CN113755967B - Polyvinylidene fluoride flexible piezoelectric material and preparation method thereof - Google Patents
Polyvinylidene fluoride flexible piezoelectric material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of electronic ceramic materials, in particular to a polyvinylidene fluoride flexible piezoelectric material and a preparation method thereof, and the polyvinylidene fluoride flexible piezoelectric material comprises the following raw materials: polyvinylidene fluoride, nylon 1111, rare earth modified graphene oxide and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 ‑BaTiO 3 Polybutylene succinate; the rare earth modified graphene oxide is treated by the silane coupling agent, so that the prepared piezoelectric material has good piezoelectric performance and flexibility, maintains the flexibility of the polymer, improves the piezoelectric performance of the material, and has wide application prospect on wearable equipment.
Description
Technical Field
The invention relates to the field of electronic ceramic materials, in particular to a polyvinylidene fluoride flexible piezoelectric material and a preparation method thereof.
Background
The piezoelectric material is a functional material which can rapidly convert stress/strain such as pressure and vibration into an electric signal or convert the electric signal into signals such as deformation and vibration. The sensor has the advantages of positive and negative piezoelectric effect, large bandwidth, quick electromechanical response frequency, high energy conversion rate, strong recovery capability and the like, can be used as a sensor and a driver, and is often used as a preferred smart material widely applied to an intelligent structural system.
Conventional piezoelectric materials are mainly classified into piezoelectric crystals (including organic and oxide, salt, etc. crystals, particularly nanocrystals having a specific structure and orientation), piezoelectric ceramics, and piezoelectric polymers 3. The piezoelectric polymer has good mechanical property, high chemical stability, natural flexibility, easy processing, low manufacturing cost, easy matching with light load, capability of manufacturing extremely thin components, and good prospect in the aspects of intelligent sensing, wearable self-powered devices and the like.
However, compared with inorganic piezoelectric materials, the piezoelectric performance of organic piezoelectric materials is lower, which limits the application thereof. Therefore, how to improve the piezoelectric performance of the organic piezoelectric material while maintaining the flexibility thereof is an important point of current research.
Disclosure of Invention
The invention aims to: aiming at the defects or improvement demands of the prior art, the invention provides a polyvinylidene fluoride flexible piezoelectric material and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials:
polyvinylidene fluoride, nylon 1111, rare earth modified graphene oxide and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Polybutylene succinate;
the rare earth modified graphene oxide is treated by a silane coupling agent.
Further, the material comprises the following raw materials in parts by weight:
60-80 parts of polyvinylidene fluoride, 1111 30-50 parts of nylon, 1-5 parts of rare earth modified graphene oxide and polyamide-imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10-20 parts of polybutylene succinate and 2-4 parts of polybutylene succinate;
the rare earth modified graphene oxide is treated by a coupling agent.
Further, the preparation method of the rare earth modified graphene oxide comprises the following steps:
dissolving rare earth oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, regulating the pH of the system to 4-6 with citric acid to obtain rare earth modified liquid, heating to 40-60 ℃, soaking graphene oxide with concentrated nitric acid for 30-50s, taking out, washing with water to neutral, drying, adding into the rare earth modified liquid, performing ultrasonic dispersion for 5-10h, taking out, washing and drying.
Further, the rare earth modified liquid consists of the following raw materials in parts by weight:
1-2 parts of rare earth oxide, 0.1-0.5 part of ethylenediamine tetraacetic acid, 0.1-1 part of urea, 0.1-1 part of ammonium chloride, a proper amount of citric acid and 90-100 parts of ethanol.
Further, the rare earth oxide is lanthanum oxide.
Further, the silane coupling agent treatment method is as follows:
adding acetic acid into 95% ethanol to make pH 4.5-5.5, adding silane coupling agent, hydrolyzing for 5-10min, adding rare earth modified graphene oxide, heating to 30-50deg.C, ultrasonically oscillating for 5-10min, taking out, and oven drying.
Further, the polyamideimide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding, ultrasonic oscillating for 30-50min, removing water at 60-70deg.C under reduced pressure, and oven drying the obtained solid.
Further, aqueous polyamideimide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:70-85.
The preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, electrostatic spinning to obtain crude product, hot-pressing at 130-150deg.C and 2-4MPa for 30-60s, removing pressure, maintaining at 80-100deg.C for 10-50min, and recovering room temperature.
Further, electrospinning parameters: the spinning speed is 2-4mL/h, the voltage is 10-16kV, and the spinning time is 2-4h.
The invention has the beneficial effects that:
the invention provides a polyvinylidene fluoride flexible piezoelectric material, polyvinylidene fluoride utensilThe piezoelectric polymer has the advantages of high flexibility, small density, easiness in processing, long-term stability under a high electric field and the like, is a piezoelectric polymer with great development prospect, compared with an inorganic piezoelectric material, the piezoelectric capability of a polyvinylidene fluoride base material is weaker, but the unique flexibility of the piezoelectric polymer endows the piezoelectric polymer with good processing performance, interaction exists between nylon 1111 and a polyvinylidene fluoride dipole, the piezoelectric polymer has better compatibility, the electric activity of the polyvinylidene fluoride can be improved after the piezoelectric polymer is added, the piezoelectric performance is improved, polybutylene succinate is used as a semi-crystalline polymer, the mechanical property is excellent, the mechanical property of the material can be improved after the piezoelectric polymer is added, the mechanical property of the material is reduced due to the addition of inorganic matters, the piezoelectric performance is not adversely affected after the piezoelectric polymer is added, the graphene oxide can be used as a conductive material to form micro-capacitance, the piezoelectric performance of the material is improved, a large number of folds exist on the surface of the graphene oxide after the rare earth modification, the electrochemical current density of the graphene oxide can be improved, and the electrochemical performance of the BaTiO is greatly improved at present 3 Report of complex use with polyvinylidene fluoride, bi was used after the test by the inventors 0.5 Na 0.5 TiO 3 -BaTiO 3 Replacement of BaTiO 3 And for Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method has the advantages that the polyamide-imide grafting treatment is carried out, the consumption of electronic ceramic powder is reduced, the piezoelectric performance of the material is further improved, the material has good compatibility with high polymers after the grafting treatment, the flexibility of the material is good, and the piezoelectric material prepared by the preparation method has good piezoelectric performance and flexibility, the piezoelectric constant is more than or equal to 44.19pC/N, the plane electromechanical coupling coefficient is more than or equal to 0.31, the dielectric loss is less than or equal to 1.08, the tensile strength is more than or equal to 6.45MPa, the elongation at break is more than or equal to 220%, the piezoelectric performance of the material is improved while the flexibility of the polymer is maintained, and the piezoelectric material has wide application prospect on wearable equipment.
Drawings
Fig. 1 is an SEM image of a polyvinylidene fluoride-based flexible piezoelectric material prepared in example 1 of the present invention.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
70 parts of polyvinylidene fluoride, 1111 40 parts of nylon, 3 parts of rare earth modified graphene oxide treated by coupling agent and polyamide-imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 2 parts of polybutylene succinate;
the method for treating rare earth modified graphene oxide by using the coupling agent comprises the following steps:
dissolving lanthanum oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, and regulating the pH value of the system to 4 by using citric acid to obtain rare earth modified liquid, wherein the rare earth modified liquid comprises the following raw materials in parts by weight: 1 part of rare earth oxide, 0.1 part of ethylenediamine tetraacetic acid, 0.2 part of urea, 0.1 part of ammonium chloride, a proper amount of citric acid and 90 parts of ethanol, heating the rare earth modified liquid to 50 ℃, soaking graphene oxide with concentrated nitric acid for 30 seconds, taking out, washing with water to neutral, drying, adding the rare earth modified liquid, carrying out ultrasonic dispersion for 10 hours, taking out, washing, drying for standby, adding acetic acid into 95% ethanol to enable the pH value to be 4.5, adding a silane coupling agent A151, hydrolyzing for 10 minutes, adding the rare earth modified graphene oxide, heating to 30 ℃, carrying out ultrasonic oscillation for 10 minutes, and taking out and drying.
Wherein, the polyamide imide is grafted with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding aqueous polyamideimide and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:80, carrying out ultrasonic oscillation for 30min, then decompressing and removing water at 60 ℃, and drying the obtained solid.
The preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, and after electrostatic spinning, obtaining crude products, wherein the electrostatic spinning parameters are as follows: the spinning speed is 2mL/h, the voltage is 10kV, the spinning time is 2h, the crude product is hot-pressed for 40s at 130 ℃ and 2MPa, the pressure is removed, and the temperature is kept at 80 ℃ for 20min and then the room temperature is restored.
Example 2:
a polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
60 parts of polyvinylidene fluoride, 1111 30 parts of nylon, 1 part of rare earth modified graphene oxide treated by coupling agent and polyamide-imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 2 parts of polybutylene succinate;
the method for treating rare earth modified graphene oxide by using the coupling agent comprises the following steps:
dissolving lanthanum oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, and regulating the pH value of the system to 4 by using citric acid to obtain rare earth modified liquid, wherein the rare earth modified liquid comprises the following raw materials in parts by weight: 1 part of rare earth oxide, 0.1 part of ethylenediamine tetraacetic acid, 0.1 part of urea, 0.1 part of ammonium chloride, a proper amount of citric acid and 90 parts of ethanol, heating a rare earth modified solution to 40 ℃, soaking graphene oxide with concentrated nitric acid for 30 seconds, taking out, washing with water to neutral, drying, adding the rare earth modified solution, carrying out ultrasonic dispersion for 5 hours, taking out, washing, drying for later use, adding acetic acid into 95% ethanol to enable the pH value to be 4.5, adding a silane coupling agent A151, hydrolyzing for 5 minutes, adding the rare earth modified graphene oxide, heating to 30 ℃, carrying out ultrasonic oscillation for 5 minutes, and taking out and drying.
Wherein, the polyamide imide is grafted with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding aqueous polyamideimide and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:70, carrying out ultrasonic oscillation for 30min, then decompressing and removing water at 60 ℃, and drying the obtained solid.
The preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, and after electrostatic spinning, obtaining crude products, wherein the electrostatic spinning parameters are as follows: the spinning speed is 2mL/h, the voltage is 10kV, the spinning time is 2h, the crude product is hot-pressed for 30s at 130 ℃ and 2MPa, the pressure is removed, and the temperature is kept at 80 ℃ for 10min and then the room temperature is restored.
Example 3:
a polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
80 parts of polyvinylidene fluoride, 1111 50 parts of nylon, 5 parts of rare earth modified graphene oxide treated by coupling agent and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 20 parts of polybutylene succinate and 4 parts of polybutylene succinate;
the method for treating rare earth modified graphene oxide by using the coupling agent comprises the following steps:
dissolving lanthanum oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, and regulating the pH value of the system to 6 by using citric acid to obtain rare earth modified liquid, wherein the rare earth modified liquid comprises the following raw materials in parts by weight: 2 parts of rare earth oxide, 0.5 part of ethylenediamine tetraacetic acid, 1 part of urea, 1 part of ammonium chloride, a proper amount of citric acid and 100 parts of ethanol, heating the rare earth modified solution to 60 ℃, soaking graphene oxide in concentrated nitric acid for 50 seconds, taking out, washing to neutral, drying, adding the rare earth modified solution, carrying out ultrasonic dispersion for 10 hours, taking out, washing, drying for later use, adding acetic acid into 95% ethanol to enable the pH value to be 5.5, adding a silane coupling agent A151, hydrolyzing for 10 minutes, adding the rare earth modified graphene oxide, heating to 50 ℃, carrying out ultrasonic oscillation for 10 minutes, and taking out and drying.
Wherein, the polyamide imide is grafted with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding aqueous polyamideimide and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:85, carrying out ultrasonic oscillation for 50min, decompressing and removing water at 70 ℃, and drying the obtained solid.
The preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, and after electrostatic spinning, obtaining crude products, wherein the electrostatic spinning parameters are as follows: the spinning speed is 4mL/h, the voltage is 16kV, the spinning time is 4h, the crude product is hot-pressed for 60s at 150 ℃ and 4MPa, the pressure is removed, and the temperature is kept at 100 ℃ for 50min and then the room temperature is restored.
Example 4:
a polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
60 parts of polyvinylidene fluoride, 1111 50 parts of nylon, 1 part of rare earth modified graphene oxide treated by coupling agent and polyamide-imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 20 parts of polybutylene succinate and 2 parts of polybutylene succinate;
the method for treating rare earth modified graphene oxide by using the coupling agent comprises the following steps:
dissolving lanthanum oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, and regulating the pH value of the system to 6 by using citric acid to obtain rare earth modified liquid, wherein the rare earth modified liquid comprises the following raw materials in parts by weight: 1 part of rare earth oxide, 0.5 part of ethylenediamine tetraacetic acid, 0.1 part of urea, 1 part of ammonium chloride, a proper amount of citric acid and 90 parts of ethanol, heating a rare earth modified solution to 60 ℃, soaking graphene oxide with concentrated nitric acid for 30 seconds, taking out, washing with water to neutral, drying, adding the rare earth modified solution, carrying out ultrasonic dispersion for 10 hours, taking out, washing, drying for later use, adding acetic acid into 95% ethanol to enable the pH value to be 4.5, adding a silane coupling agent A151, hydrolyzing for 10 minutes, adding the rare earth modified graphene oxide, heating to 30 ℃, carrying out ultrasonic oscillation for 10 minutes, and taking out and drying.
Wherein, the polyamide imide is grafted with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding aqueous polyamideimide and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:70, carrying out ultrasonic oscillation for 50min, then decompressing and removing water at 60 ℃, and drying the obtained solid.
The preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, and after electrostatic spinning, obtaining crude products, wherein the electrostatic spinning parameters are as follows: the spinning speed is 4mL/h, the voltage is 10kV, the spinning time is 4h, the crude product is hot-pressed for 30s at 130 ℃ and 4MPa, the pressure is removed, and the temperature is kept at 100 ℃ for 10min and then the room temperature is restored.
Example 5:
a polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
80 parts of polyvinylidene fluoride, 1111 30 parts of nylon, 5 parts of rare earth modified graphene oxide treated by coupling agent and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 4 parts of polybutylene succinate;
the method for treating rare earth modified graphene oxide by using the coupling agent comprises the following steps:
dissolving lanthanum oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, and regulating the pH value of the system to 4 by using citric acid to obtain rare earth modified liquid, wherein the rare earth modified liquid comprises the following raw materials in parts by weight: 2 parts of rare earth oxide, 0.1 part of ethylenediamine tetraacetic acid, 1 part of urea, 0.1 part of ammonium chloride, a proper amount of citric acid and 100 parts of ethanol, heating a rare earth modified solution to 40 ℃, soaking graphene oxide with concentrated nitric acid for 50 seconds, taking out, washing with water to neutral, drying, adding the rare earth modified solution, carrying out ultrasonic dispersion for 5 hours, taking out, washing, drying for later use, adding acetic acid into 95% ethanol to enable the pH value to be 5.5, adding a silane coupling agent A151, hydrolyzing for 5 minutes, adding the rare earth modified graphene oxide, heating to 50 ℃, carrying out ultrasonic oscillation for 5 minutes, and taking out and drying.
Wherein, the polyamide imide is grafted with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding aqueous polyamideimide and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:85, ultrasonically oscillating for 30min, decompressing and removing water at 70 ℃, and drying the obtained solid.
The preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, and after electrostatic spinning, obtaining crude products, wherein the electrostatic spinning parameters are as follows: the spinning speed is 2mL/h, the voltage is 16kV, the spinning time is 2h, the crude product is hot-pressed for 60s at 150 ℃ and 2MPa, the pressure is removed, and the temperature is kept at 80 ℃ for 50min and then the room temperature is restored.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that nylon 1111 is not added.
A polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
70 parts of polyvinylidene fluoride, 3 parts of rare earth modified graphene oxide treated by coupling agent and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 2 parts of polybutylene succinate.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that polybutylene succinate is not added.
A polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
70 parts of polyvinylidene fluoride, 1111 40 parts of nylon, 3 parts of rare earth modified graphene oxide treated by coupling agent and polyamide-imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the graphene oxide is not treated with the coupling agent.
A polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
70 parts of polyvinylidene fluoride, 1111 40 parts of nylon, 3 parts of rare earth modified graphene oxide and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 2 parts of polybutylene succinate.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that the graphene oxide is not subjected to rare earth modification.
A polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
70 parts of polyvinylidene fluoride, 1111 40 parts of nylon, 3 parts of coupling agent treated graphene oxide and polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 2 parts of polybutylene succinate.
The method for treating graphene oxide by using the coupling agent comprises the following steps:
adding acetic acid into 95% ethanol to make pH 4.5, adding silane coupling agent A151, hydrolyzing for 10min, adding graphene oxide, heating to 30deg.C, ultrasonic oscillating for 10min, taking out, and oven drying.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Not grafted with polyamideimide.
A polyvinylidene fluoride flexible piezoelectric material is composed of the following raw materials in parts by weight:
70 parts of polyvinylidene fluoride, 1111 40 parts of nylon, 3 parts of rare earth modified graphene oxide treated by coupling agent and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10 parts of polybutylene succinate and 2 parts of polybutylene succinate.
Performance test:
the piezoelectric materials prepared in examples 1 to 5 and comparative examples 1 to 5 of the present invention were cut into 2cm×5cm sheets, copper conductive paste was applied to both sides of the sheets, and after polyimide single-sided tape was further applied to the surface of the copper conductive paste, the test samples were obtained by packaging, and performance test was performed on the samples.
Piezoelectric constant d 33 Testing at room temperature on ZJ-6A piezoelectric analyzer, polarizing the sample according to common method, testing resonance and antiresonance frequency of sample at room temperature and equivalent resistance and equivalent capacitance at 1kHz with impedance analyzer, calculating plane electromechanical coupling coefficient K of sample p Dielectric loss tan delta.
The tensile strength and elongation at break were measured by an intensity meter, and were set to radial stretching, gauge 30mm, stretching rate 100mm/min, and initial tracking force 2.0N.
The results of the performance tests are shown in table 1 below:
TABLE 1
As shown in the table 1, the piezoelectric material prepared by the invention has good piezoelectric performance and flexibility, the piezoelectric constant is more than or equal to 44.19pC/N, the plane electromechanical coupling coefficient is more than or equal to 0.31, the dielectric loss is less than or equal to 1.08%, the tensile strength is more than or equal to 6.45MPa, the elongation at break is more than or equal to 220%, the piezoelectric performance of the material is improved while the flexibility of the polymer is maintained, and the piezoelectric material has wide application prospect on wearable equipment.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. The polyvinylidene fluoride-based flexible piezoelectric material is characterized by comprising the following raw materials in parts by weight:
60-80 parts of polyvinylidene fluoride, 1111 30-50 parts of nylon, 1-5 parts of rare earth modified graphene oxide and polyamide-imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 10-20 parts of polybutylene succinate and 2-4 parts of polybutylene succinate;
the rare earth modified graphene oxide is treated by a silane coupling agent;
the preparation method of the rare earth modified graphene oxide comprises the following steps:
dissolving rare earth oxide with ethanol, adding ethylenediamine tetraacetic acid, urea and ammonium chloride, stirring and mixing uniformly, regulating the pH of the system to 4-6 with citric acid to obtain rare earth modified liquid, heating to 40-60 ℃, soaking graphene oxide with concentrated nitric acid for 30-50s, taking out, washing with water to neutral, drying, adding the rare earth modified liquid, performing ultrasonic dispersion for 5-10h, taking out, washing and drying;
the rare earth modified liquid consists of the following raw materials in parts by weight:
1-2 parts of rare earth oxide, 0.1-0.5 part of ethylenediamine tetraacetic acid, 0.1-1 part of urea, 0.1-1 part of ammonium chloride, a proper amount of citric acid and 90-100 parts of ethanol;
the polyamide imide grafted Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The preparation method of (2) is as follows:
dissolving aqueous polyamide-imide with water, dissolving Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding, ultrasonic oscillating for 30-50min, removing water at 60-70deg.C under reduced pressure, and oven drying the obtained solid;
the preparation method of the polyvinylidene fluoride flexible piezoelectric material comprises the following steps:
adding polyvinylidene fluoride, nylon 1111 and polybutylene succinate into a mixed solution composed of DMF and acetone, uniformly stirring, and grafting rare earth modified graphene oxide and polyamide imide with Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 Adding to obtain spinning solution, electrostatic spinning to obtain crude product, hot-pressing at 130-150deg.C and 2-4MPa for 30-60s, removing pressure, maintaining at 80-100deg.C for 10-50min, and recovering room temperature.
2. The polyvinylidene fluoride-based flexible piezoelectric material according to claim 1, wherein the rare earth oxide is lanthanum oxide.
3. The polyvinylidene fluoride-based flexible piezoelectric material according to claim 1, wherein the silane coupling agent treatment method is as follows:
adding acetic acid into 95% ethanol to make pH 4.5-5.5, adding silane coupling agent, hydrolyzing for 5-10min, adding rare earth modified graphene oxide, heating to 30-50deg.C, ultrasonically oscillating for 5-10min, taking out, and oven drying.
4. The polyvinylidene fluoride-based flexible piezoelectric material according to claim 1,characterized in that the aqueous polyamide-imide and Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 The mass ratio of (2) is 1:70-85.
5. The polyvinylidene fluoride-based flexible piezoelectric material according to claim 1, wherein the electrospinning parameters are as follows: the spinning speed is 2-4mL/h, the voltage is 10-16kV, and the spinning time is 2-4h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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