CN117580436A - Heterocyclic aramid resin-based composite piezoelectric material and preparation method thereof - Google Patents
Heterocyclic aramid resin-based composite piezoelectric material and preparation method thereof Download PDFInfo
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- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 176
- 239000004760 aramid Substances 0.000 title claims abstract description 174
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title claims abstract description 129
- 239000000805 composite resin Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 74
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000000919 ceramic Substances 0.000 claims abstract description 68
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 53
- 239000011550 stock solution Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 32
- -1 heterocyclic diamine Chemical class 0.000 claims description 24
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 12
- 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 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- 229910002113 barium titanate Inorganic materials 0.000 claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 4
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000013078 crystal Substances 0.000 abstract description 13
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 10
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
-
- 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
- H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
-
- 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
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a heterocyclic aramid resin-based composite piezoelectric material and a preparation method thereof, belonging to the technical field of piezoelectric materials, wherein the piezoelectric material comprises the following components: a continuous phase and a dispersed phase encapsulated in the continuous phase; the surface of the disperse phase comprises a polymer crystal structure; the preparation method of the heterocyclic aramid resin-based composite piezoelectric material comprises the following steps: and adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and crystallizing the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material. According to the invention, the high-temperature-resistant heterocyclic aramid resin-based material is used as a continuous phase, so that the tensile strength and the piezoelectric performance of the composite material at a high temperature (200 ℃) are improved, the composite material can be used for a long time in a high-temperature environment, a polymer crystal structure is formed on the surface of the piezoelectric ceramic particles, the piezoelectric modulus is increased, the force-electric coupling of the composite material is improved, the stress loss is reduced, and the piezoelectric performance of the composite material is improved.
Description
Technical Field
The invention relates to the technical field of piezoelectric materials, in particular to a heterocyclic aramid resin-based composite piezoelectric material and a preparation method thereof.
Background
The piezoelectric material can generate electric charge when being extruded or stretched, or can generate electric power when being deformed due to external action due to the characteristic that the material is stretched or shortened after voltage is applied to two ends of the material, so that mechanical energy can be converted into electric energy. Piezoelectric materials are widely used in daily life and industrial production, ranging from piezoelectric electronic lighters to piezoelectric speakers and even vibration measuring sensors in airships and missiles.
The existing piezoelectric materials are mainly divided into two major types of inorganic piezoelectric materials and organic piezoelectric materials, wherein the inorganic piezoelectric materials comprise common piezoelectric crystals represented by quartz crystals and piezoelectric polycrystal represented by piezoelectric ceramics; the organic piezoelectric material is prepared by stretching and electrically polarizing certain high molecular polymers to prepare high molecular piezoelectric films with piezoelectricity, such as polyvinyl fluoride (PVF), polyvinyl chloride (PVC), polycarbonate, polyvinylidene fluoride (PVDF), polyurethane and the like.
The inorganic piezoelectric material in the prior art has extremely high piezoelectric coefficient and higher working temperature, can bear higher pressure, but has poor toughness and external force impact resistance, and poor deformability after molding, so that the application expansion of the inorganic piezoelectric material is limited; the organic piezoelectric material has the advantages of light weight, softness, high tensile strength, small creep and impact resistance, but has the defects of poor high temperature resistance, poor aging resistance and short service life. At present, a piezoelectric material which has high-efficiency piezoelectric performance and can be used for a long time in a high-temperature environment is urgently needed in the market.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a heterocyclic aramid resin-based composite piezoelectric material and a preparation method thereof, which are used for solving one of the problems of poor piezoelectric performance, poor high temperature resistance, short service life and the like of the piezoelectric material at high temperature in the prior art.
The aim of the invention is mainly realized by the following technical scheme:
a heterocyclic aramid resin-based composite piezoelectric material comprising: a continuous phase and a dispersed phase encapsulated in the continuous phase;
the preparation method of the heterocyclic aramid resin-based composite piezoelectric material comprises the following steps:
and adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and crystallizing the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material.
Preferably, the continuous phase comprises a heterocyclic aramid resin-based polymer;
the dispersed phase comprises piezoelectric ceramic particles; the piezoelectric ceramic particles wrapped in the heterocyclic aramid resin-based polymer are dispersed in the heterocyclic aramid resin-based polymer.
Preferably, the particle size of the piezoelectric ceramic particles is 20-30 μm.
Preferably, in the heterocyclic aramid resin-based composite piezoelectric material, the using amount of the piezoelectric ceramic particles is 10-25 wt%.
Preferably, the piezoelectric ceramic particles are any one of lead zirconate titanate, barium titanate, and lead titanate.
Preferably, the piezoelectric ceramic particles are lead zirconate titanate.
Preferably, the heterocyclic aramid resin-based polymer comprises: aramid resin III;
the aramid resin III comprises two structural units (I) and (II).
A preparation method of a heterocyclic aramid resin-based composite piezoelectric material, comprising the following steps: adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and curing and crystallizing the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material.
Preferably, the preparation method comprises the following steps:
s101: dissolving heterocyclic diamine monomer or phenyl diamine monomer in polar solvent to obtain mixed solution;
s102: the mixed solution reacts with phenyl binary acyl chloride monomer to prepare a heterocyclic aramid resin-based polymer stock solution;
s103: adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution, blending and stirring to prepare an aramid piezoelectric composite stock solution;
s104: the prepared aramid fiber piezoelectric composite material stock solution is prepared to form a film in a die;
s105: and crystallizing the prepared film to obtain the heterocyclic aramid resin-based composite piezoelectric material.
Preferably, the heterocyclic diamine monomer in S101 comprises a benzene ring and a benzimidazole group.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) According to the invention, the high-temperature-resistant heterocyclic aramid resin-based material is used as a continuous phase, so that the tensile strength and the piezoelectric performance of the composite material at a high temperature (200 ℃) are improved, the composite material can be used for a long time in a high-temperature environment, and the composite material is 12.1d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus is 11.8d33, pc/N-51.9d33 and pc/N at 200 ℃; the tensile strength is 102MPa to 191MPa at 25 ℃; the tensile strength is 99.6MPa to 186MPa at 200 ℃; the average output voltage is tested to be 0.15 to 0.18V under the conditions of 25 ℃ and 160N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz.
(2) The invention is beneficial to increasing the piezoelectric modulus by crystallizing the piezoelectric material, improving the force-electric coupling of the composite material, reducing the stress loss and improving the piezoelectric performance of the composite material; meanwhile, the polymer crystal structure is oriented, the compatibility of the continuous phase and the disperse phase is enhanced, and the overall tensile strength of the composite material is improved.
(3) The invention adopts lead zirconate titanate as piezoelectric ceramic particles, has better mechanical property and piezoelectric coefficient at high temperature, and the piezoelectric modulus of the heterocyclic aramid resin-based composite piezoelectric material is 12.1d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus is 11.8d33, pc/N-51.9d33 and pc/N at 200 ℃; the tensile strength of the heterocyclic aramid resin-based composite piezoelectric material is 102 MPa-191 MPa at 25 ℃; the tensile strength is 99.6MPa to 186MPa at 200 ℃; the average output voltage of the heterocyclic aramid resin-based composite piezoelectric material is 0.15-0.18V under the conditions of 25 ℃ and 160N; the piezoelectric coefficient of the heterocyclic aramid resin-based composite piezoelectric material is 0.093-0.1 under the conditions of g33Vm/N and 10 Hz-5 MHz.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is a graph showing the average output voltage detection result in embodiment 2 of the present invention;
FIG. 2 shows the average output voltage detection result of embodiment 4 of the present invention;
FIG. 3 shows the average output voltage detection result of embodiment 5 of the present invention;
FIG. 4 is a graph showing the average output voltage measurement of comparative example 2 of the present invention;
FIG. 5 is an AFM characterization result of example 2 of the present invention;
FIG. 6 is an AFM characterization result of example 7 of the present invention;
FIG. 7 is an AFM characterization result of comparative example 1 of the present invention;
FIG. 8 shows the AFM characterization of comparative example 7 of the present invention.
Detailed Description
Regarding aramid III: belongs to para-aramid and is obtained by copolycondensation of three monomers of p-phenylenediamine, terephthaloyl chloride and diamine containing a heterocyclic structure, so that the para-aramid III contains a heterocyclic structure, namely heterocyclic aramid and comprises Two structural units.
The invention discloses a heterocyclic aramid resin-based composite piezoelectric material, which comprises the following components: the heterocyclic aramid resin-based composite piezoelectric material comprises a continuous phase and a disperse phase wrapped in the continuous phase;
the preparation method of the heterocyclic aramid resin-based composite piezoelectric material comprises the following steps:
and adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and crystallizing the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material.
Specifically, the continuous phase comprises a heterocyclic aramid resin-based polymer;
the disperse phase comprises piezoelectric ceramic particles; the piezoelectric ceramic particles wrapped in the heterocyclic aramid resin-based polymer are dispersed in the heterocyclic aramid resin-based polymer.
In the implementation, the piezoelectric ceramic particles are dispersed in the polymer stock solution of the heterocyclic aramid resin-based polymer, and after the monomer of the heterocyclic aramid resin-based polymer in the stock solution is polymerized, a sea-island structure is formed, wherein the piezoelectric ceramic particles are uniformly dispersed in the heterocyclic aramid resin-based polymer; the crystallization treatment is carried out on the island structure to obtain the crystallization modified heterocyclic aramid resin-based composite piezoelectric material.
In the heterocyclic aramid resin-based composite piezoelectric material, the heterocyclic aramid resin-based polymer wraps the piezoelectric ceramic particles, and the inorganic piezoelectric ceramic particles are uniformly distributed in the composite material, so that the composite material has excellent and stable piezoelectric performance.
Compared with the prior art, the method has the advantages that the piezoelectric material is crystallized, so that the piezoelectric modulus is increased, the force-electric coupling of the composite material is improved, the stress loss is reduced, and the piezoelectric performance of the composite material is improved; meanwhile, due to the directional orientation after crystallization treatment, the compatibility of a continuous phase and a disperse phase is improved, and the overall tensile strength of the composite material is improved.
It should be noted that, as one possible explanation, the crystallization process may have the following effects:
the crystallization treatment forms a polymer crystal structure on the surface of the piezoelectric ceramic particles, the polymer crystal structure is formed by controlling the heating time of high-temperature treatment, the heat transfer is uneven, the specific heat of a continuous phase and a disperse phase is different, the disperse phase forms a low-temperature area relative to the continuous phase, so that the continuous phase forms a displacement gradient near the disperse phase, and a transition area near the disperse phase is formed; meanwhile, as the expansion coefficients of the disperse phase and the continuous phase are different, the deformation amount of the disperse phase is less when heated, and the continuous phase in the transition area forms an oriented polymer crystal structure under the combined action of the disperse phase and the continuous phase.
It should be noted that the thickness of the polymer crystal structure is mainly affected by the particle size of the piezoelectric ceramic particles and the thermal expansion coefficient of the piezoelectric ceramic particles: the smaller the particle size of the piezoelectric ceramic particles is, the smaller the thickness of the polymer crystal structure is; the smaller the thermal expansion coefficient of the piezoelectric ceramic particles is, the larger the difference between the thermal expansion coefficient of the continuous phase is, and the larger the thickness of the polymer crystal structure is.
It is understood that the thermal expansion coefficient of the continuous phase heterocyclic aramid resin-based polymer is not greatly affected by the monomer type of the heterocyclic aramid resin-based polymer, and the thickness of the polymer crystal structure is mainly affected by the change of the thermal expansion coefficient of the piezoelectric ceramic particles.
Preferably, the piezoelectric ceramic particles have a thermal expansion coefficient of 3.8X10 -6 /℃-4.2×10 -6 /℃。
Preferably, the piezoelectric ceramic particles have a particle size of 20 μm to 30. Mu.m.
Specifically, the piezoelectric ceramic particles are any one of lead zirconate titanate (PZT), barium titanate, and lead titanate.
Preferably, the piezoelectric ceramic particles are lead zirconate titanate (PZT) because of the lead zirconate titanate (PZT), pb (Zr) 1-x TiO 3 ) The ceramic has excellent electric and dielectric properties, wherein x is the mole coefficient of Zr, and the requirements are as follows: x is more than 0 and less than 1; the lead zirconate titanate piezoelectric ceramic particles have good stability, high precision, high energy conversion efficiency and high response speed, and the mechanical factor electrical coefficient and the electromechanical coupling constant are obviously superior to those of lead-free piezoelectric ceramics and common lead-containing piezoelectric ceramics.
Specifically, when the content of piezoelectric ceramic particles in the heterocyclic aramid resin-based composite piezoelectric material is 10-25 wt%, the piezoelectric performance of the composite material does not reach the standard and is unfavorable for use when the content of the piezoelectric ceramic particles in the composite piezoelectric material is smaller, and when the addition amount of the piezoelectric ceramic particles is too large, the piezoelectric ceramic particles are difficult to uniformly disperse in the heterocyclic aramid resin-based high polymer aramid resin III and easy to aggregate, so that the piezoelectric effect in the composite material is unevenly distributed.
The density of the heterocyclic aramid resin-based composite piezoelectric material is mainly influenced by the addition amount of the piezoelectric ceramic particles and the density of the piezoelectric ceramic particles; the larger the addition amount of the piezoelectric ceramic particles and the self density of the piezoelectric ceramic particles, the higher the density of the corresponding heterocyclic aramid resin-based composite piezoelectric material.
Specifically, the thickness of the heterocyclic aramid resin-based composite piezoelectric material is 30-60 mu m.
The thickness of the heterocyclic aramid resin-based composite piezoelectric material influences the piezoelectric modulus, and the larger the thickness is, the larger the piezoelectric modulus is.
Specifically, the heterocyclic aramid resin-based polymer includes: aramid resin III.
In one possible embodiment, the polymerized monomers of the heterocyclic aramid resin-based polymer include: terephthaloyl chloride, 2- (4-aminophenyl) -5-aminobenzimidazole, and p-phenylenediamine.
Specifically, the molar ratio of terephthaloyl chloride to 2- (4-aminophenyl) -5-aminobenzimidazole to p-phenylenediamine is 100: (20-100): (0-80), and the sum of the molar numbers of 2- (4-aminophenyl) -5-aminobenzimidazole and p-phenylenediamine is equal to the molar number of terephthaloyl chloride.
Preferably, the molar ratio of terephthaloyl chloride to 2- (4-aminophenyl) -5-aminobenzimidazole to p-phenylenediamine is 100:20-40:60-80.
Preparation of structural units by reacting 2- (4-aminophenyl) -5-aminobenzimidazole with terephthaloyl chloridePreparation of the structural unit +.>The piezoelectric modulus of the heterocyclic aramid resin-based composite piezoelectric material is 6.2d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus at 200℃is 6.05d33, pc/N to 51.9d33, pc/N.
In the embodiment, the breakdown strength of the heterocyclic aramid resin-based composite piezoelectric material is 152 kV/mm-200 kV/mm.
In the embodiment, the tensile strength of the heterocyclic aramid resin-based composite piezoelectric material at 25 ℃ is 102-200 MPa; the tensile strength is 99 MPa-200 MPa at 200 ℃.
In the embodiment, the average output voltage of the heterocyclic aramid resin-based composite piezoelectric material is 0.08-0.18V under the conditions of 25 ℃ and 160N.
The breakdown strength and the average output voltage of the heterocyclic aramid resin-based composite piezoelectric material under the pressure test react with the intrinsic index of the heterocyclic aramid resin-based composite piezoelectric material, wherein the breakdown strength reacts with the safety performance, the service life is influenced, the average output voltage reacts with the signal output capability of the piezoelectric performance, and the average output voltage does not influence the size of the piezoelectric material.
In the embodiment, the piezoelectric coefficient of the heterocyclic aramid resin-based composite piezoelectric material is 0.067-0.1 under the conditions of g33Vm/N and 10 Hz-5 MHz.
The piezoelectric coefficient is affected by the piezoelectric ceramic particles, and the intrinsic index of the piezoelectric ceramic particles is irrelevant to the addition of the heterocyclic aramid resin-based polymer and the piezoelectric ceramic particles.
In a preferred embodiment, the molar ratio of terephthaloyl chloride to 2- (4-aminophenyl) -5-aminobenzimidazole to paraphenylenediamine is 100: (20-40) to (60-80).
In the embodiment, the piezoelectric modulus of the heterocyclic aramid resin-based composite piezoelectric material is 52d33 and pc/N at 25 ℃; the piezoelectric modulus was 51.9d33, pc/N at 200 ℃.
In the embodiment, the tensile strength of the heterocyclic aramid resin-based composite piezoelectric material at 25 ℃ is 102MPa; the tensile strength at 200℃was 99.6MPa.
In this embodiment, the average output voltage of the heterocyclic aramid resin-based composite piezoelectric material is 0.18V under 160N at 25 ℃.
In a preferred embodiment, the piezoelectric ceramic particles in the composite piezoelectric material are lead zirconate titanate.
In the embodiment, the piezoelectric modulus of the heterocyclic aramid resin-based composite piezoelectric material is 6.2d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus at 200℃is 6.05d33, pc/N to 51.9d33, pc/N.
In the embodiment, the piezoelectric modulus of the heterocyclic aramid resin-based composite piezoelectric material is 12.1d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus at 200 ℃ is 11.8d33, pc/N-51.9 d33, pc/N.
In the embodiment, the tensile strength of the heterocyclic aramid resin-based composite piezoelectric material at 25 ℃ is 102-191 MPa; the tensile strength is 99.6 MPa-186 MPa at 200 ℃.
In the embodiment, the average output voltage of the heterocyclic aramid resin-based composite piezoelectric material is 0.15V-0.18V under the conditions of 25 ℃ and 160N.
It should be noted that the average output voltage of the composite piezoelectric material directly reflects the performance of the composite piezoelectric material and is not affected by the size of the material; under the same test conditions, the higher the output voltage signal, the stronger the piezoelectric performance.
In this embodiment, the piezoelectric coefficient of the heterocyclic aramid resin-based composite piezoelectric material is 0.093 to 0.1 under the conditions of g33Vm/N,10Hz to 5 MHz.
On the other hand, the invention discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material, which comprises the following steps: adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and carrying out in-mold curing and crystallization treatment on the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material.
Specifically, the preparation method comprises the following steps:
s101: dissolving heterocyclic diamine monomer or phenyl diamine monomer in polar solvent to obtain mixed solution;
s102: the mixed solution reacts with phenyl binary acyl chloride monomer to prepare a heterocyclic aramid resin-based polymer stock solution;
s103: adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution, blending and stirring to prepare an aramid piezoelectric composite stock solution;
s104: the prepared aramid fiber piezoelectric composite material stock solution is prepared to form a film in a die;
s105: and crystallizing the prepared film to obtain the heterocyclic aramid resin-based composite piezoelectric material.
Specifically, the phenylenediamine monomer may be p-phenylenediamine (hereinafter PPD).
Specifically, the phenyl dicarboxylic acid chloride monomer may be terephthaloyl chloride (hereinafter referred to as TPC)
Specifically, the heterocyclic diamine monomer comprises a benzene ring and a benzimidazole group.
Specifically, the heterocyclic diamine monomer is 2- (4-aminophenyl) -5-aminobenzimidazole (hereinafter referred to as PAZ).
It is understood that the addition of 2- (4-aminophenyl) -5-aminobenzimidazole and para-phenylenediamine to the DMAC reaction system facilitates complete dissolution of the two non-reactive materials.
Specifically, the molar ratio of the phenyl dibasic acyl chloride monomer to the heterocyclic diamine monomer to the phenyl diamine monomer is 100: (20-100): (0-80), and the sum of the molar numbers of the heterocyclic diamine monomer and the phenyl diamine monomer is equal to the molar number of the phenyl dibasic acyl chloride monomer.
Specifically, the obtaining of the mixed solution in S101 includes: after the heterocyclic diamine monomer is dissolved in the polar solvent, the phenyl diamine monomer is added and mixed uniformly.
Specifically, the obtaining of the mixed solution in S101 includes: mechanically stirring (8000-10200 r/min) the polar solvent and the heterocyclic diamine monomer at 20-25 ℃ for 20-25 min; adding the phenyl diamine monomer for continuous mixing at 18-20 deg.c for 20-25 min.
Specifically, in step S101, dimethylacetamide (abbreviated as DMAC) is selected as the polar solvent.
Specifically, step S101 further includes a polar solvent dehydration treatment.
Specifically, the dehydration treatment includes the use of a physical desiccant to remove water from the solvent DMAC.
In particular, the physical desiccant is a molecular sieve, which can remove very small amounts of water relative to conventional desiccants without introducing new impurities.
Specifically, in the step S102, the phenyl dibasic acid chloride monomer is added into the prepolymer solution for 4 to 6 times, and the feeding process is as follows: the reaction time of each section is 25-30 min, and the reaction temperature is controlled to be 10-15 ℃.
It is understood that when the temperature is higher than 15 ℃, the reaction speed is too high, and the polymerization degree is reduced; meanwhile, side reactions are increased, each molecular chain is crosslinked, the linearity of the polymer is damaged, and the mechanical property is reduced; heterocyclic diamine monomer incorporation is affected below 10 c due to the lower reactivity of the heterocyclic diamine monomer.
Preferably, the dynamic viscosity of the heterocyclic aramid resin-based polymer in the heterocyclic aramid resin-based polymer stock solution is 20000 to 80000cP; preferably 40000cP to 70000cP; more preferably, 40000cP to 60000cP.
Preferably, an automatic feeding device for adjusting the reaction speed according to the temperature in the prior art can be adopted to assist in controlling the feeding speed.
In S103, the mass ratio of the heterocyclic aramid resin-based polymer stock solution to the piezoelectric ceramic powder is 3-9:1.
In the step S103, the stirring time is 20-40 min, and the stirring speed is 8000-10200 r/min.
S104 is preferably formed in a coagulation bath, and has the following advantages over dry film forming: the dry film-forming film generates larger cavities during solidification, and the film-forming film also needs to be stretched at high temperature, so that the crystallinity of the finished film is larger, and the mechanical property is poorer.
Specifically, the coagulating bath is a solution of DMAC and water in a mass ratio of 3-4:1.
The film forming method in S104 includes: and coating the prepared aramid fiber piezoelectric composite material stock solution in a die to form a film.
The film forming in S104 further includes a drying step: drying at 105-110 deg.c and vacuum degree of 115-125 Pa for 15-20 min to eliminate solvent and water.
In S104, the mold may be a concave mold having a uniform depth, the depth of which is adjusted according to the film formation target thickness.
The crystallization process in S105 includes: in a vacuum baking oven, the vacuum degree is 115 Pa-125 Pa, and the baking is carried out for 20 min-25 min at 152 ℃ to 160 ℃.
The crystallization treatment is helpful to form a polymer crystal structure in the transition area of the disperse phase and the continuous phase, is helpful to increase the modulus of the composite piezoelectric film, improve the force-electric coupling, reduce the stress loss and endow the composite material with better piezoelectric effect.
In order to better illustrate the invention, the following examples and comparative examples are further provided:
example 1
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material.
S101: removing water from the solvent DMAC by using a molecular sieve (DMAC is placed in the molecular sieve for 10 h), mechanically stirring the DMAC and PAZ at 25 ℃ for 25min (10200 r/min), and continuously adding PPD to uniformly mix;
s102: adding TPC for reaction for 4 times, wherein the reaction time is 25min, the reaction temperature is controlled at 10 ℃, the material molar ratio is TPC to PAZ to PPD=100 to 30 to 70, and the polymer stock solution of the aramid resin III is prepared, and the dynamic viscosity is 46940cP;
s103: after the reaction is finished, adding piezoelectric ceramic PZT powderFinally, the molecular formula Pb (Zr) 0.3 TiO 3 ) Blending and stirring (the mass fraction accounts for 20% of the whole system) for 30min to uniformly disperse the mixture in the aramid resin III polymer stock solution to prepare the heterocyclic aramid resin-based composite piezoelectric material stock solution;
s104: coating the prepared aramid resin III piezoelectric composite material stock solution in a mould (made of polytetrafluoroethylene), placing the mould in a DMAC mixed aqueous solution for curing to form a film (DMAC: water=4:1), drying the film in a vacuum drying oven at 110 ℃ for 20min after the film is completely formed, and removing the solvent and the water;
s105: and (3) placing the dried film in a vacuum baking oven, and baking for 20min at 152 ℃ for crystallization treatment to obtain the treated aramid resin III piezoelectric composite film.
Measured, the density of the obtained film is 2670kg/m 3 The breakdown strength is 181kV/mm, the piezoelectric modulus at 25 ℃ is 12.1d33, pc/N, and the piezoelectric modulus at 200 ℃ is 11.8d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 191MPa, and tensile strength at 200 ℃ is 186MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 20-25 mu m, and the maximum average output voltage can reach 0.15V.
The piezoelectric coefficient is only related to the type of piezoelectric ceramic.
Example 2
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material.
S101: removing water from the solvent DMAC by using a molecular sieve (DMAC is placed in the molecular sieve for 10 h), mechanically stirring the DMAC and PAZ at 25 ℃ for 25min (10200 r/min), and continuously adding PPD to uniformly mix;
s102: adding TPC for reaction for 4 times, wherein the reaction time is 25min, the reaction temperature is controlled at 10 ℃, the material molar ratio is TPC to PAZ to PPD=100 to 20 to 80, and the polymer stock solution of the aramid resin III is prepared, and the dynamic viscosity is 42920cP;
s103: after the reaction is finished, adding piezoelectric ceramic PZT powder and molecular formula Pb (Zr) 0.5 TiO 3 ) (mass fraction is 25% of the whole system),blending and stirring for 30min to uniformly disperse the mixture in the aramid resin III polymer stock solution to prepare an aramid resin III piezoelectric composite stock solution;
s104: coating the prepared aramid resin III piezoelectric composite material stock solution in a mould (made of polytetrafluoroethylene), placing the mould in a DMAC mixed aqueous solution for curing to form a film (DMAC: water=4:1), drying in a vacuum drying oven at 110 ℃ for 15min after the film is completely formed, and removing the solvent and the water;
s105: and (3) placing the dried film in a vacuum baking oven, and baking for 25min at 152 ℃ to obtain the treated aramid resin III piezoelectric composite film.
The PZT aramid resin III piezoelectric composite material film obtained after treatment has the measured density of 6480kg/m 3 The breakdown strength is 202kV/mm, the piezoelectric modulus at 25 ℃ is 52.0d33, pc/N, and the piezoelectric modulus at 200 ℃ is 51.9d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 102MPa, and tensile strength at 200 ℃ is 99MPa; the usable temperature is between-152 ℃ and 200 ℃; the film thickness is 50-60 μm, and as shown in FIG. 1, the average output voltage can reach 0.18V at maximum.
Example 3
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material.
S101: removing water from the solvent DMAC by using a molecular sieve (DMAC is placed in the molecular sieve for 10 h), mechanically stirring the DMAC and PAZ at 25 ℃ for 25min (10200 r/min), and continuously adding PPD to uniformly mix;
s102: adding TPC for reaction for 4 times, wherein the reaction time is 25min, the reaction temperature is controlled to be 10 ℃, the material molar ratio is TPC to PAZ to PPD=100 to 40 to 60, and the polymer stock solution of the aramid resin III is prepared, and the dynamic viscosity is 53160cP;
s103: after the reaction is finished, adding piezoelectric ceramic PZT powder and molecular formula Pb (Zr) 0.2 TiO 3 ) Blending and stirring (the mass fraction accounts for 20% of the whole system) for 30min to uniformly disperse the mixture in the aramid resin III polymer stock solution to prepare the aramid resin III piezoelectric composite stock solution;
s104: coating the prepared aramid resin III piezoelectric composite material stock solution in a mould (made of polytetrafluoroethylene), placing the mould in a DMAC mixed aqueous solution for curing to form a film (DMAC: water=3:1), drying the film in a vacuum drying oven at 105 ℃ for 20min after the film is completely formed, and removing the solvent and the water;
s105: and (3) placing the dried film in a vacuum baking oven, and baking for 25min at 160 ℃ to obtain the treated aramid resin III piezoelectric composite film.
The density of the PZT aramid resin III piezoelectric composite material film obtained after treatment is 3470kg/m 3 The breakdown strength is 178kV/mm, the piezoelectric modulus at 25 ℃ is 20.0d33, the piezoelectric modulus at 200 ℃ is 19.6d33, and the piezoelectric modulus at 25 ℃ is pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 178 MPa, and tensile strength at 200 ℃ is 174MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 30-40 mu m, and the maximum average output voltage can reach 0.16V.
Example 4
This example discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, in which the piezoelectric ceramic is replaced by barium titanate with the same particle size and the same amount, and the rest is the same as in example 2.
The density of the aramid resin III piezoelectric composite material film obtained after treatment is 4210kg/m 3 The breakdown strength is 128kV/mm, the piezoelectric modulus at 25 ℃ is 15.1d33, pc/N, and the piezoelectric modulus at 200 ℃ is 14.7d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 152MPa, and tensile strength at 200 ℃ is 148MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 30-40 μm, and as shown in FIG. 2, the average output voltage can reach 0.08V at maximum.
Example 5
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, wherein piezoelectric ceramics are replaced by lead titanate with the same particle size and equivalent quantity, and the rest is the same as in the embodiment 2.
The aramid resin III piezoelectric composite material film obtained after treatment has the densityThe degree of the reaction is 3760kg/m 3 The breakdown strength is 169kV/mm, the piezoelectric modulus at 25 ℃ is 17.3d33, pc/N, and the piezoelectric modulus at 200 ℃ is 17.1d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 160MPa; the tensile strength at 200 ℃ is 156MPa, and the usable temperature is between-152 ℃ and 200 ℃; as shown in FIG. 3, the average output voltage can reach 0.09V at maximum, with the film thickness of 30-40 μm.
Example 6
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material, which comprises the following steps of 10% of the total system by mass of piezoelectric ceramic PZT powder, and the balance of the method is as in embodiment 2.
The density of the treated aramid resin III piezoelectric composite film is 3110kg/m 3 The breakdown strength is 148kV/mm, the piezoelectric modulus at 25 ℃ is 6.2d33, pc/N, and the piezoelectric modulus at 200 ℃ is 6.05d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 152MPa; the tensile strength at 200 ℃ is 148MPa, and the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 30-40 mu m, and the maximum average output voltage can reach 0.10V.
Example 7
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, wherein the material molar ratio is TPC to PAZ to PPD=100 to 50, and the prepared aramid resin III polymer stock solution has dynamic viscosity of 59920cP, and the rest is the same as in the embodiment 2.
The experimental results of the aramid resin III piezoelectric composite film obtained after the treatment are shown in Table 1.
Comparative example 1
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, wherein the step of crystallizing S105 is not provided, and the rest is the same as in the embodiment 2.
The density of the aramid resin III piezoelectric composite material film obtained after treatment is 2180kg/m 3 Breakdown strength of 181kV/mm, piezoelectric modulus of 7.4d33 at 25 ℃, pc/N, piezoelectric at 200 DEG CModulus 7.1d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 140MPa; the tensile strength at 200 ℃ is 136MPa, and the usable temperature is between-152 ℃ and 200 ℃; as shown in FIG. 4, the average output voltage can reach 0.12V at maximum, with the film thickness of 30-40 μm.
Comparative example 2
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, S104 adopts a dry film forming process, wherein the dry film forming process is to form a film at 105-110 ℃ and a vacuum degree of 115-125 Pa, and the rest is the same as in the embodiment 2.
The density of the aramid resin III piezoelectric composite material film obtained after treatment is 2960kg/m 3 The breakdown strength is 122kV/mm, the piezoelectric modulus at 25 ℃ is 10.3d33, pc/N, and the piezoelectric modulus at 200 ℃ is 10.1d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 191MPa, and tensile strength at 200 ℃ is 186MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 30-40 mu m, and the maximum average output voltage can reach 0.118V.
Comparative example 3
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, wherein the reaction temperature in S102 is 5 ℃, and the rest is the same as in the embodiment 2.
The density of the aramid resin III piezoelectric composite material film obtained after treatment is 4390kg/m 3 The breakdown strength is 162kV/mm, the piezoelectric modulus at 25 ℃ is 31.8d33, the pc/N, and the piezoelectric modulus at 200 ℃ is 31.4d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 178 MPa, and tensile strength at 200 ℃ is 174MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 30-40 mu m, and the maximum average output voltage can reach 0.13V.
Comparative example 4
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, wherein the reaction temperature in S102 is 25 ℃, and the rest is the same as in the embodiment 2.
The density of the treated aramid resin III piezoelectric composite film is 4550kg/m 3 The breakdown strength is 122kV/mm, the piezoelectric modulus at 25 ℃ is 32.7d33, the pc/N, and the piezoelectric modulus at 200 ℃ is 31.8d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 178 MPa, and tensile strength at 200 ℃ is 173MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 30-40 μm, and the maximum average output voltage can reach 0.124V.
Comparative example 5
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material, which comprises the following steps of taking the mass fraction of PZT powder of the heterocyclic aramid resin-based composite piezoelectric material as 5% of the whole system, and the rest is the same as in the embodiment 2.
The density of the treated aramid resin III piezoelectric composite film is 2152kg/m 3 The breakdown strength is 113kV/mm, the piezoelectric modulus at 25 ℃ is 6.4d33, pc/N,
the piezoelectric modulus at 200 ℃ is 6.3d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; a tensile strength of 185MPa at 25 ℃ and 180MPa at 200 ℃; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 20-25 mu m, and the maximum average output voltage can reach 0.125V.
Comparative example 6
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material, which comprises the following steps of taking 30% of the total system by mass of piezoelectric ceramic PZT powder, and the rest is the same as in the embodiment 2.
The density of the aramid resin III piezoelectric composite material film obtained after treatment is 6210kg/m 3 The breakdown strength is 163kV/mm, the piezoelectric modulus at 25 ℃ is 49.6d33, pc/N, and the piezoelectric modulus at 200 ℃ is 46.5d33, pc/N; the piezoelectric coefficient is 0.093-0.1 under the conditions of g33Vm/N,10 Hz-5 MHz; tensile strength at 25 ℃ is 102MPa, and tensile strength at 200 ℃ is 99MPa; the usable temperature is between-152 ℃ and 200 ℃; the thickness of the film is 50-60 mu m, and the maximum average output voltage can reach 0.13V.
Comparative example 7
The embodiment discloses a preparation method of a heterocyclic aramid resin-based composite piezoelectric material and the heterocyclic aramid resin-based composite piezoelectric material, wherein the material molar ratio is TPC to PAZ to PPD=100:20:80, and the rest is the same as in the embodiment 2.
The experimental results of the aramid resin III piezoelectric composite film obtained after the treatment are shown in Table 1.
The method for measuring the piezoelectric property of the film comprises the steps of applying 160N force through an electronic universal testing machine and measuring voltage changes at two ends of the film; the testing machine is manufactured according to the standard of GB/T16491-2008 electronic universal testing machine, wherein the extensometer meets the requirements of the extensometer for single-shaft test of GB/T12160-2002, and the experimental results are shown in Table 1:
TABLE 1
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Conclusion of the test:
as can be seen from examples 1-7, the heterocyclic aramid resin-based composite piezoelectric material prepared by the invention has a piezoelectric modulus of 6.2d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus is 6.05d33, pc/N-51.9 d33, pc/N at 200 ℃; the breakdown strength is 152 kV/mm-200 kV/mm; the tensile strength is 102MPa to 191MPa at 25 ℃; the tensile strength is 99MPa to 186MPa at 200 ℃; the average output voltage is tested to be 0.08-0.18V under the conditions of 25 ℃ and 160N; the change rate of the piezoelectric modulus at 25 ℃ to 200 ℃ is less than 2.65%, and the change rate of the tensile strength at 25 ℃ to 200 ℃ is less than 3%, so that the piezoelectric ceramic can be used at high temperature for a long time.
From examples 1 to 3 and 7, it is found that the dynamic viscosity of the polymer is 40000cP to 70000cP, preferably 40000cP to 60000cP.
As can be seen from the AFM test of FIGS. 5 and 6, the surface roughness of the heterocyclic aramid resin-based composite piezoelectric materials prepared in example 1 and example 7 is less than 10nm.
As is known from comparative example 2, example 7 and comparative example 7, the molar ratio of terephthaloyl chloride to 2- (4-aminophenyl) -5-aminobenzimidazole to paraphenylenediamine is 100:20-40:60-80; the piezoelectric modulus, tensile strength and average output voltage of the heterocyclic aramid resin-based composite piezoelectric material are obviously improved compared with those of the composite piezoelectric material outside the range of the proportion under the conditions of 25 ℃ and 160N; comparing the AFM tests of FIG. 5, FIG. 7 and FIG. 8, it can be seen that the particle uniformity of the piezoelectric composite material is better when the molar ratio of terephthaloyl chloride to 2- (4-aminophenyl) -5-aminobenzimidazole to p-phenylenediamine is 100:20-40:60-80.
When the piezoelectric ceramic particles in the aramid resin III heterocyclic aramid resin-based composite piezoelectric material are lead zirconate titanate; the piezoelectric modulus of the heterocyclic aramid resin-based composite piezoelectric material is 12.1d33, pc/N-52d33 and pc/N at 25 ℃; the piezoelectric modulus is 11.8d33, pc/N-51.9d33 and pc/N at 200 ℃; the tensile strength of the heterocyclic aramid resin-based composite piezoelectric material is 102 MPa-191 MPa at 25 ℃; the tensile strength is 99.6MPa to 186MPa at 200 ℃; the average output voltage of the heterocyclic aramid resin-based composite piezoelectric material is 0.15-0.18V under the conditions of 25 ℃ and 160N; the piezoelectric coefficient of the heterocyclic aramid resin-based composite piezoelectric material is 0.093-0.1 under the conditions of g33Vm/N and 10 Hz-5 MHz.
As is clear from comparative example 2 and comparative example 1, the piezoelectric modulus, tensile strength and average output voltage of the piezoelectric composite material without crystallization were all significantly reduced under the same conditions; comparing the AFM tests of fig. 5 and 7, it can be seen that the roughness of the piezoelectric composite material without crystallization in fig. 7 is between 20 nm and 100nm, the surface roughness and uniformity of the particles are poor, which may be an important cause for significantly decreasing the piezoelectric modulus, the tensile strength and the average output voltage.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A heterocyclic aramid resin-based composite piezoelectric material, characterized by comprising: a continuous phase and a dispersed phase encapsulated in the continuous phase;
the preparation method of the heterocyclic aramid resin-based composite piezoelectric material comprises the following steps:
and adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and crystallizing the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material.
2. The heterocyclic aramid resin-based composite piezoelectric material of claim 1, wherein the continuous phase comprises a heterocyclic aramid resin-based polymer;
the dispersed phase comprises piezoelectric ceramic particles; the piezoelectric ceramic particles wrapped in the heterocyclic aramid resin-based polymer are dispersed in the heterocyclic aramid resin-based polymer.
3. The heterocyclic aramid resin-based composite piezoelectric material according to claim 2, wherein the piezoelectric ceramic particles have a particle size of 20 μm to 30 μm.
4. The heterocyclic aramid resin-based composite piezoelectric material according to claim 3, wherein the amount of the piezoelectric ceramic particles in the heterocyclic aramid resin-based composite piezoelectric material is 10-25 wt%.
5. The heterocyclic aramid resin-based composite piezoelectric material according to claim 4, wherein the piezoelectric ceramic particles are any one of lead zirconate titanate, barium titanate, and lead titanate.
6. The heterocyclic aramid resin-based composite piezoelectric material according to claim 5, wherein the piezoelectric ceramic particles are lead zirconate titanate.
7. The heterocyclic aramid resin-based composite piezoelectric material according to any one of claims 1 to 6, wherein the heterocyclic aramid resin-based polymer comprises: aramid resin III;
the aramid resin III contains Two structural units;
wherein n is in the moleculeNumber of units.
8. The preparation method of the heterocyclic aramid resin-based composite piezoelectric material is characterized by comprising the following steps of: adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution to prepare a mixture, and crystallizing the mixture to obtain the heterocyclic aramid resin-based composite piezoelectric material.
9. The method of manufacturing according to claim 8, characterized in that the method of manufacturing comprises:
s101: dissolving heterocyclic diamine monomer or phenyl diamine monomer in polar solvent to obtain mixed solution;
s102: the mixed solution reacts with phenyl binary acyl chloride monomer to prepare a heterocyclic aramid resin-based polymer stock solution;
s103: adding piezoelectric ceramic powder into the heterocyclic aramid resin-based polymer stock solution, blending and stirring to prepare an aramid piezoelectric composite stock solution;
s104: the prepared aramid fiber piezoelectric composite material stock solution is prepared to form a film in a die;
s105: and crystallizing the prepared film to obtain the heterocyclic aramid resin-based composite piezoelectric material.
10. The method of claim 9, wherein the heterocyclic diamine monomer in S101 comprises a benzene ring and a benzimidazole group.
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