CN103408775B - A kind of preparation method with the flexible compound dielectric materials of high-k and low-dielectric loss - Google Patents
A kind of preparation method with the flexible compound dielectric materials of high-k and low-dielectric loss Download PDFInfo
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Abstract
The invention discloses a kind of preparation method with the flexible compound dielectric materials of high-k and low-dielectric loss.The feature of this composite dielectric material is by the barium titanate (BaTiO of surface modification
3) or magnesium titanate (MgTiO
3) nanofiber and fluoropolymer composition.Particularly, with silicon fluoride to crystal type BaTiO
3or MgTiO
3nanofiber surface carries out chemically modified, by the BaTiO of finishing
3or MgTiO
3nanofiber and fluoropolymer and their blend carry out compound, adopt solution casting technique to obtain flexible composite dielectric material.The method technique is simple, can significantly improve the specific inductivity of composite dielectric material, reduce its dielectric loss simultaneously, overcomes the shortcoming that existing organic/inorganic compounding technology can cause dielectric loss to increase while obtaining high-k.
Description
Technical field
The present invention relates to the preparation method of a kind of high-k, low-dielectric loss composite dielectric material, specifically relate to one silicon fluoride surface-treated barium titanate (BaTiO
3) or magnesium titanate (MgTiO
3) preparation method of flexible dielectric of nanofiber and fluoropolymer composition.
Background technology
Have high energy storage density, low-dielectric loss dielectric materials with it in electron trade, widespread use particularly in microelectronic device and obtain increasing concern, especially polymer-based carbon composite dielectric material become the focus of high-performance dielectric materials research and development in recent years due to good processing characteristics, high-flexibility and high energy storage density.
Traditional ferroelectric ceramic(s) dielectric materials mainly contains barium titanate (BaTiO
3), magnesium titanate (MgTiO
3) and rutile titanium dioxide (TiO
2) etc.Although these stupaliths have very large specific inductivity, its fragility, high processing temperature and low disruptive strength limit the application of this kind of material in collapsible electronic product.The homopolymer that polymer dielectric material for electrical is mainly fluorine-containing and multipolymer, as vinylidene (PVDF), vinylidene-trifluoro-ethylene copolymer (PVDF-TrFE) and epoxy resin etc.Compared with inorganic ceramic class dielectric materials, the specific inductivity of polymer dielectric material for electrical is usually less, but has good kindliness and higher disruptive strength.Organic/inorganic materials compounding technology is the advantage of integrated ceramic dielectric material and fluoropolymer dielectric materials, the important technology route of the better dielectric materials of processability.
With conductive filler material and ceramic dielectric material for filler, take polymkeric substance as matrix be the common method preparing composite material with high dielectric constant.As nickel/polyvinylidene difluoride (PVDF), silver/epoxy resin, multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF), the Graphene/polydimethylsiloxane etc. of carbon black/epoxy resin and functionalization, can obtain the matrix material of high-k.Usually there is a seepage flow threshold values in this kind of matrix material, namely when the volume fraction of conductive filler material is greater than certain value, matrix material becomes electrical conductor by isolator, and the boundary defect between conductive filler material and polymeric matrix often becomes the passage of leakage current, causes the increase of matrix material dielectric loss.And ceramic dielectric filler/polymeric matrix composite material, as BaTiO
3/ epoxy resin, BaTiO
3/ PVDF etc. also can significantly improve the specific inductivity of matrix material.But due to interface inconsistent problem between inorganic ceramic dielectric filler and polymeric matrix, bring the defect in this kind of dielectric materials microstructure, affect dielectric properties and the mechanical property of material.Solution to the problems described above carries out surface chemical modification to inorganic ceramic dielectric filler, as Surface coating and surface grafting.Such as, with the nanometer BaTiO of Dopamine HCL modification
3particle, can improve the compatible problem in interface of itself and PVDF, with silane coupler modified nanometer BaTiO
3particle-filled epoxy resin, dielectric properties obtain larger improvement.Also surface initiation-atom transfer radical polymerization (SI-ATRP) can be adopted in addition to carry out chemical graft on dielectric filler surface, as PMMA@BaTiO
3, PS@TiO
2and PTFEMA@BaTiO
3, the interface compatibility of inorganic materials and organic materials can be improved significantly, improve the dielectric properties of matrix material.But this kind of material usually only has and just has remarkable effect when the packing volume mark of filler reaches 70v%, this increases not only the rigidity of polymer composites, and bring the forming process difficulty of matrix material.
The filler of big L/D ratio is when identical packing volume mark, more effective to the specific inductivity increasing matrix material.The such as BaTiO of Dopamine HCL surface modification
3the dielectric properties of the matrix material of nanofiber and vinylidene and trifluoro-ethylene copolymer (PVDF-TrFE).At less BaTiO
3under nanofiber-filled volume fraction, the specific inductivity of matrix material improves about 2 times (Song Y, Shen Y, Liu HY, Lin YH, Li M, Nan CW.J Mater Chem, 2012,22:8063-8068).Patent CN101508841A discloses a kind of with the high polymer alloy dielectric materials of nylon and fluoropolymer, obtains specific inductivity large, the flexible compound dielectric materials that mechanical property is good.Recently, we find in dielectric filler, as BaTiO
3nanoparticle, chemical grafting treated one deck fluoropolymer, can improve the specific inductivity of matrix material significantly, reduces dielectric loss (the Zhang XH of material simultaneously, Chen HC, Ma YH, Zhao CW, YangWT.Appl Surf Sci, 2013,277:121-127).The people such as Yang reports with the BaTiO of grafting fluoro thing modification afterwards
3nano-particles filled PVDF, the dielectric materials of preparation also significantly can reduce dielectric loss (Yang K, the Huang XY of material while enlarging markedly material dielectric constant, Huang YH, Xie LY, Jiang PK.Chem Mater, 2013,25:2327-2338).The matrix material formed based on the titanate nanofiber and fluoropolymer and composition thereof of the graft modification of surperficial fluoro thing is the flexible high-k of preparation, the dielectric materials of low-dielectric loss provides a kind of method.But the complex process of surface grafting technology, the residual of catalyst metal ion may cause dielectric materials puncturing in use procedure.Therefore, be necessary that research and development technique is simple, without the process for modifying surface of the inorganic dielectric stupalith of ion residues, and compounding technology on this basis.
Summary of the invention
Usually, composite dielectric material is while raising specific inductivity, dielectric loss can be made also significantly to increase, and the present invention is intended to solve the contradiction between composite dielectric material specific inductivity and dielectric loss, for the more practical flexible compound dielectric materials of preparation provides a kind of method.Principle of the present invention is: the BaTiO adopting big L/D ratio
3or MgTiO
3inorganic nano-fiber improves the specific inductivity of matrix material, carries out chemically modified introduce carbon-fluorine bond at fiber surface, and the introducing of carbon-fluorine bond significantly improves the consistency of nanofiber and polymeric matrix on the one hand, reduces boundary defect; The polarization loss of carbon-fluorine bond is little on the other hand, and the effect of two aspects significantly reduces the dielectric loss of matrix material.Concrete technical scheme of the present invention is: first use silicon fluoride coupling agent to BaTiO
3or MgTiO
3chemically modified is carried out on inorganic nano-fiber surface, by the hydroxyl of nanofiber surface and the hydrolytic action of silicon fluoride coupling agent, introduces fluorocarbon group in the mode that covalent chemical bond connects at nanofiber surface; Then using silicon fluoride surface-treated nanofiber as filler, preparation and the matrix material of fluoropolymer.Further, flexible composite dielectric material film can be obtained by solution casting technique.
The silicon fluoride that the present invention relates to is the organoalkoxysilane containing fluorine substituted alkyl, as perfluoro capryl Trimethoxy silane, perfluoro capryl triethoxyl silane, 17 fluorine decyl Trimethoxy silanes, ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptyl hydroxypropyl methyl dimethoxysilane, 3-seven fluorine isopropoxide propyl Trimethoxy silane and perfluoro decyl Trimethoxy silane, and the mixture etc. of these silicon fluorides.Silicon fluoride used in the present invention includes but not limited to above-mentioned enumerating.To BaTiO
3and MgTiO
3during the modification of nanofiber surface silicon fluoride, first fluorine containing silane or its mixture diluted are become ethanol or the aqueous isopropanol of 0.5-2wt%; Then by BaTiO
3or MgTiO
3nanofiber is added in the solution of silicon fluoride, drips a small amount of catalyzer example hydrochloric acid, Glacial acetic acid, after ultrasonic 0.5-2 hour, at 40-60 DEG C, stirs 6-12 hour; Finally by mixing solutions through centrifugal, washing, dry in 50 DEG C of vacuum drying ovens.
The preparation of matrix material adopts solution blended process.First the fluoropolymer solutions of 5wt%-10wt% is prepared, by fluoropolymer as polyvinylidene difluoride (PVDF) (PVDF), polyvinylidene difluoride (PVDF)-trifluoro-ethylene (PVDF-TrFE) multipolymer, polyvinylidene difluoride (PVDF)-tetrafluoroethylene (PVDF-PTFE) multipolymer, adds in corresponding solvent after any one or mixture in polyvinylidene difluoride (PVDF)-R 1216 (PVDF-HFE) multipolymer and vinylidene and trifluorochloroethylene (PVDF-CTFE) multipolymer weigh.Then be stirred to and dissolve completely.The solvent that solvent can be DMF, N,N-dimethylacetamide, hexafluoro propyl alcohol etc. can dissolve fluoropolymer, also can adopt mixed solvent.Dissolution process also can carry out accelerate dissolution process by heating.
The preparation of the composite dielectric material that the present invention relates to, by the barium titanate (BaTiO of silicon fluoride modification
3) or magnesium titanate (MgTiO
3) nanofiber volume fraction is in the composite 5v%-25v%, by the BaTiO of silicon fluoride modification
3or MgTiO
3nanofiber ultrasonic disperse in a solvent, then adds the fluoropolymer solutions of the respective amount of 5wt%-10wt%, stirring 4-8h to mixing, being prepared the flexible compound dielectric film material of different shape and thickness by solution casting.
Composite dielectric material prepared by the present invention has good kindliness, with modification BaTiO
3or MgTiO
3the increase of nanofiber-filled volume fraction, the specific inductivity of material also increases; On the contrary, the dielectric loss of material significantly reduces.
Accompanying drawing explanation
Fig. 1 is matrix material specific inductivity and modification BaTiO
3the graph of a relation of nanofiber-filled volume fraction, as can be seen from the figure the specific inductivity of matrix material is along with modification BaTiO
3the increase of nanofiber-filled volume fraction and increasing.
Fig. 2 is matrix material dielectric loss and modification BaTiO
3the graph of a relation of nanofiber-filled volume fraction, as can be seen from the figure the dielectric loss of matrix material is along with modification BaTiO
3the increase of nanofiber-filled volume fraction and reducing.
Embodiment
Embodiment one
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml0.5wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 0.5wt% silicon fluoride, drip 0.015g drip Glacial acetic acid, at 40 DEG C, stir 6h after ultrasonic disperse 30min, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF is mixed with the DMF solution that massfraction is 10wt%; 3) by modification BaTiO
3nanofiber volume filling fraction is 5v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 7.5.
Embodiment two
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml0.5wt%, take the MgTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 0.5wt% silicon fluoride, drip 0.015g drip Glacial acetic acid, at 40 DEG C, stir 6h after ultrasonic disperse 30min, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF is mixed with the DMF solution that massfraction is 10wt%; 3) by modification MgTiO
3nanofiber volume filling fraction is 10v%, by modification MgTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 10.
Embodiment three
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml0.5wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 0.5wt% silicon fluoride, drips 0.015g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF is mixed with the DMF solution that massfraction is 5wt%; 3) by modification BaTiO
3nanofiber volume filling fraction is 15v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 11.
Embodiment four
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml0.5wt%, take the MgTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 0.5wt% silicon fluoride, drips 0.015g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 3) PVDF is mixed with the DMF solution that massfraction is 5wt%; 4) by modification MgTiO
3nanofiber volume filling fraction is 20v%, by modification MgTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 12.5.
Embodiment five
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml0.5wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 0.5wt% silicon fluoride, drips 0.009g hydrochloric acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF is mixed with the DMF solution that massfraction is 5wt%; 3) by modification BaTiO
3nanofiber volume filling fraction is 25v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 14.
Embodiment six
1) ten trifluoro octyltri-ethoxysilane are mixed with the ethanolic soln of 30ml1wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 1wt% silicon fluoride, drips 0.009g hydrochloric acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) the DMF solution (PVDF=50wt%) that PVDF and PVDF-TrFE massfraction is 5wt% is prepared; 3) by modification BaTiO
3nanofiber volume filling fraction is 10v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 14.
Embodiment seven
1) 17 fluorine decyl Trimethoxy silanes are mixed with the aqueous isopropanol of 30ml2wt%, take the MgTiO of 0.4g
3nanofiber is also joined in the aqueous isopropanol of 1wt% silicon fluoride, drips 0.015g Glacial acetic acid, stirs 12h after ultrasonic disperse 30min at 60 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) the DMF solution that PVDF and PVDF-PTFE (PVDF=80wt%) massfraction is 5wt% is prepared; 3) by modification MgTiO
3nanofiber volume filling fraction is 15v%, by modification MgTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 8h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 13.
Embodiment eight
1) ten difluoro heptyl propyl trimethoxy silicanes are mixed with the aqueous isopropanol of 30ml1wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the aqueous isopropanol of 1wt% silicon fluoride, drips 0.015g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, is placed in 50 DEG C of vacuum drying ovens and dries after three centrifugal and washings; 2) the DMF solution that PVDF-PTFE and PVDF-TrFE (PVDF-TrFE=40wt%) massfraction is 5wt% is prepared; 3) by modification BaTiO
3nanofiber volume filling fraction is 25v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 6h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, recording specific inductivity is 22.
Embodiment nine
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml1wt%, take the MgTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 1wt% silicon fluoride, drips 0.003g hydrochloric acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF-HFE is mixed with the DMF solution that massfraction is 5wt%; 3) by modification MgTiO
3nanofiber volume filling fraction is 20v%, by modification MgTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 18.
Embodiment ten
1) ten difluoro heptyl hydroxypropyl methyl dimethoxysilane are mixed with the ethanolic soln of 30ml2wt%, take the BaTiO of 0.4g
3nanofiber is also joined in the ethanolic soln of 2wt% silicon fluoride, drips 0.012g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, is placed in 50 DEG C of vacuum drying ovens and dries after three centrifugal and washings; 2) the DMF solution that PVDF and PVDF-HFE (PVDF-HFE=20wt%) massfraction is 5wt% is prepared; 3) by modification BaTiO
3nanofiber volume filling fraction is 10v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 16.
Embodiment 11
1) ten trifluoro octyl group Trimethoxy silanes are mixed with the ethanolic soln of 30ml1wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 1wt% silicon fluoride, drips 0.015g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) the DMF solution that PVDF-CTFE massfraction is 5wt% is prepared; 3) by modification BaTiO
3nanofiber volume filling fraction is 15v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 15.
Embodiment 12
1) ten difluoro heptyl hydroxypropyl methyl dimethoxysilane are mixed with the ethanolic soln of 30ml1wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 1wt% silicon fluoride, drips 0.009g hydrochloric acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF-HFE is mixed with the DMF solution that massfraction is 5wt%; 3) by modification BaTiO
3nanofiber volume filling fraction is 15v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 20.
Embodiment 13
1) ten difluoro heptyl hydroxypropyl methyl dimethoxysilane are mixed with the ethanolic soln of 30ml1wt%, take the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 1wt% silicon fluoride, drips 0.012g hydrochloric acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF-HFE and PVDF-CTFE(PVDF-HFE=40wt% is prepared) massfraction is the DMF solution of 5wt%; 3) by modification BaTiO
3nanofiber volume filling fraction is 15v%, by modification BaTiO
3nanofiber ultrasonic disperse, in DMF, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 25.
Embodiment 14
1) 3-seven fluorine isopropoxide propyl Trimethoxy silane is mixed with the ethanolic soln of 30ml1wt%, takes the MgTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 1wt% silicon fluoride, drips 0.015g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF and PVDF-CTFE(PVDF-CTFE=40wt% is prepared) massfraction is the N,N-dimethylacetamide solution of 5wt%; 3) by modification MgTiO
3nanofiber volume filling fraction is 10v%, by modification MgTiO
3nanofiber ultrasonic disperse, in N,N-dimethylacetamide, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 13.
Embodiment 15
1) perfluoro decyl Trimethoxy silane is mixed with the ethanolic soln of 30ml2wt%, takes the BaTiO of 0.2g
3nanofiber is also joined in the ethanolic soln of 2wt% silicon fluoride, drips 0.009g hydrochloric acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, through centrifugal, wash and dry in 50 DEG C of vacuum drying ovens; 2) PVDF-PTFE and PVDF-CTFE(PVDF-CTFE=50wt% is prepared) massfraction is the hexafluoroisopropanol solution of 5wt%; 3) by modification BaTiO
3nanofiber volume filling fraction is 5v%, by modification BaTiO
3nanofiber ultrasonic disperse, in hexafluoroisopropanol, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 8.5.
Embodiment 16
1) ten difluoro heptyl hydroxypropyl methyl dimethoxysilane are mixed with the ethanolic soln of 30ml2wt%, take the MgTiO of 0.4g
3nanofiber is also joined in the ethanolic soln of 2wt% silicon fluoride, drips 0.012g Glacial acetic acid, stirs 6h after ultrasonic disperse 30min at 40 DEG C, is placed in 50 DEG C of vacuum drying ovens and dries after three centrifugal and washings; 2) the N,N-dimethylacetamide solution that PVDF and PVDF-HFE (PVDF-HFE=20wt%) massfraction is 5wt% is prepared; 3) by modification MgTiO
3nanofiber volume filling fraction is 15v%, by modification MgTiO
3nanofiber ultrasonic disperse, in hexafluoroisopropanol, adds respective amount step 2) in the solution for preparing, stirring 4h to being uniformly dispersed, finally to transfer in thermal station to solvent evaporates compacting film forming and with cold water cooling, measured specific inductivity is 12.
Claims (3)
1. there is a preparation method for the flexible compound dielectric materials of high-k and low-dielectric loss, it is characterized in that: this material is by the BaTiO of fluoropolymer matrix and silicon fluoride surface modification
3or MgTiO
3nanofiber composition; Wherein fluoropolymer volume fraction is in the composite the BaTiO of 75v%-95v%, silicon fluoride modification
3or MgTiO
3nanofiber volume fraction is in the composite 5v%-25v%;
BaTiO
3or MgTiO
3the surface modifying method of nanofiber is: the solution described silicon fluoride ethanol or isopropanol floride being interpreted into 0.5wt%-2wt%, then BaTiO
3or MgTiO
3nanofiber is added in the solution of silicon fluoride, the catalyst drops of total mass mark 0.01wt%-0.05wt% is added in above-mentioned solution, ultrasonic 0.5-2h, then stirs 6-12h at 40-60 DEG C, finally by mixing solutions through centrifugal, washing after dry in vacuum drying oven;
The solution of preparation fluoropolymer; By modification BaTiO
3or MgTiO
3nanofiber volume filling fraction is that 5v%-25v% measures, by modification BaTiO
3or MgTiO
3nanofiber ultrasonic disperse in a solvent, joins in the solution of above-mentioned fluoropolymer, is stirred to and is uniformly dispersed, and is heated to solvent evaporates compacting film forming and lowers the temperature with cold water;
Fluoropolymer refers to the mixture of the homopolymer of vinylidene, the multipolymer of vinylidene or polyvinylidene difluoride (PVDF) and polyvinylidene fluoride copolymer; Catalyzer used is Glacial acetic acid or hydrochloric acid.
2. method according to claim 1, is characterized in that: the multipolymer of vinylidene comprises the multipolymer of the multipolymer of vinylidene and trifluoro-ethylene, vinylidene and tetrafluoroethylene, vinylidene and the multipolymer of R 1216 or the multipolymer of vinylidene and trifluorochloroethylene.
3. method according to claim 1, it is characterized in that: the silicon fluoride for the modification of titanate nanofiber surface comprises perfluoro capryl Trimethoxy silane, perfluoro capryl triethoxyl silane, 17 fluorine decyl Trimethoxy silanes, ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptyl hydroxypropyl methyl dimethoxysilane, 3-seven fluorine isopropoxide propyl Trimethoxy silane or perfluoro decyl Trimethoxy silane.
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CN110511410B (en) * | 2019-08-27 | 2020-06-05 | 东莞东阳光科研发有限公司 | Polyvinylidene fluoride dielectric film and preparation method thereof |
CN112759870A (en) * | 2019-10-21 | 2021-05-07 | 中国科学院上海硅酸盐研究所 | PTFE/MgTiO with ultralow dielectric loss3Composite dielectric material and preparation method thereof |
CN110922702B (en) * | 2019-11-29 | 2021-09-21 | 湖南工程学院 | Oriented flexible magnetoelectric composite material and preparation method thereof |
CN111100425B (en) * | 2020-01-03 | 2020-12-25 | 西安交通大学 | High-dielectric photosensitive resin-based composite material and preparation method and application thereof |
CN111234423B (en) * | 2020-03-05 | 2022-02-08 | 济南大学 | Preparation method of stretchable high-energy-storage-density dielectric composite material |
CN111607125B (en) * | 2020-06-05 | 2021-11-09 | 国家电网有限公司 | Method for improving dielectric constant of polypropylene film |
-
2013
- 2013-07-20 CN CN201310312778.1A patent/CN103408775B/en active Active
Non-Patent Citations (2)
Title |
---|
Enhanced dielectric and ferroelectric properties induced by dopamine-modified BaTiO3 nanofibers in flexible poly(vinylidene fluoride-trifluoroethylene) nanocomposites;Yu Song等;《Journal of Materials Chemistry》;20120221(第22期);8063-8068 * |
Xianhong Zhang等.Preparation and dielectric properties of core–shell structural composites of poly(1H,1H,2H,2H-perfluorooctyl methacrylate)BaTiO3 nanoparticles.《Applied Surface Science》.2013,(第277期),121-127. * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106291911A (en) * | 2016-08-10 | 2017-01-04 | 华南师范大学 | Hydrophobicity dielectric layer, its preparation method and the Electrowetting device of lamination layer structure |
CN106291911B (en) * | 2016-08-10 | 2019-06-11 | 华南师范大学 | Hydrophobicity dielectric layer, preparation method and the Electrowetting device of lamination layer structure |
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