交流和纳秒脉冲Ar/H2O介质阻挡放电聚丙烯材料表面亲水改性对比研究

为了提高等离子体对聚合物材料表面处理的应用效果,优化亲水处理的条件,研究了交流和纳秒脉冲氩气介质阻挡放电（DBD）中添加适量H₂O,对聚丙烯（PP）亲水改性的处理效果。利用电学和光学诊断方法,系统地对比了交流DBD和纳秒脉冲DBD的放电特性,结果表明,纳秒电源驱动DBD具有更高的放电瞬时功率,更好的放电均匀性和更高的能量效率。通过测量不同水蒸气含量下DBD的OH发射光谱强度,确定了PP材料亲水性处理中H₂O添加的最优含量。利用交流和纳秒脉冲电源驱动DBD分别对PP材料进行亲水改性的处理,测量了不同条件下改性处理后的表面水接触角,并利用原子力显微镜（AFM）和傅里叶红外光谱（FTIR）分别对处理前后PP材料的表面物理形貌和表面化学成分进行分析。结果发现,经DBD处理后PP材料的水接触角明显降低,表面粗糙度明显增大,表面的亲水性含氧基团,羟基（?OH）和羰基（C=O）的数量大幅增加。相比交流电源,纳秒脉冲DBD处理的改性效果更好,其处理后的材料表面水接触角,比交流DBD处理的低5°左右,表面粗糙度也有所提升。而水蒸气的加入可使PP材料的表面水接触角进一步减小4°左右,表面粗糙度明显提升。研究结果为优化DBD聚合物材料表面改性实验条件及处理的效果提供了重要的参考依据。     

纳秒脉冲放电对聚对苯二甲酸乙二酯憎水改性

基于自主研制的ns脉冲电源(上升沿约70ns,脉宽约100ns)激励介质阻挡放电产生大气压低温等离子体,在CF4气氛下对聚对苯二甲酸乙二酯(PET)表面进行了憎水改性处理,测量了改性前后的薄膜表面的水接触角,给出了CF4气流量、放电电压、处理时间和CF4比例等参数对改性效果的影响规律。结果表明,大气压ns脉冲DBD表面处理能够实现PET材料的憎水性,改性后的PET表面水接触角由66°提高到最大100°。     

纳秒脉冲表面介质阻挡放电特性实验研究

在常规大气环境条件下,基于单极性纳秒脉冲电源对表面介质阻挡放电特性进行了实验研究。结果表明:纳秒脉冲表面介质阻挡放电的本质是丝状放电,放电集中在电压脉冲的上升沿;激励电压和脉冲重复频率越大,放电越强烈,越接近均匀放电,但电压的作用更侧重于均匀性,而频率的作用则侧重于放电的强度;电极间隙的优化可以使表面介质阻挡放电特性最好;玻璃作为阻挡介质时容易发生沿面闪络。     

Experimental study on characteristics of nanosecond-pulse surface dielectric barrier discharge

在常规大气环境条件下,基于单极性纳秒脉冲电源对表面介质阻挡放电特性进行了实验研究.结果表明:纳秒脉冲表而介质阻挡放电的本质是丝状放电,放电集中在电压脉冲的上升沿;激励电压和脉冲重复频率越大,放电越强烈,越接近均匀放电,但电压的作用更侧重于均匀性,而频率的作用则侧重于放电的强度;电极间隙的优化可以使表面介质阻挡放电特性最好;玻璃作为阻挡介质时容易发生沿面闪络.     

米量级常压等离子体改性装置及其在纺织材料改性中的应用

介绍了自制的1m尺度介质阻挡电连续表面改性处理装置。论述了米量级常压介质阻挡放电的物理特性,探讨了介质阻挡放电的电压、功率、频率等电学参量之间的关系。给出了使用此装置连续对涤纶(PET)织物、熔喷PBT非织造布和羊毛织物三种纺织材料进行改性实验结果,得到了相应的扫描电子显微镜(SEM)图片,分析了材料表面改性的原因。     

High speed imaging of nanosecond-pulse dielectric barrier discharge in atmospheric air

使用上升沿40 ns、脉宽70 ns的重复频率单极性纳秒脉冲电源,采用双水电极结构产生大气压空气中介质阻挡放电.测量了纳秒脉冲下介质阻挡电压和电流,并获得长曝光时间和ns级曝光时间的放电特性,采用曝光时间为2 ns的高速摄影拍摄放电发展过程.结果表明:大气压空气中,水电极结构纳秒脉冲介质阻挡放电能够产生稳定均匀的放电等离子体,且存在二次放电.高速摄影对放电发展过程的拍摄结果表明:放电首先由电极中部开始发展,径向扩展至整个电极范围.     

空气中纳秒脉冲介质阻挡放电高速摄影

使用上升沿40 ns、脉宽70 ns的重复频率单极性纳秒脉冲电源,采用双水电极结构产生大气压空气中介质阻挡放电。测量了纳秒脉冲下介质阻挡电压和电流,并获得长曝光时间和ns级曝光时间的放电特性,采用曝光时间为2 ns的高速摄影拍摄放电发展过程。结果表明:大气压空气中,水电极结构纳秒脉冲介质阻挡放电能够产生稳定均匀的放电等离子体,且存在二次放电。高速摄影对放电发展过程的拍摄结果表明:放电首先由电极中部开始发展,径向扩展至整个电极范围。     

锯齿波频率对介质阻挡放电光谱特性的影响

采用微间隙平行平板介质阻挡放电(DBD)装置,以氩气作为工作气体,研究了锯齿波激励下DBD的放电图像、发光信号、发射光谱与锯齿波频率的关系。研究发现随锯齿波频率增加,DBD会从均匀模式(低于10 kHz),经历微放电丝与均匀放电共存,并最终过渡到微放电丝占据全部的电极区(频率高于35 kHz)。外加电压和发光波形表明,锯齿波频率较低时的均匀放电对应高占空比的阶梯放电。随频率增大,出现微放电丝后,发光波形呈现多脉冲形式,且电压半周期中的发光脉冲个数随着锯齿波频率的增大而减小。当锯齿波频率高于35 kHz时,每半个电压周期的发光脉冲个数减小为一个(单脉冲放电)。通过对放电的发射光谱进行研究,发现发射光谱中包含氮分子的第二正带系(C3Π_u→B3Π_u),OH(A2Σ+→X2Π)和ArI的特征谱线。研究表明OH(308.8 nm)和ArI(750.4 nm)的谱线强度均随锯齿波频率的增大而增大。     

μs振荡脉冲电源激励下同轴电极介质阻挡放电特性

 采用μs振荡脉冲电源激励同轴电极结构产生空气中介质阻挡放电(DBD),通过电压-电流波形的测量及发光图像拍摄研究了放电特性,计算得到了放电功率及传输电荷量等重要放电参量,研究了电压幅值、气隙距离对放电特性及放电参量的影响,在分析放电机理的基础上对实验结果进行了解释。结果表明:μs振荡脉冲电源激励下,DBD平均放电功率可达上百W,传输电荷量可达几千nC;增大电压幅值和减小放电气隙距离能获得更剧烈的放电,平均放电功率和传输电荷量均增加。     

正弦削波电压调控大气压氦气非平滑表面介质阻挡放电均匀性的仿真研究

在大气压介质阻挡放电的实际应用中,等离子体通常作用于非平滑表面.其表面形貌导致的电场畸变和表面电荷分布不均匀,会对放电的均匀稳定产生不利影响.建立了下介质板为波浪状的大气压氦气介质阻挡放电仿真模型,并采用正弦削波电压对放电均匀性进行调控.结果表明:相比于未削波情况下,放电均匀性提高,介质阻挡放电从柱状放电模式转换为准均匀放电模式.这可以归因于气隙电压降低而产生的不完全放电消散;随后的电子回流过程使残余空间电子与表面电荷中和,限制了表面电荷积累.随着削波比例增加,表面电荷分布更为均匀,进而导致电场分布在径向上波动减弱.此外,在一定削波范围内放电效率也有所提高.本研究揭示了削波电压对非平滑表面介质阻挡放电的影响机理,为介质阻挡放电均匀性调控提供了新的思路.     

New insights into corona discharge surface ionization of polyethylene terephthalate via a combined computational and experimental assessment

The aim of the present work is to demonstrate the influence of corona discharge ionization on chemical and physical properties of polyethylene terephthalate (PET) fibers using computational and experimental studies. In the computational section, the vibrational frequencies of proposed models for PET before and after corona discharge treatment were predicted in the liquid phase at both the B3LYP/6-31G/COSMO and B3PW91/6-31G/COSMO level of theories using the harmonic approximation. When compared to B3LYP, the frequencies obtained for the B3PW91 show a better linear correlation with the experimental data. Furthermore, experimental studies were carried out by the use of Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and reflectance spectroscopy (RS). Experimental evidence indicated that the corona discharge modifies the surface of fibers and also increases the reactivity of PET toward cationic dyes. Our combined computational and experimental parametric study clearly confirms that the changes occurred on the PET surface due to corona discharge ionization.     

Uniformity analysis of dielectric barrier discharge (DBD) processed polyethylene terephthalate (PET) surface

A dielectric barrier discharge (DBD) plasma, operating in air at atmospheric pressure, has been used to induce changes in the surface properties of polyethylene terephthalate (PET) films. The effects that the key DBD operating parameters: discharge power, processing speed, processing duration, and electrode configurations, have on producing wettability changes in the PET surface region have been investigated. The approach taken involves the application of an Taguchi experimental design and robust analysis methodology. The various data sets obtained from these analyses have been used to studies the effect of the operating parameters on the surface uniformity and efficiency of the said treatment.In general, the results obtained indicate that DBD plasma processing is an effective method for the controlled surface modification of PET. Relatively short exposures to the atmospheric pressure discharge produces significant wettability changes at the polymer film surface, as indicted by pronounced reductions in the water contact angle measured. It was observed that the wettability of the resultant surface shows no significant differences in respect to orientation parallel (L-direction) or perpendicular (T-direction) to the electrode long axis. However, there was significant differences between the data obtained from these two orientations. Analysis of the role of each of the operating parameters concerned shows that they have a selective effectiveness with respect to resultant surface modification in terms of uniformity of modification and wettability. The number of treatment cycles and the electrode configuration used were found to have the most significant effects on the homogeneity of the resultant PET surface changes in L- and T-orientation, respectively. On the other hand, the applied power showed no significant role in this regard. The number of treatment cycles was found to be the dominant factor (at significance level of 0.05) in respect of water contact angle changes at the processed PET surface in both orientations. The driven metal electrodes (stainless steel or aluminium) were apparently superior to the driven dielectric electrode (ceramic or quartz) configurations. The grounded electrode in each case was a silicon rubber-covered aluminium plate (see later). The nature and scale of the surface changes that originate from the various processing conditions employed have been considered so as to determine the optimum treatment conditions in respect of processing outcomes, properties and any orientation dependence. Thus, it was revealed that higher processing speeds and longer processing durations are key for uniformity along the electrode axial orientation, while lower processing speeds and short exposure durations are key considerations, in the corresponding perpendicular orientation. In general, longer processing durations (low processing speeds and a high number of treatment cycles) and higher plasma powers induced greater changes in the surface wettability of the PET, as demonstrated by the observed water contact angles. This behaviour is taken to indicate that different combinations of DBD operating parameters and electrodes produce discharge conditions that can result in different plasma chemical processes in respect of uniformity, treatment efficiency and orientation dependence.     

The effect of discharge power density on polyethylene terephthalate film surface modification by dielectric barrier discharge in atmospheric air

Polyethylene terephthalate (PET) films are modified using non-equilibrium plasma generated by DBD in atmospheric air, and the effects of discharge power density on the surface modification are studied. It is found that increasing discharge power density can induce more effective treatment of PET films, because this leads to a faster decrease in water contact angle and a faster increase in surface energy due to more creation of polar groups and more obvious etching occurring on the PET surface. So the treatment time needed to achieve the same level of surface treatment can be reduced by increasing the discharge power density.     

高直流电场下PET薄膜的电致发光及其可靠性

用自制电致发光(Electrolum inescence-EL)测量装置测试了直流高电场下聚对苯二甲酸乙二酯[poly(ethylene terephthalate)-PET]薄膜EL的光强和光谱。实验表明:PET的发光光强随所加电场而增大,在4.00MV/cm附近发生预击穿。EL光谱在300~400nm、400~460nm、500~600nm和680nm附近存在发射峰,其中500~600nm峰带相对较强,预击穿信号出现后680nm附近的峰带增加很快。为了评价PET的介电性能,本文对实验数据用双参数Weibull分布解析法计算,得出了该薄膜在(24±1)℃,阶跃加压条件下的寿命和击穿电场的累积失效概率和可靠度方程,Weibull假设检验结果表明,实验结果服从Weibull分布。     

Electron beam induced modification of poly(ethylene terephthalate) films

Electron beam processing of poly(ethylene terephthalate) (PET) films is found to promote significant changes in the melting heat, intrinsic viscosity and polymer film-liquid (water, isooctane and toluene) boundary surface tension. These properties are featured with several maximums depending on the absorbed dose and correlating with the modification of PET surface functionality. Studies using adsorption of acid-base indicators and IR-spectroscopy revealed that the increase of PET surface hydrophilicity is determined by the oxidation of methylene and methyne groups. Electron beam treatment of PET films on the surface of N-vinylpyrrolidone aqueous solution provided graft copolymerization with this comonomer at optimum process parameters (energy 700 keV, current 1 mA, absorbed dose 50 kGy).     

Effects of l-arginine immobilization on the anticoagulant activity and hemolytic property of polyethylene terephthalate films

Surface modification of polyethylene terephthalate (PET) films was performed with l-arginine (l-Arg) to gain an improved anticoagulant surface. The surface chemistry changes of modified films were characterized by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The in vitro anticoagulant activities of the surface-modified PET films were evaluated by blood clotting test, hemolytic test, and the measurement of clotting time including plasma recalcification time (PRT), activated partial thromboplastin time (APTT), and prothrombin time (PT). The data of blood coagulation index (BCI) for l-arginine modified PET films (PET-Arg) was larger than that for PET at the same blood-sample contact time. The hemolysis ratio for PET-Arg was less than that for PET and within the accepted standard for biomaterials. The PRT and APTT for PET-Arg were significantly prolonged by 189 s and 25 s, respectively, compared to those for the unmodified PET. All results suggested that the currently described modification method could be a possible candidate to create antithrombogenic PET surfaces which would be useful for further medical applications.     

Structural, electrical and optical properties of Ga-doped ZnO films on PET substrate

The effects of O₂ plasma pretreatment on the properties of Ga-doped ZnO films on PET substrate were studied. Ga-doped ZnO films were fabricated by RF magnetron sputtering process. To improve surface energy and adhesion of PET substrate, O₂ plasma pretreatment process was used prior to GZO sputtering. With increasing O₂ plasma treatment time, the contact angle decreases and the RMS surface roughness increases significantly. The transmittance of GZO films on PET substrate in a wavelength of 550 nm was 70-84%. With appropriate O₂ plasma treatment, the resistivity of GZO films on PET substrate was 3.4 × 10⁻³ Ω cm.     

单层单晶石墨烯与柔性基底界面性能的实验研究

单晶石墨烯具有更优异的力学及电学性能,有望成为新一代柔性电子器件的核心材料.因此,有必要从实验的角度精细分析化学气相沉积法制得的大尺度单晶石墨烯与柔性基底复合结构的界面力学行为.本文通过显微拉曼光谱实验方法测量了不同长度的单层单晶石墨烯/PET(聚对苯二甲酸乙二醇酯)基底的界面力学性能参数及其在长度方向上界面边缘的尺度效应.实验给出了石墨烯在PET基底加载过程中与基底间黏附、滑移、脱黏三个界面状态的演化过程与应力分布规律.实验发现,单晶石墨烯与柔性基底间由范德瓦耳斯力控制的界面应变传递过程存在明显的边缘效应,并且与石墨烯的长度有关.界面的切应力具有尺度效应,其值随石墨烯长度的增加而减小,而石墨烯界面传递最大应变以及界面脱黏极限则不受试件尺度的影响.     

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO₃) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO₃ solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 × 10⁴ Ω/□ to 2.65 × 10³ Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.