CN109306142A - A kind of new dielectric composite material - Google Patents
A kind of new dielectric composite material Download PDFInfo
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- CN109306142A CN109306142A CN201811147071.9A CN201811147071A CN109306142A CN 109306142 A CN109306142 A CN 109306142A CN 201811147071 A CN201811147071 A CN 201811147071A CN 109306142 A CN109306142 A CN 109306142A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract
The invention belongs to dielectric composite material fields, and in particular to a kind of new dielectric composite material.A kind of technical solution of use are as follows: dielectric composite material, the dielectric composite material is ceramic nano line/polymer composites, by percent by volume, in the dielectric composite material, the ceramic nano line accounting is 1%~10%, and the polymer accounting is 90%~99%；The ceramic nano line carries out ordered arrangement in any direction in dielectric composite material.The present invention aligns the ceramic nano line in slurry using 3D printing technique, and has regulated and controled the distribution arrangement of nano wire, and then effectively improve the performance of composite material.
Description
Technical field
The invention belongs to dielectric composite material fields, and in particular to a kind of new dielectric composite material.
Background technique
In recent years, to alleviate environmental pollution brought by fossil energy and energy shortage the problems such as, solar battery, lithium electricity
The renewable energy technologies such as pond and capacitor are rapidly developed, wherein capacitor has compared to energy storage devices such as lithium batteries to be filled
The velocity of discharge is fast, stability is good and the advantages such as at low cost, is suitably applied high power electronic equipment.But current high power capacitor
The too low defect of generally existing energy density.Therefore, the bottleneck that the energy density of capacitor is the area research how is improved.
The energy density for improving dielectric material, needs to improve its relative dielectric constant and electric field value is worn in resistance.Ferroelectricity pottery
Porcelain generally has thousands of high dielectric constant, but its anti-breakdown electric field is lower, on the contrary, polymer has highly resistance breakdown potential
, but its dielectric constant is usually as low as 10 or less, it is clear that the ceramics or polymer of one pack system are not ideal dielectric material
Material.Ceramic/polymer dielectric composite material is due to having both the high dielectric constant of ceramics and highly resistance breakdown electric field, the low damage of polymer
The features such as consumption and flexibility, it is considered to be one of current most potential dielectric material.Spherical ferroelectric ceramic grain, such as
BaTiO3, Pb (Zr1-xTix)O3(PZT) and Pb (Mg1/3Nb2/3)O3–PbTiO3(PMN-PT) etc. due to high dielectric constant and
Mature preparation process, commonly selected are filled into polymeric matrix, and content is typically up to 50vol.%.Add high-content pottery
After porcelain filling, the dielectric constant of compound is significantly increased, but the ceramic packing of high-content not only introduces in the composite
The defects of hole and crackle, also destroys its flexibility, therefore high dielectric constant often wears electric field value with the resistance of expendable material
For cost, the raising of compound energy density is limited.
Research has shown that, replaces the spherical nanoparticle of zero dimension mutually can be effective as filling using one-dimensional ceramic nano line
Ground overcomes the above problem.Since ceramic nano line/polymer has low percolation threshold, usually need to only add lower than 10vol.%'s
Ceramic nano line can reach the peak value of dielectric constant, and compare ceramic nanoparticles, and ceramic nano line is easier polymerizeing
It is uniformly dispersed in object matrix, therefore maintains the advantage of polymeric matrix highly resistance breakdown electric field.In addition, the ceramics of high length-diameter ratio are received
The relatively spherical ceramic nanoparticles of rice noodles have bigger dipole moment, can more effectively improve compound under the same conditions
Dielectric constant, therefore, nano wire becomes the current research hotspot in the field.
However, being still confined to adjust its synthesis technology at present to the research of ceramic nano line, for example change ceramic nano
The system of line, content and regulate and control its draw ratio etc., although the opposite filling spherical ceramic particles of the energy density values of compound
Compound has raising by a relatively large margin, but has been in one at present and has continued to improve difficult bottleneck stage.Therefore, how to dash forward
Current bottleneck is broken, the energy density of compound is improved to a greater degree, needs to change current conventional thought.
University of Michigan Henry A.Sodano teaches team and changes the row of PZT nano wire in the composite using pulling method
Column, it was demonstrated that in PVDF matrix, compare its random distribution, when PZT nano wire is parallel to field distribution, in phase same electric field and
The energy density of compound can be more effectively improved under the conditions of PZT nano wire content.Tongji University Zhai Jiwei teaches team and closes
At titanium dioxide (TiO2) nano-wire array, and Kynoar (PVDF) base dielectric composite wood is prepared for as filler
Material, (340kV/mm) is obtained compared to TiO under acting under the electric field for being parallel to nanowire growth direction2Nano wire random distribution
The discharge energy density (10.62J/cm that significantly improves of compound3).Central China University of Science and Technology Jiang Shenglin teaches team using curtain coating
Method is prepared for BaTiO3The compound that nano wire aligns, energy storage density are achieved at lower electric field (240kV/mm)
Greatly improve (10.8J/cm3).Pennsylvania State University C.A.Randall et al. reports montmorillonite-based nano piece in an orderly manner
It is dispersed in polyethylene (PE), the compound that the dielectric constant of compound compares its random distribution with anti-breakdown electric field is significant
It improves.It can be seen that regulation ceramic nano structure distributional pattern in the composite is not change ceramic systems and increase is filled out
One of the effective way of compound energy density is improved under conditions of charge.
But all there are some defects in existing method.Biaxial stretching process major defect are as follows: composite inner it is uneven
Inconsistency causes composite material that different deformation occurs under identical tensile force effect, thus internal nanowire alignment
The change in direction can not accomplish unanimously, meanwhile, it is biaxial stretch-formed to be easy to seriously affect composite inner structural disorganization multiple
Close physical performance.The tape casting technique is very coarse, and the shearing force by scraping diaphragm plate is orientated nano wire, this shearing force
It is small and different in the thickness direction active force of fluid, so the effect that nano wire is orientated is not obvious, in addition it is cast work
The size of skill parameter, such as speed, power can not be accurate, and causing to test every time can not repeat unanimously.Hydro-thermal method prepares nano-wire array,
Process conditions are harsh, at high cost, can only prepare small sample.
Therefore it provides a kind of orderly controllable dielectric composite material of ceramic nano line arrangement mode, not only has important
Industrial production value, and the research to nano wire in other fields has important scientific research directive significance.
Summary of the invention
The object of the present invention is to provide a kind of new dielectric composite materials.
For achieving the above object, the technical scheme adopted by the invention is that: a kind of dielectric composite material, the dielectric
Composite material is ceramic nano line/polymer composites, by percent by volume, in the dielectric composite material, and the ceramics
Nano wire accounting is 1%~10%, and the polymer accounting is 90%~99%；
The ceramic nano line carries out ordered arrangement in any direction in dielectric composite material.
Correspondingly, a kind of dielectric composite material, the dielectric composite material is made by the steps and obtains:
(1) ceramic nano line/polymer paste is prepared, by percent by volume, the ceramic nano line is 1%~10%,
The polymer is 90%~99%；The slurry is in shear thinning phenomenon in 0.1~100 1/s range of shear rate；
(2) bubble in the slurry is removed；
(3) slurry is squeezed out from the slurry extrusion device that discharge port bore is 10~200 μm, obtains characteristic line
Fluid, control discharge port motion profile make slurry form required structure to get dielectric composite material.
Preferably, step (1) the ceramic nano line is modified through fluoropolymer.
Preferably, it is the fluorine-containing crust type liquid crystal high score of different end group that the fluoropolymer, which is the fluoropolymer,
Son.
Preferably, the polymeric matrix is Kynoar and/or polyvinylidene fluoride copolymer.
Preferably, in step (2), the bubble in ultrasonic vibration removal slurry is used.
Preferably, step (3) slurry extrusion device is 3D printer.
Correspondingly, the dielectric of the method preparation of ceramic nano line orientation is compound in regulation composite material described in one kind
Material.
Preferably, the dielectric composite material be three-dimensional structure, each interlayer relative angle of three-dimensional structure be 0 °~
90°。
The invention has the following advantages:
1, the present invention aligns the ceramic nano line in slurry using 3D printing technique (3D direct write forming technique), and
Regulate and control the distribution arrangement of nano wire, and then provides a kind of dielectric composite material of high energy storage density.The present invention is at least two
A place realizes pioneering: firstly, the present invention is for the first time organically combined 3D printing technique and the arrangement of ceramic nano line,
Realize low cost, efficiently arranged ceramic nano line, and the dielectric composite material prepared can be compound by previous two-dimentional dielectric
Material membrane is extended to the composite construction of the three-dimensional dielectric composite material of arbitrary shape；Meanwhile previous method can only make ceramics receive
Rice noodles are arranged in parallel, and the present invention realizes the controllable of ceramic nano line direction arrangement for the first time, can according to need realization random angle
The arrangement of degree.
Dielectric composite material is prepared using traditional casting and spin-coating method, can not be arranged at all to nano wire；Make
, can only be after dielectric composite material be prepared with the method for existing other arranging nano-wires, such as pulling method, then drawn
It stretches, nano wire is made to carry out arrangement to a certain extent, it can not shape, thickness, flatness, size etc. to dielectric composite material
It control effectively, and nano wire can only also carry out the arrangement of some single direction (draw direction).
3D direct write forming technique is creatively applied in the preparation of ceramic/polymer composites by the present invention, not only may be used
To regulate and control the ordered arrangement direction of ceramic nano line in a polymer matrix, and it is opposite with the single arrangement direction of the past, it can
To realize any angle arrangement of nano wire in dielectric composite material, the shape of dielectric composite material can also be controlled, thickness, put down
The series of parameters such as whole degree, size are offered reference to be currently related to the Related Research Domain that nano wire aligns, it is also proposed that
A kind of new method preparing dielectric composite material.
2, when preparing slurry, ceramic nano line is easy to appear reunion, disperses the problems such as uneven, uses RAFT living polymerization
Method it is in situ fluorine-containing dressing agent is coated on barium titanate nano line surface, dispersion problem has been solved perfectly.
3, the present invention further defines the acceptability limit of slurry viscosity and bullet amount.In slurry preparation process, strict control is needed
Viscosity and elasticity modulus, viscosity is excessive, can not be successfully extrusion；The too small then elasticity modulus of viscosity is too small, and the lines of printing can not be protected
Hold it is cylindric, can to both sides trickle, be changed so as to cause the direction of nano wire, cannot achieve goal of the invention.Therefore, slurry
Formula and preparation method are most important.
Detailed description of the invention
Fig. 1 is the acceptability limit schematic diagram of slurry viscosity and bullet amount modulus；
Fig. 2 is to print dielectric composite material schematic diagram using technical solution of the present invention in laboratory；
Fig. 3 is that different angle arrangement printing dielectric composite material schematic diagram is carried out using technical solution of the present invention；
Fig. 4 is composite material contrast schematic diagram prepared by comparative example and embodiment.
Specific embodiment
Conventional ceramic nano wire (such as BaTiO3、TiO2、Pb(Zr1-xTix)O3、Ba1-xSrxTiO3、Pb(Mg1/3Nb2/3)O3-
PbTiO3、Na0.5Bi0.5TiO3Deng) method provided by the invention can be used to be arranged, nano wire after being arranged, and then make
The standby new dielectric composite material required for the present invention.
Concrete operation method of the invention are as follows: with the total amount of the ceramic nano line and polymer for 1, by volume basis
Than the ceramic nano line is 1%~10%；The polymer is 90%~99%.Because ceramic nano line and polymer are all
It is solid, therefore is configured to flowable slurry by medium of solvent.Specific method polymer can be added in solvent, dissolution
Afterwards, ceramic nano line is added, ultrasonic agitation is uniformly mixed and obtains suspension slurry；Solvent can also be added in ceramic nano line
In, ultrasonic agitation mixing adds polymer after being uniformly dispersed, then is uniformly mixed so as to obtain suspension slurry.The solvent be acetone and N,
Dinethylformamide is by the mixed solution, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide of the formation of any mixing ratio
Any one；The amount of the polymer is the 4~12% of solvent quality.As shown in Figure 1, the slurry viscosity finally prepared is qualified
Standard are as follows: be in significant shear thinning phenomenon in the range of shear rate of 0.1~100 (1/s).The shear thinning phenomenon:
Refer to that the viscosity of fluid reduces with the increase of shear rate or shear stress.
It, can be with fluoropolymer to ceramic nano line in order to improve the degree of scatter of ceramic nano line in the composite
It is modified.The fluoropolymer is the fluorine-containing Mesogen-jacketed Liquid Crystalline Polymers of different end group, is specifically as follows: polyvinyl pair
Phthalic acid two (to trifluoro-methoxy-phenol) ester, polyvinyl terephthalic two (to five fluorine methoxyl group phenol) ester, poly- second
(to the hexafluoro metoxyphenol) ester of alkenyl terephthalic acid (TPA) two and polyvinyl terephthalic two (to seven fluorine methoxyl group phenol)
One of ester.
As shown in Fig. 2, the slurry is fitted into barrel, the bubble in slurry is removed by modes such as ultrasounds.The packet
Include slurry extrusion device, the discharge port bore of the slurry extrusion device is 10~200 μm, practical bore can according to need into
Row adjustment.The barrel connects pressure apparatus, preferably air compressor, adjusts barrel internal pressure, by slurry from discharge port
It squeezes out, obtains characteristic line fluid, control discharge port motion profile to get sample, the sample is transferred in baking oven 80 DEG C
It is 24 hours dry, it removes solvent and so that sample is formed to get required dielectric composite material is arrived.
More optimal solution is directly to use 3D printer, the slurry is fitted into the feed bin of 3D printer, and adjustment 3D is beaten
The raw material discharge port bore of print machine is arranged the three-dimensional structure direct write program of control terminal, raw material is squeezed from discharge port to required bore
Out.X-Y axis is mobile according to the track of program setting, obtains first layer structure.Then, Z axis motor drives conveying device accurately
It is moved upwards up to the height that organization plan determines, the second formable layer will carry out in first layer structure, and can be by predetermined
Second layer print routine change upper and lower level ceramic nano line alignment angle (angle can be adjusted according to actual needs, 0 °
~90 °).And so on, the number of plies of needs is printed to get dielectric composite material.
As shown in figure 3, forming a film using 3D printer, the walking of discharge port can be more efficiently controlled by the way that program is arranged
Track, the orientation of the regular shape of dielectric composite material film and ceramic nano line needed for conveniently and efficiently obtaining.Moreover, making
Dielectric composite material film can be not only obtained with 3D printer, the dielectric that can also obtain various 3D shapes as needed is compound
Material can also control the angle between 3D shape different levels according to actual needs.
3D printer used herein is the model Desktop Robot DR-2200N's purchased from Nordson company
Machine.In real work, mobile accuracy >=200 μm of 3D printer can preferably reach goal of the invention.
Below to prepare completely new BaTiO3For/P (VDF-CTFE) dielectric composite material, pass through comparative example and embodiment
Further show the effect of this programme.
Comparative example: conventional method prepares BaTiO3/ P (VDF-CTFE) composite material
1, in-situ modification BaTiO3Nano wire
(1) by 10gBaTiO3Nano wire is dispersed in the H of 100ml 30wt%2O2Middle ultrasonic treatment 30min, then 105 DEG C
Oil bath return stirring 6h.After reaction, product is centrifugated, and with deionized water to BaTiO3Nano wire is washed,
It is then centrifuged, washs again again, repeating 2~3 times, then by BaTiO3Nano wire is placed in drying in 80 DEG C of vacuum oven and for 24 hours, obtains
To hydroxylated BaTiO3Nano wire (hereinafter referred to as: BT-OH).
(2) 10g BT-OH, ultrasonic vibration 30min are added in 100mlTHF.7.5g (3- is added under nitrogen protection again
Aminopropyl) dimethylethoxysilane (referred to as are as follows: r-APS), in N2Protect lower 80 DEG C of reactions for 24 hours.After reaction, to production
Object is centrifuged, and product obtained after separation is dispersed using THF, then is centrifuged, redisperse, repeats 2~3 times, then will
To product be dried in vacuo at 80 DEG C and obtain the BaTiO of surface amination for 24 hours3Nano wire is (hereinafter referred to as: BT-NH2)。
(3) by CPDB (1.6g, 5.7mmol), N, N'- Dicyclohexylcarbodiimide (1.2g, 5.8mmol), 2- sulfydryl thiophene
Oxazoline (0.74g, 6.2mmol), 4-dimethylaminopyridine (0.024g, 0.2mmol) and 10ml dry CH2Cl2It is added to list
In mouth bottle, reaction 12h is stirred at room temperature.After reaction, the liquid in single port bottle is filtered, collects filtrate and is steamed with rotation
It sends out instrument and removes solvent, obtained product is purified with column chromatography, collects the solution of RED sector, then use rotary evaporation
Instrument removes solvent, thus the CPDB activated, hereinafter referred to as CPDB-NHS.
(4) by 10g BT-NH2It is added in single port bottle, 50mlTHF solvent is added, be ultrasonically treated 30min with by BT-NH2
It is uniformly dispersed.1.8g CPDB-NHS is dissolved with 50mlTHF in advance, as RAFT reagent.By scattered BT-NH2With THF's
Mixed system is added drop-wise in the RAFT reagent, is stirred to react 12h at room temperature, product is centrifuged after reaction,
Product after separation is dispersed with THF again, then is centrifuged, redisperse repeats 2~3 times, then obtained product is true at 60 DEG C
Sky is dry for 24 hours, obtains the BaTiO of surface grafting CPDB3Nano wire (hereinafter referred to as: BT-CPDB).
(5) it is polymerize by RAFT, by the macromolecular grafted surface to BT-CPDB nano particle of fluorinated liquid crystal, detailed process
Are as follows: by BT-CPDB (1.3g), vinyl terephthalic acid (TPA) two (to trifluoro-methoxy-phenol) ester (TFMPCS) (0.523g,
1.3mmol), AIBN (2.6mg, 0.015mmol) and chlorobenzene (8.8g) are added sequentially in clean teat glass, then to examination
Pipe carries out pumping air-drum nitrogen circulation and operates five times, the air in test tube is excluded, finally under vacuum conditions with alcohol blast burner pair
Test tube carries out termination process, and test tube is then placed in in 80 DEG C of oil bath pan and is carried out magnetic agitation, and after reacting 6h, test tube is set
To terminate polymerization reaction in ice-water bath.Test tube is broken to admit air into, mixed solution is centrifuged after being diluted with 10mlTHF,
Obtained product THF is dispersed, then is centrifuged, is repeated 3 times.Finally products therefrom is placed in 60 DEG C of vacuum oven dry
For 24 hours, the BaTiO of PTFMPCS modification is obtained3Nano wire (hereinafter referred to as BT-6F).
2, BaTiO is prepared3/ P (VDF-CTFE) composite material
0.0635g, 0.0866g, 0.177g, 0.274g BT-6F are weighed respectively, are added to (nanometer in 12.5gDMF solvent
The volume accounting of line in the composite is respectively 1.5%, 2.5%, 5% and 7.5%), and ultrasonic disperse 10min is added
1.2gP (VDF-CTFE) resin, after ultrasonic disperse, ball milling two days, on the glass sheet by the casting of scattered suspension, using scraping
Knife is cast in one direction, at 80 DEG C forced air drying for 24 hours with vacuum drying for 24 hours, composite material film is obtained, then 160
DEG C, it is hot pressed into fine and close complexes membrane under 15MPa pressure condition, obtains four groups of composite materials not arranged, as a comparison case 1.Point
It is other that nano wire arrangement carried out using pulling method to four groups of comparative examples 1, as a comparison case 2.
Embodiment: this programme prepares BaTiO3/ P (VDF-CTFE) composite material
1, in-situ modification BaTiO in step 13The scheme of nano wire is identical as comparative example.Compared with comparative example, the present embodiment
Complexes membrane is prepared using 3D direct writing technology, the specific steps are as follows:
The BaTiO of 0.0635g, 0.0866g, 0.177g, 0.274gPTFMPCS modification is weighed respectively3Nano wire is added to
In 12.5gDMF solvent (the volume accounting of nano wire in the composite is respectively 1.5%, 2.5%, 5% and 7.5%), ultrasound
Disperse 10min, add 1.2gP (VDF-CTFE) resin, after ultrasonic disperse, ball milling two days, obtains finely dispersed suspension
Slurry, respectively as each group embodiment.
The slurry of each embodiment is transferred in barrel respectively, connection air compressor adjusts pressure, makes to be mounted on Z axis
Slurry extrusion device obtain characteristic line fluid, then be arranged control terminal three-dimensional structure direct write program.X-Y axis is according to program
The track of setting is mobile, obtains first layer structure.Then, Z axis motor drives conveying device to be moved to structure side exactly up
The height and angle that case determines, the second layer are molded in first layer structure and carry out, and obtain second layer structure.It can be according to practical need
It constantly to be constructed, the number of plies needed for obtaining and shape.In the present embodiment, for convenience of comparing, first layer structure is only prepared, by it
As each group embodiment composite material, performance comparison is carried out.
2, performance test: comparative example composite material and embodiment composite material are clipped in two pieces of metal mask plates respectively
Between, upper symmetrical gold electrode is sputtered using magnetic control sputtering device.Using Agilent 4294A precise impedance analyzer and ferroelectricity analyzer
Dielectric constant, dielectric loss, anti-breakdown electric field and the energy density of TF2000E characterization composite material film.
Wherein, (nano wire exists as shown in Figure 4 for comparative example 1 and the electron-microscope scanning figure of the composite material of embodiment preparation
5%) volume accounting in composite material is.Specific performance comparing result is as shown in table 1.
1 comparative example of table and the comparison of each embodiment composite property
Claims (10)
1. a kind of dielectric composite material, it is characterised in that: the dielectric composite material is ceramic nano line/polymer composite
Material, by percent by volume, in the dielectric composite material, the ceramic nano line accounting is 1%~10%, and the polymer accounts for
Than being 90%~99%；
The ceramic nano line carries out ordered arrangement in any direction in dielectric composite material.
2. a kind of dielectric composite material, it is characterised in that: the dielectric composite material is made by the steps and obtains:
(1) ceramic nano line/polymer paste is prepared, by percent by volume, the ceramic nano line is 1%~10%, described
Polymer is 90%~99%；The slurry is in shear thinning phenomenon in 0.1~100 1/s range of shear rate；
(2) bubble in the slurry is removed；
(3) slurry is squeezed out from the slurry extrusion device that discharge port bore is 10~200 μm, obtains characteristic line stream
Body, control discharge port motion profile make slurry form required structure to get dielectric composite material.
3. dielectric composite material according to claim 2, it is characterised in that: step (1) the ceramic nano line is through fluorine-containing
It is polymer-modified.
4. dielectric composite material according to claim 3, it is characterised in that: the fluoropolymer is that different end group is fluorine-containing
Mesogen-jacketed Liquid Crystalline Polymers.
5. dielectric composite material according to claim 2, it is characterised in that: the polymer is thermoplastic polymer.
6. dielectric composite material according to claim 6, it is characterised in that: the polymer be Kynoar and/or
Polyvinylidene fluoride copolymer.
7. dielectric composite material according to claim 2, it is characterised in that: the ceramic nano line includes BaTiO3、
TiO2、Pb(Zr1-xTix)O3、Ba1-xSrxTiO3、Pb(Mg1/3Nb2/3)O3-PbTiO3、Na0.5Bi0.5TiO3Ceramic nano line.
8. dielectric composite material according to claim 2, it is characterised in that: in step (2), removed and starched using ultrasonic vibration
Bubble in material.
9. dielectric composite material according to claim 2, it is characterised in that: step (3) slurry extrusion device is 3D
Printer.
10. dielectric composite material according to claim 9, it is characterised in that: the dielectric composite material is three-dimensional structure,
Each interlayer relative angle of three-dimensional structure is 0 °~90 °.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109291428A (en) * | 2018-09-29 | 2019-02-01 | 中南大学 | A kind of method of ceramic nano line orientation in regulation composite material |
| CN109626992A (en) * | 2019-02-15 | 2019-04-16 | 哈尔滨理工大学 | A kind of bismuth sodium titanate-barium titanate/polyimide-based dielectric composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751241A (en) * | 2016-11-21 | 2017-05-31 | 中南大学 | A kind of barium titanate/polymer composites, preparation method and application |
| CN106891524A (en) * | 2017-04-21 | 2017-06-27 | 吉林大学 | Fluid matrix middle short fiber NW-TFT 3D printing method and device |
| US20180036946A1 (en) * | 2016-08-04 | 2018-02-08 | The Regents Of The University Of Michigan | Fiber-reinforced 3d printing |
| CN108495877A (en) * | 2016-01-21 | 2018-09-04 | 3M创新有限公司 | Fluoropolymer-containing increasing material processing |
-
2018
- 2018-09-29 CN CN201811147071.9A patent/CN109306142B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108495877A (en) * | 2016-01-21 | 2018-09-04 | 3M创新有限公司 | Fluoropolymer-containing increasing material processing |
| US20180036946A1 (en) * | 2016-08-04 | 2018-02-08 | The Regents Of The University Of Michigan | Fiber-reinforced 3d printing |
| CN106751241A (en) * | 2016-11-21 | 2017-05-31 | 中南大学 | A kind of barium titanate/polymer composites, preparation method and application |
| CN106891524A (en) * | 2017-04-21 | 2017-06-27 | 吉林大学 | Fluid matrix middle short fiber NW-TFT 3D printing method and device |
Non-Patent Citations (4)
| Title |
|---|
| KUN QIAN等: ""Interfacial engineering tailoring the dielectric behavior and energy density of BaTiO3/P (VDF-TrFE-CTFE) nanocomposites by regulating a liquid-crystalline polymer modifier structure"", 《DALTON TRANS.》 * |
| PHATHARAPEETRANUN, N.等: ""3D printed barium titanate/poly-(vinylidene fluoride) nano-hybrid with anisotropic dielectric properties"", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| SAMPADA BODKHE等: ""One-Step Solvent Evaporation-Assisted 3D Printing of Piezoelectric PVDF Nanocomposite Structures"", 《ACS APPL. MATER. INTERFACES》 * |
| SHENG CHEN等: ""Significantly improved energy density of BaTiO3 nanocomposites by accurate interfacial tailoring using a novel rigid-fluoro-polymer"", 《POLYM. CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109291428A (en) * | 2018-09-29 | 2019-02-01 | 中南大学 | A kind of method of ceramic nano line orientation in regulation composite material |
| CN109291428B (en) * | 2018-09-29 | 2020-01-14 | 中南大学 | Method for regulating and controlling arrangement direction of ceramic nanowires in composite material |
| CN109626992A (en) * | 2019-02-15 | 2019-04-16 | 哈尔滨理工大学 | A kind of bismuth sodium titanate-barium titanate/polyimide-based dielectric composite material and preparation method thereof |
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