CN102604280B - Mixed crystal form inorganic nanometer filler/polymer-based composite dielectric film - Google Patents
Mixed crystal form inorganic nanometer filler/polymer-based composite dielectric film Download PDFInfo
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Abstract
The invention discloses a mixed crystal form inorganic nanometer filler/polymer-based composite dielectric film. The film is formed by mixing a fluorine-containing polymer with mixed crystal form nanometer TiO2 and casting. The molar components of two crystal forms in mixed crystal nanometer TiO2 can be controlled according to reaction time: the content of anatase is 36-45 percent, and the content of rutile is 55-64 percent. The composite dielectric film consists of the following components in percentage by mass: 5-40 percent of mixed crystal nanometer TiO2 and 60-95 percent of fluorine-containing polymer. The composite dielectric film is a novel dielectric material with higher dielectric constant and lower dielectric loss. The composite dielectric film with a required dielectric constant can be prepared by controlling the adding proportion of a filler and the crystal form proportion of the filler. The composite dielectric film has a simple preparation process, low composite temperature and wide application prospect, and is environmental-friendly.
Description
Technical field
The invention belongs to the compound dielectric film preparation field, particularly a kind of mixing crystal formation nano-TiO
2/ polymer-based carbon compound dielectric film.
Background technology
Polymer-based carbon composite dielectric material with high-k, low-dielectric loss, workability is due to good snappiness and store the ability of electric charge, uniform electric field, therefore, widely used functional materials unique as a kind of function, have application very widely in hybrid locomotrives, sensor, space flight military affairs and power storage field etc.At present, dielectric materials mainly contains three classes:
1, common dielectric ceramic material: as CaCu 3 Ti 4 O (CCTO), its electric capacity is larger, and specific inductivity is up to 10
4-10
5(Lin Zhang, et al., Ferroelectrics.2010,405,92.), but this material sintering temperature is high, frangible, and workability is affected.2, polymer materials: as high in polyvinylidene difluoride (PVDF) (PVDF) snappiness, dielectric loss is little, but the specific inductivity of itself too small (Baojin Chu, et al., science.2006,313,334.) seriously limits its application.3, high dielectric property polymer matrix composite: with conductive carbonized titanium (TiC) as additive, be filled in PVDF and form matrix material, under 100Hz, the specific inductivity of matrix material can reach 540 (Fajun Wang, et al., Phys.Status Solidi (RRL) .2009,3,22.), but it is subject to the serious restriction of percolation threshold, and dielectric loss can improve a lot near percolation threshold, wayward loading level.And by general ceramic material, be additive, polymkeric substance is substrate, combines the high dielectric property of pottery and the advantage of polymkeric substance workability, it has the advantages such as dielectric properties preferably, higher voltage breakdown field intensity and easy-formation, therefore very large using value is arranged.As the barium titanate (BaTiO with surface modification such as Philseok Kim
3) be additive, vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] is substrate, works as BaTiO
3When addition was 50%, under 100Hz, the specific inductivity of matrix material can reach 33 (Philseok Kim, et al., ACSNANO.2009,3,2581.).
But the shortcoming of the method is that the preparation method of most of pottery interpolation material is comparatively complicated, and poor with the polymer phase capacitive, is difficult for making film.Ultra-high dielectric coefficient and the polymeric substrates of most of stupalith differ larger, and in the used time of doing that is subject to external electric field, composite inner can produce inhomogenous electric field, can greatly reduce the compressive strength of matrix material.
Summary of the invention
The object of the invention is to provide a kind of mixing crystal formation inorganic nano-filler/polymer-based carbon compound dielectric film.This laminated film has dielectric properties preferably.
This mixes crystal formation inorganic nano-filler/polymer-based carbon compound dielectric film by the mixed crystal nano-TiO
2Form with fluoropolymer.Its mass percent consists of:
The mixed crystal nano-TiO
25%-40%;
Fluoropolymer 60%-95%.
Described fluoropolymer is a kind of in vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)], vinylidene-trifluoro-ethylene-fluorine vinyl chloride copolymer [P (VDF-TrFE-CFE)], vinylidene-trifluoro-ethylene-chlorotrifluoroethylene [P (VDF-TrFE-CTFE)].
Described mixed crystal nano-TiO
2Be comprised of anatase octahedrite, two kinds of crystal formations of rutile, its molar percentage consists of:
Rutile 55%-64%.
The present invention's mixing crystal formation inorganic nano-filler/polymer-based carbon compound dielectric film can be made by following methods:
1, prepare different crystal forms ratio mixed crystal nano-TiO by circumfluence method
2, mixed crystal TiO
2Different crystal form ratio can be controlled by the reaction times, and its molar percentage consists of:
Rutile 55%-64%.
Described return time is 6-18h.
2, with the mixed crystal TiO of step 1 preparation
2, after fluoropolymer and solvent DMF (DMF) mix, ultrasonic agitation is uniformly dispersed, and forms stable colloidal sol; Its mass percent consists of:
The mixed crystal nano-TiO
25%-40%;
Fluoropolymer 60%-95%.
Mixed crystal TiO
2With the mass ratio of fluoropolymer total mass and DMF be 1: 7-10.
3, with colloidal sol 80 ± 1 ℃ of casting film-formings on mould of step 2 preparation, dry 18 ± 1h, pass through again naturally cooling, 120 ± 1 ℃ of annealing 8 ± 1h, remove residual solvent, namely obtain thickness and be the mixing crystal formation inorganic nano-filler of 110-150 μ m/polymer-based carbon compound dielectric film.
According to above-mentioned preparation method, at described nano-TiO
2In mass ratio range, regulate its mass ratio, namely make the compound dielectric film of required differing dielectric constant, the preferred mass ratio is: mixed crystal TiO
2Be 40%, fluoropolymer is 60%.
According to above-mentioned preparation method, at described nano-TiO
2Mix in the crystal formation proportional range, regulate its two kinds of crystal form ratio, namely make the compound dielectric film of required differing dielectric constant, preferred crystal form ratio is: anatase octahedrite is 37%, and rutile is 63%.
The present invention has following beneficial effect:
A. this mixed crystal nano-TiO
2Filler has overcome the problems that exist in the background technology, and its preparation condition is simple, easy to operate, and the different ratios of two kinds of crystal formations can be controlled by the reaction times.The advantage that it combines two kinds of different crystal forms, have higher specific inductivity and low-dielectric loss very.
B. this filler and substrate dielectric constant differ less, and good with the substrate consistency, therefore compound dielectric film has dielectric properties preferably, and its dielectric loss does not significantly promote (see photo), still maintaining a lower position, is a kind of novel high-dielectric composite material.
C. this film is by adjusting mixing crystal formation TiO
2The mass ratio range of component and TiO
2Two kinds of crystal form ratio scopes, can significantly change the dielectric properties of material, thereby prepare required high dielectric constant film.
D. the preparation technology of this film is simple, combined temp is low and environmentally friendly, can change as requested the shape size of mould, thereby be applicable in different electronicss, energy storage material.
Laminated film of the present invention, dielectric properties, along with the variation of frequency is relatively stable, do not have very large sudden change to occur.Laminated film, specific inductivity can be brought up to 26 left and right.
Description of drawings
Fig. 1 is the different mixed crystal TiO of preparation in embodiment 1,2,3,6
2The relation of the specific inductivity of massfraction compound dielectric film (ε) and dielectric loss (tan δ) and frequency.
Fig. 2 is the different mixed crystal ratio TiO of preparation in embodiment 3,4,5,6
2The relation (100Hz and 1000Hz) of the specific inductivity of compound dielectric film (ε) and dielectric loss (tan δ) and frequency, wherein mixed crystal TiO
2Mass percent is 40%.
Embodiment
Below by product and preparation method in specific embodiment narration the present invention.Unless stated otherwise, in the present invention, technique means used is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention are only limited by claims.To those skilled in the art, under the prerequisite that does not deviate from essence of the present invention and scope, various changes or change that the conditions such as the ratio in these embodiments and solvent are carried out also belong to protection scope of the present invention.
Embodiment 1:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 6h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 45%, and rutile is 55%;
Circumfluence method prepares mixed crystal nano TiO 2 method: use the 100mL deionized water, the 10mL hydrogen peroxide is made into mixed solvent, slowly drips wherein butyl (tetra) titanate 2.2g, stirs 30min under room temperature, the 6h that refluxes under 98 ℃ afterwards, and the precipitation that obtains is from washing, 80 ℃ of dry 20h.
B. with the mixed crystal TiO2 of 0.0054g step a preparation, after 0.1000g vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] and 1.0005g solvent DMF are mixed, ultrasonic agitation is uniformly dispersed, and forms stable colloidal sol, and this batching mass percent consists of: mixed crystal TiO
2Be 5%, polymkeric substance is 95%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO again
2/ P (VDF-TrFE) compound dielectric film.Specific inductivity can reach 11.7.Specific inductivity can reach 11.7.
Embodiment 2:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 6h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 45%, and rutile is 55%;
B. with the mixed crystal TiO of 0.0247g step a preparation
2, after 0.1000g vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] and 11313g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol, and this batching mass percent consists of: mixed crystal TiO
2Be 20%, polymkeric substance is 80%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO again
2/ P (VDF-TrFE) compound dielectric film.Specific inductivity can reach 17.3.Embodiment 3:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 6h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 45%, and rutile is 55%;
B. with the mixed crystal TiO of 0.0667g step a preparation
2, after 0.1000g vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] and 1.2830g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol, and this batching mass percent consists of: mixed crystal TiO
2Be 40%, polymkeric substance is 60%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO again
2/ P (VDF-TrFE) compound dielectric film.Specific inductivity can reach 23.9.
Embodiment 4:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 9h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 37%, and rutile is 63%;
B. with the mixed crystal TiO of 0.0667g step a preparation
2, after 0.1000g vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] and 1.5009g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol, mixed crystal TiO
2Be 40%, polymkeric substance is 60%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO again
2/ P (VDF-TrFE) compound dielectric film.Specific inductivity can reach 25.8.
Embodiment 5:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 18h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 36%, and rutile is 64%;
B. with the mixed crystal TiO of 0.0667g step a preparation
2, after 0.1000g vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] and 1.5009g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol, mixed crystal TiO
2Be 40%, polymkeric substance is 60%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO2/P (VDF-TrFE) compound dielectric film again.Specific inductivity can reach 22.7.
Embodiment 6:
This group embodiment is the comparative example.0.1000g after vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] and 1.0000g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol; With colloidal sol 80 ℃ of casting film-formings on mould of preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare P (VDF-TrFE) compound dielectric film again.Specific inductivity can reach 12.4.
Embodiment 7:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 6h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 45%, and rutile is 55%;
B. with the mixed crystal TiO of 0.0054g step a preparation
2, after 0.1000g vinylidene-trifluoro-ethylene-fluorine vinyl chloride copolymer [P (VDF-TrFE-CFE)] and 1.0005g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol, and this batching mass percent consists of: mixed crystal TiO
2Be 5%, polymkeric substance is 95%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO again
2/ P (VDF-TrFE-CFE) compound dielectric film.
Embodiment 8:
A. prepare the mixed crystal nano-TiO by circumfluence method
2, return time is 6h, and wherein the molar constituent of two kinds of crystal formations is: anatase octahedrite is 45%, and rutile is 55%;
B. with the mixed crystal TiO of 0.0247g step a preparation
2, after 0.1000g vinylidene-trifluoro-ethylene-chlorotrifluoroethylene [P (VDF-TrFE-CTFE)] and 1.1313g solvent DMF were mixed, ultrasonic agitation was uniformly dispersed, and forms stable colloidal sol, and this batching mass percent consists of: mixed crystal TiO
2Be 20%, polymkeric substance is 80%;
C. with colloidal sol 80 ℃ of casting film-formings on mould of step b preparation, dry 18h; , through naturally cooling, 120 ℃ of annealing 8h, namely prepare TiO again
2/ P (VDF-TrFE-CTFE) compound dielectric film.
Claims (3)
1. one kind is mixed crystal formation inorganic nano-filler/polymer-based carbon compound dielectric film, it is characterized in that, described compound dielectric film is by fluoropolymer and mixed crystal nano-TiO
2Form, its mass percent consists of: the mixed crystal nano-TiO
2Be 40%, fluoropolymer is 60%; Described mixed crystal nano-TiO
2Middle anatase octahedrite and rutile molar constituent are that anatase octahedrite is 37%, and rutile is 63%; Described mixing crystal formation inorganic nano-filler/polymer-based carbon compound dielectric film is made by following methods usually, by circumfluence method, by anatase octahedrite, two kinds of crystal formations of rutile, prepares the mixed crystal nano-TiO
2, with the mixed crystal nano-TiO
2, after fluoropolymer and solvent DMF mix, ultrasonic agitation is uniformly dispersed, and forms stable colloidal sol; Dry after casting film-forming, cooling, 120 ± 1 ℃ of annealing, remove residual solvent, must mix crystal formation inorganic nano-filler/polymer-based carbon compound dielectric film.
2. mixing crystal formation inorganic nano-filler according to claim 1/polymer-based carbon compound dielectric film, it is characterized in that, described fluoropolymer is a kind of in vinylidene-trifluoro-ethylene copolymer, vinylidene-trifluoro-ethylene-fluorine vinyl chloride copolymer, vinylidene-trifluoro-ethylene-chlorotrifluoroethylene.
3. mixing crystal formation inorganic nano-filler according to claim 1/polymer-based carbon compound dielectric film, is characterized in that, described mixed crystal nano-TiO
2With the mass ratio of fluoropolymer total mass and DMF be 1:7-10.
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