CN102070318A - Preparation method of piezoelectric gel composite - Google Patents
Preparation method of piezoelectric gel composite Download PDFInfo
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- CN102070318A CN102070318A CN 201010573978 CN201010573978A CN102070318A CN 102070318 A CN102070318 A CN 102070318A CN 201010573978 CN201010573978 CN 201010573978 CN 201010573978 A CN201010573978 A CN 201010573978A CN 102070318 A CN102070318 A CN 102070318A
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Abstract
The invention relates to a preparation method of a piezoelectric gel composite. The preparation method comprises the following special steps: weighting the mixture of Pb3O4, ZrO2, TiO2 and Nb2O5 and the mixture of CaCO3, Al2O3 and CaSO4.2H2O or CaSO4 according to a weight ratio of (80-90):(10-20), wherein the molar ratio of Pb3O4 to ZrO2, TiO2 and Nb2O5 is 1/3:0.52:0.48:0.01 and the molar ratio of CaCO3 to Al2O3 and CaSO4.2H2O or CaSO4 is 3:3:1; mixing evenly; forming columns or flakes at 10-200MPa, preburning at 850-1000 DEG C for 2-4h; and grinding the obtained columns or flakes to powder, adding polyvinyl alcohol which accounts for 1-2wt% of the powder, forming columns or flakes at 10-200 MPa, calcining at 1150-1250 DEG C for 2-4h, and grinding again to obtain powder of which fineness is less than 100mu m and prepare the anhydrous calcium sulphoaluminate piezoelectric gel composite. As containing 80-90% of lead niobium zirconate titanate, the composite has piezoelectricity; as containing 10-20% of anhydrous calcium sulphoaluminate, the composite has gelling property; and the hydration speed of anhydrous calcium sulphoaluminate is high. By adopting the preparation method of the invention, the defects that the cement-based piezoelectric composite has low early piezoelectric property and long preparation time, is not stable, etc., can be solved.
Description
Technical field
The invention belongs to building material field, be specifically related to a kind of by calcining preparation both have a gelling, have the preparation method of the piezoelectricity latex composite material of piezoelectricity again.
Background technology
So far, the China railways length overall will reach the hundreds of thousands of kilometer, the millions of kilometers of highway length overall, and several thousand kilometers of urban track traffics, large reservoir reaches more than 100,000.These Infrastructure involve the interests of the state and the people, and in large scale, and complex structure in case lost efficacy, will cause catastrophic effect.Therefore, adopt smart material and structure, alternate manner is carried out in vibration, deformation and damage express, great civil engineering work is implemented on-line monitoring be of great practical significance.Because piezoelectric self both can be used as sensing material, also can be used as driving material, was widely used in smart material and structure.
The kind of piezoelectric comprises piezoelectric ceramics, piezopolymer and piezo-electricity composite material.Wherein piezoelectric ceramics is representative with Pb-based lanthanumdoped zirconate titanates (PZT) and barium titanate (BT), and its electromechanical Coupling is strong, piezoelectric strain constant
d 33Height, but specific inductivity is higher, so piezoelectric voltage constant
g 33Generally lower.And poor toughness, the fragility cracking causes the device reliability of its making not high, poor durability.Piezopolymer is representative with poly(vinylidene fluoride) (PVDF), has piezoelectric voltage constant
g 33Height, flexible good, advantage such as easy-formation and density are low, but also show
d 33Low, shortcomings such as polarizing voltage is high, difficult polarization.In order to overcome their shortcoming, people expect the two compound naturally, with Resins, epoxy, polymkeric substance such as rubber or PVDF are matrix, are functive with the piezoelectric ceramics, by trickle sight structure of regulating matrix material and the performance of selecting each phase material, make the various piezo-electricity composite material of piezoelectric property, be fit to various needs, but still there have been some shortcomings in polymer piezoelectric composite material, as 0-3 type matrix material polarization difficulty, piezoelectric property is not high.And this mixture is by Resins, epoxy, and polymkeric substance etc. are as body material, and cost is higher relatively.The more important thing is that in field of civil engineering, structured material in the highest flight is a cement-based material, because the aquation of cement can cause concrete contraction usually.Therefore all and between the concrete parent there is compatibility problem in traditional piezoelectric (piezoelectric ceramics, piezopolymer and polymer-based carbon piezo-electricity composite material), as problems such as volume stability harmony impedance matchings.For addressing these problems, with normal silicate and aluminosulfate cement is matrix, piezoelectric ceramics is that the piezo-electricity composite material of functive has obtained significant progress, but because of ordinary Portland cement and aluminosulfate cement need certain length of time, aquation just can tend towards stability, so this is that the piezo-electricity composite material of matrix exists the low and unstable properties of piezoelectric property in early stage with cement, the shortcoming that preparation time is relatively long.And this matrix material needs the calcining respectively and the grinding of matrix and functive, and the last mixing of matrix and functive, and energy expenditure is big.The present invention utilizes the fast characteristics of the main mineral composition anhydrous calcium sulphoaluminate of aluminosulfate cement hydration rate, with the anhydrous calcium sulphoaluminate is matrix, with the piezoelectric ceramics is functive, adopt incinerating mode together, prepare a kind of anhydrous calcium sulphoaluminate base piezoelectricity latex composite material, solve these problems that cement base piezoelectric composite material exists.
Summary of the invention
It is low that the present invention overcomes cement base piezoelectric composite material piezoelectric property in early stage, unstable properties, preparation time is long, prepares shortcomings such as energy expenditure is big, a kind of preparation method of piezoelectricity latex composite material is provided, and the gained piezo-electricity composite material is in the field of civil engineering widespread use.
The preparation method of the piezoelectricity latex composite material that the present invention proposes, concrete steps are:
With mol ratio is the P of 1/3:0.52:0.48:0.01
B3O
4, ZrO
2, TiO
2And Nb
2O
5Mixture and mol ratio be the CaCO of 3:3:1
3, Al
2O
3, CaSO
42H
2O or CaSO
4Mixture, two kinds of mixtures are (80～90) by mass ratio: (10～20) mix; Under the pressure of 10～200 Mpa, become cylinder or lamellar body, 850～1000 ℃ of pre-burnings 2～4 hours; Cylinder or lamellar body that pre-burning is formed become powder through grinding, the polyvinyl alcohol that adds powder quality 1～2%, become cylinder or lamellar body under the pressure of 10～200 Mpa, 1150～1250 ℃ of temperature lower calcinations 2～4 hours, becoming fineness through grinding once more was that the following powder of 100 μ m can make.
Among the present invention, described P
B3O
4, ZrO
2, TiO
2, Nb
2O
5, CaCO
3, Al
2O
3, CaSO
42H
2O or CaSO
4Compound adopts industrial chemicals, and raw mineral materials or chemical reagent make, and effective content is greater than 95%, and fineness is less than 100 μ m.
Ordinary Portland cement is mainly by tricalcium silicate (C
3S), Dicalcium Phosphate (Feed Grade) (C
2S), tricalcium aluminate (C
3A) and iron phase form; Aluminosulfate cement mainly is made up of anhydrous calcium sulphoaluminate, iron phase and Dicalcium Phosphate (Feed Grade).These two kinds of cement remove early hydration speed C faster
3S, C
3A, C
4Outside AF and the anhydrous calcium sulphoaluminate, also has the slower C of hydration rate
2S.The general aquation that just can finish most cement the length of time that needs several days to more than 20 days.Compare with aluminosulfate cement with ordinary Portland cement, the anhydrous calcium sulphoaluminate hydration rate is than very fast, can be in more than 20 hour aquation fully.Therefore, have following major advantage with anhydrous calcium sulphoaluminate piezoelectricity latex composite material provided by the invention:
Because the anhydrous calcium sulphoaluminate hydration rate is fast, can be in more than 20 hours aquation fully, therefore, with the phase composite is that anhydrous calcium sulphoaluminate is as matrix, with the phase composite be zirconium niobium lead titanate (PZT) piezoelectric ceramics be the piezoelectricity latex composite material of functive at the aquation initial stage, the pore in the aquation matrix is little; Matrix combines well with interface between the functive; Reduce in the slit; Can slacken existence owing to the slit, the shock absorption of counter stress, it is lower to improve the early stage piezoelectric property of piezo-electricity composite material, the problem of unstable properties; Shorten the time that piezo-electricity composite material prepares piezoelectric device.And this piezo-electricity composite material is different with cement base piezoelectric material preparation mode, and employing matrix and functive are calcined the mode with grinding together, has reduced cement base piezoelectric composite material matrix and functive and has calcined the energy that consumes with mixing once more respectively.
Embodiment
Further specify the present invention below by embodiment.
The present invention is a kind of multiple compound incinerating piezoelectricity latex composite material that utilizes, and its raw material comprises P
B3O
4, ZrO
2, TiO
2, Nb
2O
5, CaCO
3, Al
2O
3, CaSO
42H
2O or CaSO
4And make: at first be the P of 1/3:0.52:0.48:0.01 mol ratio by following method
B3O
4, ZrO
2, TiO
2And Nb
2O
5Mixture and mol ratio be the CaCO of 3:3:1
3, Al
2O
3, CaSO
42H
2O or CaSO
4Mixture, by mass ratio (80～90): (10～20) take by weighing each component (seeing Table 1), through mixing; Under the pressure of 10～200 Mpa, become cylinder or lamellar body, 850～1000 ℃ of pre-burnings 2～4 hours; Cylinder that pre-burning is formed or lamellar body become powder through grinding then, the polyvinyl alcohol of adding 1～2%, become cylinder or lamellar body under the pressure of 10～200 Mpa, 1150～1250 ℃ of temperature lower calcinations 2～4 hours, becoming fineness through grinding once more was that the following powder of 100 μ m can make.
Above-mentioned P
B3O
4, ZrO
2, TiO
2, Nb
2O
5And Al
2O
3Can adopt industrial chemicals or the chemical reagent of effective content more than 95, fineness is less than 100 μ m.CaCO
3And CaSO
42H
2O or CaSO
4Can adopt the effective content of selling on the market greater than raw mineral materials more than 95 or chemical reagent, fineness is less than 100 μ m.
Be elaborated below by embodiment and testing data.
The proportion scheme of numbering A and B is two independently examples in the table one.
Press the A embodiment, take by weighing P respectively
B3O
4, ZrO
2, TiO
2, Nb
2O
5, CaCO
3, Al
2O
3, CaSO
42H
2The O percentage composition is 43.8,22,13.2,1.0, and each compound of 7.7,7.9 and 4.4 becomes cylinder or lamellar body, 850～1000 ℃ of pre-burnings 2～4 hours under the pressure of 10～200 Mpa; Cylinder that pre-burning is formed or lamellar body become powder through grinding then, the polyvinyl alcohol of adding 1～2%, under the pressure of 10～200 Mpa, become cylinder or lamellar body, 1150～1250 ℃ of temperature lower calcinations 2～4 hours, grinding becomes the following powder of 100 μ m, can make the piezoelectricity latex composite material, the piezoelectric property of testing each length of time is as shown in table 2.
Table 2 A scheme piezoelectricity latex composite material piezoelectric constant in the different length of time
| The length of time (d) | 1 | 1.5 | 2 | 3 | 4 | 5 | 6 |
| Piezoelectric constant (pCN -1) | 25.4 | 28.7 | 28.9 | 29.1 | 28.9 | 29.0 | 28.9 |
Press the B embodiment, take by weighing P respectively
B3O
4, ZrO
2, TiO
2, Nb
2O
5, CaCO
3, Al
2O
3, CaSO
42H
2The O percentage composition is 43.8,22,13.2,1.0, and each compound of 7.7,7.9 and 4.4 becomes cylinder or lamellar body, 850～1000 ℃ of pre-burnings 2～4 hours under the pressure of 10～200 Mpa; Cylinder that pre-burning is formed or lamellar body become powder through grinding then, the polyvinyl alcohol of adding 1～2%, under the pressure of 10～200 Mpa, become cylinder or lamellar body, 1150～1250 ℃ of temperature lower calcinations 2～4 hours, behind grinding once more, be prepared into the piezoelectricity latex composite material, the piezoelectric property of testing each length of time is as shown in table 3.
Table 3 B scheme piezoelectricity latex composite material piezoelectric constant in the different length of time
| The length of time (d) | 1 | 1.5 | 2 | 3 | 4 | 5 | 6 |
| Piezoelectric constant (pCN -1) | 27.8 | 29.6 | 29.9 | 30.1 | 29.9 | 30.0 | 29.9 |
From table 2 and table 3 data as seen, the piezoelectricity latex composite material of the present invention's preparation, owing to added hydration rate calcium sulphoaluminate faster, so just show good piezoelectricity stability at the aquation initial stage.Thereby it is low to be of value to solution cement base piezoelectric material piezoelectricity in early stage, problem of unstable.Because this material adopts incinerating mode together, so saved because of the energy of calcining respectively and grinding is consumed.
In sum, the present invention has used the piezoelectricity of lead titanate piezoelectric ceramics, and the gelling that the anhydrous calcium sulphoaluminate hydration rate is fast has been given full play to the synergy between the differing materials, thereby the piezoelectricity gelling material that makes has good piezoelectricity at the aquation initial stage, and stability.Shorten the cement base piezoelectric composite material preparation time greatly.
Claims (2)
1. the preparation method of a piezoelectricity latex composite material is characterized in that concrete steps are:
With mol ratio is the P of 1/3:0.52:0.48:0.01
B3O
4, ZrO
2, TiO
2And Nb
2O
5Mixture and mol ratio be the CaCO of 3:3:1
3, Al
2O
3, CaSO
42H
2O or CaSO
4Mixture, two kinds of mixtures are (80～90) by mass ratio: (10～20) mix; Under the pressure of 10～200 Mpa, become cylinder or lamellar body, 850～1000 ℃ of pre-burnings 2～4 hours; Cylinder or lamellar body that pre-burning is formed become powder through grinding, the polyvinyl alcohol that adds powder quality 1～2%, become cylinder or lamellar body under the pressure of 10～200 Mpa, 1150～1250 ℃ of temperature lower calcinations 2～4 hours, becoming fineness through grinding once more was that the following powder of 100 μ m can make.
2. the preparation method of piezoelectricity latex composite material according to claim 1 is characterized in that: P
B3O
4, ZrO
2, TiO
2, Nb
2O
5, CaCO
3, Al
2O
3, CaSO
42H
2O or CaSO
4Compound adopts industrial chemicals, and raw mineral materials or chemical reagent make, and effective content is greater than 95%, and fineness is less than 100 μ m.
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|---|---|---|---|
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|---|---|---|---|
| CN2010105739789A CN102070318B (en) | 2010-12-06 | 2010-12-06 | Preparation method of piezoelectric gel composite |
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| CN102070318B CN102070318B (en) | 2012-07-25 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105633270A (en) * | 2016-02-24 | 2016-06-01 | 南京邮电大学 | Helix tube type piezoelectric spring and preparation method therefor |
| CN109273591A (en) * | 2018-08-30 | 2019-01-25 | 广州大学 | A kind of alkali-activated carbonatite fly-ash slag piezoelectric transducer and preparation method thereof |
| CN112759385A (en) * | 2021-01-06 | 2021-05-07 | 中国科学院福建物质结构研究所 | Perovskite ceramic material and preparation method and application thereof |
| CN113135754A (en) * | 2021-04-29 | 2021-07-20 | 安徽工业大学 | Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof |
| CN114656256A (en) * | 2022-03-25 | 2022-06-24 | 安徽工业大学 | Piezoelectric composite material prepared from titanium-containing mineral and method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054278A (en) * | 2007-04-11 | 2007-10-17 | 山东大学 | Carbon enhanced lead zirconate titanate/cement piezoelectricity composite material and preparation method thereof |
| CN101054279A (en) * | 2007-04-11 | 2007-10-17 | 山东大学 | Nano lead zirconate titanate/cement piezoelectricity composite material and preparation method thereof |
| CN101531490A (en) * | 2009-04-16 | 2009-09-16 | 山东大学 | Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material and preparation method thereof |
-
2010
- 2010-12-06 CN CN2010105739789A patent/CN102070318B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054278A (en) * | 2007-04-11 | 2007-10-17 | 山东大学 | Carbon enhanced lead zirconate titanate/cement piezoelectricity composite material and preparation method thereof |
| CN101054279A (en) * | 2007-04-11 | 2007-10-17 | 山东大学 | Nano lead zirconate titanate/cement piezoelectricity composite material and preparation method thereof |
| CN101531490A (en) * | 2009-04-16 | 2009-09-16 | 山东大学 | Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105633270A (en) * | 2016-02-24 | 2016-06-01 | 南京邮电大学 | Helix tube type piezoelectric spring and preparation method therefor |
| CN105633270B (en) * | 2016-02-24 | 2018-08-21 | 南京邮电大学 | A kind of helix tube type piezoelectric spring and preparation method thereof |
| CN109273591A (en) * | 2018-08-30 | 2019-01-25 | 广州大学 | A kind of alkali-activated carbonatite fly-ash slag piezoelectric transducer and preparation method thereof |
| CN109273591B (en) * | 2018-08-30 | 2022-02-18 | 广州大学 | Alkali-excited fly ash slag piezoelectric sensor and preparation method thereof |
| CN112759385A (en) * | 2021-01-06 | 2021-05-07 | 中国科学院福建物质结构研究所 | Perovskite ceramic material and preparation method and application thereof |
| CN113135754A (en) * | 2021-04-29 | 2021-07-20 | 安徽工业大学 | Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof |
| CN113135754B (en) * | 2021-04-29 | 2022-06-03 | 安徽工业大学 | Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof |
| CN114656256A (en) * | 2022-03-25 | 2022-06-24 | 安徽工业大学 | Piezoelectric composite material prepared from titanium-containing mineral and method thereof |
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| CN102070318B (en) | 2012-07-25 |
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