CN117042582B - Self-supporting stretchable piezoelectric film, ultrasonic sensor and preparation method of ultrasonic sensor - Google Patents
Self-supporting stretchable piezoelectric film, ultrasonic sensor and preparation method of ultrasonic sensor Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/48—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using wave or particle radiation means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
- H10N30/302—Sensors
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Abstract
The invention discloses a self-supporting stretchable piezoelectric film, an ultrasonic sensor and a preparation method thereof, wherein the self-supporting stretchable piezoelectric film comprises a piezoelectric active phase of a self-supporting flexible sponge structure and a three-dimensional communicated elastic phase; the self-supporting stretchable piezoelectric film can be used as a core element of a self-supporting stretchable ultrasonic sensor, and an additional matching layer composite material is not needed for acoustic impedance matching. The self-supporting stretchable ultrasonic sensor can be applied to the fields of ultrasonic detection, ultrasonic imaging and the like, can be self-adaptive to the surface profile of an object to be detected with a complex shape, is beneficial to ensuring the consistency of the distance from the ultrasonic sensor to the surface of the object to be detected, can effectively inhibit the conditions of acoustic energy reflection, waveform distortion and the like, and can obtain a relatively accurate ultrasonic detection or high ultrasonic imaging result with relatively high quality.
Description
Technical Field
The invention relates to the technical field of ultrasonic detection and ultrasonic imaging, in particular to a self-supporting stretchable piezoelectric film applied to an ultrasonic detection and ultrasonic imaging system, an ultrasonic sensor and a preparation method thereof.
Background
Because of the noninvasive, high-precision, high-sensitivity and strong penetrating power of ultrasonic detection and ultrasonic imaging technologies, the ultrasonic detection and ultrasonic imaging technology has been widely applied to a plurality of fields such as industrial nondestructive detection, life health monitoring and material analysis. However, most of the ultrasonic sensors developed at present are rigid sensors with flat bottoms, the sensors can be in parallel interface contact with a plane sample to be measured, and most of the rigid sensors are provided with an acoustic matching layer at the front end of the sensor to realize acoustic matching between the sample to be measured and the sensor, and the requirements on the thickness of the matching layer are high (the acoustic wave transmission efficiency is high when the thickness of the matching layer is generally 0.25λ), but the manufacturing process of the sensor is obviously complicated. In addition, the rigid planar sensor cannot achieve good interface contact with the irregular non-planar sample to be measured, and a large amount of couplant is often required to eliminate the air gap between the sensor and the sample to be measured. The use of the couplant can significantly suppress or even cancel out a significant amount of energy loss in the response echo in the ultrasonic signal and the transmission of the acoustic wave between interfaces, making it difficult to further improve the accuracy of the final detection result.
Thus, the preparation of flexible stretchable ultrasonic sensors is an important ring for improving the test accuracy of samples to be tested having irregular contours. The flexible stretchable piezoelectric film, which is a core element of the flexible stretchable ultrasonic sensor, is also a hot spot and a difficult point in research in recent years. The stretchable ultrasonic sensor and the stretchable piezoelectric film developed at present are mostly provided with stretchable properties by mechanical structural design, for example, they are designed into a spring shape, a spiral shape, a fold shape and the like. The tensile property endowed by the mechanical structure design is often limited, and phenomena such as active structure collapse and the like easily occur after multiple times of stretching, so that the ultrasonic sensor is invalid.
Meanwhile, inorganic piezoelectric phase particles in the existing flexible piezoelectric composite film are easy to agglomerate, the interfacial bonding force of the inorganic phase and the organic phase is relatively limited, the inherent stretching performance of the existing flexible piezoelectric film is poor, a piezoelectric active structure collapses due to repeated stretching, and the consistency of the interfacial distance between a non-stretchable ultrasonic sensor and an irregular sample to be measured is poor, so that huge acoustic energy reflection and waveform distortion can be caused due to air gaps or poor contact generated at the interface.
Therefore, it is necessary to prepare a self-supporting stretchable piezoelectric film and an ultrasonic sensor to cope with ultrasonic detection of an irregularly contoured object to be detected.
Disclosure of Invention
Aiming at the defects in the prior art and solving the technical problems, the application provides a self-supporting stretchable piezoelectric film, an ultrasonic sensor and a preparation method thereof.
According to a first aspect of an embodiment of the present invention, there is provided a self-supporting stretchable piezoelectric film, including a piezoelectric active phase of a self-supporting flexible sponge structure and a three-dimensionally connected elastic phase; the piezoelectric active phase is formed by compositing an organic piezoelectric phase, a conductive phase with a functional group and an inorganic piezoelectric phase with a chemically modified surface; the elastic phase is formed by compositing elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles with chemically modified surfaces.
According to a second aspect of an embodiment of the present invention, there is provided a method for preparing a self-supporting stretchable piezoelectric film, the method comprising: preparing a piezoelectric active phase of the self-supporting flexible sponge structure based on a sacrificial template method; bonding the piezoelectric active phase of the self-supporting flexible sponge structure on a glass sheet, and placing the glass sheet into a mold; preparing inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified; mixing uncured elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles with chemically modified surfaces, and carrying out ultrasonic stirring to disperse the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces and induce the surface active structures of the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces to fully generate molecular bridge entanglement with elastic non-piezoelectric active phase molecules so as to obtain precursor solution of the three-dimensional communicated elastic phase; pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into pores of a piezoelectric active phase of a self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and a glass sheet, and carrying out hot pressing, curing and forming to obtain the self-supporting stretchable piezoelectric film.
According to a third aspect of embodiments of the present invention, there is provided a self-supporting stretchable ultrasonic sensor comprising a self-supporting stretchable piezoelectric film and stretchable electrodes composited on two opposite surfaces of the piezoelectric film.
According to a fourth aspect of embodiments of the present invention there is provided the use of a self-supporting stretchable ultrasound sensor in ultrasound detection or ultrasound imaging.
The technical scheme provided by the embodiment of the application can comprise the following beneficial effects: (1) The self-supporting stretchable piezoelectric film provided by the embodiment of the invention has excellent inherent stretching performance, and the structure of the self-supporting stretchable piezoelectric film is not required to be designed into a fold-shaped or spiral-shaped structure and the like, so that the performance and the structure of the self-supporting stretchable piezoelectric film are still kept relatively intact after multiple stretching.
(2) The self-supporting stretchable piezoelectric film provided by the invention has higher piezoelectric performance, higher electromechanical coupling performance, lower acoustic impedance and excellent stretching performance. The stretchable piezoelectric film with excellent performance effectively solves the technical problems that inorganic piezoelectric phase particles in the existing flexible piezoelectric composite film are easy to agglomerate and the interfacial binding force between the inorganic phase and the organic phase is relatively limited by forming strong chemical bond coupling between the organic phase and the inorganic phase. The stretchable piezoelectric film with excellent performance can avoid the problem of poor consistency of interface distances between the sensor and the surface of an irregular sample to be detected caused by the inextensibility of the ultrasonic sensor, and further cause acoustic energy reflection and waveform distortion, thereby generating unreliable detection results; the stretchable piezoelectric film has lower acoustic impedance, can avoid the phenomenon that small echoes are remarkably counteracted due to the high-pass filtering effect of ultrasonic signals caused by using a large amount of couplant, can effectively reduce energy loss in the acoustic wave transmission process, and improves the sensitivity of the sensor.
(3) The self-supporting stretchable piezoelectric film provided by the invention can be used as a core element of a self-supporting stretchable ultrasonic sensor, and an additional matching layer composite material is not needed for acoustic impedance matching. The self-supporting stretchable ultrasonic sensor can be applied to the fields of ultrasonic detection, ultrasonic imaging and the like, can be self-adaptive to the surface profile of an object to be detected with a complex shape, is beneficial to ensuring the consistency of the distance from the ultrasonic sensor to the surface of the object to be detected, can effectively inhibit the conditions of acoustic energy reflection, waveform distortion and the like, and can obtain a relatively accurate ultrasonic detection or high ultrasonic imaging result with relatively high quality.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
Fig. 1 is a schematic flow chart of a method for preparing a self-supporting stretchable piezoelectric film according to an embodiment of the present invention.
Fig. 2 is a schematic flow chart of a process for preparing a piezoelectric active phase of a self-supporting flexible sponge structure based on a sacrificial template method according to an embodiment of the present invention.
Fig. 3 is a schematic flow chart of preparing surface chemically modified inorganic piezoelectric phase heterojunction particles according to an embodiment of the present invention.
FIG. 4 is a graph showing the retention of piezoelectric strain constants at different stretching ratios for a self-supporting stretchable piezoelectric film according to an exemplary embodiment.
FIG. 5 is a graph illustrating a signal amplitude rate versus peak response hold rate for a self-supporting stretchable ultrasonic sensor at different stretching times, according to an exemplary embodiment.
Detailed Description
The invention provides a self-supporting stretchable piezoelectric film, an ultrasonic sensor and a preparation method thereof, which are described in detail below with reference to the accompanying drawings. The features of the examples and embodiments described below may be combined with each other without conflict.
The embodiment of the invention provides a self-supporting stretchable piezoelectric film, which comprises a piezoelectric active phase of a self-supporting flexible sponge structure and an elastic phase of a load. The piezoelectric active phase of the self-supporting flexible sponge structure is provided with a three-dimensional communicated pore structure; the three-dimensional communicated elastic phase is loaded in the pore of the piezoelectric active phase with the self-supporting sponge structure; the volume percentage of the piezoelectric active phase of the self-supporting flexible sponge structure is 8-25%, and the volume percentage of the elastic phase is 75-92%.
The piezoelectric active phase of the self-supporting flexible sponge structure has low surface energy and a rough surface structure, and can better adsorb and compound the elastic phase; the piezoelectric active phase of the self-supporting flexible sponge structure has a three-dimensional communicated pore structure, and has higher porosity and can load a large amount of elastic phases. The elastic phase has a three-dimensional communication structure and has excellent elasticity, piezoelectric property and electromechanical coupling property.
The self-supporting stretchable piezoelectric film has higher piezoelectric performance, higher electromechanical coupling performance and lower acoustic impedance, and an additional acoustic impedance matching layer is not required to be prepared when the ultrasonic sensor is prepared, so that the performance consistency in the development process of the ultrasonic sensor can be improved, the preparation process of the ultrasonic sensor is simplified, and more accurate detection results are expected to be obtained.
The piezoelectric active phase of the self-supporting flexible sponge structure is formed by compounding an organic piezoelectric phase, a conductive phase with a functional group and an inorganic piezoelectric phase with a chemically modified surface; the mass percentage of the organic piezoelectric phase in the piezoelectric active phase of the self-supporting flexible sponge structure is 20-50wt%, the mass percentage of the conductive phase with the functional group is 2-5wt%, and the mass percentage of the inorganic piezoelectric phase after surface chemical modification is 45-75wt%.
Further, the organic piezoelectric phase may be selected from PVDF, P (VDF-TrFE), and the like; the conductive phase with functional groups can be selected from carboxylated or hydroxylated multiwall carbon nanotubes, reduced graphene oxide and the like; the inorganic piezoelectric phase may be selected from PZT, barium titanate, PLZT, and the like.
The introduction of the conductive phase with the functional group has the following beneficial effects: firstly, the conductive phase with functional groups can form a plurality of submicron structures, so that the prepared piezoelectric active phase with the self-supporting flexible sponge structure has lower surface energy and higher roughness, the piezoelectric active phase with the sponge structure and the elastic non-piezoelectric active phase which is communicated in three dimensions can be compounded more tightly without air gaps and the like, and the finally prepared stretchable piezoelectric film has excellent stretching life and excellent acoustic impedance performance in consistency; secondly, the introduction of the conductive phase can reduce the overall polarization voltage of the self-supporting stretchable piezoelectric film, is favorable for enabling the polarization of the composite piezoelectric film to be more sufficient when the polarization voltage is lower, and shows more excellent piezoelectric performance and electromechanical coupling performance; thirdly, the conductive phase with the functional group can form a hydrogen bond with the organic piezoelectric phase to guide the orientation arrangement of the organic piezoelectric phase in the solidification and crystallization process, so that the crystallinity of the organic piezoelectric phase and the content of beta phase are improved, and the piezoelectric performance and the electromechanical coupling performance of the self-supporting stretchable piezoelectric film are improved; fourth, the conductive phase with functional group can be connected with the inorganic piezoelectric material with surface chemically modified through chemical bond, which can effectively avoid agglomeration phenomenon and greatly improve the binding force between each item.
The inorganic piezoelectric phase with the surface chemically modified in the piezoelectric active phase of the self-supporting flexible sponge structure and the conductive phase with the functional group are dispersed in the organic piezoelectric phase in a 0-dimensional mode.
The inorganic piezoelectric phases in the piezoelectric active phases are subjected to surface chemical modification so as to perform bridging action and further improve the compatibility between inorganic piezoelectric phase particles and organic piezoelectric phases, and the surface active structures of the inorganic piezoelectric phases subjected to surface chemical modification can fully generate molecular bridge entanglement with organic piezoelectric phase molecules, namely, the inorganic piezoelectric phases are connected with the organic piezoelectric phases in a chemical bond mode through modification bridges, so that the interfacial bonding force of the inorganic piezoelectric phases and the organic piezoelectric phases can be effectively improved, and the bonding force is far greater than Van der Waals acting force between the organic piezoelectric phases in other composite materials; the inorganic piezoelectric phase heterojunction particles in the three-dimensional communicated elastic phase are subjected to surface chemical modification so as to perform bridging action and further improve the compatibility between the inorganic piezoelectric phase heterojunction particles and the elastic non-piezoelectric active phase, and the surface active structure of the inorganic piezoelectric phase heterojunction particles subjected to surface chemical modification can fully generate molecular bridge entanglement with the elastic non-piezoelectric active phase molecules, namely the inorganic piezoelectric phase heterojunction particles and the elastic non-piezoelectric active phase are connected in a chemical bond mode through a modified bridge, so that the interfacial bonding force between the inorganic piezoelectric phase heterojunction particles and the elastic non-piezoelectric active phase can be effectively improved, and the bonding force is far greater than Van der Waals force between the inorganic piezoelectric phase heterojunction particles and the elastic non-piezoelectric active phase in other composite materials.
The three-dimensional connected elastic phase is formed by compositing an elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles subjected to surface chemical modification, wherein the mass percentage of the elastic non-piezoelectric active phase in the three-dimensional connected elastic phase is 40-55wt%, and the mass percentage of the inorganic piezoelectric phase heterojunction particles subjected to surface chemical modification is 45-60wt%.
Further, the elastic non-piezoelectric active phase may be selected from polydimethylsiloxane, polyurethane, and the like.
Further, the inorganic piezoelectric phase heterojunction particles after surface chemical modification are dispersed in the elastic non-piezoelectric active phase in a 0-dimensional mode.
The inorganic piezoelectric phases in the piezoelectric active phases are subjected to surface chemical modification so as to perform bridging action and further improve the compatibility between the inorganic piezoelectric phase particles and the organic piezoelectric phase; the inorganic piezoelectric phase heterojunction particles in the three-dimensional communicated elastic phase are subjected to surface chemical modification to perform bridging action so as to improve the compatibility between the inorganic piezoelectric phase heterojunction particles and the elastic non-piezoelectric active phase.
Further, the organic piezoelectric phase, the conductive phase with functional groups and the inorganic piezoelectric phase after surface chemical modification in the piezoelectric active phase and the elastic phase are connected in pairs by chemical bonds through the elastic non-piezoelectric active phase and the inorganic piezoelectric phase heterojunction particles after surface chemical modification.
The embodiment of the invention provides a preparation method of a self-supporting stretchable piezoelectric film, which is characterized in that a piezoelectric active phase of a self-supporting flexible sponge structure is prepared by a sacrificial template method, and then a three-dimensional communicated elastic phase is compounded, so that the self-supporting stretchable piezoelectric film is better in integration. According to the method, non-toxic, easily-obtained and extremely-good-water-solubility table salt is adopted as a sacrificial template, and the piezoelectric active phase with the self-supporting flexible sponge structure is finally prepared by compounding a mixture of organic piezoelectric phase powder, conductive phase powder with functional groups, inorganic piezoelectric phase powder with chemically-modified surfaces and table salt particles, and then removing the sacrificial table salt template. It is worth noting that when the sacrificial salt template is removed, the method directly adopts a method of dissolving salt by high-temperature deionized water, and any organic solvent is not used or released in the whole process, so that the method is simple, safer and environment-friendly.
As shown in fig. 1, the preparation method comprises the following steps: and step S1, preparing a piezoelectric active phase of the self-supporting flexible sponge structure based on a sacrificial template method. And the piezoelectric active phase of the self-supporting flexible sponge structure is adhered to the glass sheet and placed in a mold.
Specifically, as shown in fig. 2, the step S1 specifically includes the following substeps: and S101, dispersing inorganic piezoelectric phase particles in an ethanol solution of 1.2wt% of a silane coupling agent, magnetically stirring for 3 hours to uniformly disperse the inorganic piezoelectric phase particles, chemically modifying the surfaces of the inorganic piezoelectric phase particles completely, and then drying the inorganic piezoelectric phase particles in a drying oven at 40 ℃ for 5 hours to prepare the inorganic piezoelectric phase with the chemically modified surfaces. The silane coupling agent is selected from one of vinyl trimethoxy silane, 3-glycidol propoxy trimethoxy silane and 3-aminopropyl triethoxy silane.
Step S102, uniformly mixing an organic piezoelectric phase, a conductive phase with a functional group, an inorganic piezoelectric phase with a chemically modified surface and salt, and grinding to obtain mixed powder; wherein the mass of the salt is 7-10 times of the total mass of the organic piezoelectric phase, the conductive phase with functional groups and the inorganic piezoelectric phase with chemically modified surface.
And step S103, placing the mixed powder into a silicon dioxide boat, heating the mixed powder at a high temperature in a drying oven to obtain a molten composite solution, so that the surface active structure of the inorganic piezoelectric phase powder with the surface chemically modified surface, organic piezoelectric phase molecules and conductive phases with functional groups are fully entangled by molecular bridges, and closing the drying oven to cool to room temperature after the molten composite solution is solidified to obtain the solid composite material.
And step S104, polishing the surface of the solid composite material, and soaking the solid composite material at high temperature by deionized water to completely remove salt, thereby obtaining the piezoelectric active phase of the self-supporting flexible sponge structure.
Step S105, in the example, the piezoelectric active material of the self-supporting flexible sponge structure obtained in the step S104 is adhered to a glass sheet by using a polyimide high-temperature-resistant double-sided adhesive tape, and then the structure is covered by using a hollow cylindrical die with the length of more than 1 cm.
And S2, preparing the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
Specifically, as shown in fig. 3, the step S2 specifically includes the following substeps: and step S201, adding the inorganic piezoelectric phase particles into the metal nitrate aqueous solution, and stirring to uniformly disperse to obtain an inorganic piezoelectric/metal nitrate mixed solution. The aqueous metal nitrate solution concentration may be selected from 0.007 to 5 mol/L.
Step S202, dropwise adding a hydrazine hydrate solution into an inorganic piezoelectric/metal nitrate mixed solution until the solution is completely discolored from an initial color, and continuously stirring in a nitrogen atmosphere at room temperature to fully perform the reaction so as to obtain a mixed solution containing metal@inorganic piezoelectric phase chemical heterojunction particles. The hydrazine hydrate solution: the amount ratio of the solute of the metal nitrate may be selected from the range of 0.5 to 1.8. The concentration of the hydrazine hydrate solution is 88% of the aqueous solution of hydrazine hydrate by mass fraction.
In this example, the metal@inorganic piezoelectric phase chemical heterojunction particles are metal and inorganic piezoelectric phase composite chemical heterojunction particles, and the symbol "@" indicates that a strong chemical heterostructure is constructed between the conductive particles and the common inorganic piezoelectric phase.
And S203, separating out metal@inorganic piezoelectric phase chemical heterojunction particles by using a centrifugal machine, and washing and drying to obtain the inorganic piezoelectric phase heterojunction particles.
And S204, dispersing the inorganic piezoelectric phase heterojunction particles in an ethanol solution of 1wt% of a silane coupling agent, so that the surfaces of the inorganic piezoelectric phase particles are completely modified by chemical modification, and drying to obtain the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified. The silane coupling agent can be selected from one of vinyl trimethoxy silane, 3-glycidol propoxy trimethoxy silane and 3-aminopropyl triethoxy silane.
And S3, mixing uncured elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles with chemically modified surfaces, and carrying out ultrasonic stirring to disperse the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces and induce the surface active structures of the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces to fully generate molecular bridge entanglement with the elastic non-piezoelectric active phase molecules so as to obtain a precursor solution.
And S4, pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and the glass sheet, and obtaining the self-supporting stretchable piezoelectric film through hot pressing, curing and forming.
The embodiment of the invention also provides a self-supporting stretchable ultrasonic sensor, which comprises the self-supporting stretchable piezoelectric film and stretchable electrodes compounded on two opposite surfaces of the piezoelectric film.
Further, the self-supporting stretchable piezoelectric film can be used as a core element of a self-supporting stretchable ultrasonic sensor, and an additional matching layer composite material is not needed for acoustic impedance matching.
The embodiment of the invention also provides a preparation method of the self-supporting stretchable ultrasonic sensor, which comprises the following steps: and respectively coating silver nanowire networks on the upper side and the lower side of the self-supporting stretchable ultrasonic sensor, applying a direct current electric field to polarize the silver nanowire networks, and respectively leading out the electrode lugs from the electrode layers to obtain the self-supporting stretchable ultrasonic sensor.
Specifically, the method comprises the following steps: (1) Sodium polystyrene sulfonate aqueous solution, na 2 S 2 O 8 ，Fe 2 (SO 4 ) 3 Mixing with deionized water at room temperature under argon atmosphere, and stirring to disperse uniformly.
(2) And (3) adding the conductive powder into the solution obtained in the step (1), mixing and stirring at room temperature in an argon atmosphere until the conductive powder is uniformly dispersed. The conductive powder is selected from one or more of nano Ag particles, nano copper particles, hydroxylated or carboxylated carbon nanotubes and MXene; preferably, the conductive powder is selected from conductive powders with functional groups such as hydroxylated or carboxylated carbon nanotubes, MXene and the like.
(3) And (3) adding 3, 4-ethylenedioxythiophene into the mixed solution obtained in the step (2), and stirring at room temperature under argon atmosphere to finally obtain a dark blue poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate solution.
(4) Dissolving cellulose powder in deionized water, and stirring at high temperature until the cellulose powder is uniformly dispersed. The cellulose powder can be hydroxyethyl cellulose, carboxymethyl cellulose sodium salt and the like.
(5) Adding the poly (3, 4-ethylenedioxythiophene) obtained in the step (3) into the polystyrene sulfonate solution, dimethyl sulfoxide and glycerol, and stirring at high temperature until the poly (3, 4-ethylenedioxythiophene) is uniformly dispersed.
(6) And (3) coating the mixed solution obtained in the step (5) on two sides of the self-supporting stretchable piezoelectric film, drying at high temperature, curing and forming to obtain the sandwich structure of the stretchable electrode/the self-supporting stretchable piezoelectric film/the stretchable electrode.
(7) And (3) applying a direct current electric field to the sandwich structure of the stretchable electrode/the self-supporting stretchable piezoelectric film/the stretchable electrode in the step (6) for polarization, and then respectively leading out the electrode lugs from the electrode layers to obtain the stretchable ultrasonic sensor.
The embodiment of the invention also provides an application of the self-supporting stretchable ultrasonic sensor in ultrasonic detection or ultrasonic imaging. The self-supporting stretchable ultrasonic sensor can be self-adaptive to the surface profile of an object to be detected with a complex shape in the fields of ultrasonic detection, ultrasonic imaging and the like, is beneficial to ensuring the consistency of the distance from the ultrasonic sensor to the surface of the object to be detected, can effectively inhibit the conditions of acoustic energy reflection, waveform distortion and the like, and can obtain a relatively accurate ultrasonic detection or high ultrasonic imaging result with relatively high quality.
In summary, the self-supporting stretchable piezoelectric film provided by the invention comprises a piezoelectric active phase of a self-supporting flexible sponge structure and an elastic phase loaded in pores of the piezoelectric active phase; the elastic phase is formed by compositing elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles with chemically modified surfaces, wherein the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces are dispersed in the elastic non-piezoelectric active phase in a 0-dimensional mode; the surface chemically modified inorganic piezoelectric phase heterojunction particles can establish stronger electric coupling between the surface chemically modified inorganic piezoelectric phase particles and the organic elastic non-piezoelectric active phase, so that voltage distribution applied to a dispersing unit of the surface chemically modified inorganic piezoelectric phase particles in the self-supporting stretchable piezoelectric film is improved, the polarization degree of the surface chemically modified inorganic piezoelectric phase particles is greatly improved, and the piezoelectric performance and the electromechanical coupling performance of the self-supporting stretchable piezoelectric film are further improved.
The piezoelectric active phase is formed by compositing an organic piezoelectric phase, a conductive phase with a functional group and an inorganic piezoelectric phase with a chemically modified surface. The inorganic piezoelectric phase with the surface chemically modified and the conductive phase with the functional group are dispersed in the organic piezoelectric phase in a 0-dimensional mode, so that higher piezoelectric performance and electromechanical coupling performance can be provided for the composite material. The inorganic piezoelectric phases in the piezoelectric active phases are subjected to surface chemical modification so as to perform bridging action and further improve the compatibility between inorganic piezoelectric phase particles and organic piezoelectric phases, the surface active structures of the inorganic piezoelectric phases subjected to surface chemical modification can fully generate molecular bridge entanglement with organic piezoelectric phase molecules and conducting phases with functional groups, namely, the inorganic piezoelectric phases are connected with the organic piezoelectric phases and the conducting phases with the functional groups in a chemical bond mode through modification bridges, so that the interfacial bonding force between the inorganic piezoelectric phases and the organic piezoelectric phases can be effectively improved, the bonding force is far greater than Van der Waals force between the organic piezoelectric phases and the inorganic piezoelectric phases in other composite materials, and the agglomeration problem during dispersion of the inorganic piezoelectric phases can be effectively improved. The piezoelectric active phase of the self-supporting flexible sponge structure is prepared by a sacrificial template method; in the sacrificial template method, non-toxic, easily available and extremely good water-soluble salt is adopted as a sacrificial template, and the piezoelectric active phase with the self-supporting flexible sponge structure is finally prepared by compounding a mixture of organic piezoelectric phase powder, conductive phase powder with functional groups, inorganic piezoelectric phase powder with chemically modified surfaces and salt particles, and then removing the sacrificial salt template. It is worth noting that when the sacrificial salt template is removed, the method directly adopts a method of dissolving salt by high-temperature deionized water, and any organic solvent is not used or released in the whole process, so that the method is simple, safer and environment-friendly.
The conductive phase with the functional group can form a hydrogen bond with the organic piezoelectric phase to guide the orientation arrangement of the organic piezoelectric phase to improve the crystallinity, can enable the piezoelectric active phase of the self-supporting flexible sponge structure to have lower surface energy and higher roughness, and can also effectively reduce the polarization voltage of the composite material; the self-supporting stretchable piezoelectric film has higher piezoelectric performance, higher electromechanical coupling performance and lower acoustic impedance. The piezoelectric active phase of the self-supporting flexible sponge structure has a three-dimensional pore structure and higher porosity, and excellent elasticity can be ensured. The piezoelectric active phase of the self-supporting flexible sponge structure has lower surface energy and a rough surface structure, and can better adsorb and compound the elastic phase. The elastic phase has excellent elasticity, the dependence support has a piezoelectric active phase with a sponge structure to form a three-dimensional communicated elastic phase, and the consistency and the integration of the two phases are good. When the self-supporting stretchable piezoelectric film is compounded with the elastic phase, the self-supporting stretchable piezoelectric film needs to be vacuumized and then placed for a period of time, so that the uncured elastic phase can be ensured to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure, bubbles can be effectively removed, and the phenomenon of sound attenuation caused by tiny air gaps in the ultrasonic transmission process is avoided.
The introduction of the conductive phase with the functional group has the following beneficial effects: firstly, the conductive phase with functional groups can form a plurality of submicron structures, so that the prepared piezoelectric active phase with the self-supporting flexible sponge structure has lower surface energy and higher roughness, the piezoelectric active phase with the sponge structure and the elastic non-piezoelectric active phase which is communicated in three dimensions can be compounded more tightly without air gaps and the like, and the finally prepared stretchable piezoelectric film has excellent stretching life and excellent acoustic impedance performance in consistency; secondly, the introduction of the conductive phase can reduce the overall polarization voltage of the self-supporting stretchable piezoelectric film, is favorable for enabling the polarization of the composite piezoelectric film to be more sufficient when the polarization voltage is lower, and shows more excellent piezoelectric performance and electromechanical coupling performance; thirdly, the conductive phase with the functional group can form a hydrogen bond with the organic piezoelectric phase to guide the orientation arrangement of the organic piezoelectric phase in the solidification and crystallization process, so that the crystallinity of the organic piezoelectric phase and the content of beta phase are improved, and the piezoelectric performance and the electromechanical coupling performance of the self-supporting stretchable piezoelectric film are improved; fourth, the conductive phase with functional group can be connected with the inorganic piezoelectric material with surface chemically modified through chemical bond, which can effectively avoid agglomeration phenomenon and greatly improve the binding force between each item.
Further, the surface chemically modified inorganic piezoelectric phase heterojunction particles can establish stronger electric coupling between the inorganic piezoelectric phase particles and the organic elastic non-piezoelectric active phase, so as to improve the voltage distribution applied to the dispersion units of the inorganic piezoelectric phase particles in the self-supporting stretchable piezoelectric film, greatly improve the polarization degree of the inorganic piezoelectric phase particles, and further improve the piezoelectric performance and the electromechanical coupling performance of the self-supporting stretchable piezoelectric film.
Further, strong chemical bond coupling is formed between the inorganic piezoelectric phase and the organic piezoelectric phase, so that the interfacial bonding capability of the organic phase and the inorganic phase can be effectively improved, and the agglomeration phenomenon of the inorganic piezoelectric phase can be effectively avoided.
Further, the surface chemically modified inorganic piezoelectric phase heterojunction particles and the elastic non-piezoelectric active phase form strong chemical bond coupling, so that the interface bonding capacity of the organic phase and the inorganic phase can be effectively improved, and the agglomeration phenomenon of the inorganic piezoelectric phase heterojunction particles can be effectively avoided.
Example 1: the preparation method of the self-supporting stretchable piezoelectric film provided in the embodiment 1 comprises the following steps: step S1, preparing a piezoelectric active phase of a self-supporting flexible sponge structure based on a sacrificial template method; and the piezoelectric active phase of the self-supporting flexible sponge structure is adhered to the glass sheet and placed in a mold.
Specifically, the step S1 specifically includes the following substeps: and step S101, dispersing PZT powder in an ethanol solution of 1.2wt% of vinyltrimethoxysilane, magnetically stirring for 3 hours to ensure that the dispersion is uniform, and completely modifying the surfaces of the inorganic piezoelectric phase particles by chemical modification, and then drying in a drying oven at 40 ℃ for 5 hours to obtain the inorganic piezoelectric phase powder with the chemically modified surfaces.
Step S102, uniformly mixing PZT inorganic piezoelectric phase powder with chemically modified surface, carboxylated multi-wall carbon nano tube, PVDF powder and salt particles, putting the mixture into a ball mill for ball milling at the speed of 335 r/min for 12h to obtain uniform mixed powder, wherein the final components comprise 5.625wt% of PZT powder with chemically modified surface, 0.625wt% of hydroxylated multi-wall carbon nano tube, 6.25wt% of organic piezoelectric phase and 87.5wt% of salt particles.
And step S103, placing the mixed powder obtained in the step S102 in a silicon dioxide boat, placing in a drying box, heating at a high temperature for a period of time to ensure that the surface active structure of the inorganic piezoelectric phase powder with the chemically modified surface, organic piezoelectric phase molecules and carboxylated multiwall carbon nanotubes are fully entangled by molecular bridges, heating at a temperature of 200 ℃ for 45min, closing the drying box, waiting for solidification of the melted composite solution, and cooling to room temperature in a furnace.
Step S104, taking out the prepared solid composite material from the silicon dioxide boat in the step S103, and removing the outer layer of the composite material by using 400-mesh sand paper.
And step 105, placing the composite material obtained in the step 104 in a beaker, pouring deionized water, fully soaking the composite material, placing the beaker on a hot table, setting the temperature of the hot table to be 85 ℃, and continuously heating.
And S106, replacing deionized water at regular intervals, repeating the step S105, wherein the total soaking time of the prepared composite material is more than 30 hours to completely remove salt, so as to obtain a piezoelectric active phase of a self-supporting flexible sponge structure, and the components of the piezoelectric active phase are 45wt% of PZT powder with chemically modified surface, 5wt% of hydroxylated multi-wall carbon nano tubes and 50wt% of an organic piezoelectric phase.
And S107, adhering the piezoelectric active material with the self-supporting flexible sponge structure obtained in the step S106 to a glass sheet by using a polyimide high-temperature-resistant double-sided adhesive tape, and covering the structure by using a hollow cylinder with the length of more than 1 cm.
And S2, preparing the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
Step S201, adding 2mol/L CuNO into the inorganic piezoelectric phase particle PMN-PT powder 3 Stirring in water solution to obtain inorganic piezoelectric phase PMN-PT/CuNO 3 The solution was mixed.
Step S202, dropwise adding a hydrazine hydrate solution with the concentration mass fraction of 88% into an inorganic piezoelectric phase PMN-PT/CuNO 3 Mixing the solution until the solution is completely discolored from the initial color, and finally adding hydrazine hydrate solute: the ratio of the amount of copper ions is 1.8:1, and stirring is continued at room temperature in a nitrogen atmosphere to fully carry out the reaction, so as to obtain the mixed solution containing Cu@PMN-PT chemical heterojunction particles.
And S203, separating the prepared Cu@PMN-PT chemical heterojunction particles by using a centrifugal machine, washing for a plurality of times by using deionized water, and drying at 85 ℃ in a nitrogen atmosphere to finally prepare Cu@PMN-PT chemical heterojunction particle powder, namely obtaining PMN-PT inorganic piezoelectric phase heterojunction particles, wherein the mass ratio of the copper particles to the inorganic piezoelectric phase PMN-PT in the finally prepared inorganic piezoelectric phase composite particles is 0.5:99.5.
And S204, dispersing the inorganic piezoelectric phase particles in an ethanol solution of 1wt% of vinyl trimethoxy silane, magnetically stirring for 3 hours to uniformly disperse the inorganic piezoelectric phase particles, chemically modifying the surfaces of the inorganic piezoelectric phase particles completely, and then drying the inorganic piezoelectric phase particles in a drying oven at 40 ℃ for 5 hours to obtain the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
And S3, mixing uncured elastic non-piezoelectric active phase PDMS and surface chemically modified PMN-PT inorganic piezoelectric phase heterojunction particles, and carrying out ultrasonic stirring to disperse the surface chemically modified inorganic piezoelectric phase heterojunction particles and induce the surface active structure of the surface chemically modified inorganic piezoelectric phase heterojunction particles to fully generate molecular bridge entanglement with elastic non-piezoelectric active phase molecules so as to obtain a precursor solution.
The mass percentage of the elastic non-piezoelectric active phase in the finally obtained precursor solution is 55wt%, and the mass percentage of the inorganic piezoelectric phase heterojunction particles with the surface chemically modified is 45wt%.
And S4, pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and the glass sheet, and obtaining the self-supporting stretchable piezoelectric film through hot pressing, curing and forming.
Specifically, the step S4 specifically includes the following substeps: and S401, pouring the precursor solution into the die structure obtained in the step S107, vacuumizing to remove bubbles, and standing for 15min to enable the uncured precursor solution to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure.
And step S402, taking the composite sample obtained in the step S401 off a die and an adhesive tape, hot-pressing, curing and forming to obtain the self-supporting stretchable piezoelectric film.
The volume percentage of the piezoelectric active phase of the self-supporting flexible sponge structure in the self-supporting stretchable piezoelectric film is 8%, the volume percentage of the elastic phase of the three-dimensional communication is 92%, and the elastic stretching limit in the self-supporting stretchable piezoelectric film obtained by the embodiment is 2.8 times of the original total length after stretching.
Example 2: the preparation method of the self-supporting stretchable piezoelectric film provided in the embodiment 2 comprises the following steps: and step S1, preparing a piezoelectric active phase of the self-supporting flexible sponge structure based on a sacrificial template method. And the piezoelectric active phase of the self-supporting flexible sponge structure is adhered to the glass sheet and placed in a mold.
The difference from step S1 in example 1 was only that the components in example 2 were 6.82wt% of the surface-chemically modified PZT powder, 0.182wt% of the hydroxylated multi-walled carbon nanotube, 2.09wt% of the organic piezoelectric phase, and 90.908wt% of the salt particles. The components in the piezoelectric active phase finally obtained account for 75wt% of PZT powder with chemically modified surface, 2wt% of hydroxylated multi-wall carbon nano tube and 23wt% of organic piezoelectric phase.
And S2, preparing the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
The substep of step S2 in this embodiment 2 is the same as the substep of step S2 in embodiment 1, and will not be described here again.
And S3, mixing uncured elastic non-piezoelectric active phase PDMS and surface chemically modified PMN-PT inorganic piezoelectric phase heterojunction particles, and carrying out ultrasonic stirring to disperse the surface chemically modified inorganic piezoelectric phase heterojunction particles and induce the surface active structure of the surface chemically modified inorganic piezoelectric phase heterojunction particles to fully generate molecular bridge entanglement with elastic non-piezoelectric active phase molecules so as to obtain a precursor solution.
The only difference from step S1 in example 1 is that the mass percentage of the elastic non-piezoelectrically active phase in the precursor solution in example 2 is 40wt% and the mass percentage of the surface chemically modified inorganic piezoelectrically phase heterojunction particles is 60wt%.
And S4, pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and the glass sheet, and obtaining the self-supporting stretchable piezoelectric film through hot pressing, curing and forming.
The volume percentage of the piezoelectric active phase of the self-supporting flexible sponge structure in the self-supporting stretchable piezoelectric film is 25%, the volume percentage of the elastic phase of the three-dimensional communication is 75%, and the elastic stretching limit in the self-supporting stretchable piezoelectric film obtained by the embodiment is 2.1 times of the original total length after stretching.
Example 3: the preparation method of the self-supporting stretchable piezoelectric film provided in the embodiment 3 comprises the following steps: and step S1, preparing a piezoelectric active phase of the self-supporting flexible sponge structure based on a sacrificial template method. And the piezoelectric active phase of the self-supporting flexible sponge structure is adhered to the glass sheet and placed in a mold.
The difference from step S1 in example 1 was only that the components in example 2 were 9.375wt% of the surface chemically modified PZT powder, 0.625wt% of the hydroxylated multi-walled carbon nanotubes, 2.5wt% of the organic piezoelectric phase, and 87.5wt% of the salt particles. The components in the final piezoelectric active phase account for 75wt% of PZT powder, 5wt% of hydroxylated multi-wall carbon nano tube and 20wt% of organic piezoelectric phase.
And S2, preparing the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
The substep of step S2 in this embodiment 2 is the same as the substep of step S2 in embodiment 1, and will not be described here again.
And S3, mixing uncured elastic non-piezoelectric active phase PDMS and surface chemically modified PMN-PT inorganic piezoelectric phase heterojunction particles, and carrying out ultrasonic stirring to disperse the surface chemically modified inorganic piezoelectric phase heterojunction particles and induce the surface active structure of the surface chemically modified inorganic piezoelectric phase heterojunction particles to fully generate molecular bridge entanglement with elastic non-piezoelectric active phase molecules so as to obtain a precursor solution.
The only difference from step S1 in example 1 is that the mass percentage of the elastic non-piezoelectrically active phase in the precursor solution in example 2 is 50wt% and the mass percentage of the surface chemically modified inorganic piezoelectrically phase heterojunction particles is 50wt%.
And S4, pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and the glass sheet, and obtaining the self-supporting stretchable piezoelectric film through hot pressing, curing and forming.
The volume percentage of the piezoelectric active phase of the self-supporting flexible sponge structure in the self-supporting stretchable piezoelectric film is 15%, the volume percentage of the three-dimensional communicated elastic phase is 85%, and the elastic stretching limit in the self-supporting stretchable piezoelectric film obtained by the embodiment is 2.4 times of the original total length after stretching.
Example 4: the preparation method of the self-supporting stretchable piezoelectric film provided in the embodiment 4 comprises the following steps: and step S1, preparing a piezoelectric active phase of the self-supporting flexible sponge structure based on a sacrificial template method. And the piezoelectric active phase of the self-supporting flexible sponge structure is adhered to the glass sheet and placed in a mold.
The difference from step S1 in example 1 was only that the components in example 2 were 7wt% of the surface-chemically modified PZT powder, 0.5wt% of the hydroxylated multiwall carbon nanotubes, 5wt% of the organic piezoelectric phase, and 87.5wt% of the salt particles. The components in the final piezoelectric active phase account for 56wt% of PZT powder, 4wt% of hydroxylated multi-wall carbon nano tube and 40wt% of organic piezoelectric phase.
And S2, preparing the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
The substep of step S2 in this embodiment 2 is the same as the substep of step S2 in embodiment 1, and will not be described here again.
And S3, mixing uncured elastic non-piezoelectric active phase PDMS and surface chemically modified PMN-PT inorganic piezoelectric phase heterojunction particles, and carrying out ultrasonic stirring to disperse the surface chemically modified inorganic piezoelectric phase heterojunction particles and induce the surface active structure of the surface chemically modified inorganic piezoelectric phase heterojunction particles to fully generate molecular bridge entanglement with elastic non-piezoelectric active phase molecules so as to obtain a precursor solution.
The only difference from step S1 in example 1 is that the mass percentage of the elastic non-piezoelectrically active phase in the precursor solution in example 2 was 55wt% and the mass percentage of the inorganic piezoelectrically active phase heterojunction particles was 45wt%.
And S4, pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into the pores of the piezoelectric active phase of the self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and the glass sheet, and obtaining the self-supporting stretchable piezoelectric film through hot pressing, curing and forming.
The volume percentage of the piezoelectric active phase of the self-supporting flexible sponge structure in the self-supporting stretchable piezoelectric film is 10%, the volume percentage of the three-dimensional communicated elastic phase is 90%, and the elastic stretching limit in the self-supporting stretchable piezoelectric film obtained by the embodiment is 2.6 times of the original total length after stretching.
Example 5: the preparation method of the self-supporting stretchable ultrasonic sensor provided in the embodiment 5 specifically comprises the following steps: (1) Sodium polystyrene sulfonate aqueous solution with the mass fraction of 4wt percent, na 2 S 2 O 8 ，Fe 2 (SO 4 ) 3 Mixing with deionized water at room temperature under argon atmosphere, and stirring for 2h.
(2) And (3) adding the reduced graphene oxide into the solution obtained in the step (1), mixing and stirring at room temperature in an argon atmosphere until the graphene oxide is uniformly dispersed.
(3) Adding 3, 4-ethylenedioxythiophene into the mixed solution obtained in the step (2), and stirring for 20 hours at room temperature under argon atmosphere, wherein the 3, 4-ethylenedioxythiophene is Na 2 S 2 O 8 And 3, 4-ethylenedioxythiophene Fe 2 (SO 4 ) 3 The molar ratio of the poly (3, 4-ethylenedioxythiophene) to the polystyrene sulfonate is 1:0.9 and 1:0.02 respectively, and finally the dark blue poly (3, 4-ethylenedioxythiophene) to the polystyrene sulfonate solution is obtained, wherein the mass ratio of the poly (3, 4-ethylenedioxythiophene) to the polystyrene sulfonate is 1:2.
(4) The carboxymethyl cellulose sodium salt is dissolved in deionized water and stirred at 40 ℃ until the carboxymethyl cellulose sodium salt is uniformly dispersed, wherein the molecular weight of the carboxymethyl cellulose sodium salt is 250000.
(5) Adding the poly (3, 4-ethylenedioxythiophene) obtained in the step (3) into the polystyrene sulfonate solution, dimethyl sulfoxide and glycerol into the solution obtained in the step (4), and stirring at 40 ℃ until the mixture is uniformly dispersed, wherein the volume ratio of carboxymethyl cellulose sodium salt to the poly (3, 4-ethylenedioxythiophene) to the polystyrene sulfonate solution is 1:13, the volume ratio of carboxymethyl cellulose sodium salt to dimethyl sulfoxide is 1:9, and the volume ratio of carboxymethyl cellulose sodium salt to glycerol is 1:2.
(6) And (3) uniformly coating the mixed solution obtained in the step (5) on two sides of the self-supporting stretchable piezoelectric film, then drying at 50 ℃ for 24 hours, and curing and forming to obtain the sandwich structure of the stretchable electrode/the self-supporting stretchable piezoelectric film/the stretchable electrode.
(7) And (3) applying a direct current electric field to polarize the sandwich structure of the stretchable electrode/the self-supporting stretchable piezoelectric film/the stretchable electrode in the step (6) (wherein the electric field strength is 85kV/cm, the polarization time is 3.5h, and the polarization temperature is 80 ℃), and then respectively leading out the electrode lugs from the electrode layers to obtain the self-supporting stretchable ultrasonic sensor.
Example 6: the application scenario of the self-supporting stretchable ultrasonic sensor provided by the embodiment is that the self-supporting stretchable ultrasonic sensor is applied to an ultrasonic detection system. The ultrasonic detection system can be specifically a photoacoustic spectrum detection system. The photoacoustic spectrum detection system comprises a modulatable laser, a photoacoustic cell, the self-supporting stretchable ultrasonic sensor, a lock-in amplifier and the like. After the irregularly-shaped sample to be detected absorbs the modulated laser energy, the photoacoustic effect causes thermoelastic expansion, so that ultrasonic waves are excited, the ultrasonic waves can be detected by the self-supporting stretchable sensor, the energy loss in the acoustic wave transmission process can be effectively restrained, and the sensitivity of photoacoustic spectrum detection can be effectively improved.
Fig. 4 is a graph showing a correspondence relationship between a piezoelectric strain coefficient and a stretching ratio (i.e., stretching ratio=stretching length/original length, stretching length=total length after stretching-original length) of a self-supporting stretchable piezoelectric film according to an exemplary embodiment, and it can be seen from fig. 4 that the piezoelectric strain coefficient of the self-supporting stretchable piezoelectric film according to the present invention is almost unchanged with increasing stretching ratio, and it is seen that the self-supporting stretchable piezoelectric film has excellent stretchability. Fig. 5 is a graph showing the signal amplitude rate-peak response retention (180% elongation) of a self-supporting stretchable ultrasonic sensor at various elongation times according to an exemplary embodiment, and it can be seen that the signal amplitude rate-peak response of the ultrasonic sensor remains almost unchanged with the increase of the elongation times, demonstrating excellent stretchability.
It is to be understood that the present application is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (9)
1. A self-supporting stretchable piezoelectric film is characterized by being formed by compositing a piezoelectric active phase of a self-supporting flexible sponge structure and a three-dimensional communicated elastic phase;
The piezoelectric active phase is formed by compositing an organic piezoelectric phase, a conductive phase with a functional group and an inorganic piezoelectric phase with a chemically modified surface;
the elastic phase is formed by compositing elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles with chemically modified surfaces;
the elastic phase is loaded in the pores of the piezoelectric active phase; the volume percentage of the piezoelectric active phase is 8-25%, and the volume percentage of the elastic phase is 75-92%;
the mass percentage of the organic piezoelectric phase in the piezoelectric active phase of the self-supporting flexible sponge structure is 20-50wt%, the mass percentage of the conductive phase with the functional group is 2-5wt%, and the mass percentage of the inorganic piezoelectric phase after surface chemical modification is 45-75wt%;
the mass percentage of the elastic non-piezoelectric active phase in the elastic phase is 40-55wt%, and the mass percentage of the inorganic piezoelectric phase heterojunction particles after surface chemical modification is 45-60wt%;
the organic piezoelectric phase, the conductive phase with functional groups and the inorganic piezoelectric phase after surface chemical modification in the piezoelectric active phase and the elastic phase are connected in pairs through chemical bonds by the elastic non-piezoelectric active phase and the inorganic piezoelectric phase heterojunction particles after surface chemical modification.
2. The self-supporting stretchable piezoelectric film according to claim 1, wherein the organic piezoelectric phase is selected from PVDF or P (VDF-TrFE); the conductive phase with functional groups is selected from carboxylated or hydroxylated multi-walled carbon nanotubes or reduced graphene oxide; the inorganic piezoelectric phase is selected from PZT, barium titanate or PLZT; the elastic non-piezoelectrically active phase is selected from polydimethylsiloxane or polyurethane.
3. The self-supporting stretchable piezoelectric film according to claim 1, wherein the conductive phase having a functional group and the surface-chemically-modified inorganic piezoelectric phase are dispersed in the organic piezoelectric phase in a 0-dimensional manner; the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified are dispersed in an elastic non-piezoelectric active phase in a 0-dimensional mode.
4. A method of preparing a self-supporting stretchable piezoelectric film according to any one of claims 1 to 3, comprising:
preparing a piezoelectric active phase of the self-supporting flexible sponge structure based on a sacrificial template method; bonding the piezoelectric active phase of the self-supporting flexible sponge structure on a glass sheet, and placing the glass sheet into a mold;
preparing inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified;
mixing uncured elastic non-piezoelectric active phase and inorganic piezoelectric phase heterojunction particles with chemically modified surfaces, and carrying out ultrasonic stirring to disperse the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces and induce the surface active structures of the inorganic piezoelectric phase heterojunction particles with chemically modified surfaces to fully generate molecular bridge entanglement with elastic non-piezoelectric active phase molecules so as to obtain precursor solution of the elastic phase;
Pouring the precursor solution into a mould, vacuumizing to remove bubbles, standing to enable the uncured precursor solution to be completely filled into pores of a piezoelectric active phase of a self-supporting flexible sponge structure, obtaining a composite sample, taking the composite sample out of the mould and a glass sheet, and carrying out hot pressing, curing and forming to obtain the self-supporting stretchable piezoelectric film.
5. The method of producing a self-supporting stretchable piezoelectric film according to claim 4, wherein the step of producing the piezoelectric active phase of the self-supporting flexible sponge structure based on the sacrificial template method comprises:
preparing an inorganic piezoelectric phase with a chemically modified surface;
uniformly mixing an organic piezoelectric phase, a conductive phase with a functional group, an inorganic piezoelectric phase with a chemically modified surface and salt, and grinding to obtain mixed powder; wherein the mass of the salt is 7-10 times of the total mass of the organic piezoelectric phase, the conductive phase with functional groups and the inorganic piezoelectric phase with the surface chemically modified;
placing the mixed powder in a silicon dioxide boat, heating at high temperature in a drying oven to obtain a molten composite solution, enabling the surface active structure of the inorganic piezoelectric phase powder with the surface chemically modified to fully generate molecular bridge entanglement with organic piezoelectric phase molecules and conductive phases with functional groups, solidifying the molten composite solution, and cooling to room temperature in a furnace to obtain a solid composite material;
Polishing the surface of the solid composite material, and soaking the solid composite material by deionized water at high temperature to completely remove salt, thereby obtaining the piezoelectric active phase of the self-supporting flexible sponge structure.
6. The method of preparing a self-supporting stretchable piezoelectric film according to claim 4, wherein preparing the surface chemically modified inorganic piezoelectric phase heterojunction particles comprises:
adding inorganic piezoelectric phase particles into a metal nitric acid aqueous solution, and stirring to uniformly disperse the inorganic piezoelectric phase particles to obtain an inorganic piezoelectric/metal nitrate mixed solution;
dropwise adding the hydrazine hydrate solution into the inorganic piezoelectric/metal nitrate mixed solution until the inorganic piezoelectric/metal nitrate mixed solution is completely discolored from an initial color, and continuously stirring at room temperature in a nitrogen atmosphere to fully perform the reaction so as to obtain a mixed solution containing metal and inorganic piezoelectric phase composite chemical heterojunction particles;
separating out metal and inorganic piezoelectric phase composite chemical heterojunction particles by using a centrifugal machine, washing and drying under the nitrogen atmosphere to obtain inorganic piezoelectric phase heterojunction particles;
dispersing the inorganic piezoelectric phase heterojunction particles in an ethanol solution of 1wt% of a silane coupling agent, so that the surfaces of the inorganic piezoelectric phase particles are completely modified by chemical modification, and drying to obtain the inorganic piezoelectric phase heterojunction particles with the surfaces chemically modified.
7. The method of producing a self-supporting stretchable piezoelectric film according to claim 6, wherein the silane coupling agent is one selected from the group consisting of vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
8. A self-supporting stretchable ultrasonic sensor comprising a self-supporting stretchable piezoelectric film according to any one of claims 1-3 and stretchable electrodes composited on two opposing surfaces of the piezoelectric film.
9. Use of the self-supporting stretchable ultrasonic sensor of claim 8 in ultrasonic detection or imaging.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170062641A (en) * | 2015-11-27 | 2017-06-08 | 건국대학교 산학협력단 | Structure and manufacturing method of organic-inorganic hybrid piezoelectric nano-generator |
| CN114023874A (en) * | 2021-10-14 | 2022-02-08 | 之江实验室 | Composite piezoelectric material, self-focusing composite piezoelectric film, ultrasonic transducer and preparation method thereof |
| CN218211699U (en) * | 2022-09-30 | 2023-01-03 | 广西大学 | Piezoelectric film structure |
| CN115975253A (en) * | 2023-03-22 | 2023-04-18 | 之江实验室 | Stretchable piezoelectric film and ultrasonic transducer |
| CN115991937A (en) * | 2023-03-23 | 2023-04-21 | 之江实验室 | Stretchable piezoelectric film, preparation method thereof and stretchable ultrasonic transducer |
| CN116023705A (en) * | 2023-03-22 | 2023-04-28 | 之江实验室 | Transparent piezoelectric film, ultrasonic transducer and preparation method thereof |
| CN116828960A (en) * | 2022-03-17 | 2023-09-29 | 清华大学 | Preparation method of stretchable piezoelectric composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9444030B2 (en) * | 2013-05-10 | 2016-09-13 | Wisconsin Alumni Research Foundation | Nanoporous piezoelectric polymer films for mechanical energy harvesting |
| US11968904B2 (en) * | 2020-07-06 | 2024-04-23 | City University Of Hong Kong | Flexible piezoceramic composites and method for fabricating thereof |
-
2023
- 2023-10-08 CN CN202311291758.0A patent/CN117042582B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170062641A (en) * | 2015-11-27 | 2017-06-08 | 건국대학교 산학협력단 | Structure and manufacturing method of organic-inorganic hybrid piezoelectric nano-generator |
| CN114023874A (en) * | 2021-10-14 | 2022-02-08 | 之江实验室 | Composite piezoelectric material, self-focusing composite piezoelectric film, ultrasonic transducer and preparation method thereof |
| CN116828960A (en) * | 2022-03-17 | 2023-09-29 | 清华大学 | Preparation method of stretchable piezoelectric composite material |
| CN218211699U (en) * | 2022-09-30 | 2023-01-03 | 广西大学 | Piezoelectric film structure |
| CN115975253A (en) * | 2023-03-22 | 2023-04-18 | 之江实验室 | Stretchable piezoelectric film and ultrasonic transducer |
| CN116023705A (en) * | 2023-03-22 | 2023-04-28 | 之江实验室 | Transparent piezoelectric film, ultrasonic transducer and preparation method thereof |
| CN115991937A (en) * | 2023-03-23 | 2023-04-21 | 之江实验室 | Stretchable piezoelectric film, preparation method thereof and stretchable ultrasonic transducer |
Non-Patent Citations (4)
| Title |
|---|
| "A wearable and sensitive carbon black-porous polydimethylsiloxane based pressure sensor for human physiological signals monitoring";Ningyu Yuan等;《J Mater Sci: Mater Electron》;第32卷;27656-27665页 * |
| "Advance on flexible pressure sensors based on metal and carbonaceous nanomaterial";Meng-Yang Liu等;《Nano Energy》;第87卷;1-21页 * |
| BTO/PDMS/C柔性复合薄膜的制备及压电性能研究;苏晓晓;李银辉;李廷鱼;李朋伟;;压电与声光(第04期);全文 * |
| 低声阻抗0―3型PZT/PT/PVDF压电复合材料的研制;熊贵;张洋洋;;电子元件与材料(第12期);全文 * |
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