CN103980638B - A kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof - Google Patents
A kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof Download PDFInfo
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Abstract
A kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 50-60% and the surface modification of 40-50% by mass percentage; Raw material is mixed respectively through oxidation, powder, colds pressing, the process such as hot pressing is prepared from.Present invention utilizes the multiple interfacial polarization pattern between composite zinc particle and polymkeric substance, by changing ZnO thickness Effective Regulation system specific inductivity, the change of loss and specific conductivity improves the specific inductivity of polymer dielectric, and reduces dielectric loss.Lower composite particles consumption makes composite dielectrics have higher force intensity and toughness.
Description
Technical field
The intersection that the invention belongs to electrical material and Chemicals manufactures field, is specifically related to a kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof.
Background technology
The high dielectric constant polymer dielectric medium of low cost, easily processing, lightweight and excellent mechanical performances combines many performances of conventional dielectric material and the feature such as excellent in toughness, low cost, easily machine-shaping of polymkeric substance, causes the extensive concern in the world and research.High dielectric constant polymer dielectric medium has been used widely in preparation embedded multilayer film electrical condenser and high energy storage capacitor etc.; In addition, they also obtain important application in fields such as microelectronics, electric works, micro electronmechanical and biotechnology, and its research is a very active area, obtains remarkable progress.
At present, the high-k prepared by conductor, ferroelectric ceramic(s) particle and polymkeric substance compound, low-dielectric loss polymkeric substance composite dielectrics also exist following drawback and problem in engineer applied:
1) in the Polymeric dielectric unstable properties of conductive particle excess effusion value consumption vicinity, and high-k is normal with higher dielectric loss.
So far, the research and development of the conductor/polymer dielectric of the high-k based on seepage theory is done a lot of work, it is worthy of note have an insoluble key issue to annoying people, i.e. circulation ratio (stability) problem of dielectric properties always.Be in particular in that the dielectric properties of this kind of matrix material are very responsive to its influence factor (especially the associated arguments of conductor), as amount of filler is exceeding the trace change of oozing near threshold and can cause the sharply change of system specific conductivity, this brings extreme difficulties and challenge to the stability etc. of its production control and material property.
In addition, near conductive filler percolation threshold, when the specific inductivity of conductor/polymer dielectric reaches the highest, its dielectric loss is often also large especially, and this can reduce its voltage breakdown and use properties undoubtedly.
2) when high filler grain consumption (>=70wt%), ferroelectric ceramic(s) particle/polymer dielectric often just obtains high-k, and this seriously can reduce dielectric substance mechanical strength and toughness, also brings high dielectric loss simultaneously.
Due to the forfeiture of mechanical strength and impelling strength, the high dielectric constant polymer dielectric medium when practical engineering application cannot be applied, and loss is high in addition, can reduce the voltage breakdown of polymkeric substance.
Numerous research shows that relying on merely the conductive particle such as metal and carbon material or ferroelectric particle to obtain has stable specific inductivity and low-loss polymer dielectric substance.
Summary of the invention
The object of the invention is to overcome the problems of the prior art, provide a kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof, the dielectric medium of preparation has higher force intensity and toughness, stablizes high-k and low-loss.
For achieving the above object, the present invention adopts following technical scheme:
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 50-60% and the surface modification of 40-50% by mass percentage; Wherein, the composite structure zinc particles of surface modification obtains by the following method:
1), after being oxidized in air at 400-500 DEG C by spherical metal zinc powder, composite structure zinc particles is obtained;
2) composite structure zinc particles is dispersed in dehydrated alcohol, obtains composite zinc particle/alcohol mixed solution; Titanate coupling agent is joined in dehydrated alcohol, stirring makes titanate coupling agent dissolve and obtains coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, filter after Keep agitation 6-8h under 80-90 DEG C of condensing reflux, obtain filter cake, filter cake is dried the composite structure zinc particles obtaining surface modification; Wherein, in coupling agent solution, titanate coupling agent is the 1.2-1.5% of composite structure zinc particles quality.
The particle diameter of described composite structure zinc particles is 6-8 μm.
The time of described oxidation is 2-3h.
Describedly dispersedly specifically under ultrasonication, carry out mechanical stirring realization.
The temperature of described oven dry is 100-120 DEG C, and the time of oven dry is 8-10h.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises the following steps:
1) preparation of composite structure zinc particles: after being oxidized in atmosphere at 400-500 DEG C by spherical metal zinc powder, obtain composite structure zinc particles;
2) surface modification of composite structure zinc particles: be dispersed in dehydrated alcohol by composite structure zinc particles, obtains composite zinc particle/alcohol mixed solution; Titanate coupling agent is joined in dehydrated alcohol, stirring makes titanate coupling agent dissolve and obtains coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, filter after Keep agitation 6-8h under 80-90 DEG C of condensing reflux, obtain filter cake, filter cake is dried the composite structure zinc particles obtaining surface modification;
3) preparation of composite structure zinc particles/PVDF polymer dielectric: in mass ratio (50-60): the composite structure zinc particles of PVDF and surface modification mixes by (40-50), obtain mixed powder, by after mixed powder coldmoulding again in 180-200 DEG C, hot pressing 10-15 minute under 12-16MPa, obtain core/shell structure zinc particles/PVDF dielectric medium.
Described step 1) in the particle diameter of composite structure zinc particles be 6-8 μm.
Described step 1) in oxidation time be 2-3h.
Described step 2) in dispersedly specifically under ultrasonication, carry out mechanical stirring; The model of titanate coupling agent is NDZ-201, NDZ-101, NDZ-102 or A27.
Described step 2) in dry temperature be 100-120 DEG C, the time of oven dry is 8-10h.
Compared with prior art, the beneficial effect that the present invention has: present invention utilizes the multiple interfacial polarization pattern between composite zinc particle and polymkeric substance, by changing ZnO thickness Effective Regulation system specific inductivity, the change of loss and specific conductivity improves the specific inductivity of polymer dielectric, and reduces dielectric loss.Lower composite particles consumption makes composite dielectrics have higher force intensity and toughness.
The present invention adopts powder to mix, colds pressing, pressure sintering prepares polymer dielectric, relatively traditional solution method fast, and preparation technology's environmental protection, solvent-free pollution, relative ease, be easy to realize suitability for industrialized production; And preparation technology's relative ease, processing characteristics is good.
With comparing of compound Al particle system, compound ZnO/Zn/ polymeric system prepared by the present invention is because make use of the multiple polarization feature of nucleocapsid zinc particles, therefore system has following clear superiority: 1) more high-k and good mechanical strength and toughness.Under comparatively low sizing consumption, ZnO/Zn/ polymeric system has more high-k; ZnO/Zn massfraction gathers inclined fluorine divinyl specific inductivity close to 100 when being 40%, and the specific inductivity of Al/ polymkeric substance is 30, Al consumptions when massfraction is 40% when reaching 70%, and system specific inductivity just reaches 50.Along with amount of filler increases, the mechanical property of polymeric system must be caused to worsen; 2) outer crystal ZnO thermal conductivity (50W/mK) is far above noncrystal Al
2o
3the thermal conductivity of housing (2-8W/mK), so whole system thermal conductivity is higher than compound Al particle system.
Polymer dielectric prepared by the present invention gathers inclined fluorine styrene powder primarily of raw material and has the composite zinc particle of core/shell structure through drying, powder mixes, cold pressing, the processes such as hot pressing are prepared from, it is a kind of high-k possessing good mechanical strength and impelling strength based on multiple interfacial polarization pattern, low-loss polymer dielectric substance, can be used for preparing embedded without coupling condenser, chip organic multilayer film electrical condenser, high energy storage capacitor components and parts etc., at high frequency communications, LED illumination, automotive electronics, computer, the circuit assembly of the equipment such as switch power supply there is extensive use.
Accompanying drawing explanation
Fig. 1 is nucleocapsid structure composite zinc particle structure schematic diagram.
Fig. 2 is the composite zinc particle XRD spectra after metallic zinc particle is oxidized under differing temps and time;
Fig. 3 is ZnOZn/PVDF polymer dielectric preparation technology schema.
Embodiment
Below by specific embodiment, the present invention is described in detail.
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 50-60% and the surface modification of 40-50% by mass percentage.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises 3 steps below, is respectively the preparation of composite structure zinc particles, the surface modification of composite structure zinc particles and composite structure zinc particles and PVDF resin compounded 3 part, as shown in Figure 3.
1) composite structure zinc particles preparation:
Take about 30g spherical metal zinc powder, spread in high temperature resistant porcelain crucible with thin layer form, the porcelain crucible holding zinc powder is inserted in retort furnace, at 500 DEG C, be oxidized about 2-3h in air, take out high-temperature crucibles, be cooled to room temperature, take out sample, namely obtain composite structure zinc particles, stand-by.
2) surface modification of composite structure zinc particles:
Get about 20g composite structure zinc particles and put into three-necked flask, add the dehydrated alcohol of 120-150mL again, under ul-trasonic irradiation after mechanical stirring 10-15 minute, under ultrasonication, and carry out mechanical stirring and make composite structure zinc particles dispersed in dehydrated alcohol, obtain composite zinc particle/alcohol mixed solution.Titanate coupling agent NDZ-201 composite structure zinc particles weight being about 1.2-1.5% joins and is equipped with in the 50ml small beaker of dehydrated alcohol, stirring forms coupling agent solution after it dissolves completely, then under agitation coupling agent solution is added in composite zinc particle/alcohol mixed solution, and be warming up to 80-90 DEG C, after under condensing reflux, Keep agitation is about 6-8h, be down to room temperature, reactant in flask is taken out after leaving standstill 24-26h again, filter, obtain filter cake, put into baking oven after repeatedly being cleaned by filter cake dehydrated alcohol, at 100-120 DEG C, dry about 8-10h.Then be cooled to room temperature, obtain the composite structure zinc particles of surface modification; The model of titanate coupling agent is NDZ-201, NDZ-101, NDZ-102 or A27.
3) preparation of composite structure zinc particles/PVDF polymer dielectric:
According to mass ratio PVDF: composite structure zinc particles=(50-60) of surface modification: (40-50), the composite structure zinc particles of PVDF, surface modification to be inserted in high mixed cup after tentatively mixing, turn again after speed carries out about 20-25min to 2000-3000r/min and take out mixed powder sample, load coldmoulding in advance in mould, then by the mixed powder being cold-pressed into parison in vacuum hotpressing machine 180-200 DEG C, under 12-16MPa hot pressing be about 10-15 minute.Hot pressing is complete, slowly cools to room temperature, takes out sample, namely obtain core/shell structure zinc particles/PVDF dielectric medium from mould.
Be described below by specific embodiment.
Embodiment 1
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 50% and the surface modification of 50% by mass percentage.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take about 30g spherical metal zinc powder, spread in high temperature resistant porcelain crucible with thin layer form, the porcelain crucible holding zinc powder is inserted in retort furnace, at 400 DEG C, be oxidized about 2h in air, take out high-temperature crucibles, be cooled to room temperature, take out sample, namely obtain composite structure zinc particles, stand-by.
2) surface modification of composite structure zinc particles:
Get about 20g composite structure zinc particles and put into three-necked flask, add the dehydrated alcohol of 120mL again, under ul-trasonic irradiation, mechanical stirring is after 10 minutes, under ultrasonication, and carry out mechanical stirring and make composite structure zinc particles dispersed in dehydrated alcohol, obtain composite zinc particle/alcohol mixed solution.Being joined by the titanate coupling agent NDZ-201 accounting for composite structure zinc particles weight about 1.5% is equipped with in the 50mL small beaker of dehydrated alcohol, stirring forms coupling agent solution after it dissolves completely, then under agitation coupling agent solution is added in composite zinc particle/alcohol mixed solution, and be warming up to 85 DEG C, after under condensing reflux, Keep agitation is about 6h, be down to room temperature, reactant in flask is taken out after leaving standstill 25h again, filter, obtain filter cake, put into baking oven after repeatedly being cleaned by filter cake dehydrated alcohol, at 100 DEG C, dry about 10h.Then be cooled to room temperature, obtain the composite structure zinc particles of surface modification.
3) preparation of composite structure zinc particles/PVDF polymer dielectric:
According to mass ratio PVDF: the composite structure zinc particles=50:50 of surface modification, the composite structure zinc particles of PVDF, surface modification to be inserted in high mixed cup after tentatively mixing, turn again after speed carries out about 20min to 2000r/min and take out mixed powder sample, load coldmoulding in advance in mould, then by be cold-pressed into parison mixed powder in vacuum hotpressing machine 200 DEG C, hot pressing about 15 minutes under 12MPa.Hot pressing is complete, slowly cools to room temperature, takes out sample, namely obtain core/shell structure zinc particles/PVDF dielectric medium from mould.
Embodiment 2
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 60% and the surface modification of 40% by mass percentage.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, spread in high temperature resistant porcelain crucible with thin layer form, the porcelain crucible holding zinc powder is inserted in retort furnace, at 400 DEG C, be oxidized 3h in air, take out high-temperature crucibles, be cooled to room temperature, take out sample, namely obtain composite structure zinc particles, stand-by.
2) surface modification of composite structure zinc particles:
Get 20g composite structure zinc particles and put into three-necked flask, add the dehydrated alcohol of 130mL again, under ul-trasonic irradiation, mechanical stirring is after 12 minutes, under ultrasonication, and carry out mechanical stirring and make composite structure zinc particles dispersed in dehydrated alcohol, obtain composite zinc particle/alcohol mixed solution.Being joined by the titanate coupling agent NDZ-101 of composite structure zinc particles weight 1.3% is equipped with in the 50mL small beaker of dehydrated alcohol, stirring forms coupling agent solution after it dissolves completely, then under agitation coupling agent solution is added in composite zinc particle/alcohol mixed solution, and be warming up to 83 DEG C, under condensing reflux after Keep agitation 6.5h, be down to room temperature, reactant in flask is taken out after leaving standstill 24h again, filter, obtain filter cake, put into baking oven after repeatedly being cleaned by filter cake dehydrated alcohol, at 120 DEG C, dry 8.5h.Then be cooled to room temperature, obtain the composite structure zinc particles of surface modification.
3) preparation of composite structure zinc particles/PVDF polymer dielectric:
According to mass ratio PVDF: the composite structure zinc particles=60:40 of surface modification, the composite structure zinc particles of PVDF, surface modification to be inserted in high mixed cup after tentatively mixing, turn again after speed carries out 22min to 3000r/min and take out mixed powder sample, load coldmoulding in advance in mould, then by be cold-pressed into parison mixed powder in vacuum hotpressing machine 180 DEG C, hot pressing 12 minutes under 13MPa.Hot pressing is complete, slowly cools to room temperature, takes out sample, namely obtain core/shell structure zinc particles/PVDF dielectric medium from mould.
Embodiment 3
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 55% and the surface modification of 45% by mass percentage.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, spread in high temperature resistant porcelain crucible with thin layer form, the porcelain crucible holding zinc powder is inserted in retort furnace, at 450 DEG C, be oxidized 2h in air, take out high-temperature crucibles, be cooled to room temperature, take out sample, namely obtain composite structure zinc particles, stand-by.
2) surface modification of composite structure zinc particles:
Get 20g composite structure zinc particles and put into three-necked flask, add the dehydrated alcohol of 150mL again, under ul-trasonic irradiation, mechanical stirring is after 10 minutes, under ultrasonication, and carry out mechanical stirring and make composite structure zinc particles dispersed in dehydrated alcohol, obtain composite zinc particle/alcohol mixed solution.Being joined by the titanate coupling agent NDZ-102 of composite structure zinc particles weight 1.4% is equipped with in the 50mL small beaker of dehydrated alcohol, stirring forms coupling agent solution after it dissolves completely, then under agitation coupling agent solution is added in composite zinc particle/alcohol mixed solution, and be warming up to 80 DEG C, under condensing reflux after Keep agitation 8h, be down to room temperature, reactant in flask is taken out after leaving standstill 24h again, filter, obtain filter cake, put into baking oven after repeatedly being cleaned by filter cake dehydrated alcohol, at 105 DEG C, dry 9h.Then be cooled to room temperature, obtain the composite structure zinc particles of surface modification.
3) preparation of composite structure zinc particles/PVDF polymer dielectric:
According to mass ratio PVDF: the composite structure zinc particles=55:45 of surface modification, the composite structure zinc particles of PVDF, surface modification to be inserted in high mixed cup after tentatively mixing, turn again after speed carries out 25min to 2500r/min and take out mixed powder sample, load coldmoulding in advance in mould, then by be cold-pressed into parison mixed powder in vacuum hotpressing machine 190 DEG C, hot pressing 10 minutes under 14MPa.Hot pressing is complete, slowly cools to room temperature, takes out sample, namely obtain core/shell structure zinc particles/PVDF dielectric medium from mould.
Embodiment 4
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 57% and the surface modification of 43% by mass percentage.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, spread in high temperature resistant porcelain crucible with thin layer form, the porcelain crucible holding zinc powder is inserted in retort furnace, at 500 DEG C, be oxidized 2h in air, take out high-temperature crucibles, be cooled to room temperature, take out sample, namely obtain composite structure zinc particles, stand-by.
2) surface modification of composite structure zinc particles:
Get 20g composite structure zinc particles and put into three-necked flask, add the dehydrated alcohol of 140mL again, under ul-trasonic irradiation, mechanical stirring is after 14 minutes, under ultrasonication, and carry out mechanical stirring and make composite structure zinc particles dispersed in dehydrated alcohol, obtain composite zinc particle/alcohol mixed solution.Being joined by the titanate coupling agent A27 of composite structure zinc particles weight 1.2% is equipped with in the 50mL small beaker of dehydrated alcohol, stirring forms coupling agent solution after it dissolves completely, then under agitation coupling agent solution is added in composite zinc particle/alcohol mixed solution, and be warming up to 90 DEG C, under condensing reflux after Keep agitation 7.5h, be down to room temperature, reactant in flask is taken out after leaving standstill 26h again, filter, obtain filter cake, put into baking oven after repeatedly being cleaned by filter cake dehydrated alcohol, at 110 DEG C, dry 8h.Then be cooled to room temperature, obtain the composite structure zinc particles of surface modification.
3) preparation of composite structure zinc particles/PVDF polymer dielectric:
According to mass ratio PVDF: the composite structure zinc particles=57:43 of surface modification, the composite structure zinc particles of PVDF, surface modification to be inserted in high mixed cup after tentatively mixing, turn again after speed carries out 20min to 2200r/min and take out mixed powder sample, load coldmoulding in advance in mould, then by be cold-pressed into parison mixed powder in vacuum hotpressing machine 200 DEG C, hot pressing 13 minutes under 15MPa.Hot pressing is complete, slowly cools to room temperature, takes out sample, namely obtain core/shell structure zinc particles/PVDF dielectric medium from mould.
Embodiment 5
A kind of core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the polyvinylidene fluoride resin of 52% and the surface modification of 48% by mass percentage.
The dielectric preparation method of a kind of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, spread in high temperature resistant porcelain crucible with thin layer form, the porcelain crucible holding zinc powder is inserted in retort furnace, at 500 DEG C, be oxidized 3h in air, take out high-temperature crucibles, be cooled to room temperature, take out sample, namely obtain composite structure zinc particles, stand-by.
2) surface modification of composite structure zinc particles:
Get 20g composite structure zinc particles and put into three-necked flask, add the dehydrated alcohol of 125mL again, under ul-trasonic irradiation, mechanical stirring is after 15 minutes, under ultrasonication, and carry out mechanical stirring and make composite structure zinc particles dispersed in dehydrated alcohol, obtain composite zinc particle/alcohol mixed solution.Being joined by the titanate coupling agent NDZ-201 of composite structure zinc particles weight 1.5% is equipped with in the 50mL small beaker of dehydrated alcohol, stirring forms coupling agent solution after it dissolves completely, then under agitation coupling agent solution is added in composite zinc particle/alcohol mixed solution, and be warming up to 87 DEG C, under condensing reflux after Keep agitation 7h, be down to room temperature, reactant in flask is taken out after leaving standstill 26h again, filter, obtain filter cake, put into baking oven after repeatedly being cleaned by filter cake dehydrated alcohol, at 115 DEG C, dry 9.5h.Then be cooled to room temperature, obtain the composite structure zinc particles of surface modification.
3) preparation of composite structure zinc particles/PVDF polymer dielectric:
According to mass ratio PVDF: the composite structure zinc particles=52:48 of surface modification, the composite structure zinc particles of PVDF, surface modification to be inserted in high mixed cup after tentatively mixing, turn again after speed carries out 24min to 2800r/min and take out mixed powder sample, load coldmoulding in advance in mould, then by be cold-pressed into parison mixed powder in vacuum hotpressing machine 185 DEG C, hot pressing 15 minutes under 16MPa.Hot pressing is complete, slowly cools to room temperature, takes out sample, namely obtain core/shell structure zinc particles/PVDF dielectric medium from mould.
The acquisition of stable high-k, low-loss polymer needs a kind ofly novel both have certain insulativity, there is again the composite structure particle of higher local specific conductivity, utilize certain insulativity of such composite structure particle can reduce the dielectric loss of polymkeric substance, high-k-low-loss can be obtained by its local seep effect.The present invention adopts a kind of composite zinc particle with special construction, and namely nucleocapsid structure ZnOZn particle as shown in Figure 1, is namely core with metallic zinc, with thin layer insulating oxide zinc for shell.Utilize the electroconductibility of metallic zinc core, local seep effect significantly improves specific inductivity, the zinc oxide shell of characteristic of semiconductor not only improves compound material insulation, electric breakdown strength, also reduce dielectric loss, polymkeric substance is exceeded at filler and oozes consumption place and can obtain comparatively stable dielectric properties.
In the present invention, the preparation of core/shell structure composite zinc particle adopts oxidation style, at a certain temperature in atmosphere by the direct oxidation of metallic zinc particle, determines suitable oxidizing temperature and time processing parameter according to the thickness of zone of oxidation.Zinc powder is oxidized the XRD spectra of the composite structure zinc particles of the core/shell structure of generation as shown in Figure 2 under different process, as can be seen from Figure 2, after pure Zn powder of comparing oxidation respectively in 2 θ=31,34,47,56,63, there is the diffraction peak of ZnO crystal in the places such as 68, show to define zinc oxide shell on zinc particles surface after oxidation, and improve with oxidization time and temperature, diffraction peak intensity strengthens, and shows that zinc oxide thickness is in increase.
The polymer dielectric of the core/shell structure compound ZnOZn particulate reinforcement prepared by the present invention can produce multiple polarization under the electric field: the interfacial polarization namely between ZnO shell and insulating resin, interfacial polarization between ZnO and center Zn, and the polarization of other type.These multiple polarization of ZnO/Zn/ polymeric system can give dielectric medium higher specific inductivity, and contrast effect is shown in Table 1.The most important thing is to change ZnO layer thickness can Effective Regulation system specific inductivity.Other metal/polymer system relatively, ZnOZn/ polymkeric substance system can obtain high-k under lower composite particles consumption, this significantly improves and improves mechanical strength and the impelling strength of composite dielectrics, the high dielectric constant polymer dielectric medium with good strength and toughness can be prepared, effectively improve the dielectric mechanical property of high dielectric constant polymer, for its practical engineering application of solution, there is positive effect.
Table 1 sample result and Zn, Al polymeric system dielectric properties contrast
Claims (5)
1. the dielectric preparation method of core/shell structure zinc particles/PVDF, is characterized in that, comprise the following steps:
1) preparation of composite structure zinc particles: after being oxidized in air at 400-500 DEG C by spherical metal zinc powder, obtain composite structure zinc particles;
2) surface modification of composite structure zinc particles: be dispersed in dehydrated alcohol by composite structure zinc particles, obtains composite zinc particle/alcohol mixed solution; Titanate coupling agent is joined in dehydrated alcohol, stirring makes titanate coupling agent dissolve and obtains coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, filter after Keep agitation 6-8h under 80-90 DEG C of condensing reflux, obtain filter cake, filter cake is dried the composite structure zinc particles obtaining surface modification;
3) preparation of composite structure zinc particles/PVDF polymer dielectric: in mass ratio (50-60): the composite structure zinc particles of PVDF and surface modification mixes by (40-50), obtain mixed powder, by after mixed powder coldmoulding again in 180-200 DEG C, hot pressing 10-15 minute under 12-16MPa, obtain core/shell structure zinc particles/PVDF dielectric medium;
Described step 2) in dispersedly specifically under ultrasonication, carry out mechanical stirring.
2. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 1, is characterized in that, described step 1) in the particle diameter of composite structure zinc particles be 6-8 μm.
3. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 1, is characterized in that, described step 1) in oxidation time be 2-3h.
4. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 1, is characterized in that, the model of titanate coupling agent is NDZ-201, NDZ-101 or NDZ-102.
5. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 1, is characterized in that, described step 2) in dry temperature be 100-120 DEG C, the time of oven dry is 8-10h.
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