Many primitives piezo-electricity composite material and its preparation method and application
Technical field
The present invention relates to a kind of piezo-electricity composite material and its preparation method and application, particularly a kind of many primitives piezo-electricity composite material that is applied to transmitting transducer array element part and its preparation method and application.
Background technology
Piezo-electricity composite material refers to the piezoelectric being formed by two-phase or multiphase Material cladding, and it integrates the piezoelectric effect of piezoelectric ceramic and the pliability of polymer, has overcome to a certain extent the defect of pure piezoelectric ceramic aspect intensity, fragility.1-3-2 type piezo-electricity composite material is the novel piezoelectric composite material with the design feature of 1-3 type in parallel and 2-2 Piezoelectric Composites with Series Model.It has low-density, high hydrostatic pressure piezoelectric property, acoustic impedance and is easy to Yu Shuihe biological tissue coupling, Stability Analysis of Structures, and the material parameter feature such as customizable within the specific limits.One of such material main application is exactly to design and produce transducer and array thereof, for fields such as the underwater sound and supersonic sounding, imaging of medical, Non-Destructive Testings.
Traditional method of preparing transducer array is complicated and not easy to operate, first to prepare a large amount of composite material samples, then pick out therein material sample that performance is consistent as the primitive of transducer array, then these primitives are arranged in to required array according to certain formation.Therefore be difficult to meet transducer array to the conforming requirement of the height of each primitive performance, and can waste raw material, time-consuming.This has just limited the application of transducer array to a great extent.
Therefore, excellent performance, consistency research and development high, that prepare simple composite material have great importance to the research and development of field of transducer.
Summary of the invention
The present invention is directed to above-mentioned deficiency, two kinds of many primitives that structure is slightly different piezo-electricity composite materials are provided, this primitive piezo-electricity composite material more than two kinds all has advantages of excellent performance, consistency is high, coupling is low.
The present invention also provides the preparation method of many primitives piezo-electricity composite material, and its technique is simple, many primitives of gained piezo-electricity composite material excellent performance, high conformity.
The present invention also provides the application of many primitives piezo-electricity composite material, in the application in transducer array field.
The concrete technical scheme of the present invention is as follows:
A kind of many primitives piezo-electricity composite material, it is characterized in that: the 1-3-2 type composite material that described many primitives piezo-electricity composite material is comprised of piezoelectric ceramics/polymer 1-3 thing composite material and decoupling material, described piezoelectric ceramics/polymer 1-3 thing composite material be take piezoelectric ceramic as skeleton, take polymer as matrix, and with upper, bottom electrode, described piezoelectric ceramic skeleton comprises substrate and the piezoelectric ceramic post being connected thereon, described decoupling material is filled in piezoelectric ceramics/polymer 1-3 thing composite material and by piezoelectric ceramics/polymer 1-3 thing composite material and is divided into the primitive that a plurality of structures are identical, the top electrode of each primitive is discontinuous.Its structure as shown in Figure 1.
Above-mentioned many primitives piezo-electricity composite material is on the basis of 1-3-2 type piezo-electricity composite material, to carry out improvedly, so it is also 1-3-2 type piezo-electricity composite material.Existing 1-3-2 type piezo-electricity composite material is a kind of novel piezoelectric composite material, it is functional, Stability Analysis of Structures, and structure is as shown in Figure 2, piezoelectric ceramic skeleton, polymer and electrode, consist of, wherein piezoelectric ceramic skeleton comprises the ceramics pole on top and the substrate of bottom.The present invention has carried out further improvement to 1-3-2 type piezo-electricity composite material, on the basis of 1-3-2 type piezo-electricity composite material, adds decoupling material, thereby obtains many primitives piezo-electricity composite material of the present invention.Decoupling material has the function of damping, sound insulation, sound absorption, decoupling, and it is divided into a plurality of independently primitives composite material, can effectively intercept the transmission of acoustic vibration between each primitive, thereby makes composite material become the array being comprised of a plurality of primitives.Each primitive of many primitives piezo-electricity composite material can be launched sound wave independently, and the transducer array being made by it can be launched multi-beam simultaneously, and form beam scanning, or form specific beam direction, be therefore the ideal material of preparing transducer array element.
In above-mentioned many primitives piezo-electricity composite material, the filling mode of polymer in each primitive, loading are identical, and each primitive by same substrate in combination together, forms the array with same substrate.In each primitive, the number of piezoelectric ceramic post and dimensional parameters can regulate according to the requirement of performance, because each primitive of many primitives piezo-electricity composite material is identical, and between each primitive, add decoupling material, so its consistency, low coupling are all fine.
In above-mentioned many primitives piezo-electricity composite material, described decoupling material is silica gel, and described polymer is epoxy resin, and described upper and lower electrode is silver electrode.Here the silica gel of use is mould silica gel, in market, can buy concrete product.
Many primitives piezo-electricity composite material prepares by cut-completion method of two steps, wherein each primitive structure is identical, it is all a two-phase piezo-electricity composite material, these two-phase piezo-electricity composite materials are combined by same piezoelectric ceramic substrate, formation has the array of same substrate, has effectively guaranteed high consistency and high stability ground requirement.Preparation technology is simple for many primitives piezo-electricity composite material, can cut into as required different formations, thereby has made up the shortcoming and deficiency of the method for traditional fabrication transducer array.
The preparation method of many primitives of the present invention piezo-electricity composite material, is characterized in that comprising the following steps:
(1) on the piezoelectric ceramic surface perpendicular to piezoelectric ceramic polaxis, along orthogonal both direction cutting piezoelectric ceramic, obtain piezoelectric ceramic skeleton, the top of gained skeleton is piezoelectric ceramic post, bottom is piezoelectric ceramic substrate;
(2) the piezoelectric ceramic skeleton cutting is cleaned up, then water wherein polymer injection, the sample after pouring vacuumizes discharge bubble, and then normal temperature cure obtains piezoelectric ceramics/polymer 1-3 thing two-phase composite material;
(3) the piezoelectric ceramics/polymer 1-3 thing two-phase composite material being cured cuts for the second time according to the method for step (1), and the composite material after cutting cleans up;
(4) cast of the piezoelectric ceramics/polymer 1-3 thing two-phase composite material after cleaning decoupling material, the sample after pouring vacuumizes discharge bubble, and then normal temperature cure obtains piezoelectric ceramics/polymer 1-3 thing/decoupling material three-phase composite material;
(5) by piezoelectric ceramics/polymer 1-3 thing/decoupling material three-phase composite material sanding and polishing, then at the upper surface coating top electrode of each primitive, many primitives piezo-electricity composite material.
Above-mentioned many primitives piezo-electricity composite material is by piezoelectric ceramic, the three-phase composite material that polymer and decoupling material form, in order further to simplify preparation process, many primitives of the present invention piezo-electricity composite material can be also the two-phase composite material only being formed by piezoelectric ceramic and decoupling material, in this many primitives composite material, decoupling material plays the effect of matrix, play again the effect of each primitive of isolation, be that decoupling material has replaced polymer, each primitive be take decoupling material as line of demarcation, in each primitive, be the two-phase composite material that piezoelectric ceramic and decoupling material form in addition, only need so in the preparation a step cutting to complete, simple.
The present invention also provides a kind of many primitives piezo-electricity composite material of two-phase, it is characterized in that: take piezoelectric ceramic as skeleton, take decoupling material as matrix, described piezoelectric ceramic skeleton comprises substrate and is positioned at the piezoelectric ceramic post on substrate, described decoupling material is filled in and in piezoelectric ceramic skeleton, forms piezoelectric ceramic/decoupling material composite material, on described piezoelectric ceramic/decoupling material composite material, have upper, bottom electrode, wherein, top electrode be take decoupling material as border, discontinuous investing on piezoelectric ceramic/decoupling material composite material and by piezoelectric ceramic/decoupling material composite material is divided into the primitive that a plurality of structures are identical, all primitives form the array with same substrate.
In above-mentioned many primitives piezo-electricity composite material, the filling mode of decoupling material in each primitive, loading are identical, and each primitive by same substrate in combination together, forms the array with same substrate.
In above-mentioned many primitives piezo-electricity composite material, described decoupling material is silica gel, and described upper and lower electrode is silver electrode.Here the silica gel of use is mould silica gel, in market, can buy concrete product.
In order to simplify preparation technology, many primitives three-phase piezo-electricity composite material also can be two-phase piezo-electricity composite material, with decoupling material, directly as polymer, fill, decoupling material plays the effect of matrix, play again the effect of each primitive of isolation, each primitive be take decoupling material as line of demarcation, technique is simpler, just because decoupling material is elastomeric material, hardness does not have general polymerization thing large, may reduce stability and the compressive property of material itself, but preparation technology is simple, it comprises the following steps:
(1) on the piezoelectric ceramic surface perpendicular to piezoelectric ceramic polaxis, along orthogonal both direction cutting piezoelectric ceramic, obtain piezoelectric ceramic skeleton, the top of gained skeleton is piezoelectric ceramic post, bottom is substrate;
(2) the piezoelectric ceramic skeleton cutting is cleaned up, then pour into a mould wherein decoupling material, the sample after pouring vacuumizes discharge bubble, and then normal temperature cure obtains piezoelectric ceramic/decoupling material two-phase composite material;
(3) by piezoelectric ceramic/decoupling material two-phase composite material sanding and polishing, delimit according to demand the number of primitive, then at the upper surface coating top electrode of each primitive, discontinuous between each primitive top electrode, much final primitive piezo-electricity composite material.
Inventive point of the present invention is to lay particular emphasis in the consistency and low coupling of whole material, and its key that realizes above-mentioned advantage is, by decoupling material, whole composite material is divided into a plurality of primitives, and between each primitive, property consistent with each other is good, and coupling is low, and effect is fine.For single primitive, the difference of ceramics pole content can exert an influence to its single performance, but can not affect consistency and the coupling of whole material, so the post of ceramics pole is high, the thickness of substrate, ceramics pole length-width ratio can be selected in the prior art.For example, substrate thickness is unsuitable blocked up, also should not be too thin, and the too thick piezoelectricity dielectric property that can affect material etc., the too thin stability that can reduce material, generally in 1.5mm left and right.For example, length and width size can be 1.5 * 1.5,1 * 1,1.5 * 3,2 * 1,4 * 1,1.5 * 1,2 * 4 etc., and those skilled in the art can carry out as required routine and select.In addition, the content of piezoelectric ceramic can be selected according to the performance requirement of required product in actual applications, this selection should just can realize without creative work for those skilled in the art, and the content of general piezoelectric ceramic accounts for the more than 80% of whole product.The loading of decoupling material is according to the big or small difference of the number of primitive, piezo-electricity composite material and difference can be determined according to actual conditions.
Exactly because the design feature of many primitives piezoceramic material, thereby make its each primitive can launch independently sound wave, the transducer array being made by it can be launched multi-beam simultaneously, form beam scanning, or form specific beam direction, therefore be the ideal material of preparing transducer array element, the research and development of such composite material have great importance to the research and development of field of transducer.
The present invention adds decoupling material on the basis of original 1-3-2 type piezo-electricity composite material, forms many primitives piezo-electricity composite material, and composite material preparation process is simple, and many primitives of gained piezo-electricity composite material excellent performance, high conformity, coupling are low.Each primitive in composite material can be launched sound wave independently, and the transducer array being made by it can be launched multi-beam simultaneously, forms beam scanning, or forms specific beam direction, in field of transducer, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the structural representation of many primitives of the present invention piezo-electricity composite material;
Fig. 2 is the structural representation of existing 1-3-2 type piezo-electricity composite material;
Fig. 3 is many primitives of the present invention piezo-electricity composite material secondary cut process chart;
Fig. 4 is each primitive numbering schematic diagram of embodiment 1, embodiment primitive more than 2 piezo-electricity composite material;
Fig. 5 is the impedance characteristic of embodiment primitive more than 1 piezo-electricity composite material;
Fig. 6 is the response wave shape figure of embodiment 1 primitive 2#~4#;
Fig. 7 is the impedance characteristic of embodiment primitive more than 2 piezo-electricity composite material;
Fig. 8 is the response wave shape figure of embodiment 2 primitive 2#~4#;
Fig. 9 is the tested primitive schematic diagram of embodiment 3;
Figure 10 is the impedance characteristic of embodiment primitive more than 3 piezo-electricity composite material;
Figure 11 is the tested primitive schematic diagram 1 of embodiment 3;
Figure 12 is the tested primitive schematic diagram 2 of embodiment 3;
Figure 13 is the response wave shape figure of embodiment 3 primitive 2#~6#;
In figure, 1, primitive, 2, piezoelectric ceramic post, 3, decoupling material, 4, polymer, 5, electrode, 6, substrate.
Embodiment
Below by specific embodiment, the present invention will be further elaborated, should be understood that, following explanation is only in order to explain the present invention, its content is not limited.
many elementary materials in following embodiment adopt two-step method or one-step method cutting to form, and its step is as follows:
adopt two step cutting-completion methods to prepare many primitives piezo-electricity composite material, comprise the following steps:
First step cutting step:
(1) in the first half of piezoelectric ceramic, on the piezoelectric ceramic surface perpendicular to piezoelectric ceramic polaxis, along orthogonal both direction cutting piezoelectric ceramic, obtain piezoelectric ceramic skeleton, the top of gained skeleton is piezoelectric ceramic post, and bottom is piezoelectric ceramic substrate;
(2) the piezoelectric ceramic skeleton cutting is put into supersonic wave cleaning machine and repeatedly clean, remove ceramic residue;
(3) the piezoelectric ceramic skeleton after cleaning is fixed in mould, waters polymer injection, the piezoelectric ceramic of having poured into a mould and mould are placed in to vacuum tank and vacuumize, after the complete emptying of bubble, more than normal temperature cure 12h, obtain piezoelectric ceramics/polymer 1-3 thing two-phase composite material;
Second step cutting step:
(1) polymer cuts along orthogonal direction by the method for first step cutting after solidifying completely more for the second time;
(2) the composite material skeleton cutting is put into supersonic wave cleaning machine and repeatedly clean, the pottery producing in removing cutting process and the residue of polymer;
(3) the composite material skeleton after cleaning is fixed in mould, cast decoupling material, vacuumizes processing by the composite material of having poured into a mould, and discharges bubble, more than normal temperature cure 12h, obtains piezoelectric ceramics/polymer 1-3 thing/decoupling material three-phase composite material;
After (4) two steps have been cut, by sample sanding and polishing, then in the upper surface coating silver electrode of each primitive, obtain many primitives of 1-3-2 type piezo-electricity composite material.
adopt a step cutting-completion method to prepare many primitives piezo-electricity composite material, comprise the following steps:
(1) in the first half of piezoelectric ceramic, on the piezoelectric ceramic surface perpendicular to piezoelectric ceramic polaxis, along orthogonal both direction cutting piezoelectric ceramic, obtain piezoelectric ceramic skeleton, the top of gained skeleton is piezoelectric ceramic post, and bottom is piezoelectric ceramic substrate;
(2) the piezoelectric ceramic skeleton cutting is put into supersonic wave cleaning machine and repeatedly clean, remove ceramic residue;
(3) the piezoelectric ceramic skeleton after cleaning is fixed in mould, cast decoupling material, the piezoelectric ceramic of having poured into a mould and mould are placed in to vacuum tank and vacuumize, after the complete emptying of bubble, more than normal temperature cure 12h, obtain piezoelectric ceramic/decoupling material two-phase composite material;
(4) by two-phase sample sanding and polishing, the number of then dividing as required primitive, take decoupling material as the upper surface coating silver electrode of boundary at each primitive, and UNICOM not between each primitive top electrode, obtains many primitives of 1-3-2 type piezo-electricity composite material.
embodiment 1
Adopt PZT4 piezoelectric ceramic piece, piezoelectric constant
d 33for 210pCN
-1, electromechanical coupling factor
k tbe 49.67%, mechanical quality factor
q mbe 48.6, relative dielectric constant
ε rbe 999, material thickness is 15.1mm.Polymer adopts the epoxy resin (AB be in the milk resin) of good fluidity, and the ratio of epoxy resin and curing agent is 4:1.Decoupling material is HL-2288 type silica gel, and filling width is 0.5mm, and the ratio of silica gel and curing agent is 1:0.02.According to aforementioned preparation process, making primitive number is 6(3 * 2), to comprise ceramics pole number be 9(3 * 3 to each primitive), each ceramics pole cross sectional dimensions is many primitives piezo-electricity composite material of 1.5mm * 1.5mm, the high 13.3mm of ceramics pole, ceramics pole volume fraction 52.29%, the thick 1.8mm of substrate, the performance of many primitives piezo-electricity composite material of acquisition is as follows:
(1) piezoelectricity, dielectric and mechanical-electric coupling performance
Table 1 is piezoelectricity, dielectric and the mechanical-electric coupling performance (each primitive numbering is as Fig. 4) of many primitives piezo-electricity composite material.Piezoelectricity, dielectric, mechanical-electric coupling performance by visible each primitive of table are all more consistent, illustrate that the consistency of each primitive is better, and have inherited the advantage of 1-3 type piezo-electricity composite material, thickness electromechanical coupling coefficient K
thigh, acoustic impedance Z is low, pulse echo signal band is wide, is of value to practical application.
(2) frequency characteristic
The impedance characteristic of many primitives piezo-electricity composite material as shown in Figure 5.As seen from the figure, the frequency invariance of each primitive is better, all, in about 100kHz, calculates the relative frequency difference of each primitive and is 1.76% to the maximum, and I reaches 0.68%.Random peak, the not assorted peak of curve, frequency is 25kHz and 100 kHz places, has all occurred sequence peak on the impedance characteristic of each primitive, these peaks are respectively plane resonance peak and thickness resonance peak.And curve smoothing between two peaks, illustrative material thickness mode is pure, is conducive to practical application.
(3) coupling performance
With signal generator and oscilloscope, test the coupling performance between each primitive.The sine wave of signal generator tranmitting frequency 100kHz, peak value 10V, excitation primitive 1# vibrates, and records respectively the response signal of primitive 1#~4#.Fig. 6 is the response wave shape figure of primitive 2#~4#, and table 2 is amplitude and the attenuation rate of each primitive response signal.Visible: along with each receives primitive and the increase that encourages primitive distance, response signal amplitude reduces, and rate of signal attenuation increases, and waveform is constant, and the response signal of excitation primitive itself does not decay.
embodiment 2
Adopt PZT4 piezoelectric ceramic piece, piezoelectric constant
d 33for 210pCN
-1, electromechanical coupling factor
k tbe 49.67%, mechanical quality factor
q mbe 48.6, relative dielectric constant
ε rbe 999, material thickness is 15.1mm.Polymer adopts the epoxy resin (AB be in the milk resin) of good fluidity, and epoxy resin is 4:1 with the quality of curing agent than ratio.Decoupling material is HL-2288 type silica gel, and filling width is 0.5mm, and the ratio of silica gel and curing agent is 1:0.02.According to aforementioned preparation process, making primitive number is 6(3 * 2), to comprise ceramics pole number be 9(3 * 3 to each primitive), each ceramics pole cross sectional dimensions is many primitives piezo-electricity composite material of 1 mm * 1mm, the high 13.3mm of ceramics pole, ceramics pole volume fraction 42.06%, the thick 1.8mm of substrate, the performance of many primitives piezo-electricity composite material of acquisition is as follows:
(1) piezoelectricity, dielectric and mechanical-electric coupling performance
Table 3 is piezoelectricity, dielectric and the mechanical-electric coupling performance (each primitive numbering is as Fig. 4) of many primitives piezo-electricity composite material.Piezoelectricity, dielectric, mechanical-electric coupling performance by visible each primitive of table are all more consistent, illustrate that the consistency of each primitive is better, and have inherited the advantage of 1-3 type piezo-electricity composite material, thickness electromechanical coupling coefficient K
thigh, acoustic impedance Z is low, pulse echo signal band is wide, is of value to practical application.
(2) frequency characteristic
The impedance characteristic of many primitives piezo-electricity composite material as shown in Figure 7.By Tu Ke get, the resonance frequency of each primitive is respectively 90.8kHz, 92.23 kHz, 91.16 kHz, 89.29 kHz, 89.56 kHz, 89.03 kHz, and relatively frequency difference is 2.09% to the maximum, and I reaches 0.5%, and the frequency invariance of visible composite material is better.On the impedance characteristic of each primitive, all occurred sequence peak, these peaks are respectively plane resonance peak and thickness resonance peak.And curve smoothing between two peaks, material thickness mode is pure, is conducive to practical application.
(3) coupling performance
With signal generator and oscilloscope, test the coupling performance between each primitive.The sine wave of signal generator tranmitting frequency 100kHz, peak value 10V, excitation primitive 1# vibrates, and records respectively the response signal of primitive 1#~4#.Fig. 8 is the response wave shape figure of primitive 2#~4#, and table 4 is amplitude and the attenuation rate of each primitive response signal.Visible: along with each receives primitive and the increase that encourages primitive distance, response signal amplitude reduces, and rate of signal attenuation increases, and waveform is constant, and the response signal of excitation primitive itself does not decay.
embodiment 3
Adopt PZT4 piezoelectric ceramic piece, piezoelectric constant
d 33for 281pCN
-1, electromechanical coupling factor
k tbe 34.3%, relative dielectric constant
ε rbe 1121, material thickness is 15.5mm.Polymer and decoupling material all adopt HL-2288 type silica gel, and the ratio of silica gel and curing agent is 1:0.02.Because polymer is identical with decoupling material, so adopt once cutting, once fill, making primitive number is 45(9 * 5), to comprise ceramics pole number be 9(3 * 3 to each primitive), each ceramics pole cross sectional dimensions is many primitives piezo-electricity composite material of 2mm * 2mm, the high 13.5mm of ceramics pole, ceramics pole volume fraction 64.36%, the thick 2mm of substrate, the performance of many primitives piezo-electricity composite material of acquisition is as follows:
(1) piezoelectricity, dielectric and mechanical-electric coupling performance
Random 5 primitives (as shown in Figure 7) of selecting, the piezoelectricity of each primitive, dielectric and mechanical-electric coupling performance are in Table 5.As seen from table, the piezoelectricity of each primitive, dielectric, mechanical-electric coupling performance are all more consistent, illustrate that the consistency of each primitive is better.And thickness electromechanical coupling coefficient
k t high, acoustic impedance
zlow, pulse echo signal band is wide.
(2) frequency characteristic
The impedance characteristic of many primitives piezo-electricity composite material is as Fig. 8.As seen from the figure, the frequency invariance of each primitive is better, be respectively 98.17 kHz, 99.18 kHz, 97.17 kHz, 97.17 kHz, 97.20 kHz, on the impedance characteristic of each primitive, all occurred that sequence peak, these peaks are respectively plane resonance peak and thickness resonance peak.Curve smoothing between two peaks, thickness mode is pure, is conducive to practical application.
(3) coupling performance
The random panel region (as shown in Figure 9) of selecting, by the sine wave of signal generator tranmitting frequency 100kHz, peak value 5V, excitation primitive 1# vibrates, and records respectively the response signal of primitive 1#~9#.The response voltage and the attenuation rate that record each primitive are as shown in table 6.By Biao Ke get, all there is signal attenuation in various degree in the primitive that closes on of excitation primitive, and attenuation rate is all larger, illustrates that the decoupling effect of silica gel is remarkable.
The random row primitive (as shown in figure 10) of selecting, by the sine wave of signal generator tranmitting frequency 100kHz, crest voltage 5V, excitation primitive 1# vibrates, and records respectively the response signal of primitive 1#~6# with oscilloscope, as shown in figure 11, table 7 is amplitude and the attenuation rate of each primitive response signal.Visible: along with each primitive and the increase response signal amplitude of excitation primitive distance reduce, rate of signal attenuation increases, and waveform is constant, and the response signal of excitation primitive itself does not decay.