Preparation and performance of biaxially oriented modified zirconia/polypropylene composite dielectric films

doi:10.19491/j.issn.1001-9278.2025.12.006

Abstract

Abstract:

Nano⁃zirconia （nano⁃ZrO₂） was surface⁃grafted with amino groups （NH₂） and then melt⁃blended with polypropylene⁃g⁃maleic anhydride （PP⁃g⁃MAH） and polypropylene （PP） to form composite pellets. These pellets were processed into dielectric films via casting followed by biaxial orientation. The grafting reaction between the NH₂ groups on ZrO₂ and the anhydride groups of PP⁃g⁃MAH improved the dispersion and compatibility of the nanoparticles within the PP matrix. The resulting NH₂⁃ZrO₂/PP⁃g⁃MAH/PP composite films exhibited enhanced dielectric， thermal， and mechanical properties. Specifically， at a test frequency of 1 kHz and with 2.5 wt% NH₂⁃ZrO₂ content， the composite film achieved a dielectric constant of 4.46， significantly higher than that of pure PP （2.25）， along with high breakdown strength of 492 MV/m and a low dielectric loss of only 0.002 5. These results demonstrated that the applied modification strategy effectively yielded a composite film with a high dielectric constant and breakdown voltage while significantly suppressing dielectric loss.

Key words: zirconia, polypropylene, compatibilizer, dielectric constant, breakdown field strength

CLC Number:

TQ325.

GUO Jiang, XU Mengyi, HUANG Xiang, HAO Hao, YOU Feng, LI Chenjian, JIANG Xueliang. Preparation and performance of biaxially oriented modified zirconia/polypropylene composite dielectric films[J]. China Plastics, 2025, 39(12): 33-38.

Figures/Tables 8

Fig.1. Preparation process of NH2⁃ZrO2

Fig.2. FTIR spectra of ZrO2 and NH2⁃ZrO2

Fig.3. Reaction process of PP⁃g⁃MAH grafting nano⁃ZrO2

Fig.4. Cross⁃section SEM images of the PP and composite film

Fig.5. Thermogravimetric curve

Fig.6. Dielectric constant and loss curves with variation frequencies of PP， 3 %NH2⁃ZrO2/PP and 3 %NH2⁃ZrO2/PP⁃g⁃MAH/PP composite film

Fig.7. Dielectric constant and loss curves with variation frequencies of 0.75 %~3.00 %NH2⁃ZrO2/PP⁃g⁃MAH/PP composite film

Fig.8. Breakdown field strength of PP and 0.75 %~3 %NH2⁃ZrO2/PP⁃g⁃MAH/PP composite film

References 20

[1]	TAN Daniel Q. Review of polymer⁃based nanodielectric exploration and film scale⁃up for advanced capacitors［J］. Adv Funct Mater， 2019， 1808567： 1⁃23.
[2]	HUANG Xingyi， SUN Bin， ZHU Yingke， et al. High⁃k polymer nanocomposites with 1D filler for dielectric and energy storage applications［J］.Prog Mater Sci，2019， 100： 187⁃225.
[3]	WANG Pengjian， ZHOU Di， LI Jing， et al. Significantly enhanced electrostatic energy storage performance of P（VDF⁃HFP）/BaTiO₃⁃Bi（Li_0.5Nb_0.5）O₃ nanocomposites［J］.Nano Energy， 2020， 78： 105247.
[4]	HU Jin， ZHANG Shufen， TANG Bingtao. 2D filler⁃reinforced polymer nanocomposite dielectrics for high⁃k dielectric and energy storage applications［J］. Energy Storage Mater，2021， 34：260⁃281.
[5]	PAN Xiaoren， WANG Mao， QI Xiaodong. Fabrication of sandwich⁃structured PPy/MoS₂/PPy nanosheets for polymer composites with high dielectric constant， low loss and high breakdown strength［J］， Compos A， 2020， 137： 106032.
[6]	ZHANG Xin， SHEN Yang， XU Ben， et al. Giant energy density and improved discharge efficiency of solution⁃processed polymer nanocomposites for dielectric energy storage［J］. Advanced Materials， 2016， 28 （10）： 2 055⁃2 061.
[7]	GONG Honghong， JI Qinglong， CHENG Yipin， et al. Controllable synthesis and structural design of novel all⁃organic polymers toward high energy storage dielectrics［J］. Frontiers in Chemistry， 2022， 10： 979926
[8]	Zhong， Shaoyuan， et al. Improved Dielectric and Energy Storage Properties of Polypropylene⁃Based Organic Films through Construction of a Microcompatible “Sea⁃Island” Structure［J］. ACS Applied Polymer Materials，2024，13 （6）： 7 449⁃7 457.
[9]	YAN Yong Zhu， PARK Sung Soo， MOON Ha Ram， et al. Thermally robust zirconia nanorod/polyimide hybrid films as a highly flexible dielectric material ［J］. ACS Applied Nano Materials， 2021， 4（8）： 8 217⁃8 230.
[10]	Dang B， Li Q， Zhou Y，et al. Suppression of elevated temperature space charge accumulation in polypropylene/elastomer blends by deep traps induced by surface⁃modified ZnO nanoparticles［J］.Composites Science and Technology， 2017， 153（1）：103⁃110.
[11]	WANG Ciyao， XING Zhaoliang， YAN Shiyu， et al. Dielectric film with high energy density based on polypropylene/maleic anhydride⁃grafted polypropylene/boron nitride nanosheet ternary system［J］. Materials Research Bulletin， 2022， 155： 111978.
[12]	Zhou Y， Yuan C， Shaojie W，et al. Interface⁃modulated nanocomposites based on polypropylene for high⁃temperature energy storage［J］.Energy Storage Materials， 2020， 28：255⁃263.
[13]	Tong Z， Jiang T， Qiu R，et al.Tong， Zhonghe，et al. Effect of different silane coupling agent modified SiO2 on the properties of silicone rubber composites： Based on molecular dynamics［J］. Colloids and Surfaces A： Physicochemical and Engineering Aspects，2025，705： 135615.
[14]	Ding Ning. Preparation of vanillin⁃based polyurethane/SiO₂ nanocomposite foams with excellent flame retardancy and thermal insulation performance［J］. Composites Communications，2024，51： 102108.
[15]	LIN Tingan， BAO Limin， LIN Meichen， et al. Impact⁃resistant polypropylene/thermoplastic polyurethane blends： Compatible effects of maleic anhydride on thermal degradation properties and crystallization behaviors［J］. Journal of Materials Research and Technology，2019， 8（4）： 3 389⁃3 398.
[16]	ZHU Yingke， ZHU Yujie， HUANG Xingyi， et al. High energy density polymer dielectrics interlayered by assembled boron nitride nanosheets［J］. Adv. Energy Mater， 2019， 9（36）： 1⁃10.
[17]	QIU Jie， GU Qun， SHA Ye， et al. Preparation and application of dielectric polymers with high permittivity and low energy loss： A mini review ［J］. Journal of Applied Polymer Science， 2022， 139（24）： 52 367.
[18]	Cheng Lu. Enhanced breakdown strength and restrained dielectric loss of polypropylene/maleic anhydride grafted polypropylene/core⁃shell ZrO₂@SiO₂nanocomposites［J］. Polymer Composites，2022，43（4）： 2 175⁃2 183.
[19]	Hu J， Zhao X. Effect of organic Na⁺‐montmorillonite on the dielectric and energy storage properties of polypropylene nanocomposites with polypropylene‐graft‐maleic anhydride as compatibilizer［J］. Journal of Applied Polymer Science，2022，139 （17）： 52047.
[20]	IRFAN M， SHAKOOR A， MAJID A， et al. Study of structural， thermal and dielectric modulus of PPy⁃DBSA⁃zirconium oxide composites［J］. Russian Journal of Physical Chemistry B， 2019， 13（6）： 1 057⁃1 063.