CN111233465A - Sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and preparation method thereof - Google Patents

Sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and preparation method thereof Download PDF

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CN111233465A
CN111233465A CN202010125948.5A CN202010125948A CN111233465A CN 111233465 A CN111233465 A CN 111233465A CN 202010125948 A CN202010125948 A CN 202010125948A CN 111233465 A CN111233465 A CN 111233465A
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张昌松
赵珂迪
魏立柱
王楚
王世元
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and a preparation method thereof3Powder of BiO2、Na2CO3And TiO2Ball milling, drying and sintering are carried out to prepare Na0.5Bi0.5TiO3Pre-sintering powder, uniformly stirring the pre-sintered powder and organic binder on a magnetic stirrer to prepare slurry, and then, preparing flaky BaTiO3Adding the powder, stirring to obtain injection slurry, injection molding under pressure and external electric field, defatting, drying, and sintering to obtain 0.94Na0.5Bi0.5TiO3‑0.06BaTiO3Piezoelectric ceramic, 0.94Na prepared0.5Bi0.5TiO3‑0.06BaTiO3The piezoelectric ceramic solves the problems that the traditional ceramic green body preparation process has low diaphragm density, and the green body is easy to deform and crack in the rubber discharging process to influence the product quality and the like; meanwhile, the orientation effect of the ceramic is improved, and the obtained ceramic membrane has the characteristics of uniform structure, smooth surface, excellent piezoelectric property and the like; and the injection molding preparation of the piezoelectric ceramic has high efficiency and short period, and is easy for batch production.

Description

Sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and preparation method thereof
Technical Field
The invention belongs to the field of lead-free piezoelectric ceramic materials, and particularly relates to sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and a preparation method thereof.
Background
Piezoelectric materials are important materials in the information era as sensitive functional materials related to electricity, force, heat and light, and are widely applied to the fields of laser, information, navigation, integrated circuits, ocean mapping, automatic control, biology and the like. In the field of piezoelectric ceramics, lead zirconate titanate (Pb (Ti, Zr) O3PZT for short) based ceramics is the most successful piezoelectric ceramics in both basic research and practical application. However, lead oxide, a main raw material of PZT-based ceramic materials, is a volatile toxic substance, and can bring serious harm to human beings and ecological environment in the processes of production, use and waste treatment, so that the novel environment-friendly piezoceramic materials become hot spots of extensive attention and research and development in the world. The bismuth sodium titanate based lead-free piezoelectric ceramic is one of the lead-free piezoelectric ceramic systems which are most concerned at present because of the superior piezoelectric performance and the higher Curie temperature.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric ceramic mainly comprises the following steps: the traditional solid phase method, hydrothermal synthesis method, sol-gel synthesis method (sol-gel), template Grain Growth method (TGG), reaction-template Grain Growth method (RTGG) and the like, but different preparation processes have great influence on the performance of the ceramic. Among them, the solid-phase sintering method is one of the most commonly used methods, and has the characteristics of simple preparation process, low cost and the like, but the period is long, and the performance stability of the prepared ceramic is poor; the sol-gel method has low preparation cost, and the obtained powder particles are fine but the process is relatively complex; the TGG and RTGG methods adopt the texturing growth technology, so that the prepared ceramic has high anisotropy, and the obtained textured piezoelectric ceramic has excellent performance.
At present, tape casting is mostly adopted for forming textured piezoelectric ceramic green bodies, but the problems of low density of ceramic diaphragms, easy deformation and cracking of green bodies in the glue discharging process and the like are caused due to more organic matter content in the tape casting process, so that the product quality is influenced, and the production efficiency is lower. Therefore, the research on the forming process which is characterized by high production efficiency and excellent quality of the obtained ceramic membrane is not only suitable for the requirements of production and economic development, but also is an urgent requirement for improving the performance of the textured ceramic, but no report about the preparation of the sodium bismuth titanate-based textured piezoelectric ceramic by adopting the ceramic injection forming process is found.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a sodium bismuth titanate based textured piezoelectric ceramic injection molding method, which is beneficial to realizing the preparation of the textured piezoelectric ceramic membrane of the system material and obtaining a product with excellent quality and performance.
The purpose of the invention is realized by the following technical scheme: a preparation method of sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic comprises the following steps:
step 1, preparing sheet BaTiO by molten salt method3A template;
step 2, adding BiO2、Na2CO3And TiO2After being uniformly mixed, absolute ethyl alcohol is added for ball milling, drying and sintering in sequence to prepare presintering powder, and the presintering powder is Na0.5Bi0.5TiO3Ceramic powder;
step 3, mixing the binder and the pre-sintered powder obtained in the step 2, and then performing ball milling to obtain matrix slurry; adding the flaky BaTiO obtained in the step 1 into the base body slurry3The template is stirred and mixed evenly to obtain injection slurry;
step 4, performing injection molding on the injection slurry obtained in the step 3 under the conditions of pressure and an external electric field to obtain a ceramic green body;
and 5, degreasing and drying the ceramic green body obtained in the step 4, then carrying out sintering heat treatment, and cooling to obtain the textured ceramic wafer.
The BaTiO in the step 1)3The template preparation process is as follows:
step 11, analytically pure BaCO2And TiO2Mixing the ingredients, and adding NaCl and KCl; mixing the powder, performing ball milling, and drying, grinding and presintering after the ball milling is finished; the pre-sintering process is that the temperature is increased to 950 ℃ at the speed of 5 ℃/minute and is preserved for 3 hours, then the temperature is reduced to 550 ℃ at the speed of 2 ℃/minute, and then the pre-sintering block is obtained after the pre-sintering process is cooled to the room temperature along with the furnace;
step 12, cooking the pre-sintered block obtained in the step 11 by using deionized water until the pre-sintered block is completely crushed; then washing to remove residual chloride, and drying to obtain intermediate product Ba4Ti13O30Will Ba4Ti13O30With BaCO3According to the chemical reaction formula Ba4Ti13O30+9BaCO3→13BaTiO3+9CO2Proportionally mixing, wet ball milling, and drying to obtain Ba4Ti13O30With BaCO3The powder mixture of (a) and (b),
step 13, adding Ba4Ti13O30With BaCO3The mixed powder is subjected to synthetic reaction for 3 hours at 1050 ℃ to obtain flaky BaTiO3And repeatedly washing with deionized water until no white precipitate is detected by silver nitrate, and drying for later use.
In step 11, BaCO2、TiO2And the proportion of NaCl to KCl is as follows: BaCO2With TiO2The mass ratio of (A) is 43.186: 56.814; the NaCl and the KCl are proportioned according to the eutectic point, and the mass ratio is 1: 1; the mass sum of NaCl and KCl accounts for 50 percent of the mass sum of the mixed powder.
In step 2, the composition of the pre-sintered powder is as follows: BiO2、Na2CO3And TiO2The ratio is calculated according to the following equation:
0.25Na2CO3+0.25Bi2O3+TiO2→Na0.5Bi0.5TiO3+0.25CO2↑。
in the step 3, the adhesive is polyvinyl alcohol solution with the concentration of 8 wt%, and accounts for 70% by mass.
In step 3, the molar ratio of the content of the flaky BaTiO3 to the calcined powder was 0.06: 0.94.
The electric field strength is not more than 5KV/mm, the duration of action is 20 minutes, the temperature during injection operation is 60 ℃, and the injection pressure is 3 Mpa.
Heating to 120 ℃ at the speed of 2 ℃/min before degreasing, preserving the temperature for 30min to remove the water in the green body, heating to 500 ℃ at the speed of 2 ℃/min after preserving the temperature, and preserving the temperature for 2 h.
And (3) heating to 1050 ℃ at a heating rate of 5 ℃/min, sintering, keeping the temperature for 2h, reducing the temperature to 500 ℃ at the same rate, and cooling along with the furnace to obtain the ceramic diaphragm.
The sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic prepared by the preparation method has the composition of (1-x) Na0.5Bi0.5TiO3-xBaTiO3And x is 0.06 binary system, and the piezoelectric constant is not lower than 140 pC/N.
Compared with the prior art, the invention has at least the following beneficial effects: the invention adopts ceramic injection molding to prepare ceramic green body, continuously applies electric field in the injection process, aims to realize the double orientation of the crystal grain orientation in the injection process and the orientation of the electric field to the electric domain in the external application process, improves the problems of low diaphragm density caused by more organic matter content in the traditional ceramic green body preparation molding process, influence on product quality due to easy deformation and cracking of the green body in the glue discharging process and the like, and simultaneously improves the orientation effect of the ceramic, and the obtained ceramic diaphragm has uniform structure, smooth surface and excellent piezoelectric performance3Piezoelectric constant d33Up to 149 pC/N.
Furthermore, the temperature is increased to 120 ℃ at the speed of 2 ℃/min before degreasing, so that the problem that the ceramic green body cracks due to the excessively high temperature increase speed is solved.
Drawings
FIG. 1 is a schematic diagram of the improved injection molding of the sodium bismuth titanate-based piezoelectric textured ceramic.
FIG. 2a shows BaTiO produced by the molten salt method in example 13SEM image of template crystal.
FIG. 2b shows BaTiO produced by the molten salt method in example 13XRD pattern of template crystals.
FIG. 3a shows the final 0.94Na obtained in example 10.5Bi0.5TiO3-0.06BaTiO3SEM images of textured ceramics.
FIG. 3b shows the final 0.94Na obtained in example 10.5Bi0.5TiO3-0.06BaTiO3XRD pattern of textured ceramics.
FIG. 4 is a XRD diffraction pattern of the textured ceramic with electric field intensity of 3KV/mm and 0 KV/mm.
FIG. 5a is the XRD patterns of the texture ceramic sintered at different temperatures, wherein the patterns are sequentially 1200 ℃, 1050 ℃, 1100 ℃ and 1150 ℃ from top to bottom.
Fig. 5b is a graph of the texture degree f of a textured ceramic sintered at different temperatures.
FIG. 6 shows 0.94Na prepared at different sintering temperatures0.5Bi0.5TiO3-0.06BaTiO3The variation curve of the piezoelectric coefficient of the textured ceramic with the sintering temperature.
In the drawings: 1-material cylinder, 2-screw, 3-hopper, 4-heating device, 5-external electric field, 6-nozzle, 7-mould, 8-degreasing device and 9-sintering device.
Detailed Description
A sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic prepared by a ceramic injection molding process specifically comprises the following preparation steps:
1) preparation of template crystalline BaTiO3: mixing BaCO3、TiO2According to the mass ratio of 43.186:56.814, adding 50% NaCl-KCl solution and BaCO3And TiO2Adding absolute ethyl alcohol, ball milling for 12 hours to obtain ball grinding material, drying at 80 ℃ for later use, and carrying out synthetic reaction on the obtained powder at 950 ℃ for 3 hours to obtain an intermediate product Ba4Ti13O30Intermediate Ba4Ti13O30Repeatedly washing with deionized water until no white precipitate is detected with silver nitrate, drying the white precipitate, and adding Ba4Ti13O30With BaCO3Mixing according to the mass ratio of 48.187:51.813, namely proportioning Ba according to a chemical reaction formula4Ti13O30+9BaCO3→13BaTiO3+9CO2Then adding absolute ethyl alcohol into the mixture, ball-milling the mixture for 8 hours, drying the mixture at 80 ℃, and carrying out synthetic reaction on the obtained powder for 3 hours at 1050 ℃ to obtain flaky BaTiO3And repeatedly washing with hot deionized water until no white precipitate is detected by silver nitrate, and drying for later use.
2) Preparing pre-sintering powder: adding BiO2、Na2CO3And TiO2The materials are mixed according to the following molar ratio, ball milled for 4 hours, dried for 24 hours at 80 ℃, subjected to synthesis reaction for 2 hours at 900 ℃, and dried for later use after secondary ball milling.
0.25Na2CO3+0.25Bi2O3+TiO2——Na0.5Bi0.5TiO3+CO2↑
3) Proportioning injection slurry: uniformly mixing the pre-sintered powder and the binder according to the mass ratio of 10:7, and magnetically stirring for 12 hours to prepare uniform matrix slurry; the flaky BaTiO obtained in the step 13Adding the matrix slurry, wherein the molar ratio of the content of the flaky BaTiO3 to the pre-sintered powder is 0.06:0.94, and continuously stirring for 6 hours to obtain uniform injection slurry.
4) Injection molding: injecting prepared injection slurry into a hopper, pushing a screw rod 2 to move towards a mold 7 by hydraulic pressure, enabling granules to flow into a charging barrel 1 through the hopper, pushing the granules in the charging barrel 1 by the screw rod 2 to pass through an electric field generating device 5 and a temperature heating zone 4 along the barrel wall, and injecting the granules into a square mold through a nozzle 6, wherein the length, the width and the height of the square mold are 1.8cm, 1.8cm and 0.2cm respectively. The parameters during the injection were: controlling the injection temperature at 60 ℃, the injection pressure at 3Mpa, the electric field strength not more than 5KV/mm, the duration of action time at 20 minutes, and obtaining the ceramic green body after demoulding.
5) Degreasing and sintering: in order to improve the preparation efficiency, degreasing and sintering of the ceramic green body are completed in one step in a normal pressure sintering furnace, in order to prevent the green body from generating moisture gradient in the thickness direction and the radial direction in the heating process to cause uneven shrinkage of the green body and cause cracking of a sample, the temperature is increased to 120 ℃ at the speed of 2 ℃/min before degreasing, the temperature is kept for 30min to remove moisture of the green body, the temperature is increased to 500 ℃ at the speed of 2 ℃/min after heat preservation, and the temperature is kept for 2h to ensure that a binder is completely removed; and then, heating to 1050 ℃ at the heating rate of 5 ℃/min for sintering, keeping the temperature for 2 hours, cooling to 500 ℃ at the same rate, and cooling along with the furnace to obtain the ceramic diaphragm.
6) Polarization: coating silver paste on two sides of the obtained ceramic membrane, drying for 2 hours at 80 ℃, then heating to 550 ℃ at the heating rate of 2 ℃/minute in a normal pressure sintering furnace, preserving heat for 30 minutes, then cooling to room temperature along with the furnace to obtain a silver-sintered ceramic piece, placing the silver-sintered ceramic piece in a polarization device, and polarizing for 20 minutes at the temperature of 70 ℃ under methyl silicone oil at the voltage of 3kV/mm to obtain the bismuth sodium titanate-barium titanate leadless piezoelectric textured ceramic.
Example 1:
step 1, preparing template crystal grain BaTiO3
Weighing BaCO321.593g powder, TiO228.407g of powder, 25g of NaCl powder and 25g of KCl powder (the content of molten salt accounts for 50 percent of the total mass of the powder). And mixing the powder, performing planetary ball milling for 12 hours at the rotating speed of 500 revolutions per minute, and drying, grinding and presintering in sequence after the ball milling is finished. During pre-sintering, the temperature is increased to 950 ℃ at the speed of 5 ℃/minute and is preserved for 3 hours, and then the temperature is slowly reduced to 500 ℃ at the speed of 5 ℃/minute; after pre-firing, Ba is obtained4Ti13O3Steaming the block with 95 deg.C deionized water until the block is completely pulverized, washing with 70 deg.C deionized water for 10 times, removing residual molten salt to obtain intermediate powder Ba4Ti13O30。
Then 24.093g of Ba4Ti13O30With 25.906g of BaCO3After being mixed evenly, the mixture is subject to planetary ball milling for 6 hours, and then is dried, ground and sintered in sequence. The sintering system is as follows: at a rate of 5 ℃/min toKeeping the temperature at 1050 ℃ for 3 hours, and then slowly cooling to 500 ℃ at the speed of 5 ℃/minute; after sintering, the powder was fired into a block and cooked with 95 ℃ deionized water until the block was completely ground. Then washing with 70 deg.C deionized water for 10 times to remove residual molten salt to obtain sheet BaTiO3The crystal has Scanning Electron Micrograph (SEM) and XRD patterns shown in figure 2a and figure 2b respectively.
Step 2, preparing pre-sintering powder
Weighing Na2CO35.945g powder, TiO2Powder 17.92g and Bi2O326.135g of powder, taking absolute ethyl alcohol as a grinding medium, mixing the materials, performing planetary ball milling for 4 hours at the rotating speed of 500 revolutions per minute, and drying, grinding and presintering in sequence after the ball milling is finished; the presintering system is that the temperature is increased to 900 ℃ at the speed of 200 ℃/hour and is preserved for 2 hours, the temperature is cooled to room temperature along with the furnace, the presintering is carried out, the ball milling is continued for 4 hours, the presintering is carried out after the ball milling is finished, the drying, the grinding and the sieving are carried out in sequence, and the presintering powder is obtained, and the presintering powder is Na0.5Bi0.5TiO3Ceramic powder.
Step 3, weighing 18.5g of the pre-sintered powder obtained in the step 2 and 12.95g of a binder (PVA solution with the concentration of 8 wt%) and placing the mixture in a magnetic stirrer to be mixed for 12 hours, and adding 1.18g of the flaky BaTiO obtained in the step 1 after the materials are uniform3And stirring was continued for 6 hours to obtain an injection slurry.
Step 4, preparing texture ceramic green body
And (4) pouring the injection slurry obtained in the step (3) into a hopper of an injection molding machine, and starting the injection molding machine to perform injection operation. Injecting prepared injection slurry into a hopper, pushing a screw rod 2 to move towards a mold 7 by hydraulic pressure, enabling granules to flow into a charging barrel 1 through the hopper, pushing the granules in the charging barrel 1 by the screw rod 2 to pass through an electric field generating device 5 and a temperature heating zone 4 along the barrel wall, and injecting the granules into a square mold through a nozzle 6, wherein the length, the width and the height of the square mold are 1.8cm, 1.8cm and 0.2cm respectively. The injection temperature is 60 ℃, the injection pressure is 3Mpa, no external electric field is added, and the ceramic green body with the thickness of 1.8cm multiplied by 1.8cm is obtained after demoulding.
Step 5, preparing textured ceramic
The pottery obtained in the step 4Placing the ceramic green body in a muffle furnace, heating to 120 ℃ at the speed of 2 ℃/min before degreasing, preserving the temperature for 30min to remove the water in the green body, heating to 500 ℃ at the speed of 2 ℃/min after preserving the temperature, preserving the temperature for 2h to ensure that the binder is completely removed; then the temperature is raised to 1050 ℃ at the heating rate of 5 ℃/min for sintering, the temperature is kept for 2 hours, then the temperature is lowered to 500 ℃ at the same rate, and then the product is cooled along with the furnace, and finally 0.94Na is obtained0.5Bi0.5TiO3-0.06BaTiO3Textured ceramic coupons, FIG. 3a and FIG. 3b are 0.94Na without applied electric field0.5Bi0.5TiO3-0.06BaTiO3The SEM and XRD patterns show that the obtained ceramic grains exist in small cubic particles, and the grains are uniform in size and are closely arranged. The density of the resulting ceramic was measured by Archimedes drainage and found to be 5.59g/cm3The density is very close to the theoretical density, and the prepared material is 0.94Na as can be seen from an XRD pattern0.5Bi0.5TiO3-0.06BaTiO3, which shows a reduced (110) diffraction peak compared to the diffraction peak of the oriented ceramic, and (200) a higher peak, and which gives an oriented ceramic with a degree of texture of 65% by injection molding, and the sintered sample is ground, polished, coated with silver paste, fired at 550 ℃ for 30min, and after polarization, shows a typical piezoelectric coefficient of 138 pC/N.
Example 2:
step 1, preparing template crystal grain BaTiO3
Weighing BaCO321.593g powder, TiO228.407g of powder, 25g of NaCl powder and 25g of KCl powder (the content of molten salt accounts for 50 percent of the total mass of the powder). Mixing the powder materials, and performing planetary ball milling for 12 hours at the rotating speed of 500 revolutions per minute; after the ball milling is finished, drying, grinding and presintering are sequentially carried out; the pre-sintering system is that the temperature is increased to 950 ℃ at the speed of 5 ℃/minute and is preserved for 3 hours, and then the temperature is slowly reduced to 500 ℃ at the speed of 5 ℃/minute; after pre-burning, the powder is burned into a block, and the block is steamed and boiled by deionized water at 95 ℃ until the block is completely crushed; then washing with 70 deg.C deionized water for 10 times to remove residual molten salt to obtain intermediate powder Ba4Ti13O30. Then 24.093g of intermediate powder Ba were mixed4Ti13O30With 25.906g of BaCO3After being mixed evenly, the mixture is subject to planetary ball milling for 6 hours, and then is dried, ground and sintered in sequence. The sintering system is that the temperature is increased to 1050 ℃ at the speed of 5 ℃/minute and is preserved for 3 hours, and then the temperature is slowly reduced to 500 ℃ at the speed of 5 ℃/minute; after sintering, the powder was fired into a block and cooked with 95 ℃ deionized water until the block was completely ground. Then washing with 70 deg.C deionized water for 10 times to remove residual molten salt to obtain sheet BaTiO3And (4) crystals.
Step 2, preparing pre-sintering powder
Weighing Na2CO35.945g powder, Bi2O326.135g powder, TiO2Mixing 17.92g of powder and absolute ethyl alcohol as a medium, and performing planetary ball milling on the mixture for 4 hours at the rotating speed of 500 revolutions per minute; after the ball milling is finished, drying, grinding and presintering are sequentially carried out; the pre-sintering system is that the temperature is increased to 900 ℃ at the speed of 200 ℃/hour and is preserved for 2 hours, and the temperature is cooled to the room temperature along with the furnace; and (4) continuing ball milling for 4 hours after presintering, and drying, grinding and sieving the ball milled powder in sequence to obtain presintering powder.
Step 3, preparing injection slurry
Weighing 18.5g of the pre-sintered powder obtained in the step 2 and 12.95g of a binder (PVA solution with the concentration of 8 wt%) in a magnetic stirrer, mixing for 12 hours, and adding 1.18g of the flaky BaTiO obtained in the step 1 after the materials are uniform3And stirring was continued for 6 hours to obtain an injection slurry.
Step 4, preparing texture ceramic green body
Pouring the injection slurry obtained in the step (3) into a hopper of an injection molding machine, starting the injection molding machine, and performing injection operation; injecting prepared injection slurry into a hopper, pushing a screw rod 2 to move towards a mold 7 by hydraulic pressure, enabling granules to flow into a charging barrel 1 through the hopper, pushing the granules in the charging barrel 1 by the screw rod 2 to pass through an electric field generating device 5 and a temperature heating zone 4 along the barrel wall, and injecting the granules into a square mold through a nozzle 6, wherein the length, the width and the height of the square mold are 1.8cm, 1.8cm and 0.2cm respectively. The injection temperature is 60 ℃, the injection pressure is 3Mpa, and the electric field intensity is 3 KV/mm; demoulding to obtain the ceramic green body with the thickness of 1.8cm multiplied by 1.8 cm.
Step 5, preparing textured ceramic
Placing the ceramic green body obtained in the step 4 in a muffle furnace, heating to 120 ℃ at the speed of 2 ℃/min before degreasing, preserving the temperature for 30min to remove the water of the green body, heating to 500 ℃ at the speed of 2 ℃/min after preserving the temperature, preserving the temperature for 2h to ensure that the binder is completely removed; then, the temperature is raised to 1050 ℃ at the heating rate of 5 ℃/min for sintering, the temperature is kept for 2 hours, then the temperature is reduced to 500 ℃ at the same rate, and the sintered compact texture ceramic sample wafer is finally obtained, compared with an XRD (X-ray diffraction) pattern without the action of an electric field, the diffraction peak (200) under 3KV/mm is obviously enhanced, and the texture degree of the sample wafer is 75% by calculation; grinding, polishing and coating the sintered sample wafer with silver paste, firing at 550 ℃ for 30min, and after polarization, measuring that the typical piezoelectric coefficient is also improved compared with that without an external electric field, and d is33Is 143pC/N, as shown in FIG. 4.
Examples 3 to 5; steps 1-4 are the same as example 2, and in step 5, the action of the applied electric field is changed to reflect the change rule of the texture degree and the piezoelectric coefficient along with the applied electric field, wherein the applied electric field is respectively 2KV/mm, 4KV/mm and 5 KV/mm.
Example 6:
step 1) preparation of template crystalline BaTiO3
Weighing BaCO321.593g powder, TiO228.407g of powder, 25g of NaCl powder and 25g of KCl powder (the content of molten salt accounts for 50 wt% of the total mass of the powder). The powder materials are mixed and then are subjected to planetary ball milling for 12 hours at the rotating speed of 500 revolutions per minute. And drying, grinding and presintering after the ball milling is finished. The pre-sintering system is that the temperature is raised to 950 ℃ at the speed of 5 ℃/minute and is preserved for 3 hours, and then the temperature is slowly reduced to 500 ℃ at the speed of 5 ℃/minute. After pre-sintering, the powder is sintered into a block and is steamed and boiled by deionized water at 95 ℃ until the block is completely crushed. Then washing with 70 deg.C deionized water for 10 times to remove residual molten salt to obtain intermediate powder Ba4Ti13O30. Then 24.093g Ba4Ti13O30With 25.906g BaCO3Mixing, ball milling for 6 hr, stoving, grinding and sintering. The sintering system is that the temperature is increased to 1050 ℃ at the speed of 5 ℃/min and is preserved for 3 hours, and then the temperature is slowly decreased at the speed of 5 ℃/minThe temperature was raised to 500 ℃. After sintering, the powder was fired into a block and cooked with 95 ℃ deionized water until the block was completely ground. Then washing with 70 deg.C deionized water for 10 times to remove residual molten salt to obtain sheet BaTiO3And (4) crystals.
Step 2) preparation of preburning powder
Weighing Na2CO35.945g powder, Bi2O326.135g powder, TiO217.92g of powder and absolute ethyl alcohol as a medium, and the materials are mixed and subjected to planetary ball milling for 4 hours at the rotating speed of 500 revolutions per minute. And after the ball milling is finished, drying, grinding and presintering in sequence. The pre-sintering system is that the temperature is increased to 900 ℃ at the speed of 200 ℃/hour and is preserved for 2 hours, and the temperature is cooled to the room temperature along with the furnace; and after presintering, continuing ball milling for 4 hours, and after finishing ball milling, sequentially drying, grinding and sieving to obtain presintering powder.
Step 3) preparation of injection slurry
Weighing 18.5g of pre-sintered powder and 12.95g of binder (PVA solution with the concentration of 8 wt%) and placing the mixture in a magnetic stirrer to be mixed for 12 hours, and adding 1.18g of the flaky BaTiO obtained in the step 1 after the materials are uniform3And stirring was continued for 6 hours to obtain an injection slurry.
Step 4, preparing texture ceramic green body
Pouring the injection slurry obtained in the step (3) into a hopper of an injection molding machine, starting the injection molding machine, and performing injection operation; injecting prepared injection slurry into a hopper, pushing a screw rod 2 to move towards a mold 7 by hydraulic pressure, enabling granules to flow into a charging barrel 1 through the hopper, pushing the granules in the charging barrel 1 by the screw rod 2 to pass through an electric field generating device 5 and a temperature heating zone 4 along the barrel wall, and injecting the granules into a square mold through a nozzle 6, wherein the length, the width and the height of the square mold are 1.8cm, 1.8cm and 0.2cm respectively. The injection temperature is 60 ℃, the injection pressure is 3Mpa, and the electric field intensity is 3 KV/mm. Demoulding to obtain the ceramic green body with the thickness of 1.8cm multiplied by 1.8 cm.
And step 5, respectively carrying out heat treatment on the ceramic green body obtained in the step 4 at 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ for 2 hours to reflect the rule that the texture degree and the piezoelectric coefficient change along with the heat treatment temperature.
Step 5, preparing textured ceramic
Preparing a plurality of ceramic green bodies according to the steps 1) to 4); placing the ceramic green body obtained in the step 4) in a muffle furnace, heating to 120 ℃ at the speed of 2 ℃/min before degreasing, preserving the temperature for 30min to remove the water of the green body, heating to 500 ℃ at the speed of 2 ℃/min after preserving the temperature, preserving the temperature for 2h to ensure that the binder is completely removed; then, respectively raising the temperature to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ at the heating rate of 5 ℃/min for sintering, preserving the heat for 2 hours, reducing the temperature to 500 ℃ at the same rate, and then cooling along with the furnace to finally obtain a sintered compact texture ceramic sample wafer; the piezoelectric coefficients of the respective samples are shown in fig. 6; the texture degrees are 71%, 65%, 72%, 76% and 78%, respectively, and the graph of the texture degrees is shown in fig. 5b along with the change of the temperature, and as can be seen by combining XRD in fig. 5b, the (110) diffraction peak of BNT-BT shows a general trend of decreasing along with the increase of the temperature, and the opposite (200) diffraction peak is obviously enhanced, and as can also be seen from the graph, the (200) diffraction peak changes most and the orientation is more obvious when the sintering temperature is 1200 ℃, and the texture degree of the sample is 78%. This indicates that the BaTiO is in a flake form3The BNT-BT ceramic generates the oriented growth in the (l00) direction under the action of different sintering temperatures for the template, and the oriented growth of crystal grains is the same as expected. The sintered sample wafer is polished, coated with silver paste, fired at 550 ℃ for 30min, and after polarization, the typical change curve of the piezoelectric coefficient with temperature is shown in fig. 6. When the electric field intensity of 3KV/mm acts, the maximum piezoelectric coefficient measured at different temperatures can reach 149 pC/N.

Claims (10)

1. A preparation method of sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic is characterized by comprising the following steps:
step 1, preparing sheet BaTiO by molten salt method3A template;
step 2, adding BiO2、Na2CO3And TiO2After being uniformly mixed, absolute ethyl alcohol is added for ball milling, drying and sintering in sequence to prepare presintering powder, and the presintering powder is Na0.5Bi0.5TiO3Ceramic powder;
step 3, mixing the binder and the pre-sintering powder obtained in the step 2, and thenThen carrying out ball milling to obtain matrix slurry; adding the flaky BaTiO obtained in the step 1 into the base body slurry3The template is stirred and mixed evenly to obtain injection slurry;
step 4, performing injection molding on the injection slurry obtained in the step 3 under the conditions of pressure and an external electric field to obtain a ceramic green body;
and 5, degreasing and drying the ceramic green body obtained in the step 4, then carrying out sintering heat treatment, and cooling to obtain the textured ceramic wafer.
2. The method for preparing the bismuth sodium titanate-barium titanate lead-free piezoelectric textured ceramic according to claim 1, wherein the BaTiO in the step 1) is3The template preparation process is as follows:
step 11, analytically pure BaCO2And TiO2Mixing the ingredients, and adding NaCl and KCl; mixing the powder, performing ball milling, and drying, grinding and presintering after the ball milling is finished; the pre-sintering process is that the temperature is increased to 950 ℃ at the speed of 5 ℃/minute and is preserved for 3 hours, then the temperature is reduced to 550 ℃ at the speed of 2 ℃/minute, and then the pre-sintering block is obtained after the pre-sintering process is cooled to the room temperature along with the furnace;
step 12, cooking the pre-sintered block obtained in the step 11 by using deionized water until the pre-sintered block is completely crushed; then washing to remove residual chloride, and drying to obtain intermediate product Ba4Ti13O30Will Ba4Ti13O30With BaCO3According to the chemical reaction formula Ba4Ti13O30+9BaCO3→13BaTiO3+9CO2Proportionally mixing, wet ball milling, and drying to obtain Ba4Ti13O30With BaCO3The powder mixture of (a) and (b),
step 13, adding Ba4Ti13O30With BaCO3The mixed powder is subjected to synthetic reaction for 3 hours at 1050 ℃ to obtain flaky BaTiO3And repeatedly washing with deionized water until no white precipitate is detected by silver nitrate, and drying for later use.
3. The sodium bismuth titanate-barium titanate according to claim 2The preparation method of the lead-free piezoelectric textured ceramic is characterized in that in step 11, BaCO2、TiO2And the proportion of NaCl to KCl is as follows: BaCO2With TiO2The mass ratio of (A) is 43.186: 56.814; the NaCl and the KCl are proportioned according to the eutectic point, and the mass ratio is 1: 1; the mass sum of NaCl and KCl accounts for 50 percent of the mass sum of the mixed powder.
4. The preparation method of the sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic according to claim 1, which is characterized in that in the step 2, the composition of the pre-sintered powder is as follows: BiO2、Na2CO3And TiO2The ratio is calculated according to the following equation:
0.25Na2CO3+0.25Bi2O3+TiO2→Na0.5Bi0.5TiO3+0.25CO2↑。
5. the method for preparing the bismuth sodium titanate-barium titanate lead-free piezoelectric textured ceramic according to claim 1, wherein in the step 3, the adhesive is polyvinyl alcohol solution with the concentration of 8 wt%, and accounts for 70% by mass.
6. The method for preparing the bismuth sodium titanate-barium titanate lead-free piezoelectric textured ceramic according to claim 1, which is characterized in that in the step 3, the molar ratio of the content of the flaky BaTiO3 to the pre-sintered powder is 0.06: 0.94.
7. The process of preparing lead-free piezoelectric textured bismuth sodium titanate-barium titanate ceramic as set forth in claim 1, wherein the electric field strength is not more than 5KV/mm, the duration is 20 min, the temperature during injection is 60 deg.C, and the injection pressure is 3 MPa.
8. The preparation method of the sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic according to claim 1 is characterized in that the temperature is raised to 120 ℃ at the speed of 2 ℃/minute before degreasing, the temperature is preserved for 30 minutes to remove the water in the green body, the temperature is raised to 500 ℃ at the speed of 2 ℃/minute after the temperature is preserved, and the temperature is preserved for 2 hours.
9. The preparation method of the sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic according to claim 1 is characterized in that the temperature is raised to 1050 ℃ at the heating rate of 5 ℃/minute for sintering, the temperature is kept for 2 hours, then the temperature is reduced to 500 ℃ at the same rate, and then the ceramic membrane is cooled along with a furnace to obtain the ceramic membrane.
10. The sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic obtained by the preparation method of claim 1 is characterized by having the composition of (1-x) Na0.5Bi0.5TiO3-xBaTiO3And x is 0.06 binary system, and the piezoelectric constant is not lower than 140 pC/N.
CN202010125948.5A 2020-02-27 2020-02-27 Sodium bismuth titanate-barium titanate lead-free piezoelectric textured ceramic and preparation method thereof Pending CN111233465A (en)

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CN111875389A (en) * 2020-08-13 2020-11-03 西安科技大学 Method for regulating and controlling performance of lead-free piezoelectric ceramic
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