相较于金属填料(密度大、易腐蚀)、陶瓷填料(导电性差、脆性高),碳系填料(炭黑、碳纳米管、石墨烯等)兼具优异导电性、可控维度(零维至二维)、π电子共轭结构及与聚合物的适配性,是构建高性能导电聚合物复合材料(CPCs)的最优选择,故基于多维度碳基杂化填料维度与协同导电机理,从“填料维度-界面锚定-网络重构”角度评述其对参数的调控机制,阐述“多维协同”降低渗流阈值、共价π-π网络降低室温电阻率、临界网络重构提升正温度系数效应(PTC)强度、多维阻隔-锚定增强PTC重现性的路径等方法,为高性能聚合物基PTC材料设计与工程化提供理论支撑。
Compared with metal fillers (with high density and prone to corrosion) and ceramic fillers (with poor conductivity and high brittleness),carbon-based fillers (such as carbon black,carbon nanotubes,graphene,etc.) possess excellent conductivity,controllable dimensions (from zero-dimensional to two-dimensional),π-electron conjugated structure,and compatibility with polymers.These advantages make them ideal candidates for constructing high-performance conductive polymer composite materials (CPCs).Based on the dimensions and the synergistic conductive mechanisms of multidimensional carbon-based hybrid fillers,this paper discussed the regulation mechanisms of parameters from the perspective of “filler dimensions-interface anchoring-network reconstruction”.It elaborated on methods by which “multidimensional synergy” reduced seepage threshold,covalent π-π network lowered room-temperature resistivity,critical network reconstruction enhanced the positive temperature coefficient (PTC) effect,and multidimensional barrier-anchoring enhanced the reproducibility of PTC,providing theoretical support for the design and engineering of high-performance polymer-based PTC materials.
[1] Xue F,Li K,Cai L,et al.Effects of POE and carbon black on the PTC performance and flexibility of high-density polyethylene composites[J].Advances in Polymer Technology,2021,2021(1):1124981.
[2] Luo X,Yang G,Schubert D W.Electrically conductive polymer composite containing hybrid graphene nanoplatelets and carbon nanotubes:synergistic effect and tunable conductivity anisotropy[J].Advanced Composites and Hybrid Materials,2022,5(1):250-262.
[3] 程建国,马文博,李斐婕,等.碳系填料对硅橡胶电性能和力学性能的影响[J].特种橡胶制品,2023,44(3):27-31.
[4] 丁瑜.基于碳基复合材料的印刷弯曲传感器制备及性能研究[D].北京:北京印刷学院,2021.
[5] 李阳,任鹏刚,许勐璠.隔离结构石墨烯-多壁碳纳米管/超高分子量聚乙烯导电复合材料阻温特性[J].化工新型材料,2015,43(3):58-60,99.
[6] Zha J W,Li W K,Liao R J,et al.High performance hybrid carbon fillers/binary-polymer nanocomposites with remarkably enhanced positive temperature coefficient effect of resistance[J].Journal of Materials Chemistry A,The Royal Society of Chemistry,2012,1(3):843-851.
[7] Lee J H,Kim S K,Kim N H.Effects of the addition of multi-walled carbon nanotubes on the positive temperature coefficient characteristics of carbon-black-filled high-density polyethylene nanocomposites[J].Scripta Materialia,2006,55(12):1119-1122.
[8] Hu H,Zhao J,Jiang D,et al.Preparation and PTC properties of multilayer graphene/CB/HDPE conductive composites with different cross-linking systems[J].Materials Science in Semiconductor Processing,2024,173:108124.
[9] 张林,王家京,宗宪波,等.水性石墨烯/碳纳米管/炭黑PTC电热涂料的制备[J].广州化学,2020,45(5):29-35.
[10] 方洁,曹卫锋,段现星,等.一种正温度系数热敏电阻及其制备方法:CN104867636B[P].2016-06-15.
[11] Liu K,Xu Z,Mei J,et al.Strategies for improving positive temperature effects in conductive polymer composites-a review[J].Journal of Materials Chemistry C,2023,11(15):4966-4992.
[12] Nan X,Zhang Y,Shen J,et al.A review of the establishment of effective conductive pathways of conductive polymer composites and advances in electromagnetic shielding[J].Polymers,2024,16(17):2539.
[13] Lu L,Guo H,Wang Y,et al.Dual enhancement of Joule heating and positive temperature coefficient behaviour in biodegradable nanocomposites via hybrid carbon nanofiller networks[J].Composites Part A:Applied Science and Manufacturing,2025,199:109167.
[14] 狄莹莹,任鹏刚,张倩.石墨烯-多壁碳纳米管/超高分子量聚乙烯导电复合材料的制备及性能[J].复合材料学报,2012,29(4):36-41.
[15] 徐壮.低成本高性能EVA/PA基正温度系数复合材料的制备及其PTC性能研究[D].桂林:广西师范大学,2025.
[16] 刘园,王天琪,许培炎,等.导电聚合物复合材料正温度系数效应的研究进展[J].材料工程,2025,53(10):28-39.
[17] Shen L,Wang F Q,Yang H,et al.The combined effects of carbon black and carbon fiber on the electrical properties of composites based on polyethylene or polyethylene/polypropylene blend[J].Polymer Testing,2011,30(4):442-448.
[18] Dang Z M,Li W K,Xu H P.Origin of remarkable positive temperature coefficient effect in the modified carbon black and carbon fiber cofillled polymer composites[J].Journal of Applied Physics,2009,106(2):024913.
[19] Jeevananda T,Kim N H,Lee J H,et al.Investigation of multi-walled carbon nanotube-reinforced high-density polyethylene/carbon black nanocomposites using electrical,DSC and positron lifetime spectroscopy techniques[J].Polymer International,2009,58(7):775-780.
[20] 刘静,潘颐,张向武.Sn-Pb合金填充聚合物导电复合材料的PTC效应[J].复合材料学报,2002(6):116-119.
[21] 胡洪亮,丁旭,金玉杰.交联体系对聚合物基PTC复合材料性能的影响论述[J].化工新型材料,2025,53(6):10-14,21.
[22] Li Q,Siddaramaiah,Kim N H,et al.Positive temperature coefficient characteristic and structure of graphite nanofibers reinforced high density polyethylene/carbon black nanocomposites[J].Composites Part B:Engineering,2009,40(3):218-224.
[23] 秦艳丽.含石墨烯及碳纳米管复合材料制备及PTC性能研究[D].上海:上海第二工业大学,2018.
[24] Zha J W,Wu D H,Yang Y,et al.Enhanced positive temperature coefficient behavior of the high-density polyethylene composites with multi-dimensional carbon fillers and their use for temperature-sensing resistors[J].RSC Advances,2017,7(19):11338-11344.
[25] Liang J Z.Electrical conductivities of high-density polyethylene composites reinforced with carbon fiber and nanometer carbon black[J].Polymer Composites,2019,40(S2):E1801-E1807.
[26] Zhou C,Zhang Y,Cen F,et al.Polymer positive temperature coefficient composites with room-temperature curie point and superior flexibility for self-regulating heating devices[J].Polymer,2023,265:125587.
[27] Chen X,Gao J,Qi Y,et al.Safe and negligible-loss overcurrent protection:a novel macromolecular voltage stabilizer for conductive polymer composites[J].Composites Science and Technology,2025,260:110965.
[28] Setnescu R,Lungulescu E M.Novel PTC composites for temperature sensors (and related applications)[M].UK:IntechOpen,2023.
[29] Jin H Z,Han X F,Radjenovic P M,et al.Facile and effective positive temperature coefficient(PTC) layer for safer lithium-ion batteries[J].The Journal of Physical Chemistry C,American Chemical Society,2021,125(3):1761-1766.
[30] Fu S,Luo R,Wang Z,et al.Excellent stability and repeatability of temperature self-regulating HDPE/PVDF/CNF composites at high temperature via locally anchored conductive ‘bridges’[J].Composites Science and Technology,2025,269:111239.
[31] 谢鸿峰,董丽松,孙家珍.辐射交联对聚合物/炭黑导电复合物影响的评述[J].辐射研究与辐射工艺学报,2003(1):49-53.
[32] Go G M,Park S,Lim M,et al.Enhanced positive temperature coefficient intensity and reproducibility with synergistic effect of 0-D and 2-D filler composites[J].Journal of Materials Science,2022,57(38):18037-18050.
基金资助
吉林省科技发展计划项目(20230508042RC)
PDF
