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Preparation method of polyvinylidene fluoride composite material with high piezoelectricity

A technology of polyvinylidene fluoride and composite materials, applied in the direction of electrospinning, single-component halogenated hydrocarbon artificial filaments, non-woven fabrics, etc., which can solve the problems of high β crystal phase transition, uneven filler mixing, and preparation process Complicated and other issues, to achieve the effect of high β crystal phase content, good piezoelectric performance, and good flexibility

Pending Publication Date: 2018-06-29
TIANJIN UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The purpose of the present invention is to overcome the shortcomings of uneven mixing between the two fillers or complicated preparation process when two fillers (carbon nanotubes and nano-barium titanate) are doped in the existing polyvinylidene fluoride composite material, and provide A method for preparing a polyvinylidene fluoride composite piezoelectric fiber membrane that realizes high β crystal phase transformation of PVDF and ordered orientation arrangement of β crystal phase, and the prepared polyvinylidene fluoride composite fiber membrane has a higher β crystal phase transformation and a higher piezoelectric strain constant D 33

Method used

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  • Preparation method of polyvinylidene fluoride composite material with high piezoelectricity
  • Preparation method of polyvinylidene fluoride composite material with high piezoelectricity
  • Preparation method of polyvinylidene fluoride composite material with high piezoelectricity

Examples

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Embodiment 1

[0032] Preparation of polyvinylidene fluoride / CNT@BaTiO according to the method provided by the present invention 3 Composite fiber material:

[0033] 1. CNT@BaTiO 3 Preparation of core-shell structure

[0034] (1) Mixed acid modification of carbon nanotubes: prepare 180 mL of mixed acid of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, and cool to room temperature. Then put 2g of original MWCNT into the mixed acid, sonicate at room temperature for 30min, and at 50℃ for 6h, then cool to room temperature, centrifuge, add deionized water to wash, repeat several times, until PH=7, the obtained CNT Vacuum dry at 80°C to constant weight for later use.

[0035] (2) Amidation of acid-modified carbon nanotubes: The acid-modified carbon nanotubes and 200 mL of 1mol / L HCl were ultrasonically stirred for 30 minutes, and then an excess of p-phenylenediamine was added and refluxed at 90°C for 24 hours to obtain the Need products. The product was centrifuged...

Embodiment 2

[0044] Preparation of polyvinylidene fluoride / CNT@BaTiO according to the method provided by the present invention 3 Composite fiber material:

[0045] 1. CNT@BaTiO 3 Preparation of core-shell structure

[0046] (1) Mixed acid modification of carbon nanotubes: prepare 180 mL of mixed acid with a volume ratio of 1:1 concentrated sulfuric acid and concentrated nitric acid, and cool to room temperature. Then put 2g of the original multi-walled carbon nanotubes into the mixed acid, sonicate at room temperature for 60 minutes, then at 80°C for 8 hours, then cool to room temperature, centrifuge, add deionized water to wash, and repeat several times until PH= 7. Then the obtained CNT was vacuum dried at 80°C to constant weight for later use.

[0047] (2) Amidation of acid-modified carbon nanotubes: The acid-modified carbon nanotubes and 200 mL of 1mol / L HCl were ultrasonically stirred for 60 minutes, and then an excess of p-phenylenediamine was added and refluxed at 130°C for 24 hours to o...

Embodiment 3

[0057] Preparation of polyvinylidene fluoride / CNT@BaTiO according to the method provided by the present invention 3 Composite fiber material:

[0058] 1. CNT@BaTiO 3 Preparation of core-shell structure

[0059] (1) Mixed acid modification of carbon nanotubes: prepare 300 mL of mixed acid of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, and cool to room temperature. Then put 2g of the original multi-walled carbon nanotubes into the mixed acid, sonicate at room temperature for 45 minutes, then at 40°C for 4 hours, then cool to room temperature, centrifuge, add deionized water to wash, repeat several times, until PH = 7. Then the obtained CNT was vacuum dried at 120°C to constant weight for later use.

[0060] (2) Amidation of acid-modified carbon nanotubes: The acid-modified carbon nanotubes and 200mL of 1mol / L HCl were ultrasonically stirred for 30 minutes, and then an excess of p-phenylenediamine was added and refluxed at 60°C for 26 hours to o...

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Abstract

The invention provides a preparation method of a polyvinylidene fluoride composite material with high piezoelectricity, and relates to a preparation technology of piezoelectric flexible materials. Thepolyvinylidene fluoride composite material is a composite fiber membrane prepared by means of an electrospinning method using polyvinylidene fluoride as a matrix and a core-shell structure formed bynano-barium titanate and carbon nanotubes as a reinforcement. The preparation method aims at solving the problems of uneven mixing of two kinds of reinforcements doped in an existing polyvinylidene fluoride piezoelectric fiber membrane, self agglomeration of the two reinforcements or low content of the beta crystal phase in the fiber membrane, and poor piezoelectric performance. The CNT@BaTiO3 (core / shell) particles prepared by adopting a chemical method can be uniformly dispersed in a polymer, and the prepared composite fiber membrane has good flexibility and mechanical properties. The crystallinity is 55%-80%, the content of the beta crystal phase is 60%-91%, the piezoelectric constant D33 is 35-50 pC / N, and the composite fiber membrane can be applied to devices such as piezoelectric sensors, piezoelectric nanogenerators and the like.

Description

Technical field [0001] The invention relates to a high-performance polyvinylidene fluoride / CNT@BaTiO 3 A preparation method of a composite material piezoelectric flexible device belongs to the technical field of preparation of new materials. Background technique [0002] With the development of science and technology and the improvement of people's living standards, flexible wearable devices have attracted more and more attention because of their excellent performance, such as monitoring people's pulse and heart rate, and improving people's comfort in life. Polyvinylidene fluoride (PVDF) is a widely used polymer piezoelectric material. It has the advantages of strong piezoelectric performance, wide frequency response, high sensitivity and low price. However, PVDF is a typical polycrystalline polymer. The energy storage properties are closely related to the crystalline form. Studies have shown that only the polar zigzag β crystal form exhibits higher piezoelectricity and pyroelec...

Claims

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Application Information

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IPC IPC(8): D04H1/4326D04H1/728D01D5/00D01F6/48D01F1/10
CPCD01D5/003D01D5/0061D01D5/0076D01D5/0092D01F1/10D01F6/48D04H1/4326D04H1/728Y02E60/10
Inventor 马叙蒋莉丁燕红
Owner TIANJIN UNIVERSITY OF TECHNOLOGY
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