CN101955621A - Method for preparing polymer-based nanocomposite material with high dielectric constant - Google Patents
Method for preparing polymer-based nanocomposite material with high dielectric constant Download PDFInfo
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- CN101955621A CN101955621A CN2009100892718A CN200910089271A CN101955621A CN 101955621 A CN101955621 A CN 101955621A CN 2009100892718 A CN2009100892718 A CN 2009100892718A CN 200910089271 A CN200910089271 A CN 200910089271A CN 101955621 A CN101955621 A CN 101955621A
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Abstract
The invention relates to a method for preparing a polymer-based nanocomposite material with high dielectric constant, and belongs to the field of high polymer nanomaterials. The method comprises the following steps of: adding barium titanate powder with the granularity of 30 to 60nm and polyvinylidene fluoride with the granularity of 0.1 to 0.2mu m into anhydrous ethanol for ultrasonic dispersion, drying, and hot-pressing on a powder tablet machine at the temperature of between 180 and 200 DEG C and under the pressure of between 10 and 15MPa to obtain the polymer-based nanocomposite material with high dielectric constant, wherein the barium titanate powder accounts for 10 to 60 percent of the total volume of the barium titanate powder and the polyvinylidene fluoride. The method has the advantages of simple process, easy operation, low cost and light environmental pollution.
Description
Technical field
The invention belongs to the high molecule nano material field, be specifically related to a kind of preparation method of high-k polymer based nanocomposites.
Background technology
Nanometer composite inorganic particle/polymer material had both had low processing temperature of polymkeric substance and snappiness, had the high specific inductivity of inorganic materials again, so in recent years, was subjected to paying attention to widely in the electronics industry that develops rapidly.But the inorganic particulate powder that is filled at present in the polymkeric substance approaches micro-meter scale more, and the diameter of some particle even reach 10 μ m has limited the thickness of composite material film
At present, generally adopt mechanical mixing-prepare the high dielectric nano composite material of inorganic particle/polymer both at home and abroad as ball mill mixing, melting mixing or sol-gel method.Yet this class preparation method energy consumption is big, and complex process and material microstructure are wayward.For example the people such as Rao of the U.S. adopt ball milling machinery blended method, make dispersion agent with phosphoric acid salt fat, fill PMN-PT (PMN-PT) and the barium titanate (BaTiO that median size is respectively 0.90 μ m and 0.050 μ m with 4: 1 ratios
3), with 220r/min speed ball milling one day, prepared specific inductivity up to Resins, epoxy (EXPOY)/PMN-PT/BaTiO of 150
3High dielectric nano composite material (Rao Y, Ogitani S, C.P.Wong.Novel Polymer-Ceramic Nanocomposite Based on High Dielectric Constant Epoxy Formula for Embedded Capacitor pplication[J], Journal of Applied Polymer Science, 2002,83,1084-1090 (2002)).People such as the Dong Li outstanding person of Wuhan University adopt IN-SITU SOL-GEL to prepare polyvinylidene difluoride (PVDF) (PVDF)/BaTiO
3Nano composite material, BaTiO in the matrix material
3Particle diameter is 50-100nm, and the specific inductivity measured at 1MHz is not high, and dielectric loss also big (Dong Lijie, bear passes small stream .PVDF/ modification BaTiO3 matrix material Dielectric Properties [J]. polymer material science and engineering, 2003,9 (1): 153-155).In sum, adopt the mechanical mixing energy consumption big, the cost height; And with chemical process (as sol-gel method) complicated process of preparation, processing condition are strict more, and employed chemical reagent causes certain pollution to environment.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and provide a kind of preparation technology simple, energy consumption is low, and is with low cost, pollutes the preparation method of few high-k polymer based nanocomposites.
The preparation method of high-k polymer based nanocomposites provided by the present invention may further comprise the steps:
With granularity is that the barium carbonate powder of 30～60nm and polyvinylidene difluoride (PVDF) that granularity is 0.1～0.2 μ m add in the dehydrated alcohol after the ultrasonic dispersing, oven dry, and, obtain the high-k polymer based nanocomposites in hot pressing under 180～200 ℃ and 10～15MPa pressure on the powder compressing machine; Wherein, the consumption of barium carbonate powder is 10～60% of barium carbonate powder and a polyvinylidene difluoride (PVDF) cumulative volume.
The present invention has following beneficial effect:
1) the present invention by with dehydrated alcohol as dispersion medium, make the nano barium phthalate particle be adsorbed onto polyvinylidene fluoride surface, effectively reduced the thickness of matrix material, simultaneously prepared matrix material dielectric properties and good toughness.
2) method provided by the present invention is easy and simple to handle, and preparation cycle is short, and energy consumption and cost are low, pollutes few.
Description of drawings
Fig. 1, A and B are respectively the TEM photo of the mixed powder of preparation among embodiment two and the embodiment four; C and D are the brittle failure face TEM photos that is respectively the high-k polymer based nanocomposites of preparation among embodiment two and the embodiment four.
The X-ray diffractogram of Fig. 2, barium titanate and high-k polymer based nanocomposites; Wherein, the corresponding pure barium titanate powder of a, the corresponding Comparative Examples of b, the corresponding embodiment one of c, the corresponding embodiment three of d, the corresponding embodiment five of e.
Fig. 3, when room temperature and 1KHz and 10MHz the relation of the shared volume fraction of barium titanate in the specific inductivity of high-k polymer based nanocomposites and dielectric loss and the matrix material; Built-in figure is the result of Maxwell-Garnett's Equation for Calculating.
Fig. 4, (a) are the specific inductivity of high-k polymer based nanocomposites and the relation of frequency; (b) be the dielectric loss of high-k polymer based nanocomposites and the relation of frequency; Among two width of cloth figure, the corresponding Comparative Examples (f of curve a
BaTiO3Be the shared volume fraction of barium titanate in the matrix material), the corresponding embodiment one of b, the corresponding embodiment two of c, the corresponding embodiment three of d, the corresponding embodiment four of e, the corresponding embodiment five of f.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
The granularity of employed barium carbonate powder is 30～60nm among following Comparative Examples and the embodiment; The granularity of polyvinylidene difluoride (PVDF) is 0.1～0.2 μ m.
Comparative Examples
With 0.537 gram polyvinylidene difluoride (PVDF) powder hot pressing on thermocompressor (temperature is 200 ℃, and pressure is 15MPa, and the time is 20min) moulding.The XRD analysis of sample is shown in (b) among Fig. 2, and the dielectric characteristics of sample is shown in (a) among Fig. 4.
Embodiment one
Behind ultrasonic dispersing 10min in the 0.1755 gram nano barium carbonate powder adding 10ml dehydrated alcohol, add 0.4833 gram polyvinylidene difluoride (PVDF) and continue supersound process 30min, gained suspension is placed glass disc, and in 50 ℃ the baking 3hr (ethanol is evaporated fully) obtain mixed powder, (temperature is 200 ℃ with mixed powder hot pressing on thermocompressor, pressure is 15MPa, and the time is 20min) moulding, the volume fraction that obtains barium titanate is 10% high-k polymer based nanocomposites.The XRD analysis of sample is shown in (c) among Fig. 2, and the dielectric characteristics of sample is shown in (b) among Fig. 4.
Embodiment two
Behind ultrasonic dispersing 10min in the 0.3510 gram nano barium carbonate powder adding 10ml dehydrated alcohol, add 0.4296 gram polyvinylidene difluoride (PVDF) and continue supersound process 30min, gained suspension is placed glass disc, and in 50 ℃ the baking 3hr (ethanol is evaporated fully) obtain mixed powder, (temperature is 200 ℃ with mixed powder hot pressing on thermocompressor, pressure is 15MPa, and the time is 20min) moulding, the volume fraction that obtains barium titanate is 20% high-k polymer based nanocomposites.The microstructure picture of sample is shown in Fig. 1 (c), and the dielectric characteristics of sample is shown in (c) among Fig. 4.
Embodiment three
Behind ultrasonic dispersing 10min in the 0.5265 gram nano barium carbonate powder adding 10ml dehydrated alcohol, add 0.3759 gram polyvinylidene difluoride (PVDF) and continue supersound process 30min, gained suspension is placed glass disc, and in 50 ℃ the baking 3hr (ethanol is evaporated fully) obtain mixed powder, (temperature is 200 ℃ with mixed powder hot pressing on thermocompressor, pressure is 15MPa, and the time is 20min) moulding, the volume fraction that obtains barium titanate is 30% high-k polymer based nanocomposites.The XRD analysis of sample is shown in (d) among Fig. 2, and the dielectric characteristics of sample is shown in (d) among Fig. 4.
Embodiment four
Behind ultrasonic dispersing 10mi n in the 0.7020 gram nano barium carbonate powder adding 10ml dehydrated alcohol, add 0.3222 gram polyvinylidene difluoride (PVDF) and continue supersound process 30min, gained suspension is placed glass disc, and in 50 ℃ the baking 3hr (ethanol is evaporated fully) obtain mixed powder, (temperature is 200 ℃ with mixed powder hot pressing on thermocompressor, pressure is 15MPa, and the time is 20min) moulding, the volume fraction that obtains barium titanate is 40% high-k polymer based nanocomposites.The microstructure picture of sample is shown in Fig. 1 (d), and the dielectric characteristics of sample is shown in (e) among Fig. 4.
Embodiment five
Behind ultrasonic dispersing 10min in the 0.8775 gram nano barium carbonate powder adding 10ml dehydrated alcohol, add 0.2685 gram polyvinylidene difluoride (PVDF) and continue supersound process 30min, gained suspension is placed glass disc, and in 50 ℃ the baking 3hr (ethanol is evaporated fully) obtain mixed powder, (temperature is 200 ℃ with mixed powder hot pressing on thermocompressor, pressure is 15MPa, and the time is 20min) moulding, the volume fraction that obtains barium titanate is 50% high-k polymer based nanocomposites.The XRD analysis of sample is shown in (e) among Fig. 2, and the dielectric characteristics of sample is shown in (f) among Fig. 4.
Claims (1)
1. the preparation method of a high-k polymer based nanocomposites is characterized in that, may further comprise the steps:
With granularity is that the barium carbonate powder of 30～60nm and granularity are that 0.1～0.2 μ m polyvinylidene difluoride (PVDF) adds in the dehydrated alcohol after the ultrasonic dispersing, oven dry, and, obtain the high-k polymer based nanocomposites in hot pressing under 180～200 ℃ and 10～15MPa pressure on the powder compressing machine; Wherein, the consumption of barium carbonate powder is 10～60% of barium carbonate powder and a polyvinylidene difluoride (PVDF) cumulative volume.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102810407A (en) * | 2012-07-31 | 2012-12-05 | 中国科学院化学研究所 | Preparation method of high energy storage and pure solid supercapacitor |
| CN102875939A (en) * | 2012-10-22 | 2013-01-16 | 北京工业大学 | Preparation method of potassium niobate/ polyvinylidene fluoride high-dielectric composite material |
| CN103531268A (en) * | 2012-06-29 | 2014-01-22 | 施耐德电器工业公司 | Dielectric compositions containing nanoparticles |
| CN104151586A (en) * | 2014-08-22 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Dielectric composite thin film |
| CN105681497A (en) * | 2015-12-29 | 2016-06-15 | 东莞市青麦田数码科技有限公司 | Anti-theft mobile phone shell based on piezoelectric fingerprint sensors |
| CN110452421A (en) * | 2019-08-30 | 2019-11-15 | 中南大学 | A kind of dielectric composite material based on core-shell structure filler |
| CN113999427A (en) * | 2021-11-23 | 2022-02-01 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of barium titanate dielectric composite material |
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2009
- 2009-07-15 CN CN2009100892718A patent/CN101955621A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531268A (en) * | 2012-06-29 | 2014-01-22 | 施耐德电器工业公司 | Dielectric compositions containing nanoparticles |
| CN103531268B (en) * | 2012-06-29 | 2017-08-15 | 施耐德电器工业公司 | Dielectric combination containing nano particle |
| CN102810407A (en) * | 2012-07-31 | 2012-12-05 | 中国科学院化学研究所 | Preparation method of high energy storage and pure solid supercapacitor |
| CN102875939A (en) * | 2012-10-22 | 2013-01-16 | 北京工业大学 | Preparation method of potassium niobate/ polyvinylidene fluoride high-dielectric composite material |
| CN102875939B (en) * | 2012-10-22 | 2014-09-03 | 北京工业大学 | Preparation method of potassium niobate/ polyvinylidene fluoride high-dielectric composite material |
| CN104151586A (en) * | 2014-08-22 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Dielectric composite thin film |
| CN105681497A (en) * | 2015-12-29 | 2016-06-15 | 东莞市青麦田数码科技有限公司 | Anti-theft mobile phone shell based on piezoelectric fingerprint sensors |
| CN110452421A (en) * | 2019-08-30 | 2019-11-15 | 中南大学 | A kind of dielectric composite material based on core-shell structure filler |
| CN110452421B (en) * | 2019-08-30 | 2021-05-07 | 中南大学 | Dielectric composite material based on core-shell structure filler |
| CN113999427A (en) * | 2021-11-23 | 2022-02-01 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of barium titanate dielectric composite material |
| CN113999427B (en) * | 2021-11-23 | 2022-12-06 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of barium titanate dielectric composite material |
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