020-06-09 | 航天特种材料及工艺技术研究所 | High-temperature-resistant alumina nanocrystalline aerogel material and preparation method thereof |
| CN111252789B (en) * | 2020-01-18 | 2022-05-31 | 航天特种材料及工艺技术研究所 | High-temperature-resistant alumina nanocrystalline aerogel material and preparation method thereof |
| CN111848205A (en) * | 2020-07-13 | 2020-10-30 | 航天特种材料及工艺技术研究所 | Method for preparing high-temperature-resistant aerogel heat-insulating material by normal-pressure drying |
| CN111848140A (en) * | 2020-07-13 | 2020-10-30 | 航天特种材料及工艺技术研究所 | Alumina nanowire aerogel thermal insulation material and preparation method thereof |
| CN111943654A (en) * | 2020-08-18 | 2020-11-17 | 航天特种材料及工艺技术研究所 | High-temperature-resistant and radiation-resistant aerogel composite material and preparation method thereof |
| CN111943704A (en) * | 2020-08-18 | 2020-11-17 | 航天特种材料及工艺技术研究所 | Reusable high-temperature-resistant nanocrystalline aerogel material and preparation method thereof |
| CN111943654B (en) * | 2020-08-18 | 2022-04-12 | 航天特种材料及工艺技术研究所 | High-temperature-resistant and radiation-resistant aerogel composite material and preparation method thereof |
| CN111925194A (en) * | 2020-08-18 | 2020-11-13 | 航天特种材料及工艺技术研究所 | High-temperature-resistant high-performance aerogel composite material and preparation method thereof |
| CN112536004A (en) * | 2020-12-03 | 2021-03-23 | 航天特种材料及工艺技术研究所 | High-temperature-resistant elastic graphene aerogel material and preparation method thereof |
| WO2022263623A1 (en) * | 2021-06-17 | 2022-12-22 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Method for producing a sintered ceramic foam |
| CN114804816A (en) * | 2022-05-23 | 2022-07-29 | 航天特种材料及工艺技术研究所 | High-temperature-resistant high-toughness nanowire aerogel material and preparation method thereof |
| CN114920539A (en) * | 2022-05-23 | 2022-08-19 | 航天特种材料及工艺技术研究所 | High-toughness radiation-resistant aerogel heat-insulating material and preparation method thereof |
| CN114920539B (en) * | 2022-05-23 | 2023-03-10 | 航天特种材料及工艺技术研究所 | High-toughness radiation-resistant aerogel heat-insulating material and preparation method thereof |
| CN114853453A (en) * | 2022-05-27 | 2022-08-05 | 航天特种材料及工艺技术研究所 | Hydrophobic ceramic aerogel material with micro-nano structure and preparation method thereof |
| CN114853457A (en) * | 2022-06-02 | 2022-08-05 | 航天特种材料及工艺技术研究所 | Alumina-carbon composite nanofiber aerogel material and preparation method thereof |
| CN114853457B (en) * | 2022-06-02 | 2023-03-10 | 航天特种材料及工艺技术研究所 | Alumina-carbon composite nanofiber aerogel material and preparation method thereof |
| CN115246745A (en) * | 2022-07-14 | 2022-10-28 | 航天特种材料及工艺技术研究所 | High-temperature-resistant composite component aerogel material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110282958B (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110282958A (en) | Nanocrystalline aerogel material of a kind of high temperature resistant abnormity and preparation method thereof | |
| CN111925194B (en) | High-temperature-resistant high-performance aerogel composite material and preparation method thereof | |
| CN107312166B (en) | A kind of modified PET polyester and its preparation method and application | |
| CN109019614B (en) | Rare earth toughened silicon aerogel precursor | |
| CN111943654B (en) | High-temperature-resistant and radiation-resistant aerogel composite material and preparation method thereof | |
| CN108249901A (en) | A kind of preparation method of high temperature resistant aeroge material | |
| CN106120439A (en) | A kind of aeroge composite fibre paper and preparation method thereof | |
| CN109251005B (en) | Preparation method of reinforced silica aerogel material | |
| CN111943704B (en) | Reusable high-temperature-resistant nanocrystalline aerogel material and preparation method thereof | |
| CN111848140B (en) | Alumina nanowire aerogel thermal insulation material and preparation method thereof | |
| CN108751969A (en) | A kind of high temperature resistant, heat-insulated, wave transparent ceramic matric composite and preparation method thereof | |
| CN111252789A (en) | High-temperature-resistant alumina nanocrystalline aerogel material and preparation method thereof | |
| CN108249943A (en) | A kind of preparation method of water-fast aerogel material | |
| CN106809842A (en) | A kind of preparation method of high temperature oxidation resisting Silica Aerogels | |
| CN113831581A (en) | High-elasticity anti-radiation nanofiber aerogel material and preparation method thereof | |
| CN113663611A (en) | High-temperature-resistant composite nanofiber aerogel material and preparation method thereof | |
| CN109095883A (en) | A kind of fiber reinforcement aluminium oxide-silicon oxide binary aerogel composite material and preparation method | |
| CN108689680A (en) | A kind of preparation method of effectively insulating heat preservation aerogel blanket | |
| CN108774072A (en) | A kind of rigidity thermal insulation tile and preparation method thereof | |
| CN108191403A (en) | A kind of preparation method of shock resistance radiation nano ceramic material | |
| CN112705129B (en) | Metal organic framework composite aerogel material and preparation method thereof | |
| CN110284318B (en) | Preparation method of low-thermal-conductivity TiO2/SiC-Al2O3 aerogel-SiO 2 fibrofelt composite material | |
| CN106564905A (en) | Method for large-scale preparation of low-cost silicon dioxide composite aerogel | |
| CN111518518A (en) | Multi-wall graphene oxide phase-change microcapsule material and preparation method thereof | |
| CN105669207B (en) | A kind of SiC Mo4.8Si3C0.6The preparation method of composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |