CN103980638A - Core/shell structural zinc particle/PVDF (polyvinylidene fluoride) dielectric medium and preparation method thereof - Google Patents
Core/shell structural zinc particle/PVDF (polyvinylidene fluoride) dielectric medium and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a core/shell structural zinc particle/PVDF (polyvinylidene fluoride) dielectric medium and a preparation method thereof. The core/shell structural zinc particle/PVDF dielectric medium comprises 50 to 60wt% of PVDF resin and 40 to 50 wt% of surface modified composite structural zinc particles; the core-shell structural zinc particle/PVDF dielectric medium is prepared in the steps such as peroxidation, powder mixing, cold pressing, hot pressing and the like. Based on a multi-interface polarization mode between the composite zinc particle and the polymer, the dielectric constant of polymer dielectric medium is improved by changing the thickness of ZnO so as to effectively control the variation of system dielectric constant, loss and electric conductivity, and the dielectric loss is reduced. Through the little consumption of composite particles, the composite dielectric medium has high mechanic strength and flexibility.
Description
Technical field
The intersection that the invention belongs to electrical material and Chemicals is manufactured field, is specifically related to a kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof.
Background technology
The high-k polymer dielectric of low-cost, easily processing, lightweight and excellent mechanical performances combines many performances of conventional dielectric material and the excellent in toughness of polymkeric substance, low cost, the easy feature such as machine-shaping, has caused extensive concern and the research in the world.High-k polymer dielectric has been used widely at aspects such as the embedded multilayer film electrical condenser of preparation and high energy storage capacitors; In addition, they also obtain important application in fields such as microelectronics, electric works, micro electronmechanical and biotechnology, and its research is one and enlivens very much field, has obtained remarkable progress.
At present, high-k, the low-dielectric loss polymkeric substance composite dielectrics by conductor, ferroelectric ceramic(s) particle and the compound preparation of polymkeric substance exists following drawback and problem in engineering application:
1) unstable in the polymkeric substance dielectric properties of conductive particle excess effusion value consumption vicinity, and high-k is often followed higher dielectric loss.
So far, research and development to 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 perplexing people, i.e. the circulation ratio of dielectric properties (stability) problem always.The dielectric properties that are in particular in this class matrix material are very responsive to its influence factor (the especially associated arguments of conductor), as amount of filler is exceeding near the trace variation of oozing threshold values and can cause the sharply variation of system specific conductivity, this has brought very big difficulty and challenge to stability etc. of its production control and material property.
In addition, near conductor filler percolation threshold, the specific inductivity of conductor/polymer dielectric reaches when the highest, and 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 can seriously reduce dielectric substance mechanical strength and toughness, also brings high dielectric loss simultaneously.
Due to the forfeiture of mechanical strength and impelling strength, high-k polymer dielectric when practical engineering application cannot be applied, loss is high in addition, can reduce the voltage breakdown of polymkeric substance.
Numerous research shows to rely on merely the conductive particles such as metal and carbon material or ferroelectric particle to obtain to have 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, a kind of core/shell structure zinc particles/PVDF dielectric medium and preparation method thereof is provided, the dielectric medium of preparation has higher force and learns intensity and toughness, stablizes high-k and low-loss.
For achieving the above object, the present invention adopts following technical scheme:
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 makes by the following method:
1) after spherical metal zinc powder is oxidized in air at 400-500 ℃, obtain composite structure zinc particles;
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 is dissolved titanate coupling agent and is obtained coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, continue to stir 6-8h under 80-90 ℃ of condensing reflux after, filter, obtain filter cake, filter cake is dried to the composite structure zinc particles that obtains 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 μ m.
The time of described oxidation is 2-3h.
Described dispersed specifically under ultrasonication and carry out mechanical stirring realization.
The temperature of described oven dry is 100-120 ℃, and the time of oven dry is 8-10h.
The dielectric preparation method of core/shell structure zinc particles/PVDF, comprises the following steps:
1) preparation of composite structure zinc particles: after spherical metal zinc powder is oxidized at 400-500 ℃ in air, obtain composite structure zinc particles;
2) surface modification of composite structure zinc particles: 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 is dissolved titanate coupling agent and is obtained coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, continue to stir 6-8h under 80-90 ℃ of condensing reflux after, filter, obtain filter cake, filter cake is dried to the composite structure zinc particles that obtains surface modification;
3) preparation of composite structure zinc particles/PVDF polymer dielectric: (50-60) in mass ratio: (40-50) the composite structure zinc particles of PVDF and surface modification is mixed, obtain mixed powder, by hot pressing 10-15 minute under 180-200 ℃, 12-16MPa again after mixed powder coldmoulding, obtain core/shell structure zinc particles/PVDF dielectric medium.
Described step 1) in, the particle diameter of composite structure zinc particles is 6-8 μ m.
Described step 1) in, the time of oxidation is 2-3h.
Described step 2) dispersed specifically under ultrasonication and carry out mechanical stirring in; The model of titanate coupling agent is NDZ-201, NDZ-101, NDZ-102 or A27.
The temperature of drying described step 2) is 100-120 ℃, and the time of oven dry is 8-10h.
Compared with prior art, the beneficial effect that the present invention has: the present invention has utilized the multiple interfacial polarization pattern between composite zinc particle and polymkeric substance, by changing the variation of ZnO thickness Effective Regulation system specific inductivity, loss and specific conductivity, improve the specific inductivity of polymer dielectric, and reduce dielectric loss.Lower composite particles consumption makes composite dielectrics have higher force and learns intensity and toughness.
The present invention adopts that powder mixes, colds pressing, pressure sintering is prepared polymer dielectric fast, relatively traditional solution method, and preparation technology's environmental protection, solvent-free pollution, relatively easy, be easy to realize suitability for industrialized production; And preparation technology is relatively easy, and processing characteristics is good.
With comparing of compound Al particle system, compound ZnO/Zn/ polymeric system prepared by the present invention is because utilized the multiple polarization feature of nucleocapsid zinc particles, therefore system has following clear superiority: 1) more high-k and well mechanical strength and toughness.ZnO/Zn/ polymeric system has more high-k under compared with low sizing consumption; When ZnO/Zn massfraction is 40%, poly-inclined to one side fluorine divinyl specific inductivity approaches 100, and the specific inductivity of Al/ polymkeric substance is 30 when massfraction is 40%, and when Al consumption reaches 70%, system specific inductivity just reaches 50.Along with amount of filler increases, must cause the mechanical property of polymeric system to worsen; 2) outer crystal ZnO thermal conductivity (50W/m K) is far above noncrystal Al
2o
3the thermal conductivity of housing (2-8W/m K), so whole system thermal conductivity is higher than compound Al particle system.
Polymer dielectric prepared by the present invention is mainly dried by the poly-inclined to one side fluorine divinyl toner of raw material and the composite zinc particle process with core/shell structure, powder mixes, cold pressing, the processes such as hot pressing are prepared from, it is a kind of high-k based on the good mechanical strength of possessing of multiple interfacial polarization pattern and impelling strength, 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., in high frequency communication, LED illumination, automotive electronics, computer, on 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.
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 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 parts, as shown in Figure 3.
1) composite structure zinc particles preparation:
Take about 30g spherical metal zinc powder, with thin layer form, spread in high temperature resistant porcelain crucible, the porcelain crucible that holds zinc powder is inserted in retort furnace, at 500 ℃, in air, be oxidized about 2-3h, take out high-temperature crucibles, be cooled to room temperature, take out sample, 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, the dehydrated alcohol that adds again 120-150mL, 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.The titanate coupling agent NDZ-201 of the about 1.2-1.5% of composite structure zinc particles weight is joined in the 50ml small beaker that dehydrated alcohol is housed, 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 ℃, under condensing reflux, continue after stir about 6-8h, be down to room temperature, after standing 24-26h, take out again reactant in flask, filter, obtain filter cake, after filter cake is cleaned repeatedly with dehydrated alcohol, put into baking oven, at 100-120 ℃, 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: the composite structure zinc particles of surface modification=(50-60): (40-50), the composite structure zinc particles of PVDF, surface modification is inserted in high mixed cup after preliminary mixing, turn speed carries out taking out mixed powder sample after about 20-25min to 2000-3000r/min again, pack coldmoulding in advance in mould into, then by the mixed powder that is cold-pressed into parison in vacuum hotpressing machine under 180-200 ℃, 12-16MPa the about 10-15 minute of hot pressing.Hot pressing is complete, slowly cools to room temperature, from mould, takes out sample, obtains core/shell structure zinc particles/PVDF dielectric medium.
Below by specific embodiment, describe.
Embodiment 1
Core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the surface modification of 50% polyvinylidene fluoride resin and 50% by mass percentage.
The dielectric preparation method of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take about 30g spherical metal zinc powder, with thin layer form, spread in high temperature resistant porcelain crucible, the porcelain crucible that holds zinc powder is inserted in retort furnace, at 400 ℃, in air, be oxidized about 2h, take out high-temperature crucibles, be cooled to room temperature, take out sample, 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, the dehydrated alcohol that adds again 120mL, 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.The titanate coupling agent NDZ-201 that accounts for composite structure zinc particles weight approximately 1.5% is joined in the 50mL small beaker that dehydrated alcohol is housed, 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 ℃, under condensing reflux, continue after stir about 6h, be down to room temperature, after standing 25h, take out again reactant in flask, filter, obtain filter cake, after filter cake is cleaned repeatedly with dehydrated alcohol, put into baking oven, at 100 ℃, 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 is inserted in high mixed cup after preliminary mixing, turn speed carries out taking out mixed powder sample after about 20min to 2000r/min again, pack coldmoulding in advance in mould into, then by the mixed powder that is cold-pressed into parison hot pressing approximately 15 minutes under 200 ℃, 12MPa in vacuum hotpressing machine.Hot pressing is complete, slowly cools to room temperature, from mould, takes out sample, obtains core/shell structure zinc particles/PVDF dielectric medium.
Embodiment 2
Core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the surface modification of 60% polyvinylidene fluoride resin and 40% by mass percentage.
The dielectric preparation method of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, with thin layer form, spread in high temperature resistant porcelain crucible, the porcelain crucible that holds zinc powder is inserted in retort furnace, at 400 ℃, in air, be oxidized 3h, take out high-temperature crucibles, be cooled to room temperature, take out sample, 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, the dehydrated alcohol that adds again 130mL, 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.The titanate coupling agent NDZ-101 of composite structure zinc particles weight 1.3% is joined in the 50mL small beaker that dehydrated alcohol is housed, 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 ℃, under condensing reflux, continue to stir after 6.5h, be down to room temperature, after standing 24h, take out again reactant in flask, filter, obtain filter cake, after filter cake is cleaned repeatedly with dehydrated alcohol, put into baking oven, at 120 ℃, 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 is inserted in high mixed cup after preliminary mixing, turn speed carries out taking out mixed powder sample after 22min to 3000r/min again, pack coldmoulding in advance in mould into, then by the mixed powder that is cold-pressed into parison hot pressing 12 minutes under 180 ℃, 13MPa in vacuum hotpressing machine.Hot pressing is complete, slowly cools to room temperature, from mould, takes out sample, obtains core/shell structure zinc particles/PVDF dielectric medium.
Embodiment 3
Core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the surface modification of 55% polyvinylidene fluoride resin and 45% by mass percentage.
The dielectric preparation method of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, with thin layer form, spread in high temperature resistant porcelain crucible, the porcelain crucible that holds zinc powder is inserted in retort furnace, at 450 ℃, in air, be oxidized 2h, take out high-temperature crucibles, be cooled to room temperature, take out sample, 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, the dehydrated alcohol that adds again 150mL, 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.The titanate coupling agent NDZ-102 of composite structure zinc particles weight 1.4% is joined in the 50mL small beaker that dehydrated alcohol is housed, 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 ℃, under condensing reflux, continue to stir after 8h, be down to room temperature, after standing 24h, take out again reactant in flask, filter, obtain filter cake, after filter cake is cleaned repeatedly with dehydrated alcohol, put into baking oven, at 105 ℃, 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 is inserted in high mixed cup after preliminary mixing, turn speed carries out taking out mixed powder sample after 25min to 2500r/min again, pack coldmoulding in advance in mould into, then by the mixed powder that is cold-pressed into parison hot pressing 10 minutes under 190 ℃, 14MPa in vacuum hotpressing machine.Hot pressing is complete, slowly cools to room temperature, from mould, takes out sample, obtains core/shell structure zinc particles/PVDF dielectric medium.
Embodiment 4
Core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the surface modification of 57% polyvinylidene fluoride resin and 43% by mass percentage.
The dielectric preparation method of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, with thin layer form, spread in high temperature resistant porcelain crucible, the porcelain crucible that holds zinc powder is inserted in retort furnace, at 500 ℃, in air, be oxidized 2h, take out high-temperature crucibles, be cooled to room temperature, take out sample, 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, the dehydrated alcohol that adds again 140mL, 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.The titanate coupling agent A27 of composite structure zinc particles weight 1.2% is joined in the 50mL small beaker that dehydrated alcohol is housed, 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 ℃, under condensing reflux, continue to stir after 7.5h, be down to room temperature, after standing 26h, take out again reactant in flask, filter, obtain filter cake, after filter cake is cleaned repeatedly with dehydrated alcohol, put into baking oven, at 110 ℃, 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 is inserted in high mixed cup after preliminary mixing, turn speed carries out taking out mixed powder sample after 20min to 2200r/min again, pack coldmoulding in advance in mould into, then by the mixed powder that is cold-pressed into parison hot pressing 13 minutes under 200 ℃, 15MPa in vacuum hotpressing machine.Hot pressing is complete, slowly cools to room temperature, from mould, takes out sample, obtains core/shell structure zinc particles/PVDF dielectric medium.
Embodiment 5
Core/shell structure zinc particles/PVDF dielectric medium, comprises the composite structure zinc particles of the surface modification of 52% polyvinylidene fluoride resin and 48% by mass percentage.
The dielectric preparation method of core/shell structure zinc particles/PVDF, comprises the following steps:
1) composite structure zinc particles preparation:
Take 30g spherical metal zinc powder, with thin layer form, spread in high temperature resistant porcelain crucible, the porcelain crucible that holds zinc powder is inserted in retort furnace, at 500 ℃, in air, be oxidized 3h, take out high-temperature crucibles, be cooled to room temperature, take out sample, 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, the dehydrated alcohol that adds again 125mL, 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.The titanate coupling agent NDZ-201 of composite structure zinc particles weight 1.5% is joined in the 50mL small beaker that dehydrated alcohol is housed, 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 ℃, under condensing reflux, continue to stir after 7h, be down to room temperature, after standing 26h, take out again reactant in flask, filter, obtain filter cake, after filter cake is cleaned repeatedly with dehydrated alcohol, put into baking oven, at 115 ℃, 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 is inserted in high mixed cup after preliminary mixing, turn speed carries out taking out mixed powder sample after 24min to 2800r/min again, pack coldmoulding in advance in mould into, then by the mixed powder that is cold-pressed into parison hot pressing 15 minutes under 185 ℃, 16MPa in vacuum hotpressing machine.Hot pressing is complete, slowly cools to room temperature, from mould, takes out sample, obtains core/shell structure zinc particles/PVDF dielectric medium.
Stable high-k, the acquisition of low-loss polymer need a kind of novel certain insulativity that both has, the composite structure particle again with higher local specific conductivity, utilize certain insulativity of such composite structure particle can reduce the dielectric loss of polymkeric substance, by its local seep effect, can obtain high-k-low-loss.The present invention adopts a kind of composite zinc particle with special construction, and nucleocapsid structure ZnOZn particle as shown in Figure 1, be take metallic zinc as core, and the thin layer insulating oxide zinc of take is shell.Utilize electroconductibility, the local seep effect of metallic zinc core to significantly improve specific inductivity, the zinc oxide shell of characteristic of semiconductor not only improves compound material insulation, electric breakdown strength, also reduce dielectric loss, make polymkeric substance exceed and ooze consumption place and can obtain comparatively stable dielectric properties at filler.
In the present invention, core/shell structure composite zinc particle preparation adopts oxidation style, at a certain temperature in air by the direct oxidation of metallic zinc particle, according to the thickness of zone of oxidation, determine suitable oxidizing temperature and time processing parameter.Zinc powder under different process, be oxidized the core/shell structure generating composite structure zinc particles XRD spectra as shown in Figure 2, as can be seen from Figure 2, compare after the oxidation of pure Zn powder respectively in 2 θ=31,34,47,56,63, the diffraction peaks of having located to occur ZnO crystal such as 68, show on zinc particles surface, to have formed zinc oxide shell after oxidation, and improve with oxidization time and temperature, diffraction peak intensity strengthens, and shows that zinc oxide thickness is increasing.
The polymer dielectric of the compound ZnOZn particulate reinforcement of core/shell structure that the present invention is prepared can produce multiple polarization under electric field: i.e. interfacial polarization between interfacial polarization between ZnO shell and insulating resin, ZnOYu center Zn, and the polarization of other type.These multiple polarization of ZnO/Zn/ polymeric system can be given the specific inductivity that dielectric medium is higher, and contrast effect is shown in Table 1.The most important thing is to change ZnO layer thickness can Effective Regulation system specific inductivity.Relative other metal/polymer system, ZnOZn/ polymkeric substance can system obtain high-k under lower composite particles consumption, this significantly improves and has improved mechanical strength and the impelling strength of composite dielectrics, can prepare the high-k polymer dielectric with good strength and toughness, effectively improve the mechanical property of high-k polymer dielectric, for solving its practical engineering application, there is positive effect.
Table 1 sample result and Zn, the contrast of Al polymeric system dielectric properties
Claims (10)
1. core/shell structure zinc particles/PVDF dielectric medium, is characterized in that, comprises by mass percentage the composite structure zinc particles of the polyvinylidene fluoride resin of 50-60% and the surface modification of 40-50%; Wherein, the composite structure zinc particles of surface modification makes by the following method:
1) after spherical metal zinc powder is oxidized in air at 400-500 ℃, obtain composite structure zinc particles;
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 is dissolved titanate coupling agent and is obtained coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, continue to stir 6-8h under 80-90 ℃ of condensing reflux after, filter, obtain filter cake, filter cake is dried to the composite structure zinc particles that obtains surface modification; Wherein, in coupling agent solution, titanate coupling agent is the 1.2-1.5% of composite structure zinc particles quality.
2. a kind of core/shell structure zinc particles/PVDF dielectric medium according to claim 1, is characterized in that, the particle diameter of described composite structure zinc particles is 6-8 μ m.
3. a kind of core/shell structure zinc particles/PVDF dielectric medium according to claim 1, is characterized in that, the time of described oxidation is 2-3h.
4. a kind of core/shell structure zinc particles/PVDF dielectric medium according to claim 1, is characterized in that, described dispersed specifically under ultrasonication and carry out mechanical stirring realization.
5. a kind of core/shell structure zinc particles/PVDF dielectric medium according to claim 1, is characterized in that, the temperature of described oven dry is 100-120 ℃, and the time of oven dry is 8-10h.
6. the dielectric preparation method of core/shell structure zinc particles/PVDF, is characterized in that, comprises the following steps:
1) preparation of composite structure zinc particles: after spherical metal zinc powder is oxidized in air at 400-500 ℃, obtain composite structure zinc particles;
2) surface modification of composite structure zinc particles: 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 is dissolved titanate coupling agent and is obtained coupling agent solution, under stirring, coupling agent solution is joined in composite zinc particle/alcohol mixed solution, continue to stir 6-8h under 80-90 ℃ of condensing reflux after, filter, obtain filter cake, filter cake is dried to the composite structure zinc particles that obtains surface modification;
3) preparation of composite structure zinc particles/PVDF polymer dielectric: (50-60) in mass ratio: (40-50) the composite structure zinc particles of PVDF and surface modification is mixed, obtain mixed powder, by hot pressing 10-15 minute under 180-200 ℃, 12-16MPa again after mixed powder coldmoulding, obtain core/shell structure zinc particles/PVDF dielectric medium.
7. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 6, is characterized in that described step 1) in the particle diameter of composite structure zinc particles be 6-8 μ m.
8. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 6, is characterized in that described step 1) in oxidation time be 2-3h.
9. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 6, is characterized in that described step 2) in dispersed specifically under ultrasonication and carry out mechanical stirring; The model of titanate coupling agent is NDZ-201, NDZ-101, NDZ-102 or A27.
10. the dielectric preparation method of a kind of core/shell structure zinc particles/PVDF according to claim 6, is characterized in that described step 2) in the temperature of drying be 100-120 ℃, the time of oven dry is 8-10h.
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