CN101531490A - Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material and preparation method thereof - Google Patents

Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material and preparation method thereof Download PDF

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CN101531490A
CN101531490A CN200910020659A CN200910020659A CN101531490A CN 101531490 A CN101531490 A CN 101531490A CN 200910020659 A CN200910020659 A CN 200910020659A CN 200910020659 A CN200910020659 A CN 200910020659A CN 101531490 A CN101531490 A CN 101531490A
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cement
composite material
lead zirconate
nano tube
carbon nano
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CN101531490B (en
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龚红宇
张玉军
李宗津
李爱菊
全静
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Shandong University
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Shandong University
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5076Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
    • C04B41/5079Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004Compounds chosen for the nature of their cations
    • C04B2103/0015Noble metal or copper compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008Obtaining or using nanotechnology related materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00844Uses not provided for elsewhere in C04B2111/00 for electronic applications

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to a carbon nano tube/lead zirconate titanate/cement piezoelectric composite material for a civil engineering sensor and a preparation method thereof. The piezoelectric composite material consists of the carbon nano tube, the lead zirconate titanate and cement. The preparation method comprises the following steps: evenly mixing the carbon nano tube, lead zirconate titanate powder and cement powder; shaping the mixture with water; and hydrating and drying the mixture. The material can be used for preparing the civil engineering sensor after polarizing and aging. The piezoelectric composite material has excellent piezoelectric responsivity.

Description

Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material and preparation method thereof
Technical field
The present invention relates to the preparation method of the carbon nano tube/lead zirconate titanate/cement piezoelectric composite material that a kind of civil engineering sensors uses, belong to the functional composite material technical field.
Background technology
In recent years, the research of lead zirconate-titanate ceramic/cement piezoelectric composite material causes people's attention gradually.This kind matrix material carries out lead zirconate titanate (PZT) piezoelectric ceramics powder and cement compound, by adjusting both relative components, can obtain the piezo-electricity composite material with building concrete structure-borne sound impedance phase coupling, can be used as sensing member and be embedded in the civil structure, internal defects is done instant detection.In this matrix material, Pb-based lanthanumdoped zirconate titanates with piezoelectric property is disperse and distributes in cement, because cement is isolator, make the piezoelectric phase that is dispersed in wherein be difficult to polarization, also hindered simultaneously the transmission of electric charge that piezoelectric phase produces, reduced the connectedness between the lead zirconate titanate piezoelectric phase particle, made the piezoelectric response of matrix material lower.CN101054278A (200710014518.0) discloses a kind of carbon enhanced lead zirconate titanate lead/cement piezoelectric composite material and preparation method thereof, by improve the electric conductivity method of cement matrix with carbon black, has improved the piezoelectric property of cement-base composite material.But the piezoelectric response of comparing this kind cement base piezoelectric composite material with present actual demand is still lower, exists the shortcoming that signal response is little, signal to noise ratio is high in actual applications.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the preparation method of the high carbon nano tube/lead zirconate titanate/cement piezoelectric composite material of a kind of piezoelectric response is provided.
A kind of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material is made up of carbon nanotube, Pb-based lanthanumdoped zirconate titanates and cement, makes by the following method, and the raw material consumption is weight part:
(1) 55~80 parts of Pb-based lanthanumdoped zirconate titanatess and 20~45 parts of cement dry methods are mixed, add 0.1~0.6 part carbon nanotube again, make grinding aid with acetone, the ball milling mixing is after 30-50 minute, and drying makes the acetone volatilization, gets mixed powder.
(2) add water in the mixed powder of step (1) gained, amount of water is the 5-7% of mixed powder weight, and uniform mixing is pressed into the disk shape, and the environment aquation of putting into humidity 100% was drying to obtain after 20-24 hour.
Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material of the present invention can be used for preparing the transmitter of the concrete building structures that is used for civil engineering work.Application product can prepare by the following method:
The exsiccant lamellar body two sides of step (2) gained is coated with silver electrode, in silicone oil, polarize under the room temperature with high-voltage DC power supply, promptly obtain a kind of application product with the carbon nano tube/lead zirconate titanate/cement piezoelectric composite material preparation after aging, this product can be used for the preparation of the sensing member of the concrete building structures in the civil engineering work.
Raw material used in the inventive method is preferably as follows:
Pb-based lanthanumdoped zirconate titanates is the powder that ball milled obtains, and mean particle size is 115 microns.Commercially available lead zirconate-titanate ceramic sheet is obtained behind the ball milling in ball mill.
The mean diameter of described carbon nanotube is 60~100 nanometers, and length-to-diameter ratio is greater than 100, but market is buied.
Compared with prior art, technical characterstic of the present invention is: 1, the present invention is with carbon nanotube and lead zirconate-titanate ceramic and cementitious composite, the piezoelectric response of the matrix material that unexpected discovery is prepared is significantly increased, and piezoelectric constant (pC/N) improves 1-3 doubly than currently available products; Find after deliberation because carbon nanotube not only has good electric conductivity, and has certain length-to-diameter ratio, therefore carbon nanotube is easy to be interconnected to form conductive channel in cement matrix, thereby the electroconductibility of cement matrix is significantly improved, cement base piezoelectric composite material is at room temperature polarized, improved inner lead zirconate-titanate ceramic particulate polarization efficiency, thereby the piezoelectric response of matrix material is significantly increased.Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material of the present invention and preparation method thereof does not appear in the newspapers so far.2, the present invention makes grinding aid with acetone, compares acetone with use ethanol and has evaporation rate faster, can improve the rate of drying of mixing raw material powder, thereby improves the preparation efficiency of matrix material.
The concrete main body material of this piezo-electricity composite material and detected construction work has good interface and impedance matching, is a kind of sensor material of excellent property.
Embodiment
The present invention will be further described below in conjunction with embodiment, if no special instructions, is weight part or weight percent.The mean particle size of used PZT powder is 115 microns among the embodiment, and commercially available lead zirconate-titanate ceramic sheet ball milling in ball mill was obtained after 5 hours.The mean diameter of used carbon nanotube is 60~100 nanometers, and length-to-diameter ratio is greater than 100, nanometer port, Shenzhen company product.
Embodiment 1:
A kind of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material, component is as follows, is weight part:
70 parts of Pb-based lanthanumdoped zirconate titanatess,
30 parts of cement,
0.3 part of carbon nanotube.
The preparation method of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material, step is as follows:
(1) 70 parts of Pb-based lanthanumdoped zirconate titanatess and 30 parts of cement dry methods are mixed, add 0.3 part of carbon nanotube, make grinding aid with acetone, ball milling mixed after 30 minutes, and drying makes the acetone volatilization, gets mixed powder.
(2) add water in the mixed powder of step (1) gained, amount of water is 5% of a mixed powder weight, and uniform mixing is pressed into the disk shape with compound under 100MPa pressure, and the environment aquation of putting into humidity 100% is after 24 hours, drying.
After the drying, the disk two sides is coated with silver electrode, polarizes 30 minutes in silicone oil under the volts DS of 7kV.Disk after the polarization is coated tinfoil paper, in 60 ℃, place and wore out in 12 hours.The specific inductivity of resulting carbon nano tube/lead zirconate titanate/cement piezoelectric composite material is 113, and piezoelectric constant is 74.5pC/N, and electromechanical coupling factor is 12%, and dielectric loss is 0.38.
Embodiment 2:
A kind of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material, component is as follows, is weight part:
70 parts of Pb-based lanthanumdoped zirconate titanatess,
30 parts of cement,
0.5 part of carbon nanotube.
The preparation method of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material, step is as follows:
(1) 80 parts of Pb-based lanthanumdoped zirconate titanatess and 20 parts of cement dry methods are mixed, add 0.5 part of carbon nanotube, make grinding aid with acetone, ball milling mixed after 30 minutes, and drying makes the acetone volatilization, gets mixed powder.
(2) add water in the mixed powder of step (1) gained, amount of water is 6% of a mixed powder weight, and uniform mixing is pressed into the disk shape with compound under 100MPa pressure, and the environment aquation of putting into humidity 100% is after 24 hours, drying.
After the drying, the disk two sides is coated with silver electrode, polarizes 30 minutes in silicone oil under the volts DS of 6.5kV, and the polarization temperature is a room temperature.Disk after the polarization is coated tinfoil paper, in 60 ℃, place and wore out in 12 hours.The specific inductivity of resulting carbon nano tube/lead zirconate titanate/cement matrix material is 118, and piezoelectric constant is 65.2pC/N, and electromechanical coupling factor is 11%, and dielectric loss is 0.40.
Embodiment 3:
A kind of carbon enhanced lead zirconate titanate lead/cement piezoelectric composite material, component is as follows, is weight part:
60 parts of Pb-based lanthanumdoped zirconate titanatess,
40 parts of cement,
0.3 part of carbon nanotube.
The preparation method of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material, step is as follows:
(1) 60 parts of Pb-based lanthanumdoped zirconate titanatess and 40 parts of cement dry methods are mixed, add 0.3 part of carbon nanotube, make grinding aid with acetone, ball milling mixed after 40 minutes, and drying makes the acetone volatilization, gets mixed powder.
(2) add water in the mixed powder of step (1) gained, amount of water is 7% of a mixed powder weight, and uniform mixing is pressed into the disk shape with compound under 100MPa pressure, and the environment aquation of putting into humidity 100% is after 22 hours, drying.
After the drying, the disk two sides is coated with silver electrode, polarizes 30 minutes in silicone oil under the volts DS of 7.5kV.Disk after the polarization is coated tinfoil paper, in 60 ℃, place and wore out in 12 hours.The specific inductivity of resulting carbon nano tube/lead zirconate titanate/cement matrix material is 107, and piezoelectric constant is 56.5pC/N, and electromechanical coupling factor is 10%, and dielectric loss is 0.32.
The contrast experiment:
Comparative Examples 1: as described in embodiment 1, different is the carbon dust that in this Comparative Examples carbon nanotube is changed into equal in quality part, and used carbon dust mean particle size is 70 nanometers, U.S. Cabot (Cabot) company product.
Comparative Examples 2-3: raw material is identical with embodiment 2,3 respectively, and different is the carbon dust (mean particle size is 70 nanometers, U.S. Cabot (Cabot) company product) that carbon nanotube changes equal in quality part into.Also the embodiment with corresponding is identical respectively for preparation method, condition.
Comparative Examples 1-3 and embodiment 1-3 contrast properties table are as follows:
Specific inductivity Piezoelectric constant (pC/N) Electromechanical coupling factor (%) Dielectric loss
Embodiment 1 113 74.5 12 0.38
Embodiment 2 118 65.2 11 0.40
Embodiment 3 107 56.5 10 0.32
Comparative Examples 1 142 20.2 11 0.24
Comparative Examples 2 154 24.4 10 0.26
Comparative Examples 3 126 25.1 10 0.20
As seen from table, under the situation that raw material is formed and preparation technology is identical, embodiment 1-3 has higher electromechanical coupling factor, and this shows that embodiment 1-3 has higher energy transformation ratio.The piezoelectric constant of embodiment 1-3 is significantly increased than the piezoelectric constant of Comparative Examples 1-3, shows that embodiment 1-3 has good piezoelectric response.

Claims (3)

1, a kind of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material is made up of carbon nanotube, Pb-based lanthanumdoped zirconate titanates and cement, prepares according to the following steps:
(1) 55~80 parts of Pb-based lanthanumdoped zirconate titanatess and 20~45 parts of cement dry methods are mixed, add 0.1~0.6 part carbon nanotube again, make grinding aid with acetone, the ball milling mixing is after 30-50 minute, and drying makes the acetone volatilization, gets mixed powder.
(2) add water in the mixed powder of step (1) gained, amount of water is the 5-7% of mixed powder weight, and uniform mixing is pressed into the disk shape, and the environment aquation of putting into humidity 100% was drying to obtain after 20-24 hour;
Above raw material is weight part.
2, the application of the described carbon nano tube/lead zirconate titanate/cement piezoelectric composite material of claim 1 is used for preparing the transmitter of the concrete building structures that is used for civil engineering work.
3, the application of carbon nano tube/lead zirconate titanate/cement piezoelectric composite material as claimed in claim 2, it is characterized in that the described carbon nano tube/lead zirconate titanate/cement piezoelectric composite material lamellar body of exsiccant two sides is coated with silver electrode, in silicone oil, polarize and wear out under the room temperature with high-voltage DC power supply.
CN2009100206592A 2009-04-16 2009-04-16 Carbon nano tube/lead zirconate titanate/cement piezoelectric composite material and preparation method thereof Expired - Fee Related CN101531490B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070318A (en) * 2010-12-06 2011-05-25 同济大学 Preparation method of piezoelectric gel composite
CN102903842A (en) * 2012-09-27 2013-01-30 深圳大学 Polarization system and polarization method of cement-based piezoelectric ceramic composite material
WO2013063771A1 (en) * 2011-11-02 2013-05-10 Empire Technology Development Llc Salt resistant cement
CN105837178A (en) * 2016-03-16 2016-08-10 哈尔滨工程大学 Preparation method for promoting polarization of asphalt-based piezoelectric ceramic piezoelectric composite
CN106673564A (en) * 2017-02-22 2017-05-17 青岛理工大学 Intelligent concrete for GO (graphene oxide) strengthened CNT (carbon nano tube) precoated sand, wireless sensor and preparation method
CN108801336A (en) * 2018-05-04 2018-11-13 东南大学 A kind of method of piezoelectric-array monitoring vehicle speed and load-carrying
CN111620611A (en) * 2020-05-13 2020-09-04 河南理工大学 Carbon-synergistic lead-free cement-based piezoelectric composite material and preparation method and application thereof
CN111662051A (en) * 2020-05-13 2020-09-15 河南理工大学 Lead-free cement-based piezoelectric composite material, and preparation method and application thereof
CN112194180A (en) * 2020-10-14 2021-01-08 北京化工大学 Modification method for enhancing mechanical property of aerogel

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* Cited by examiner, † Cited by third party
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CN100457670C (en) * 2007-04-11 2009-02-04 山东大学 Carbon enhanced lead zirconate titanate/cement piezoelectricity composite material and preparation method thereof
CN100432002C (en) * 2007-04-11 2008-11-12 山东大学 Nano lead zirconate titanate/cement piezoelectricity composite material and preparation method thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070318B (en) * 2010-12-06 2012-07-25 同济大学 Preparation method of piezoelectric gel composite
CN102070318A (en) * 2010-12-06 2011-05-25 同济大学 Preparation method of piezoelectric gel composite
WO2013063771A1 (en) * 2011-11-02 2013-05-10 Empire Technology Development Llc Salt resistant cement
US9556076B2 (en) 2011-11-02 2017-01-31 Empire Technology Development Llc Salt resistant cement
CN102903842A (en) * 2012-09-27 2013-01-30 深圳大学 Polarization system and polarization method of cement-based piezoelectric ceramic composite material
CN105837178B (en) * 2016-03-16 2019-04-19 哈尔滨工程大学 It obtains and promotes the polarized preparation method of pitch base piezoelectric ceramic piezo-electricity composite material
CN105837178A (en) * 2016-03-16 2016-08-10 哈尔滨工程大学 Preparation method for promoting polarization of asphalt-based piezoelectric ceramic piezoelectric composite
CN106673564A (en) * 2017-02-22 2017-05-17 青岛理工大学 Intelligent concrete for GO (graphene oxide) strengthened CNT (carbon nano tube) precoated sand, wireless sensor and preparation method
CN106673564B (en) * 2017-02-22 2019-09-24 青岛理工大学 Intelligent concrete, wireless sensor and the preparation method of GO enhancing CNT precoated sand
CN108801336A (en) * 2018-05-04 2018-11-13 东南大学 A kind of method of piezoelectric-array monitoring vehicle speed and load-carrying
CN111620611A (en) * 2020-05-13 2020-09-04 河南理工大学 Carbon-synergistic lead-free cement-based piezoelectric composite material and preparation method and application thereof
CN111662051A (en) * 2020-05-13 2020-09-15 河南理工大学 Lead-free cement-based piezoelectric composite material, and preparation method and application thereof
CN112194180A (en) * 2020-10-14 2021-01-08 北京化工大学 Modification method for enhancing mechanical property of aerogel

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