Zhang Baode, Clausi Marialaura, Heck Barbara, Laurenzi Susanna, Santonicola M Gabriella, Kleperis Janis, Antuzevičs Andris, Reiter Günter, Aleshin Andrey N, Lobach Anatoly S
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, People's Republic of China.
Institute of Physics, Albert-Ludwig-University of Freiburg, Hermann-Herder-Str. 3, Freiburg 79104, Germany.
ACS Appl Mater Interfaces. 2021 May 26;13(20):24218-24227. doi: 10.1021/acsami.1c02654. Epub 2021 May 14.
Changes in surface energy and electrical conductivity of polyimide (PI)-based nanocomposite films filled with carbon nanotubes (CNTs) induced by UV exposure are gaining considerable interest in microelectronic, aeronautical, and aerospace applications. However, the underlying mechanism of PI photochemistry and oxidation reactions induced by UV irradiation upon the surface in the presence of CNTs is still not clear. Here, we probed the interplay between CNTs and PIs under UV exposure in the surface properties of CNT/PI nanocomposite films. Changes in contact angles and surface electrical conductivity at the surface of CNT/PI nanocomposite films after UV exposure were measured. The unpaired electron intensity of free radicals generated by UV exposure was monitored by electron paramagnetic resonance. Our study indicates that the covalent interactions between CNTs and radicals generated by UV irradiation on the PI surfaces tailor the surface energy and surface conductivity through anchoring radicals on CNTs. Surprisingly, adding CNTs into PI films exposed to UV leads to antagonistic contributions of dispersion and polar components to the surface energy. The surface electrical conductivity of the CNT/PI nanocomposite films has been improved due to an enhanced hopping behavior with dense π-conjugated CNT sites. To explain the observed changes in surface energy and surface conductivity of CNT/PI nanocomposite films induced by UV exposure, a qualitative model was put forward describing the covalent interactions between UV-induced PI free radicals and CNTs, which govern the chemical nature of surface components. This study is helpful for characterizing and optimizing nanocomposite surface properties by tuning the covalent interactions between components at the nanoscale.
由紫外线照射引起的、填充有碳纳米管(CNT)的聚酰亚胺(PI)基纳米复合薄膜的表面能和电导率变化,在微电子、航空和航天应用中引起了相当大的关注。然而,在碳纳米管存在的情况下,紫外线照射在表面引发的聚酰亚胺光化学和氧化反应的潜在机制仍不清楚。在这里,我们探究了在紫外线照射下碳纳米管与聚酰亚胺之间的相互作用对碳纳米管/聚酰亚胺纳米复合薄膜表面性质的影响。测量了紫外线照射后碳纳米管/聚酰亚胺纳米复合薄膜表面的接触角和表面电导率的变化。通过电子顺磁共振监测紫外线照射产生的自由基的未成对电子强度。我们的研究表明,碳纳米管与聚酰亚胺表面紫外线照射产生的自由基之间的共价相互作用,通过将自由基锚定在碳纳米管上来调整表面能和表面电导率。令人惊讶的是,向暴露于紫外线的聚酰亚胺薄膜中添加碳纳米管会导致分散和极性成分对表面能产生拮抗作用。由于具有密集π共轭碳纳米管位点的跳跃行为增强,碳纳米管/聚酰亚胺纳米复合薄膜的表面电导率得到了提高。为了解释紫外线照射引起的碳纳米管/聚酰亚胺纳米复合薄膜表面能和表面电导率的变化,我们提出了一个定性模型,描述紫外线诱导的聚酰亚胺自由基与碳纳米管之间的共价相互作用,这种相互作用决定了表面成分的化学性质。这项研究有助于通过调节纳米级成分之间的共价相互作用来表征和优化纳米复合材料的表面性质。