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.     

Fluorination of polymethylmethaacrylate with tetrafluoroethane using DC glow discharge plasma

Fluorination of polymer surfaces has technological applications in various fields such as microelectronics, biomaterials, textile, packing, etc. In this study PMMA surfaces were fluorinated using DC glow discharge plasma. Tetrafluoroethane was used as the fluorinating agent. On the fluorinated PMMA surface, static water contact angle, surface energy, optical transmittance (UV-vis), XPS and AFM analyses were carried out. After the fluorination PMMA surface becomes hydrophobic with water contact angle of 107° without losing optical transparency. Surface energy of fluorine plasma-treated PMMA decreased from 35 mJ/cm² to 21.2 mJ/cm². RMS roughness of the fluorinated surface was 4.01 nm and XPS studies revealed the formation of C-CF_x and CF₃ groups on the PMMA surface.     

Surface wettability of atmospheric dielectric barrier discharge processed Armos fibers

Wettability of Armos fibers has been investigated after exposed to dielectric barrier discharge (DBD) plasma, which was performed at atmospheric pressure in air while varying the sample treatment time between 9 and 27 s. Contact angles and surface free energy of the original and plasma-treated fibers were measured with dynamic contact angle analysis (DCAA) to reveal the correlation between the fiber wettability and the surface treatment, including surface composition and topography modifications, which were evaluated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. It was found by XPS analysis that the O/C atomic ratio on Armos fiber surface can be increased from 0.134 to 0.248 after the 18 s exposure to the plasma and many polar functional groups were proved to be incorporated into the surface, which aided good wetting. In addition, AFM observations revealed the changes of fiber surface microstructure, showing significant enhancement of the surface roughness after the treatment, which could also bring the fiber better wettability. What's more, the impacts of fiber surface treatment on its tensile properties were characterized by single fiber tensile strength (SFTS) testing. Results showed that Armos fibers exhibited only slight reductions in their tensile strengths with the great enhancement in fiber surface free energy.     

大气压氩气介质阻挡辉光放电的一维仿真研究

为了研究氩气(Ar)中介质阻挡大气压辉光放电(APGD)的放电机理, 通过建立一个一维的多粒子自洽耦合流体模型, 采用有限元方法进行数值计算, 得到了气体间隙压降、介质表面电荷密度、放电电流密度随时间的周期变化波形, 以及电子、离子、亚稳态粒子密度和空间电场强度的时空分布. 仿真计算结果表明：介质表面积聚的电荷对于放电的过程的起始及熄灭具有重要作用;当增大外施电压时, 放电击穿时刻提前, 放电电流密度和介质表面电荷密度峰值增大, 表明放电过程更加剧烈;随着阻挡介质相对介电常数的增大, 放电电流密度也随之增大. 各粒子密度及电场的时空分布表明放电过程在外施电压半个周期中只有一次放电, 且存在明显的阴极位降区、负辉区、等离子体正柱区等辉光放电的典型区域, 为大气压辉光放电(APGD).     

Surface modification of magnetic metal nanoparticles through irradiation graft polymerization

To tailor the interfacial interaction in magnetic metal nanoparticles filled polymer composites, the surfaces of iron, cobalt and nickel nanoparticles were grafted by irradiation polymerization. In the current report, effects of grafting conditions, including irradiation atmosphere, irradiation dose and monomer concentration, on the grafting reaction are presented. The interaction between the nanoparticles and the grafted polymer was studied by thermal analysis and X-ray photoelectron spectrometry. It was found that there is a strong interfacial interaction in the form of electrostatic bonding in the polymer-grafted nanoparticles. The dispersibility of the modified nanoparticles in chloroform was significantly improved due to the increased hydrophobicity.     

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.     

Surface modification of polytetrafluoroethylene film using single liquid electrode atmospheric- pressure glow discharge

Polytetrafluoroethylene films are treated by room temperature helium atmospheric pressure plasma plumes, which are generated with a home-made single liquid electrode plasma device. After plasma treatment, the water contact angle of polytetrafluoroethylene film drops from 114°to 46°and the surface free energy increases from 22.0 mJ/m2 to 59.1 mJ/m2. The optical emission spectrum indicates that there are reactive species such as O2+ , O and He in the plasma plume. After plasma treatment, a highly crosslinking structure is formed on the film surface and the oxygen element is incorporated into the film surface in the forms of -C-O-C-, -C=O, and -O-C=O groups. Over a period of 10 days, the contact angle of the treated film is recovered by only about 10 , which indicates that the plasma surface modification is stable with time.     

Laser-induced surface modification of polystyrene

The modification induced in polystyrene (PS) by the ArF excimer laser radiation has been investigated. Various numbers of the laser pulses of the energies below the material ablation threshold were applied. Changes in the chemical composition of the PS surface layer were studied by the X-ray photoelectron spectroscopy (XPS). Analysis of the morphological changes in the polymer surface layer was performed via the atomic force microscopy (AFM). The contact angles of test liquids (water and diiodomethane) were measured with use of a goniometer while the surface energy (SE) was calculated by the Owens-Wendt method. It was found that the surface energy change was mainly affected by surface roughness caused by the laser radiation and that surface oxidation had not considerably contributed to this change. The increase in the SE was mostly due to its disperse component.     

Surface tension and density measurements for indium and uranium using a sessile-drop apparatus with glow discharge cleaning

The sessile-drop method is used to measure the surface tension and density of liquid indium and uranium under high vacuum. Measurements are made over the temperature range 156–500°C for In and at the melting point for U. Surface oxides are efficiently removed with a glow discharge system. Drop profiles are captured by photograph and processed using nonlinear regression to yield the surface tension and density. In this regression procedure, normal distances from calculated profiles to data points are minimized. For indium, the density and surface tension measurements yield _mp = 7.05 × 10³kg/m³, d/dT = −0.776 kg/m³·°C, and γ_mp = 0.568 N/m, dγ/dT = −9.45 × 10⁻⁵ N/m·°C. The results for uranium at the melting point are _mp = 17.47 × 10³ kg/m³ and γ_mp = 1.653 N/m.     

Surface modification for the perfluorosulfonate proton-conducting electrolyte membrane

The positively charged ions of palladium particles are obtained by reducing the solution containing metallic ions in the presence of PDDA (poly-diallyldimethylammonium chloride) medium. The nascent palladium particles are dispersed evenly on the surface of the perfluorosulfonate proton-conducting electrolyte membrane and bonded firmly to the activation center of the membrane. The mechanical strength of membrane is greatly enhanced by surface modification. And the methanol diffusion coefficients of the modified membrane are decreased prominently by the deposition of palladium particles on the surface, which serves as a natural barrier for methanol crossing.     

Corona-induced graft polymerization for surface modification of porous polyethersulfone membranes

Graft polymerization of acrylic acid (AA) onto porous polyethersulfone (PES) membrane surfaces was developed using corona discharge in atmospheric ambience as an activation process followed by polymerization of AA in aqueous solution. The effects of the corona parameters and graft polymerization conditions on grafting yield (GY) of AA were investigated. The grafting of AA on the PES membranes was confirmed by ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis. Porosimetry measurements indicate the average pore diameters and porosities of the modified membranes decrease with the increase of the GY. The hydrophilicity and surface wetting properties of the original and modified membranes were evaluated by observing the dynamic changes of water contact angles. It is found that the grafting of AA occurs not only on the membrane surfaces, but also on the pore walls of the cells inside the membrane. The permeability experiments of protein solution reveal that the grafting of PAA endows the modified membranes with enhanced fluxes and anti-fouling properties. The optimized GY of AA is in the range of 150-200 μg/cm². In addition, the tensile experiments show the corona discharge treatment with the power lower than 150 W yields little damage to the mechanical strength of the membranes.     

Surface modification of polyvalent element-containing glasses

Seven soda-lime silicate glasses, each of which contains one of the following polyvalent metals: Fe, Mn, Cu, Ce, Ti, V, and Cr, are oxidized in air and reduced in H₂/N₂ (1/99) at their respective glass transition temperature for some period. A crystalline oxide surface layer is created on the glasses (except the vanadium-bearing glass) under the oxidizing condition, since the metallic ions are oxidized from lower to higher valence state, and thereby calcium ions diffuse outward and react with oxygen ions. In contrast, a silica-rich surface layer is created on the glasses under the reducing condition, since sodium and calcium ions diffuse inward. It is found that the extents of both outward and inward diffusions strongly depend on the type of the polyvalent ions for the same conditions of heat-treatment. Out of the seven polyvalent metals studied in this work, copper induces the highest extent of both the inward and outward diffusion, and hence, the thickest surface layer of both amorphous silica and crystalline alkaline earth oxides. The oxide layer lowers the onset temperature of the primary crystallization. The silica-rich surface layer enhances the chemical resistance of the glass in a hot basic solution.     

不同润湿性石英表面吸附页岩油的分子动力学模拟

根据吉木萨尔凹陷芦草沟组储层特征,利用分子动力学方法研究了不同润湿性石英狭缝表面吸附页岩油的特征.用甲基和羟基按照-CH₃:-OH=100:0、 75:25、 50:50、 25:75、 0:100修饰石英表面以构造不同润湿性的表面,并构建10 nm裂缝模型,以研究其对C₁₅H₃₂页岩油的吸附特性.研究结果表明,通过调节修饰官能团的比例,成功构造了润湿角为122.0°、 116.5°、 92.5°、 82.6°、 65.4°的吸附模型.由于水分子与石英表面间的相互作用能变化剧烈,水分子在修饰的石英表面的吸附是导致润湿角不断改变的主要原因.(C₁₅H₃₂在甲基改性石英表面的第一吸附层峰值是羟基改性的石英表面的1.37倍,说明润湿性会导致吸附特征发生明显改变.)通过对游离态页岩油含量的计算发现,随着羟基改性程度的增加,游离态页岩油质量占比从68%逐渐增长到83.7%,说明表面的润湿性改造有利于页岩油的解吸进而提高页岩油开发能力.     

Surface oxidation of a Melinex 800 PET polymer material modified by an atmospheric dielectric barrier discharge studied using X-ray photoelectron spectroscopy and contact angle measurement

Surface properties of a Melinex 800 PET polymer material modified by an atmospheric-pressure air dielectric barrier discharge (DBD) have been studied using X-ray photoelectron microscopy (XPS) and contact angle measurement. The results show that the material surface treated by the DBD was modified significantly in chemical composition, with the highly oxidised carbon species increasing as the surface processing proceeds. The surface hydrophilicity was dramatically improved after the treatment, with the surface contact angle reduced from 81.8° for the as-supplied sample to lower than 50° after treatment. Post-treatment recovery effect is found after the treated samples were stored in air for a long period of time, with the ultimate contact angles, as measured, being stabilised in the range 58-69° after the storage, varying with the DBD-treatment power density. A great amount of the C-O type bonding formed during the DBD treatment was found to be converted into the CO type during post-treatment storage. A possible mechanism for this bond conversion has been suggested.     

Modification of hydrophobic acrylic intraocular lens with poly(ethylene glycol) by atmospheric pressure glow discharge: A facile approach

To improve the anterior surface biocompatibility of hydrophobic acrylic intraocular lens (IOL) in a convenient and continuous way, poly(ethylene glycol)s (PEGs) were immobilized by atmospheric pressure glow discharge (APGD) treatment using argon as the discharge gas. The hydrophilicity and chemical changes on the IOL surface were characterized by static water contact angle and X-ray photoelectron spectroscopy to confirm the covalent binding of PEG. The morphology of the IOL surface was observed under field emission scanning electron microscopy and atomic force microscopy. The surface biocompatibility was evaluated by adhesion experiments with platelets, macrophages, and lens epithelial cells (LECs) in vitro. The results revealed that the anterior surface of the PEG-grafted IOL displayed significantly and permanently improved hydrophilicity. Cell repellency was observed, especially in the PEG-modified IOL group, which resisted the attachment of platelets, macrophages and LECs. Moreover, the spread and growth of cells were suppressed, which may be attributed to the steric stabilization force and chain mobility effect of the modified PEG. All of these results indicated that hydrophobic acrylic IOLs can be hydrophilic modified by PEG through APGD treatment in a convenient and continuous manner which will provide advantages for further industrial applications.     

Surface modification of active metals through atom transfer radical polymerization grafting of acrylics

The objective of this work is to investigate the fundamentals of surface-initiated atom transfer radical polymerization (s-ATRP) on metal substrates. Acrylic polymers were grafted from active metal surfaces such as cold rolled steel (CRS), stainless steel (SS) and nickel (Ni) through s-ATRP. Severe deactivation was found with copper bromide bipyridine catalyst. Controlled polymerization with relatively low polydispersities, 1.18-1.35, was achieved using iron bromide triphenylphosphine catalyst. Polymer films up to 80 nm in thickness were obtained within 80 min. Grafting densities were estimated to be 0.58 chains/nm² for CRS-g-PMMA, 0.55 chains/nm² for Ni-g-PMMA, 0.18 chains/nm² for SS-g-PMMA, and 0.66 chains/nm² for SS-g-PDMAEMA. Electrochemical experiments were also carried out to measure the polarization resistance and corrosion potential of CRS-g-PMMA substrates. Metal surfaces with grafted brush polymer coatings showed significant corrosion resistance. This work demonstrated that the surface-initiated ATRP is a versatile means for the surface modification of active metals with well-defined and functionalized polymer brushes.     

Surface modification of metallic Co nanoparticles

Monodisperse Co nanoparticles were synthesized by thermal decomposition in the presence of aluminium alkyls yielding air-stable Co nanoparticles after surface passivation. Several procedures for surface modification of these pre-stabilized, metallic Co nanoparticles are presented, including direct anchoring of surface-active functional groups and biocompatible dextran layers as well as silica and polymer coatings. As a result, individually coated nanoparticles as well as microspheres can be obtained.     

Surface diffuse discharge mechanism of well-aligned atmospheric pressure microplasma arrays

A stable and homogeneous well-aligned air microplasma device for application at atmospheric pressure is designed and its electrical and optical characteristics are investigated. Current-voltage measurements and intensified charge coupled device(ICCD) images show that the well-aligned air microplasma device is able to generate a large-area and homogeneous discharge at the applied voltages ranging from 12 kV to 14 kV, with a repetition frequency of 5kHz, which is attributed to the diffusion effect of plasma on dielectric surface. Moreover, this well-aligned microplasma device may result in the uniform and large-area surface modification of heat-sensitive PET polymers without damage, such as optimization in hydrophobicity and biocompatibility. In the biomedical field, the utility of this well-aligned microplasma device is further testified. It proves to be very efficient for the large-area and uniform inactivation of E. coli cells with a density of 103/cm~2 on LB agar plate culture medium, and inactivation efficiency can reach up to 99% for 2-min treatment.     

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。