CN117715500A - Potassium sodium niobate-based flexible piezoelectric sensor and preparation method and application thereof - Google Patents
Potassium sodium niobate-based flexible piezoelectric sensor and preparation method and application thereof Download PDFInfo
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- CN117715500A CN117715500A CN202311677273.5A CN202311677273A CN117715500A CN 117715500 A CN117715500 A CN 117715500A CN 202311677273 A CN202311677273 A CN 202311677273A CN 117715500 A CN117715500 A CN 117715500A
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001721 polyimide Polymers 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000003466 welding Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- H10N30/093—Forming inorganic materials
- H10N30/097—Forming inorganic materials by sintering
-
- 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
- H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
-
- 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
-
- 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
- H10N30/853—Ceramic compositions
- H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
-
- 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
- H10N30/87—Electrodes or interconnections, e.g. leads or terminals
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Measurement Of Mechanical Vibrations Or Ultrasonic Waves (AREA)
Abstract
The invention relates to the technical field of piezoelectric sensing, and particularly discloses a potassium-sodium niobate-based flexible piezoelectric sensor, a preparation method and application thereof. The method comprises the following steps: sequentially performing first ball milling and second ball milling on sodium carbonate, potassium carbonate, niobium pentoxide, zirconium oxide and bismuth oxide, performing first contact mixing with polyvinyl butyral, coating silver paste, and polarizing to obtain a mixture I; and then the mixture I is thinned and cut into a fiber array, epoxy resin is filled in gaps of the fiber array, a piezoelectric composite sheet is obtained after solidification, and the piezoelectric composite sheet is sputtered and integrally packaged by a nickel electrode, so that the potassium-sodium niobate-based flexible piezoelectric sensor is finally obtained. The potassium-sodium niobate based flexible piezoelectric sensor prepared by the method has excellent flexibility and high sensing sensitivity, and can overcome the problem of large-size preparation of the traditional potassium-sodium niobate based sensor.
Description
Technical Field
The invention relates to the technical field of piezoelectric sensing, in particular to a potassium-sodium niobate-based flexible piezoelectric sensor, a preparation method and application thereof.
Background
In the preparation of the sensor, the flexible piezoelectric fiber composite material is a common typical piezoelectric device, has the advantage of driving and sensing integration, and is formed by compounding piezoelectric ceramics and high-molecular polymers such as epoxy resin. The material overcomes the problems of high brittleness and poor toughness of the traditional piezoelectric ceramic material, has good flexibility and rigidity, and is widely applied to the fields of sensing, energy collection and health monitoring. Among them, lead zirconate titanate (PZT) -based piezoelectric fiber composites have been used in structural health monitoring of wind turbine blades. Meanwhile, PZT is used for structure identification based on a frequency response model, and tests are carried out on a main rotor blade of a helicopter, so that the frequency spectrum response of the composite material in a low frequency domain is found to have high accuracy.
However, lead element in PZT is required to be strictly limited as an element with great harm to the environment and human health, so that the application of the piezoelectric material in the medical field is greatly limited, and the waste treatment cost is increased. Therefore, it is urgent to develop a new lead-free piezoelectric material to replace the original lead-containing piezoelectric material.
Among the conventional lead-free systems of bismuth sodium titanate-based piezoelectric material (BNT), barium titanate-based piezoelectric material (BT), potassium sodium niobate-based piezoelectric material (KNN) and the emerging calcium barium zirconate titanate-based piezoelectric material (BCZT) and bismuth ferrite-based piezoelectric material (BFO), KNN is the lead-free system which is hopeful to replace PZT due to the excellent piezoelectric performance and the high Curie temperature.
However, KNN still has a gap in piezoelectric performance from PZT-based piezoelectric performance. Secondly, because the optimal sintering temperature and time of potassium sodium niobate are difficult to grasp, the existing potassium sodium niobate-based piezoelectric ceramic can only be used for preparing small-size ceramic plates in a dry pressing mode, and once the size of a die is enlarged, adverse phenomena such as uneven pressing and the like can be generated, and the potassium sodium niobate-based piezoelectric ceramic has no wide usability, so that the problem of research and development of a large-size flexible sensor is limited.
CN114094008A prepares the piezoelectric fiber composite material by cutting, filling resin and semi-packaging one side electrode, and then integrally packaging, but the piezoelectric fiber composite material prepared by the method has the problem that the piezoelectric effect of each piezoelectric ceramic fiber generated by the electrode structure design is not fully utilized.
Therefore, the forming technology for preparing the KNN-based piezoelectric ceramic plate which is large in size, compact and excellent in sensing performance has important practical significance, so that the preparation of the large-size flexible sensor is realized.
Disclosure of Invention
The invention aims to solve the problems that the sintering stability of a potassium-sodium niobate-based piezoelectric material is poor, and the preparation of a large-size piezoelectric ceramic sheet is difficult to realize in the prior art, so that the research and development of a large-size flexible potassium-sodium niobate-based sensor are limited.
To achieve the above object, a first aspect of the present invention provides a method for manufacturing a potassium-sodium niobate-based flexible piezoelectric sensor, the method comprising the steps of:
(1) Calcining sodium carbonate, potassium carbonate, niobium pentoxide, zirconium oxide and bismuth oxide after first ball milling to obtain calcined powder;
(2) In the presence of a solvent, carrying out second ball milling on the calcined powder, carrying out first contact mixing with polyvinyl butyral, and carrying out extrusion molding and sintering to obtain a potassium sodium niobate-based piezoelectric ceramic sheet;
(3) Coating silver paste on two sides of the potassium sodium niobate-based piezoelectric ceramic wafer, and polarizing in silicone oil under an electric field of 3-4kV/mm to obtain a mixture I;
(4) Thinning the mixture I, cutting the mixture I into a fiber array, filling epoxy resin in gaps of the fiber array, and curing to obtain a piezoelectric composite sheet;
(5) Performing nickel electrode sputtering on two sides of the piezoelectric composite sheet by magnetron sputtering in the presence of argon to obtain a mixture II;
(6) And (3) integrally packaging the upper and lower surfaces of the mixture II with copper electrodes and polyimide films to obtain a potassium-sodium niobate-based piezoelectric fiber composite material, and leading out wires from welding spots to obtain the potassium-sodium niobate-based flexible piezoelectric sensor.
The second aspect of the invention provides the potassium sodium niobate-based flexible piezoelectric sensor prepared by the method of the first aspect.
The third aspect of the invention provides an application of the potassium-sodium niobate-based flexible piezoelectric sensor in the technical field of piezoelectric sensing.
Compared with the prior art, the invention has at least the following advantages:
1. the method provided by the invention does not generate toxic and harmful substances containing lead in the production process, is environment-friendly and human-friendly, can be widely applied to the intelligent medical field, does not need to additionally treat wastes in the production process, and reduces the preparation cost;
2. the method provided by the invention can realize the preparation of the potassium-sodium niobate-based flexible piezoelectric sensor with any size and any shape, and the prepared potassium-sodium niobate-based flexible piezoelectric sensor has excellent flexibility;
3. the potassium-sodium niobate based flexible piezoelectric sensor provided by the invention has higher sensing sensitivity and energy collection efficiency;
4. compared with the traditional grid electrode, the method provided by the invention has the advantages that the piezoelectric effect of the piezoelectric ceramic fiber is fully utilized, so that the preparation of the flexible piezoelectric sensor with more excellent performance and larger sensing sensitivity is realized.
Drawings
FIG. 1 is a flow chart of a preferred method of making a potassium sodium niobate based flexible piezoelectric sensor provided by the present invention;
fig. 2 is a schematic structural diagram of a preferred potassium-sodium niobate-based flexible piezoelectric sensor prepared according to the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
It should be noted that, in the aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components or terms in the aspects, and those skilled in the art should not understand the limitation of the present invention.
As previously described, a first aspect of the present invention provides a method of making a potassium sodium niobate-based flexible piezoelectric sensor, the method comprising the steps of:
(1) Calcining sodium carbonate, potassium carbonate, niobium pentoxide, zirconium oxide and bismuth oxide after first ball milling to obtain calcined powder;
(2) In the presence of a solvent, carrying out second ball milling on the calcined powder, carrying out first contact mixing with polyvinyl butyral, and carrying out extrusion molding and sintering to obtain a potassium sodium niobate-based piezoelectric ceramic sheet;
(3) Coating silver paste on two sides of the potassium sodium niobate-based piezoelectric ceramic wafer, and polarizing in silicone oil under an electric field of 3-4kV/mm to obtain a mixture I;
(4) Thinning the mixture I, cutting the mixture I into a fiber array, filling epoxy resin in gaps of the fiber array, and curing to obtain a piezoelectric composite sheet;
(5) Performing nickel electrode sputtering on two sides of the piezoelectric composite sheet by magnetron sputtering in the presence of argon to obtain a mixture II;
(6) And (3) integrally packaging the upper and lower surfaces of the mixture II with copper electrodes and polyimide films to obtain a potassium-sodium niobate-based piezoelectric fiber composite material, and leading out wires from welding spots to obtain the potassium-sodium niobate-based flexible piezoelectric sensor.
Preferably, the silicone oil is methyl silicone oil.
Preferably, in the step (1), the molar ratio of the sodium carbonate to the potassium carbonate to the niobium pentoxide to the zirconium oxide to the bismuth oxide is 1:0.781:1.735:0.091:0.046. the inventors found that in this preferred case, the prepared potassium-sodium niobate-based flexible piezoelectric sensor has a higher sensing sensitivity.
Preferably, in step (1), the calcining operation comprises: and (3) raising the temperature of the product after the first ball milling to 850-950 ℃ at a heating rate of 3 ℃/min, preserving heat for 6 hours, and cooling to obtain the calcined powder.
Preferably, in step (2), the sintering operation includes: firstly, the temperature of the green body obtained after the first contact mixing and extrusion molding is raised to 600 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 3 hours, then the temperature is raised to 1120-1200 ℃ at the heating rate of 3 ℃/min, and the temperature is kept for 3 hours, so that the potassium-sodium niobate-based piezoelectric ceramic sheet is obtained.
Preferably, the extrusion is performed using a twin roller extrusion apparatus.
Preferably, the thickness of the green body is 4mm.
Preferably, in step (2), the green body is cut to 60mm x 20mm in size before the temperature of the green body is raised to 600 ℃ at a rate of 1 ℃/min.
Preferably, the conditions of the first ball mill and/or the second ball mill at least satisfy: the grinding balls are zirconia balls with the average volume diameter of 8mm, and the ball-to-material ratio is 4:1, the ball milling medium is ethanol, the rotating speed is 300-350rpm, and the time is 22-26h.
Preferably, the first ball milling and/or the second ball milling is performed in a nylon ball milling tank.
Preferably, in step (2), the method further comprises: and drying the product obtained after the second ball milling at 60 ℃ for 24 hours, sieving to obtain a mixture III with the average volume diameter of 60-150 mu m, and carrying out first contact mixing on the mixture III and the polyvinyl butyral.
Preferably, the drying is performed using a forced air drying oven.
Preferably, the weight ratio of the amount of the mixture III to the amount of the polyvinyl butyral is 1:0.01-0.1.
Preferably, in step (2), the solvent is cyclohexanone.
Preferably, in step (3), the method further comprises: before the polarization, the potassium-sodium niobate base piezoelectric ceramic plate with silver paste coated on both sides is dried for 10min at 150 ℃ and then the polarization is carried out.
More preferably, the temperature of the polarization is 25 ℃ and the time is 30min.
Preferably, in step (4), the mixture I is thinned to a thickness of 0.1-0.5mm.
According to a preferred embodiment, in step (4), the fiber width of the fiber array is 0.05-0.6mm, the fiber length is 5-150mm, and the fiber gap is 0.05-0.3mm. The inventors found that in this preferred case, the sensing accuracy of the prepared potassium-sodium niobate-based flexible piezoelectric sensor can be improved.
Preferably, in the step (4), the epoxy resin is epoxy resin ab glue, and the volume ratio of the glue a to the glue b is 3:1.
preferably, in step (4), the product of filling the gaps of the fiber array with epoxy resin is subjected to bubble removal under vacuum of 0.1MPa before the curing is performed, and then the product is applied to the curing.
In the present invention, the filling of the gaps of the fiber array with the epoxy resin is performed by a method conventional in the art, and may be performed by a direct filling method, for example.
Preferably, the curing temperature is 22-28 ℃ and the time is 23-26h.
According to a preferred embodiment, in step (5), the nickel electrode sputtering uses metallic nickel with a mass purity of 99.99% as a target.
Preferably, in step (5), the nickel electrode sputtering is performed under vacuum conditions, and at least: vacuum degree of 3X 10 -3 Pa, the sputtering power is 30-120W, and the time is 2-4min.
Preferably, in step (5), the piezoelectric composite sheet is wiped with ethanol before the nickel electrode sputtering is performed.
Preferably, in step (6), the copper electrode is a grid-like planar copper electrode.
Preferably, in step (6), the conditions of the integral package at least satisfy: the epoxy resin is adopted as an adhesive, a latex pad is adopted as a buffer layer, and the epoxy resin is carried out in a vacuum hot press, wherein the temperature is 90 ℃, and the vacuum degree is 88kPa.
A preferred potassium sodium niobate-based flexible piezoelectric sensor structure is illustratively provided below in conjunction with fig. 2, the piezoelectric sensor comprising: the device comprises a fiber array layer, two nickel electrode layers with the thickness of 10nm, two epoxy resin layers with the thickness of 0.7 mu m, two copper electrode-polyimide film layers with the thickness of 40 mu m, welding spots on the copper electrode-polyimide film layers and lead wires.
It should be noted that, in the present invention, the manner of the integral packaging is not particularly limited, and may be performed by conventional technical means in the art.
As previously described, the second aspect of the present invention provides a potassium sodium niobate-based flexible piezoelectric sensor prepared by the method of the first aspect.
As described above, the third aspect of the present invention provides the application of the potassium-sodium niobate-based flexible piezoelectric sensor according to the second aspect in the piezoelectric sensing technology field.
The invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials used are commercially available.
Unless otherwise specified, "room temperature" in the present invention means 25.+ -. 3 ℃.
Solvent: cyclohexanone;
silicone oil: is methyl silicone oil;
epoxy resin: the volume of the adhesive a and the adhesive b is 3:1, purchased from Ailaoda company with the brand of Ailaoda 2020;
grid-like planar copper electrode: the thickness of the electrode is 20 mu m, and the brand of the electrode is 0.5OZ rolled copper;
polyimide film: thickness 20 μm, available from Asahi electronics Co., ltd;
double rollers: model number LRHI-300, available from Guangzhou City laboratory analytical instruments Inc.
Example 1
This example is for illustrating the method of the present invention for manufacturing a potassium-sodium niobate-based flexible piezoelectric sensor, referring to the manufacturing flow shown in fig. 1, and is performed according to the operation comprising the steps of:
(1) In a nylon ball milling pot, sodium carbonate (29.01 g), potassium carbonate, niobium pentoxide, zirconium oxide and bismuth oxide were mixed in a molar ratio of 1:0.781:1.735:0.091: performing first ball milling according to the proportion of 0.046, then raising the temperature of the product obtained after the first ball milling to 850 ℃ in a box furnace at the heating rate of 3 ℃/min, preserving heat for 6 hours to perform calcination, and cooling to obtain the calcined powder;
(2) Pouring the calcined powder into a nylon ball milling tank, adding a solvent, performing second ball milling on the calcined powder, drying in a blast drying oven at 60 ℃ for 24 hours, and sieving to obtain a mixture III with the average volume diameter of 74 mu m;
and then mixing said mixture III with said polyvinyl butyral in an amount of 1: performing first contact mixing in a weight ratio of 0.015, and then performing extrusion molding by adopting double-roller extrusion equipment to obtain a green body with the thickness of 4 mm;
cutting the green body into 60 mm-20 mm by using double rollers, then raising the temperature to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 3 hours, raising the temperature to 1180 ℃ at a heating rate of 3 ℃/min, and preserving heat for 3 hours to obtain the potassium-sodium niobate-based piezoelectric ceramic sheet;
wherein the conditions of the first ball milling and the second ball milling at least satisfy: the grinding balls are zirconia balls with the average volume diameter of 8mm, and the ball-to-material ratio is 4:1, the ball milling medium is ethanol, the rotating speed is 300rpm, and the time is 24 hours;
(3) Coating silver paste on two sides of the potassium sodium niobate-based piezoelectric ceramic wafer, drying at 150 ℃ for 10min, and polarizing in silicone oil for 30min at 25 ℃ and under an electric field of 3kV/mm to obtain a mixture I;
(4) Thinning the mixture I to a thickness of 0.2mm, cutting into a fiber array with a fiber width of 0.25mm, a fiber length of 5mm and a fiber gap of 0.08mm, filling epoxy resin in the gap of the fiber array, removing bubbles under a vacuum of 0.1MPa, and curing at 25 ℃ for 24 hours to obtain a piezoelectric composite sheet with a fiber array layer;
(5) The piezoelectric composite sheet was wiped with ethanol and then subjected to vacuum of 3×10 -3 Performing nickel electrode sputtering on two sides of the piezoelectric composite sheet by magnetron sputtering under the existence of argon (the volume content fraction is 99 vol%) under the condition that the sputtering power is 80W and the time is 2min, and adopting metallic nickel with the mass purity of 99.99% as a target material to obtain a mixture II with a nickel electrode layer;
(6) Respectively coating epoxy resin on the upper and lower surfaces of the mixture II as an adhesive to obtain an epoxy resin layer, respectively integrally packaging the upper and lower surfaces of the mixture II with a grid-shaped planar copper electrode and a polyimide film in a vacuum hot press by using a latex pad as a buffer at the temperature of 90 ℃ and the vacuum degree of 88kPa to obtain a potassium sodium niobate-based piezoelectric fiber composite material with a copper electrode-polyimide film layer, and leading out wires from welding spots to obtain a potassium sodium niobate-based flexible piezoelectric sensor which is named as P1;
the structure is shown in FIG. 2, and comprises a fiber array layer, two nickel electrode layers with the thickness of 10nm, two epoxy resin layers with the thickness of 0.7 μm, and two copper electrode-polyimide film layers with the thickness of 40 μm.
Example 2
This example was conducted in a similar manner to example 1 except that in step (1), the molar ratio of the amounts of sodium carbonate, potassium carbonate, niobium pentoxide, zirconium oxide, and bismuth oxide was 1:0.788:1.752:0.073:0.036;
finally, the potassium-sodium niobate-based flexible piezoelectric sensor is obtained and is named as P2.
Example 3
This example was conducted in a similar manner to example 1 except that in step (4), the fiber width of the fiber array was 0.65mm, the fiber length was 5mm, and the fiber gap was 0.35mm;
finally, the potassium-sodium niobate-based flexible piezoelectric sensor is obtained and is named as P3.
Comparative example 1
This example was conducted in a similar manner to example 1 except that in step (2), the second ball milling was not conducted, specifically, the first contact mixing was conducted directly with the calcined powder obtained in step (1) instead of the mixture III with polyvinyl butyral;
finally, the potassium-sodium niobate-based flexible piezoelectric sensor is obtained and named as DP1.
Comparative example 2
This example was conducted in a similar manner to example 1 except that the operation in step (5) was not conducted, but instead the piezoelectric composite sheet was directly integrally packaged with the copper electrode and the polyimide film instead of the mixture II obtained in step (4);
finally, the potassium-sodium niobate-based flexible piezoelectric sensor is obtained and named as DP2.
Test example 1
The sensor prepared in the above example is subjected to vibration exciter output voltage performance and sensing sensitivity performance test, and the results are shown in table 1;
the method comprises the steps of generating vibration with constant acceleration of 3g through a vibration exciter, and detecting output voltage of a potassium-sodium niobate-based flexible piezoelectric sensor;
and detecting corresponding output voltages of the potassium-sodium niobate based flexible piezoelectric sensor under different structural strains by using a sigma strain tester, thereby obtaining the sensing sensitivity.
TABLE 1
From the results, the anti-potassium sodium niobate based flexible piezoelectric sensor provided by the invention has excellent sensing sensitivity and flexibility, so that the preparation problem of a large-size potassium sodium niobate based sensor can be solved, and particularly, the sensing Lin Min degrees can reach 1.193 mV/mu epsilon.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method of making a potassium sodium niobate based flexible piezoelectric transducer, the method comprising the steps of:
(1) Calcining sodium carbonate, potassium carbonate, niobium pentoxide, zirconium oxide and bismuth oxide after first ball milling to obtain calcined powder;
(2) In the presence of a solvent, carrying out second ball milling on the calcined powder, carrying out first contact mixing with polyvinyl butyral, and carrying out extrusion molding and sintering to obtain a potassium sodium niobate-based piezoelectric ceramic sheet;
(3) Coating silver paste on two sides of the potassium sodium niobate-based piezoelectric ceramic wafer, and polarizing in silicone oil under an electric field of 3-4kV/mm to obtain a mixture I;
(4) Thinning the mixture I, cutting the mixture I into a fiber array, filling epoxy resin in gaps of the fiber array, and curing to obtain a piezoelectric composite sheet;
(5) Performing nickel electrode sputtering on two sides of the piezoelectric composite sheet by magnetron sputtering in the presence of argon to obtain a mixture II;
(6) And (3) integrally packaging the upper and lower surfaces of the mixture II with copper electrodes and polyimide films to obtain a potassium-sodium niobate-based piezoelectric fiber composite material, and leading out wires from welding spots to obtain the potassium-sodium niobate-based flexible piezoelectric sensor.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the sodium carbonate, the potassium carbonate, the niobium pentoxide, the zirconium oxide, and the bismuth oxide is 1:0.781:1.735:0.091:0.046.
3. the method according to claim 1 or 2, wherein in step (2), the sintering operation comprises: firstly, the temperature of the green body obtained after the first contact mixing and extrusion molding is raised to 600 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 3 hours, then the temperature is raised to 1120-1200 ℃ at the heating rate of 3 ℃/min, and the potassium-sodium niobate-based piezoelectric ceramic plate is obtained after the temperature is kept for 3 hours.
4. The method according to claim 1 or 2, wherein the conditions of the first ball mill and/or the second ball mill at least satisfy: the grinding balls are zirconia balls with the average volume diameter of 8mm, and the ball-to-material ratio is 4:1, the ball milling medium is ethanol, the rotating speed is 300-350rpm, and the time is 22-26h.
5. The method according to claim 1 or 2, wherein in step (2), the method further comprises: and drying the product obtained after the second ball milling at 60 ℃ for 24 hours, sieving to obtain a mixture III with the average volume diameter of 60-150 mu m, and carrying out first contact mixing on the mixture III and the polyvinyl butyral.
6. The method of claim 5, wherein the weight ratio of the amount of mixture III to the amount of polyvinyl butyral is 1:0.01-0.1.
7. A method according to claim 1 or 2, wherein in step (4) the fibre array has a fibre width of 0.05-0.6mm, a fibre length of 5-150mm and a fibre gap of 0.05-0.3mm.
8. The method according to claim 1 or 2, wherein in step (5), the nickel electrode sputtering is performed under vacuum conditions and at least: vacuum degree of 3X 10 -3 Pa, the sputtering power is 30-120W, and the time is 2-4min.
9. A potassium sodium niobate-based flexible piezoelectric sensor prepared by the method of any one of claims 1 to 8.
10. The use of the potassium-sodium niobate based flexible piezoelectric sensor of claim 9 in the field of piezoelectric sensing technology.
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