CN106495559A - A kind of 03 type composite piezoelectric materials and preparation method thereof and device - Google Patents
A kind of 03 type composite piezoelectric materials and preparation method thereof and device Download PDFInfo
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- CN106495559A CN106495559A CN201610912966.1A CN201610912966A CN106495559A CN 106495559 A CN106495559 A CN 106495559A CN 201610912966 A CN201610912966 A CN 201610912966A CN 106495559 A CN106495559 A CN 106495559A
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Abstract
The invention discloses a kind of 03 type polymer and Ceramic Composite piezoelectric, including ceramic phase piezoelectric and piezopolymer, the ceramic phase piezoelectric material surface is coated by Graphene powder.Additionally, also disclosing the method for preparing composite piezoelectric material and the device comprising which.The present invention using special ratios Graphene ceramic phase powder is coated in advance after so that the conduction of power is more continuous, to shaping after the piezoelectric property of 03 type piezo-electricity composite materials there is castering action.Meanwhile, by adding Graphene in piezopolymer, the electrical conductivity of polymer phase can be improved to the scope close with ceramic phase, reduce the polarization difficulty of ceramic phase.Additionally, Graphene has toughening effect to 03 type piezo-electricity composite material systems, the mechanical property of whole system is improve.
Description
Technical field
The invention belongs to piezoelectric field；Be related to a kind of polymer and Ceramic Composite piezoelectric and preparation method thereof and
Device, more particularly, to a kind of 0-3 types polymer and Ceramic Composite piezoelectric and preparation method thereof and device.
Technical background
The features such as piezoceramic material (such as lead zirconate titanate, PZT) has piezoelectric property high big with electromechanical coupling factor, but
Its impact resistance is poor, and application is subject to a definite limitation.Some macromolecular materials (such as polyvinylidene fluoride, PVDF) flexible
Property is good, but piezoelectric modulus and electromechanical coupling factor are less, and in addition temperature characterisitic and aging characteristics there is also problem.By piezoelectric ceramics
After material is combined by certain mode of communicating with polymeric material, can be made into, and the pressure with flexibility
Composite.
This ceramic powder is scattered in the composite that formed in three-dimensional continuous polymeric matrix and is referred to as 0-3 types
Piezo-electricity composite material.Compared with pure ceramic piezoelectric material, 0-3 types piezo-electricity composite material can not only weaken beyond fragility, also hold
The elastomer of various forms, such as thin slice, column, threadiness, and moulded by casting is easily made, a large amount of productions are suitable to.
In general, piezoelectric of the performance of 0-3 types composite better than other forms.But this kind of composite has
Three major defects：
(1) polymer self-conductance rate is (such as PVDF～10-14) and piezoelectric ceramics electrical conductivity (PZT～10 S/m-8S/m between)
Gap is larger, and, in polarization, most Electric Field Distributions are on polymer so that in 0-3 type piezo-electricity composite materials for composite
The polarization of pottery is relatively difficult；
(2) between two-phase, physical and chemical performance and mechanical property have larger difference, cause two-phase generally to be disperseed uneven and power
Conduction is more difficult, ultimately results in its piezoelectric property bad；
(3) for ensureing preferable piezoelectric property, need to improve ceramic Phase Proportion, but the toughness of composite is with ceramic phase
Ratio improve and reduce.
In order to solve the above problems, it usually needs piezo-electricity composite material is modified, so as to improve interfacial bonding property, and
And improve or improve electric property.
For example, Chinese patent application CN104157784A discloses a kind of preparation method of composite Nano piezoelectric generator.
Nanometer piezoelectricity particle and organic piezoelectric materials are combined by the method, and the piezoelectricity for preparing the flexibility of even particle distribution is thin
Film, the piezoelectric nano generator that height output is obtained by high voltage polarization.Nanometer piezoelectricity particle has high piezoelectric property, used as base
The organic piezoelectric materials of body not only itself have a piezoelectric property, and its solution has the ground toughness can will be equal for piezoelectricity particle
Even is dispersed therein, while with good mechanical performance.However, the patent application is provided using ceramic phase piezoresistive material
The complex method of the polymer piezo material such as material and PVDF, P (VdF-HFP).This is a kind of 0-3 type piezoelectrics on basis, right
Above-mentioned 3 shortcomings do not propose a solution.The preparation method of piezoceramic-polymer composite.
Additionally, Chinese patent application CN105789431A discloses a kind of preparation side of piezoceramic-polymer composite
Method.The method sandwiches one layer of conductive particle polymeric material in two-layer 0-3 type piezoceramic-polymer piezo-electricity composite material, flat
On plate vulcanizer, 170～180 DEG C are prepared into final piezoceramic-polymer composite in hot-forming 12 hours.However, should
Patent application causes poor toughness primarily to solving ceramic Phase Proportion in 0-3 types piezo-electricity composite material disadvantages mentioned above (3) and improving
Problem.(1) and (2) two shortcomings cannot be solved.For shortcoming (2), the patented solutions are to adopt sandwich structure, make
Ensure pliability in centre as supporting layer with the conducting polymer without ceramic phase, which respectively has a floor height ceramic phase up and down
The 0-3 section bars bed of material is providing high tension performance.But the technical disadvantages are that intermediate layer is unrelated with piezoelectric property, increased piezoelectrics
Extra volume, such as presses volume average computation, and the ratio of ceramic phase is still relatively low.
Additionally, there is some non-patent literature reports to add conductive material increase matrix electrical conductivity, improve polarization tired
Be difficult to and ceramic phase and polymer phase combine not closely the problems such as.However, conductive material increases to percolation threshold, composite electricity
Conductance is sharply increased, and conductive material easily forms connection circuit, so as to be susceptible to punch-through in polarization.
Therefore, for drawbacks described above, in the urgent need to finding a kind of preparation method of new simple economy, to obtain high pottery
Phase toughness preferably, easily polarizes and ceramic phase and the compact 0-3 types polymer of polymer phase and Ceramic Composite piezoresistive material
Material.
Content of the invention
For the deficiencies in the prior art, inventor has found, when the Graphene using special ratios is to the pre- of ceramic phase powder
After processing and coating, it is possible to resolve high ceramic phase toughness deficiency, difficult polarization and ceramic phase and polymer phase combine not tight etc.
Problem.On this basis, the present invention proposes new 0-3 types polymer and Ceramic Composite piezoelectric and preparation method thereof and device
Part.
It is well known that Graphene is theoretical most thin and most tough material known today, its fracture strength is than best
Steel taller 200 times.It has good elasticity, stretch range reach the 20% of own dimensions again simultaneously.This new
Material also has excellent conductive capability, and its resistivity ratio copper or silver are lower, is the minimum material of current resistivity.In existing skill
In art, exist by add conductive material reduce polymer resistive rate means, but added can at most cause be lost excessive.Send out
A person of good sense is had found by lot of experiments, because of its excellent electric conductivity, less amount of Graphene can be added to can achieve polymer entirety
The raising of electric conductivity, minimum so as to the loss for bringing to be down to.
For achieving the above object, on the one hand, the invention provides a kind of 0-3 types polymer and Ceramic Composite piezoelectric,
Including ceramic phase piezoelectric and piezopolymer, it is characterised in that the ceramic phase piezoelectric material surface is Graphene powder
Coated.
According to aforesaid composite piezoelectric material, wherein, the ceramic phase piezoelectric is selected from binary system, ternary system, quaternary
Any one or more in system and polynary system ceramic phase piezoelectric.Wherein, binary system ceramics phase piezoelectric includes, but not
Be limited to, barium titanate BT, lead zirconate titanate PZT, modified lead zirconate titanate, lead zirconates PG, lead titanates PT, modified lead titanate, bismuth-sodium titanate,
Tellurium mangaic acid lead PMS, manganese niobium lead acid PMN, lead zinc niobate PZN, niobates, tantalates.In the present invention, term " modified lead titanate "
Represent the lead titanates being modified using Mn, W, Ca, Bi, La and Nb.Term " modified lead zirconate titanate " represent using Sr, Ca, Mg,
The lead zirconate titanate that Nb, La, Sb, Cr and Mn are modified.Term " niobates " includes but is not limited to (Pb, Ba) NbO3、(Na,K)
NbO3(Na, Cd) NbO3Etc..Ternary system ceramics phase piezoelectric includes, but not limited to PMN-PZT and PMN-PZN-PT etc.
Deng quaternary system ceramic phase piezoelectric includes, but not limited to PMN-PZN-PZT, PLN-PMN-PZT and PZN-PNN-PZT etc.
Deng.
Preferably, the ceramic phase piezoelectric is selected from barium titanate BT, lead zirconate titanate PZT, modified lead zirconate titanate, lead zirconates
PG, lead titanates PT, modified lead titanate, bismuth-sodium titanate, tellurium mangaic acid lead PMS, manganese niobium lead acid PMN, lead zinc niobate PZN, niobates, tantalum
Any one or more in hydrochlorate.It is highly preferred that the ceramic phase piezoelectric is selected from barium titanate BT, lead zirconate titanate PZT, changes
In property lead zirconate titanate, lead zirconates PG, lead titanates PT, modified lead titanate, bismuth-sodium titanate, niobates, tantalates any one or
Multiple.Most preferably, the ceramic phase piezoelectric is selected from barium titanate BT, lead zirconate titanate PZT, lead zirconates PG, lead titanates PT, titanium
Any one or more in sour bismuth sodium, niobates, tantalates.
In a specific embodiment, the ceramic phase piezoelectric is selected from lead zirconate titanate PZT.
According to aforesaid composite piezoelectric material, wherein, the piezopolymer is selected from Kynoar, polyvinyl chloride, gathers
Any one or more in difluoroethylene and polyacrylonitrile and its copolymer.Preferably, the piezopolymer is selected from poly- inclined
Any one or more in PVF, polyvinyl chloride and polyacrylonitrile and its copolymer.It is highly preferred that the piezopolymer
Any one or more in Kynoar and polyacrylonitrile and its copolymer.Most preferably, the piezopolymer
Any one or more in Kynoar and its copolymer.
In a specific embodiment, the piezopolymer is selected from Kynoar.
According to aforesaid composite piezoelectric material, wherein, the Graphene powder bed of material number is 1-10 layers, particle diameter on direction in layer
For 50-200 μm.Preferably, the Graphene powder bed of material number is 1-8 layers, and in layer, on direction, particle diameter is 50-150 μm.More preferably
Ground, the Graphene powder bed of material number are 1-6 layers, and in layer, on direction, particle diameter is 50-120 μm.Most preferably, the Graphene powder
The number of plies is 1-4 layers, and in layer, on direction, particle diameter is 50-80 μm.
In a specific embodiment, the Graphene powder bed of material number is 3 layers, and in layer, on direction, particle diameter is 60 μm.
According to aforesaid composite piezoelectric material, wherein, the weight of the ceramic phase piezoelectric and the Graphene powder
Than for (90-99.95)：(0.05-10).Preferably, the ceramic phase piezoelectric with the weight ratio of the Graphene powder is
(92-99.95)：(0.05-8).It is highly preferred that the ceramic phase piezoelectric is (95- with the weight ratio of the Graphene powder
99.95)：(0.05-5).Most preferably, the ceramic phase piezoelectric is (97- with the weight ratio of the Graphene powder
99.95)：(0.05-3).
In a specific embodiment, the ceramic phase piezoelectric with the weight ratio of the Graphene powder is
99：1.
According to aforesaid composite piezoelectric material, wherein, the cladding is carried out by following means, by the ceramic phase piezoelectricity
Material carries out wet ball grinding with the Graphene powder and suitable auxiliary agent, crosses 500 mesh after the dry materials grinding after ball milling
Sieve.
According to aforesaid composite piezoelectric material, wherein, the auxiliary agent includes dispersant and solvent.
Wherein, the solvent selected from absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane, chloroform, ethyl acetate, acetonitrile,
N, any one or more in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide.Preferably, the solvent
Any one or more in absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane, chloroform, ethyl acetate, acetonitrile.More excellent
Selection of land, the solvent are selected from any one or more in absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane, chloroform.Optimum
Selection of land, the solvent are selected from any one or more in absolute ethyl alcohol, methyl alcohol, acetone.
In a specific embodiment, the solvent is selected from absolute ethyl alcohol.
The dispersant is selected from polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, sodium tripolyphosphate, six inclined phosphorus
Any one in sour sodium, sodium pyrophosphate, triethyl group hexyl phosphoric acid, cellulose derivative, guar gum, fatty acid polyethylene glycol ester
Or it is multiple.Preferably, the dispersant selected from polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, sodium tripolyphosphate,
Any one or more in calgon, sodium pyrophosphate.It is highly preferred that the dispersant is selected from polyethylene glycol, polypropylene
Any one or more in acid amides, polyacrylate, polyvinyl alcohol.Most preferably, the dispersant selected from polyethylene glycol and
Any one or more in polyacrylic acid.
In a specific embodiment, the dispersant is selected from PEG-400.
The consumption of the dispersant is consumption well-known to those skilled in the art.For example, based on the ceramic phase piezoelectricity
The 0.5-3wt% of material and the Graphene powder gross weight.
According to aforesaid composite piezoelectric material, wherein, the time of the wet ball grinding is 2-12 hours, and preferably 4-12 is little
When, more preferably 4-10 hours, and most preferably 4-8 hours.
According to aforesaid composite piezoelectric material, wherein, the piezopolymer adds the Graphene of its weight 0.01-1%
Powder.
According to aforesaid composite piezoelectric material, wherein, the Graphene powder bed of material number is 1-10 layers, particle diameter on direction in layer
For 50-200 μm.Preferably, the Graphene powder bed of material number is 1-8 layers, and in layer, on direction, particle diameter is 50-150 μm.More preferably
Ground, the Graphene powder bed of material number are 1-6 layers, and in layer, on direction, particle diameter is 50-120 μm.Most preferably, the Graphene powder
The number of plies is 1-4 layers, and in layer, on direction, particle diameter is 50-80 μm.
In a specific embodiment, the Graphene powder bed of material number is 3 layers, and in layer, on direction, particle diameter is 60 μm.
According to aforesaid composite piezoelectric material, wherein, the interpolation is carried out by following means, by the piezopolymer
It is scattered in solvent, adds the Graphene powder of its weight 0.01-1%, heats and stir and be sufficiently mixed.
According to aforesaid composite piezoelectric material, wherein, the solvent selected from absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane,
Chloroform, ethyl acetate, acetonitrile, N, any one in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide
Or it is multiple.Preferably, the solvent selected from acetone, dichloromethane, chloroform, ethyl acetate, N, 1-METHYLPYRROLIDONE, two
Any one or more in NMF, dimethyl acetamide.It is highly preferred that the solvent selected from acetone, ethyl acetate,
N, any one or more in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide.Most preferably, described molten
Agent is selected from acetone, N, any one or more in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide.
In a specific embodiment, the solvent is selected from N, 1-METHYLPYRROLIDONE.
According to aforesaid composite piezoelectric material, wherein, the heating-up temperature is 30-60 DEG C, preferably 40-60 DEG C, more excellent
Elect 40-55 DEG C as, and most preferably 40-50 DEG C.
On the other hand, the present invention provides a kind of method for preparing aforementioned 0-3 types polymer and Ceramic Composite piezoelectric, bag
Include following steps：
1) the ceramic phase piezoelectric is carried out wet ball grinding, ball milling with the Graphene powder and suitable auxiliary agent
500 mesh sieves are crossed after dry materials grinding afterwards, Graphene/Ceramic Composite powder is obtained；
2) piezopolymer is scattered in solvent, adds the Graphene powder of its weight 0.01-1%, heating is simultaneously
Stirring is sufficiently mixed, and obtains mixed material；
3) by step 1) Graphene/Ceramic Composite powder add step 2) mixed material in, stirring is homogenized
Material.
According to aforesaid preparation method, wherein, the step 1) ceramic phase piezoelectric selected from binary system, ternary system,
Any one or more in quaternary system and polynary system ceramic phase piezoelectric.Wherein, binary system ceramics phase piezoelectric includes,
But it is not limited to, barium titanate BT, lead zirconate titanate PZT, modified lead zirconate titanate, lead zirconates PG, lead titanates PT, modified lead titanate, metatitanic acid
Bismuth sodium, tellurium mangaic acid lead PMS, manganese niobium lead acid PMN, lead zinc niobate PZN, niobates, tantalates.In the present invention, term " Modified Titanium
Lead plumbate " represents the lead titanates being modified using Mn, W, Ca, Bi, La and Nb.Term " modified lead zirconate titanate " represent using Sr,
The lead zirconate titanate that Ca, Mg, Nb, La, Sb, Cr and Mn are modified.Term " niobates " includes but is not limited to (Pb, Ba) NbO3、
(Na,K)NbO3(Na, Cd) NbO3Etc..Ternary system ceramics phase piezoelectric includes, but not limited to PMN-PZT and PMN-
PZN-PT etc., quaternary system ceramic phase piezoelectric include, but not limited to PMN-PZN-PZT, PLN-PMN-PZT and PZN-
PNN-PZT etc..
Preferably, the step 1) ceramic phase piezoelectric selected from barium titanate BT, lead zirconate titanate PZT, modified zirconium metatitanic acid
Lead, lead zirconates PG, lead titanates PT, modified lead titanate, bismuth-sodium titanate, tellurium mangaic acid lead PMS, manganese niobium lead acid PMN, lead zinc niobate PZN,
Any one or more in niobates, tantalates.It is highly preferred that the ceramic phase piezoelectric is selected from barium titanate BT, zirconium titanium
In lead plumbate PZT, modified lead zirconate titanate, lead zirconates PG, lead titanates PT, modified lead titanate, bismuth-sodium titanate, niobates, tantalates
Any one or more.Most preferably, the ceramic phase piezoelectric selected from barium titanate BT, lead zirconate titanate PZT, lead zirconates PG,
Any one or more in lead titanates PT, bismuth-sodium titanate, niobates, tantalates.
In a specific embodiment, the step 1) ceramic phase piezoelectric be selected from lead zirconate titanate PZT.
According to aforesaid preparation method, wherein, the step 1) ceramic phase piezoelectric and the Graphene powder
Weight ratio is (90-99.95)：(0.05-10).Preferably, the weight of the ceramic phase piezoelectric and the Graphene powder
Than for (92-99.95)：(0.05-8).It is highly preferred that the ceramic phase piezoelectric with the weight ratio of the Graphene powder is
(95-99.95)：(0.05-5).Most preferably, the ceramic phase piezoelectric is (97- with the weight ratio of the Graphene powder
99.95)：(0.05-3).
In a specific embodiment, the step 1) ceramic phase piezoelectric and the Graphene powder weight
Amount is than being 99：1.
According to aforesaid preparation method, wherein, the step 1) auxiliary agent include dispersant and solvent.
Wherein, the step 1) solvent be selected from absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane, chloroform, acetic acid second
Ester, acetonitrile, N, any one or more in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide.Preferably,
The solvent selected from absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane, chloroform, ethyl acetate, in acetonitrile any one or
Multiple.It is highly preferred that the solvent selected from absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane, in chloroform any one or
Multiple.Most preferably, the solvent is selected from any one or more in absolute ethyl alcohol, methyl alcohol, acetone.
In a specific embodiment, the solvent is selected from absolute ethyl alcohol.
The step 1) dispersant be selected from polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, tripolyphosphate
In sodium, calgon, sodium pyrophosphate, triethyl group hexyl phosphoric acid, cellulose derivative, guar gum, fatty acid polyethylene glycol ester
Any one or more.Preferably, the dispersant selected from polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol,
Any one or more in sodium tripolyphosphate, calgon, sodium pyrophosphate.It is highly preferred that the dispersant is selected from poly- second
Any one or more in glycol, polyacrylamide, polyacrylate, polyvinyl alcohol.Most preferably, the dispersant is selected from
Any one or more in polyethylene glycol and polyacrylic acid.
In a specific embodiment, the step 1) dispersant be selected from PEG-400.
The step 1) the consumption of dispersant be consumption well-known to those skilled in the art.For example, based on the pottery
The 0.5-3wt% of porcelain phase piezoelectric and the Graphene powder gross weight.
According to aforesaid preparation method, wherein, the step 1) wet ball grinding time be 2-12 hours, preferably 4-
12 hours, more preferably 4-10 hours, and most preferably 4-8 hours.
According to aforesaid preparation method, wherein, the step 2) piezopolymer be selected from Kynoar, polychlorostyrene second
Any one or more in alkene, poly- difluoroethylene and polyacrylonitrile and its copolymer.Preferably, the piezopolymer is selected from
Any one or more in Kynoar, polyvinyl chloride and polyacrylonitrile and its copolymer.It is highly preferred that the piezoelectricity is poly-
Compound any one or more in Kynoar and polyacrylonitrile and its copolymer.Most preferably, the piezoelectricity gathers
Compound any one or more in Kynoar and its copolymer.
In a specific embodiment, the step 2) piezopolymer be selected from Kynoar.
According to aforesaid preparation method, wherein, the step 2) solvent be selected from absolute ethyl alcohol, methyl alcohol, acetone, dichloromethane
Alkane, chloroform, ethyl acetate, acetonitrile, N, any in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide
One or more.Preferably, the solvent selected from acetone, dichloromethane, chloroform, ethyl acetate, N, N- crassitudes
Any one or more in ketone, dimethylformamide, dimethyl acetamide.It is highly preferred that the solvent selected from acetone, acetic acid
Ethyl ester, N, any one or more in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide.Most preferably, institute
State solvent selected from acetone, N, any one or more in 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide.
In a specific embodiment, the step 2) solvent be selected from N, 1-METHYLPYRROLIDONE.
According to aforesaid preparation method, wherein, the step 2) heating-up temperature be 30-60 DEG C, preferably 40-60 DEG C,
More preferably 40-55 DEG C, and most preferably 40-50 DEG C.
According to aforesaid preparation method, wherein, the step 1) and Graphene powder bed of material number 2) be 1-10 layers, side in layer
Particle diameter is 50-200 μm upwards.Preferably, the Graphene powder bed of material number is 1-8 layers, and in layer, on direction, particle diameter is 50-150 μm.
It is highly preferred that the Graphene powder bed of material number is 1-6 layers, in layer, on direction, particle diameter is 50-120 μm.Most preferably, the graphite
The alkene powder number of plies is 1-4 layers, and in layer, on direction, particle diameter is 50-80 μm.
In a specific embodiment, the step 1) and Graphene powder bed of material number 2) be 3 layers, in layer on direction
Particle diameter is 60 μm.
According to aforesaid preparation method, wherein, the step 3) mixing time be 0.5-4 hours, preferably 1-4 is little
When, more preferably 1.5-4 hours, and most preferably 2-4 hours.
Finally, present invention also offers a kind of 0-3 types polymer and Ceramic Composite piezoelectric device, including aforesaid compound pressure
Electric material or made by aforesaid preparation method.
In one embodiment, aforesaid composite piezoelectric material is by the mode film forming such as spin coating, curtain coating, blade coating, cast.
In another embodiment, aforesaid composite piezoelectric material is fully dried, by extrusion molding, injection, molding etc.
Mode is into film, sheet material, tubing, bar etc..
Compared with prior art, the present invention has following Advantageous Effects：
(1) under normal circumstances, polymer phase and ceramic phase electrical conductivity difference are larger, and ceramic phase polarization is insufficient.The present invention
By adding a small amount of Graphene, effectively the electrical conductivity of polymer phase can be improved to the scope close with ceramic phase, reduce pottery
The polarization difficulty of porcelain phase；
(2) by Graphene cladding in advance to ceramic phase particles, reduce the gap of ceramic phase and polymer physics performance,
Make capable conduction more continuous, improve the overall piezoelectric property of 0-3 types piezo-electricity composite material；
(3) the excellent intensity of Graphene and toughness can effectively improve the toughness of polymeric material, play conductive filler work
With while, also played strengthen phase effect, such that it is able to ensure composite flexibility on the premise of, improve ceramic phase
Ratio.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than restriction the scope of the present invention.In addition, it is to be understood that after present disclosure has been read, those skilled in the art
The present invention can be made various changes or modifications, these equivalent form of values equally fall within what the application appended claims were limited
Scope.
Will be helpful to understand the present invention by following embodiments, but the scope of the present invention can not be limited.
Embodiment 1
(1) 99% PZT powders are mixed with 1% Graphene powder, add the PEG-400 of powder gross weight 2%,
Wet ball grinding is carried out 8 hours after adding absolute ethyl alcohol.500 mesh sieves are crossed after the abundant drying and grinding of 60 DEG C of material after ball milling.
(2) according to 1:1 ratio weighs PVDF and the obtained composite powder of previous step.0.05% is added in PVDF powder
Graphene powder, be heated to 45 DEG C and stir in input NMP, be subsequently added weighed Graphene/PZT composite powders, hold
Continuous stirring 2 hours, obtains uniform sizing material.
(3) slurry is dried by casting film-forming and fully.Its electrical conductivity is about 1.5x10-8S/m, entirety is uniform and has one
Determine pliability.
Embodiment 2
(1) 95% barium titanate powder is mixed with 5% Graphene powder, adds the PEG- of powder gross weight 1%
400, wet ball grinding is carried out 4 hours after adding absolute ethyl alcohol.500 mesh sieves are crossed after the abundant drying and grinding of 60 DEG C of material after ball milling.
(2) according to 1:2 ratio weighs PVDF and the obtained Graphene of upper step/barium titanate powder.Add in PVDF powder
Enter 1% Graphene powder, 50 DEG C are heated in input DMF and are stirred, be subsequently added weighed Graphene/barium titanate and be combined
Powder, persistently stirs 4 hours, obtains uniform sizing material.
(3) slurry is dried 12 hours at 80 DEG C, is obtained dry feedstock, is machined to sheet material by compression molding.The sheet material
Bulk conductivity is 5.2x10-4S/m, with preferable mechanical property.
Embodiment 3
(1) 97% PZT powders are mixed with 3% Graphene powder, add the PEG-400 of powder gross weight 3%,
Wet ball grinding is carried out 12 hours after adding absolute ethyl alcohol.500 mesh sieves are crossed after the abundant drying and grinding of 60 DEG C of material after ball milling.
(2) according to 1:4 ratio weighs PVDF and the obtained Graphene of upper step/PZT powders.Add in PVDF powder
0.01% Graphene powder, is heated to 50 DEG C in input DMA and stirs, be subsequently added weighed Graphene/PZT composite powders
Material, persistently stirs 2 hours, obtains uniform sizing material.
(3) slurry is dried 8 hours at 80 DEG C, obtains dry feedstock, is processed into block by molding.Block PZT phases contain
Amount is high, and after polarization, piezoelectric property is good, and bulk conductivity is 6.1x10-8S/m, and there is some strength.
Compared with prior art, after the Graphene using special ratios of the invention is coated in advance to ceramic phase powder,
Make capable conduction more continuous, to shaping after the piezoelectric property of 0-3 type piezo-electricity composite materials there is castering action.The opposing party
Face, by adding Graphene in piezopolymer, can improve the electrical conductivity of polymer phase to the scope close with ceramic phase
Interior, reduce the polarization difficulty of ceramic phase.Additionally, Graphene has toughening effect to 0-3 type piezo-electricity composite material systems, improve
The mechanical property of whole system.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., be all contained within protection scope of the present invention.
Claims (10)
1. a kind of 0-3 types polymer and Ceramic Composite piezoelectric, including ceramic phase piezoelectric and piezopolymer, its feature
It is, the ceramic phase piezoelectric material surface is coated by Graphene powder.
2. composite piezoelectric material according to claim 1, wherein, the ceramic phase piezoelectric is selected from binary system, ternary
Any one or more in system, quaternary system and polynary system ceramic phase piezoelectric.
3. composite piezoelectric material according to claim 1, wherein, the piezopolymer is selected from Kynoar, polychlorostyrene
Any one or more in ethene, poly- difluoroethylene and polyacrylonitrile and its copolymer.
4. composite piezoelectric material according to claim 1, wherein, the Graphene powder bed of material number is 1-10 layers, side in layer
Particle diameter is 50-200 μm upwards.
5. composite piezoelectric material according to claim 1, wherein, the ceramic phase piezoelectric and the Graphene powder
Weight ratio be (90-99.95)：(0.05-10).
6. composite piezoelectric material according to claim 1, wherein, the cladding is carried out by following means, by the pottery
Porcelain phase piezoelectric carries out wet ball grinding with the Graphene powder and suitable auxiliary agent, after the dry materials grinding after ball milling
Cross 500 mesh sieves.
7. composite piezoelectric material according to claim 1, wherein, the piezopolymer adds its weight 0.01-1%
Graphene powder.
8. composite piezoelectric material according to claim 7, wherein, the interpolation is carried out by following means, by the pressure
Electric polymer is scattered in solvent, adds the Graphene powder of its weight 0.01-1%, is heated and is stirred and is sufficiently mixed.
9. a kind of method of 0-3 types polymer prepared described in any one of claim 1-8 and Ceramic Composite piezoelectric, including
Following steps：
1) the ceramic phase piezoelectric is carried out wet ball grinding with the Graphene powder and suitable auxiliary agent, after ball milling
500 mesh sieves are crossed after dry materials grinding, Graphene/Ceramic Composite powder is obtained；
2) piezopolymer is scattered in solvent, adds the Graphene powder of its weight 0.01-1%, heat and stir
It is sufficiently mixed, obtains mixed material；
3) by step 1) Graphene/Ceramic Composite powder add step 2) mixed material in, stirring obtains uniform sizing material.
10. a kind of 0-3 types polymer and Ceramic Composite piezoelectric device, it is characterised in that including described in any one of claim 1-8
0-3 types polymer and Ceramic Composite piezoelectric or made by the preparation method described in claim 9.
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