CN109957194A - A kind of laminated film and preparation method thereof - Google Patents
A kind of laminated film and preparation method thereof Download PDFInfo
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- CN109957194A CN109957194A CN201711336734.7A CN201711336734A CN109957194A CN 109957194 A CN109957194 A CN 109957194A CN 201711336734 A CN201711336734 A CN 201711336734A CN 109957194 A CN109957194 A CN 109957194A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention discloses a kind of laminated films and preparation method thereof, including nano-ceramic particle filler and polymeric matrix, the nano-ceramic particle filler includes basis material and doped chemical, and the mass percent that the content of the doped chemical accounts for the nano-ceramic particle filler is no more than 1%.In unleaded laminated film of the invention, high dielectric electric card performance, the high breakdown strength of polymer and good workability, the small light and thin of film and its flexibility of nano ceramics are had both, production method is simple, and practicability is stronger.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of laminated film and preparation method thereof.
Background technique
Currently, power equipment and electronic device etc. just develop towards the directions such as high-power, miniaturization and lightweight, to exhausted
The performance of edge material and functional dielectrics material proposes requirements at the higher level, and film is since it has the characteristics that miniaturization,
Relatively meet the development of hyundai electronics component.
The variation of the additional field strength of electric card material use increases to excite the Entropy Changes for generating phase transformation and dipole in vivo by entropy
Heat absorption is to achieve the effect that refrigeration.Based on unleaded electric card material solid state refrigerator film, without using having to external environment
The refrigerants such as the freon of serious harm, and possess comparatively ideal refrigerating efficiency.The application of electric card material is to realize high-efficiency environment friendly
The important channel of refrigerator, the development for the following solid-state integrated refrigerating technology lay a good foundation.
Electric card material is divided into inorganic ceramic electric card material and organic polymer electric card material.Inorganic ceramic electric card material has
Higher electric card performance, but disruptive field intensity is lower, does not have flexibility, and organic polymer electric card material needs larger extra electric field just may be used
To reach higher electric card performance, but its processing performance is good.
2014, Zhengdong Luo [Appl.Phys.Lett.105,102904 (2014)] et al. announce Ba (Ti,
Sn)O3The change of ceramic material electric card temperature has reached 0.61K.2016, and Jianting Li [Appl.Phys.Lett.109,162902
Et al. (2016)] (Na, K) (Nb, the Sb) O announced3The change of ceramic material electric card temperature reaches 0.41K.Single electric card material is still not
It is able to satisfy the requirement of integrated refrigerating technology, also fails to reach small light and thin flexibility.
In conclusion single electric card material is difficult to obtain higher dielectric constant and electric card performance, by polymer
Adding high dielectric constant particles in matrix and forming composite material is a kind of more effective mode of current promotion electric card performance.Gao Jie
Charged particle such as nano-ceramic particle can be improved dielectric constant and the polarization of composite material, and then promote the Entropy Changes of electric card material
Become with temperature, promotes its refrigeration effect.Ceramic material, which makees electric card material, at present there is no preferably specific raising dielectric and electric card performance
Solution, the complexity for processing preparation is larger, and the raising of performance needs further to be researched and developed.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of laminated films, including nano-ceramic particle filler
And polymeric matrix, the nano-ceramic particle filler include basis material and doped chemical, the content of the doped chemical accounts for
The mass percent of the nano-ceramic particle filler is no more than 1%.
Preferably, described matrix material is BaTiO3、SrTiO3、BaZnO3、BaSnO3、(Ba,Sr)TiO3、(Ba,Ca)
TiO3With Ba (Ti, Zn) O3At least one of.
Preferably, the doped chemical is any one in Sc, Y, Cr, Fe, Co, Ga, Sb, Nb and Mo or at least two
Combination.
Preferably, the polymeric matrix is fluoropolymer.
Preferably, the fluoropolymer is PVDF, P (E-TFE), P (VDF-HFP), P (VDF-TrFE), P (VDF-
CTFE), at least one of P (VDF-TrFE-CTFE) and P (VDF-TrFE-CFE).
Preferably, the mass percent that the content of the nano-ceramic particle filler accounts for the laminated film is no more than
30%.
The present invention also provides a kind of production methods of laminated film, include the following steps:
S1, it will be dried after basis material powder and doped chemical mixed grinding, obtain mixed-powder；Wherein, the doping
The content of element accounts for described matrix material powder and the mass percent of doped chemical summation is no more than 1%；
S2, the mixed-powder is added in ball grinder, using dehydrated alcohol or deionized water as medium, zirconium oxide is added
Ball carries out ball milling mixing, obtains slurry；
S3, the slurry is dried, is ground up, sieved, obtaining the first powder；
S4, calcining first powder, then keep the temperature, obtain ceramic powders；
S5, the ceramic powders are added in ball grinder, zirconia ball is added and carries out ball milling mixing, obtains the second powder
End；
S6, second powder and polymeric matrix powder are added to N,N-dimethylformamide or third with setting ratio
In ketone solvent, magnetic agitation and ultrasonication are then carried out, mixing liquid is obtained；
S7, the mixing liquid is cast on substrate and is dried, then made annealing treatment, obtain the laminated film.
Preferably, in step s3, the temperature of drying is 70 DEG C~100 DEG C.
Preferably, in step s 4, the temperature of calcining is 800 DEG C~1100 DEG C.
Preferably, in the step s 7, the temperature of drying is 70 DEG C~110 DEG C, and the temperature of annealing is 110 DEG C~130
℃。
The utility model has the advantages that
In unleaded laminated film of the invention, the high dielectric electric card performance of nano ceramics, the high breakdown of polymer are had both
Intensity and good workability, the small light and thin of film and its flexibility, production method is simple, and practicability is stronger.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples, in attached drawing:
Fig. 1 is the nano-ceramic particle filler SEM figure that doping type is prepared in the embodiment of the present invention 1；
Fig. 2 is the flow chart of the production method of the laminated film of the embodiment of the present invention 1.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
A kind of production method of laminated film, includes the following steps:
S10, doped nano ceramic particle filler is prepared
S101,15.11g BaTiO is taken3、6.403g SrTiO3With 0.03387g Y2O3, grinding is uniform, is put into 70 DEG C of bakings
Case drying sieving, obtains mixed-powder.
S102, the mixed-powder is added in ball grinder again, ethanol medium and yttrium stable zirconium oxide ball (wherein second is added
The amount of alcohol medium there was not powder and zirconia ball), place into planetary ball mill ball milling for 24 hours.Take out the slurry in ball grinder
It is dried in 80 DEG C of baking ovens, is ground up, sieved to obtain powder.
S103, later again step S102 obtain mixed-powder be put among alumina crucible, in Muffle furnace
It is calcined at a temperature of 1000 DEG C, keeps the temperature 6h.Second of ball milling is carried out after taking-up, it is current not have to add medium, subtract powder particle
It is small, it is taken out after ball milling and obtains the nano-ceramic particle filler of doping type.
S20, to prepare unleaded composite membrane thin
S201, the above-mentioned nano-ceramic particle filler 0.0222g for taking step S103 to obtain take P (VDF-TrFE-CFE) poly-
Close object powder 0.2g.First nano-ceramic particle filler is poured into 4mL n,N-Dimethylformamide, is obtained using ultrasonic treatment 6h
To emulsion.
S202, polymer powder poured into above-mentioned emulsion again, magnetic agitation 12h, then carries out ultrasonic treatment 6h, obtained
The mixing liquid of homogeneous distribution.
S203, transparency glass plate is taken on a glass by the casting of above-mentioned mixing liquid to do in 90 DEG C of baking ovens as substrate
Dry 12h, to form film on a glass.
S204, it takes the film off from glass plate, then to film drying 12h in 80 DEG C of baking ovens, removes extra molten
Agent.
S205, the film is finally put in 105 DEG C of annealing 12h, unleaded laminated film obtained, with a thickness of 10 μm~15
μm。
Embodiment 2
The present embodiment 2 and the difference of embodiment 1 are only in that: in step s101, taking 15.11g BaTiO3、6.403g
SrTiO3With 0.06774g Y2O3, grinding is uniform, is put into 70 DEG C of baking ovens drying sievings, obtains mixed-powder.
Embodiment 3
The present embodiment 3 and the difference of embodiment 1 are only in that: in step s101, taking 15.11g BaTiO3、6.403g
SrTiO3With 0.1016g Y2O3, grinding is uniform, is put into 70 DEG C of baking ovens drying sievings, obtains mixed-powder.
Embodiment 4
The present embodiment 4 and the difference of embodiment 1 are only in that: in step s 103, Muffle furnace calcination temperature is 800 DEG C.
Embodiment 5
The present embodiment 5 and the difference of embodiment 1 are only in that: in step s 103, Muffle furnace calcination temperature is 900 DEG C.
Embodiment 6
The present embodiment 6 and the difference of embodiment 1 are only in that: in step s 103, in tube furnace rather than in Muffle
Furnace calcining.
Embodiment 7
The present embodiment 7 and the difference of embodiment 1 are only in that: in step s 201, taking nano-ceramic particle filler
0.0151g is poured into 4mL n,N-Dimethylformamide, obtains emulsion using ultrasonic treatment 12h.
Embodiment 8
The present embodiment 8 and the difference of embodiment 1 are only in that: in step s 201, taking nano-ceramic particle filler
0.0105g is poured into 4mL n,N-Dimethylformamide, obtains emulsion using ultrasonic treatment 12h.
Embodiment 9
The present embodiment 9 and the difference of embodiment 1 are only in that: in step s 201, taking nano-ceramic particle filler
0.0062g is poured into 4mL n,N-Dimethylformamide, obtains emulsion using ultrasonic treatment 12h.
Claims (10)
1. a kind of laminated film, characterized in that including nano-ceramic particle filler and polymeric matrix, the nano-ceramic particle
Filler includes basis material and doped chemical, and the content of the doped chemical accounts for the quality percentage of the nano-ceramic particle filler
Number is no more than 1%.
2. laminated film as described in claim 1, characterized in that described matrix material is BaTiO3、SrTiO3、BaZnO3、
BaSnO3、(Ba,Sr)TiO3、(Ba,Ca)TiO3With Ba (Ti, Zn) O3At least one of.
3. laminated film as described in claim 1, characterized in that the doped chemical is Sc, Y, Cr, Fe, Co, Ga, Sb, Nb
With in Mo any one or at least two combination.
4. laminated film as described in claim 1, characterized in that the polymeric matrix is fluoropolymer.
5. laminated film as claimed in claim 4, characterized in that the fluoropolymer is PVDF, P (E-TFE), P (VDF-
HFP), at least one of P (VDF-TrFE), P (VDF-CTFE), P (VDF-TrFE-CTFE) and P (VDF-TrFE-CFE).
6. laminated film as described in claim 1, characterized in that the content of the nano-ceramic particle filler accounts for described compound
The mass percent of film is no more than 30%.
7. a kind of production method of laminated film, characterized in that include the following steps:
S1, it will be dried after basis material powder and doped chemical mixed grinding, obtain mixed-powder；Wherein, the doped chemical
Content account for the mass percent of described matrix material powder and doped chemical summation and be no more than 1%；
S2, the mixed-powder is added in ball grinder, using dehydrated alcohol or deionized water as medium, be added zirconia ball into
Row ball milling mixing, obtains slurry；
S3, the slurry is dried, is ground up, sieved, obtaining the first powder；
S4, calcining first powder, then keep the temperature, obtain ceramic powders；
S5, the ceramic powders are added in ball grinder, zirconia ball is added and carries out ball milling mixing, obtains the second powder；
S6, by second powder and polymeric matrix powder is added to N,N-dimethylformamide with setting ratio or acetone is molten
In agent, magnetic agitation and ultrasonication are then carried out, mixing liquid is obtained；
S7, the mixing liquid is cast on substrate and is dried, then made annealing treatment, obtain the laminated film.
8. production method as claimed in claim 7, characterized in that in step s3, the temperature of drying is 70 DEG C~100 DEG C.
9. production method as claimed in claim 7, characterized in that in step s 4, the temperature of calcining is 800 DEG C~1100
℃。
10. production method as claimed in claim 7, characterized in that in the step s 7, the temperature of drying is 70 DEG C~110 DEG C,
The temperature of annealing is 110 DEG C~130 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233047A (en) * | 2019-07-03 | 2019-09-13 | 华中科技大学 | A kind of preparation method of high energy storage density dielectric substance |
| CN115057701A (en) * | 2022-06-09 | 2022-09-16 | 哈尔滨工业大学 | Composite film material with room-temperature large electrocaloric effect and preparation method thereof |
| WO2023050639A1 (en) * | 2021-09-29 | 2023-04-06 | 墨现科技(东莞)有限公司 | Piezoresistive film and preparation method therefor and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040159835A1 (en) * | 2001-08-13 | 2004-08-19 | Krieger Juri Heinrich | Memory device |
| CN101503293A (en) * | 2009-03-06 | 2009-08-12 | 湖北大学 | Barium strontium titanate doped high dielectric property ferroelectric ceramic material and preparation thereof |
| CN104985896A (en) * | 2015-06-26 | 2015-10-21 | 广东工业大学 | Ceramic/polymer composite with high dielectric constant and preparation method thereof |
-
2017
- 2017-12-14 CN CN201711336734.7A patent/CN109957194A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040159835A1 (en) * | 2001-08-13 | 2004-08-19 | Krieger Juri Heinrich | Memory device |
| CN101503293A (en) * | 2009-03-06 | 2009-08-12 | 湖北大学 | Barium strontium titanate doped high dielectric property ferroelectric ceramic material and preparation thereof |
| CN104985896A (en) * | 2015-06-26 | 2015-10-21 | 广东工业大学 | Ceramic/polymer composite with high dielectric constant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 黄新友等: "稀土氧化物在(Ba,Sr)TiO3基陶瓷材料中的应用", 《现代技术陶瓷》 * |
| 黄良等: "无机颗粒填充聚合物复合材料的介电性能研究", 《材料导报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233047A (en) * | 2019-07-03 | 2019-09-13 | 华中科技大学 | A kind of preparation method of high energy storage density dielectric substance |
| WO2023050639A1 (en) * | 2021-09-29 | 2023-04-06 | 墨现科技(东莞)有限公司 | Piezoresistive film and preparation method therefor and application thereof |
| CN115057701A (en) * | 2022-06-09 | 2022-09-16 | 哈尔滨工业大学 | Composite film material with room-temperature large electrocaloric effect and preparation method thereof |
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Application publication date: 20190702 |