碳等离子体诱导柔性PET薄膜表面原位生长非晶碳薄膜

李玥; 王永欣; 王莹; 吴于涛

引用本文:	李玥,王永欣,王莹,吴于涛.碳等离子体诱导柔性PET薄膜表面原位生长非晶碳薄膜[J].中国表面工程,2023,36(1):168~178
	LI Yue,WANG Yongxin,WANG Ying,WU Yutao.Carbon Plasma-induced In-situ Growth of Amorphous Carbon Film on the Surface of Flexible PET Film[J].China Surface Engineering,2023,36(1):168~178

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碳等离子体诱导柔性PET薄膜表面原位生长非晶碳薄膜
李玥^1,2, 王永欣¹, 王莹², 吴于涛¹
1.中国科学院宁波材料技术与工程研究所海洋新材料与应用技术重点实验室宁波 315201;2.常州大学江苏省光伏科学与工程协同创新中心常州 213164

摘要:

等离子体改性由于效果持久、环境友好而备受关注，其中碳等离子体改性不仅具有轰击效应，同时还具有沉积效应，然而碳等离子体对柔性聚对苯二甲酸乙二醇酯(PET)薄膜改性研究较少。柔性 PET 薄膜在使用过程中常因磨损和降解等原因，其光学透过性能以及力学性能受到影响。研究不同碳等离子体轰击电流(0.5 A、1.0 A、1.5 A、2.0 A)对柔性 PET 薄膜结构及性能的影响。通过 FTIR、Raman 光谱、双光束扫描电子显微镜(FIB-SEM)、扫描探针显微镜(SPM)、接触角测量仪、UV-Vis、氙灯老化试验箱、多功能摩擦磨损试验机等分析手段对薄膜的表截面结构、润湿性能、透光性、耐老化性、耐磨防护性及柔性的变化进行表征，并分析其生长机理。结果表明：低电流(0.5 A)下碳等离子体主要起到轰击效应，使得 PET 薄膜表面有机碳质结构发生断裂重排，样品透光率与基底相比仅下降 0.439%，同时该电流下制得的样品具有疏水性、耐老化性及韧性。而高电流下制得的样品的硬度显著提升，具有良好的耐磨性能，表面薄膜在弯曲过程中因应力的释放出现裂纹，但薄膜并未剥落。非晶碳薄膜与柔性 PET 薄膜具有良好结合力。通过碳等离子体诱导法生长的非晶碳薄膜可以有效延缓柔性 PET 薄膜在使用过程中的降解并提高其力学性能。

关键词: 柔性 PET 薄膜碳等离子体原位生长

DOI：10.11933/j.issn.1007?9289.20220408001

分类号:TB324

基金项目:国家自然科学基金(51975563)、中科院科技服务网络计划(STS)——东莞专项(20201600200092)和中国科学院青年创新促进会(2018336)资助项目

Carbon Plasma-induced In-situ Growth of Amorphous Carbon Film on the Surface of Flexible PET Film

LI Yue^1,2, WANG Yongxin¹, WANG Ying², WU Yutao¹

1.Key Laboratory of Marine New Materials and Related Technology, Ningbo Institute of MaterialsTechnology and Engineering, Chinese Academy of Sciences, Ningbo 315201 , China;2.Jiangsu Province Cultivation Base for State Key Laboratory of Photovoltaic Science and Technology,Changzhou University, Changzhou 213164 , China

Abstract:

Polyethylene terephthalate (PET) films are among the most commonly used synthetic polymers in light-emitting diodes, touch screens, solar cells, and other applications owing to their high tensile strength, flexibility, and corrosion resistance. However, there are functional groups on the surface of flexible PET films that lead to low surface free energy, poor wettability, and poor biocompatibility. The optical transmittance and mechanical properties of flexible PET films are also affected by abrasion and degradation while in use. Surface modifications can be performed to broaden the application field of PET films and improve their service life. Plasma modification methods have attracted much attention owing to their lasting effect and environment-friendliness. Among these, carbon plasma modification not only has a bombardment effect but also a deposition effect that can be used to prepare amorphous carbon films on the sample surface. However, studies on the carbon plasma modification of flexible PET films remain few. Therefore, the effects of different carbon plasma bombardment currents (0.5 A, 1.0 A, 1.5 A, and 2.0 A) on the structure and properties of flexible PET films are studied. The surface cross-sectional structure, wettability, transmittance, and aging resistance of the samples were characterized by Fourier-transform infrared spectroscopy, Raman spectroscopy, dual-beam scanning electron microscopy, scanning probe microscopy, contact angle measurement, UV-Vis spectroscopy, a xenon lamp aging test chamber, and a multifunctional friction and wear testing machine. The growth mechanism of amorphous carbon films on the surface of flexible PET films was also analyzed. The experimental results show that the growth of carbon plasma on the surface of flexible PET films has three parts: the bombardment of the plasma that causes the organic polymer chains on the polymer surface to randomly break and activate the sample surface; the random reaction of fractured living active chains with carbon radicals to form an in-situ transition layer in which organic and inorganic chains are connected; and the epitaxy-like growth of amorphous carbon films. At a low current (0.5 A), the main role played by the carbon plasma is bombardment, which results in the random fracture and rearrangement of the organic carbonaceous structures on the surface of the PET films. The transmittance at 550 nm of the sample prepared at this current was 87.077%, which is 0.439% lower than that of the substrate. In addition, the samples prepared at this current were hydrophobic, aging-resistant, and tough. The films neither peeled nor cracked during bending. In contrast, the samples prepared at a high current (1.0 A, 1.5 A, and 2.0 A) had significantly improved surface hardness and wear resistance. The increased thickness of the amorphous carbon films significantly reduced the light transmittance of the sample surface. At the same time, the stress in the films increased as the carbon plasma treatment current increased. Therefore, the amorphous carbon film on the sample surface released the stress during the bending process, which caused the films to crack but not peel off. In conclusion, the existence of the in-situ transformation layer improved the bonding force of the amorphous carbon films on the surface of flexible PET films. The amorphous carbon films grown by the carbon plasma induction method can delay the degradation of flexible PET films while in service, and improve their mechanical properties.

Key words: flexible PET film carbon plasma in-situ growth