CN101067042A - Conductive polyaniline/piezoelectric ceramic powder composite material and its prepn process - Google Patents
Conductive polyaniline/piezoelectric ceramic powder composite material and its prepn process Download PDFInfo
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- CN101067042A CN101067042A CN 200710052452 CN200710052452A CN101067042A CN 101067042 A CN101067042 A CN 101067042A CN 200710052452 CN200710052452 CN 200710052452 CN 200710052452 A CN200710052452 A CN 200710052452A CN 101067042 A CN101067042 A CN 101067042A
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Abstract
The present invention relates to one kind of conductive polyaniline/piezoelectric ceramic powder composite material and its preparation process. The composite material is prepared with piezoelectric ceramic powder 50-150 weight portions, aniline monomer 10 weight portions, oxidant (NH4)2S2O8 20-25 weight portions, and 1.0 ml/l concentration hydrochloric acid solution as the doping acid solution 500-1000 weight portions. The present invention has the features of good machining performance and high electric energy-to-heat energy conversion rate.
Description
Technical field
The present invention relates to a kind of conduction/piezo-electricity composite material and preparation method thereof.
Technical background
Piezoelectric ceramics be a kind of can be with mechanical energy and the electric energy ceramic material of conversion mutually, it is by some kinds of different oxide compounds, such as aluminum oxide, barium oxide, zirconium white, titanium oxide, niobium oxides, sodium oxide etc., proportionally cooperate, through overmolding, high temperature solid state reaction, sintering, synthetic produced at last.The structure of piezoelectric ceramics is asymmetric, and there is certain electric field in inside, when a certain direction at pottery applies mechanical pressure, then can cause polarization, correspondingly make between the surface appearance potential poor at specific direction, otherwise, as applying electric field at certain orientation, certain deformation and displacement also can take place in pottery.
Conducting polymer composite also claims conductive polymers, have tangible polymer features,, promptly have electric current to pass through in the material if add certain voltage at the material two ends, the character that promptly has electrical conductor, the material that has above two character simultaneously is called conducting polymer composite.Typical conducting polymer composite has: polyaniline (PANI), Polythiophene (PTH), polyacetylene (PA), polypyrrole (PPy) etc., they self can provide current carrier, have the conjugated structure, through chemistry or electrochemistry " doping ", specific conductivity increases substantially.Wherein polyaniline is because its raw material is cheap and easy to get, and the preparation method is simple, the good and good stability of conductivity, thereby become and have one of kind of application prospect in the conducting polymer composite most.But its molecular chain has very strong conjugacy is arranged very, make it become the polymkeric substance of a kind of infusibility, indissoluble, processing characteristics is relatively poor.
Conduction/piezo-electricity composite material is a kind of functional composite material of application prospect broadness, and after the piezoelectric phase in the matrix material was subjected to the effect of external mechanical force, the electric charge of generation was converted into heat energy by the conduction of the conductive phase around it.Common method is that the minute quantity carbon black particle is joined in the composite system as conductive phase at present, but the weak point that this method exists is that carbon black particle is distributed in around each piezoelectric ceramic particle fully, most of piezoelectric ceramic particle may not brought into play corresponding effectiveness, and promptly electric energy is not high to the turnover ratio of heat energy.
Summary of the invention
The purpose of this invention is to provide a kind of good processability, electric energy to high electrically conductive polyaniline/piezoelectric ceramic powder composite material of thermal energy conversion rate and preparation method thereof.
To achieve these goals, technical scheme of the present invention is: electrically conductive polyaniline/piezoelectric ceramic powder composite material, it is characterized in that it is prepared from by piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, the shared parts by weight of each raw material are: piezoelectric ceramic powder 50~150, aniline monomer 10, oxygenant 20~25, dopant acid solution 500~1000; Wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L or the Witco 1298 Soft Acid of 1.0ml/L (DBSA) solution.
Described piezoelectric ceramic powder is Pb-based lanthanumdoped zirconate titanates (PZT), lead lanthanum zirconate titanate (PLZT), barium titanate (BaTiO
3), lead titanate (PbTiO
3) or magnesium niobium lead zirconate titanate piezoelectric ceramics powder such as (PMN).
The particle diameter of described piezoelectric ceramic powder is 1~10 μ m.
The preparation method of above-mentioned electrically conductive polyaniline/piezoelectric ceramic powder composite material at piezoelectric ceramic powder particle surface coated with conductive polyaniline, is characterized in that it comprises the steps: with the chemical oxidation situ aggregation method
1) by the shared parts by weight of each raw material be: it is standby that piezoelectric ceramic powder 50~150, aniline monomer 10, oxygenant 20~25, dopant acid solution 500~1000 are chosen piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L or the Witco 1298 Soft Acid of 1.0ml/L (DBSA) solution;
2) aniline monomer and piezoelectric ceramic powder are joined in 3/5~4/5 the dopant acid solution, suspension liquid; Place 0 ℃ of ice bath to stir this suspension liquid and be aided with ultra-sonic dispersion 1~3 hour, the suspension liquid behind the ultra-sonic dispersion;
3) again oxygenant is dissolved in the remaining dopant acid solution, slowly drops to after stirring in the suspension liquid behind the aforementioned ultra-sonic dispersion, in 0.5~1 hour, dropwise; React and with B reaction solution is carried out suction filtration after 5~24 hours, the washing precipitation product vacuumizes drying with the precipitated product after the washing and promptly prepared product in 48 hours under 50 ℃ of conditions.
The invention has the beneficial effects as follows: by the chemical oxidation situ aggregation method, electrically conductive polyaniline is coated on the piezoelectric ceramic particle surface, both solved the unmanageable difficult problem of polyaniline, and made piezoelectric ceramic particle all play effectiveness again, promptly good processability, electric energy are to the thermal energy conversion rate height.Simple, the easily realization of preparation method of the present invention.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention in conjunction with the embodiments down, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Electrically conductive polyaniline/piezoelectric ceramic powder composite material, it is prepared from by piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and the shared parts by weight of each raw material are: piezoelectric ceramic powder 100, aniline monomer 10, oxygenant 25, dopant acid solution 500; Wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L; Described piezoelectric ceramic powder is magnesium niobium lead zirconate titanate (PMN) powder; The particle diameter of piezoelectric ceramic powder is 1~10 μ m.
The preparation method of above-mentioned electrically conductive polyaniline/piezoelectric ceramic powder composite material, at piezoelectric ceramic powder particle surface coated with conductive polyaniline, it comprises the steps: with the chemical oxidation situ aggregation method
1) by the shared parts by weight of each raw material be: it is standby that piezoelectric ceramic powder 100, aniline monomer 10, oxygenant 25, dopant acid solution 500 are chosen piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L; Described piezoelectric ceramic powder is magnesium niobium lead zirconate titanate (PMN) powder; The particle diameter of magnesium niobium lead zirconate titanate (PMN) powder is 1~10 μ m;
2) aniline monomer and piezoelectric ceramic powder are joined in 3/5 the dopant acid solution, suspension liquid; Place 0 ℃ of ice bath to stir (stirring velocity is 2000-3000 rev/min) this suspension liquid and be aided with ultra-sonic dispersion 1 hour, the suspension liquid behind the ultra-sonic dispersion;
3) again oxygenant is dissolved in the remaining dopant acid solution, slowly drops to after stirring in the suspension liquid behind the aforementioned ultra-sonic dispersion, in 1 hour, dropwise; React and with B reaction solution is carried out suction filtration after 5 hours, the washing precipitation product vacuumizes drying with the precipitated product after the washing and promptly prepared electrically conductive polyaniline/piezoelectric ceramic powder composite material (being product) in 48 hours under 50 ℃ of conditions.
Embodiment 2:
Electrically conductive polyaniline/piezoelectric ceramic powder composite material, it is prepared from by piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and the shared parts by weight of each raw material are: piezoelectric ceramic powder 50, aniline monomer 10, oxygenant 20, dopant acid solution 500; Wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L; Described piezoelectric ceramic powder is Pb-based lanthanumdoped zirconate titanates (PZT) powder; The particle diameter of piezoelectric ceramic powder is 1~10 μ m.
The preparation method of above-mentioned electrically conductive polyaniline/piezoelectric ceramic powder composite material, at piezoelectric ceramic powder particle surface coated with conductive polyaniline, it comprises the steps: with the chemical oxidation situ aggregation method
1) by the shared parts by weight of each raw material be: it is standby that piezoelectric ceramic powder 50, aniline monomer 10, oxygenant 20, dopant acid solution 500 are chosen piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L; Described piezoelectric ceramic powder is Pb-based lanthanumdoped zirconate titanates (PZT) powder; The particle diameter of Pb-based lanthanumdoped zirconate titanates (PZT) powder is 1~10 μ m;
2) aniline monomer and piezoelectric ceramic powder are joined in 3/5 the dopant acid solution, suspension liquid; Place 0 ℃ of ice bath to stir (stirring velocity is 2000-3000 rev/min) this suspension liquid and be aided with ultra-sonic dispersion 1 hour, the suspension liquid behind the ultra-sonic dispersion;
3) again oxygenant is dissolved in the remaining dopant acid solution, slowly drops to after stirring in the suspension liquid behind the aforementioned ultra-sonic dispersion, in 0.5 hour, dropwise; React and with B reaction solution is carried out suction filtration after 5 hours, the washing precipitation product vacuumizes drying with the precipitated product after the washing and promptly prepared electrically conductive polyaniline/piezoelectric ceramic powder composite material (being product) in 48 hours under 50 ℃ of conditions.
Embodiment 3:
Electrically conductive polyaniline/piezoelectric ceramic powder composite material, it is prepared from by piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and the shared parts by weight of each raw material are: piezoelectric ceramic powder 100, aniline monomer 10, oxygenant 22, dopant acid solution 700; Wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is Witco 1298 Soft Acid (DBSA) solution of 1.0ml/L; Described piezoelectric ceramic powder is lead lanthanum zirconate titanate (PLZT) powder, and the particle diameter of lead lanthanum zirconate titanate (PLZT) powder is 1~10 μ m.
The preparation method of above-mentioned electrically conductive polyaniline/piezoelectric ceramic powder composite material, at piezoelectric ceramic powder particle surface coated with conductive polyaniline, it comprises the steps: with the chemical oxidation situ aggregation method
1) by the shared parts by weight of each raw material be: it is standby that piezoelectric ceramic powder 100, aniline monomer 10, oxygenant 22, dopant acid solution 700 are chosen piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is Witco 1298 Soft Acid (DBSA) solution of 1.0ml/L; Described piezoelectric ceramic powder is lead lanthanum zirconate titanate (PLZT) powder, and the particle diameter of lead lanthanum zirconate titanate (PLZT) powder is 1~10 μ m;
2) aniline monomer and piezoelectric ceramic powder are joined in 4/5 the dopant acid solution, suspension liquid; Place 0 ℃ of ice bath to stir (stirring velocity is 2000-3000 rev/min) this suspension liquid and be aided with ultra-sonic dispersion 2 hours, the suspension liquid behind the ultra-sonic dispersion;
3) again oxygenant is dissolved in the remaining dopant acid solution, slowly drops to after stirring in the suspension liquid behind the aforementioned ultra-sonic dispersion, in 0.8 hour, dropwise; React and with B reaction solution is carried out suction filtration after 15 hours, the washing precipitation product vacuumizes drying with the precipitated product after the washing and promptly prepared product in 48 hours under 50 ℃ of conditions.
Embodiment 4:
Electrically conductive polyaniline/piezoelectric ceramic powder composite material, it is prepared from by piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and the shared parts by weight of each raw material are: piezoelectric ceramic powder 150, aniline monomer 10, oxygenant 25, dopant acid solution 1000; Wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is Witco 1298 Soft Acid (DBSA) solution of 1.0ml/L, described piezoelectric ceramic powder is barium titanate (BaTiO
3) powder, barium titanate (BaTiO
3) particle diameter of powder is 1~10 μ m.
The preparation method of above-mentioned electrically conductive polyaniline/piezoelectric ceramic powder composite material, at piezoelectric ceramic powder particle surface coated with conductive polyaniline, it comprises the steps: with the chemical oxidation situ aggregation method
1) by the shared parts by weight of each raw material be: it is standby that piezoelectric ceramic powder 150, aniline monomer 10, oxygenant 25, dopant acid solution 1000 are chosen piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is Witco 1298 Soft Acid (DBSA) solution, and described piezoelectric ceramic powder is lead lanthanum zirconate titanate (PLZT) powder, and the particle diameter of piezoelectric ceramic powder is 1~10 μ m;
2) aniline monomer and piezoelectric ceramic powder are joined in 4/5 the dopant acid solution, suspension liquid; Place 0 ℃ of ice bath to stir (stirring velocity is 2000-3000 rev/min) this suspension liquid and be aided with ultra-sonic dispersion 3 hours, the suspension liquid behind the ultra-sonic dispersion;
3) again oxygenant is dissolved in the remaining dopant acid solution, slowly drops to after stirring in the suspension liquid behind the aforementioned ultra-sonic dispersion, in 1 hour, dropwise; React and with B reaction solution is carried out suction filtration after 24 hours, the washing precipitation product vacuumizes drying with the precipitated product after the washing and promptly prepared electrically conductive polyaniline/piezoelectric ceramic powder composite material (being product) in 48 hours under 50 ℃ of conditions.
Claims (4)
1. electrically conductive polyaniline/piezoelectric ceramic powder composite material, it is characterized in that it is prepared from by piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, the shared parts by weight of each raw material are: piezoelectric ceramic powder 50~150, aniline monomer 10, oxygenant 20~25, dopant acid solution 500~1000; Wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L or the dodecylbenzenesulfonic acid solution of 1.0ml/L.
2. electrically conductive polyaniline/piezoelectric ceramic powder composite material according to claim 1 is characterized in that: described piezoelectric ceramic powder is Pb-based lanthanumdoped zirconate titanates, lead lanthanum zirconate titanate, barium titanate, lead titanate or magnesium niobium lead zirconate titanate powder.
3. electrically conductive polyaniline/piezoelectric ceramic powder composite material according to claim 1 and 2 is characterized in that: the particle diameter of described piezoelectric ceramic powder is 1~10 μ m.
4. the preparation method of electrically conductive polyaniline/piezoelectric ceramic powder composite material according to claim 1 is characterized in that it comprises the steps:
1) by the shared parts by weight of each raw material be: it is standby that piezoelectric ceramic powder 50~150, aniline monomer 10, oxygenant 20~25, dopant acid solution 500~1000 are chosen piezoelectric ceramic powder, aniline monomer, oxygenant and dopant acid solution materials, and wherein oxygenant is selected (NH for use
4)
2S
2O
8, dopant acid solution is the hydrochloric acid soln of 1.0ml/L or the dodecylbenzenesulfonic acid solution of 1.0ml/L;
2) aniline monomer and piezoelectric ceramic powder are joined in 3/5~4/5 the dopant acid solution, suspension liquid; Place 0 ℃ of ice bath to stir this suspension liquid and be aided with ultra-sonic dispersion 1~3 hour, the suspension liquid behind the ultra-sonic dispersion;
3) again oxygenant is dissolved in the remaining dopant acid solution, slowly drops to after stirring in the suspension liquid behind the aforementioned ultra-sonic dispersion, in 0.5~1 hour, dropwise; React and with B reaction solution is carried out suction filtration after 5~24 hours, the washing precipitation product vacuumizes drying with the precipitated product after the washing and promptly prepared product in 48 hours under 50 ℃ of conditions.
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CN102516709A (en) * | 2011-12-01 | 2012-06-27 | 昆明理工大学 | Polyaniline urea resin electric conductive composite material and preparation method thereof |
CN102775604A (en) * | 2012-08-17 | 2012-11-14 | 中北大学 | Method for preparing core-shell type barium titanate/polyaniline composite wave-absorbing material |
CN103289363A (en) * | 2013-06-08 | 2013-09-11 | 哈尔滨工程大学 | Polyurethane-base piezoelectric conductive intelligent composite damping material and preparation method thereof |
CN103966549A (en) * | 2014-05-07 | 2014-08-06 | 哈尔滨工业大学 | Method for preparing patterned electrochromatic polyaniline film |
CN108084593A (en) * | 2016-11-22 | 2018-05-29 | 洛阳尖端技术研究院 | A kind of ternary piezo-electric damping material and preparation method thereof |
CN110819106A (en) * | 2018-08-09 | 2020-02-21 | 中国科学院大连化学物理研究所 | Preparation of PANI/BaTiO3Method (2) |
CN115748005A (en) * | 2022-12-21 | 2023-03-07 | 浙江工业大学 | Preparation method and application of BTO @ PANI-nfs nano fiber |
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2007
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516709A (en) * | 2011-12-01 | 2012-06-27 | 昆明理工大学 | Polyaniline urea resin electric conductive composite material and preparation method thereof |
CN102775604A (en) * | 2012-08-17 | 2012-11-14 | 中北大学 | Method for preparing core-shell type barium titanate/polyaniline composite wave-absorbing material |
CN103289363A (en) * | 2013-06-08 | 2013-09-11 | 哈尔滨工程大学 | Polyurethane-base piezoelectric conductive intelligent composite damping material and preparation method thereof |
CN103966549A (en) * | 2014-05-07 | 2014-08-06 | 哈尔滨工业大学 | Method for preparing patterned electrochromatic polyaniline film |
CN108084593A (en) * | 2016-11-22 | 2018-05-29 | 洛阳尖端技术研究院 | A kind of ternary piezo-electric damping material and preparation method thereof |
CN110819106A (en) * | 2018-08-09 | 2020-02-21 | 中国科学院大连化学物理研究所 | Preparation of PANI/BaTiO3Method (2) |
CN115748005A (en) * | 2022-12-21 | 2023-03-07 | 浙江工业大学 | Preparation method and application of BTO @ PANI-nfs nano fiber |
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