具有超高介电常数的海绵/炭黑-硼酸盐/硅橡胶复合材料
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摘要
通过浸渍法制备了密胺海绵(MS)/导电炭黑-硼酸盐(CB@B)复合物,并进一步真空灌注硅橡胶(SR)后制备了MS/CB@B/SR复合材料。使用XRD、SEM对复合材料的物相、微观结构进行表征并测试了其导电与介电性能、压敏特性和吸波性能。研究发现,CB@B复合物利用MS模板在复合材料内部构建了三维逾渗网络,其导电逾渗阈值为1.48%(体积分数),CB与B对提高复合材料性能具有显著的协同作用。随着CB浓度提高,复合材料的导电性和介电常数逐步提高,当CB浓度为14 mg/mL时,复合材料的体积电阻率最低可达到6.7×10~4Ω·cm,介电常数在1 kHz时高达1.67×10~4,当样品厚度为3 mm时,在30.97 GHz处出现最低反射率(RL=-33.17 dB),吸波带宽(RL<-10 dB)为5.38 GHz。当CB浓度为10 mg/mL时,复合材料的电阻和介电常数还表现出较高的压缩应变灵敏度。
Melamine sponge(MS)/conductive carbon black-borates(CB@B) compound(MS/CB@B) were prepared by impregnation method, and then infused by silicone rubber(SR) to obtain the MS/CB@B/SR composite. The chemical composition and microstructure of the composites were characterized by XRD and SEM, and the conductivity, dielectric properties, pressure sensitive behaviors and microwave absorbing properties were tested. It was found that the CB@B compound had constructed a three-dimensional percolation network inside the composite using MS template with the conductive percolation threshold of 1.48 vol%. CB and B had a significant synergistic effect on improving the properties of the composite. With the increase of CB concentration, the conductivity and dielectric constant of the composites increased gradually. At the CB concentration of 14 mg/mL, the composite had the volume resistivity of 6.7×10~4 Ω·cm, and an ultra-high dielectric constant of 1.67×10~4 at 1 kHz. The composite with sample thickness of 3 mm showed the excellent microwave absorbing performance with the strongest absorption peak of-33.17 dB at 30.97 GHz and the absorption bandwidth of 5.38 GHz. At the CB concentration of 10 mg/mL, the resistance and dielectric constant of the composite also exhibited high compressive strain sensitivity.
Melamine sponge(MS)/conductive carbon black-borates(CB@B) compound(MS/CB@B) were prepared by impregnation method, and then infused by silicone rubber(SR) to obtain the MS/CB@B/SR composite. The chemical composition and microstructure of the composites were characterized by XRD and SEM, and the conductivity, dielectric properties, pressure sensitive behaviors and microwave absorbing properties were tested. It was found that the CB@B compound had constructed a three-dimensional percolation network inside the composite using MS template with the conductive percolation threshold of 1.48 vol%. CB and B had a significant synergistic effect on improving the properties of the composite. With the increase of CB concentration, the conductivity and dielectric constant of the composites increased gradually. At the CB concentration of 14 mg/mL, the composite had the volume resistivity of 6.7×10~4 Ω·cm, and an ultra-high dielectric constant of 1.67×10~4 at 1 kHz. The composite with sample thickness of 3 mm showed the excellent microwave absorbing performance with the strongest absorption peak of-33.17 dB at 30.97 GHz and the absorption bandwidth of 5.38 GHz. At the CB concentration of 10 mg/mL, the resistance and dielectric constant of the composite also exhibited high compressive strain sensitivity.
引文
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[3] Liu Y,Zheng H,Liu M.High performance strain sensors based on chitosan/carbon black composite sponges[J].Materials & Design,2018,141:276-285.
[4] Qiu N,Liu Y,Xiang M,et al.A facile and stable colorimetric sensor based on three-dimensional graphene/mesoporous Fe3O4,nanohybrid for highly sensitive and selective detection of p-nitrophenol[J].Sensors & Actuators B Chemical,2018,266:86-94.
[5] Chen J,Cui X,Zhu Y,et al.Design of superior conductive polymer composite with precisely controlling carbon nanotubes at the interface of a co-continuous polymer blend via a balance of π-π interactions and dipole-dipole interactions[J].Carbon,2017,114:441-448.
[6] Huang Ying,Huang Yu,Gao Feng,et al.Effect of carbon black filling on the properties of conductive silicone rubber for flexible tactile sensors[J].Journal of Functional Materials,2010,41(2):225-227(in Chinese).黄英,黄钰,高峰,等.填充炭黑对柔性触觉传感器用导电硅橡胶性能的影响[J].功能材料,2010,41(2):225-227.
[7] Liao Bo,Wang Yingjie.Microstructure and conductive properties of carbon black/silicone rubber conductive composites[J].Journal of Functional Materials,2014,45(2):2040-2043(in Chinese).廖波,王英杰.炭黑/硅橡胶导电复合材料微观结构及其导电特性[J].功能材料,2014,45(2):2040-2043.
[8] Bu Shi,Zhou Jin.Relationship between dielectric constant and compressive stress of conductive carbon black/silicone rubber composites[J].Physics and Engineering,2011,21(3):59-61(in Chinese).卜时,周进.导电炭黑/硅橡胶复合材料介电常数与压应力的关系[J].物理与工程,2011,21(3):59-61.
[9] Dang Z M,Xia B,Yao S H,et al.High-dielectric-permittivity high-elasticity three-component nanocomposites with low percolation threshold and low dielectric loss[J].Applied Physics Letters,2009,94(4):042902.
[10] Lapshin A E,Medvedev E F,Polyakova I G,et al.Synthesis and crystal structure of a new modification of sodium tetrahydroxyborate NaB(OH)4[J].Glass Physics and Chemistry,2009,35(3):308-312.
[11] Wang Daohong,Xu Yifei,Zhang Jiyan.Physicochemical properties and characterization of carbon black[J].Chemical Industry and Engineering,2002,19(1):76-82(in Chinese).王道宏,徐亦飞,张继炎.炭黑的物化性质及表征[J].化学工业与工程,2002,19(1):76-82.
[12] Yuan J K,Yao S H,Sylvestre A,et al.Biphasic polymer blends containing carbon nanotubes:heterogeneous nanotube distribution and its influence on the dielectric properties[J].Journal of Physical Chemistry C,2012,116(2):2051-2058.
[13] Hamidinejad M,Zhao B,Chu R K M,et al.Ultralight microcellular polymer-graphene nanoplatelet foams with enhanced dielectric performance[J].ACS Applied Materials & Interfaces,2018,10(23):19987-19998.
[14] Wu S Q,Wang J W,Shao J,et al.An approach to developing enhanced dielectric property nanocomposites based on acrylate elastomer[J].Materials & Design,2018,146:208-218.
[15] Boland C S,Khan U,Binions M,et al.Graphene-coated polymer foams as tuneable impact sensors.[J].Nanoscale,2018,10(11):5366-5375.
[16] Yang Y,Xia L,Zhang T,et al.Fe3O4@LAS/RGO composites with a multiple transmission-absorption mechanism and enhanced electromagnetic wave absorption performance[J].Chemical Engineering Journal,2018,352:510-518.