钛酸钡-氮化硼/聚间苯二甲酰间苯二胺复合电介质的制备与导热性能

段广宇; 胡凤英; 胡祖明; 迟长龙; 李玥; 于翔

doi:10.13801/j.cnki.fhclxb.20210513.005

钛酸钡-氮化硼/聚间苯二甲酰间苯二胺复合电介质的制备与导热性能

doi: 10.13801/j.cnki.fhclxb.20210513.005

段广宇^1,,
胡凤英^1,,
胡祖明²,
迟长龙^1,,
李玥¹,
于翔^1, ,

1.
河南工程学院　材料工程学院，郑州 450007
2.
东华大学　纤维材料改性国家重点实验室，上海 201620

基金项目: 国家自然科学基金(51608175)；河南省高校科技创新人才计划(20HASTIT016)；河南省科技攻关项目(202102310605)

详细信息

通讯作者:
于翔，博士研究生，副教授，研究方向为功能高分子复合电介质　E-mail：yxpolymer@sina.com

中图分类号: TB332
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出版历程
- 收稿日期: 2021-03-08
- 修回日期: 2021-04-24
- 录用日期: 2021-04-27
- 网络出版日期: 2021-05-13
- 刊出日期: 2021-03-01

Preparation and thermal conductivity of barium titanate-boron nitride/poly(m-phenyleneisophthalamide) dielectric composites

1.
College of Materials Engineering, Henan University of Engineering, Zhengzhou 450007, China
2.
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China

摘要

摘要: 选用聚多巴胺(PDA)和十八烷基异氰酸酯分别改性钛酸钡纳米线(BTW)和氮化硼纳米片(BNNSs)来构筑D@BTW-fBNNSs高介电导热填料。研究了D@BTW-fBNNSs高介电导热填料对芳香族聚酰胺(PMIA)基复合电介质介电性能、击穿强度和导热性能的影响。结果表明：随着复合电介质中D@BTW-fBNNSs含量的增加，PMIA基复合电介质的介电常数提升明显；当D@BTW-fBNNSs含量为15wt%时，PMIA基复合电介质在10³ Hz时的介电常数相较于PMIA基体提高了75%，同时在高温环境中(>150℃)PMIA基复合电介质的介电性能保持稳定，能够满足高温环境的使用要求。此外，D@BTW-fBNNSs还明显改善了PMIA基复合电介质的导热性能；含有15wt%D@BTW-fBNNSs的PMIA基复合电介质，其导热系数相较于PMIA基体提升了1.5倍。本研究将为设计具有高介电常数、低热效应的耐高温聚合物基电介质提供新的方法和思路。
- 聚间苯二甲酰间苯二胺 /
- 钛酸钡纳米线 /
- 氮化硼纳米片 /
- 介电性能 /
- 导热系数 /
- 聚合物电介质
Abstract: Polydopamine (PDA) and octadecyl isocyanate were selected to functionalize barium titanate nanowires (BTW) and boron nitride nanosheets (BNNSs) respectively, and construct D@BTW-fBNNSs particles. The influences of D@BTW-fBNNSs on dielectric property, breakdown strength and thermal conductivity of poly (m-phenyleneisophthalamide) (PMIA) dielectric were investigated. The results show that, with increasing content of D@BTW-fBNNSs, the dielectric constant of PMIA dielectric significantly increases. The dielectric constant of PMIA composite with 15wt%D@BTW-fBNNSs displays 75% improvement at 10³ Hz compared with PMIA matrix, and the dielectric loss of corresponding PMIA composite maintains at relatively low value. Furthermore, the dielectric properties of D@BTW-fBNNSs/PMIA dielectric are stable under high temperature (>150℃), which can meet the requirement in high temperature environment. Additionally, the thermal conductivity of PMIA dielectric is obviously improved with increased content of D@BTW-fBNNSs. The thermal conductivity of PMIA dielectric with 15wt% D@BTW-fBNNSs is 1.5 times higher than that of PMIA matrix. This research will provide new method and idea for the design of high-temperature polymer dielectric with enhanced dielectric constant and low thermal effect.
- poly(m-phenyleneisophthalamide) /
- barium titanate nanowire /
- boron nitride nanosheets /
- dielectric property /
- thermal conductivity /
- polymer dielectric

HTML全文

图 1 D@BTW-fBNNSs/PMIA复合电介质制备流程图

Figure 1. Diagram of preparation of D@BTW-fBNNSs/PMIA composite

BTW—Barium titanate nanowires; D@BTW—Polydopamine@barium titanate nanowires; BN—Boron nitride; fBNNSs—Functional boron nitride nanosheets; PMIA—Poly(m-phenyleneisophthalamide)

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图 2 BTW的SEM图(a)和高分辨率TEM图(b)；(c) D@BTW的高分辨率TEM图；BNNSs的高分辨率TEM图(右上角为BNNSs的电子衍射图，左下角为BNNSs溶液(1 mg/mL)的丁达尔效应) (d)和AFM图(e)；(f) D@BTW-fBNNSs的TEM图

Figure 2. SEM image (a) and high-resolution TEM image (b) of BTW; (c) High-resolution TEM image of D@BTW; High-resolution TEM image of BNNSs (insert in upper right corner is electron diffraction pattern of BNNSs, insert in lower left corner is Tyndall effect of BNNSs solution (1 mg/mL)) (d) and AFM image of BNNSs (e); (f) TEM image of D@BTW-fBNNSs

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图 3 BNNSs、fBNNSs、D@BTW-fBNNSs、BTW和D@BTW的FTIR图谱(a)和XRD图谱(b)

Figure 3. FTIR spectra (a) and XRD pattern (b) of BNNSs，fBNNSs，D@BTW-fBNNSs，BTW and D@BTW

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图 4 D@BTW-fBNNSs/PMIA复合电介质FTIR图谱(a)和XRD图谱(b)

Figure 4. FTIR spectra (a) and XRD pattern (b) of D@BTW-fBNNSs/PMIA composites

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图 5 D@BTW-fBNNSs/PMIA复合电介质的SEM图: (a) PMIA；(b) 5wt%D@BTW-fBNNSs/PMIA；(c) 7wt%D@BTW-fBNNSs/PMIA；(d) 10wt%D@BTW-fBNNSs/PMIA；(e) 15wt%D@BTW-fBNNSs/PMIA；(f) 图(e)中矩形区域

Figure 5. SEM images of D@BTW-fBNNSs/PMIA composites: (a) PMIA; (b) 5wt%D@BTW-fBNNSs/PMIA; (c) 7wt%D@BTW-fBNNSs/PMIA; (d) 10wt%D@BTW-fBNNSs/PMIA; (e) 15wt%D@BTW-fBNNSs/PMIA; (f) Magnified area of rectangle in figure (e)

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图 6 D@BTW-fBNNSs/PMIA复合电介质的应力应变曲线(a)和拉伸强度(左)与弹性模量(右) (b)

Figure 6. Stress-strain curves (a) and tensile strength (left) and modulus of elasticity (right) (b) of D@BTW-fBNNSs/PMIA composites

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图 7 D@BTW-fBNNSs/PMIA复合电介质介电常数(a)、介电损耗(b)和电导率|σ| (插图为0.1~10 Hz的放大图) (c)

Figure 7. Dielectric constant (a), dielectric loss (b) and conductivity |σ| (c) (inset: the enlarged curves in the frequency range from 0.1-10 Hz) of D@BTW-fBNNSs/PMIA composites

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图 8 12wt%D@BTW-fBNNSs/PMIA介电常数(a)和介电损耗与温度的关系(b)

Figure 8. Dielectric constant (a) and dielectric loss as a function of temperature (b) of 12wt%D@BTW-fBNNSs/PMIA

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图 9 D@BTW-fBNNSs/PMIA复合电介质威布尔分布(a)、威布尔击穿强度和威布尔分布参数β值(b)

Figure 9. Weibull plots (a), weibull breakdown strength and Weibull distribution parameters β values (b) of D@BTW-fBNNSs/PMIA composites

P—Probability of failure; E—Electric field

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图 10 D@BTW-fBNNSs/PMIA复合电介质的面向导热系数(a)和增长指数(b)

Figure 10. Through-plane thermal conductivity (a) and enhancement factor (b) of D@BTW-fBNNSs/PMIA composite

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参考文献(26)

[1]	ZHANG T, CHEN X, THAKURA Y, et al. Highly scalable dielectric metamaterial with superior capacitor performance over a broad temperature[J]. Science Advances,2020,6(4):eaax6622. doi: 10.1126/sciadv.aax6622
[2]	GUO M F, JIANG J Y, SHEN Z H, et al. High-energy-density ferroelectric polymer nanocomposites for capacitive energy storage: enhanced breakdown strength and improved discharge efficiency[J]. Materials Today,2019,29:49-67. doi: 10.1016/j.mattod.2019.04.015
[3]	HUANG X Y, SUN B, ZHU Y K, et al. High-k polymer nanocomposites with 1D filler for dielectric and energy storage applications[J]. Progress in Materials Science,2019,100:187-225. doi: 10.1016/j.pmatsci.2018.10.003
[4]	ZHANG D, MA C, ZHOU X F, et al. High-performance capacitors using BaTiO₃ nanowires engineered by rigid liquid-crystalline polymers[J]. Journal of Physical Chemistry C,2017,121(37):20075-20083. doi: 10.1021/acs.jpcc.7b03391
[5]	WANG M, LIA W L, FENG, Y, et al. Effect of BaTiO₃ nanowires on dielectric properties and energy storage density of polyimide composite films[J]. Ceramics International,2015,41(10):13582-13588. doi: 10.1016/j.ceramint.2015.07.153
[6]	HARRY P. Composite for energy storage takes the heat[J]. Nature,2015,523(7562):536-537. doi: 10.1038/523536a
[7]	XU X F, CHEN J, ZHOU J, et al. Thermal conductivity of polymers and their nanocomposites[J]. Advanced Materials,2018,30(17):1705544. doi: 10.1002/adma.201705544
[8]	SHEN Z H, WANG J J, JIANG J Y, et al. Phase-field model of electrothermal breakdown in flexible high-temperature nanocomposites under extreme conditions[J]. Advanced Energy Materials,2018,8(20):1800509. doi: 10.1002/aenm.201800509
[9]	DUAN G Y, WANG Y, YU J R, et al. Improved thermal conductivity and dielectric properties of flexible PMIA composites with modified micro- and nano-sized hexagonal boron nitride[J]. Frontiers of Materials Science,2019,13(1):64-76. doi: 10.1007/s11706-019-0446-3
[10]	DUAN G Y, WANG Y, YU J R, et al. Novel poly(m-phenyleneisophthalamide) dielectric composites with enhanced thermal conductivity and breakdown strength utilizing functionalized boron nitride nanosheets[J]. Macromolecular Materials and Engineering,2019,304(11):1900310. doi: 10.1002/mame.201900310
[11]	WENG Q H, WANG X B, WANG X, et al. Functionalized hexagonal boron nitride nanomaterials: emerging properties and applications[J]. Chemical Society Reviews,2016,45(14):3989-4012. doi: 10.1039/C5CS00869G
[12]	JIANG Y, LIU Y J, MIN P, et al. BN@PPS core-shell structure particles and their 3D segregated architecture composites with high thermal conductivities composites[J]. Composites Science and Technology,2017,144:63-69.
[13]	YU B, XING W Y, GUO W W, et al. Thermal exfoliation of hexagonal boron nitride for effective enhancements on thermal stability, flame retardancy and smoke suppression of epoxy resin nanocomposites via sol-gel process[J]. Journal of Materials Chemistry A,2016,4(19):7330-7340. doi: 10.1039/C6TA01565D
[14]	WANG N, YANG G, WANG H X, et al. A universal method for large-yield and high-concentration exfoliation of two-dimensional hexagonal boron nitride nanosheets[J]. Materials Today,2019,27:33-42. doi: 10.1016/j.mattod.2018.10.039
[15]	XIE Y C, YU Y Y, FENG Y F, et al. Fabrication of stretchable nanocomposites with high energy density and low loss from cross-linked PVDF filled with poly(dopamine) encapsulated BaTiO₃[J]. ACS Applied Materials & Interfaces,2017,9(3):2995-3005.
[16]	DUAN G Y, WANG Y, YU J R, et al. Preparation of PMIA dielectric nanocomposite with enhanced thermal conduc-tivity by filling with functionalized graphene-carbon nano-tube hybrid fillers[J]. Applied Nanoscience,2019,9(8):1743-1757. doi: 10.1007/s13204-019-00955-0
[17]	XIE Y C, WANG J, Yu Y Y, et al. Enhancing breakdown strength and energy storage performance of PVDF-based nanocomposites by adding exfoliated boron nitride[J]. Applied Surface Science,2018,440:1150-1158. doi: 10.1016/j.apsusc.2018.01.301
[18]	KOICHI S, MASASHI A, NAOYUKI U, et al. Transparent BaTiO₃/PMMA nanocomposite films for display technologies: facile surface modification approach for BaTiO₃ nanoparticles[J]. ACS Applied Nano Materials,2018,1(5):2430-2437. doi: 10.1021/acsanm.8b00650
[19]	ZHANG X, SHEN Y, ZHANG Q H, et al. Ultrahigh energy density of polymer nanocomposites containing BaTiO₃@TiO₂ nanofibers by atomic-scale interface engineering[J]. Advanced Materials,2015,27(5):819-824. doi: 10.1002/adma.201404101
[20]	HE D L, WANG Y, CHEN X Q, et al. Core-shell structured BaTiO₃@Al₂O₃ nanoparticles in polymer composites for dielectric loss suppression and breakdown strength enhancement[J]. Composites: Part A,2017,93:137-143. doi: 10.1016/j.compositesa.2016.11.025
[21]	XIE B, ZHANG H B, ZHANG Q, et al. Enhanced energy density of polymer nanocomposites at a low electric field through aligned BaTiO₃ nanowires[J]. Journal of Materials Chemistry A,2017,5(13):6070-6078. doi: 10.1039/C7TA00513J
[22]	HUA P H, SUN W D, FAN M Z, et al. Large energy density at high-temperature and excellent thermal stability in polyimide nanocomposite contained with small loading of BaTiO₃ nanofibers[J]. Applied Surface Science,2018,458:743-750. doi: 10.1016/j.apsusc.2018.07.128
[23]	LV X G, LUO H, CHEN S, et al. BaTiO₃ platelets and poly (vinylidene fluoride-trifluoroethylenechlorofluoroethy-lene) hybrid composites for energy storage application[J]. Mechanical Systems and Signal Processing,2018,108:48-57. doi: 10.1016/j.ymssp.2018.02.011
[24]	LIU F H, LI Q, LI Z Y, et al. Poly (methyl methacrylate)/boron nitride nanocomposites with enhanced energy density as high temperature dielectrics[J]. Composites Science and Technology,2017,142:139-144. doi: 10.1016/j.compscitech.2017.02.006
[25]	LAO J P, XIE H A, SHI Z Q, et al. Flexible regenerated cellulose/boron nitride nanosheet high-temperature dielectric nanocomposite films with high energy density and breakdown strength[J]. ACS Sustainable Chemistry & Engineering,2018,6(5):7151-7158.
[26]	ZHU Y K, ZHU Y J, HUANG X Y, et al. High energy density polymer dielectrics interlayered by assembled boron nitride nanosheets[J]. Advanced Energy Materials,2019,9(36):1901826.