Ultrasonic response piezoelectric material loaded with cerium oxide

Abstract

The invention provides a cerium oxide-loaded ultrasonic response piezoelectric material, and relates to the technical field of functional materials, the cerium oxide-loaded ultrasonic response piezoelectric material is characterized in that a polymer chain intermediate is continuously subjected to oxidative polymerization reaction and cross-linking to form a polymer matrix, the surface of the polymer matrix is of a three-dimensional nanometer network structure, and the cerium oxide-loaded ultrasonic response piezoelectric material is prepared. Surface modification and drying are carried out on the polymer matrix precursor to obtain the piezoelectric polymer matrix, the surface modification comprises centrifugal separation and deionized water washing, the drying temperature is 40-60 DEG C, and the drying time is 6-12 hours. The cerium oxide nanoparticles grow on the surface of the piezoelectric polymer matrix in situ, the cerium ions are selectively enriched under the drive of local potential difference, and the cerium oxide nanoparticles are formed through an interface conversion reaction, so that cerium oxide is successfully loaded, and the ultrasonic response capability and piezoelectric property of the material are improved.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, specifically to an ultrasonically responsive piezoelectric material loaded with cerium oxide. Background Technology

[0002] Piezoelectric materials enable the conversion between mechanical and electrical energy. In recent years, these materials have been widely used in the biomedical field, forming a research direction called "piezoelectric medicine." Piezoelectric materials can induce electrons or holes through stress, catalyzing chemical reactions or intervening in cellular activity, playing a role in disease treatment and tissue repair. Chinese patent CN120132062A discloses a 3D-printed piezoelectric bone repair scaffold composed of polyvinylidene fluoride and polylactic acid, possessing the ability to actively promote bone regeneration. Chinese patent CN115458676B introduces a phenylalanine derivative piezoelectric material that can be used in electronic skin and health monitoring devices. Chinese patent CN119392403B proposes a dopamine-coated polylactic acid piezoelectric material that utilizes an interface anchoring effect to enhance piezoelectric performance. Chinese patent CN118557811A relates to a biopiezoelectric material composed of sodium potassium niobate and extracellular matrix, which can promote bone tissue repair under ultrasonic stimulation. These technologies demonstrate the diversified development of piezoelectric materials in medical applications.

[0003] Existing piezoelectric materials can generate reactive oxygen species under ultrasonic stimulation for disease treatment. However, after treatment, the materials lack the ability to remove excess reactive oxygen species, which may cause tissue or organ damage due to the accumulation of reactive oxygen species. This defect is particularly evident in treatment scenarios that require precise control of reactive oxygen species dosage, and may cause secondary damage, especially in tissue environments that are sensitive to oxidative damage. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an ultrasonically responsive piezoelectric material loaded with cerium oxide. The technical problem this invention aims to solve is: how to address the lack of ability to remove excess reactive oxygen species in existing piezoelectric materials by loading cerium oxide nanoparticles onto a piezoelectric polymer matrix.

[0005] To achieve the above objectives, the present invention provides the following technical solution: an ultrasonically responsive piezoelectric material loaded with cerium oxide, comprising the following components by mass percentage: Piezoelectric polymer matrix: 90%-99.9%; Cerium oxide nanoparticles: 0.1%-10%.

[0006] Preferably, the piezoelectric polymer matrix is ​​formed by oxidative polymerization of pyrrole monomers, wherein the pyrrole monomers include pyrrole, thiophene, and phenylacetylene.

[0007] Preferably, the step of forming the piezoelectric polymer matrix is ​​as follows: S1. The pyrrole monomer is dispersed in an aqueous medium to form a monomer solution, the concentration of the monomer solution being 1wt%-20wt%, and the pyrrole monomer is stirred in the aqueous medium at a temperature of 25℃-40℃, a rotation speed of 200rpm-800rpm, and a stirring time of 0.5 hours-2 hours. S2. An oxidant is added to the monomer solution to carry out an oxidative polymerization reaction to form a polymer chain intermediate. The oxidant is ferric ions. The amount of oxidant added is 20%-35% of the molar number of the pyrrole monomer. The temperature of the oxidative polymerization reaction is 60℃-80℃ and the reaction time is 3 hours-8 hours. S3. The polymer chain intermediate continues to undergo oxidative polymerization and cross-linking to form a polymer matrix, the surface of which is a three-dimensional nano-network structure; S4. The polymer matrix precursor is surface modified and dried to obtain the piezoelectric polymer matrix. The surface modification includes centrifugation and washing with deionized water. The drying temperature is 40℃-60℃ and the drying time is 6 hours-12 hours.

[0008] Preferably, the cerium oxide nanoparticles have a particle size of 2nm-50nm.

[0009] Preferably, the cerium oxide nanoparticles are formed by in-situ growth of a trivalent cerium ion precursor on the surface of the piezoelectric polymer matrix, wherein the cerium ion precursor is cerium nitrate.

[0010] Preferably, the formation step of the cerium oxide nanoparticles is as follows: S1. A trivalent cerium ion precursor is added to the surface of the piezoelectric polymer matrix to form a cerium ion precursor; S2. The cerium ion precursor is selectively enriched on the surface of the piezoelectric polymer matrix to form a cerium ion enrichment interface; S3. The cerium ion enrichment interface is subjected to an interfacial transformation reaction to form the cerium oxide nanoparticles.

[0011] Preferably, the selective enrichment is driven by a local potential difference in the piezoelectric polymer matrix, the local potential difference being formed by the inherent polarization components of the piezoelectric polymer matrix, the local region including surface depressions, defect sites, and chain ends of the piezoelectric polymer matrix.

[0012] Preferably, the interface conversion reaction includes adding an alkaline solution to the cerium ion enrichment interface, wherein the alkaline solution converts the trivalent cerium ions at the cerium ion enrichment interface into tetravalent cerium ions, the alkaline solution being ammonia water with a concentration of 0.1M-1.0M, and the alkaline solution adjusting the pH of the cerium ion enrichment interface to be greater than 10.

[0013] This invention provides an ultrasonically responsive piezoelectric material supported on cerium oxide. It possesses the following beneficial effects: This ultrasonically responsive piezoelectric material loaded with cerium oxide was successfully loaded with cerium oxide by in-situ growth of cerium oxide nanoparticles on the surface of a piezoelectric polymer matrix, selective enrichment of cerium ions driven by local potential difference, and formation of cerium oxide nanoparticles through interfacial conversion reaction, thereby improving the ultrasonic response capability and piezoelectric properties of the material.

[0014] By combining a piezoelectric polymer matrix with cerium oxide nanoparticles, the piezoelectric properties of the material are improved. Furthermore, surface modification and drying treatments enhance the material's stability and response sensitivity, thereby improving its performance in ultrasonic sensors and other piezoelectric applications. Attached Figure Description

[0015] Figure 1 This is a flowchart illustrating the matrix preparation process for realizing the invention; Figure 2 This is a flowchart illustrating the in-situ growth process of nanoparticles to achieve the invention. Figure 3 This is a schematic diagram of a selective enrichment mechanism for achieving an invention; Figure 4 This is a schematic diagram illustrating the preparation and working principle of an invention. Detailed Implementation

[0016] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 like Figure 1-4 As shown, an embodiment of the present invention provides an ultrasonically responsive piezoelectric material supported on cerium oxide, comprising the following components by mass percentage: Piezoelectric polymer matrix: 90%.

[0018] The piezoelectric polymer matrix is ​​formed by the oxidative polymerization of pyrrole monomers, including pyrrole, thiophene, and phenylacetylene. The formation steps of the piezoelectric polymer matrix are as follows: S1. The pyrrole monomer is dispersed in an aqueous medium to form a monomer solution with a concentration of 1 wt%. The pyrrole monomer is stirred in the aqueous medium at a temperature of 25°C, a speed of 200 rpm, and a time of 0.5 hours.

[0019] S2. An oxidant is added to the monomer solution to carry out an oxidative polymerization reaction to form a polymer chain intermediate. The oxidant is ferric ions, and the amount of oxidant added is 20% of the molar number of pyrrole monomer. The temperature of the oxidative polymerization reaction is 60℃ and the reaction time is 3 hours.

[0020] S3. The polymer chain intermediates continue to undergo oxidative polymerization and cross-linking to form a polymer matrix, the surface of which has a three-dimensional nano-network structure.

[0021] S4. The polymer matrix precursor is surface modified and dried to obtain the piezoelectric polymer matrix. The surface modification includes centrifugation and washing with deionized water. The drying temperature is 40℃ and the time is 6 hours.

[0022] Cerium oxide nanoparticles: 10%.

[0023] The cerium oxide nanoparticles have a particle size of 2 nm. They are formed by in-situ growth of trivalent cerium ion precursors on the surface of a piezoelectric polymer matrix. The cerium ion precursor is cerium nitrate. The formation steps of the cerium oxide nanoparticles are as follows: S1. Trivalent cerium ion precursors are added to the surface of a piezoelectric polymer matrix to form cerium ion precursors.

[0024] S2. Cerium ion precursors selectively accumulate on the surface of the piezoelectric polymer matrix, forming a cerium ion enrichment interface. Selective enrichment is driven by the local potential difference of the piezoelectric polymer matrix, which is formed by the intrinsic polarization components of the piezoelectric polymer matrix. The local region includes surface depressions, defect sites, and chain ends of the piezoelectric polymer matrix.

[0025] S3. An interfacial transformation reaction is carried out at the cerium ion enrichment interface to form cerium oxide nanoparticles. The interfacial transformation reaction includes adding an alkaline solution to the cerium ion enrichment interface. The alkaline solution converts the trivalent cerium ions at the cerium ion enrichment interface into tetravalent cerium ions. The alkaline solution is ammonia water with a concentration of 0.1M. The pH of the cerium ion enrichment interface is adjusted to be greater than 10 by the alkaline solution.

[0026] Under the conditions of this embodiment, the higher proportion of cerium oxide improves the ultrasonic response performance of the material. The smaller size of the cerium oxide particles, due to their larger specific surface area, helps to enhance the material's performance in ultrasonic applications. However, the relatively low proportion of the piezoelectric polymer matrix somewhat limits the material's piezoelectric properties. Therefore, the material of this embodiment is suitable for applications requiring high ultrasonic response performance, but may be insufficient in applications with high piezoelectric performance requirements.

[0027] Example 2 This invention provides an ultrasonically responsive piezoelectric material loaded with cerium oxide, comprising the following components by mass percentage: Piezoelectric polymer matrix: 94.95%.

[0028] The piezoelectric polymer matrix is ​​formed by the oxidative polymerization of pyrrole monomers, including pyrrole, thiophene, and phenylacetylene. The formation steps of the piezoelectric polymer matrix are as follows: S1. The pyrrole monomer is dispersed in an aqueous medium to form a monomer solution with a concentration of 10.5 wt%. The pyrrole monomer is stirred in the aqueous medium at a temperature of 32.5℃, a speed of 500 rpm, and a time of 1 hour.

[0029] S2. An oxidant is added to the monomer solution to carry out an oxidative polymerization reaction to form a polymer chain intermediate. The oxidant is ferric ions, and the amount of oxidant added is 22.5% of the molar number of pyrrole monomer. The temperature of the oxidative polymerization reaction is 70℃ and the reaction time is 5.5 hours.

[0030] S3. The polymer chain intermediates continue to undergo oxidative polymerization and cross-linking to form a polymer matrix, the surface of which has a three-dimensional nano-network structure.

[0031] S4. The polymer matrix precursor is surface modified and dried to obtain the piezoelectric polymer matrix. The surface modification includes centrifugation and washing with deionized water. The drying temperature is 50℃ and the time is 9 hours.

[0032] Cerium oxide nanoparticles: 5.05%.

[0033] The cerium oxide nanoparticles have a particle size of 26 nm. They are formed by in-situ growth of trivalent cerium ion precursors on the surface of a piezoelectric polymer matrix. The cerium ion precursor is cerium nitrate. The formation steps of the cerium oxide nanoparticles are as follows: S1. Trivalent cerium ion precursors are added to the surface of a piezoelectric polymer matrix to form cerium ion precursors.

[0034] S2. Cerium ion precursors selectively accumulate on the surface of the piezoelectric polymer matrix, forming a cerium ion enrichment interface. Selective enrichment is driven by the local potential difference of the piezoelectric polymer matrix, which is formed by the intrinsic polarization components of the piezoelectric polymer matrix. The local region includes surface depressions, defect sites, and chain ends of the piezoelectric polymer matrix.

[0035] S3. An interfacial transformation reaction is carried out at the cerium ion enrichment interface to form cerium oxide nanoparticles. The interfacial transformation reaction involves adding an alkaline solution to the cerium ion enrichment interface. The alkaline solution converts the trivalent cerium ions at the cerium ion enrichment interface into tetravalent cerium ions. The alkaline solution is ammonia water with a concentration of 0.55M. The pH of the cerium ion enrichment interface is adjusted to be greater than 10 by the alkaline solution.

[0036] In this embodiment, the ratio of cerium oxide to the piezoelectric polymer matrix is ​​moderate. The relatively large particle size of cerium oxide may affect the interfacial reaction and uniformity of the material. Increasing the proportion of the piezoelectric polymer matrix improves the piezoelectric properties of the material. The material with the values ​​in this embodiment achieves a balance between ultrasonic response and piezoelectric properties, making it suitable for applications such as ultrasonic sensors and medical imaging equipment where both are required.

[0037] Example 3 This invention provides an ultrasonically responsive piezoelectric material loaded with cerium oxide, comprising the following components by mass percentage: Piezoelectric polymer matrix: 99.9%.

[0038] The piezoelectric polymer matrix is ​​formed by the oxidative polymerization of pyrrole monomers, including pyrrole, thiophene, and phenylacetylene. The formation steps of the piezoelectric polymer matrix are as follows: S1. The pyrrole monomer is dispersed in an aqueous medium to form a monomer solution with a concentration of 20 wt%. The pyrrole monomer is stirred in the aqueous medium at a temperature of 40°C, a speed of 800 rpm, and a time of 2 hours.

[0039] S2. An oxidant is added to the monomer solution to carry out an oxidative polymerization reaction to form a polymer chain intermediate. The oxidant is ferric ions, and the amount of oxidant added is 35% of the molar number of pyrrole monomer. The temperature of the oxidative polymerization reaction is 80℃ and the reaction time is 8 hours.

[0040] S3. The polymer chain intermediates continue to undergo oxidative polymerization and cross-linking to form a polymer matrix, the surface of which has a three-dimensional nano-network structure.

[0041] S4. The polymer matrix precursor is surface modified and dried to obtain the piezoelectric polymer matrix. The surface modification includes centrifugation and washing with deionized water. The drying temperature is 60℃ and the time is 12 hours.

[0042] Cerium oxide nanoparticles: 0.1%.

[0043] The cerium oxide nanoparticles have a particle size of 50 nm. They are formed by in-situ growth of trivalent cerium ion precursors on the surface of a piezoelectric polymer matrix. The cerium ion precursor is cerium nitrate. The formation steps of the cerium oxide nanoparticles are as follows: S1. Trivalent cerium ion precursors are added to the surface of a piezoelectric polymer matrix to form cerium ion precursors.

[0044] S2. Cerium ion precursors selectively accumulate on the surface of the piezoelectric polymer matrix, forming a cerium ion enrichment interface. Selective enrichment is driven by the local potential difference of the piezoelectric polymer matrix, which is formed by the intrinsic polarization components of the piezoelectric polymer matrix. The local region includes surface depressions, defect sites, and chain ends of the piezoelectric polymer matrix.

[0045] S3. An interfacial transformation reaction is carried out at the cerium ion enrichment interface to form cerium oxide nanoparticles. The interfacial transformation reaction includes adding an alkaline solution to the cerium ion enrichment interface. The alkaline solution converts the trivalent cerium ions at the cerium ion enrichment interface into tetravalent cerium ions. The alkaline solution is ammonia water with a concentration of 1.0M. The pH of the cerium ion enrichment interface is adjusted to be greater than 10 by the alkaline solution.

[0046] In this embodiment, the piezoelectric polymer matrix dominates, enhancing the piezoelectric properties of the material. Due to the extremely low proportion of cerium oxide, the ultrasonic response performance of the material is somewhat limited, and larger cerium oxide particles may reduce its interfacial reactivity. Therefore, the material in this embodiment is suitable for applications requiring high piezoelectric performance but low ultrasonic response performance, and is suitable for precision instruments or sensors requiring high stability and durability.

[0047] Example 4 This embodiment focuses on an ultrasonically responsive piezoelectric material based on cerium oxide loading. By applying different reaction conditions and cerium oxide loading amounts, the effects on the material's performance are investigated, aiming to optimize its stability, mechanical properties, and ultrasonic responsiveness. Specific implementation details are as follows: 1. Preparation and stirring conditions of monomer solution Experiment A: The selected monomer was pyrrole monomer. Pyrrole monomer, as the main monomer of the polymer matrix, was added to the aqueous medium at a concentration of 1 wt%.

[0048] The pyrrole monomer was dissolved in water and stirred at 25°C and 200 rpm for 0.5 hours to ensure uniform dispersion of the monomer.

[0049] The conditions in Experiment A are suitable for slow polymerization reactions, avoiding the premature formation of large polymer molecules and maintaining the free movement between molecules.

[0050] Experiment B: Pyrrole monomer was selected and its concentration was increased to 10.5 wt% to make the monomer solution more viscous.

[0051] Stirring at 500 rpm for 1 hour at 32.5°C rapidly dissolves and accelerates the polymerization reaction.

[0052] Experiment B, by increasing temperature and stirring intensity, ensured complete monomer dissolution and accelerated the reaction rate, thus promoting more efficient polymerization.

[0053] Experiment C: Using pyrrole monomer at a concentration of 20 wt%. Heat to 40°C and stir at 800 rpm for 2 hours to fully dissolve the monomer and accelerate the polymerization reaction.

[0054] Experiment C uses a higher stirring rate and temperature, which can promote the efficiency of the reaction and obtain polymers with a greater degree of crosslinking.

[0055] Control group: Pyrrole, thiophene, and phenylacetylene are used in a mixture to ensure that each monomer is balanced, with each monomer having a concentration of 5 wt%.

[0056] Stir at 400 rpm for 0.5 hours at 25°C to dissolve and ensure uniform dispersion of the monomer.

[0057] Using appropriate concentrations and stirring conditions helps to achieve uniform mixing in a short time and avoids over-polymerization.

[0058] Comparative analysis: Experiment A, with its mild stirring conditions, is suitable for applications requiring high control over polymer chain length. Experiment B, with its higher reaction temperature and stirring speed, is suitable for scenarios requiring rapid polymer formation. Experiment C, using higher temperature and stirring speed, is beneficial for forming highly cross-linked polymers, but may affect their flexibility.

[0059] The control group, by reasonably controlling monomer concentration and stirring conditions, achieved moderate reaction conditions, which helped to obtain a stable and uniform polymer matrix.

[0060] 2. The addition of oxidizing agents and the polymerization reaction Experiment A: Ferrous ions were added to the monomer solution as an oxidant, and the amount added was 20% of the molar number of pyrrole monomer.

[0061] The reaction temperature was set to 60°C to ensure a gentle reaction and avoid triggering side reactions. The reaction was allowed to proceed for 3 hours to ensure that the polymerization reached a relatively stable stage.

[0062] Mild reaction conditions promote polymerization but may result in insufficient crosslinking and relatively low material strength.

[0063] Experiment B: Ferric ions were added to the monomer solution in an amount equal to 22.5% of the molar number of pyrrole monomers.

[0064] The reaction temperature was set to 70℃; increasing the temperature accelerated the polymerization reaction. Extending the reaction time to 5.5 hours helped improve the degree of crosslinking and stability of the polymer.

[0065] Experiment B, with its longer temperature and time, allowed for a more complete polymerization reaction, resulting in a polymer matrix with a higher degree of cross-linking.

[0066] Experiment C: Add ferric ions to the monomer solution, the amount of which is 35% of the molar number of pyrrole monomer.

[0067] The reaction is carried out at 80°C to promote efficient polymerization. The reaction time is extended to 8 hours to ensure complete polymerization and obtain a polymer with a high degree of cross-linking.

[0068] Experiment C had the highest oxidizing dose, and the most stringent reaction time and temperature, resulting in a polymer matrix with high strength and the highest degree of crosslinking.

[0069] Control group: Add 1 wt% ferric chloride to the monomer solution as an oxidant to ensure the stability of the reaction process.

[0070] The reaction temperature was set at 70℃ to control the reaction intensity. The reaction time was controlled at 5 hours to ensure the polymerization reaction was complete and to avoid overpolymerization.

[0071] Comparative analysis: Experiment A had a low amount of oxidant, a low temperature, and a short reaction time, resulting in incomplete polymerization, low crosslinking degree of the polymer, and limited strength and stability of the polymer.

[0072] The reaction conditions in Experiment B were relatively balanced, with both the oxidant and reaction time being moderately increased, resulting in better polymer performance.

[0073] Excessive reaction in Experiment C may lead to over-hardening of the polymer, potentially reducing the dispersibility of cerium oxide nanoparticles.

[0074] The reaction conditions in the control group ensured sufficient reaction while avoiding over-reaction, thus ensuring a balance in material properties.

[0075] 3. Surface finishing and drying conditions Experiment A: The polymer matrix was separated by centrifugation and washed with deionized water.

[0076] Drying at 40°C for 6 hours provides a relatively mild drying condition, preventing excessive hardening of the polymer surface and ensuring that the material is dry without losing its flexibility.

[0077] Experiment B: Centrifugation and washing with deionized water to remove excess solvent.

[0078] Dry at 50°C for 9 hours. Moderate drying conditions ensure complete drying of the polymer matrix and gentle drying to guarantee the stability of the polymer structure.

[0079] Experiment C: Centrifugation and washing with deionized water to ensure the cleanliness of the polymer.

[0080] Drying at 60°C for 12 hours, using a higher drying temperature and time, makes the polymer matrix more robust and enhances the hardness of the material.

[0081] Control group: centrifugation and washing with deionized water to remove residual monomers and solvents.

[0082] Dry at 40°C for 15 minutes and centrifuge at 4000 rpm to effectively remove solvent and moisture.

[0083] Comparative analysis: Experiment A has a shorter drying time and a more flexible polymer matrix, making it suitable for materials that need to maintain flexibility.

[0084] The drying conditions in Experiment B were relatively moderate, which ensured that the polymer matrix maintained a certain degree of flexibility while ensuring strength.

[0085] The drying conditions in Experiment C are quite harsh, which may result in higher polymer hardness, making it suitable for applications requiring high-strength materials.

[0086] The control group had moderate drying conditions and a shorter drying time, which helped maintain the stability of the material while removing excess moisture.

[0087] 4. Loading of cerium oxide nanoparticles Experiment A: Adding 10% concentration of cerium oxide nanoparticles with a particle size of 2 nm to the polymer matrix helps to improve the surface activity of the material.

[0088] Experiment B: Adding 5.05% concentration of cerium oxide nanoparticles with a particle size of 26 nm to the polymer matrix may affect its dispersibility in the polymer.

[0089] Experiment C: Adding 0.1% concentration of cerium oxide nanoparticles with a particle size of 50 nm to the polymer matrix may reduce the ultrasonic response performance due to the larger particle size.

[0090] Control group: Adding 1.5 wt% cerium oxide nanoparticles to the polymer matrix, with the cerium oxide having a moderate particle size and being uniformly dispersed in the material, optimizes the ultrasonic response performance.

[0091] Comparative analysis: Experiment A has the smallest cerium oxide particles and better reactivity, but due to its high content, it may result in a more rigid material.

[0092] The cerium oxide particles in Experiment B have a larger particle size and may have poorer dispersibility, which may affect the ultrasonic response performance.

[0093] Experiment C had the lowest cerium oxide particle content and the largest particle size, which may have resulted in the worst ultrasonic response.

[0094] The control group had a moderate cerium oxide particle content and particle size, which provided a relatively balanced ultrasonic response and material properties.

[0095] By comparing and analyzing the preparation processes of polymer matrices and cerium oxide nanoparticles under different experimental conditions, the following conclusions were drawn: Experiment A, with its milder reaction conditions, yielded a material suitable for applications requiring high ultrasonic responsiveness but low mechanical properties. Experiment B, with optimized reaction conditions and cerium oxide content, obtained a polymer with balanced properties, suitable for a wide range of applications. Experiment C enhanced the mechanical properties of the polymer matrix through higher reaction temperatures and times, but the larger cerium oxide particles may have reduced ultrasonic responsiveness. The control group, with moderate reaction conditions and cerium oxide content, achieved optimal ultrasonic responsiveness, mechanical properties, and stability, making it suitable for various practical applications.

[0096] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. An ultrasonically responsive piezoelectric material loaded with cerium oxide, characterized in that, It consists of the following components by mass percentage: Piezoelectric polymer matrix: 90%-99.9%; Cerium oxide nanoparticles: 0.1%-10%.

2. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 1, characterized in that: The piezoelectric polymer matrix is ​​formed by oxidative polymerization of pyrrole monomers, including pyrrole, thiophene, and phenylacetylene.

3. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 2, characterized in that: The steps for forming the piezoelectric polymer matrix are as follows: S1. The pyrrole monomer is dispersed in an aqueous medium to form a monomer solution, the concentration of the monomer solution being 1wt%-20wt%, and the pyrrole monomer is stirred in the aqueous medium at a temperature of 25℃-40℃, a rotation speed of 200rpm-800rpm, and a stirring time of 0.5 hours-2 hours. S2. An oxidant is added to the monomer solution to carry out an oxidative polymerization reaction to form a polymer chain intermediate. The oxidant is ferric ions. The amount of oxidant added is 20%-35% of the molar number of the pyrrole monomer. The temperature of the oxidative polymerization reaction is 60℃-80℃ and the reaction time is 3 hours-8 hours. S3. The polymer chain intermediate continues to undergo oxidative polymerization and cross-linking to form a polymer matrix, the surface of which is a three-dimensional nano-network structure; S4. The polymer matrix precursor is surface modified and dried to obtain the piezoelectric polymer matrix. The surface modification includes centrifugation and washing with deionized water. The drying temperature is 40℃-60℃ and the drying time is 6 hours-12 hours.

4. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 1, characterized in that: The cerium oxide nanoparticles have a particle size of 2nm-50nm.

5. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 1, characterized in that: The cerium oxide nanoparticles are formed by in-situ growth of a trivalent cerium ion precursor on the surface of the piezoelectric polymer matrix, wherein the cerium ion precursor is cerium nitrate.

6. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 1, characterized in that: The steps for forming the cerium oxide nanoparticles are as follows: S1. A trivalent cerium ion precursor is added to the surface of the piezoelectric polymer matrix to form a cerium ion precursor; S2. The cerium ion precursor is selectively enriched on the surface of the piezoelectric polymer matrix to form a cerium ion enrichment interface; S3. The cerium ion enrichment interface is subjected to an interfacial transformation reaction to form the cerium oxide nanoparticles.

7. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 6, characterized in that: The selective enrichment is driven by a local potential difference in the piezoelectric polymer matrix, which is formed by the intrinsic polarization components of the piezoelectric polymer matrix. The local region includes surface depressions, defect sites, and chain ends of the piezoelectric polymer matrix.

8. The ultrasonically responsive piezoelectric material supported on cerium oxide according to claim 6, characterized in that: The interface conversion reaction includes adding an alkaline solution to the cerium ion enrichment interface, wherein the alkaline solution converts the trivalent cerium ions at the cerium ion enrichment interface into tetravalent cerium ions, the alkaline solution being ammonia water with a concentration of 0.1M-1.0M, and the alkaline solution adjusting the pH of the cerium ion enrichment interface to be greater than 10.

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