重复频率纳秒脉冲介质阻挡放电对聚对苯二甲酸乙二酯表面改性

介绍了0.1 MPa下的纳秒脉冲介质阻挡放电(DBD)对聚对苯二甲酸乙二酯(PET)材料表面进行的亲水性改善。分别采用均匀和丝状放电模式对PET表面改性处理,并采用水接触角测量、原子力显微镜观察、X射线光电子能谱分析对改性材料进行表面分析。实验发现介质阻挡放电处理后PET表面水接触角明显减小,接触角从78°下降到25°,但随处理时间的增加有饱和效应;PET表面粗糙程度增加,亲水性含氧基团被引入,从而改善了材料表面亲水性;纳秒脉冲下的均匀DBD比丝状DBD处理效果更为显著。     

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°。     

紫外/臭氧法PDMS表面亲水改性机理研究

紫外/臭氧改性法是一种操作简单、成本低廉的PDMS表面亲水改性方法。采用该方法对PDMS表面进行亲水改性,利用接触角测量仪对改性效果进行评价,并与PDMS无臭氧紫外法进行了比较。测试表明PDMS表面经紫外/臭氧法处理12小时后,表面接触角达到60°左右,在空气中放置两周后仍保持较好的亲水性。其改性机理可以通过多种表征手段进行分析。红外光谱测试可以看出,PDMS在经过紫外/臭氧改性后,其表面官能团变化明显,随改性时间延长,疏水基团—CH₃逐渐减少,亲水基团Si—OH和—OH逐步增加,二氧化硅典型红外光谱峰也同时出现。通过扫描电镜和能谱测试可以看出,PDMS表面经过改性产生了二氧化硅为主的硅的氧化物。综合上述结果,紫外/臭氧处理法能够使PDMS表面亲水基团增多,同时生成类玻璃态SiO_x薄层,既改善了PDMS表面的亲水性,又阻止了PDMS表面疏水性的完全恢复,亲水性可以长时间保持。     

用于聚四氟乙烯表面处理的重复频率高压脉冲电源

采用自行研制的μs级重复频率高压单极性脉冲电源,应用于聚四氟乙烯(PTFE)膜表面改性,研究脉冲放电等离子体对PTFE薄膜表面改性的作用规律。测量处理前后PTFE薄膜表面的水接触角,结果显示,在特定的脉冲参数及更严格的对比条件下其平均水接触角从112°下降到85°,PTFE薄膜表面亲水性改善效果非常显著。脉冲电源采用脉宽调制控制方式,通过逆变升压及波形整形,得到脉冲电压幅值0~20kV、重复频率0~20kHz、脉宽5~15μs、上升沿500ns~2μs、下降沿大于20μs的单极性脉冲。     

分子动力学模拟方解石和白云石润湿性

利用分子动力学模拟研究油水分子在方解石和白云石表面的吸附,分析体系的平衡构型、相对浓度、径向分布函数和吸附能,研究方解石和白云石的亲水性并对比二者差异.根据油水分子吸附规律分析方解石/白云石-油水体系作用机理.研究表明：白云石-油水体系更易达到热力学稳定状态并且体系更加稳定;方解石和白云石表面均能够优先吸附水分子并在表面形成双层结构的水膜.其中,白云石表面对水分子吸附强度大于方解石;稳定吸附过程分为两步：范德华力、静电力和O（CaCO₃,CaMg（CO₃）₂）-H（H₂O）氢键共同影响下水分子向晶体表面移动并吸附形成紧密吸附层;O（H₂O）-H（H₂O）氢键作用下游离的H₂O向晶体表面靠近形成扩散层.从分子尺度解释方解石/白云石亲水特性,为碳酸盐岩储层润湿性研究奠定理论基础.     

等离子体介质阻挡放电氟化改性环氧树脂的时效性

等离子体对材料的改性效果随放置时间会有所减弱,即表现出一定的时效性,限制了等离子体改性技术的进一步发展。为了探究等离子体介质阻挡放电（DBD）氟化改性环氧树脂的时效性,利用等离子体介质阻挡放电实现了环氧树脂表面氟化改性,并利用扫描电镜（SEM）、表面轮廓仪、X射线光电子能谱分析（XPS）、接触角测试仪、高阻计和闪络电压、表面电位测试系统对改性前和改性后放置在25 ℃老化箱中0～30 d的环氧树脂表面进行了物理形貌和化学组分的表征以及电气性能的测试。测试结果表明,DBD氟化改性实现了氟元素在环氧树脂表面接枝,这使得环氧树脂表面能降低,表面电阻率减小,陷阱能级变浅,从而加快了表面电位衰减速度,进而提升了沿面闪络电压。同时,等离子体DBD氟化改性环氧树脂表现出一定的时效性,放置30 d后,氟元素含量减少,表面能增大,表面电位衰减速度略有减慢,闪络电压也有所下降,但仍高于未处理的试样。     

基于近红外光谱的柔性基底紫外臭氧改性效果表征研究

近年来,随着纳米科技、聚合物材料和先进制造技术的发展,以柔性传感器为代表的新兴柔性电子器件在可穿戴、健康医疗、物联网终端等领域发挥着越来越重要的作用。作为柔性电子器件的载体,柔性基底对传感器的机械可靠性和电学传感性能等方面有着重要的意义。但由于其表面非极性键造成的高疏水性限制了功能性材料在其表面的沉积,常常造成柔性基底层与电极层/敏感层之间不稳定的界面结合。因此,利用紫外臭氧处理对柔性基底表面改性受到了广泛的关注。利用近红外光谱技术对柔性基底的紫外臭氧处理效果进行快速精准评估,旨在从基团分子层面探究其改性效果,在实际应用中是对传统依靠接触角测量评估方法的有效补充。具体而言,对四种常见的柔性基底材料聚二甲基硅氧烷(PDMS)、聚萘二甲酸乙二醇酯（PEN）、聚对苯二甲酸乙二醇酯（PET）和聚酰亚胺（PI）进行了1/2/5/10 min不同时长的紫外臭氧（UVO）改性处理,并利用近红外光谱对其改性效果进行表征研究,最后利用接触角测量方法对上述的表征结果进行了验证分析。近红外光谱分析表明：对于柔性PDMS基底,紫外光能量不足以切断其中的甲基（—CH₃）官能团和（—C—Si—）等化学键,无法引入羟基、羧基等亲水性基团。对于柔性PEN和PET基底而言,紫外臭氧处理的效果要优于柔性PDMS基底,且对柔性PET基底的处理效果要优于柔性PEN基底,其原因可能是PEN基底材料中萘环的双环结构具有很强的紫外光吸收能力,阻隔了380 nm以下的大部分紫外线能量。对于柔性PI基底,紫外臭氧处理可以有效引入羟基（—OH）和羧基（—COOH）等活性基团,且这些官能团的强度和数量随着处理时间的增加而增加,从而在短时间内使得PI基底表面能增大、接触角减小、湿润性提高。接触角测试结果验证：紫外臭氧处理对于柔性PDMS基底处理效果不明显（接触角下降幅度为8.4%）;对柔性PET基底处理的效果（接触角下降幅度为39.6%）要优于柔性PEN基底的处理效果（接触角下降幅度为9.4%）;紫外臭氧处理的效果对柔性PI基底处理效果最佳,接触角下降幅度达到了62.7%。     

纳秒脉冲空气辉光放电等离子体及应用

采用基于半导体断路开关的纳秒脉冲高压电源,在两个金属电极之间产生放电区间为1 600mm×100 mm×25 mm的常压辉光空气等离子体。等离子体发生器采用负高压针电极阵列与平板阳极结构,针电极的直径为1 mm,长度为20 mm,针电极之间的间隔为20 mm,针电极与平板零电位之间的距离为25mm,在每个负高压针电极末端周围同时形成圆锥形辉光放电,在平板地电极则形成大面积辉光放电。采用电压探针测量了该新型等离子体的放电特性,结果表明:放电脉冲的上升时间为26 ns,最高脉冲输出峰值电压为27 kV;利用该辉光等离子体对幅宽为1 000 mm聚四氟乙烯薄膜进行了表面改性处理,处理后其表面接触角由原来的124°降到69°,亲水性能大为提高。     

基于连续谱的氩气纳秒脉冲放电中电子温度的研究

采用了一种针对针的放电结构,将其放置在一个高纯氩气的密闭腔室中,通过施加正极性的过电压产生可重复的大气压纳秒脉冲放电,并提出建立大气压放电的连续辐射模型来诊断氩气纳秒脉冲放电中的电子温度。实验利用电压和电流探头分别获取放电过程中的电压和电流波形图,其放电脉宽约为20 ns。通过消色差透镜、单色仪和ICCD等光学系统的组合来测量放电正柱区在不同时刻（0<t<20 ns）的时间分辨发射光谱。结果表明,放电中连续谱的强度随时间先增加（0<t<10 ns）后减小（10 ns<t<20 ns）,但是氩原子的谱线强度则随时间的增加而一直增大。研究表明连续谱强度与电子密度成正相关,因而电子密度随着时间也是先增加而后减小,这与放电电流的变化规律是完全一致的。根据连续谱模型拟合得到放电过程中（0<t<10 ns）的电子温度为(1.4±0.2) eV。随着驱动电压的下降（10 ns<t<20 ns）,电子温度逐步减小至0.9 eV。在0<t<10 ns中,激发态氩原子主要是由电子碰撞激发产生的,因而谱线强度随着电子密度的增加而增大。然后,随着电子温度的减小,Ar+₂复合反应速率激增,导致电子与离子的复合过程主导产生激发态氩原子,即谱线强度继续增大。通过加入0.5%的水蒸气以获取OH的振转光谱。实验发现,OH(A)的产生机制使其偏离玻尔兹曼平衡分布,本文采用了双温的OH(A-X)光谱模型来考察气体温度。在放电过程中,气体温度保持不变,大约为400 K。此外,水蒸气的加入使得短波长的连续谱发生显著增强。光谱分析认为H₂O在放电中能够解离产生H₂,继而与氩原子的亚稳态发生能量转移生成激发态H₂(a3Σ+_g)。H₂(a3Σ+_g)将会自发辐射跃迁到排除态H₂(b3Σ+_u),同时发射短波长的连续谱。由于短波长的连续谱对电子温度（T_e>1 eV）的响应较为灵敏,所以载气中少量的水蒸气将会对连续谱诊断电子温度带来较大的影响。     

H2O分子在Fe（100）, Fe（110）, Fe（111）表面吸附的第一性原理研究

采用第一性原理研究了H₂O分子在Fe（100）,Fe（110）,Fe（111）三个高对称晶面上的表面吸附.结果表明,H₂O分子在三个晶面上的最稳定结构皆为平行于基底表面的顶位吸附结构.H₂O分子与三个晶面相互作用的吸附能及几何结构计算结果表明H₂O分子与三个晶面的相互作用程度不同,H₂O分子与Fe（111）晶面的相互作用最强,其次是Fe（100）,相互作用最弱的是Fe（110）表面,而这与晶面原子 关键词： 第一性原理 Fe单晶表面 2O分子')" href="#">H₂O分子 分子吸附     

Formation of hydrophobic coating on PMMA surface using unipolar nanosecond-pulse DBD in atmospheric air

Dielectric barrier discharge (DBD) can modify the material surface and result in complicated physical and chemical reactions to improve the surface hydrophilicity, which is proved to be an effective method for surface modification. Compared with the traditional ac-excitation DBD, the DBD using unipolar pulses can avoid local overheat of microdischarges and can improve discharge efficiency under some conditions. In this paper, DBD excited by repetitive unipolar nanosecond generator was used to improve the hydrophobicity of Plexiglass (PMMA) surface by means of the interaction between air plasma and silicone oil. The output voltage had a rise time of 40 ns and a full width at half maximum of about 70 ns. The surface hydrophobicity of the PMMA, before and after the surface modification, was evaluated via the contact angle measurement under different experimental conditions. The values of the contact angle shown in this paper were the average of eight measured values, and the standard deviations were also calculated. The surface energy including polar and dispersion components was calculated using the measured average contact angles of distilled water and polyethyleneglycol. The results showed that, as the increase of the discharge voltage, the contact angle increased but the surface energy decreased. With the increase of treatment time, the water contact angle of the modified surface increased at the beginning, and it would reach to a maximum at 7.5 min treatment, and then decreased. The effect of pulse frequency on the modification results was different at various treatment times. In addition, the possible physical and chemical reaction among the DBD plasma, silicone oil and the PMMA surface was discussed.     

Surface modification of polypropylene non-woven fabric using atmospheric nitrogen dielectric barrier discharge plasma

In this paper, a dielectric barrier discharge operating in nitrogen at atmospheric pressure has been used to improve the surface hydrophilic property of polypropylene (PP) non-woven fabric. The changes in the hydrophilic property of the modified PP samples are investigated by the contact angle measurements and the variation of water contact angle is obtained as a function of the energy density; micrographs of the PP before and after plasma treatment are observed by scanning electron microscopy (SEM) and the chemical composition of the PP surface before and after plasma treatment is also analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the surface hydrophilic property of the PP samples is greatly improved with plasma treatment for a few seconds, as evidenced by the fact that the contact angle of the treated PP samples significantly decreases after plasma treatment. The analysis of SEM shows that the surface roughness of the treated PP samples increases due to bonding and etching in plasma processing. The analyses of FTIR and the C1s peak in the high-resolution XPS indicate that oxygen-containing and nitrogen-containing polar functional groups are introduced into PP surface in plasma processing. It can be concluded that the surface hydrophilic property of the modified PP samples has been obviously improved due to the introduction of oxygen-containing and nitrogen-containing polar groups and the increase of the surface roughness on the PP surface.     

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.     

Preparation of hydrophobic coating on glass surface by dielectric barrier discharge using a 16 kHz power supply

A 16 kHz power supply was used to investigate the preparation of hydrophobic film on glass surface by means of atmospheric pressure dielectric barrier discharge (DBD). Air nonthermal plasma was induced between the two parallel electrodes with a glass plate as dielectric barrier. The process for hydrophobic film includes two parts: one is plasma pretreatment to produce active layer on glass surface, another is to form hydrophobic film on glass surface by means of the interaction between air plasma and polydimethylsiloxane oil. The surface changes were observed using contact angle measurement and atomic force microscope. The results show DBD can increase surface roughness, and effectively improve glass surface activation and form a hydrophobic coating on glass surface, and it is possibility to prepare hydrophobic glass with middle frequency power supply.     

Effect of atmospheric pressure dielectric barrier discharge air plasma on electrode surface

In order to study the influence of plasma on electrode, atmospheric pressure dielectric barrier discharge (DBD) air plasma is employed here to treat copper electrode surface. Plasma is generated between the parallel plate electrodes by means of high voltage produced by a high-frequency power supply with transformer. Electrode surface alterations induced by air plasma are investigated by using field emission scanning electron microscope (FE-SEM), X-ray energy dispersion spectroscopy (EDS) and contact angle measurement. The results show that DBD air plasma removes the organic contaminant on surface and causes electrode surface roughness, oxidization and nitridation. In addition, surface wettability is also improved, as concluded from contact angle measurements.     

Surface modification of polyimide films using unipolar nanosecond-pulse DBD in atmospheric air

DBD-induced surface modification is very versatile to increase the adhesion or hydrophilicity of polymer films. In this paper, the DBD is produced by repetitive unipolar nanosecond pulses with a rise time of 15 ns and a full width at half maximum of about 30 ns. The power densities of the homogeneous and filamentary DBDs during plasma treatment are 158 and 192 mW/m², respectively, which are significantly less than that using ac DBD processing, and the corresponding plasma dose is also mild compared to AC DBD treatment. Surface treatment of polyimide films using the homogeneous and filamentary DBDs is studied and compared. The change of chemical and physical modification of the surface before and after plasma processing has been evaluated. It can be found that both surface morphology and chemical composition are modified, and the modification includes the rise of hydrophilicity, surface oxidation and the enhancement of surface roughness. Furthermore, the homogeneous DBD is more effective for surface processing than the filamentary DBD, which can be attributed to the fact that the homogeneous DBD can modify the surface more uniformly and introduce more polar functional groups.     

Statistical analysis of the effect of dielectric barrier discharge (DBD) operating parameters on the surface processing of poly(methylmethacrylate) film

A dielectric barrier discharge (DBD) plasma, operating in air at atmospheric pressure, has been used to induce changes in the surface properties of poly(methylmethacrylate) (PMMA) films. The relative effects that key DBD operating parameters, specifically: discharge power, electrode gap and duration of exposure have on producing chemical and microstructural changes in the polymer surface region have been investigated. The approach taken involves the application of an orthogonal array experimental design and statistical analysis methodology. The various data sets obtained from these analyses have been used to develop an equation in which induced changes in the surface properties of the DBD modified PMMA films are expressed in terms of the effectiveness of the various processing parameters in producing them.In general, the results obtained clearly indicate that DBD plasma processing is an effective method for the controlled surface modification of PMMA. Relatively short exposures to the atmospheric pressure discharge produces a significant amount of oxygen incorporation at the surface as indicted by a pronounced reduction in water contact angle. Analysis of the role of each of the operating parameters concerned shows that they do indeed have selective effectiveness for inducing resultant surface modification. Duration of exposure to the DBD plasma, expressed here as the number of treatment cycles at a given speed of specimen transit through the electrode gap, was found to play a major role in decreasing the surface wettability of PMMA. Conversely, the magnitude of the discharge power was not a significant parameter in this regard. In contrast, the value of the applied power played the dominant role in achieving the observed enrichment of the surface oxygen abundance, as measured by XPS, with the duration of exposure to the discharge playing a secondary role in this case.The nature and scale of the induced surface changes that originate from the various processing conditions employed have been further considered to determine if an interrelationship exists between them. Non-parametric data analysis indicates that no significant correlation exists between the observed changes in measured polymer wettability and the attendant surface oxygen enrichment. This result suggests that the increase in surface wettability caused by DBD processing, as manifested in a reduced contact angle, is not merely attributable to changes in the surface chemistry. As such, it is postulated that changes in the surface microstructure may also contribute to this change in surface wettability.     

Functionalization of PET and PA6.6 woven fabrics

In the present work as received woven fabrics of polyethylene terephthalate (PET) and polyamide 6.6 (PA6.6) were exposed to a continuous dielectric barrier discharge (DBD), in air at atmospheric pressure, at selected discharge power values and conveyor speeds. The chemical modification of the fabric surface was studied by contact angle analysis, attenuated total reflection (ATR)-FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The results confirmed that the treatment changed the fabric surface chemistry, increasing its wettability by polar liquids and its oxygen content. Contact angle results showed different behaviour of the two polymer fabrics toward ageing effects; while PET showed a contact angle increase along the subsequent days of treatment, the PA6.6 fabric maintained its hydrophilicity even 15 days after treatment. The surface morphology analysed by scanning electron microscopy (SEM), did not show any significant difference before and after treatment.