CN107742671B - 3-1-2 type polymer/cement piezoelectric composite material and preparation method thereof - Google Patents
3-1-2 type polymer/cement piezoelectric composite material and preparation method thereof Download PDFInfo
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- H10N30/00—Piezoelectric or electrostrictive devices
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention discloses a 3-1-2 type polymer/cement piezoelectric composite material, which is formed by preparing a porous piezoelectric ceramic framework which is partially provided with tubular pore canals and partially provided with a compact ceramic body as a functional body by adopting a sodium alginate ionic gel process, pouring cement slurry into the tubular pore canals of the functional body of the ceramic framework to form a matrix, and filling organic high molecular polymers into micropores between the functional body of the ceramic framework and the cement matrix. The piezoelectric composite material has good heat resistance and external impact resistance, more excellent piezoelectric performance, good acoustic impedance matching and electromechanical coupling effect and lower mechanical quality factor, and is suitable for the requirement of a high-sensitivity sensor in civil structure detection.
Description
Technical Field
The invention relates to a 3-1-2 type polymer/cement piezoelectric composite material and a preparation method thereof, belonging to the technical field of piezoelectric intelligent composite materials and preparation thereof.
Background
Large civil engineering structures such as large-span bridges, nuclear power plants, stadiums and the like are large in scale and complex in structure, and are continuously influenced by adverse factors such as environmental load action, material aging, fatigue effect, corrosion effect and the like in the service process, and once the structures fail, the consequences are unreasonable. Therefore, the intelligent material and the intelligent structure are of great significance to health monitoring and damage assessment of civil engineering structures and important components thereof in service.
The piezoelectric material has excellent electromechanical coupling characteristics, can be used as a sensing material and a driving material, and is a preferred material in intelligent materials and structures. However, in civil engineering structures, the compatibility problems of poor interface adhesion and mismatch of acoustic impedance of traditional piezoelectric materials (piezoelectric ceramics, piezoelectric polymers and polymer-based piezoelectric composite materials) and concrete matrixes exist, so that the sensing precision of the intelligent material is greatly reduced, and the driving force is also obviously weakened.
The cement piezoelectric intelligent composite material takes a cement material as a matrix and takes a piezoelectric ceramic material as a functional body, so that the interface bonding strength and the acoustic impedance matching degree with a concrete structure material can be obviously improved, and the cement piezoelectric intelligent composite material has great application potential in the health monitoring of civil engineering structures.
The piezoelectric composite material can be generally divided into ten basic types according to different communication modes of the ceramic phase and the matrix phase, namely 0-0 type, 0-1 type, 0-2 type, 0-3 type, 1-1 type, 1-2 type, 1-3 type, 2-2 type, 2-3 type and 3-3 type, wherein the former number refers to the communication mode of the piezoelectric ceramic phase of the matrix, and the latter number refers to the communication mode of the matrix phase. Among them, the 0-3 type, 1-3 type and 2-2 type cement-based piezoelectric composite materials have received extensive and intensive attention from researchers.
CN 1569423A discloses a 0-3 type cement piezoelectric composite material, a preparation method and an application thereof, wherein the cement and piezoelectric ceramic powder are subjected to ball milling and mixing and then are subjected to compression molding, and the preparation method has the advantages of simple and easy operation, low cost and strong durability. However, the conduction of electrical signals between the piezoelectric ceramics is easily blocked by the cement matrix, the electromechanical coupling effect of the piezoelectric composite material is influenced, and the sensing precision of the piezoelectric composite material is weakened.
CN 103456879A and CN 103594616A disclose a preparation method and application of 2-2 type and 1-3 type cement piezoelectric composite materials, respectively, the preparation methods of the two piezoelectric composite materials are that a compact piezoelectric ceramic block is cut into regularly arranged sheet-shaped or column-shaped bodies, and then a cement matrix is poured into the internal gap of the piezoelectric ceramic block. The 2-2 type and 1-3 type piezoelectric intelligent composite materials have high piezoelectric response, but the piezoelectric ceramic materials have the defects of high hardness and high brittleness, are very easy to crack in the cutting process, have long processing period and extremely low production efficiency.
CN 103739285A relates to a preparation method of oxide toughened porous lead zirconate titanate piezoelectric ceramic, the 3-1 type honeycomb porous piezoelectric ceramic prepared by the method has small aperture which is only 100-300 mu m, and the cement slurry is difficult to fully fill the pores in the ceramic blank. In addition, the 3-1 type honeycomb ceramic having a through-hole structure is low in strength and easily damaged during subsequent operations.
Disclosure of Invention
The invention aims to provide a 3-1-2 type polymer/cement piezoelectric composite material which has the advantages of high stability, high sensing precision, excellent piezoelectric performance, good compatibility with a concrete structure and strong durability.
The invention also aims to provide a preparation method of the piezoelectric composite material, which provides technical support for realizing the 3-1-2 type polymer/cement piezoelectric composite material.
The 3-1-2 type polymer/cement piezoelectric composite material is a polymer reinforced 3-1-2 type polymer/cement piezoelectric composite material which is prepared by adopting a sodium alginate ionic gel process, wherein a porous piezoelectric ceramic framework which is partially provided with a pore canal and partially provided with a compact ceramic body is used as a functional body, cement slurry is poured into the pore canal of the ceramic framework functional body to form a matrix, and organic high molecular polymers are filled in micropores between the ceramic framework functional body and the cement matrix.
The organic high molecular polymer can be polyurethane, liquid silicon rubber, epoxy resin and other organic materials.
Furthermore, the invention provides a preparation method of the 3-1-2 type polymer/cement piezoelectric composite material, which comprises the following steps:
1) mixing water, sodium alginate and piezoelectric ceramic powder, performing ball milling to obtain uniformly dispersed ceramic slurry, placing the ceramic slurry in a mold, spraying a calcium chloride solution on the surface of the slurry, and performing a curing reaction to form an initial film;
2) slowly adding a calcium chloride solution dissolved with a metal ion adsorbent and accounting for 40-60% of the volume of the ceramic slurry into the mold, standing, so that calcium ions permeate downwards through the initial film, and forming a uniformly distributed tubular pore structure in the ceramic slurry along the permeation direction;
3) when the length of the formed tubular pore channel reaches 40-50% of the height of the liquid level of the ceramic slurry in the mold, placing the mold in a water bath at 40-65 ℃ to ensure that the liquid level of the water bath is higher than the liquid level of the tubular pore channel, standing, enabling calcium ions to be subjected to the action of an external thermal field and to randomly diffuse in the ceramic slurry below the liquid level of the water bath to ensure that the ceramic slurry below the tubular pore channel gradually forms a pore-free complete gel to obtain an alginate ion gel blank body with a cellular structure above and compact below, demolding, and sintering at high temperature to obtain the 3-1-2 type porous piezoelectric ceramic;
4) pouring cement paste into the honeycomb structure of the 3-1-2 type porous piezoelectric ceramic, curing and solidifying to obtain a 3-1-2 type cement piezoelectric composite material;
5) and repeatedly brushing the liquid organic high molecular polymer on the surface of the 3-1-2 type cement piezoelectric composite material to completely fill the organic high molecular polymer into micropores in the cement piezoelectric composite material, thereby obtaining the 3-1-2 type polymer/cement piezoelectric composite material.
And then, respectively polishing the upper surface and the lower surface of the prepared 3-1-2 type polymer/cement piezoelectric composite material to expose a piezoelectric ceramic phase, and uniformly coating low-temperature conductive silver paste or plating electrodes after polishing.
The piezoelectric ceramic powder can be fine powder of piezoelectric ceramic materials such as lead zirconate titanate, lead magnesium niobate zirconate titanate or lead lithium niobate zirconate titanate.
Preferably, in the ceramic slurry obtained by the invention, the mass fraction of the piezoelectric ceramic powder is 5-30%, the mass fraction of the sodium alginate is 0.5-3%, and the balance is water.
More preferably, the water, the sodium alginate and the piezoelectric ceramic powder are mixed and ball-milled for 6-12 hours to obtain the ceramic slurry with uniform dispersion.
According to the invention, calcium chloride solution is added into the ceramic slurry, so that calcium ions and sodium alginate in the ceramic slurry generate an ionic gel reaction to form water-insoluble calcium alginate gel. Preferably, the concentration of the calcium chloride solution is 0.5-2 mol/L.
Furthermore, a certain amount of metal ion adsorbent is dissolved in the calcium chloride solution, so that calcium ion agglomerated particles are formed, the quantity of calcium ions which are subjected to ion gel reaction with sodium alginate in unit area is increased, and a gel blank with large aperture is formed.
The metal ion adsorbent is water soluble polysaccharide or water soluble chitosan, such as soluble soybean polysaccharide, chitin, carboxymethyl chitosan, etc. Preferably, the mass concentration of the metal ion adsorbent in the calcium chloride solution is 0.1-1.5%.
Generally, the thickness of the initial film formed by spraying the calcium chloride solution on the surface of the ceramic slurry should be not less than 5 mm.
In the invention, after calcium chloride solution dissolved with metal ion adsorbent is added into ceramic slurry, the ceramic slurry is kept stand, calcium ions can permeate downwards through the initial film and form a uniformly distributed tubular pore structure along the permeation direction, and a cellular-structured alginate ion gel blank is formed in the ceramic slurry.
And further, when the die is placed in a water bath at the temperature of 40-65 ℃ for standing, calcium ions below the liquid level of the water bath do not permeate downwards along the formed pore channel, but randomly diffuse in the ceramic slurry, and a pore-free complete gel is gradually formed below the tubular pore channel.
More specifically, the wet gel blank obtained by demolding is dried at 60 ℃ for 12-48 hours and then sintered at high temperature.
Preferably, the high-temperature sintering temperature is controlled to be 1150-1200 ℃, and the heat preservation sintering is carried out for 2 hours at the temperature.
The porosity of the 3-1-2 type porous piezoelectric ceramic prepared by the method is 35-70%, and the pore diameter is 1-2 mm.
The cement used in the present invention is various conventional cement products such as portland cement, phosphate cement, and sulfoaluminate cement. The cement is prepared into cement paste according to the mass ratio of water to cement of 0.3-0.5.
And then, pouring cement paste into the pore channel of the 3-1-2 type porous piezoelectric ceramic, and then placing the porous piezoelectric ceramic into a standard curing box for curing for 7-28 days. The preferable curing conditions are that the curing temperature is controlled to be 20 +/-1 ℃ and the relative humidity is more than or equal to 90 percent.
After the surface of the cement piezoelectric composite material is coated with the liquid organic high molecular polymer, the polymer can be pumped to be completely filled in the internal micropores of the cement piezoelectric composite material in a vacuumizing mode.
The organic high molecular polymer can be coated on the surface of the cement piezoelectric composite material and enter the micropores in the cement piezoelectric composite material only in a liquid state. Some organic high molecular polymers are liquid and can be directly used. However, for the organic high molecular polymer which is solid at room temperature, it is necessary to convert it into a liquid form for use, including dissolving the solid organic high molecular polymer in a volatile organic solvent to obtain a liquid organic high molecular polymer solution, or heating and melting the solid organic high molecular polymer to make it liquid.
Generally, the number of times of coating the liquid organic high molecular polymer on the surface of the cement piezoelectric composite material is 5-10 times.
In the preparation method of the 3-1-2 type polymer/cement piezoelectric composite material, a large amount of calcium ion agglomerated particles can be obtained by adding the metal ion adsorbent into a calcium chloride solution. In the ion permeation process, each calcium ion group is used as a whole to react with sodium alginate sol, the quantity of calcium ions reacting with sodium alginate in unit area is increased, the diameter of a tubular pore channel formed by reaction is obviously expanded, and the subsequent filling of the tubular pore channel of the porous piezoelectric ceramic by using cement slurry is facilitated.
In the ionic gel process adopted by the invention, if the ionic permeation is carried out at room temperature all the time, calcium ions can continue to permeate towards the lower ceramic slurry along the pore channel until reaching the bottom of the mould, and the 3-1 type porous piezoelectric ceramic is formed. However, when calcium ions permeate to a certain stage, the die is placed in a water bath at 40-65 ℃, so that the calcium ions permeating to the liquid surface of the water bath are randomly diffused in the ceramic slurry, a compact ceramic blank without pore channels is formed below the previously obtained tubular pore channels, the 3-1-2 type porous piezoelectric ceramic is prepared by one-step direct molding through an ionic gel process, and then cement and a high molecular polymer are added into the tubular pore channels to obtain the piezoelectric composite material, so that the problems that the material is easy to crack and the production efficiency is low when the piezoelectric ceramic block is cut in the process of preparing the 2-2 type and 1-3 type cement-based piezoelectric composite materials are effectively solved.
The 3-1-2 type polymer/cement piezoelectric composite material prepared by the method is formed by connecting the 3-1 type cement piezoelectric composite material and a piezoelectric ceramic substrate in series, and has high-strength piezoelectric ceramic supports in the directions parallel to and perpendicular to the polarization direction, so that the structure is more stable than that of the 3-1 type polymer/cement piezoelectric composite material, and the 3-1-2 type polymer/cement piezoelectric composite material has good heat resistance and external impact resistance. Meanwhile, after the organic high molecular polymer is filled in the micropores in the cement piezoelectric composite material, the compressive strength of the composite material is close to that of the cement material with the same grade, and the service life of the composite material is prolonged.
In the 3-1-2 type polymer/cement piezoelectric composite material prepared by the invention, the piezoelectric ceramic phases are in three-dimensional communication, and charges formed by the positive piezoelectric effect can be continuously conducted in the piezoelectric ceramic phases, so that a stress amplification effect is generated in the composite material.
Drawings
FIG. 1 is a schematic structural view of a 3-1-2 type polymer/cement piezoelectric composite material of the present invention.
In the figure, 1 is an upper electrode, 2 is a lower electrode, and 3 is a ceramic substrate.
FIG. 2 is a SEM image of the cross-section of a 3-1-2 type polymer/cement piezoelectric composite prepared in example 1.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The structure of the 3-1-2 type polymer/cement piezoelectric composite material is shown in figure 1, and is formed by integrally connecting the 3-1 type polymer/cement piezoelectric composite material and a piezoelectric ceramic substrate 3 in series, and an upper electrode 1 and a lower electrode 2 are respectively coated or plated on the end faces of the 3-1 type polymer/cement piezoelectric composite material and the piezoelectric ceramic substrate 3.
The piezoelectric ceramic matrix of the 3-1 type polymer/cement piezoelectric composite material is regularly provided with vertical tubular pore canals, the cement matrix is filled in the tubular pore canals, and organic high molecular polymers are filled in micropores between the piezoelectric ceramic matrix and the cement matrix.
Example 1.
And adding 2g of sodium alginate and 6g of lead zirconate titanate piezoelectric ceramic powder into 100ml of water, mixing and ball-milling for 8 hours to obtain uniformly dispersed ceramic slurry.
The ceramic slurry was poured into a nylon mold, and the height of the slurry liquid surface was maintained at 60 mm. Spraying CaCl with the concentration of 1mol/L on the surface of the slurry2And (3) carrying out a curing reaction on the solution to form an initial film with the thickness of 5 mm.
11.1g of calcium chloride and 0.1g of soluble soybean polysaccharide are added into 50ml of water to prepare a calcium chloride solution with the concentration of 2mol/L and added with a metal ion adsorbent.
Slowly adding the calcium chloride solution added with the metal ion adsorbent into a nylon mould, standing for 12h to enable the ceramic slurry at the upper half part in the nylon mould to form a calcium alginate ion gel blank body with a honeycomb structure, wherein the length of a tubular pore channel in the blank body is 22 mm.
And (3) placing the nylon mold in a water bath at 40 ℃ to ensure that the liquid level of the water bath is about 33mm higher than the bottom of the mold, standing for 12h to ensure that a complete and compact gel blank body is formed below the pore channel, and demolding to obtain a ceramic wet blank.
Drying the ceramic wet blank at 60 ℃ for 20h, then heating to 1150 ℃ at the heating rate of 1.5 ℃/min, and carrying out heat preservation sintering for 2h to obtain the 3-1-2 type porous piezoelectric ceramic with the porosity of 65% and the pore diameter of 1.5 mm.
30ml of water was added to 100g of portland cement and sufficiently stirred to form a cement paste. Under continuous vibration, the cement paste is poured into the porous piezoelectric ceramic, placed in a standard curing box, and cured for 7 days at 20 ℃ and 100% relative humidity.
And repeatedly brushing liquid waterborne polyurethane on the surface of the cured cement piezoelectric material for 5 times, and vacuumizing.
The upper and lower parallel surfaces of the sample were polished with a sheet grinder to expose the piezoelectric ceramic phase on both surfaces, and after polishing, the low-temperature conductive silver paste was uniformly applied on both surfaces to produce a 3-1-2 type polymer/cement piezoelectric composite material, the properties of which are shown in table 1.
Example 2.
And adding 1.5g of sodium alginate and 15g of lead zirconate titanate piezoelectric ceramic powder into 100ml of water, mixing and ball-milling for 10 hours to obtain uniformly dispersed ceramic slurry.
Pouring the ceramic slurry into a nylon mold, keeping the liquid level of the slurry at 60mm, and spraying CaCl with the concentration of 1mol/L on the surface of the slurry2And (3) carrying out a curing reaction on the solution to form an initial film with the thickness of 6 mm.
Adding 8.3g of calcium chloride and 0.25g of chitin into 50ml of water to prepare a calcium chloride solution with the concentration of 1.5mol/L, wherein the calcium chloride solution is added with a metal ion adsorbent.
Adding the prepared calcium chloride solution into a nylon mold, and standing for 18h to form a calcium alginate ionic gel blank body with a honeycomb structure with the length of a long tubular pore passage of 25 mm.
And (3) placing the nylon mold in a water bath at 50 ℃, enabling the liquid level of the water bath to be about 30mm higher than the bottom of the mold, standing for 10h, forming a complete and compact gel blank below the pore channel, and demolding to obtain a ceramic wet blank.
Drying the ceramic wet blank at 60 ℃ for 24h, then heating to 1175 ℃ at the heating rate of 1.5 ℃/min, and carrying out heat preservation sintering for 2h to obtain the 3-1-2 type porous piezoelectric ceramic with the porosity of 53% and the pore diameter of 1.2 mm.
40ml of water was added to 100g of magnesium phosphate cement and thoroughly stirred to form a cement paste. Under continuous vibration, the cement paste is poured into the porous piezoelectric ceramic, and the porous piezoelectric ceramic is placed in a standard curing box and cured for 14 days at the temperature of 20 ℃ and the relative humidity of 100%.
And repeatedly brushing liquid silicon rubber on the surface of the cured cement piezoelectric material for 8 times, and vacuumizing.
The upper and lower parallel surfaces of the sample were polished with a sheet grinder to expose the piezoelectric ceramic phase on both surfaces, and after polishing, the low-temperature conductive silver paste was uniformly applied on both surfaces to produce a 3-1-2 type polymer/cement piezoelectric composite material, the properties of which are shown in table 1.
Example 3.
And adding 1g of sodium alginate and 25g of lead zirconate titanate piezoelectric ceramic powder into 100ml of water, mixing and ball-milling for 10 hours to obtain uniformly dispersed ceramic slurry.
Pouring the ceramic slurry into a nylon mold, keeping the liquid level of the slurry at 60mm, and spraying CaCl with the concentration of 1mol/L on the surface of the slurry2And (3) carrying out a curing reaction on the solution to form an initial film with a certain thickness.
5.6g of calcium chloride and 0.75g of carboxymethyl chitosan are added into 50ml of water to prepare a calcium chloride solution with the concentration of 1mol/L added with a metal ion adsorbent.
Adding the prepared calcium chloride solution into a nylon mold, standing for 24h to form a calcium alginate ionic gel blank body with a honeycomb structure, wherein the length of a tubular pore in the blank body is 25 mm.
And (3) placing the nylon mold in a water bath at 60 ℃ to ensure that the liquid level of the water bath is about 30mm higher than the bottom of the mold, standing for 12h to form a complete and compact gel blank below the pore channel, and demolding to obtain a ceramic wet blank.
Drying the ceramic wet blank at 60 ℃ for 36h, heating to 1200 ℃ at the heating rate of 1.5 ℃/min, and sintering for 2h under the condition of heat preservation to obtain the 3-1-2 type porous piezoelectric ceramic with the porosity of 43% and the pore diameter of 1 mm.
50ml of water was added to 100g of sulphoaluminate cement and stirred well to form a cement paste. And pouring the cement paste into the porous piezoelectric ceramic under continuous vibration, placing the porous piezoelectric ceramic in a standard curing box, and curing for 28 days at the temperature of 20 ℃ and the relative humidity of 100%.
And (3) dissolving the epoxy resin by using a small amount of normal hexane, repeatedly brushing the epoxy resin on the surface of the cured cement piezoelectric material for 10 times, and vacuumizing the brushing process.
And (2) respectively polishing the upper and lower parallel surfaces of the sample by using a sheet grinding machine to enable the piezoelectric ceramic phases to be completely exposed on the two surfaces, and uniformly coating low-temperature conductive silver adhesive on the two surfaces after polishing treatment to obtain the 3-1-2 type polymer/cement piezoelectric composite material, wherein the performances of the composite material are shown in Table 1.
As shown in Table 1, when the polymer/cement piezoelectric composite material is prepared by using the 3-1-2 type porous piezoelectric ceramic as the matrix, the material has excellent mechanical properties, and the service life and the durability are prolonged. Moreover, the mutually communicated piezoelectric ceramic phases ensure that the material has high piezoelectric strain constant and piezoelectric voltage constant, and the piezoelectric performance of the material is obviously improved. Meanwhile, the material shows good acoustic impedance matching and electromechanical coupling effect, and a lower mechanical quality factor, and is suitable for the requirement of a high-sensitivity sensor in civil structure detection.
Claims (9)
1. A3-1-2 type polymer/cement piezoelectric composite material is a polymer reinforced 3-1-2 type polymer/cement piezoelectric composite material which is prepared by adopting a sodium alginate ionic gel process and taking a porous piezoelectric ceramic framework which is partially provided with a tubular pore passage and partially provided with a compact ceramic body as a functional body, pouring cement slurry into the tubular pore passage of the ceramic framework functional body to form a matrix, and filling organic high molecular polymers into micropores between the ceramic framework functional body and the cement matrix, wherein the organic high molecular polymers are waterborne polyurethane, liquid silicon rubber or epoxy resin.
2. A method of making a polymer/cement piezoelectric composite as claimed in claim 1, comprising:
1) mixing water, sodium alginate and piezoelectric ceramic powder, performing ball milling to obtain uniformly dispersed ceramic slurry, placing the ceramic slurry in a mold, spraying a calcium chloride solution on the surface of the slurry, and curing to form an initial film;
2) slowly adding a calcium chloride solution dissolved with a metal ion adsorbent and accounting for 40-60% of the volume of the ceramic slurry into the mold, standing, so that calcium ions permeate downwards through the initial film, and forming a uniformly distributed tubular pore structure in the ceramic slurry along the permeation direction;
3) when the length of the formed tubular pore channel reaches 40-50% of the height of the slurry liquid level in the mold, placing the mold in a water bath at 40-65 ℃ to ensure that the liquid level of the water bath just exceeds the tail end of the tubular pore channel, standing to ensure that calcium ions under the liquid level of the water bath randomly diffuse in the ceramic slurry, gradually forming the ceramic slurry under the tubular pore channel into a pore-free complete gel to obtain an alginate ion gel blank body with a honeycomb tubular pore channel structure above and a compact gel below, demolding, and sintering at high temperature to obtain the 3-1-2 type porous piezoelectric ceramic;
4) pouring cement paste into the tubular pore canal of the 3-1-2 type porous piezoelectric ceramic, and curing and solidifying to obtain a 3-1-2 type cement piezoelectric composite material;
5) and repeatedly brushing the liquid organic high molecular polymer on the surface of the 3-1-2 type cement piezoelectric composite material to ensure that the organic high molecular polymer completely fills micropores in the cement piezoelectric composite material, thereby obtaining the 3-1-2 type polymer/cement piezoelectric composite material.
3. The method for preparing a polymer/cement piezoelectric composite material according to claim 2, wherein said piezoelectric ceramic powder is lead zirconate titanate, lead magnesium niobate zirconate titanate or lead lithium niobate zirconate titanate.
4. The preparation method of the polymer/cement piezoelectric composite material as claimed in claim 2, wherein in the ceramic slurry, the mass fraction of the piezoelectric ceramic powder is 5-30%, the mass fraction of sodium alginate is 0.5-3%, and the balance is water.
5. The method for preparing the polymer/cement piezoelectric composite material according to claim 2, wherein the concentration of the calcium chloride solution is 0.5-2 mol/L.
6. The method for preparing a polymer/cement piezoelectric composite material according to claim 2, wherein the metal ion adsorbent is water-soluble polysaccharide or water-soluble chitosan, and the mass concentration of the metal ion adsorbent in the calcium chloride solution is 0.1-1.5%.
7. The method for preparing polymer/cement piezoelectric composite material according to claim 6, wherein the metal ion adsorbent is soluble soybean polysaccharide, chitin or carboxymethyl chitosan.
8. The method of claim 2 wherein said high temperature sintering temperature is 1150 ℃.
9. The method for preparing a polymer/cement piezoelectric composite material according to claim 2, wherein the curing is performed for 7 to 28 days after the cement paste is solidified.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260061A (en) * | 2011-05-24 | 2011-11-30 | 济南大学 | 1-3 type polymer/cement-based piezoelectric composite material and preparation method thereof |
| CN103456879A (en) * | 2013-09-01 | 2013-12-18 | 济南大学 | 2-2 type piezoelectric composite material with matrixes arranged in inhomogeneous and periodical mode and preparation method thereof |
| CN103474569A (en) * | 2013-09-01 | 2013-12-25 | 济南大学 | 2-2 type piezoelectric composite material with non-uniform periodic arrangement of piezoelectric ceramics and preparation method thereof |
| CN103508714A (en) * | 2013-09-22 | 2014-01-15 | 济南大学 | Intelligent damping material compounded of piezoelectric composite material and cement and preparation method of intelligent damping material |
| CN103594616A (en) * | 2013-09-01 | 2014-02-19 | 济南大学 | 1-3 type piezoelectric composite material with matrixes being periodically arranged in non-uniform mode and preparation method thereof |
| CN105552212A (en) * | 2015-12-16 | 2016-05-04 | 中北大学 | 3-3 type piezoelectric ceramic/cement piezoelectric composite material and preparation method thereof |
-
2017
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260061A (en) * | 2011-05-24 | 2011-11-30 | 济南大学 | 1-3 type polymer/cement-based piezoelectric composite material and preparation method thereof |
| CN103456879A (en) * | 2013-09-01 | 2013-12-18 | 济南大学 | 2-2 type piezoelectric composite material with matrixes arranged in inhomogeneous and periodical mode and preparation method thereof |
| CN103474569A (en) * | 2013-09-01 | 2013-12-25 | 济南大学 | 2-2 type piezoelectric composite material with non-uniform periodic arrangement of piezoelectric ceramics and preparation method thereof |
| CN103594616A (en) * | 2013-09-01 | 2014-02-19 | 济南大学 | 1-3 type piezoelectric composite material with matrixes being periodically arranged in non-uniform mode and preparation method thereof |
| CN103508714A (en) * | 2013-09-22 | 2014-01-15 | 济南大学 | Intelligent damping material compounded of piezoelectric composite material and cement and preparation method of intelligent damping material |
| CN105552212A (en) * | 2015-12-16 | 2016-05-04 | 中北大学 | 3-3 type piezoelectric ceramic/cement piezoelectric composite material and preparation method thereof |
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