CN109627693A - A method of preparing completely new dielectric composite material - Google Patents
A method of preparing completely new dielectric composite material Download PDFInfo
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- CN109627693A CN109627693A CN201811567758.8A CN201811567758A CN109627693A CN 109627693 A CN109627693 A CN 109627693A CN 201811567758 A CN201811567758 A CN 201811567758A CN 109627693 A CN109627693 A CN 109627693A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
The invention belongs to dielectric composite material fields, and in particular to a method of prepare completely new dielectric composite material.The specific technical proposal is: can be obtained required dielectric composite material to freeze the layered porous ceramic structure of casting building oriented alignment, then the filled polymer into layered porous ceramic structure.The present invention creatively combines freezing casting with the preparation of dielectric composite material, simply and effectively obtains the material with orientation, stratiform and porous character.Since solvent multiplicity is optional in slurry configuration, this method is applicable to the material systems such as ceramics, metal;Technological parameter is simple simultaneously, and regulates and controls conveniently, it can be achieved that the porous laminated structure of highly directional degree.
Description
Technical field
The invention belongs to dielectric composite material fields, and in particular to a method of prepare completely new dielectric composite material.
Background technique
In recent years, conventional fossil fuel increasingly consume, environment it is continuous worsening, severe Energy situation has caused people to clear
Clean, renewable energy concern and attention.Solar battery, fuel cell, lithium battery, capacitor etc. are used as high-efficiency energy-storage device
As research hotspot.Wherein, capacitor is with its high power density, fast discharge rate, the advantage of low production cost, in smart grid
There is more importantly practical value with fields such as high energy weapons (laser gun, radar).But it is possible to the too low serious limitation of metric density
The development of high power capacitor.Therefore, its energy density and efficiency how are improved, for further developing and widening answering for it
With being of great significance.
Theoretically, the relative dielectric constant ε of material is improvedrWith disruptive field intensity E be obtain two of high-energy density it is important
Parameter.Ferroelectric ceramics such as BaTiO3, Pb (Zr1-xTix)O3(PZT)、Ba(Zr0.3TiO0.7)O3(BZT) etc., dielectric constant values are very
Greatly, it is even up to ten thousand to may achieve thousand, but its anti-breakdown electric field is very low;On the contrary, polymer have high anti-breakdown electric field, but its
Dielectric constant is typically less than ten.Therefore, ceramic/polymer dielectric composite material can have both high breakdown fields in conjunction with two-phase advantage
Strong and dielectric constant advantage, becomes one of the research hotspot of current dielectric material.
In two-phase composites, the distribution of ceramic phase in a polymer matrix has weight to the performance of composite material
The influence wanted.Document report, for the distribution of ceramic packing in the polymer, compared to random random distribution, filler
Grain present orderly, rule align, can more effectively improve the dielectric constant of compound under the same conditions.Currently,
Some research teams realize ceramic phase by different processes and align in a polymer matrix, so that composite material
Obtain higher dielectric constant and energy density.
As shown in Figure 1, researcherIt is prepared for using electrostatic spinning process by BaTiO3Nanofiber is handed over
Folded fiber hassock, then by epoxy resin blind, barium titanate/epoxy resin composite material is obtained, while discussing multiple
Influence of the fiber under different orientation (parallel/perpendicular to electrode surface) state to dielectric properties in condensation material.Its studies have shown that
Composite material is under identical ceramic packing ratio (2vol%), BaTiO3The dielectric for being oriented perpendicularly to obtain under electrode mode of fiber
Constant is 11.4, is twice under parallel model.But use this technique, BaTiO3Colloidal sol carries out injection spinning in strong electrical field
Silk, the nanofiber of formation is easy diverging when being scattered in collection device, so that the nanofiber inside fiber hassock is alternately superimposed,
Orientation is difficult to completely the same;Meanwhile can not accomplish complete densification using the gap in resin fiberfill fibers hassock,
Influence composite properties.
As shown in Fig. 2, Central China University of Science and Technology Jiang Shenglin professor team is prepared for BaTiO using the tape casting3Nano wire orientation
The compound of arrangement, obtaining dielectric constant is 19, and energy storage density is achieved at lower electric field (240kV/mm) and substantially mentioned
Height (10.8J/cm3).But the technique is very coarse, and the shearing force by scraping diaphragm plate is orientated nano wire, and effect is small, and is flowing
The thickness direction active force of body is different, so the effect that nano wire is orientated is not obvious, in addition casting technique parameter, such as fast
Degree, size of power etc. can not be accurate, and causing to test every time can not repeat unanimously.
As shown in figure 3, Tongji University Zhai Jiwei professor team passes through two one-step hydrothermals synthesis height (110) orientation
BaTiO3The BaTiO that nano-wire array is mutually prepared as filling3/ PVDF compound, dielectric constant is increased to 23, in 320kV/mm
Under electric field, acquisition energy density is 11.82J/cm3.But the method process conditions are harsh, at high cost, can only prepare small sample,
An and low output, it is difficult to realize mass production.
As shown in figure 4, Zarel Valdez-Nava et al. is in BaTiO3It is applied in/epoxy resin composite mortar solidification process
Add anisotropic dielectrophoresis, ion and/or electron-transport are increased by the particle chain of alignment, realize that compound dielectric is normal
Several raisings.But the method is only applicable to the lower material of dielectric constant stress in non-uniform electric field and changes, for dielectric
The high BaTiO of constant3For equal ferroelectric ceramic grains, degree is lower, and effect is paid no attention to for aligning of being generated by electric field force
Think.
It can be seen that the distributional pattern of regulation ceramic packing in the composite is not change ceramic systems and increasing filling
One of the effective way of compound energy density is improved under conditions of amount.But the method for regulation ceramic packing distributional pattern is equal at present
There are many defects, urgent need provide it is a kind of it is reliable and stable, repeatable it is strong, can be mass, and ceramic packing is evenly distributed
The method for preparing dielectric composite material.
Summary of the invention
The object of the present invention is to provide plant it is reliable and stable, repeatable it is strong, can be mass, and ceramic packing is evenly distributed
The method for preparing dielectric composite material.
For achieving the above object, the technical scheme adopted by the invention is that: a kind of side preparing dielectric composite material
Method to freeze the layered porous ceramic structure of casting building oriented alignment, then is filled into layered porous ceramic structure
Polymer, dielectric composite material needed for obtaining.
Preferably, the method for layered porous ceramic structure is constructed are as follows:
(1) slurry that 10vol%~30vol% is prepared using ceramic powder and liquid medium, after being defoamed to slurry,
Freezing conditions are set further according to the direction of required arrangement, ice crystal oriented growth freezing processing is carried out to the slurry;
(2) liquid medium in freeze-drying removal slurry, obtains layered porous ceramic green;
(3) degreasing, sintering processes are successively carried out to layered porous ceramics green compact, layered porous ceramic junction needed for obtaining
Structure.
Preferably, the slurry is prepared by ceramic powder, deionized water, further includes making ceramic powder in the slurry
Be uniformly dispersed necessary dispersing agent.
Preferably, the setting method of step (1) described freezing conditions are as follows: the origin temp of ice-crystal growth is lower than ice-crystal growth
Outlet temperature.
Preferably, step (2) the freeze-drying condition are as follows: the freeze-drying temperature of the temperature differences such as several is set, each
Same time is handled at a temperature of freeze-drying respectively.
Preferably, the method for the filled polymer are as follows: under vacuum environment, layered porous ceramic structure is immersed in
In polymer, after keeping 3~15min, then cancel vacuum state;It vacuum, non-vacuum alternately 3~7 times, has filled
At.
Preferably, the ceramic/polymer dielectric composite material that the filling is completed is placed in vacuum and keeps at least 12h,
It is kept at 80 DEG C again at least for 24 hours.
Preferably, one of described ceramics predominantly oxide ceramics, ferroelectric ceramics and biomimetic material ceramics, and/or,
The polymer be mainly dimethyl silicone polymer, Kynoar, polyimides, polystyrene, polypropylene, in epoxy resin
One kind.
Preferably, the ceramics are barium titanate, and the polymer is epoxy resin.
Preferably, include the following steps:
(1) deionized water, BaTiO are weighed3Powder and BaTiO3BaTiO is prepared in the dispersing agent of powder 1wt%, mixing3Body
Product is than the slurry for 10vol%~30vol%;After ball milling dispersion, BaTiO is added in the slurry3The bonding of powder 1wt%
Agent solution mixes slowly at least 12h;Defoaming agent is added in resulting slurry again, carries out defoaming treatment under vacuum conditions;
(2) slurry obtained by step (1) is oriented freezing processing, 25 DEG C/min of freezing rate, cooling time 7min coagulate
Gu after process, taking out frost green compact;
Freeze-drying condition: vacuum environment is set, by frost green compact respectively in -55 DEG C, -45 DEG C, -35 DEG C, -25 DEG C, -15
DEG C, -5 DEG C, 5 DEG C, 15 DEG C, each dry 2h at 25 DEG C, obtain BaTiO3Layered porous green compact;By the BaTiO3Layered porous life
Base ungrease treatment 3h at 600 DEG C, then be sintered in 1250 DEG C of heat preservation 3h, obtain BaTiO3Layered porous ceramic structure;
(3) by the BaTiO3Layered porous ceramic structure is immersed in epoxy resin, keeps 3~15min in a vacuum
Afterwards, then cancel vacuum state;Vacuum, non-vacuum alternately 3~7 times, filling is completed, then it is protected under vacuum conditions
Lower 12h or more is held, is solidified more than for 24 hours under the conditions of 80 DEG C to get required barium titanate/resin dielectric composite material.
The invention has the following advantages: the present invention will creatively freeze the preparation of casting and dielectric composite material
Combine.In low temperature orientation temperature, crystallization and freezing, solvent are carried out along temperature gradient ceramic slurry in cooling procedure off field
Oriented growth, while pushing ceramic particle, resetting ceramic particle aggregation.By the green body of gained certain shapes after solidification
It is dried through low pressure, solvent therein is discharged in sublimation process, the green compact using solvent as template is left, most afterwards through being sintered
Up to the material with orientation, stratiform and porous character.Since solvent multiplicity is optional in slurry configuration, this method is applicable to
The material systems such as ceramics, metal;Technological parameter is simple simultaneously, and regulates and controls conveniently, it can be achieved that the porous laminated structure of highly directional degree.
Detailed description of the invention
Fig. 1 is that electrostatic spinning process prepares BaTiO3Align the artwork of compound;
Fig. 2 is that the tape casting prepares BaTiO3Align the artwork of compound;
Fig. 3 is that hydro-thermal method prepares BaTiO3Align the artwork of compound;
Fig. 4 is that dielectrophoresis method prepares BaTiO3Align the artwork of compound;
Fig. 5 is the schematic diagram for freezing casting and preparing orienting stephanoporate material;
Fig. 6 is dielectric composite material pictorial diagram prepared by group of the embodiment of the present invention 3;
Fig. 7 is the dielectric composite material electron-microscope scanning figure of various embodiments of the present invention preparation;
Fig. 8 is the dielectric composite material electron-microscope scanning figure of comparative example preparation.
Specific embodiment
Preparation method provided by the present application is suitable for preparing ceramic/polymer dielectric based on multiple material system multiple
Condensation material.Wherein, the optional type of the ceramics is a variety of, can be with are as follows: oxide ceramics such as ZrO2,Al2O3,SiO2,TiO2,
Nb2O5Deng;Including ferroelectric ceramics such as Pb (Zr, Ti) O3、BaTiO3、SrTiO3、(Ba,Sr)TiO3、PbTiO3、PbZrO3、(Na,
Bi)TiO3、(K,Na)NbO3、Ba(Zr,Ti)O3Any one in;It can also be the bionical materials such as hydroxyapatite, chitosan
Any one in material.The optional type of the polymer be also it is a variety of, can for dimethyl silicone polymer, Kynoar,
Any one in polyimides, polystyrene, polypropylene, epoxy resin etc..In actual operation, it is selected according to required
?.
For convenience of operation, following example is prepared by taking barium titanate/epoxy resin dielectric composite material as an example.
Embodiment
As shown in figure 5, including the following steps:
(1) barium titanate slurry is prepared.Weigh a certain amount of deionized water, BaTiO3Powder and BaTiO3Point of powder 1wt%
Powder, mixing, prepares BaTiO respectively3Volume ratio is respectively three groups of slurries of 10vol%, 20vol%, 30vol%.Ball milling 24
After hour, BaTiO is added in above-mentioned slurry3The binder solution of powder 1wt% mixes slowly at least 12 hours.With laggard
Row defoaming treatment: being added a few drop defoaming agents in resulting slurry, is uniformly mixed and is put into vacuum oven and vacuumizes.It is described
The dosage of defoaming agent is BaTiO3The 0.1% of powder quality.
The defoaming agent is the defoaming agents such as alcohols, esters, such as methanol, ethylene glycol, isopropanol, sec-butyl alcohol, n-octyl alcohol, phosphoric acid
Tributyl etc., for convenience of operating, the present embodiment is n-butanol.
The dispersing agent is phosphate, salt of phosphoric acid, aromatic sulfonic acid, ammonium polyacrylate etc., for convenience of operating, following embodiments
Use ammonium polyacrylate;The binder is polyethylene, polyvinyl alcohol, polyacrylate, polyvinyl butyral, ethyl cellulose
Element etc., for convenience of operating, the polyvinyl alcohol (hereinafter referred to as PVA) of the present embodiment.
(2) barium titanate stratiform porous ceramic structure is prepared.By above-mentioned three groups be uniformly mixed and defoaming treatment after BaTiO3
Slurry is poured into respectively in the silica gel mould of 2 × 2 × 0.5cm, is placed on freezing casting equipment and is carried out refrigeration processing, and design makes ice crystal
The gradient temperature field of crystalline growth since bottom is toward top, and in particular to method are as follows: bottom cold end (colder plate) temperature
It is low to spend end cooler than the top (cold plate), setting 5~25 DEG C/min of freezing rate (preferably 25 DEG C/min), cooling time 5~
30min (preferably 7min).After process of setting, the frost green compact that are taken out after demoulding from freezing casting equipment.
Freeze-drying condition is arranged: multiple temperature gradients are arranged at -60 DEG C~25 DEG C in (≤10Pa) under vacuum condition
It is dried, amounts to dry 24~40h.The freeze-drying condition of the present embodiment are as follows: respectively in -55 DEG C, -45 DEG C, -35 DEG C, -25
DEG C, -15 DEG C, -5 DEG C, 5 DEG C, 15 DEG C, each 3~4h of drying at 25 DEG C, obtain BaTiO3Layered porous green compact.It carries out at degreasing again
Reason: the green compact are handled into 3h at 600 DEG C.It is sintered again in 1250 DEG C of heat preservation 3h, obtains three groups of BaTiO3It is layered porous
Ceramic structure.
(3) barium titanate/resin dielectric composite material is prepared
By the A/B component of Araldite2020 epoxy resin according to mass ratio, A:B=10:1.5's is uniformly mixed, then will
BaTiO3Layered porous ceramic structure submergence is wherein.It is evacuated to 0.1MPa in a vacuum drying oven, keeps 15min, then cancel
Vacuum state then vacuumizes again;By layered porous ceramic structure in the state of being immersed in epoxy resin, repeat true
It is operation 3~7 times empty, cancelling vacuum, to achieve the purpose that resin is fine and close in the porous middle filling of porous ceramics.Filling is completed
Afterwards, 12h or more under it being kept under room temperature, vacuum condition;Again 80 DEG C, be communicated with the atmosphere, solidification is above to get three for 24 hours
Barium titanate/resin dielectric composite material needed for group.The dielectric composite material of preparation is machined as needed.
For convenience of comparison, above-mentioned three groups of dielectric composite materials are cut into flakiness along parallel, vertical freezing direction respectively, then
Being thinned to thickness is about 1mm, is then clipped in respectively among two pieces of metal mask plates, sputters upper symmetrical gold using magnetic control sputtering device
Electrode.Dielectric using Agilent 4294A precise impedance analyzer and ferroelectricity analyzer TF2000E characterization dielectric composite material is normal
Number, dielectric loss, anti-breakdown electric field and energy density;The results are shown in Table 1.Embodiment group 3 prepare sample (test electric field with
It is parallel to freeze direction) as shown in fig. 6, wherein the dot on compound is gold electrode.The electron-microscope scanning figure of embodiment group 1~3 is such as
(group 1~3 is from left to right respectively corresponded) shown in Fig. 7.
Comparative example
By BaTiO3Powder is that 10vol%, 20vol%, 30vol% are dispersed in Araldite2020 epoxy according to volume ratio
In Resin A/B component mass ratio 10:1.5 hybrid resin, after stirring 0.5h, thickness is scraped on smooth and clean substrate with scraper
Degree is the film of 1mm or so, and sample is kept to lower 12h under vacuum conditions, solidifies for 24 hours under the conditions of 80 DEG C, obtains three groups of comparisons
The dielectric composite material of example.Using method identical with embodiment, its dielectric constant, dielectric loss, anti-breakdown potential are tested respectively
Field and energy density;The results are shown in Table 1.The electron-microscope scanning figure of comparative example group 2 is as shown in Figure 8.
1 each group dielectric composite material performance of table shows table
Claims (10)
1. a kind of method for preparing dielectric composite material, it is characterised in that: more with the stratiform for freezing casting building oriented alignment
Hole ceramic structure, then the filled polymer into layered porous ceramic structure, that is, dielectric composite material needed for obtaining.
2. the method according to claim 1 for preparing dielectric composite material, it is characterised in that: the layered porous pottery of building
The method of porcelain structure are as follows:
(1) slurry that 10vol%~30vol% is prepared using ceramic powder and liquid medium, after being defoamed to slurry, then root
Freezing conditions are set according to the direction of required arrangement, ice crystal oriented growth freezing processing is carried out to the slurry;
(2) liquid medium in freeze-drying removal slurry, obtains layered porous ceramic green;
(3) degreasing, sintering processes are successively carried out to layered porous ceramics green compact, layered porous ceramic structure needed for obtaining.
3. the method according to claim 2 for preparing dielectric composite material, it is characterised in that: the slurry is by ceramic powder
It is prepared with water, further includes that ceramic powder is made to be uniformly dispersed necessary dispersing agent in the slurry.
4. the method according to claim 2 for preparing dielectric composite material, it is characterised in that: step (1) the freezing item
The setting method of part are as follows: the origin temp of ice-crystal growth is lower than the outlet temperature of ice-crystal growth.
5. the method according to claim 2 for preparing dielectric composite material, it is characterised in that: step (2) freezing is dry
Dry condition are as follows: the freeze-drying temperature of the temperature differences such as several is set, handles same time respectively at a temperature of each freeze-drying.
6. the method according to claim 1 for preparing dielectric composite material, it is characterised in that: the side of the filled polymer
Method are as follows: under vacuum environment, layered porous ceramic structure is immersed in polymer, after keeping 3~15min, then is cancelled true
Dummy status;Vacuum, non-vacuum alternately 3~7 times, filling is completed.
7. the method according to claim 6 for preparing dielectric composite material, it is characterised in that: the pottery for completing the filling
Porcelain/Polymeric dielectric composite material, which is placed in vacuum, keeps at least 12h, then keeps at least for 24 hours at 80 DEG C.
8. the method for dielectric composite material is prepared described in any one according to claim 1~7, it is characterised in that: the pottery
Porcelain is mainly any one in oxide ceramics, ferroelectric ceramics and biomimetic material ceramics, and/or, the polymer is mainly
Dimethyl silicone polymer, Kynoar, polyimides, polystyrene, polypropylene, any one in epoxy resin.
9. the method for dielectric composite material is prepared described in any one according to claim 1~7, it is characterised in that: the pottery
Porcelain is barium titanate, and the polymer is epoxy resin.
10. the method according to claim 9 for preparing dielectric composite material, characterized by the following steps:
(1) deionized water, BaTiO are weighed3Powder and BaTiO3BaTiO is prepared in the dispersing agent of powder 1wt%, mixing3Volume ratio
For the slurry of 10vol%~30vol%;After ball milling dispersion, BaTiO is added in the slurry3The binder of powder 1wt% is molten
Liquid mixes slowly at least 12h;Defoaming agent is added in resulting slurry again, carries out defoaming treatment under vacuum conditions;
(2) slurry obtained by step (1) is oriented freezing processing, 25 DEG C/min of freezing rate, cooling time 7min solidified
After journey, frost green compact are taken out;
Be arranged freeze-drying condition: vacuum environment, will frost green compact respectively -55 DEG C, -45 DEG C, -35 DEG C, -25 DEG C, -15 DEG C, -
Each 3~4h of drying, obtains BaTiO at 5 DEG C, 5 DEG C, 15 DEG C, 25 DEG C3Layered porous green compact;By the BaTiO3Layered porous green compact
The ungrease treatment 3h at 600 DEG C, then be sintered in 1250 DEG C of heat preservation 3h, obtain BaTiO3Layered porous ceramic structure;
(3) by the BaTiO3Layered porous ceramic structure is immersed in epoxy resin, after keeping 3~15min in a vacuum, then
Cancel vacuum state;Vacuum, non-vacuum alternately 3~7 times, filling is completed, then under it is kept under vacuum conditions
12h or more solidifies more than for 24 hours under the conditions of 80 DEG C to get required barium titanate/resin dielectric composite material.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110964294A (en) * | 2019-12-02 | 2020-04-07 | 江苏科技大学 | Epoxy resin-based high-dielectric composite material, preparation method and application |
CN113320061A (en) * | 2021-05-19 | 2021-08-31 | 华中科技大学 | Flexible piezoelectric composite material with high damping performance and preparation method thereof |
CN113999427A (en) * | 2021-11-23 | 2022-02-01 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of barium titanate dielectric composite material |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20160251271A1 (en) * | 2008-11-07 | 2016-09-01 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Ceramic lamellar composites |
CN108585921A (en) * | 2018-06-14 | 2018-09-28 | 哈尔滨工业大学 | A method of it is cast based on freezing and prepares Functional Graded Ceramics/resin composite materials |
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2018
- 2018-12-21 CN CN201811567758.8A patent/CN109627693A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20160251271A1 (en) * | 2008-11-07 | 2016-09-01 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Ceramic lamellar composites |
CN108585921A (en) * | 2018-06-14 | 2018-09-28 | 哈尔滨工业大学 | A method of it is cast based on freezing and prepares Functional Graded Ceramics/resin composite materials |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110964294A (en) * | 2019-12-02 | 2020-04-07 | 江苏科技大学 | Epoxy resin-based high-dielectric composite material, preparation method and application |
CN113320061A (en) * | 2021-05-19 | 2021-08-31 | 华中科技大学 | Flexible piezoelectric composite material with high damping performance and preparation method thereof |
CN113999427A (en) * | 2021-11-23 | 2022-02-01 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of barium titanate dielectric composite material |
CN113999427B (en) * | 2021-11-23 | 2022-12-06 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of barium titanate dielectric composite material |
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