CN109019613A - A kind of preparation process of rare earth toughening solid-state silica aerogel - Google Patents
A kind of preparation process of rare earth toughening solid-state silica aerogel Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
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- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/16—Preparation of silica xerogels
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- C01P2006/32—Thermal properties
Abstract
The invention discloses under a kind of room temperature, atmospheric pressure environment carry out, the process time it is short, be suitble to industrialization, can be improved silica aerogel toughness and heat resisting temperature solid-state silica aerogel preparation method.The preparation method of the silica aerogel of solid powder, comprising the following steps: (1) prepare mixed solution, (2) colloidal sol, (3) gel, (4) aging, the displacement of (5) solvent and (6) surface modification of silicon source and solvent；A kind of preparation method of rare earth toughening solid-state silica aerogel, is that the silica aerogel presoma of preparation is put into drying kettle, nitrogen is filled in drying kettle and catches up with oxygen, until in drying kettle then oxygen content carries out micro-wave vacuum to the material in drying kettle less than 3%；The silica aerogel of solid powder is made after drying.
Description
The application is the Chinese invention patent (applying date: November 12 in 2016 that number of patent application is 201610995966.2
Day, patent name: a kind of preparation process of rare earth toughening silica aerogel presoma and solid-state silica aerogel) divisional application.
Technical field
The present invention relates to aeroge technical fields, more particularly to a kind of preparation process of solid-state silica aerogel.
Background technique
Aerosil is a kind of light nanoporous material of structure-controllable, has many excellent performances, such as
High porosity, high-specific surface area, low-density, lower thermal conductivity etc..
The preparation of aeroge is usually handled by colloidal sol, gel process and supercritical drying and is constituted.In colloidal sol, gel process
In, by controlling the poly-condensation and hydrolysis condition of solution, the nanocluster of different structure is formed in solution, between cluster
Stick to each other forms gelinite, and then full of remaining liquid reagent after chemically reacting around the solid-state skeleton of gelinite.For
Prevent the surface tension during gel drying in Micro-v oid from leading to the destruction of material structure, at the supercritical drying process
Reason is placed in gel to heat in pressure vessel and boost, the liquid in gel is made to undergo phase transition into the fluid of above-critical state, gas-liquid circle
Face disappears, and surface tension has not existed, at this time discharged this supercritical fluid from pressure vessel, and porous, nothing can be obtained
Sequence, the low-density aerogel materials with nanometer scale contiguous network structure.But supercritical drying is not standby to require height, expends big
The energy is measured, operational hazards considerably increase the cost of aeroge, and are unfavorable for large-scale production.
High production cost, preparation process time can be brought long it can be seen from the above, supercritical drying prepares silica aerogel
Disadvantage；In recent years, research staff proposes the relevant report and patent document that silica aerogel is prepared under some differential pressures about room temperature,
But be to rest on laboratory preparatory phase, and technical process is longer mostly, process implementing narrow limits cannot achieve big rule
Mould industrialization production and application.In addition, the reason of hindering aeroge development is in addition, aeroge has reticular structure, the structure side
Edge is relatively thin more crisp, and being easy to collapse under ambient pressure causes thermal coefficient to decline；In addition the use temperature of silica aerogel is relatively low,
It is generally used below also more stable at 500 DEG C.The internal structure change of 500 DEG C or more silica aerogels, will lead to thermal coefficient
Sharply decline.This will affect the further development and utilization of aeroge.
Summary of the invention
In view of the technical drawbacks of the prior art, it is an object of the present invention to provide under a kind of room temperature, atmospheric pressure environment
It carries out, the process time is short, is suitble to industrialization, can be improved the silica aerogel presoma of silica aerogel toughness and heat resisting temperature and consolidate
The preparation method of state silica aerogel.
The technical solution adopted to achieve the purpose of the present invention is: a kind of preparation side of rare earth toughening solid-state silica aerogel
Method, comprising the following steps:
(1) mixed solution of silicon source and solvent is prepared
The sodium metasilicate for several 3.0-4.0 that rub is taken to be fitted into reaction kettle, the deionized water that 1-3 times of sodium metasilicate quality is added carries out
Dilution, reaction kettle are stirred 30 minutes with 80-200 revs/min of speed, through 200 mesh screens, obtain sodium silicate solution；
The aqueous solution of sodium metasilicate is commonly called as waterglass, it is made of the alkali metal and silica of different proportion, changes
Formula is R2OnSiO2, and R2O is alkali metal oxide in formula, and n is the ratio of silica and alkali metal oxide molal quantity,
The referred to as number that rubs of waterglass, the most commonly used is sodium silicate water glass Na2OnSiO2；
(2) colloidal sol
It takes A sour, A acid metal salt is added in A acid and rare earth A hydrochlorate is added in a manner of spray to step after mixing
Suddenly the sodium silicate solution that (1) obtains；The material in reaction kettle is carried out fastly with 1200-2000 revs/min of speed while spray
Speed stirring, the pH value for controlling sodium silicate solution is 1.5-3.0, and controlling its average pore size is 15-30 nanometers, obtains colloidal sol, this
The step used time 60-120 minutes；
(3) gel
Take sodium hydroxide or ammonium hydroxide, it is 10-11.5 that deionized water, which is added, and is diluted to pH value, be added in a manner of spray to
In reaction kettle；The material in reaction kettle is quickly stirred with 1200-2000 revs/min of speed while spray, works as reaction
When the pH value of material is 4.5-5.5 in kettle, spray is terminated, obtains gel, this step used time 80-180 minutes；
(4) aging
Speed in reaction kettle with 20-50 revs/min continues stirring 3-10 hours, carries out to the material in reaction kettle old
Change, control material in reactor temperature is 35-50 degrees Celsius；The mode that standing is usually used in the prior art carries out aging, consumption
When 3-5 days, gel can't be stirred, the reason is that the prior art needs to stand during generally believing aging,
Stand the structure growth that can be convenient for aeroge；
(5) solvent is replaced
It carries out continuing stirring 60-180 minutes in reaction kettle, while being added same with aging material in step (4) reaction kettle
The displacement solvent of volume, to displace remaining moisture；The prior art worries that stirring can destroy its structure, will not generally replace
When be stirred, stewing process can be taken, cause to take a long time；Preparation method provided by the invention is stirred when solvent is replaced
It mixes 60-180 minutes, can greatly shorten period of a permutation, there is no destroyed microstructure；
(6) surface modification
It carries out continuing stirring in reaction kettle, while continuously adding and aging material same volume in step (4) reaction kettle
Coupling agent；By stirring 60-180 minutes, the silica aerogel presoma for being coated with displacement solvent and coupling agent is obtained.
The coupling agent that above-mentioned steps (6) surface modification is added cements out the water in aeroge micropore, coupling agent filling
In air inlet gel pore, the stability of microcellular structure can be improved, improve the evenness of pore size；In addition, by addition
After different coupling agents is surface modified, aeroge hydrophobicity, hydrophilic sexual function can be adjusted.
A acid described in above-mentioned steps (2) is sulfuric acid, hydrochloric acid, oxalic acid or nitric acid, is adjusted to 6-15mol/ with deionized water
L。
A acid metal salt described in above-mentioned steps (2) is A acid zirconates or A acid aluminium salt.
Rare earth A hydrochlorate described in above-mentioned steps (2) is A acid cerium salt, A acid yttrium salt or A acid lanthanum salt.
A acid metal salt and rare earth A hydrochlorate are easy the moisture absorption, will lead to metering inaccuracy, so for its addition of accurate quantitative analysis
Amount, in terms of oxide, the molar ratio of the two is 100:1-6 for A acid metal salt described in above-mentioned steps (2) and rare earth A hydrochlorate；Step
Suddenly in (2) in the oxide and sodium metasilicate of A acid metal salt silica molar ratio 2-5:100；For example, A acid metal salt is sulfuric acid
Aluminium is 2-5:100 with the molar ratio of silica in aluminium oxide and sodium metasilicate in terms of its oxide.
Displacement solvent described in above-mentioned steps (5) is one or more mixing of methanol, acetone, n-hexane or heptane
Object.
Stirring described in above-mentioned steps (5) or step (6) is to be stirred in reaction kettle；
The stirring provides for reaction kettle center and quickly forward stirs (high speed shear disk), and the periphery at reaction kettle center mentions
It is realized for baffle plate.
Coupling agent described in the step (6) is hexamethyldisilazane, bis- (trimethylsilyl) acetamides, methoxyl group front three
Base silane, dimethoxydimethylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyl trimethoxy silicon
The one or more of alkane, methyltriethoxysilane or methyl trimethoxy oxygroup alkane.
A kind of preparation method of rare earth toughening solid-state silica aerogel, which comprises the following steps: by above-mentioned preparation
Silica aerogel presoma be put into drying kettle, nitrogen is filled in drying kettle and catches up with oxygen, until drying kettle in oxygen content less than 3%,
Then micro-wave vacuum is carried out to the material in drying kettle；Negative pressure 0.08-0.12mpa in drying kettle, temperature 85-135
Degree Celsius, the silica aerogel of solid powder is made after dry.Silica aerogel presoma is coated with displacement solvent and coupling agent, belongs to
In hydroxide, become the oxide of solid powder after microwave drying.
Preferably, the 50-80 minutes microwave time of the micro-wave vacuum, microwave frequency 2450MHZ ± 10MHZ.
The working principle of the invention is: in the preparation method of silica aerogel presoma, the A acid metal that is added in gel process
Salt and rare earth A hydrochlorate can achieve the effect that toughening and improve silica aerogel heat resistance；Aging and solvent swap step be
It is carried out in the state of stirring, substantially increases reaction efficiency, have compressed the process time, be suitble to industrialization；Before silica aerogel
The technique that body prepares solid powder silica aerogel is driven, is to be carried out using the dry method of negative-pressure microwave, microwave can be directly deep
Enter the heat transfer mode realized to the microcellular structure of silica aerogel from the inside to the outside；Microwave simultaneously can be to the object in microcellular structure
Material generates " vibration " in microcosmic meaning, effectively avoids agglomeration；Under negative pressure state, the boiling of the solvent in micropore
Point, evaporating point or gasification point can reduce.
Compared with prior art, the beneficial effects of the present invention are:
(1) in recent years, there are the relevant report and patent that silica aerogel is prepared under some differential pressures about room temperature in the prior art
Document, but be to rest on laboratory preparatory phase mostly, technical process is longer, while process implementing narrow limits, it is difficult to real
Existing large-scale industrialized production and application；The present invention provides the preparation methods under normal temperature and pressure, and it is relatively quiet to change the prior art
Technique only applies in critical process process and stirs, speeded up to realize the hydrolysis, polycondensation and modification of aeroge, it is small to realize 30
When interior synthesis gas Gel Precursor technique, provide a kind of method for industrially preparing rare earth toughening silica aerogel in batches, be
A large amount of manufacture and use of aeroge provide premise；
(2) hinder aeroge development the reason of first is that aeroge have reticular structure, but the edge of the structure it is relatively thin,
More crisp, compression strength is low, is easy to be pressurized and collapse, causes performance unstable；The present invention addition rare earth A hydrochlorate and A acid metal salt,
The toughness for improving the material improves the intensity of silica aerogel；
(3) the use temperature of the silica aerogel of prior art preparation is relatively low, generally used below also relatively more steady at 500 DEG C
Fixed, 500 DEG C or more the internal structure changes that will lead to silica aerogel cause thermal coefficient to decline；The present invention is sour with rare earth A is added
Salt and A acid metal salt, improve the heat resistance of the material, improve the heat resisting temperature of silica aerogel；
(4) the methods of the prior art generallys use during preparing solid-state silica aerogel high temperature sintering, drying, meeting
Lead to structure collapses or agglomeration in material sintering process, reduce the specific surface area of material, leverages its thermal coefficient；
The present invention uses micro-wave vacuum to silica aerogel presoma, and microwave can be real directly deeply to the microcellular structure of aeroge
Heat transfer mode from the inside to the outside is showed；Under negative pressure state, boiling point, evaporating point or the gasification point of the solvent in micropore can drop
It is low；Microwave can generate microcosmic vibration to the material in microcellular structure, effectively avoid caused by the methods of high temperature sintering, drying
Material structure collapses or agglomeration phenomenon occur, effectively raise the specific surface area and thermal coefficient of material；
(5) nitrogen protection is filled with when micro-wave vacuum, negative pressure low temperature is to carry out safe retrieving displacement solvent or coupling
Agent recycles, to reduce manufacturing cost.Nitrogen protection is filled with when the micro-wave vacuum, and under negative pressure low-temperature condition into
Row；Micro-wave vacuum makes displacement solvent or coupling agent in microcellular structure gasify in negative pressure state, by it in low temperature shape
State liquefaction can be realized safe retrieving recycling, to reduce process costs.
Specific embodiment
Below in conjunction with specific embodiment, invention is further described in detail.It should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
Embodiment 1:
It elaborates below with reference to embodiment to the content of present invention:
(1) mixed solution of silicon source and solvent is prepared
It takes several 3.0 waterglass that rub to be fitted into reaction kettle, and is diluted with the deionized water of 2.5 times of quality, 180 revs/min
Clock stirs 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
It takes 8mol/L sulfuric acid, sulfuric acid zirconates is added (sulfuric acid zirconates in terms of its zirconium oxide, with the silica of water glass solution
Molar ratio is 5:100), sulfuric acid yttrium salt (sulfuric acid yttrium salt in terms of its yttrium oxide, the molar ratio with aluminium oxide is 1:100)；Mixing is equal
After even, spray is added the water glass solution obtained to step (1), and spray while is quickly stirred with 1300 revs/min of speed
It mixes, stops spray when control pH value is to 1.5, spray time was controlled at 100 minutes；Obtain colloidal sol.
(3) gel
The sodium hydroxide solution for being 11 by pH value, spray are added into colloidal sol obtained by step (2), with 1300 while spray
Rev/min speed quickly stirred, until pH value be 5 when stop spray, the used time 120 minutes, obtain gel.
(4) aging
Reaction kettle continues stirring 10 hours to gel with 40 revs/min of speed, and control reaction kettle inner gel temperature is taken the photograph for 45
Family name's degree.
(5) solvent is replaced
The displacement solvent hexane with the material same volume of aging, stirring 2 are added while being stirred in reaction kettle
Hour.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent is dimethoxy dimethyl-silicon
Alkane, by stirring 150 minutes, obtain being coated with the silica aerogel presoma of displacement solvent and coupling agent after surface modification.
A kind of preparation method of rare earth toughening solid-state silica aerogel, comprising the following steps: displacement solvent and idol will be coated with
The silica aerogel presoma for joining agent carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content less than 3% in drying kettle, negative pressure
0.08mpa, 95 degrees Celsius, microwave frequency controls in the range of 2450MHZ ± 10MHZ, obtains within 55 minutes the silicon airsetting of toughening
Glue solid powder.
Product is through detecting, average pore size 26nm, and specific surface area is 588 ㎡/g, loose specific weight 0.057g/cm, super-hydrophobic, resistance
Combustion, thermal coefficient 0.021W/MK, 880 DEG C of heat resisting temperature, compressive resistance 0.118Mpa.
Embodiment 2:
It elaborates below with reference to embodiment to the content of present invention:
(1) mixed solution of silicon source and solvent is prepared
It takes several 3.2 waterglass that rub to be fitted into reaction kettle, and is diluted with the deionized water of 3 times of quality, 200 revs/min,
Stirring 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
Take 10mol/L nitric acid, be added hydrochloric acid aluminium salt (hydrochloric acid aluminium salt in terms of aluminium oxide, oxygen in aluminium oxide and water glass solution
The molar ratio of SiClx is 2:100), (for hydrochloric acid lanthanum salt in terms of lanthana, the molar ratio with aluminium oxide is 3:100) to hydrochloric acid lanthanum salt；It is mixed
After closing uniformly, spray is added the water glass solution obtained to step (1), and spray while is carried out fast with 1200 revs/min of speed
Speed stirring controls pH value until 2.5, and spray time was controlled at 100 minutes；Obtain colloidal sol.
(3) gel
By the ammonia spirit of pH value 10.5, spray is added to colloidal sol obtained by step (2), with 1200 revs/min while spray
Speed quickly stirred, until pH value be 4.5 when stop spray, the used time 150 minutes, obtain gel.
(4) aging
Reaction kettle continues stirring 5 hours with 30 revs/min of speed, and control reaction kettle inner gel temperature is 50 degrees Celsius；
(5) solvent is replaced
The displacement solvent methanol with the material same volume of aging is added while being stirred in reaction kettle, to displace
Remaining moisture.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent is vinyl trimethoxy silicon
Alkane obtains the silica aerogel presoma for being coated with displacement solvent and coupling agent by stirring 100 minutes after surface modification.
A kind of preparation method of rare earth toughening solid-state silica aerogel, comprising the following steps: displacement solvent and idol will be coated with
The silica aerogel presoma for joining agent carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content less than 2% in drying kettle, negative pressure
0.09mpa, 110 degrees Celsius, microwave frequency controls in the range of 2450MHZ ± 10MHZ, 50 minutes, obtains the silicon gas of toughening
Gel solid state powder.
Product is through detecting, average pore size 28nm, and specific surface area is 568 ㎡/g, loose specific weight 0.056g/cm, super-hydrophobic, resistance
Combustion, thermal coefficient 0.0198W/MK, 920 DEG C of heat resisting temperature, compressive resistance 0.122Mpa.
Embodiment 3:
It elaborates below with reference to embodiment to the content of present invention:
(1) mixed solution of silicon source and solvent is prepared
It takes several 4.0 waterglass that rub to be fitted into reaction kettle, and is diluted with the deionized water of 3 times of quality, 80 revs/min,
Stirring 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
15mol/L nitric acid is taken, oxalic acid aluminium salt is added, and (in terms of aluminium oxide, the molar ratio with silica in water glass solution is
3:100), oxalic acid lanthanum salt (in terms of lanthana, the molar ratio with aluminium oxide is 6:100)；After mixing, spray is added to step
(1) water glass solution obtained, spray while, are quickly stirred with 1800 revs/min of speed, are controlled pH value to 2.5 and are
Only, spray time control was at 100 minutes；Obtain colloidal sol.
(3) gel
By the sodium hydroxide solution of pH value 11.5, spray is added to colloidal sol obtained by step (2), with 1200 while spray
Rev/min speed quickly stirred, until pH value be 5.5 when stop spray, the used time 80 minutes, obtain gel.
(4) aging
Reaction kettle continues stirring 5 hours with 50 revs/min of speed, and control reaction kettle inner gel temperature is 35 degrees Celsius；
(5) solvent is replaced
The displacement solvent acetone with the material same volume of aging is added while being stirred in reaction kettle, to displace
Remaining moisture.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent is hexamethyldisilazane, double
(trimethylsilyl) acetamide, methoxytrimethylsilane weight respectively account for the mixture of one third, by stirring 180 minutes, table
The silica aerogel presoma for being coated with displacement solvent and coupling agent is obtained after the modification of face.
A kind of preparation method of rare earth toughening solid-state silica aerogel, comprising the following steps: displacement solvent and idol will be coated with
The silica aerogel presoma for joining agent carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content less than 1% in drying kettle, negative pressure
0.12mpa, 80 degrees Celsius, microwave frequency controls in the range of 2450MHZ ± 10MHZ, 60 minutes, obtains the silicon airsetting of toughening
Glue solid powder.
Product is through detecting, average pore size 27nm, and specific surface area is 575 ㎡/g, loose specific weight 0.058g/cm, super-hydrophobic, resistance
Combustion, thermal coefficient 0.0202W/MK, 725 DEG C of heat resisting temperature, compressive resistance 0.125Mpa.
Embodiment 4:
It elaborates below with reference to embodiment to the content of present invention:
(1) mixed solution of silicon source and solvent is prepared
It takes several 3.5 waterglass that rub to be fitted into reaction kettle, and is diluted with the deionized water of 2.5 times of quality, 120 revs/min
Clock stirs 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
Take 6mol/L nitric acid, be added nitric acid zirconates (in terms of zirconium oxide, the molar ratio with silica in water glass solution is 4:
100), nitric acid cerium salt (in terms of cerium oxide, the molar ratio with zirconium oxide is 4:100)；After mixing, spray is added to step
(1) water glass solution obtained, spray while, are quickly stirred with 2000 revs/min of speed, control pH value until 5,
Spray time was controlled at 120 minutes；Obtain colloidal sol.
(3) gel
By the ammonia spirit of pH value 10.5, spray is added to colloidal sol obtained by step (2), with 1300 revs/min while spray
Speed quickly stirred, until pH value be 4.5 when stop spray, the used time 180 minutes, obtain gel.
(4) aging
Reaction kettle continues stirring 8 hours with 20 revs/min of speed, and control reaction kettle inner gel temperature is 40 degrees Celsius；
(5) solvent is replaced
Displacement solvent (acetone, n-hexane with the material same volume of aging are added while being stirred in reaction kettle
And heptane, weight respectively account for the mixture of one third), to displace remaining moisture.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent be phenyl triethoxysilane,
Phenyltrimethoxysila,e, methyl trimethoxy oxygroup alkane weight respectively account for the mixture of one third, and by stirring 60 minutes, surface was repaired
The silica aerogel presoma for being coated with displacement solvent and coupling agent is obtained after decorations.
A kind of preparation method of rare earth toughening solid-state silica aerogel, comprising the following steps: displacement solvent and idol will be coated with
The silica aerogel presoma for joining agent carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content less than 3% in drying kettle, negative pressure
0.10mpa, 100 degrees Celsius, microwave frequency controls in the range of 2450MHZ ± 10MHZ, 30 minutes, obtains the silicon gas of toughening
Gel solid state powder.
Product is through detecting, average pore size 24nm, and specific surface area is 558 ㎡/g, loose specific weight 0.061g/cm3, super-hydrophobic,
Fire-retardant, thermal coefficient 0.0196W/MK, 729 DEG C of heat resisting temperature, compressive resistance 0.121Mpa.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of rare earth toughening solid-state silica aerogel, which comprises the following steps:
(1) mixed solution of silicon source and solvent is prepared
The sodium metasilicate for several 3.0-4.0 that rub is taken to be fitted into reaction kettle, the deionized water that 1-3 times of sodium metasilicate quality is added is diluted,
Reaction kettle is stirred 30 minutes with 80-200 revs/min of speed, is filtered, obtains sodium silicate solution；
(2) colloidal sol
It takes A sour, A acid metal salt is added in A acid and rare earth A hydrochlorate is added in a manner of spray to step after mixing
(1) sodium silicate solution obtained；The material in reaction kettle is quickly stirred while spray, controls the pH of sodium silicate solution
Value is 1.5-3.0, obtains colloidal sol；
(3) gel
Sodium hydroxide or ammonium hydroxide are taken, it is 10-11.5 that deionized water, which is added, and is diluted to pH value, is added in a manner of spray to reaction kettle
In；Material while spray in reaction kettle is quickly stirred, and when the pH value of material in reactor is 4.5-5.5, is terminated
Spray, obtains gel；
(4) aging
Speed in reaction kettle with 20-50 revs/min continues stirring 3-10 hours, carries out aging, control to the material in reaction kettle
Material in reactor temperature is 35-50 degrees Celsius；
(5) solvent is replaced
It carries out continuing stirring 60-180 minutes in reaction kettle, while being added and aging material same volume in step (4) reaction kettle
Displacement solvent, to displace remaining moisture；
(6) surface modification
It carries out continuing stirring in reaction kettle, while continuously adding the coupling with aging material same volume in step (4) reaction kettle
Agent；By stirring 60-180 minutes, the silica aerogel presoma for being coated with displacement solvent and coupling agent is obtained；
Silica aerogel presoma is put into drying kettle, and nitrogen is filled in drying kettle and catches up with oxygen, until oxygen content is less than in drying kettle
3%, micro-wave vacuum then is carried out to the material in drying kettle；The silica aerogel of solid powder is made after drying.
2. a kind of preparation method of rare earth toughening solid-state silica aerogel according to claim 1, it is characterised in that step (2)
Described in A acid be sulfuric acid, hydrochloric acid, oxalic acid or nitric acid.
3. a kind of preparation method of rare earth toughening solid-state silica aerogel according to claim 1, it is characterised in that step (2)
Described in A acid metal salt be A acid zirconates or A acid aluminium salt.
4. a kind of preparation method of rare earth toughening solid-state silica aerogel according to claim 1, it is characterised in that step (2)
Described in rare earth A hydrochlorate be A acid cerium salt, A acid yttrium salt or A acid lanthanum salt.
5. a kind of preparation method of rare earth toughening solid-state silica aerogel according to claim 1, it is characterised in that step (2)
Described in A acid metal salt and rare earth A hydrochlorate in terms of oxide, the molar ratio of the two is 100:1-6.
6. a kind of preparation method of rare earth toughening solid-state silica aerogel according to claim 1, which is characterized in that drying kettle
Interior negative pressure 0.08-0.12mpa, temperature are 85-135 degrees Celsius.
7. a kind of preparation method of rare earth toughening solid-state silica aerogel according to claim 1, which is characterized in that step
(2) in the oxide and sodium metasilicate of A acid metal salt silica molar ratio 2-5:100.
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| CN110563435B (en) * | 2018-06-06 | 2022-07-01 | 厦门稀土材料研究所 | Rare earth-based aerogel material with radiation shielding effect and heat insulation performance as well as preparation and application thereof |
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| CN112403407A (en) * | 2020-11-27 | 2021-02-26 | 巩和一 | Method for preparing aerogel through negative pressure and microwave drying |
| CN113526912B (en) * | 2021-07-01 | 2023-02-17 | 中广核研究院有限公司 | Rare earth based aerogel composite material and preparation method and application thereof |
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