CN108467059B - Preparation method of lead zirconate titanate piezoelectric aerogel - Google Patents
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Abstract
A preparation method of lead zirconate titanate piezoelectric aerogel belongs to the technical field of functional materials. The invention provides a simple, easy-to-operate and low-cost preparation method of lead zirconate titanate piezoelectric aerogel, wherein the zirconium source and the titanium source are respectively zirconium n-propoxide and tetrabutyl titanate, so that the cost is low, and acetylacetone is not required to be used as a chelating agent; the obtained sol does not need to react for 4 hours under the condition of reduced pressure distillation at 150 ℃, can be obtained only under the conditions of normal temperature and normal pressure, and takes about 30 min; the PZT aerogel obtained by the method has higher transparency and larger specific surface area, and the maximum specific surface area is more than 500m2/g。
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of lead zirconate titanate piezoelectric aerogel.
Background
Lead zirconate titanate (PZT) has the advantages of excellent piezoelectric performance, high electromechanical coupling coefficient, low dielectric loss and the like, and has wide application prospect in the fields of gas cooker igniters, automobile engine spark plugs, piezoelectric ultrasonic transmitters for automobile reversing radars, underwater acoustic transducers for deep sea detection and the like. At present, most of applications of lead zirconate titanate are ceramics, but the density of PZT ceramics is large, and porous ceramics are difficult to adjust due to relative fixed density, and are increasingly difficult to meet the requirements of modern life on piezoelectric materials, especially the requirements of underwater acoustic transducers. The PZT piezoelectric aerogel has extremely low and adjustable density, becomes an optimal substitute material for piezoelectric ceramics and porous ceramics, for example, the acoustic impedance of the PZT aerogel is matched with the acoustic impedances in different water depth fields by adjusting the porosity or the density, and becomes an optimal piezoelectric material applied to an underwater acoustic transducer.
However, the preparation difficulty of the PZT aerogel is far greater than that of the bulk material and the porous ceramic, and the preparation of the PZT sol and the PZT gel is extremely difficult because the metal alkoxide can generate a rapid hydrolysis reaction after meeting water to generate precipitates. The preparation of the PZT aerogel requires the mixing of three metal salts of lead, zirconium and titanium to carry out the hydrolytic polycondensation reaction to generate the transparent gel with the three-dimensional network framework structure, the hydrolytic polycondensation reaction of the three metal salts exists in the process, the generation of the transparent gel is extremely difficult by coordinately controlling the hydrolytic polycondensation reaction, and the preparation method of the PZT piezoelectric aerogel is only rarely reported so far and still stays at the level of the preparation of the PZT piezoelectric aerogel in the last 90 th century. Peer
The group first produced PZT aerogel (Journal of Non-Crystalline Solids,1995,186:59-63, Journal of Non-Crystalline Solids,1998,225:130-134) in the last 90 s of the century, lead acetate trihydrate, zirconium isopropoxide and titanium isopropoxide were used as a lead source, a zirconium source and a titanium source, respectively, acetylacetone was used as a chelating agent, PZT wet gel was obtained by a sol-gel method using a vacuum distillation apparatus at 150 ℃, aged for 14 days at 50 ℃, and then supercritical dried with carbon dioxide to obtain PZT aerogel having a specific surface area of 323m2PZT aerogel in g. However, in the above method, titanium isopropoxide and zirconium isopropoxide are expensive and high in cost; and the mixed precursor of lead, zirconium and titanium can be obtained only by reacting for 4 hours under the condition of reduced pressure distillation at 150 ℃, and the method has the advantages of complex operation, long time consumption and great difficulty.
Disclosure of Invention
The invention aims to provide a method for preparing lead zirconate titanate piezoelectric aerogel, which is simple, easy to operate and low in cost, aiming at the defects in the background technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of lead zirconate titanate piezoelectric aerogel comprises the following steps:
step 1, preparation of PZT sol:
adding lead acetate trihydrate into ethylene glycol monomethyl ether, and stirring to fully dissolve the lead acetate trihydrate to obtain a mixed solution A; adding zirconium n-propoxide into the mixed solution A, stirring and mixing uniformly, then adding tetrabutyl titanate, stirring and mixing uniformly to obtain a lead-zirconium-titanium ternary precursor solution; adding deionized water into the obtained lead-zirconium-titanium ternary precursor solution, and stirring until uniform, transparent and stable PZT sol is formed; wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is (1.05-1.2): (0-1): (0-1): (50-200): (30 to 100) and a molar ratio nLead acetate trihydrate：(nZirconium n-propoxide+nTetrabutyl titanate)＝(1.05～1.2):1；
Step 2, preparing PZT gel:
sealing and standing the PZT sol obtained in the step (1) for more than 1h at normal temperature and pressure to form uniform, stable and transparent PZT wet gel; then aging the obtained PZT wet gel, and sequentially cleaning the obtained PZT wet gel in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol to obtain PZT gel;
step 3, preparing PZT aerogel:
placing the PZT gel obtained in the step (2) in a supercritical drying kettle, and performing supercritical drying by taking carbon dioxide or ethanol as a drying medium to obtain the PZT aerogel; when carbon dioxide is used as a drying medium, the pressure of supercritical drying is more than 7.38MPa, and the temperature is more than 31.2 ℃; when ethanol is used as the drying medium, the pressure of supercritical drying is above 6.38MPa, and the temperature is above 243.1 ℃.
Further, the preparation process of the PZT sol in step 1 may further include: (1) preparing an ethylene glycol methyl ether solution of lead acetate trihydrate to obtain a lead precursor solution; preparing ethylene glycol methyl ether solution of tetrabutyl titanate to obtain precursor solution of titanium; preparing ethylene glycol monomethyl ether solution of zirconium n-propoxideObtaining a precursor solution of zirconium; (2) mixing the zirconium precursor solution and the lead precursor solution, stirring to form a lead-zirconium binary precursor solution, adding the titanium precursor solution into the lead-zirconium binary precursor solution, and uniformly stirring and mixing to obtain a lead-zirconium-titanium ternary precursor solution; (3) adding deionized water into the obtained lead-zirconium-titanium ternary precursor solution, and stirring until uniform, transparent and stable PZT sol is formed (a red laser pen is used for carrying out a Tyndall effect experiment until a clear light path is obtained); wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is (1.05-1.2): (0-1): (0-1): (50-200): (30 to 100) and a molar ratio nLead acetate trihydrate：(nZirconium n-propoxide+nTetrabutyl titanate)＝(1.05～1.2):1。
Further, in step 1, in order to accelerate the dissolution of lead acetate trihydrate in ethylene glycol monomethyl ether, the lead acetate trihydrate is ground by using an agate mortar and then added into ethylene glycol monomethyl ether. Meanwhile, in order to compensate the volatilization of lead oxide in the subsequent sintering and crystallization process of the PZT aerogel, the content of lead in the mixture ratio is 5-20% more.
Further, when deionized water is added into the lead-zirconium-titanium ternary precursor solution obtained in the step 1, the adding speed is less than 1 drop/second, so as to prevent precipitation caused by too rapid water addition and too violent hydrolytic polycondensation reaction.
Further, the aging time in step 2 varies according to the volume: when the volume of the wet gel is below 40mL, the aging time is 12-48 h; when the volume of the wet gel is more than 40mL, the aging time is 18 h-72 h.
Further, the process of sequentially cleaning in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol in step 2 specifically comprises: firstly, soaking the aged wet gel in absolute ethyl alcohol for 24 hours, wherein the absolute ethyl alcohol does not exceed the wet gel by 2-3 cm, and repeating for 3-5 times; then, soaking the wet gel treated in the step in 15-25% ethyl orthosilicate ethanol solution by volume for 24 hours, wherein the amount of the solution does not exceed 2-3 cm of the wet gel, and repeating the step for 3-5 times; and finally, soaking the wet gel treated in the step in absolute ethyl alcohol for 24 hours, wherein the absolute ethyl alcohol does not exceed the wet gel by 2-3 cm, and repeating for 3-5 times to obtain the PZT wet gel.
Further, in the preparation process of the PZT aerogel in the step 3, when carbon dioxide is used as a drying medium, the supercritical drying pressure is above 7.38MPa, the temperature is above 31.2 ℃, and the drying time is 4-9 h. After the critical temperature is reached, the rate of adding carbon dioxide gas into the supercritical drying kettle is not higher than 0.1MPa/min, so as to prevent the gel from being blown to be broken due to the too fast adding rate. And similarly, after the drying is finished, the rate of discharging the carbon dioxide gas in the kettle is not higher than 0.1MPa/min, so that the dried aerogel is prevented from being blown to be broken.
Further, in the preparation process of the PZT aerogel in step 3, when ethanol is used as a drying medium, the supercritical drying pressure is above 6.38MPa, the temperature is above 243.1 ℃, and the drying time is 4-10 h. After reaching a critical state, drying for 4-10 h, and discharging ethanol at a rate of 1 MPa/min; then nitrogen is introduced into the kettle at the speed of 1MPa/min to replace the residual ethanol.
Further, when carbon dioxide is used as a drying medium in the step 3, the pressure of supercritical drying is 7.38-8 MPa, and the temperature is 31.2-34 ℃; when ethanol is used as a drying medium, the supercritical drying pressure is 6.38-7 MPa, and the temperature is 243.1-245 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a simple, easy-to-operate and low-cost preparation method of lead zirconate titanate piezoelectric aerogel, wherein the zirconium source and the titanium source are respectively zirconium n-propoxide and tetrabutyl titanate, so that the cost is low, and acetylacetone is not required to be used as a chelating agent; the obtained sol does not need to react for 4 hours under the condition of reduced pressure distillation at 150 ℃, can be obtained only under the conditions of normal temperature and normal pressure, and takes about 30 min; the PZT aerogel obtained by the method has higher transparency and larger specific surface area, and the maximum specific surface area is more than 500m2/g。
Drawings
FIG. 1 is the results of the specific surface area test of the PZT aerogel obtained in example 1;
fig. 2 is a XRD test result of the PZT aerogel obtained in example 1.
Detailed Description
The technical scheme of the invention is detailed below by combining the accompanying drawings and the embodiment.
A preparation method of lead zirconate titanate piezoelectric aerogel comprises the following steps:
step 1, preparation of PZT sol:
adding lead acetate trihydrate into ethylene glycol monomethyl ether, and stirring to fully dissolve the lead acetate trihydrate to obtain a mixed solution A; adding zirconium n-propoxide into the mixed solution A, stirring and mixing uniformly, then adding tetrabutyl titanate, stirring and mixing uniformly to obtain a lead-zirconium-titanium ternary precursor solution; adding deionized water into the obtained lead-zirconium-titanium ternary precursor solution, stirring, and performing a Tyndall effect experiment by using a red laser pen until a clear light path is obtained, which indicates that uniform, transparent and stable PZT sol is formed; wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is (1.05-1.2): (0-1): (0-1): (50-200): (30 to 100) and a molar ratio nLead acetate trihydrate：(nZirconium n-propoxide+nTetrabutyl titanate)＝(1.05～1.2):1；
Step 2, preparing PZT gel:
sealing and standing the PZT sol obtained in the step (1) for more than 1h at normal temperature and normal pressure until the surface of the sol is not moved after the beaker is inclined, and performing a Tyndall effect experiment by using a red laser pen until a clear light path is obtained, which indicates that uniform, stable and transparent PZT wet gel is formed; then aging the obtained PZT wet gel at normal temperature and normal pressure, soaking in absolute ethyl alcohol for a plurality of times to replace water in a gel framework, soaking in ethyl orthosilicate ethanol solution for a plurality of times to remove residual hydroxyl on the surface of the wet gel, and finally soaking in absolute ethyl alcohol for a plurality of times to clean the wet gel to obtain the PZT gel;
step 3, preparing PZT aerogel:
placing the PZT gel obtained in the step (2) in a supercritical drying kettle, sealing a kettle cover, and performing supercritical drying by using carbon dioxide or ethanol as a drying medium to obtain a blocky semitransparent PZT aerogel; when carbon dioxide is used as a drying medium, the pressure of supercritical drying is more than 7.38MPa, and the temperature is more than 31.2 ℃; when ethanol is used as the drying medium, the pressure of supercritical drying is above 6.38MPa, and the temperature is above 243.1 ℃.
Further, the preparation process of the PZT sol in step 1 may further include: (1) preparing an ethylene glycol methyl ether solution of lead acetate trihydrate to obtain a lead precursor solution; preparing ethylene glycol methyl ether solution of tetrabutyl titanate to obtain precursor solution of titanium; preparing ethylene glycol monomethyl ether solution of zirconium n-propoxide to obtain precursor solution of zirconium; (2) mixing the zirconium precursor solution and the lead precursor solution, stirring to form a lead-zirconium binary precursor solution, adding the titanium precursor solution into the lead-zirconium binary precursor solution, and uniformly stirring and mixing to obtain a lead-zirconium-titanium ternary precursor solution; (3) adding deionized water into the obtained lead-zirconium-titanium ternary precursor solution, and stirring until uniform, transparent and stable PZT sol is formed (a red laser pen is used for carrying out a Tyndall effect experiment until a clear light path is obtained); wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is (1.05-1.2): (0-1): (0-1): (50-200): (30 to 100) and a molar ratio nLead acetate trihydrate：(nZirconium n-propoxide+nTetrabutyl titanate)＝(1.05～1.2):1。
Example 1
The preparation method of the lead zirconate titanate piezoelectric aerogel comprises the following steps of:
step 1, preparation of PZT sol:
1.1 weighing 4.1726g of lead acetate trihydrate and dissolving in 20mL of ethylene glycol monomethyl ether solution to obtain lead precursor solution; measuring 0.78mL of tetrabutyl titanate, and adding the tetrabutyl titanate into 10mL of ethylene glycol monomethyl ether solution to obtain a titanium precursor solution; measuring 8.3mL of zirconium n-propoxide, and adding the zirconium n-propoxide into 10mL of ethylene glycol monomethyl ether solution to obtain a zirconium precursor solution;
1.2 mixing the prepared zirconium precursor solution with the prepared lead precursor solution, fully stirring to form a lead-zirconium binary precursor solution, adding the titanium precursor solution into the lead-zirconium binary precursor solution, and uniformly stirring and mixing to obtain a lead-zirconium-titanium ternary precursor solution;
1.3 adding 10mL of deionized water (the adding speed is less than 1 drop/second) into the obtained lead-zirconium-titanium ternary precursor solution, fully stirring, and carrying out a Tyndall effect experiment by using a red laser pen until a clear light path is obtained, which indicates that uniform, transparent and stable PZT sol is formed;
wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol methyl ether is 1.1:0.8: 0.2: 55.56: 50.7;
step 2, preparing PZT gel:
sealing and standing the PZT sol obtained in the step (1) for more than 1h at normal temperature and normal pressure until the surface of the sol is not moved after the beaker is inclined, and performing a Tyndall effect experiment by using a red laser pen until a clear light path is obtained, which indicates that uniform, stable and transparent PZT wet gel is formed; then aging the obtained PZT wet gel for 24h at normal temperature and pressure, soaking in absolute ethyl alcohol for 5 times to replace water in a gel framework, soaking in 25% by volume ethyl orthosilicate ethanol solution for 5 times to remove residual hydroxyl on the surface of the wet gel, and finally soaking in absolute ethyl alcohol for 5 times to clean the wet gel to obtain the PZT gel;
step 3, preparing PZT aerogel:
and (3) placing the PZT gel obtained in the step (2) in a supercritical drying kettle, sealing a kettle cover, and performing supercritical drying by taking carbon dioxide as a drying medium, wherein the pressure of the supercritical drying is 7.58MPa, and the temperature is 32.2 ℃, so that the blocky semitransparent PZT aerogel is finally obtained.
The aerogel prepared in the example 1 is tested by a specific surface analyzer with the model number of JW-BK132F to obtain the test result shown in the figure 1, and the specific surface area of the aerogel prepared in the example 1 ranges from 395 m to 594m2The most probable pore diameter is 16-80 nm. The crystal phase of the aerogel prepared in example 1 was tested with an X-ray diffractometer of type DX-2700BH to obtain the XRD test results of fig. 2, which indicates that the aerogel skeleton prepared in example 1 is mainly composed of crystallites and has good strength.
Example 2
This example is different from example 1 in that: the ratio of Pb, Zr and Ti in the prepared PZT aerogel is 1.1:0.5: 0.5; lead acetate trihydrate in step 1: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol methyl ether is 1.1:0.5: 0.5: 55.56: 50.7, the measured tetrabutyl titanate is 1.8mL, and the measured zirconium n-propoxide is 5.2 mL; the rest of the procedure was the same as in example 1.
Example 3
This example is different from example 1 in that: the ratio of Pb, Zr and Ti in the prepared PZT aerogel is 1.1:0.4: 0.6; the tetrabutyl titanate measured in the step 1 is 2.1mL, and the zirconium n-propoxide is 4.2 mL; the rest of the procedure was the same as in example 1.
Example 4
This example is different from example 1 in that: the ratio of Pb, Zr and Ti in the prepared PZT aerogel is 1.1:0.7: 0.3; lead acetate trihydrate in step 1: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is 1.1:0.7:0.3:111.1: 76.1; the specific process for preparing the PZT sol in the step 1 is as follows:
1.1 weighing 4.1726g of lead acetate trihydrate and dissolving in 40mL of ethylene glycol monomethyl ether solution to obtain lead precursor solution; measuring 1.1mL of tetrabutyl titanate, and adding the tetrabutyl titanate into 10mL of ethylene glycol monomethyl ether solution to obtain a titanium precursor solution; weighing 7.3mL of zirconium n-propoxide, and adding the zirconium n-propoxide into 10mL of ethylene glycol monomethyl ether solution to obtain a zirconium precursor solution;
1.2 mixing the prepared zirconium precursor solution with the prepared lead precursor solution, fully stirring to form a lead-zirconium binary precursor solution, adding the titanium precursor solution into the lead-zirconium binary precursor solution, and uniformly stirring and mixing to obtain a lead-zirconium-titanium ternary precursor solution;
1.3 adding 20mL of deionized water (the adding speed is less than 1 drop/second) into the obtained lead-zirconium-titanium ternary precursor solution, fully stirring, and carrying out a Tyndall effect experiment by using a red laser pen until a clear light path is obtained, which indicates that uniform, transparent and stable PZT sol is formed;
wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol methyl ether is 1.1:0.7:0.3:111.1: 76.1.
Claims (4)
1. A preparation method of lead zirconate titanate piezoelectric aerogel comprises the following steps:
step 1, preparation of PZT sol:
adding lead acetate trihydrate into ethylene glycol monomethyl ether, and stirring to fully dissolve the lead acetate trihydrate to obtain a mixed solution A; adding zirconium n-propoxide into the mixed solution A, uniformly mixing, and then adding tetrabutyl titanate to obtain a lead-zirconium-titanium ternary precursor solution; adding deionized water into the obtained lead-zirconium-titanium ternary precursor solution, and stirring until uniform, transparent and stable PZT sol is formed; wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is (1.05-1.2): (0-1): (0-1): (50-200): (30 to 100) and nLead acetate trihydrate：(nZirconium n-propoxide+nTetrabutyl titanate)＝(1.05～1.2):1；
Step 2, preparing PZT gel:
sealing and standing the PZT sol obtained in the step (1) for more than 1h at normal temperature and pressure to form uniform, stable and transparent PZT wet gel; then aging the obtained PZT wet gel, and sequentially cleaning the obtained PZT wet gel in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol to obtain PZT gel;
step 3, preparing PZT aerogel:
placing the PZT gel obtained in the step (2) in a supercritical drying kettle, and performing supercritical drying by taking carbon dioxide or ethanol as a drying medium to obtain the PZT aerogel; when carbon dioxide is used as a drying medium, the pressure of supercritical drying is more than 7.38MPa, and the temperature is more than 31.2 ℃; when ethanol is used as the drying medium, the pressure of supercritical drying is above 6.38MPa, and the temperature is above 243.1 ℃.
2. The method for preparing lead zirconate titanate piezoelectric aerogel according to claim 1, wherein the preparation process of the PZT sol in step 1 is as follows: (1) preparing an ethylene glycol methyl ether solution of lead acetate trihydrate to obtain a lead precursor solution; preparing ethylene glycol methyl ether solution of tetrabutyl titanate to obtain precursor solution of titanium; preparing ethylene glycol monomethyl ether solution of zirconium n-propoxide to obtain precursor solution of zirconium; (2) mixing the precursor solution of zirconium and the precursor solution of lead, and stirring to formAdding the lead-zirconium binary precursor solution into the titanium precursor solution, and uniformly stirring and mixing to obtain a lead-zirconium-titanium ternary precursor solution; (3) adding deionized water into the obtained lead-zirconium-titanium ternary precursor solution, and stirring until uniform, transparent and stable PZT sol is formed; wherein, the ratio of lead acetate trihydrate: zirconium n-propoxide: tetrabutyl titanate: deionized water: the molar ratio of ethylene glycol monomethyl ether is (1.05-1.2): (0-1): (0-1): (50-200): (30 to 100) and nLead acetate trihydrate：(nZirconium n-propoxide+nTetrabutyl titanate)＝(1.05～1.2):1。
3. The method for preparing the lead zirconate titanate piezoelectric aerogel according to claim 1, wherein deionized water is added into the lead-zirconium-titanium ternary precursor solution obtained in the step 1 at a rate of less than 1 drop/second.
4. The method for preparing the lead zirconate titanate piezoelectric aerogel according to claim 1, wherein the steps of sequentially washing in absolute ethyl alcohol, ethyl orthosilicate ethanol solution and absolute ethyl alcohol in the step 2 are as follows: firstly, soaking the aged wet gel in absolute ethyl alcohol for 24 hours, wherein the absolute ethyl alcohol does not exceed the wet gel by 2-3 cm, and repeating for 3-5 times; then, soaking the wet gel treated in the step in 15-25% ethyl orthosilicate ethanol solution by volume for 24 hours, wherein the amount of the solution does not exceed 2-3 cm of the wet gel, and repeating the step for 3-5 times; and finally, soaking the wet gel treated in the step in absolute ethyl alcohol for 24 hours, wherein the absolute ethyl alcohol does not exceed the wet gel by 2-3 cm, and repeating for 3-5 times to obtain the PZT wet gel.
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