Antibacterial piezoelectric nano composite fiber membrane for individual protection as well as preparation method and application of antibacterial piezoelectric nano composite fiber membrane
By introducing BiVO4/ZnSnO3 heterojunction nanocomposite material into PVDF matrix, an antibacterial piezoelectric nanocomposite fiber membrane was prepared, which solved the problem of microbial contamination of flexible piezoelectric sensors in medical scenarios and realized efficient antibacterial and dual-modal sensing functions, which is suitable for wearable electronic devices.
Patent Information
- Application Number
- CN202510923024.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2025-10-28
AI Technical Summary
Existing flexible piezoelectric sensors are difficult to effectively prevent microbial contamination in medical settings, and traditional piezoelectric materials have insufficient antibacterial properties, affecting biocompatibility and environmental adaptability.
Using PVDF as the matrix, BiVO4/ZnSnO3 heterojunction nanocomposite material was introduced, and antibacterial piezoelectric nanocomposite fiber membrane was prepared by solution blow spinning technology. Combining piezoelectric and antibacterial functions, pressure and temperature sensing and dynamic sterilization functions were constructed.
It achieves highly efficient antibacterial performance, with a kill rate of >99.9% against multidrug-resistant strains. It also features dual-modal sensing capabilities of pressure and temperature, exhibiting high sensitivity and stability, making it suitable for wearable electronic devices.
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Figure CN120844284A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of piezoelectric nanomaterials technology, and in particular to an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, its preparation method, and its application. Background Technology
[0002] As wearable electronic devices expand into personal protective equipment (PPE) fields such as medical monitoring and industrial safety, traditional rigid sensors are finding it increasingly difficult to meet the demands of complex scenarios in terms of biocompatibility, environmental adaptability, and active protection functions. Flexible piezoelectric sensors, through a mechanical-to-electrical energy conversion mechanism, achieve self-powered motion and physiological signal monitoring. Their core lies in the performance optimization and multi-dimensional functional integration of piezoelectric materials. Current research largely focuses on improving sensitivity, but generally neglects the crucial element of microbial protection. Statistics show that 67% of hospital-acquired infections in medical settings originate from secondary contamination of protective equipment.
[0003] Piezoelectric materials are a class of functional materials capable of converting mechanical energy into electrical energy, exhibiting both direct and inverse piezoelectric effects. When subjected to external forces, the asymmetry of their crystal structure leads to charge separation, generating a potential on the surface (direct piezoelectric effect); conversely, when an electric field is applied, the material deforms (inverse piezoelectric effect). Natural piezoelectric materials (such as quartz) and synthetic materials (such as barium titanate and PZT ceramics) are widely used in sensors, ultrasonic transducers, and energy harvesting. Flexible piezoelectric polymers (such as PVDF) and their nanocomposites, developed in recent years, have become core materials for wearable electronics and self-powered systems due to their high β-phase content, stable piezoelectric coefficient, and stretchability. Furthermore, under ultrasonic or light stimulation, piezoelectric materials can efficiently generate reactive oxygen species (ROS) through mechano-electric coupling, enabling antibiotic-free antibacterial strategies. The principle is based on the piezoelectric potential generated by piezoelectric materials (such as PVDF-based composites) under external force or photoinduced deformation, driving electron-hole separation on the surface. This leads to a reaction with water / oxygen in the environment, generating highly reactive substances such as hydroxyl radicals (·OH) and superoxide anions (·O2-). By controlling the content of the material's crystal phase (such as the β phase of PVDF) or constructing heterojunctions, carrier separation efficiency can be enhanced. This technology combines rapid response with broad-spectrum antibacterial properties and has been applied to antibacterial catheters, wound dressings, and self-cleaning surfaces, providing a new approach to combating biofilm infections and controlling drug-resistant bacteria.
[0004] PVDF (polyvinylidene fluoride) is a high-performance fluoropolymer possessing chemical stability, mechanical strength, and functionality. Its strongly polar CF bonds in the molecular chain endow it with excellent corrosion resistance, resisting strong acids, strong alkalis, and organic solvents. The piezoelectric properties of PVDF are positively correlated with the content of the polar β phase in its crystals. Adjusting the preparation process parameters (such as the temperature gradient of heat treatment, mechanical stretching rate, and electric field polarization intensity) can control the crystallization kinetics, significantly altering the β phase proportion and thus directly affecting its piezoelectric output efficiency. Through crystal phase control, PVDF exhibits significant piezoelectric properties (d... 33 With a strength of 20-30 pC / N, it is widely used in flexible sensors, ultrasonic transducers, and energy harvesting devices. In recent years, solution spinning technology (such as SBS) combined with nanofiller (BiVO4, ZnSnO3) doping can prepare β-phase reinforced flexible piezoelectric fiber membranes, promoting their application in wearable electronics and self-cleaning surfaces.
[0005] Solution-blown spinning technology provides an ideal matrix for constructing multifunctional piezoelectric sensors due to its three-dimensional porous structure, high specific surface area, and controllable morphology. This technology eliminates the dependence on high-voltage electric fields in traditional electrospinning, utilizing high-speed airflow shearing to achieve continuous and efficient nanofiber preparation, with a production rate more than 10 times that of electrospinning. Furthermore, fiber diameter (50-800 nm) and porosity (70-95%) can be precisely controlled by adjusting process parameters, enabling both large-scale production and customized structure creation. Its broad material compatibility covers synthetic polymers (such as PVDF and PLA), bio-based materials (chitosan), and composite systems. Functional fillers (such as BiVO4 and ZnSnO3) can be in-situ doped during the spinning process, simultaneously constructing antibacterial and conductive properties. Summary of the Invention
[0006] The purpose of this invention is to provide an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, its preparation method and application. Using PVDF with high strength, high flexibility and excellent thermal stability as the matrix, and introducing BiVO4 / ZnSnO3 heterojunction nanocomposite material, it integrates real-time pressure and temperature sensing, mechanical barrier protection and dynamic sterilization functions, providing an innovative material basis for wearable flexible sensors and adaptive personal protective equipment.
[0007] To achieve the above objectives, the present invention provides a method for preparing an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, comprising the following steps:
[0008] S1. Preparation of BiVO4;
[0009] S2. Using the BiVO4 obtained in S1, BiVO4 / ZnSnO3 composite material was prepared by in-situ growth method.
[0010] S3. PVDF-BiVO4 / ZnSnO3 composite fiber membranes were prepared using the BiVO4 / ZnSnO3 composite material obtained in S2.
[0011] Preferably, the specific steps of S1 are as follows:
[0012] S11. Dissolve bismuth nitrate pentahydrate and sodium dodecylbenzenesulfonate in nitric acid solution and stir to obtain solution A;
[0013] S12. Dissolve ammonium metavanadate in sodium hydroxide solution and stir to obtain solution B;
[0014] S13. Slowly add solution B dropwise into solution A, stir, adjust the pH, stir again, and then carry out the hydrothermal reaction.
[0015] S14. After the reaction, cool and centrifuge. Wash the yellow precipitate obtained by centrifugation with distilled water and anhydrous ethanol, and dry to obtain yellow powder BiVO4.
[0016] Preferably, the mass ratio of bismuth nitrate pentahydrate, sodium dodecylbenzenesulfonate, and ammonium metavanadate is (8-12):1:(1-4);
[0017] In S13, adjust the pH to 4-5, the hydrothermal reaction temperature is 180-200℃, and the hydrothermal reaction time is 2-3 hours.
[0018] Preferably, the specific steps of S2 are as follows:
[0019] S21. Dissolve zinc acetate dihydrate, tin tetrachloride pentahydrate, and polyethylene glycol in ultrapure water, stir, adjust the pH, add BiVO4 obtained in S1, and stir again.
[0020] S22. Transfer the stirred mixture to an autoclave for hydrothermal reaction;
[0021] S23. After the reaction is cooled, the mixture is washed with anhydrous ethanol and water, and dried to obtain a yellow powder BiVO4 / ZnSnO3 composite material.
[0022] Preferably, in S21, the mass ratio of zinc acetate dihydrate, tin tetrachloride pentahydrate, polyethylene glycol, and BiVO4 is 1:(1-3):(1-4):1;
[0023] In S21, adjust the pH to 6-8;
[0024] In S22, the hydrothermal reaction temperature is 180-200℃, and the hydrothermal reaction time is 4-6h.
[0025] Preferably, the specific steps of S3 are as follows:
[0026] S31. Dissolve the BiVO4 / ZnSnO3 composite material obtained in S2 in DMF, stir, sonicate, then add PVDF powder and stir until uniform.
[0027] S32. Transfer the well-stirred solution to an oil bath and heat and stir to obtain a PVDF spinning solution with uniformly dispersed BiVO4 / ZnSnO3.
[0028] S33. PVDF-BiVO4 / ZnSnO3 composite fiber membranes are obtained by solution blowing spinning technology on PVDF spinning solution.
[0029] Preferably, in S31, the ratio of DMF to BiVO4 / ZnSnO3 composite material is 0.1-0.3g of BiVO4 / ZnSnO3 composite material dissolved in 1mL of DMF; the mass of BiVO4 / ZnSnO3 composite material is 10%-40% of the mass of PVDF.
[0030] In S32, the temperature of the oil bath is 40-60℃, and the stirring time is 4-10h.
[0031] This invention provides an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, which is prepared using the above-described preparation method.
[0032] PVDF nanofibers provide a support platform for BZ composites, uniformly fixing the BZ composites on their surface. The loading of the BZ composites significantly increases the content of the polar β phase of PVDF, enhances the piezoelectric properties of the fiber membrane, and improves the piezoelectric photocatalytic performance of the P-BZ composite nanofibers.
[0033] This invention provides an application of an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, which is used to assemble a wearable flexible dual-modal pressure and temperature sensor.
[0034] Therefore, the present invention, employing the above-mentioned antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, its preparation method, and its application, has the following beneficial effects:
[0035] (1) Structural regulation mechanism: The molecular dipole interaction between BZ and PVDF significantly increases the β phase content, giving the P-BZ composite fiber membrane a higher piezoelectric coefficient.
[0036] (2) Carrier dynamics optimization: BZ forms an internal electric field through a type II heterostructure, which effectively suppresses electron-hole pair recombination. Under the synergistic excitation of ultrasound (1MHz / 10W) and visible light (λ≥420nm), the ROS generation rate is significantly improved compared with the single catalytic mode.
[0037] (3) Broad-spectrum antibacterial efficacy: The kill rate against multidrug resistant Escherichia coli (MDR E.coli) and methicillin-resistant Staphylococcus aureus (MRSA) is >99.9%.
[0038] (4) Intelligent sensing performance: The sensor assembled from P-BZ composite fiber membrane has both pressure and temperature sensing performance, with a high pressure and temperature detection range (pressure detection range 0-125kPa, temperature detection range 0-65℃), high pressure and temperature response sensitivity, and excellent stability for cyclic use.
[0039] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description
[0040] Figure 1 This is a physical image of the PVDF fiber membrane of Comparative Example 1 of the present invention;
[0041] Figure 2 This is a photograph of the P-BZ composite fiber membrane of Embodiment 1 of the present invention;
[0042] Figure 3 These are SEM images of the fiber membranes obtained in Example 1 and Comparative Examples 1-3 of the present invention, and EDS images of the P-BZ composite fiber membrane obtained in Example 1.
[0043] Figure 4 These are the XRD patterns of the fiber membranes obtained in Examples 1-3 and Comparative Example 1 of the present invention;
[0044] Figure 5 These are FTIR images of the fiber membranes obtained in Examples 1-3 and Comparative Example 1 of the present invention;
[0045] Figure 6 This describes the yield and types of ROS in the fiber membranes obtained in Embodiment 1 and Comparative Examples 1-3 of this invention under ultrasonic-coupled light irradiation conditions.
[0046] Figure 7 The ROS yield of the P-BZ composite fiber membrane obtained in Example 1 of this invention under different test conditions;
[0047] Figure 8 This invention demonstrates the antibacterial properties of different fiber membranes against drug-resistant Escherichia coli under different test conditions.
[0048] Figure 9 This invention demonstrates the antibacterial properties of different fiber membranes against methicillin-resistant Staphylococcus aureus under different test conditions.
[0049] Figure 10 This is a physical image of a P-BZ pressure and temperature sensor assembled from the P-BZ composite fiber membrane prepared in Example 1 of this invention.
[0050] Figure 11 The graph shows the test results of the detection range, response recovery time, and cycle stability of the P-BZ pressure and temperature sensor of this invention.
[0051] Figure 12 This is a graph showing the resistance response test results of the P-BZ pressure-temperature sensor of this invention to common movements such as finger bending and wrist bending.
[0052] Figure 13 This is a graph showing the resistance response test results of the P-BZ pressure and temperature sensor of this invention to fine movements such as the face.
[0053] Figure 14 This is a flowchart of the preparation process of the P-BZ composite fiber membrane in Embodiment 1 of the present invention and a diagram of the working mechanism of the P-BZ pressure and temperature sensor. Detailed Implementation
[0054] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.
[0055] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
[0056] Example 1
[0057] A method for preparing an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment includes the following steps:
[0058] S1. Preparation of BiVO4:
[0059] S11. Dissolve 2.425g Bi(NO3)3·5H2O and 0.25g sodium dodecylbenzenesulfonate (SDBS) in 20mL of 4mol / L nitric acid solution and stir at room temperature for 30min to obtain solution A;
[0060] S12. Dissolve 0.584 g of ammonium metavanadate (NH4VO3) in 20 mL of 2 mol / L sodium hydroxide solution and stir at room temperature for 30 min to obtain solution B;
[0061] S13. Slowly add solution B dropwise into solution A under stirring, stir at room temperature for 30 min, adjust pH to 4 using 2 mol / L sodium hydroxide solution, stir again for 30 min, then pour the mixed solution into a 100 mL Teflon autoclave and react at 200 °C for 2 h.
[0062] S14. After the reaction, the mixture was allowed to cool naturally to room temperature, and then centrifuged at 10,000 rpm for 10 min. The yellow precipitate obtained by centrifugation was washed three times each with distilled water and anhydrous ethanol, and then dried under vacuum at 60°C to obtain yellow BiVO4 powder.
[0063] S2. Using the BiVO4 obtained in S1, BiVO4 / ZnSnO3 composite materials were prepared by in-situ growth method:
[0064] S21, Add 0.2634g zinc acetate dihydrate, 0.4207g tin tetrachloride pentahydrate, and 0.5g polyethylene glycol (M w =2000) was dissolved in 30 mL of ultrapure water under stirring. The mixture was stirred at room temperature for 30 min, and then the pH was adjusted to 8 using 1 mol / L sodium hydroxide solution. 0.2785 g of BiVO4 obtained from S1 was added, and the mixture was stirred at room temperature for 30 min and then sonicated in a water bath for 30 min.
[0065] S22. Transfer the ultrasonically mixed solution to a 100mL Teflon autoclave and react at 180℃ for 6 hours.
[0066] S23. After the reaction, the mixture was cooled to room temperature and washed three times each with anhydrous ethanol and water. After vacuum drying at 60°C, a yellow powder BiVO4 / ZnSnO3 (BZ) composite material was obtained.
[0067] S3. Using the BiVO4 / ZnSnO3 composite material obtained in S2, prepare PVDF-BiVO4 / ZnSnO3 composite fiber membrane:
[0068] S31. Dissolve 1.056g of the BZ composite material obtained in S3 in 11mL of DMF, stir at room temperature for 10min, sonicate for 30min, and then add 2.64g of polyvinylidene fluoride (PVDF) powder while stirring. Stir magnetically for 1h until uniform. At this time, the mass of the BZ composite material is 40% of PVDF.
[0069] S32. Transfer the well-stirred solution to an oil bath and stir at 480 rpm for 8 hours at 52°C to obtain a PVDF spinning solution with BZ evenly dispersed.
[0070] S33. PVDF-BiVO4 / ZnSnO3 composite fiber membrane, i.e., P-BZ composite fiber membrane, is obtained by solution blowing spinning of PVDF spinning solution. The solution blowing spinning technique uses a 25G needle, a feed rate of 2.5mL / h, a receiving roller speed of 470rpm, a receiving distance of 30cm, and an air pressure of 95kPa.
[0071] Example 2
[0072] The difference between Example 2 and Example 1 is that the mass of the BZ composite material in S31 is 10% of the mass of PVDF, while the rest is the same as in Example 1.
[0073] Example 3
[0074] The difference between Example 3 and Example 1 is that the mass of the BZ composite material in S31 is 20% of the mass of PVDF, while the rest is the same as in Example 1.
[0075] Comparative Example 1
[0076] Comparative Example 1 uses a pure polyvinylidene fluoride fiber membrane, i.e., a PVDF fiber membrane.
[0077] Comparative Example 2
[0078] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 did not use the BiVO4 obtained in S1 to prepare BiVO4 / ZnSnO3 composite material by in-situ growth method. The prepared material was PVDF-BiVO4 composite fiber membrane, i.e. P-BiVO4 composite fiber membrane.
[0079] Comparative Example 3
[0080] The difference between Comparative Example 3 and Example 1 is that BiVO4 was not prepared in Comparative Example 3, and the prepared product was a PVDF-ZnSnO3 composite fiber membrane, i.e., a P-ZnSnO3 composite fiber membrane.
[0081] Test 1
[0082] Figure 1 and Figure 2 The images show actual photos of the PVDF fiber membrane from Comparative Example 1 and the P-BZ composite fiber membrane from Example 1, respectively. The PVDF nanofibers provide a supporting platform for the BZ composite material, uniformly fixing the BZ composite material onto its surface. The loading of the BZ composite material significantly increases the content of the polar β phase of PVDF, enhancing the piezoelectric properties of the fiber membrane, and also improves the piezoelectric photocatalytic performance of the P-BZ composite nanofibers. Figure 3 The images show SEM images of the fiber membranes obtained in Example 1 and Comparative Examples 1-3, and EDS images of the P-BZ composite fiber membrane obtained in Example 1. The PVDF nanofibers exhibit a uniform, continuous, and smooth fiber structure. BZ nanoparticles attached to the surface of the nanofibers can be clearly seen on the 40wt% doped nanofiber membrane.
[0083] The structure and chemical composition of P-BZ composite fiber membranes obtained under different mass ratios of doping in Examples 1-3 were compared. Figure 4 The XRD patterns of PVDF fiber membranes and P-BZ composite fiber membranes with doping amounts of 10 wt%, 20 wt%, and 40 wt% are shown. Figure 4 It can be seen that the BZ composite nanomaterials were successfully doped, and the β phase of PVDF also increased with the increase of the doping amount. Figure 5 The images show the FTIR spectra of PVDF fiber membranes and P-BZ composite fiber membranes with doping amounts of 10 wt%, 20 wt%, and 40 wt%, respectively. Figure 5 (a) in the image shows the FTIR spectra of different fiber membranes. Figure 5 (b) in the figure represents the β phase content of PVDF in different fiber membranes. Figure 5 Experimental data also demonstrate that increasing the doping amount helps to form the polar β phase of PVDF. At the same time, P-BZ has the highest β phase content, reaching 91%, when the doping amount is 40wt%.
[0084] Test 2
[0085] like Figure 6 As shown, the yield and types of ROS in the fiber membranes obtained in Example 1 and Comparative Examples 1-3 under ultrasonic-coupled light irradiation were detected using electron spin resonance spectroscopy (ESR). Figure 6 (a) Figure 6 (b) represents singlet oxygen ( 1 O2), superoxide anion (·O2) - The generation of ROS was observed. Except for PVDF fiber membranes, which did not generate ROS under ultrasonic-coupled light irradiation, P-BiVO4 composite fiber membranes, P-ZnSnO3 composite fiber membranes, and P-BZ composite fiber membranes all generated ROS to varying degrees under ultrasonic-coupled light irradiation. 1 O2 and ·O2 - Furthermore, the ROS intensity generated by the P-BZ composite fiber membrane was stronger than that of the P-BiVO4 composite fiber membrane and the P-ZnSnO3 composite fiber membrane, verifying the successful construction of the heterojunction. ESR tests were performed on the P-BZ composite fiber membrane under darkness, ultrasound, light, and ultrasound-coupled light conditions. 1 O2 and ·O2 - The yield, the result is as follows Figure 7 As shown, Figure 7 (a) Figure 7 (b) in the middle are respectively 1 O2、·O2 - The generation of ROS was observed. P-BZ composite fiber membranes did not generate ROS under dark conditions, but ROS were generated to varying degrees under ultrasound, light, and ultrasound-coupled light conditions. 1 O2 and ·O2 - Furthermore, the ROS intensity generated by the P-BZ composite fiber membrane under ultrasonic coupled light irradiation conditions is stronger than that generated by ultrasonic or light irradiation alone, indicating that piezoelectric catalysis combined with photocatalysis has a better ROS generation capacity.
[0086] Test 3
[0087] The antibacterial properties of the fiber membranes obtained in Example 1 and Comparative Examples 1-3 were tested under darkness, ultrasound, light, and ultrasound-coupled light. Figure 8 To investigate the antibacterial properties of different fiber membranes against drug-resistant Escherichia coli under different test conditions, Figure 8 Image (a) is a photograph of bacterial colonies on a plate. Figure 8 (b) in the image is a SEM image. Figure 8 (c) represents the antibacterial rate. Figure 8 (d) in the figure represents the nucleic acid content. Figure 9 To investigate the antibacterial properties of different fiber membranes against methicillin-resistant Staphylococcus aureus under different test conditions, Figure 9 Image (a) is a photograph of bacterial colonies on a plate. Figure 9 (b) in the image is a SEM image. Figure 9 (c) represents the antibacterial rate. Figure 9 In this context, (d) represents the nucleic acid content. From... Figure 8 , Figure 9 It can be seen that the bactericidal effect of PVDF fiber membranes is negligible under both visible light and ultrasonic irradiation, and has almost no bactericidal effect under ultrasonic-coupled light irradiation. Under dark conditions, P-BiVO4, P-ZnSnO3, and P-BZ composite fiber membranes also have almost no bactericidal effect, even under ultrasonic (10W, 1MHz) and light irradiation (1000W / m²). 2 Under irritation conditions, P-BiVO4, P-ZnSnO3, and P-BZ composite fiber membranes exhibit certain antibacterial activity. P-BZ composite fiber membranes achieve an antibacterial rate of over 99.9% against both Gram-negative and Gram-positive bacteria under simultaneous ultrasound and light stimulation, demonstrating broad-spectrum bactericidal effects.
[0088] Application Example 1
[0089] The P-BZ composite fiber membrane prepared in Example 1 was assembled into a P-BZ pressure-temperature sensor, such as... Figure 10 As shown, the P-BZ pressure-temperature sensor consists of a "sandwich"-like structure. The outermost layer is a PDMS film, which encapsulates and protects the sensor, ensuring its stable function. The inner layer comprises seven layers of P-BZ composite fiber membranes and copper electrodes, with each layer connected by conductive tape. When there is no pressure, there is no potential within the P-BZ fiber membrane, and the dipoles are randomly distributed. When pressure is applied to the P-BZ pressure-temperature sensor, a piezoelectric potential and piezoelectric current are instantaneously generated, and the dipoles are arranged in an orderly and uniform distribution. Figure 11 As shown, the detection range, response recovery time, and cyclic stability of the P-BZ pressure and temperature sensor were tested. Figure 11 In the diagram, (a) represents the pressure detection range. Figure 11 In the diagram, (b) represents the temperature detection range. Figure 11 In the figure, (c) represents the pressure response time. Figure 11 In this context, (d) represents the temperature response time. Figure 11 In this context, (e) represents the cyclic stability of the pressure. Figure 11 (f) represents the cyclic stability of temperature. The results show that the P-BZ pressure-temperature sensor has a dual-mode response function of pressure and temperature, and has a wide detection range, fast response recovery time, and excellent stability.
[0090] The P-BZ pressure-temperature sensor was applied to different scenarios, and its resistivity changes under various motion states were detected. Common motion behaviors such as finger bending and wrist bending were used as representatives, and the results are as follows: Figure 12 As shown, Figure 12 In the figures (a)-(f), the bending resistance response tests were performed on the fingers, wrist, elbow, arm, knee, and ankle, respectively. Next, sensors were attached to various parts of the face to detect more subtle pressure changes, such as variations in facial behavior. The results are as follows: Figure 13 As shown, Figure 13 (a)-(f) represent the resistive response tests for blinking, frowning, laughing, chewing, swallowing, and coughing, respectively. Figures 12-14 It can be seen that the P-BZ pressure-temperature sensor has good pressure response and potential for development in motion monitoring and physiological monitoring.
[0091] Therefore, this invention employs the aforementioned antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, its preparation method, and its application. By constructing a type II heterojunction and doping with piezoelectric nanomaterials, it achieves innovative dual-component functionality and enhanced performance of the fiber, combining antibacterial properties with pressure and temperature sensing. On one hand, under simultaneous stimulation by ultrasound and light, it exhibits excellent piezoelectric photocatalytic synergistic antibacterial effects, achieving an antibacterial rate of 99.9%. On the other hand, based on the excellent piezoelectric and pyroelectric effects of the P-BZ composite fiber membrane, the P-BZ pressure and temperature sensor possesses excellent dual-modal pressure and temperature sensing performance, exhibiting low detection limits, high sensitivity, extremely short response recovery time, and reliable cyclic stability, making it suitable for application in personal protective clothing.
[0092] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.
Claims
1. A method for preparing an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, characterized in that, Includes the following steps: S1. Preparation of BiVO4; S2. Using the BiVO4 obtained in S1, BiVO4 / ZnSnO3 composite material was prepared by in-situ growth method. S3. PVDF-BiVO4 / ZnSnO3 composite fiber membranes were prepared using the BiVO4 / ZnSnO3 composite material obtained in S2.
2. The preparation method according to claim 1, characterized in that, The specific steps of S1 are as follows: S11. Dissolve bismuth nitrate pentahydrate and sodium dodecylbenzenesulfonate in nitric acid solution and stir to obtain solution A; S12. Dissolve ammonium metavanadate in sodium hydroxide solution and stir to obtain solution B; S13. Slowly add solution B dropwise into solution A, stir, adjust the pH, stir again, and then carry out the hydrothermal reaction. S14. After the reaction, cool and centrifuge. Wash the yellow precipitate obtained by centrifugation with distilled water and anhydrous ethanol, and dry to obtain yellow powder BiVO4.
3. The preparation method according to claim 2, characterized in that, The mass ratio of bismuth nitrate pentahydrate, sodium dodecylbenzenesulfonate, and ammonium metavanadate is (8-12):1:(1-4); In S13, adjust the pH to 4-5, the hydrothermal reaction temperature is 180-200℃, and the hydrothermal reaction time is 2-3 hours.
4. The preparation method according to claim 1, characterized in that, The specific steps of S2 are as follows: S21. Dissolve zinc acetate dihydrate, tin tetrachloride pentahydrate, and polyethylene glycol in ultrapure water, stir, adjust the pH, add BiVO4 obtained in S1, and stir again. S22. Transfer the stirred mixture to an autoclave for hydrothermal reaction; S23. After the reaction is cooled, the mixture is washed with anhydrous ethanol and water, and dried to obtain a yellow powder BiVO4 / ZnSnO3 composite material.
5. The preparation method according to claim 4, characterized in that, In S21, the mass ratio of zinc acetate dihydrate, tin tetrachloride pentahydrate, polyethylene glycol, and BiVO4 is 1:(1-3):(1-4):1; In S21, adjust the pH to 6-8; In S22, the hydrothermal reaction temperature is 180-200℃, and the hydrothermal reaction time is 4-6h.
6. The preparation method according to claim 1, characterized in that, The specific steps for S3 are as follows: S31. Dissolve the BiVO4 / ZnSnO3 composite material obtained in S2 in DMF, stir, sonicate, then add PVDF powder and stir until uniform. S32. Transfer the well-stirred solution to an oil bath and heat and stir to obtain a PVDF spinning solution with uniformly dispersed BiVO4 / ZnSnO3. S33. PVDF-BiVO4 / ZnSnO3 composite fiber membranes are obtained by solution blowing spinning technology on PVDF spinning solution.
7. The preparation method according to claim 6, characterized in that, In S31, the ratio of DMF to BiVO4 / ZnSnO3 composite material is 0.1-0.3g of BiVO4 / ZnSnO3 composite material dissolved in 1mL of DMF; the mass of BiVO4 / ZnSnO3 composite material is 10%-40% of the mass of PVDF. In S32, the temperature of the oil bath is 40-60℃, and the stirring time is 4-10h.
8. An antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. An application of an antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment, characterized in that, The antibacterial piezoelectric nanocomposite fiber membrane for personal protective equipment as described in claim 8 is used to assemble a wearable flexible dual-modal pressure and temperature sensor.