Preparation method of samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor

Abstract

The application discloses a preparation method of a samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor. The application first prepares samarium trioxide doped lead zirconate titanate lead niobate ceramic; the ceramic is ground into powder and added into a sodium alginate solution, sodium dodecyl sulfate and citric acid are sequentially added, excessive water is added into the solution to obtain a low-viscosity slurry; then ball milling is carried out to break the agglomerates and obtain a uniform suspension, finally the slurry is injected into a CaCl2 solution to obtain a fiber, and the fiber is dried at room temperature and then calcined for the third time. The application precisely controls the molar ratio of raw materials, the reaction temperature, the reaction time and the doping ratio, guarantees the high-quality preparation of PNN-PZT / x Sm2O3 ceramic and fiberized piezoelectric ceramic, and makes the prepared piezoelectric fiber sensor have excellent piezoelectric performance and can more sensitively detect external signals.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of piezoelectric fiber sensor preparation, and particularly relates to a preparation method of a samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor. BACKGROUND

[0002] The piezoelectric fiber sensor can convert physical quantities such as mechanical vibration, stress fluctuation and acoustic wave signals into measurable electrical signals based on the piezoelectric effect, and can realize high-sensitivity and real-time dynamic monitoring. Its unique fiber structure (diameter ≤0.5mm) endows it with excellent flexibility and spatial adaptability, and it can be flexibly attached to complex surfaces or embedded in multi-layer materials, and is suitable for distributed and non-invasive sensing requirements.

[0003] The piezoelectric fiber sensor is prepared through a high-temperature sintering process and has excellent environmental stability, and can maintain reliable performance in a wide temperature range of-40℃ to 150℃, and can adapt to harsh working conditions in the fields of industrial equipment, aerospace, intelligent structure, medical health and the like. In the power system, the sensor is particularly suitable for the state monitoring of cables and intermediate joints, and can accurately capture weak signals such as partial discharge and mechanical deformation, and effectively overcome the limitations of traditional infrared temperature measurement and partial discharge detection. Its miniaturization feature makes it possible to be directly wound on the surface of the cable conductor or embedded in the insulation layer, thereby realizing long-term stable online monitoring.

[0004] Compared with traditional sensing technology, the sensor has higher sensitivity and response speed in micro-vibration detection, dynamic strain monitoring and ultrasonic sensing, and can accurately capture early damage or abnormal signals. In addition to power facilities, it also has excellent performance in the fields of structural health monitoring, intelligent operation and maintenance, robot touch, biomechanical analysis and the like, and provides an innovative solution for modern intelligent sensing systems.

[0005] Piezoelectric ceramic materials have excellent electromechanical coupling performance and are widely used in the fields of sensors and actuators. As a typical relaxor piezoelectric material, lead zirconate titanate lead niobate (PNN-PZT) based ceramics have high dielectric constant, low dielectric loss and good temperature stability, but the traditional bulk materials have the problems of poor flexibility, easy aggregation in the fiber preparation process and significant influence of the piezoelectric performance by the crystal boundary. Improving the performance of the material through nano-doping and fiberization process is a current research hotspot.

[0006] As a rare earth dopant, samarium trioxide can optimize the polarization characteristics and mechanical strength of the ceramic through lattice distortion and defect control, but the influence of the Sm2O3 doping amount on the performance of the PNN-PZT based material and the parameter optimization of the fiberization preparation process still need further research in the prior art. In addition, there are problems such as poor slurry uniformity, low fiber forming precision and incomplete removal of organic components in the traditional fiberization process, which limits the stability and sensitivity of the fiber sensor. SUMMARY

[0007] The present application aims at the deficiencies of the prior art, and provides a preparation method of a samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor.

[0008] The preparation method of the samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor comprises the following steps:

[0009] The nanometer nickel oxide and nanometer niobium oxide are first calcined to obtain a nickel niobium oxide precursor; the lead oxide PbO, the nickel niobium oxide precursor, nanometer zirconium dioxide and nanometer titanium dioxide are mixed, and after adding ethanol, the first ball milling is performed, and then the second ball milling is performed by adding Sm2O3 powder; the polyvinyl alcohol is added into the mixed powder after the ball milling is completed, and the second calcination is performed to remove the organic matter, so as to obtain the samarium trioxide doped lead zirconate titanate lead niobate ceramic.

[0010] The samarium trioxide doped lead zirconate titanate lead niobate ceramic powder is ground and added into a sodium alginate salt solution together with the polyvinyl alcohol, sodium dodecyl sulfate and citric acid are sequentially added, and then an excess of water is added to obtain a low-viscosity slurry.

[0011] The low-viscosity slurry is ball milled to break the agglomerates, so as to obtain a uniform suspension, and then the CaCl2 solution is injected to maintain for 60-90 minutes to obtain the samarium trioxide doped lead zirconate titanate lead niobate fiber.

[0012] After the samarium trioxide doped lead zirconate titanate lead niobate fiber is dried at room temperature, the organic components are continuously removed, and the third calcination is performed in a closed alumina crucible to obtain the samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor.

[0013] In one embodiment, the first ball milling time is 12 hours, and the second ball milling time is 12 hours.

[0014] In one embodiment, the first calcination condition is that the calcination temperature is 1000 o C, and the calcination time is 3 hours.

[0015] In one embodiment, the second calcination condition is that the temperature is increased to 1050℃ at a rate of 5℃ / min, sintered for 1 hour, then the temperature is increased to 1300℃ at a rate of 5℃ / min, sintered for 2 hours, and cooled to room temperature.

[0016] In one embodiment, the third calcination condition is that the temperature is increased at a rate of 100 ℃ / h, and is kept at 200 ℃ and 600 ℃ for 30 min respectively, the temperature is increased to 1285℃ at a rate of 200 ℃ / h and sintered for 30 min.

[0017] In one embodiment, the polyvinyl alcohol added in the preparation of the Sm2O3 doped PNN-PZT ceramic has a content of 6 wt%.

[0018] In one embodiment, the preparation of the Sm2O3 doped PNN-PZT ceramic further comprises: under a uniaxial pressure of 120 MPa, the mixed powder is pressed into a powder compact. o C is heated for 3 hours to remove the organic matter.

[0019] In one embodiment, the molar ratio of the nano nickel oxide and the nano niobium oxide is 1:1.

[0020] In one embodiment, the molar ratio of the lead oxide, the nickel niobium oxide precursor, the nano zirconium dioxide and the nano titanium dioxide is 0.42:0.42:y:(0.58-y), and the value range of y is 0.2-0.3.

[0021] In one embodiment, the molar ratio of the Sm2O3 powder and the nano nickel oxide is 0.005:1-0.03:1.

[0022] The present application ensures the high-quality preparation of the PNN-PZT / x Sm2O3 ceramic and the fiberized piezoelectric ceramic by precisely controlling the molar ratio of each raw material, the reaction temperature, the time and the doping ratio, so that the prepared piezoelectric fiber sensor has excellent piezoelectric performance and can more sensitively detect external signals.

[0023] By using the sodium alginate-CaCl2 cross-linking system combined with the ball milling dispersion process, the fiber diameter is ensured to be uniform, and the temperature of the material can be flexibly controlled by adjusting the value of y (Zr / Ti ratio), so as to meet the sensing requirements in different environments.

[0024] The whole preparation method is relatively simple, easy to operate and control, and suitable for large-scale industrial production, thereby providing technical support for the wide application of the Sm2O3 doped PNN-PZT / x Sm2O3 piezoelectric fiber sensor. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art according to these drawings without exceeding the scope of the present application.

[0026] Figure 1is a flow chart of a method for preparing a samarium trioxide doped lead zirconium titanate-lead niobate (PNN-PZT / x Sm203) piezoelectric fiber sensor according to embodiments of the present application. DETAILED DESCRIPTION

[0027] Figure 1 is a flow chart of a method for preparing a samarium trioxide doped lead zirconium titanate-lead niobate (PNN-PZT / x Sm203) piezoelectric fiber sensor according to embodiments of the present application. As shown in Figure 1 the method for preparing a samarium trioxide doped lead zirconium titanate-lead niobate (PNN-PZT / x Sm203) piezoelectric fiber sensor includes the following steps:

[0028] Step one, preparation of samarium trioxide doped lead zirconium titanate-lead niobate (PNN-PZT / x Sm203) ceramic

[0029] Nano-nickel oxide and nano-niobium oxide are first calcined to obtain a nickel niobium oxide precursor; lead oxide PbO, the nickel niobium oxide precursor, nano-zirconium dioxide, and nano-titanium dioxide are mixed, first ball milled after adding ethanol, and second ball milled after adding Sm203 powder; wherein the ball milling time can be set according to actual conditions.

[0030] Polyvinyl alcohol is added to the mixed powder after the end of ball milling, and second calcination is performed to remove organic matter to obtain PNN-PZT / x Sm203 ceramic, wherein x is the molar ratio of Sm203 to nickel oxide.

[0031] Step two, preparation of samarium trioxide doped lead zirconium titanate-lead niobate (PNN-PZT / x Sm203) piezoelectric fiber sensor

[0032] Samarium trioxide doped lead zirconium titanate-lead niobate ceramic powder is ground and added to a sodium alginate salt solution together with polyvinyl alcohol, sodium dodecyl sulfate and citric acid are sequentially added, and then excess water is added to obtain a low viscosity slurry; wherein the temperature value of the deionized water is adjusted according to the actual production process, and according to some embodiments, deionized water at 70-80°C can better dissolve with sodium alginate salt.

[0033] The low viscosity slurry is ball milled to break the agglomerates to obtain a uniform suspension, and then a CaCl2 solution is injected and kept for 60-90 minutes to obtain samarium trioxide doped lead zirconium titanate-lead niobate fibers; wherein the ball milling time can be set according to actual conditions.

[0034] After drying the samarium trioxide doped lead zirconium titanate-lead niobate fibers at room temperature, the organic components are further removed, and a third calcination is performed in a closed alumina crucible to obtain a samarium trioxide doped lead zirconium titanate-lead niobate piezoelectric fiber sensor.

[0035] In some embodiments, the first ball milling time is 12 hours and the second ball milling time is 12 hours.

[0036] In some embodiments, the first calcination condition is: the calcination temperature is 1000 o C and the calcination time is 3 hours.

[0037] In some embodiments, the second calcination condition is: heating to 1050 °C at a rate of 5 °C / min, sintering for 1 hour, then heating to 1300 °C at a rate of 5 °C / min, sintering for 2 hours, and cooling to room temperature.

[0038] In some embodiments, the third calcination condition is: heating at a rate of 100 °C / h, and holding at 200 and 600 °C for 30 min each, heating to 1285 °C at a rate of 200 °C / h and sintering for 30 min.

[0039] In some embodiments, the polyvinyl alcohol (PVA) added in the preparation of the Sm2O3 doped PNN-PZT ceramic is 6wt%.

[0040] In some embodiments, the preparation of the Sm2O3 doped PNN-PZT ceramic further comprises: pressing the mixed powder into a shape under a uniaxial pressure of 120 MPa, heating at 500 o C for 3 hours to remove the organic matter.

[0041] In some embodiments, the molar ratio of the nano-nickel oxide and the nano-niobium oxide is 1:1.

[0042] In some embodiments, the molar ratio of the lead oxide, the nickel-niobium oxide precursor, the nano-zirconium dioxide, and the nano-titanium dioxide is 0.42:0.42:y:(0.58-y), and the value of y is in the range of 0.2-0.3.

[0043] In some embodiments, the molar ratio of the Sm2O3 powder and the nano-nickel oxide is 0.005:1-0.03:1, and x=0.005-0.03.

[0044] In some embodiments, the mass content of the polyvinyl alcohol (PVA), sodium dodecyl sulfate, and 1wt% of citric acid added in the preparation of the PNN-PZT / x Sm2O3 piezoelectric fiber sensor in step two is 1wt%, 0.065wt%, and 1wt% respectively.

[0045] In some embodiments, the PNN-PZT / x Sm2O3 fiber is placed in glycerol for 10 minutes before drying.

[0046] In some embodiments, the PNN-PZT / x Sm2O3 fiber drying time is 24 hours.

[0047] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person skilled in the art without creative work fall within the protection scope of the present application.

[0048] Embodiment 1: Preparation of Sm2O3 doped lead zirconate niobate lead titanate (PNN-PZT / x Sm2O3) piezoelectric fiber sensor

[0049] Step one: Preparation of PNN-PZT / x Sm2O3 ceramic (x=0.005)

[0050] Mix the nano nickel oxide NiO and nano niobium oxide Nb2O5 powders in a molar ratio of 1:1, and calcine the mixture at 1000 o C for 3h to synthesize the precursor NiNb2O6; wherein the calcination time and the calcination temperature can be set according to the actual production situation.

[0051] Mix lead oxide PbO, the precursor NiNb2O6, nano zirconium dioxide ZrO2 and nano titanium dioxide TiO2 in a molar ratio of 0.42:0.42:0.2:0.38, and ball mill with ethanol for 12 hours, and add Sm2O3 powder with a molar ratio of 0.005 to NiO, and ball mill for 12 hours; 100 o C to dry.

[0052] Add 6wt% polyvinyl alcohol to the dried powder, and press the powder into a round sheet under a uniaxial pressure of 120 MPa, 500 o C for 3 hours to remove the organic matter; wherein the operation of pressing the powder into a solid can be determined according to the actual situation of the powder, and a suitable pressing device and pressure are used, and the shape of the pressed powder is various, such as a circle, a rectangle, a square, etc.

[0053] Rise the temperature to 1050℃ at a rate of 5℃ / min, sinter for 1 hour, then rise the temperature to 1300℃ at a rate of 5℃ / min, sinter for 2 hours, and cool to room temperature to obtain the PNN-PZT / x Sm2O3 ceramic.

[0054] Step two: Preparation of fiberized PNN-PZT / x Sm2O3 piezoelectric ceramic (x=0.005)

[0055] The sodium alginate salt is dissolved in deionized water at 70°C to form a solution, and then the PNN-PZT / 0.005 Sm2O3 ceramic powder is ground into powder and added to the above solution together with polyvinyl alcohol (PVA), the content of PVA being 1wt%; 0.065wt% of sodium dodecyl sulfate and 1wt% of citric acid are added in proportion.

[0056] An excess of water is added to obtain a low viscosity slurry, which is then ball milled for 24 hours using ZrO2 to break the agglomerates and obtain a uniform suspension, the excess water is removed by heating, and the slurry is continuously stirred. The slurry is injected through a 0.5 mm nozzle into a CaCl2 solution to obtain PNN-PZT / 0.005 Sm2O3 fibers.

[0057] The above fibers are kept in the CaCl2 solution for 60 minutes, then placed in glycerol for 10 minutes, and dried at room temperature for 24 hours;

[0058] To remove the organic components from the fibers, the temperature is raised at a rate of 100°C / h in a closed alumina crucible, and held at 200°C and 600°C for 30 minutes each, the temperature is raised at a rate of 200°C / h to 1285°C and sintered for 30 minutes to obtain a PNN-PZT / x Sm2O3 piezoelectric fiber sensor, the piezoelectric coefficient d33 being 935 pC / N.

[0059] Example 2:

[0060] On the basis of Example 1, the addition amount of the precursors NiNb2O6, nano-zirconium dioxide ZrO2 and nano-titanium dioxide TiO2 is changed to a molar ratio of 0.42:0.42:0.25:0.33, the molar ratio of Sm2O3 powder to NiO is changed to 0.02:1, and other conditions are the same, finally a PNN-PZT / x Sm2O3 piezoelectric fiber sensor is prepared, the piezoelectric coefficient d33 being 1280 pC / N.

[0061] Example 3:

[0062] On the basis of Example 1, the addition amount of the precursors NiNb2O6, nano-zirconium dioxide ZrO2 and nano-titanium dioxide TiO2 is changed to a molar ratio of 0.42:0.42:0.3:0.28, the molar ratio of Sm2O3 powder to NiO is changed to 0.03:1, and other conditions are the same, finally a PNN-PZT / x Sm2O3 piezoelectric fiber sensor is prepared, the piezoelectric coefficient d33 being 1147 pC / N.

[0063] The conventional techniques in the above-described embodiments are prior art known to those skilled in the art, and thus will not be described in detail herein. The specific embodiments described herein are merely illustrative of the principles of this application. Numerous modifications or adaptations will be readily apparent to those skilled in the art of this present application without departing from the spirit or scope of the application as defined in the following claims.

[0064] While the application has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, since various changes and / or modifications compatible with the scope and spirit of the application can be made by those skilled in the art to which the application pertains.

[0065] While the forgoing specific embodiments of the application have been described and illustrated, it is understood that various modifications and changes in form and detail can be made to the specific embodiments without departing from the spirit and scope of the disclosure. Additionally, various features and methods of the above-described embodiments can be used independently of one another or in various combinations. All possible combinations and subcombinations are intended to fall within the scope of the disclosure. Many of the embodiments described above include similar components, and thus, these similar components can be interchanged between different embodiments. Although the application has been disclosed in the context of certain embodiments and examples, it will be understood that the application extends beyond the specifically disclosed embodiments to other alternative embodiments and / or uses and obvious modifications and equivalents thereof. Accordingly, it is not intended that the application be limited by the specific disclosures of preferred embodiments herein. The disclosure is to be considered in all respects as illustrative and not restrictive.

Claims

1. A method for preparing a samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor, characterized by, The method comprises: The nanometer nickel oxide and nanometer niobium oxide are first calcined to obtain a nickel niobium oxide precursor; the lead oxide PbO, the nickel niobium oxide precursor, nanometer zirconium dioxide and nanometer titanium dioxide are mixed, first ball-milled after adding ethanol, and second ball-milled after adding Sm2O3 powder; polyvinyl alcohol is added into the mixed powder after the ball-milling is completed, and second calcination is performed to remove the organic matter, to obtain a samarium trioxide doped lead zirconate titanate lead niobate ceramic; The samarium trioxide doped lead zirconate titanate lead niobate ceramic powder is ground and added into a sodium alginate salt solution together with polyvinyl alcohol, sodium dodecyl sulfate and citric acid are sequentially added, and then excess water is added to obtain a low-viscosity slurry; The low-viscosity slurry is ball-milled to break the agglomerates, to obtain a uniform suspension, and then a CaCl2 solution is injected to keep for 60-90 minutes to obtain samarium trioxide doped lead zirconate titanate lead niobate fibers; After the samarium trioxide doped lead zirconate titanate lead niobate fibers are dried at room temperature, the organic components are further removed, third calcination is performed in a closed alumina crucible, to obtain a samarium trioxide doped lead zirconate titanate lead niobate piezoelectric fiber sensor.

2. The method of claim 1, wherein: The first ball-milling time is 12 hours, and the second ball-milling time is 12 hours.

3. The method of claim 1, wherein: The first calcination condition is that the calcination temperature is 1000 DEG C, and the calcination time is 3 hours.

4. The method of claim 1, wherein: The second calcination condition is that the temperature is raised to 1050 DEG C at a rate of 5 DEG C / min, sintered for 1 hour, then raised to 1300 DEG C at a rate of 5 DEG C / min, sintered for 2 hours, and cooled to room temperature.

5. The method of claim 1, wherein: The third calcination condition is that the temperature is raised at a rate of 100 DEG C / h, and kept at 200 DEG C and 600 DEG C for 30 min respectively, raised to 1285 DEG C at a rate of 200 DEG C / h and sintered for 30 min.

6. The method of claim 1, wherein: The polyvinyl alcohol added in the preparation process of the samarium trioxide doped lead zirconate titanate lead niobate ceramic is 6wt%.

7. The method of claim 1, wherein: The preparation process of the samarium trioxide doped lead zirconium titanate niobate ceramic further comprises: under a uniaxial pressure of 120 MPa, the mixed powder is pressed and formed into a powder, 500 o C is heated for 3 hours to remove the organic matter.

8. The method of claim 1, wherein: The molar ratio of the nanometer nickel oxide and nanometer niobium oxide is 1:

1.

9. The method of claim 1, wherein: The molar ratio of the lead oxide, the nickel niobium oxide precursor, nanometer zirconium dioxide and nanometer titanium dioxide is 0.42:0.42:y:(0.58-y), and the value range of y is 0.2-0.

3.

10. The method of claim 1, wherein: The molar ratio of the Sm2O3 powder and the nanometer nickel oxide is 0.005:1-0.03:1.

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