CN109265925B - Preparation method of polymer-based composite flexible piezoelectric sensor - Google Patents
Preparation method of polymer-based composite flexible piezoelectric sensor Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The invention relates to the field of sensors, and discloses a preparation method of a polymer-based composite flexible piezoelectric sensor, which comprises the steps of preparing lead zirconate titanate superfine ceramic and zinc oxide to prepare a nanorod array, implanting the nanorod array into a mold to prepare a polymer-based piezoelectric material, injecting a mixture of epoxy resin and a styrene-butadiene-styrene block copolymer into the mold, solidifying a polymer matrix, and carrying out polarization treatment to obtain the polymer-based composite flexible piezoelectric sensor, wherein the polymer-based composite flexible piezoelectric sensor has more excellent detection performance, the used high polymer material has good flexibility, can be prepared into a large and uniform film, has smaller piezoelectric coefficient and electromechanical coupling coefficient, is prepared into a composite material with certain piezoelectric performance after being compounded, overcomes the defects of the two materials, has strong piezoelectric property, low brittleness, low density and low dielectric coefficient, and is easy to prepare large-area sheets and products with complex shapes, the manufacturing process is simple and the cost is low.
Description
Technical Field
The invention relates to the field of sensors, in particular to a preparation method of a polymer-based composite flexible piezoelectric sensor.
Background
The sensor is an important device which can be used for detecting various kinds of sensory information in the nature by human beings and converting different signals and the sensory information into digitalization and intellectualization. In the process of the rapid development of human civilization information technology, the sensor plays an increasingly important role, and is one of important means for human beings to explore unknown world and understand real world and observe surrounding information. The sensor is an adjustable component which can convert non-electrical signals such as electricity, light, temperature, chemical action and the like into electrical signals.
The lead zirconate titanate/polymer composite material is a novel functional piezoelectric material, and the dielectric and piezoelectric properties of the composite material are closely related to the composition and percentage ratio of each component of the composite material and the communication mode of two-phase materials. The hard and brittle characteristics of lead zirconate titanate make molding difficult, make it impossible to obtain any shape, and have poor impact resistance, which severely limits its application. Some high molecular materials have good flexibility and can be made into large and uniform films, but the piezoelectric coefficient and the electromechanical coupling coefficient of the high molecular materials are small, and the temperature characteristic and the aging characteristic have problems.
In recent years, with the rapid development of flexible wearable electronic products, flexible sensors and flexible energy storage elements have attracted extensive attention. The flexible sensor and the flexible energy storage element are used as important components of the wearable electronic equipment, and have great application prospects in the fields of human motion detection, personalized health monitoring, intelligent human-computer interaction and the like. Among them, the flexible sensor should have high sensitivity, wide detection range, high flexibility and high stability, and the flexible energy storage element should have excellent electrochemical properties, good mechanical flexibility, etc.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a polymer-based composite flexible piezoelectric sensor. The invention firstly prepares lead zirconate titanate superfine ceramic powder and zinc oxide nano-rod array, the rod array is implanted into a tempering mould, a polymer-based piezoelectric material is prepared by a die casting technology, a mixture of treated epoxy resin and styrene-butadiene-styrene block copolymer is injected into the mould, and after the polymer matrix is solidified, the polymer-based composite flexible piezoelectric sensor is obtained by polarization treatment.
The specific technical scheme of the invention is as follows: a preparation method of a polymer-based composite flexible piezoelectric sensor comprises the following steps:
(1) preparing lead zirconate titanate superfine ceramic powder: the method comprises the steps of taking butyl titanate, lead acetate and zirconium dioxide as raw materials, controlling the mass ratio of zirconium to titanium to be 50-54:46-50, adding the butyl titanate, the lead acetate and the zirconium dioxide into a solvent consisting of deionized water, ethylene glycol, diethyl ether and methyl ether, heating and stirring for 3-4h to obtain lead zirconate titanate sol, drying for 6-8h, removing water and an organic solvent to form dry gel, calcining, cooling and taking out to obtain lead zirconate titanate superfine ceramic powder.
The lead zirconate titanate superfine ceramic prepared by the invention has electric functions such as dielectricity, piezoelectricity, ferroelectricity, pyroelectric property and the like, has high Curie point, small relative dielectric constant and large pyroelectric constant, has great anisotropy between transverse and longitudinal electromechanical coupling coefficients, and is very suitable for manufacturing high-frequency transducers.
(2) Preparing a zinc oxide nanorod array: and (2) adopting an electrochemical deposition method, adopting a two-electrode system, taking a zinc nitrate solution as an electrolyte, placing the electrolyte in a water bath at a constant temperature of 70-80 ℃, connecting the cut zinc foil and the conductive glass as an anode and a cathode of the electrodeposition respectively into a circuit for electrodeposition, taking out the conductive glass after the deposition is finished, and cleaning and drying the conductive glass by using deionized water to obtain the zinc oxide nanorod array.
Electrodeposition refers to the process of electrochemical deposition of a metal or alloy from an aqueous solution, non-aqueous solution or molten salt of its compound, which is carried out under certain electrolyte and operating conditions, and the ease of metal electrodeposition and the morphology of the deposit are related to the properties of the deposited metal and also depend on the composition of the electrolyte, pH, temperature, current density, and other factors.
(3) Preparing a zinc oxide nanorod array die coated with lead zirconate titanate: adding lead zirconate titanate superfine ceramic powder into a polyethylene glycol solution, carrying out ultrasonic treatment for 10-15 minutes, adding a zinc oxide nano-rod array, reacting for 2-3 hours at the temperature of 120-135 ℃, taking out the zinc oxide nano-rod array, carrying out air drying and cooling by using a nitrogen gun, and finally impressing the zinc oxide nano-rod array into a toughening mold through a coining machine to obtain the lead zirconate titanate coated zinc oxide nano-rod array mold.
When the zinc oxide is doped with transition metal or rare earth metal, the zinc oxide can show ferroelectric property, and simultaneously, the zinc oxide also has thermoelectric effect and chemical sensing characteristics and can be used for sensors and detectors.
(4) Preparation of the polymer substrate: dispersing a styrene-butadiene-styrene block copolymer in an acetone solution, adding epoxy resin, heating and stirring for 30-40 minutes, ball-milling a mixture of the styrene-butadiene-styrene block copolymer and the epoxy resin at the rotation speed of 100-300rpm for 7-9 hours, and then condensing, refluxing and evaporating the uniformly dispersed mixture at 80-85 ℃ to remove the acetone.
The lead zirconate titanate/polymer composite material is a novel functional piezoelectric material, and the dielectric and piezoelectric properties of the composite material are closely related to the composition and percentage ratio of each component of the composite material and the communication mode of two-phase materials. The hard and brittle characteristics of lead zirconate titanate make molding difficult, make it impossible to obtain any shape, and have poor impact resistance, which severely limits its application. Some high molecular materials have good flexibility and can be made into large and uniform films, but the piezoelectric coefficient and the electromechanical coupling coefficient of the high molecular materials are small, and the temperature characteristic and the aging characteristic have problems. The invention can prepare the composite material with certain piezoelectric property after compounding the lead zirconate titanate and the polymer material, overcomes the defects of the lead zirconate titanate and the polymer material, has strong piezoelectric property, low brittleness, low density and low dielectric coefficient, is easy to prepare large-area sheets and products with complex shapes, and has simple manufacturing process and low cost.
(5) Preparation of polymer-based composite material: uniformly mixing the mixture without the acetone with a curing agent, freezing and defoaming at-20-30 ℃ for 20-30 minutes, injecting into a zinc oxide nanorod array mold coated with lead zirconate titanate, and curing at 100-130 ℃ for 70-90 minutes to obtain the polymer-based composite material.
(6) And (3) polarization treatment: after covering electrodes on the upper and lower surfaces of the polymer-based composite material, applying a polarizing electric field of 50-60kV/cm for 40-50 minutes at a polarizing temperature of 90-100 ℃, and polarizing under the condition to ensure that the polymer-based composite material has piezoelectric property, thereby obtaining a finished product.
Polarization is one of the key processes for preparing piezoelectric composite materials, the non-polarized composite materials almost have no piezoelectricity, electrodes are coated on the upper surface and the lower surface of the composite materials, a high direct current electric field is applied at a proper temperature, and the composite materials can have the maximum polarization strength after a certain time. Therefore, in order to make the piezoelectric composite material have high polarization strength and fully exert the potential piezoelectricity, the polarization conditions, namely the polarization electric field, the polarization temperature and the polarization time, must be reasonably selected.
Preferably, in the step (1), the solid-to-liquid ratio of the raw material to the solvent is 10-15mg/80-100 mL.
Preferably, in the step (1), the drying temperature is 70-80 ℃; the calcination temperature is 600-700 ℃, the heat preservation time is 3-4h, and the temperature rising speed is 5 ℃/min.
Preferably, in the step (2), the concentration of the zinc nitrate solution is 0.002-0.2M.
Preferably, in the step (2), the current is controlled to be 0.9-1.1mA during the electrochemical deposition, the deposition is started, and the electrochemical deposition is finished after 4-6 h.
Preferably, in the step (2), the size of the zinc foil and the conductive glass is 4 x 4mm, and the zinc foil and the conductive glass are repeatedly cleaned by ultrasonic waves for 3-4 times by using deionized water and absolute ethyl alcohol.
Preferably, in the step (3), the polyethylene glycol has an average molecular weight of 300.
Preferably, in the step (4), the amount of the styrene-butadiene-styrene block copolymer is 0.06 to 0.07g, the amount of the acetone solution is 100-125mL, and the amount of the epoxy resin is 1.4 to 2.3g, in g and mL.
Preferably, in step (5), the molar ratio of epoxy value of the epoxy resin to the curing agent in the acetone-removed mixture is =1: 0.7.
Preferably, in the step (6), the electrode is a metal platinum electrode.
Compared with the prior art, the invention has the beneficial effects that:
1. the piezoelectric sensor is prepared by the lead zirconate titanate/polymer composite material, the polymer substrate is prepared by blending the epoxy resin and the styrene-butadiene-styrene segmented copolymer, the obtained high polymer material has good flexibility, can be prepared into a large and uniform film, has small piezoelectric coefficient and electromechanical coupling coefficient, is prepared into the composite material with certain piezoelectric property after being compounded, overcomes the defects of the two materials, has strong piezoelectric property, low brittleness, low density and low dielectric coefficient, is easy to prepare large-area sheets and products with complex shapes, and has simple manufacturing process and low cost.
2. The nanorod array is prepared from lead zirconate titanate ultrafine ceramic powder and zinc oxide, so that the contact specific surface area is increased, the zinc oxide has excellent thermoelectric effect and chemical sensing property, and the application range of the sensor is expanded.
3. Lead zirconate titanate/polymer composites were prepared using die casting techniques with electrodes on the top and bottom for final poling.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Preparing lead zirconate titanate superfine ceramic powder: taking butyl titanate, lead acetate and zirconium dioxide as raw materials, taking the raw materials as 10mg, controlling the mass ratio of zirconium to titanium to be 52:48, taking a mixed solution of deionized water, ethylene glycol, ether and methyl ether as a solvent, heating and stirring for 3h, uniformly stirring to obtain lead zirconate titanate sol, drying the lead zirconate titanate sol in a drying oven at the temperature of 70 ℃ for 8h, removing water and an organic solvent to form dry gel, putting the dry gel into a muffle furnace for calcining, heating the muffle furnace to 700 ℃, keeping the temperature for 4h at the temperature of 5 ℃/min, cooling and taking out to obtain the lead zirconate titanate superfine ceramic powder.
(2) Preparing a zinc oxide nano rod: using an electrochemical deposition method, adopting a two-electrode system, taking a zinc nitrate solution as an electrolyte, placing the electrolyte in a water bath kettle at a constant temperature of 70 ℃, enabling the concentration of the zinc nitrate solution to be 0.2M, respectively taking cut zinc foils and conductive glass as an anode and a cathode of the electrodeposition, connecting the zinc foils and the conductive glass into a circuit for electrodeposition, enabling the sizes of the zinc foils and the conductive glass to be 4 x 4mm, and repeatedly cleaning the zinc foils and the conductive glass by deionized water and absolute ethyl alcohol for 3 times by ultrasonic. And controlling the current to be 0.9mA in the electrochemical deposition process, starting the deposition, finishing the electrochemical deposition after 4 hours, and after the deposition is finished, taking out the conductive glass, cleaning with deionized water and drying to obtain the zinc oxide nanorod array.
(3) Preparing a zinc oxide nanorod array die coated with lead zirconate titanate: and (2) adding the lead zirconate titanate superfine ceramic powder obtained in the step (1) into a polyethylene glycol solution, carrying out ultrasonic treatment for 10 minutes, immersing the zinc oxide nanorod array obtained in the step (2) into the mixed solution, putting the zinc oxide nanorod array into a 120-DEG C drying oven for reaction for 2 hours, taking out the nanorod array, air-drying and cooling the nanorod array by using a nitrogen gun, and finally, impressing the zinc oxide nanorod array into a customized tempering mold through a coining press to obtain the lead zirconate titanate coated zinc oxide nanorod array mold.
(4) Preparation of the polymer substrate: styrene-butadiene-styrene block copolymer powder was dispersed in an appropriate amount of acetone solution (100 mL, 60mg of styrene-butadiene-styrene block copolymer powder). Then 1.4 g of epoxy resin was added, and stirred under heating for 30 minutes, and the mixture of styrene-butadiene-styrene block copolymer and epoxy resin was ball-milled for 7 hours at 100rpm using a ball-milling disperser, and then the uniformly dispersed mixture was condensed, refluxed and evaporated at 80 ℃ to remove acetone.
(5) Preparation of polymer-based composite material: uniformly mixing the mixture subjected to acetone removal and a curing agent in proportion, wherein the epoxy value of the epoxy resin is as follows: curing agent molar weight =1: 0.7. Freezing and defoaming at-20 ℃ for 20 minutes, injecting into the mold containing the lead zirconate titanate coated zinc oxide nanorod array in the step (3), and curing at 100-130 ℃ for 70 minutes.
(6) And (3) polarization treatment: after the upper and lower surfaces of the composite material are covered with electrodes, the electrodes are metal platinum electrodes, and a polarization electric field of 50kV/cm is applied at a polarization temperature of 90 ℃ for 40 minutes, so that the composite material is polarized under the condition to have piezoelectric performance.
Example 2
(1) Preparing lead zirconate titanate superfine ceramic powder: taking butyl titanate, lead acetate and zirconium dioxide as raw materials, taking the raw materials as 13mg, controlling the mass ratio of zirconium to titanium to be 52:48, taking a mixed solution of deionized water, ethylene glycol, ether and methyl ether as a solvent, heating and stirring for 3h, uniformly stirring to obtain lead zirconate titanate sol, drying the lead zirconate titanate sol in a drying oven at the temperature of 75 ℃ for 7h, removing water and an organic solvent to form dry gel, putting the dry gel in a muffle furnace for calcining, heating the muffle furnace to 650 ℃, keeping the temperature for 3h at the temperature of 5 ℃/min, cooling and taking out to obtain the lead zirconate titanate superfine ceramic powder.
(2) Preparing a zinc oxide nano rod: using an electrochemical deposition method, adopting a two-electrode system, taking a zinc nitrate solution as an electrolyte, placing the electrolyte in a water bath kettle at a constant temperature of 75 ℃, enabling the concentration of the zinc nitrate solution to be 0.012M, respectively connecting cut zinc foils and conductive glass as an anode and a cathode of the electrodeposition to be connected into a circuit for electrodeposition, enabling the sizes of the zinc foils and the conductive glass to be 4 x 4mm, and repeatedly cleaning the zinc foils and the conductive glass by deionized water and absolute ethyl alcohol for 3 times by ultrasonic. And controlling the current to be 1.0mA in the electrochemical deposition process, starting deposition, finishing the electrochemical deposition after 5 hours, and after the deposition is finished, taking out the conductive glass, cleaning with deionized water, and drying to obtain the zinc oxide nanorod array.
(3) Preparing a zinc oxide nanorod array die coated with lead zirconate titanate: and (2) adding the lead zirconate titanate superfine ceramic powder obtained in the step (1) into a polyethylene glycol solution, carrying out ultrasonic treatment for 13 minutes, immersing the zinc oxide nanorod array obtained in the step (2) into the mixed solution, putting the zinc oxide nanorod array into a 130-DEG C drying oven for reaction for 2 hours, taking out the nanorod array, air-drying and cooling the nanorod array by using a nitrogen gun, and finally, impressing the zinc oxide nanorod array into a customized tempering mold through a coining press to obtain the lead zirconate titanate coated zinc oxide nanorod array mold.
(4) Preparation of the polymer substrate: styrene-butadiene-styrene block copolymer powder was dispersed in an appropriate amount of acetone solution (180 mL, 65mg of styrene-butadiene-styrene block copolymer powder). Then 1.8g of epoxy resin was added, and stirred under heating for 35 minutes, and the mixture of styrene-butadiene-styrene block copolymer and epoxy resin was ball-milled with a ball-milling disperser at 225rpm for 8 hours, and then the uniformly dispersed mixture was condensed, refluxed and evaporated at 84 ℃ to remove acetone.
(5) Preparation of polymer-based composite material: uniformly mixing the mixture subjected to acetone removal and a curing agent in proportion, wherein the epoxy value of the epoxy resin is as follows: curing agent molar weight =1: 0.7. Freezing and defoaming at minus 25 ℃ for 25 minutes, injecting into the mold provided with the lead zirconate titanate coated zinc oxide nano-rod array in the step (3), and curing at 100-130 ℃ for 80 minutes.
(6) And (3) polarization treatment: after the upper and lower surfaces of the composite material are covered with electrodes, the electrodes are metal platinum electrodes, and a polarization electric field of 55kV/cm is applied at a polarization temperature of 96 ℃, the polarization time is 45 minutes, and the electrodes are polarized under the condition, so that the composite material has piezoelectric performance.
Example 3
(1) Preparing lead zirconate titanate superfine ceramic powder: the method comprises the steps of taking butyl titanate, lead acetate and zirconium dioxide as raw materials, controlling the mass ratio of zirconium to titanium to be 52:48, taking a mixed solution of deionized water, ethylene glycol, ether and methyl ether as a solvent, heating and stirring for 4 hours, uniformly stirring to obtain lead zirconate titanate sol, drying the lead zirconate titanate sol in an oven at the temperature of 80 ℃ for 6 hours, removing water and an organic solvent to form dry gel, putting the dry gel into a muffle furnace for calcination, heating the muffle furnace to 700 ℃, keeping the temperature for 4 hours at the temperature rising speed of 5 ℃/min, cooling and taking out to obtain the lead zirconate titanate superfine ceramic powder.
(2) Preparing a zinc oxide nano rod: using an electrochemical deposition method, adopting a two-electrode system, taking a zinc nitrate solution as an electrolyte, placing the electrolyte in a water bath kettle at a constant temperature of 70 ℃, enabling the concentration of the zinc nitrate solution to be 0.002M, respectively taking the cut zinc foil and conductive glass as an anode and a cathode of the electrodeposition, connecting the zinc foil and the conductive glass into a circuit for electrodeposition, enabling the size of the zinc foil and the conductive glass to be 4 x 4mm, and repeatedly cleaning the zinc foil and the conductive glass by deionized water and absolute ethyl alcohol for 3 times by ultrasonic. And controlling the current to be 1.1mA in the electrochemical deposition process, starting deposition, finishing the electrochemical deposition after 6 hours, and after the deposition is finished, taking out the conductive glass, cleaning with deionized water and drying to obtain the zinc oxide nanorod array.
(3) Preparing a zinc oxide nanorod array die coated with lead zirconate titanate: and (2) adding the lead zirconate titanate superfine ceramic powder obtained in the step (1) into a polyethylene glycol solution, carrying out ultrasonic treatment for 15 minutes, immersing the zinc oxide nanorod array obtained in the step (2) into the mixed solution, putting the zinc oxide nanorod array into a 120-DEG C drying oven for reaction for 3 hours, taking out the nanorod array, air-drying and cooling the nanorod array by using a nitrogen gun, and finally, impressing the zinc oxide nanorod array into a customized tempering mold through a coining press to obtain the lead zirconate titanate coated zinc oxide nanorod array mold.
(4) Preparation of the polymer substrate: styrene-butadiene-styrene block copolymer powder was dispersed in an appropriate amount of acetone solution (125 mL, 70mg of styrene-butadiene-styrene block copolymer powder). Then 2.3g of epoxy resin was added, and under heating and stirring for 40 minutes, the styrene-butadiene-styrene block copolymer and epoxy resin mixture was ball-milled for 7 hours at 300rpm using a ball-milling disperser, and then the uniformly dispersed mixture was condensed, refluxed and evaporated at 85 ℃ to remove acetone.
(5) Preparation of polymer-based composite material: uniformly mixing the mixture subjected to acetone removal and a curing agent in proportion, wherein the epoxy value of the epoxy resin is as follows: curing agent molar weight =1: 0.7. Freezing and defoaming at-20 ℃ for 30 minutes, injecting into the mold containing the lead zirconate titanate coated zinc oxide nanorod array in the step (3), and curing at 130 ℃ for 90 minutes.
(6) And (3) polarization treatment: after the upper and lower surfaces of the composite material are covered with electrodes, the electrodes are metal platinum electrodes, and under the condition that the polarization temperature is 100 ℃, the polarization electric field is applied to the electrodes at 60kV/cm and the polarization time is 50 minutes, polarization is carried out under the condition, so that the composite material has piezoelectric performance.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a polymer-based composite flexible piezoelectric sensor is characterized by comprising the following steps:
(1) preparing lead zirconate titanate superfine ceramic powder: taking butyl titanate, lead acetate and zirconium dioxide as raw materials, controlling the mass ratio of zirconium to titanium to be 50-54:46-50, adding the butyl titanate, the lead acetate and the zirconium dioxide into a solvent consisting of deionized water, ethylene glycol, diethyl ether and methyl ether, heating and stirring for 3-4h to obtain lead zirconate titanate sol, drying for 6-8h, removing water and an organic solvent to form dry gel, calcining, cooling and taking out to obtain lead zirconate titanate superfine ceramic powder;
(2) preparing a zinc oxide nanorod array: using an electrochemical deposition method, adopting a two-electrode system, taking a zinc nitrate solution as an electrolyte, placing the electrolyte in a water bath at a constant temperature of 70-80 ℃, connecting the cut zinc foil and the conductive glass as an anode and a cathode of the electrodeposition respectively into a circuit for electrodeposition, taking out the conductive glass after the electrodeposition is finished, and cleaning and drying the conductive glass by using deionized water to obtain a zinc oxide nanorod array;
(3) preparing a zinc oxide nanorod array die coated with lead zirconate titanate: adding the lead zirconate titanate superfine ceramic powder prepared in the step (1) into a polyethylene glycol solution, carrying out ultrasonic treatment for 10-15 minutes, adding the zinc oxide nano-rod array prepared in the step (2), reacting at the temperature of 120-135 ℃ for 2-3 hours, taking out the zinc oxide nano-rod array, air-drying and cooling by using a nitrogen gun, and finally, impressing the zinc oxide nano-rod array into a toughening mold through a coining machine to obtain a lead zirconate titanate coated zinc oxide nano-rod array mold;
(4) preparation of the polymer substrate: dispersing a styrene-butadiene-styrene block copolymer in acetone, adding epoxy resin, heating and stirring for 30-40 minutes, ball-milling a mixture of the styrene-butadiene-styrene block copolymer and the epoxy resin at the rotating speed of 100-300rpm for 7-9 hours, and then condensing, refluxing and evaporating the uniformly dispersed mixture at 80-85 ℃ to remove the acetone;
(5) preparation of polymer-based composite material: uniformly mixing the mixture subjected to acetone removal and prepared in the step (4) with a curing agent, freezing and defoaming at-20-30 ℃ for 20-30 minutes, injecting into the lead zirconate titanate coated zinc oxide nanorod array mold prepared in the step (3), and curing at 100-130 ℃ for 70-90 minutes to obtain a polymer matrix composite;
(6) and (3) polarization treatment: and (3) covering electrodes on the upper and lower surfaces of the polymer matrix composite material prepared in the step (5), applying a polarization electric field of 50-60kV/cm for 40-50 minutes at a polarization temperature of 90-100 ℃, and polarizing under the condition to ensure that the polymer matrix composite material has piezoelectric property to prepare a finished product.
2. The method for preparing a polymer-based composite flexible piezoelectric sensor according to claim 1, wherein in the step (1), the solid-to-liquid ratio of the raw material to the solvent is 10-15mg/80-100 mL.
3. The method for preparing a polymer matrix composite flexible piezoelectric sensor according to claim 1, wherein in the step (1), the drying temperature is 70-80 ℃; the calcination temperature is 600-700 ℃, the heat preservation time is 3-4h, and the temperature rising speed is 5 ℃/min.
4. The method for preparing a polymer matrix composite flexible piezoelectric sensor according to claim 1, wherein in the step (2), the concentration of the zinc nitrate solution is 0.002-0.2M.
5. The method for preparing a polymer matrix composite flexible piezoelectric sensor according to claim 1, wherein in the step (2), the current is controlled to be 0.9-1.1mA in the electrochemical deposition process, the deposition is started, and the electrochemical deposition is finished after 4-6 h.
6. The method according to claim 1, wherein in the step (2), the zinc foil and the conductive glass have a size of 4 x 4mm, and are repeatedly cleaned with deionized water and absolute ethanol for 3 to 4 times by ultrasonic cleaning.
7. The method of claim 1, wherein in step (3), the polyethylene glycol has an average molecular weight of 300.
8. The method for preparing a polymer-based composite flexible piezoelectric sensor according to claim 1, wherein in the step (4), the amount of the styrene-butadiene-styrene block copolymer is 0.06-0.07g, the amount of acetone is 100-125mL, and the amount of the epoxy resin is 1.4-2.3g, in terms of g and mL.
9. The method according to claim 1, wherein in the step (6), the electrode is a platinum electrode.
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