CN108467059A - A kind of preparation method of lead zirconate titanate piezoelectric aeroge - Google Patents
A kind of preparation method of lead zirconate titanate piezoelectric aeroge Download PDFInfo
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- 229910052451 lead zirconate titanate Inorganic materials 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 58
- 239000002243 precursor Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 28
- QNZFKUWECYSYPS-UHFFFAOYSA-N lead zirconium Chemical compound [Zr].[Pb] QNZFKUWECYSYPS-UHFFFAOYSA-N 0.000 claims description 28
- 239000011240 wet gel Substances 0.000 claims description 27
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000499 gel Substances 0.000 claims description 20
- 229940046892 lead acetate Drugs 0.000 claims description 19
- 238000000352 supercritical drying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 claims description 7
- -1 nButyl titanate Chemical compound 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003483 aging Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 239000002738 chelating agent Substances 0.000 abstract description 3
- 238000005292 vacuum distillation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of preparation method of lead zirconate titanate piezoelectric aeroge, belongs to technical field of function materials.The present invention provides a kind of preparation method of simple, easy to operate, at low cost lead zirconate titanate piezoelectric aeroge, the zirconium source used and titanium source are zirconium-n-propylate and butyl titanate respectively, at low cost, and do not need acetylacetone,2,4-pentanedione and make chelating agent；Obtained colloidal sol is not necessarily to react 4h under the conditions of vacuum distillation at 150 DEG C, need to only can be obtained under normal temperature and pressure conditions, takes about 30min；The PZT aeroge transparency highers that this method obtains, specific surface area bigger, maximum specific surface area are more than 500m2/g。
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of preparation method of lead zirconate titanate piezoelectric aeroge.
Background technology
Lead zirconate titanate (PZT) is because having the advantages that piezoelectric property is excellent, electromechanical coupling factor is high, dielectric loss is low etc., in coal
Gas kitchen fire maker, automobile engine spark plug, reversing radar of vehicle are changed with piezoelectric-type ultrasonic wave launcher, deep-sea detecting with the underwater sound
The fields such as energy device are with a wide range of applications.Currently, the application of lead zirconate titanate is ceramics mostly, and still, the density of PZT ceramics
It is larger, and porous ceramics is increasingly difficult to since its density is relatively fixed and is difficult to adjust to meet the modern life to piezoelectric material
Needs, the especially demand of underwater acoustic transducer.PZT voltage electrical gel densities are extremely low and adjustable, become piezoelectric ceramics and more
The best alternative materials of hole ceramics realize itself acoustic impedance and different water depth field for example, by the adjusting of porosity or density
Acoustic impedance matching, become the best piezoelectric material applied to underwater acoustic transducer.
But the preparation difficulty of PZT aeroges is far longer than its bulk and porous ceramics, because metal alkoxide meets meeting after water
Occur fast hydrolyzing reaction and generate precipitation, cause PZT colloidal sols, gel prepare it is extremely difficult.Prepare PZT aeroges need by
Three kinds of lead, zirconium, titanium metal salt mixing bring it about hydrolysis condensation reaction and generate the clear gel with three-dimensional network skeleton structure,
There are the hydrolysis condensation reactions of three kinds of metal salts for the process, so that it is generated clear gel to coordinate to control the hydrolysis condensation reaction
Extremely difficult, the preparation method in relation to PZT piezoelectricity aeroges is rarely reported so far, is still rested on and is just prepared the nineties in last century
The level gone out.PeerTeam prepares PZT aeroges (Journal of Non- the nineties in last century first
Crystalline Solids,1995,186:59-63, Journal of Non-Crystalline Solids, 1998,225:
130-134), using lead acetate trihydrate, zirconium iso-propoxide and isopropyl titanate as lead source, zirconium source and titanium source, using acetyl
Acetone obtains PZT wet gels using reduced pressure distillation device under the conditions of 150 DEG C as chelating agent by sol-gel method, then
At 50 DEG C after aging 14 days, it is 323m to be dried with CO 2 supercritical and specific surface area is made2The PZT aeroges of/g.On but
State in method, isopropyl titanate and zirconium iso-propoxide it is expensive, it is of high cost；And the mixing presoma of lead, zirconium and titanium need to be 150
DEG C vacuum distillation under the conditions of reaction 4h can just obtain, complicated for operation, time-consuming, and difficulty is big.
Invention content
It is an object of the invention to be directed to defect existing for background technology, a kind of simple, easy to operate, at low cost zirconium is proposed
The preparation method of lead titanates piezoelectricity aeroge.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of lead zirconate titanate piezoelectric aeroge, includes the following steps：
The preparation of step 1, PZT colloidal sols：
Lead acetate trihydrate is added in ethylene glycol monomethyl ether, stirring makes it fully dissolve, and obtains mixed liquor A；In mixed liquor A
Middle addition zirconium-n-propylate, after being uniformly mixed, adds butyl titanate, is uniformly mixed, before obtaining lead zirconium titanium ternary
Drive liquid；Deionized water is added in obtained lead zirconium titanium ternary precursor liquid, stirs, until forming PZT that is uniform, transparent, stablizing
Colloidal sol；Wherein, lead acetate trihydrate：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is (1.05
~1.2)：(0~1)：(0~1)：(50~200)：(30~100), and molar ratio nLead acetate trihydrate：(nZirconium-n-propylate+nButyl titanate)=
(1.05~1.2):1；
The preparation of step 2, PZT gels：
Sealing and standing 1h or more, formation are uniform, stable, transparent at normal temperatures and pressures for the PZT colloidal sols that step 1 is obtained
PZT wet gels；Then by after obtained PZT wet gel agings, successively in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and anhydrous
It is cleaned in ethyl alcohol, obtains PZT gels；
The preparation of step 3, PZT aeroges：
The PZT gels that step 2 obtains are placed in supercritical drying kettle, are situated between using carbon dioxide or ethyl alcohol as dry
Matter carries out supercritical drying, obtains the PZT aeroges；When using carbon dioxide as dried medium, the pressure of supercritical drying is
7.38MPa or more, temperature are 31.2 DEG C or more；When using ethyl alcohol as dried medium, the pressure of supercritical drying be 6.38MPa with
On, temperature is 243.1 DEG C or more.
Further, the preparation process of PZT colloidal sols described in step 1 can also be：(1) second two of lead acetate trihydrate is prepared
Alcohol methyl ether solution, obtains the precursor liquid of lead；The ethylene glycol monomethyl ether solution for preparing butyl titanate, obtains the precursor liquid of titanium；It prepares
The ethylene glycol monomethyl ether solution of zirconium-n-propylate, obtains the precursor liquid of zirconium；(2) precursor liquid of zirconium is mixed with the precursor liquid of lead, is stirred
Lead zirconium binary precursor liquid is formed, then the precursor liquid of titanium is added in lead zirconium binary precursor liquid, is uniformly mixed, obtains lead zirconium titanium
Ternary precursor liquid；(3) deionized water is added in obtained lead zirconium titanium ternary precursor liquid, stir, until formed it is uniform, transparent,
Stable PZT colloidal sols (carrying out Tyndall effect with red laser pen to test until obtaining clear light-path)；Wherein, three water
Close lead acetate：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is (1.05~1.2)：(0~1)：
(0~1)：(50~200)：(30~100), and molar ratio nLead acetate trihydrate：(nZirconium-n-propylate+nButyl titanate)=(1.05~1.2):1.
Further, it in step 1, in order to accelerate dissolving of the lead acetate trihydrate in ethylene glycol monomethyl ether, is ground using agate
Alms bowl will be in its levigate rear addition ethylene glycol monomethyl ether.Meanwhile in order to make up PZT aeroges lead oxide in follow-up sintering crystallization process
Volatilization, the content of lead will have more 5%~20% in proportioning.
Further, when deionized water is added in step 1 in obtained lead zirconium titanium ternary precursor liquid, rate is added need to be small
In 1 drop/sec, to prevent from adding water too fast, hydrolysis condensation reaction is excessively fierce and generates precipitation.
Further, the time of aging described in step 2 is different according to the difference of volume：When the volume of wet gel is
When 40mL or less, the time of aging is 12h~48h；When the volume of wet gel is more than 40mL, time of aging be 18h~
72h。
Further, it is cleaned in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol successively described in step 2
Process be specially：First, the wet gel after aging is impregnated for 24 hours in absolute ethyl alcohol, the amount of absolute ethyl alcohol need to not there be overly moist solidifying
Glue 2cm~3cm is repeated 3~5 times；Then, the positive silicic acid for being 15%~25% in volume fraction by upper step treated wet gel
It is impregnated in ethyl ester ethanol solution for 24 hours, the amount of the solution need to not cross wet gel 2cm~3cm, repeat 3~5 times；It finally, will be at upper step
Wet gel after reason impregnates for 24 hours in absolute ethyl alcohol, and the amount of absolute ethyl alcohol need to not cross wet gel 2cm~3cm, repeat 3~5 times,
Obtain PZT wet gels.
Further, overcritical when using carbon dioxide as dried medium in the preparation process of PZT aeroges described in step 3
Dry pressure is 7.38MPa or more, and temperature is 31.2 DEG C or more, and drying time is 4~9h.After reaching critical-temperature, to
The rate that carbon dioxide gas is added in supercritical drying kettle is not higher than 0.1MPa/min, to prevent addition rate too fast by gel
It blows broken.Equally, it is dry terminate after, the rate that carbon dioxide gas in kettle is discharged also is not higher than 0.1MPa/min, prevent by
Dried aeroge blows broken.
Further, in the preparation process of PZT aeroges described in step 3, when using ethyl alcohol as dried medium, supercritical drying
Pressure be 6.38MPa or more, temperature be 243.1 DEG C or more, drying time be 4~10h.After reaching critical condition, dry 4
Ethyl alcohol is discharged with the rate of 1MPa/min after~10h；Nitrogen is passed through into kettle with the rate of 1MPa/min again, replaces remaining second
Alcohol.
Further, when in step 3 using carbon dioxide as dried medium, the pressure of supercritical drying is 7.38~8MPa,
Temperature is 31.2~34 DEG C；When using ethyl alcohol as dried medium, the pressure of supercritical drying is 6.38~7MPa, temperature 243.1
~245 DEG C.
Compared with prior art, beneficial effects of the present invention are：
The present invention provides a kind of preparation methods of simple, easy to operate, at low cost lead zirconate titanate piezoelectric aeroge, use
Zirconium source and titanium source be zirconium-n-propylate and butyl titanate respectively, it is at low cost, and do not need acetylacetone,2,4-pentanedione and make chelating agent；It obtains
Colloidal sol is not necessarily to react 4h under the conditions of vacuum distillation at 150 DEG C, need to only can be obtained, be taken about under normal temperature and pressure conditions
30min；The PZT aeroge transparency highers that this method obtains, specific surface area bigger, maximum specific surface area are more than 500m2/g。
Description of the drawings
Fig. 1 is the specific surface area test result for the PZT aeroges that embodiment 1 obtains；
Fig. 2 is the XRD test results for the PZT aeroges that embodiment 1 obtains.
Specific implementation mode
With reference to the accompanying drawings and examples, technical scheme of the present invention is described in detail.
A kind of preparation method of lead zirconate titanate piezoelectric aeroge, includes the following steps：
The preparation of step 1, PZT colloidal sols：
Lead acetate trihydrate is added in ethylene glycol monomethyl ether, stirring makes it fully dissolve, and obtains mixed liquor A；In mixed liquor A
Middle addition zirconium-n-propylate, after being uniformly mixed, adds butyl titanate, is uniformly mixed, before obtaining lead zirconium titanium ternary
Drive liquid；Deionized water is added in obtained lead zirconium titanium ternary precursor liquid, stirs, Tyndall effect is carried out using red laser pen
Experiment shows to form PZT colloidal sols that are uniform, transparent, stablizing until obtaining clear light-path；Wherein, lead acetate trihydrate：
Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is (1.05~1.2)：(0~1)：(0~1)：
(50~200)：(30~100), and molar ratio nLead acetate trihydrate：(nZirconium-n-propylate+nButyl titanate)=(1.05~1.2):1；
The preparation of step 2, PZT gels：
The PZT colloidal sols that step 1 is obtained sealing and standing 1h or more at normal temperatures and pressures, the sol surface after beaker inclination
It is motionless, Tyndall effect experiment is carried out until obtaining clear light-path using red laser pen, shows to have been formed uniform, steady
Fixed, transparent PZT wet gels；Then by after obtained PZT wet gels aging at normal temperatures and pressures, number is impregnated in absolute ethyl alcohol
It is secondary to replace the moisture in gel skeleton, then impregnated for several times in ethyl orthosilicate ethanol solution to remove wet gel surface residual
Hydroxyl, finally impregnated in absolute ethyl alcohol and clean wet gel for several times, obtain PZT gels；
The preparation of step 3, PZT aeroges：
The PZT gels that step 2 obtains are placed in supercritical drying kettle, after kettle cover is sealed, with carbon dioxide or second
Alcohol carries out supercritical drying as dried medium, obtains blocky translucent PZT aeroges；Using carbon dioxide as dried medium
When, the pressure of supercritical drying is 7.38MPa or more, and temperature is 31.2 DEG C or more；When using ethyl alcohol as dried medium, supercritical drying
Dry pressure is 6.38MPa or more, and temperature is 243.1 DEG C or more.
Further, the preparation process of PZT colloidal sols described in step 1 can also be：(1) second two of lead acetate trihydrate is prepared
Alcohol methyl ether solution, obtains the precursor liquid of lead；The ethylene glycol monomethyl ether solution for preparing butyl titanate, obtains the precursor liquid of titanium；It prepares
The ethylene glycol monomethyl ether solution of zirconium-n-propylate, obtains the precursor liquid of zirconium；(2) precursor liquid of zirconium is mixed with the precursor liquid of lead, is stirred
Lead zirconium binary precursor liquid is formed, then the precursor liquid of titanium is added in lead zirconium binary precursor liquid, is uniformly mixed, obtains lead zirconium titanium
Ternary precursor liquid；(3) deionized water is added in obtained lead zirconium titanium ternary precursor liquid, stir, until formed it is uniform, transparent,
Stable PZT colloidal sols (carrying out Tyndall effect with red laser pen to test until obtaining clear light-path)；Wherein, three water
Close lead acetate：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is (1.05~1.2)：(0~1)：
(0~1)：(50~200)：(30~100), and molar ratio nLead acetate trihydrate：(nZirconium-n-propylate+nButyl titanate)=(1.05~1.2):1.
Embodiment 1
A kind of preparation method of lead zirconate titanate piezoelectric aeroge, wherein Pb:Zr:Ti=1.1:0.8:0.2, it specifically includes
Following steps：
The preparation of step 1, PZT colloidal sols：
1.1, which weigh 4.1726g lead acetate trihydrate, is dissolved in 20mL ethylene glycol monomethyl ether solution, obtains the precursor liquid of lead；
It measures 0.78mL butyl titanates to be added in 10mL ethylene glycol monomethyl ether solution, obtains the precursor liquid of titanium；Measure 8.3mL zirconium-n-propylates
It is added in 10mL ethylene glycol monomethyl ether solution, obtains the precursor liquid of zirconium；
1.2 mix the precursor liquid of the zirconium of preparation with the precursor liquid of lead, are sufficiently stirred to form lead zirconium binary precursor liquid, then will
The precursor liquid of titanium is added in lead zirconium binary precursor liquid, is uniformly mixed, obtains lead zirconium titanium ternary precursor liquid；
1.3 are added 10mL deionized waters (rate is added and is less than 1 drop/sec) in obtained lead zirconium titanium ternary precursor liquid, fill
Divide stirring, carries out Tyndall effect experiment until obtaining clear light-path with red laser pen, show to have been formed uniform, saturating
PZT colloidal sols that are bright, stablizing；
Wherein, lead acetate trihydrate：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is
1.1：0.8：0.2：55.56：50.7；
The preparation of step 2, PZT gels：
The PZT colloidal sols that step 1 is obtained sealing and standing 1h or more at normal temperatures and pressures, the sol surface after beaker inclination
It is motionless, Tyndall effect experiment is carried out until obtaining clear light-path using red laser pen, shows to have been formed uniform, steady
Fixed, transparent PZT wet gels；Then it by after obtained PZT wet gels aging for 24 hours at normal temperatures and pressures, is soaked in absolute ethyl alcohol
Bubble 5 times to replace the moisture in gel skeleton, then impregnate in the ethyl orthosilicate ethanol solution that volume fraction is 25% 5 times with
The hydroxyl for removing wet gel surface residual finally impregnates 5 cleaning wet gels in absolute ethyl alcohol, obtains PZT gels；
The preparation of step 3, PZT aeroges：
The PZT gels that step 2 obtains are placed in supercritical drying kettle, after kettle cover is sealed, using carbon dioxide as dry
Dry medium carries out supercritical drying, and the pressure of supercritical drying is 7.58MPa, and temperature is 32.2 DEG C, is finally obtained blocky semi-transparent
Bright PZT aeroges.
Aeroge made from embodiment 1 is tested using the surface analysis instrument of model JW-BK132F, obtains figure
1 test result shows aeroge specific surface area ranging from 395~594m made from embodiment 12/ g, most probable pore size is 16
~80nm.The crystalline phase of aeroge made from embodiment 1 is tested using the X-ray diffractometer of model DX-2700BH, is obtained
The XRD test results of Fig. 2 show that aeroge skeleton made from embodiment 1 is mainly made of crystallite, and intensity is fine.
Embodiment 2
The present embodiment compared with Example 1, difference lies in：Pb in the PZT aeroges of preparation:Zr:Ti=1.1:0.5:
0.5；Lead acetate trihydrate in step 1：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is 1.1：
0.5：0.5：55.56：50.7, the butyl titanate of measurement is 1.8mL, zirconium-n-propylate 5.2mL；Remaining step and embodiment 1
It is identical.
Embodiment 3
The present embodiment compared with Example 1, difference lies in：Pb in the PZT aeroges of preparation:Zr:Ti=1.1:0.4:
0.6；The butyl titanate measured in step 1 is 2.1mL, zirconium-n-propylate 4.2mL；Remaining step is same as Example 1.
Embodiment 4
The present embodiment compared with Example 1, difference lies in：Pb in the PZT aeroges of preparation:Zr:Ti=1.1:0.7:
0.3；Lead acetate trihydrate in step 1：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is 1.1:
0.7:0.3:111.1:76.1；The detailed process that step 1 prepares PZT colloidal sols is：
1.1, which weigh 4.1726g lead acetate trihydrate, is dissolved in 40mL ethylene glycol monomethyl ether solution, obtains the precursor liquid of lead；
It measures 1.1mL butyl titanates to be added in 10mL ethylene glycol monomethyl ether solution, obtains the precursor liquid of titanium；Measure 7.3mL zirconium-n-propylates
It is added in 10mL ethylene glycol monomethyl ether solution, obtains the precursor liquid of zirconium；
1.2 mix the precursor liquid of the zirconium of preparation with the precursor liquid of lead, are sufficiently stirred to form lead zirconium binary precursor liquid, then will
The precursor liquid of titanium is added in lead zirconium binary precursor liquid, is uniformly mixed, obtains lead zirconium titanium ternary precursor liquid；
1.3 are added 20mL deionized waters (rate is added and is less than 1 drop/sec) in obtained lead zirconium titanium ternary precursor liquid, fill
Divide stirring, carries out Tyndall effect experiment until obtaining clear light-path with red laser pen, show to have been formed uniform, saturating
PZT colloidal sols that are bright, stablizing；
Wherein, lead acetate trihydrate：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is
1.1:0.7:0.3:111.1:76.1。
Claims (4)
1. a kind of preparation method of lead zirconate titanate piezoelectric aeroge, includes the following steps：
The preparation of step 1, PZT colloidal sols：
Lead acetate trihydrate is added in ethylene glycol monomethyl ether, stirring makes it fully dissolve, and obtains mixed liquor A；Add in mixed liquor A
Enter zirconium-n-propylate, after mixing, add butyl titanate, obtains lead zirconium titanium ternary precursor liquid；In obtained lead zirconium titanium three
Deionized water is added in first precursor liquid, stirs, until forming PZT colloidal sols that are uniform, transparent, stablizing；Wherein, three hydration acetic acid
Lead：Zirconium-n-propylate：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is (1.05~1.2)：(0~1)：(0~
1)：(50~200)：(30~100), and nLead acetate trihydrate：(nZirconium-n-propylate+nButyl titanate)=(1.05~1.2):1；
The preparation of step 2, PZT gels：
Sealing and standing 1h or more, uniform, stable, the transparent PZT of formation are wet at normal temperatures and pressures for the PZT colloidal sols that step 1 is obtained
Gel；Then by after obtained PZT wet gel agings, successively in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol
Middle cleaning obtains PZT gels；
The preparation of step 3, PZT aeroges：
The PZT gels that step 2 obtains are placed in supercritical drying kettle, using carbon dioxide or ethyl alcohol as dried medium, into
Row supercritical drying obtains the PZT aeroges；When using carbon dioxide as dried medium, the pressure of supercritical drying is
7.38MPa or more, temperature are 31.2 DEG C or more；When using ethyl alcohol as dried medium, the pressure of supercritical drying be 6.38MPa with
On, temperature is 243.1 DEG C or more.
2. the preparation method of lead zirconate titanate piezoelectric aeroge according to claim 1, which is characterized in that PZT described in step 1
The preparation process of colloidal sol is：(1) the ethylene glycol monomethyl ether solution for preparing lead acetate trihydrate, obtains the precursor liquid of lead；Prepare metatitanic acid
The ethylene glycol monomethyl ether solution of four butyl esters, obtains the precursor liquid of titanium；The ethylene glycol monomethyl ether solution for preparing zirconium-n-propylate, before obtaining zirconium
Drive liquid；(2) precursor liquid of zirconium is mixed with the precursor liquid of lead, stirring forms lead zirconium binary precursor liquid, then the precursor liquid of titanium is added
Enter in lead zirconium binary precursor liquid, be uniformly mixed, obtains lead zirconium titanium ternary precursor liquid；(3) before obtained lead zirconium titanium ternary
It drives in liquid and deionized water is added, stir, until forming PZT colloidal sols that are uniform, transparent, stablizing；Wherein, lead acetate trihydrate：Just
Propyl alcohol zirconium：Butyl titanate：Deionized water：The molar ratio of ethylene glycol monomethyl ether is (1.05~1.2)：(0~1)：(0~1)：(50
~200)：(30~100), and nLead acetate trihydrate：(nZirconium-n-propylate+nButyl titanate)=(1.05~1.2):1.
3. the preparation method of lead zirconate titanate piezoelectric aeroge according to claim 1, which is characterized in that obtained in step 1
To lead zirconium titanium ternary precursor liquid in be added deionized water when, be added rate be less than 1 drop/sec.
4. the preparation method of lead zirconate titanate piezoelectric aeroge according to claim 1, which is characterized in that described in step 2
The process cleaned in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol successively is specially：It first, will be after aging
Wet gel impregnates for 24 hours in absolute ethyl alcohol, and the amount of absolute ethyl alcohol need to not cross wet gel 2cm~3cm, repeat 3~5 times；Then, will
Upper step treated wet gel impregnates for 24 hours in the ethyl orthosilicate ethanol solution that volume fraction is 15%~25%, the solution
Amount need to do not cross wet gel 2cm~3cm, repeat 3~5 times；Finally, by upper step, treated that wet gel impregnates in absolute ethyl alcohol
For 24 hours, the amount of absolute ethyl alcohol need to not cross wet gel 2cm~3cm, repeat 3~5 times, obtain PZT wet gels.
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| CN109499496A (en) * | 2018-12-29 | 2019-03-22 | 电子科技大学 | A kind of flexibility PZT/PVDF composite piezoelectric aerogel material and preparation method thereof |
| CN110981475A (en) * | 2019-12-19 | 2020-04-10 | 电子科技大学 | Sol-solvothermal method for preparing lead zirconate titanate piezoelectric aerogel |
| CN111039321A (en) * | 2019-12-19 | 2020-04-21 | 电子科技大学 | Gel-aging integrated method for preparing PZT piezoelectric aerogel |
| CN112194180A (en) * | 2020-10-14 | 2021-01-08 | 北京化工大学 | Modification method for enhancing mechanical property of aerogel |
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