CN114873636A - Lead titanate substrate crystal template and preparation method thereof - Google Patents
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Abstract
The invention discloses a lead titanate substrate crystal template and a preparation method thereof, wherein the preparation method comprises the following steps: taking the sheet Na 2 Ti 3 O 7 Mixing the powder with a set amount of PbO to obtain a mixture A, and mixing the mixture A with barium salt or strontium salt to obtain a mixture B or a mixture C; wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and barium ions is (3-3.6) to 1, and the molar ratio of the lead ions to the barium ions is (0.01-4) to 1; in the mixture C, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and strontium ions is (3-3.6): 1, and the molar ratio of the lead ions to the strontium ions is (0.01-4): 1. Adding a mixture of NaCl and KCl in an amount which is 1-4 times the mass of the mixture B or C into the mixture B or C, and preserving the heat of the mixed material in a high-temperature environment to obtain a molten salt product; washing the molten salt product with deionized water and dilute acid in sequence to obtain high-purity molten salt product<001>Oriented (M, Pb) TiO 3 Wherein M is Ba or Sr, and Pb, M ═ (0.01-4) is 1; under the condition of a certain number of templates, the Ba and Sr contents of the new template are lower than those of the original template, and the cation diffusion effect of the template is weakened.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a lead titanate substrate crystal template and a preparation method thereof.
Background
In recent years, with the deep development of the piezoelectric material field, the piezoelectric textured ceramics gradually replace ferroelectric piezoelectric single crystals by virtue of the advantages of short preparation period, low price and the like, and become the object of the key development of the next generation of piezoelectric material field. BaTiO 2 3 And SrTiO 3 Templates have been considered to be very suitable for most textured lead-based piezoelectric ceramics, but these templates suffer from barium diffusion and strontium diffusion during grain growth of the textured ceramics, and this cation diffusion problem eventually causes the operating temperature of the textured ceramics to drop greatly, thus limiting the range of applications of the ceramics (Yang S, Li J, Liu Y, et al, Nature communications, 2021, 12(1): 1-10).
At present, the measure for solving the diffusion of barium ions and strontium ions in the template is generally to reduce the content of the template in the textured ceramic matrix, but the reduction of the content of the template also means that the texture degree of the ceramic is in turn, generally speaking, the texture degree of the textured ceramic is in positive correlation with the piezoelectric performance of the textured ceramic, so the lower the texture degree, the lower the piezoelectric performance. Therefore, a weakening of BaTiO has been developed 3 Template and SrTiO 3 The effect of cation diffusion of the template without reducing the content of the template in the ceramic matrix is of practical significance for lead-based piezoelectric textured ceramics.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a lead titanate substrate crystal template and a preparation method thereof, which are used for solving the problem of BaTiO 3 With SrTiO 3 The problem of the working temperature reduction of the piezoelectric textured ceramic caused by the ion diffusion effect problem of the template.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a lead titanate substrate crystal template comprises the following steps:
step 1, taking the flaky Na 2 Ti 3 O 7 Mixing the powder with a set amount of PbO to obtain a mixture A, and mixing the mixture A with barium salt or strontium salt to obtain a mixture B or a mixture C; wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and barium ions is (3-3.6) to 1, and the molar ratio of the lead ions to the barium ions is (0.01-4) to 1; in the mixture C, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and strontium ions is (3-3.6): 1, and the molar ratio of the lead ions to the strontium ions is (0.01-4): 1;
step 2, adding a mixture of NaCl and KCl in an amount which is 1-4 times the mass of the mixture B or C into the mixture B or C, and preserving the heat of the mixture for 1-10 hours at a high temperature of 650-1050 ℃ to obtain a molten salt product;
step 3, washing the molten salt product with deionized water and dilute acid in sequence to obtain the high-purity molten salt product with high purity<001>Oriented (M, Pb) TiO 3 Wherein M is Ba or Sr, and Pb: M ═ 1 (0.01-4).
Na 2 Ti 3 O 7 The powder is prepared by a molten salt method, and comprises the following steps:
respectively weighing Na with set mass according to stoichiometric ratio 2 CO 3 And TiO 2 Adding the powder into a ball milling tank, additionally adding sodium salt which is 0.1-4 times of the weight of the powder and serves as a molten salt matrix, preserving heat for 2-48 hours in a high-temperature environment of 800-1100 ℃ to perform molten salt reaction, firstly melting the molten salt in the process, increasing the solubility of reactants in the molten salt, obtaining precursors with different sizes along with the change of temperature and heat preservation time, and finally washing and drying the precursors to obtain the flaky Na 2 Ti 3 O 7 And (3) powder.
The sodium salt is NaCl or Na 2 SO 4 。
Na 2 CO 3 And TiO 2 The purity of (A) is not less than 99.8%.
In the step 2, the molar ratio of NaCl to KCl is 1:1 to obtain a mixed material.
The barium salt is Ba (OH) 2 、BaCO 3 Or Ba (CH) 3 COO) 2 。
The strontium salt is Sr (OH) 2 、SrCO 3 Or Sr (CH) 3 COO) 2 。
In addition, the lead titanate substrate crystal template is obtained by the preparation method, is a single perovskite phase, and has the length-diameter ratio of more than 10.
The lead titanate substrate crystal template is applied to preparing the texture piezoelectric ceramics by taking the lead titanate substrate crystal template as the template.
Compared with the prior art, the invention has at least the following beneficial effects:
BaTiO 3 template and SrTiO 3 The cation diffusion effect of the template refers to BaTiO 3 With SrTiO 3 As a heterogeneous template, the heterogeneous template inevitably undergoes solid solution reaction with a lead-based ceramic matrix to different degrees in the high-temperature sintering process of the textured ceramic, and the solid solution reaction has the consequence that Ba in the template 2+ And Sr 2+ Diffusion occurs at high temperature and replaces Pb in the lead-based ceramic lattice 2+ Thereby affecting the overall performance of the textured ceramic. The invention is realized by directly adding BaTiO 3 And SrTiO 3 Introduction of Pb in the template 2+ Under the condition of a certain number of templates, the content of Ba and Sr elements of the new template is lower than that of the original template, and even if solid solution reaction occurs, the amount of Ba or Sr elements which can enter the texture ceramic matrix is reduced, so that the cation diffusion effect of the template is weakened;
at present, in order to solve the problem of template cation diffusion, the common method is to reduce the content of a template in a ceramic matrix, and essentially reduce the content of Ba or Sr element, however, the textured ceramic matrix needs to maintain a certain number of templates (seed crystals) to successfully obtain the ultra-high texture degree, once the content of the template is reduced, the high texture degree of the textured ceramic cannot be guaranteed, and the performance of the piezoelectric textured ceramic cannot be greatly improved; therefore, the method has more advantages compared with a mode of reducing the content of the template;
meanwhile, BaTiO is generally produced 3 And SrTiO 3 The idea of (1) is generally to use Bi 4 Ti 3 O 12 The bismuth-containing piezoelectric ceramic is obtained by carrying out a molten salt substitution reaction with a corresponding Ba source or Sr source, but bismuth salt is generated in the manufacturing process, is difficult to remove, deteriorates the performance of the piezoelectric ceramic due to the presence of the bismuth salt, requires complicated procedures even if the bismuth salt can be removed, and is high in cost and difficult to operate; the invention uses Na 2 Ti 3 O 7 As the precursor, the precursor does not contain bismuth, so the process is simple, the cost is low, the yield is high, and the method is suitable for mass production.
Compared with the traditional template, the template obtained by the preparation method can be used for producing the textured lead-based piezoelectric ceramic, the number of the templates is not reduced to inhibit the cation diffusion effect of the template, the texture degree of the piezoelectric textured ceramic can not be reduced, the piezoelectric textured ceramic has high piezoelectric new performance and can have higher depolarization temperature (the depolarization temperature is the working temperature of the piezoelectric material, the higher the temperature is, the wider the application range of the piezoelectric material is, the piezoelectric material can be used under the more severe condition), and the performance and the application temperature can be really achieved.
Drawings
FIG. 1 shows Ba 0.8 Pb 0.2 TiO 3 SEM photograph of the template, the reaction synthesis condition of the template is 900 ℃ heat preservation for 2h, the template has good growth under the condition, no obvious physical defect on the surface, the length is about 10 microns, and the template is suitable for being used as a texture template
FIG. 2 shows Ba 0.8 Pb 0.2 TiO 3 Template XRD showed that a template with only a single perovskite phase had been synthesized, and that there were no other heterogeneous phases in the template.
FIG. 3 is Sr 0.5 Pb 0.5 TiO 3 SEM photograph of the template. The growth condition of the template is that the temperature is kept at 950 ℃ for 3.5h, the template has uniform size and good growth under the condition, the length-diameter ratio is more than 10, and the template can be used for texture piezoelectric ceramics.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
The term "and/or" as used herein refers to any and all possible combinations of one or more of the associated listed items and includes such combinations.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
The invention provides a lead titanate substrate crystal template with a chemical formula of (A) 1-x Pb x )TiO 3 (M is Ba or Sr; x is 0-0.8), and the preparation method comprises the following steps:
step 1, firstly preparing Na by adopting a molten salt method 2 Ti 3 O 7 The powder has the following specific reaction equation:
Na 2 CO 3 +3TiO 2→ Na 2 Ti 3 O 7 +CO 2
respectively weighing Na with set mass according to stoichiometric ratio 2 CO 3 (99.8%) and TiO 2 (99.8%), adding the powder into a ball milling tank, and additionally adding sodium salt which is 0.1-4 times of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 1-48 h, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
and 3, placing the dried mixture in a corundum crucible, and melting the fused salt at 800-1100 ℃ (the melting point of NaCl is 801 ℃) to promote Na 2 Ti 3 O 7 The synthesis and growth of the (1) are carried out, but the too high temperature can cause a large amount of molten salt to volatilize, so the temperature of the molten salt is between 800 ℃ and 1100 ℃ and is more suitable for the molten salt reaction) and the temperature is kept for 1 to 40 hours for the molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing the mixture with a certain amount of PbO to obtain a mixture A, and respectively mixing the mixture A with barium salt or strontium salt to obtain a mixture B or a mixture C. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and barium ions is (3-3.6) to 1, and the molar ratio of the lead ions to the barium ions is (0-4) to 1; likewise, in mixture C, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the strontium ions is (3-3.6): 1, and the molar ratio of the lead ions to the strontium ions is (0-4): 1.
And 6, adding a mixture of NaCl and KCl in an amount which is 1-4 times the mass of the mixture B or C per se (wherein the molar ratio of NaCl to KCl is 1:1), fully mixing the materials, placing the mixture in a corundum crucible, and keeping the temperature for 0.5-10 hours at the high temperature of 650-1050 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain the high-purity product<001>Oriented (M, Pb) TiO 3 (M is Ba or Sr, and Pb: M is 0-4).
The sodium salt is NaCl or Na 2 SO 4 (ii) a The barium salt is Ba (OH) 2 、BaCO 3 Or (CH) 3 COO) 2 Ba; the strontium salt is the Sr (OH) 2 、SrCO 3 、(CH 3 COO) 2 Sr。
Example 1
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity not less than 99.8%) and TiO 2 (the purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding NaCl which is 4 times of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 24 hours, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 2 hours at the high temperature of 1100 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain a mixture A, and mixing the mixture A with BaCO 3 Mixing to obtain a mixture B; wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and barium ions is 3:1, and the molar ratio of the lead ions to the barium ions is 4: 1.
And step 6, adding a mixture of NaCl and KCl in an amount which is 1 time of the weight of the mixture B per se (wherein the molar ratio of the NaCl to the KCl is 1:1) into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 1h at the high temperature of 700 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain the high-purity product<001>Oriented (Ba, Pb) TiO 3 (wherein Pb: Ba: 4: 1).
Example 2
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity not less than 99.8%) and TiO 2 (the purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding sodium chloride which is 2 times of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 4 hours, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 48 hours in a high-temperature environment of 800 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain mixture A, and mixing mixture A with SrCO 3 Mixing to obtain a mixture B. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the strontium ions is 18:5, and the molar ratio of the lead ions to the strontium ions is 2: 1.
And step 6, adding a mixture of NaCl and KCl (wherein the molar ratio of NaCl to KCl is 1:1) which is 2 times of the mass of the mixture B into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 10 hours at 1050 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain high-purity (Sr, Pb) TiO 3 (wherein Pb: Sr ═ 2:1) template.
Example 3
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity not less than 99.8%) and TiO 2 (the purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding sodium chloride which is 2 times of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 48 hours, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 20 hours at the high temperature of 900 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain mixture A, and mixing mixture A with Ba (OH) 2 Mixing to obtain a mixture B. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and strontium ions is 18:5, and the molar ratio of the lead ions to the barium ions is 1: 100.
And step 6, adding a mixture of NaCl and KCl in an amount which is 2 times of the weight of the mixture B (wherein the molar ratio of the NaCl to the KCl is 1:1) into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 5 hours at the high temperature of 900 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain high-purity (Ba, Pb) TiO 3 (wherein Pb: Ba ═ 1: 100).
Example 4
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity is not less than 99.8%) and TiO 2 (the purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding sodium chloride which is 0.8 times of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 48 hours, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 2 hours at the high temperature of 900 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, slicing Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain mixtures A, and mixing the mixtures A with SrCO 3 Mixing to obtain a mixture B. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the strontium ions is 16:5, and the molar ratio of the lead ions to the strontium ions is 7: 2.
And step 6, adding a mixture of NaCl and KCl in an amount which is 2 times of the weight of the mixture B (wherein the molar ratio of the NaCl to the KCl is 1:1) into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 5 hours at a high temperature of 800 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain high-purity (Sr, Pb) TiO 3 (wherein Pb: Sr ═ 7:2) template.
Example 5
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity not less than 99.8%) and TiO 2 (purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding sodium chloride which is 1 time of the powder in mass as sodium chlorideA molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 48 hours, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 6 hours at the high temperature of 900 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain mixture A, and mixing mixture A with Ba (OH) 2 Mixing to obtain a mixture B. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and strontium ions is 16:5, and the molar ratio of the lead ions to the barium ions is 6: 5.
And step 6, adding a mixture of NaCl and KCl which is 2.5 times of the mixture B in mass (wherein the molar ratio of NaCl to KCl is 1:1) into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 5 hours at the high temperature of 700 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain high-purity (Sr, Pb) TiO 3 (wherein Pb: Ba ═ 6:5) template.
Example 6
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity not less than 99.8%) and TiO 2 (the purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding sodium chloride which is 3 times of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 48 hours, taking out materials in the ball milling tank, and drying in an oven at 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 2 hours at the high temperature of 800 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain mixtures A, and mixing the mixtures A with Sr (CH) 3 COO) 2 Mixing to obtain a mixture B. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the strontium ions is 7:2, and the molar ratio of the lead ions to the strontium ions is 16: 5.
And step 6, adding a mixture of NaCl and KCl in an amount which is 2 times of the weight of the mixture B (wherein the molar ratio of the NaCl to the KCl is 1:1) into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 5 hours at a high temperature of 800 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain high-purity (Sr, Pb) TiO 3 (wherein Pb: Sr: 16:5) template.
Example 7
The preparation method for producing the lead titanate substrate crystal template provided by the embodiment comprises the following steps:
step 1, according to the chemical formula Na 2 Ti 3 O 7 Respectively weighing Na according to stoichiometric ratio 2 CO 3 (purity not less than 99.8%) and TiO 2 (the purity is not lower than 99.8%), adding the powder into a ball milling tank, and additionally adding sodium chloride which is 0.1 time of the weight of the powder and is used as a molten salt matrix;
step 2, adding ethanol serving as a grinding medium into a ball milling tank, carrying out high-speed ball milling for 48 hours, taking out the materials in the ball milling tank, and drying in an oven at the temperature of 80 ℃ for later use;
step 3, placing the dried mixture in a corundum crucible, and preserving heat for 2 hours at the high temperature of 900 ℃ to perform molten salt reaction;
step 4, washing the molten salt mixture obtained by the reaction in the corundum crucible for multiple times by using deionized water, and obtaining flaky Na after washing 2 Ti 3 O 7 Drying in an oven at 100 deg.C.
Step 5, flake Na 2 Ti 3 O 7 Mixing with a predetermined amount of PbO to obtain mixture A, and mixing mixture A with Ba (OH) 2 Mixing to obtain a mixture B. Wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and strontium ions is 18:5, and the molar ratio of the lead ions to the barium ions is 5: 2.
And step 6, adding a mixture of NaCl and KCl which is 2.5 times of the mixture B in mass (wherein the molar ratio of NaCl to KCl is 1:1) into the mixture B, fully mixing the materials, and then placing the mixture in a corundum crucible to keep the temperature for 5 hours at the high temperature of 800 ℃.
Step 7, washing the product in the crucible with deionized water and dilute acid in sequence to finally obtain high-purity (Sr, Pb) TiO 3 (wherein Pb: Ba ═ 5:2) template.
The sodium salt (NaCl) in step 1 of the invention can also be Na 2 SO 4 Instead.
FIG. 1 shows Ba 0.8 Pb 0.2 TiO 3 The SEM photo of the template, the reaction synthesis condition of the template is 900 ℃ and heat preservation for 2h, the template grows well under the condition, the surface has no obvious physical defect, the length is about 10 microns, and the template is suitable for being used as a texture template; FIG. 2 shows Ba 0.8 Pb 0.2 TiO 3 Template XRD, which shows that a template with only a single perovskite phase has been synthesized, and that there are no other hetero-phases in the template, Sr is shown in FIG. 3 0.5 Pb 0.5 TiO 3 And (3) SEM (scanning electron microscope) pictures of the template, wherein the growth condition of the template is heat preservation at 950 ℃ for 3.5h, the size of the template is uniform and well grown under the condition, the length-diameter ratio is more than 10, and the template can be used for texture piezoelectric ceramics.
Claims (9)
1. A preparation method of a lead titanate substrate crystal template is characterized by comprising the following steps:
step 1, taking the flaky Na 2 Ti 3 O 7 Mixing the powder with a set amount of PbO to obtain a mixture A, and mixing the mixture A with barium salt or strontium salt to obtain a mixture B or a mixture C; wherein in the mixture B, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and barium ions is (3-3.6) to 1, and the molar ratio of the lead ions to the barium ions is (0.01-4) to 1; in the mixture C, Na 2 Ti 3 O 7 The molar ratio of the lead ions to the total amount of the lead and strontium ions is (3-3.6) to 1, and the molar ratio of the lead ions to the strontium ions is (0.01-4) to 1;
step 2, adding a mixture of NaCl and KCl in an amount which is 1-4 times the mass of the mixture B or C into the mixture B or C, and preserving the heat of the mixture for 1-10 hours at a high temperature of 650-1050 ℃ to obtain a molten salt product;
step 3, washing the molten salt product with deionized water and dilute acid in sequence to obtain the high-purity molten salt product with high purity<001>Oriented (M, Pb) TiO 3 Wherein M is Ba or Sr, and Pb: M ═ 1 (0.01-4).
2. The method for preparing a lead titanate substrate crystal template according to claim 1, wherein Na is added 2 Ti 3 O 7 The powder is prepared by a molten salt method, and comprises the following steps:
respectively weighing Na with set mass according to stoichiometric ratio 2 CO 3 And TiO 2 Adding the powder into a ball milling tank, additionally adding sodium salt which is 0.1-4 times of the weight of the powder and serves as a molten salt matrix, preserving heat for 2-48 hours in a high-temperature environment of 800-1100 ℃ to perform molten salt reaction, firstly melting the molten salt in the process, increasing the solubility of reactants in the molten salt, obtaining precursors with different sizes along with the change of temperature and heat preservation time, and finally washing and drying the precursors to obtain the flaky Na 2 Ti 3 O 7 And (3) powder.
3. The method for preparing the lead titanate substrate crystal template according to claim 2, wherein the sodium salt is NaCl or Na 2 SO 4 。
4. The method for preparing a lead titanate substrate crystal template according to claim 2, wherein Na is added 2 CO 3 And TiO 2 2 The purity of (A) is not less than 99.8%.
5. The method for preparing the lead titanate substrate crystal template according to claim 1, wherein in the step 2, the molar ratio of NaCl to KCl is 1:1 to obtain a mixed material.
6. The method for preparing the lead titanate substrate crystal template according to claim 1, wherein the barium salt is Ba (OH) 2 、BaCO 3 Or Ba (CH) 3 COO) 2 。
7. The method for preparing the lead titanate substrate crystal template according to claim 1, wherein the strontium salt is Sr (OH) 2 、SrCO 3 Or Sr (CH) 3 COO) 2 。
8. A lead titanate substrate crystal template, characterized in that it is obtained by the preparation method of any one of claims 1 to 7, is a single perovskite phase, and has an aspect ratio of more than 10.
9. The use of the lead titanate substrate crystal template of claim 8 as a template for the preparation of textured piezoelectric ceramics.
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