PVDF基介电复合膜的研究
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摘要
随着电子工业的发展，要求电介质材料具有更高的介电常数、更低的介电损耗。传统的陶瓷材料具有非常高的介电常数，但是制备工艺复杂、易脆且介电损耗较大，将它们制成电容器，在充电和放电的过程中还会发生机械共振，大大降低了其寿命。有机聚合物柔韧性好、介电损耗低、易于加工，但是介电常数较低。为了获得高介电性能的电介质材料，科研工作者们做了大量的工作。一种方法是将高介电常数的陶瓷添加到聚合物中，制备了陶瓷-聚合物复合材料。高含量的陶瓷虽然能够提高复合材料的介电常数，但是降低了复合材料的柔韧性。另一种方法是将导电材料添加到聚合物中，复合材料在渗流阈值处的介电常数可以提高几个数量级，但是介电损耗也会相应的增加。因此,制备高介电性能的聚合物基复合材料具有非常重要的意义。
本论文以聚偏氟乙烯（PVDF）、聚偏氟乙烯-三氟乙烯（PVDF-TrFE）为基体，制备了不同填料的复合膜材料。通过对复合膜的微观形貌、结晶行为、介电性能等表征，探讨了填料对复合膜性能的影响。主要研究内容如下：
（1）通过溶胶凝胶法制备了不同晶型的二氧化钛(TiO_2)，并制备了TiO_2/PVDF-TrFE复合膜。扫描电镜表明TiO_2能够较好地分散在PVDF-TrFE基体中，并对复合膜的结晶行为起着非常重要的作用。少量的TiO_2有利于PVDF-TrFE在其表面结晶，提高了复合膜的结晶度；大量的TiO_2则破坏了PVDF-TrFE的分子链的规整度，降低了复合膜的结晶度。此外，金红石型二氧化钛更有利于PVDF-TrFE在其表面结晶。介电测试结果表明复合膜的介电常数随着TiO_2掺杂量的增加而增大。在相同的掺杂量下，掺杂金红石型二氧化钛复合膜的介电常数要高于掺杂锐钛矿型二氧化钛复合膜的介电常数。高温加速了PVDF-TrFE的分子运动，增加了二氧化钛的电导率，从而提高了复合膜的介电常数和介电损耗。
（2）将纳米级的Ni-TiO_2添加到PVDF-TrFE中，研究了Ni-TiO_2对复合膜结晶性能、介电性能的影响。结果表明Ni-TiO_2的加入使得PVDF-TrFE由极性的β相向非极性的晶相转变；复合膜的介电常数随着Ni-TiO_2掺杂量的增加而增加，介电损耗依然保持着较低的数值（0.046-0.064）。在相同的Nix-TiO_2掺杂量下，复合膜的介电常数随着Nix-TiO_2中Ni含量的增加而增加，介电损耗几乎没有发生变化。
（3）通过水热法制备了Na_2Ti_2O_4(OH)_2纳米管，并将纳米管添加到PVDF中。扫描电镜表明Na_2Ti_2O_4(OH)_2纳米管能够较好的分散在PVDF中，随着掺杂量的增加，纳米管在PVDF中逐渐形成导通的网状结构。DSC结果表明Na_2Ti_2O_4(OH)_2纳米管影响了复合膜的结晶性能。少量的纳米管有利于PVDF在其表面结晶，提高了复合膜的结晶度。随着纳米管的增加，纳米管破坏了PVDF分子链的规整度，降低了复合膜的结晶度。介电测试结果表明Na_2Ti_2O_4(OH)_2纳米管大幅度的提高了Na_2Ti_2O_4(OH)_2/PVDF、Na_2Ti_2O_4(OH)_2/PVDF-TrFE复合膜的介电性能。当掺杂量为18vol%时，Na_2Ti_2O_4(OH)_2/PVDF复合膜在100Hz的介电常数高达178.7，约为PVDF的20倍；Na_2Ti_2O_4(OH)_2/PVDF-TrFE复合膜的介电常数则高达330，约为PVDF-TrFE的25倍。经过计算发现实验结果符合渗流模型。向聚合物中添加Na_2Ti_2O_4(OH)_2纳米管大幅度提高复合材料的介电常数，相关文献至今未见报道。
（4）通过水热法制备了核壳型Ag@C纳米材料，银核的大小为100-120nm，碳壳的大小为60-80nm。将核壳型Ag@C纳米材料分别添加到PVDF、PVDF-TrFE中，研究了核壳型Ag@C纳米材料对PVDF系列聚合物热力学稳定性、结晶性能、介电性能的影响。扫描电镜表明Ag@C均匀的分散在PVDF、PVDF-TrFE中，并未发生团聚现象，这是由于核壳型Ag@C纳米材料表面的羟基与氟原子产生氢键，从而提高了它们之间的相容性。DSC测试结果表明Ag@C的加入降低了复合膜的结晶度。介电测试结果表明Ag@C/PVDF、Ag@C/PVDF-TrFE复合膜的介电常数随着Ag@C的增加而增加，介电损耗保持着非常低的数值。较低的介电损耗是由于碳壳提高了Ag@C与PVDF的相容性，防止了银颗粒由于相互接触而引起较大的介电损耗。复合膜的介电常数、介电损耗对温度有较强的依赖性。
With the development of electronic industry，dielectric materials withhigh permittivity (k) and low dielectric loss are attracted much attentions.Traditional ceramic materials have high permittivity, but they are brittle, hardto fabricate, and have high dielectric loss. Besides, they will generatemechanical resonance during charging and discharging and thus reduced theirlife-span. Polymers are light-weight, flexible, and easily integrated. However,they show a relatively low permittivity. Much work has been focused onraising the k of polymer-based composites. One effective method is to addhigh-k ceramics into the polymers to form organic-ceramic composites. Highloadings of ceramic fillers can increase the k of the composites, butdramatically decrease the flexibility of the composites. Another method is tointroduce conductive materials into the polymer matrix to form percolativecomposites. The k of such composites is at least two orders of magnitudehigher than that of the polymer matrix. However, the dielectric loss increasesrapidly with increasing amount of conductive materials. Therefore, it is ofgreat importance to prepare polymer-based composites with high dielectricperformance.
In this paper, Poly(vinylidene fluoride)(PVDF) and poly(vinylidene -trifluoroethylene)(PVDF-TrFE) were chosen as the polymer matrix anddifferent membranes were prepared through solution cast method. Themicrostructure， crystallization behavior， and dielectric properties werecharacterized and the corresponding reasons were studied. The detailedinformation is listed as follows:
(1) Titanium dioxide nanoparticles with two different phases wereprepared by the sol-gel method. Poly(vinylidene-trifluoroethylene)/titaniumdioxide (TiO_2/PVDF-TrFE) membranes were prepared by the solution castmethod. Scanning electron microscope (SEM) results showed that the TiO_2nanoparticles were well dispersed in the polymer matrix and did not affect thestructure of the PVDF-TrFE matrix. Differential scanning calorimeter (DSC)results showed that crystallinity of TiO_2/PVDF-TrFE membranes increased asthe addition of TiO_2with two different phases. Besides, the crystallinity ofTiO_2/PVDF-TrFE membrane with the rutile TiO_2is higher than that of themembrane with the anatase TiO_2. Dielectric property testing showed that thepermittivity of TiO_2/PVDF-TrFE membrane increased rapidly with theincrease of TiO_2content, but the dielectric loss remains at a low level. Theincrease in permittivity is attributed to the interfacial polarization. At the sameTiO_2content, the permittivity of TiO_2/PVDF-TrFE membrane with the rutileTiO_2is higher than that of the membrane with the anatase TiO_2. Hightemperature is beneficial to the molecular polarization of PVDF-TrFE and alsoleads to the increase in conductivity of the semiconducting TiO_2nanoparticles, and thus increasing the permittivity and dielectric loss of the membranes.
(2) Nickel-doped titanium dioxide (Ni-TiO_2) nanoparticles were preparedby the sol-gel method, the particle size is about30nm. TheNi-TiO_2/PVDF-TrFE membranes waere prepared and then characterized bySEM, X-ray diffraction (XRD), and dielectric property testing. XRD resultsshowed that the phase of PVDF-TrFE was changed from the polar β crystalphase to non-polar phase with the addition of Ni-TiO_2nanoparticles. Thedielectric property testing showed that the permittivity of the membranes wereimproved gradually with the increase of Ni-TiO_2content, and the dielectricloss keeps at a low level (0.046~0.064). Besides, the permittivity of themembranes increased with the increase of nickel content in Nix-TiO_2nanoparticles, while the dielectric loss has not been changed。
(3) Na_2Ti_2O_4(OH)_2nanotube was prepared through a hydrothermalmethod and the structure of Na_2Ti_2O_4(OH)_2nanotube were characterized.Then the Na_2Ti_2O_4(OH)_2/PVDF membranes were prepared and thecorresponding properties were studied. The cross-sectional SEM images of themembranes showed that the Na_2Ti_2O_4(OH)_2nanotube were well dispersed inthe PVDF matrix and did not affect the structure of PVDF. The gooddispersion is attribute to the hydrogen bond through the oxhydryl group fromthe Na_2Ti_2O_4(OH)_2nanotube and the fluorine atom from PVDF. With theincrease of Na_2Ti_2O_4(OH)_2, Na_2Ti_2O_4(OH)_2connect with each other andformed network in PVDF matrix. DSC results showed that the crystallinity of the membranes were affect by the addition of Na_2Ti_2O_4(OH)_2nanotube. Smallamount of nanotube were embedded by the PVDF matrix and beneficial to thecrystallization of PVDF on the surface because of its large surface area, thusincreased the crystallinity of membranes. High content of nanotube willdestroy the conformation of PVDF molecular chain and thus reduced thecrystallinity of the membranes. The permittivity of Na_2Ti_2O_4(OH)_2/PVDF andNa_2Ti_2O_4(OH)_2/PVDF-TrFE membranes were improved quickly with theincrease of Na_2Ti_2O_4(OH)_2. When the content of Na_2Ti_2O_4(OH)_2nanotube isabout18vol%, the permittivity of the Na_2Ti_2O_4(OH)_2/PVDF membrane is upto178.7at100Hz, which is about20times of the PVDF. At the sameNa_2Ti_2O_4(OH)_2nanotube content, the permittivity of thePVDF-TrFE/Na_2Ti_2O_4(OH)_2membrane is up to330, about25times ofPVDF-TrFE. By calculation, the results are well fit the percolative model.Therefore, the dielectric properties of the membranes were improveddramatically with the addtion of Na_2Ti_2O_4(OH)_2nanotube, and thecorresponding literature has not been reported since now.
(4) The Ag@C core-shell nanoparticles were prepared by a hydrothermalmethod. A typical core-shell structure can be observed, the silver cores withdiameters in the range of100-120nm are each covered with a carbon shellabout60-80nm thick. Ag@C/PVDF and Ag@C/PVDF-TrFE membranes wereprepared through the solution cast method. The cross-sectional SEM imagesshowed that the Ag@C particles are well dispersed in both membranes. The good dispersion is attributed to the carbon shell which not only act asinter-particle barriers to prevent direct connection of Ag nanoparticles, butalso produce excellent compatibility between the fillers and the polymermatrix. DSC results showed that the crystallinity of the two membranesdecreased with the increase of Ag@C content. The dielectric propertiesshowed that the permittivity of the Ag@C/PVDF and Ag@C/PVDF-TrFEmembranes improved obviously over the pure polymer with increasingcontent of Ag@C particles due to the enhanced interfacial polarization, butThe dielectric loss keeps low lever. The permiitivity and the dielectric loss ofthe two membranes are affected by the temperature. High temperature isbenefit to the molecular polarization of the polymer and also accelerates themigration of free electron from the Ag core, and thus increasing thepermittivity and dielectric loss of the composites.
本论文以聚偏氟乙烯（PVDF）、聚偏氟乙烯-三氟乙烯（PVDF-TrFE）为基体，制备了不同填料的复合膜材料。通过对复合膜的微观形貌、结晶行为、介电性能等表征，探讨了填料对复合膜性能的影响。主要研究内容如下：
（1）通过溶胶凝胶法制备了不同晶型的二氧化钛(TiO_2)，并制备了TiO_2/PVDF-TrFE复合膜。扫描电镜表明TiO_2能够较好地分散在PVDF-TrFE基体中，并对复合膜的结晶行为起着非常重要的作用。少量的TiO_2有利于PVDF-TrFE在其表面结晶，提高了复合膜的结晶度；大量的TiO_2则破坏了PVDF-TrFE的分子链的规整度，降低了复合膜的结晶度。此外，金红石型二氧化钛更有利于PVDF-TrFE在其表面结晶。介电测试结果表明复合膜的介电常数随着TiO_2掺杂量的增加而增大。在相同的掺杂量下，掺杂金红石型二氧化钛复合膜的介电常数要高于掺杂锐钛矿型二氧化钛复合膜的介电常数。高温加速了PVDF-TrFE的分子运动，增加了二氧化钛的电导率，从而提高了复合膜的介电常数和介电损耗。
（2）将纳米级的Ni-TiO_2添加到PVDF-TrFE中，研究了Ni-TiO_2对复合膜结晶性能、介电性能的影响。结果表明Ni-TiO_2的加入使得PVDF-TrFE由极性的β相向非极性的晶相转变；复合膜的介电常数随着Ni-TiO_2掺杂量的增加而增加，介电损耗依然保持着较低的数值（0.046-0.064）。在相同的Nix-TiO_2掺杂量下，复合膜的介电常数随着Nix-TiO_2中Ni含量的增加而增加，介电损耗几乎没有发生变化。
（3）通过水热法制备了Na_2Ti_2O_4(OH)_2纳米管，并将纳米管添加到PVDF中。扫描电镜表明Na_2Ti_2O_4(OH)_2纳米管能够较好的分散在PVDF中，随着掺杂量的增加，纳米管在PVDF中逐渐形成导通的网状结构。DSC结果表明Na_2Ti_2O_4(OH)_2纳米管影响了复合膜的结晶性能。少量的纳米管有利于PVDF在其表面结晶，提高了复合膜的结晶度。随着纳米管的增加，纳米管破坏了PVDF分子链的规整度，降低了复合膜的结晶度。介电测试结果表明Na_2Ti_2O_4(OH)_2纳米管大幅度的提高了Na_2Ti_2O_4(OH)_2/PVDF、Na_2Ti_2O_4(OH)_2/PVDF-TrFE复合膜的介电性能。当掺杂量为18vol%时，Na_2Ti_2O_4(OH)_2/PVDF复合膜在100Hz的介电常数高达178.7，约为PVDF的20倍；Na_2Ti_2O_4(OH)_2/PVDF-TrFE复合膜的介电常数则高达330，约为PVDF-TrFE的25倍。经过计算发现实验结果符合渗流模型。向聚合物中添加Na_2Ti_2O_4(OH)_2纳米管大幅度提高复合材料的介电常数，相关文献至今未见报道。
（4）通过水热法制备了核壳型Ag@C纳米材料，银核的大小为100-120nm，碳壳的大小为60-80nm。将核壳型Ag@C纳米材料分别添加到PVDF、PVDF-TrFE中，研究了核壳型Ag@C纳米材料对PVDF系列聚合物热力学稳定性、结晶性能、介电性能的影响。扫描电镜表明Ag@C均匀的分散在PVDF、PVDF-TrFE中，并未发生团聚现象，这是由于核壳型Ag@C纳米材料表面的羟基与氟原子产生氢键，从而提高了它们之间的相容性。DSC测试结果表明Ag@C的加入降低了复合膜的结晶度。介电测试结果表明Ag@C/PVDF、Ag@C/PVDF-TrFE复合膜的介电常数随着Ag@C的增加而增加，介电损耗保持着非常低的数值。较低的介电损耗是由于碳壳提高了Ag@C与PVDF的相容性，防止了银颗粒由于相互接触而引起较大的介电损耗。复合膜的介电常数、介电损耗对温度有较强的依赖性。
With the development of electronic industry，dielectric materials withhigh permittivity (k) and low dielectric loss are attracted much attentions.Traditional ceramic materials have high permittivity, but they are brittle, hardto fabricate, and have high dielectric loss. Besides, they will generatemechanical resonance during charging and discharging and thus reduced theirlife-span. Polymers are light-weight, flexible, and easily integrated. However,they show a relatively low permittivity. Much work has been focused onraising the k of polymer-based composites. One effective method is to addhigh-k ceramics into the polymers to form organic-ceramic composites. Highloadings of ceramic fillers can increase the k of the composites, butdramatically decrease the flexibility of the composites. Another method is tointroduce conductive materials into the polymer matrix to form percolativecomposites. The k of such composites is at least two orders of magnitudehigher than that of the polymer matrix. However, the dielectric loss increasesrapidly with increasing amount of conductive materials. Therefore, it is ofgreat importance to prepare polymer-based composites with high dielectricperformance.
In this paper, Poly(vinylidene fluoride)(PVDF) and poly(vinylidene -trifluoroethylene)(PVDF-TrFE) were chosen as the polymer matrix anddifferent membranes were prepared through solution cast method. Themicrostructure， crystallization behavior， and dielectric properties werecharacterized and the corresponding reasons were studied. The detailedinformation is listed as follows:
(1) Titanium dioxide nanoparticles with two different phases wereprepared by the sol-gel method. Poly(vinylidene-trifluoroethylene)/titaniumdioxide (TiO_2/PVDF-TrFE) membranes were prepared by the solution castmethod. Scanning electron microscope (SEM) results showed that the TiO_2nanoparticles were well dispersed in the polymer matrix and did not affect thestructure of the PVDF-TrFE matrix. Differential scanning calorimeter (DSC)results showed that crystallinity of TiO_2/PVDF-TrFE membranes increased asthe addition of TiO_2with two different phases. Besides, the crystallinity ofTiO_2/PVDF-TrFE membrane with the rutile TiO_2is higher than that of themembrane with the anatase TiO_2. Dielectric property testing showed that thepermittivity of TiO_2/PVDF-TrFE membrane increased rapidly with theincrease of TiO_2content, but the dielectric loss remains at a low level. Theincrease in permittivity is attributed to the interfacial polarization. At the sameTiO_2content, the permittivity of TiO_2/PVDF-TrFE membrane with the rutileTiO_2is higher than that of the membrane with the anatase TiO_2. Hightemperature is beneficial to the molecular polarization of PVDF-TrFE and alsoleads to the increase in conductivity of the semiconducting TiO_2nanoparticles, and thus increasing the permittivity and dielectric loss of the membranes.
(2) Nickel-doped titanium dioxide (Ni-TiO_2) nanoparticles were preparedby the sol-gel method, the particle size is about30nm. TheNi-TiO_2/PVDF-TrFE membranes waere prepared and then characterized bySEM, X-ray diffraction (XRD), and dielectric property testing. XRD resultsshowed that the phase of PVDF-TrFE was changed from the polar β crystalphase to non-polar phase with the addition of Ni-TiO_2nanoparticles. Thedielectric property testing showed that the permittivity of the membranes wereimproved gradually with the increase of Ni-TiO_2content, and the dielectricloss keeps at a low level (0.046~0.064). Besides, the permittivity of themembranes increased with the increase of nickel content in Nix-TiO_2nanoparticles, while the dielectric loss has not been changed。
(3) Na_2Ti_2O_4(OH)_2nanotube was prepared through a hydrothermalmethod and the structure of Na_2Ti_2O_4(OH)_2nanotube were characterized.Then the Na_2Ti_2O_4(OH)_2/PVDF membranes were prepared and thecorresponding properties were studied. The cross-sectional SEM images of themembranes showed that the Na_2Ti_2O_4(OH)_2nanotube were well dispersed inthe PVDF matrix and did not affect the structure of PVDF. The gooddispersion is attribute to the hydrogen bond through the oxhydryl group fromthe Na_2Ti_2O_4(OH)_2nanotube and the fluorine atom from PVDF. With theincrease of Na_2Ti_2O_4(OH)_2, Na_2Ti_2O_4(OH)_2connect with each other andformed network in PVDF matrix. DSC results showed that the crystallinity of the membranes were affect by the addition of Na_2Ti_2O_4(OH)_2nanotube. Smallamount of nanotube were embedded by the PVDF matrix and beneficial to thecrystallization of PVDF on the surface because of its large surface area, thusincreased the crystallinity of membranes. High content of nanotube willdestroy the conformation of PVDF molecular chain and thus reduced thecrystallinity of the membranes. The permittivity of Na_2Ti_2O_4(OH)_2/PVDF andNa_2Ti_2O_4(OH)_2/PVDF-TrFE membranes were improved quickly with theincrease of Na_2Ti_2O_4(OH)_2. When the content of Na_2Ti_2O_4(OH)_2nanotube isabout18vol%, the permittivity of the Na_2Ti_2O_4(OH)_2/PVDF membrane is upto178.7at100Hz, which is about20times of the PVDF. At the sameNa_2Ti_2O_4(OH)_2nanotube content, the permittivity of thePVDF-TrFE/Na_2Ti_2O_4(OH)_2membrane is up to330, about25times ofPVDF-TrFE. By calculation, the results are well fit the percolative model.Therefore, the dielectric properties of the membranes were improveddramatically with the addtion of Na_2Ti_2O_4(OH)_2nanotube, and thecorresponding literature has not been reported since now.
(4) The Ag@C core-shell nanoparticles were prepared by a hydrothermalmethod. A typical core-shell structure can be observed, the silver cores withdiameters in the range of100-120nm are each covered with a carbon shellabout60-80nm thick. Ag@C/PVDF and Ag@C/PVDF-TrFE membranes wereprepared through the solution cast method. The cross-sectional SEM imagesshowed that the Ag@C particles are well dispersed in both membranes. The good dispersion is attributed to the carbon shell which not only act asinter-particle barriers to prevent direct connection of Ag nanoparticles, butalso produce excellent compatibility between the fillers and the polymermatrix. DSC results showed that the crystallinity of the two membranesdecreased with the increase of Ag@C content. The dielectric propertiesshowed that the permittivity of the Ag@C/PVDF and Ag@C/PVDF-TrFEmembranes improved obviously over the pure polymer with increasingcontent of Ag@C particles due to the enhanced interfacial polarization, butThe dielectric loss keeps low lever. The permiitivity and the dielectric loss ofthe two membranes are affected by the temperature. High temperature isbenefit to the molecular polarization of the polymer and also accelerates themigration of free electron from the Ag core, and thus increasing thepermittivity and dielectric loss of the composites.
引文
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