Effect of Corona Discharge Treatment on the Dyeability of Low-Density Polyethylene Film

The effect of corona discharge on low-density polyethylene (LDPE) film was studied in terms of surface functionality and surface energetics of the film surfaces, improving the dyeability. The introduction of a polar group (O=C-O, C=O, and C-O) to a corona-treated LDPE film with acrylic acid could be confirmed by ESCA. The Owens-Wendt and Wu models using geometric means were studied to analyze the surface free energy of corona-treated film. It was found that the corona-treated LDPE film did lead to an increase in surface free energy, mainly due to the increase of its specific (or polar) component as the corona discharge power increased. Also, the K/S values were increased as the concentrations of dye increased. From the acid-base interaction point of view, it was found that the graft polymerization of acrylic acid onto the corona-treated LDPE film plays an important role in growing the acidic character which is one of the specific components of surface free energy, resulting in improving the dyeability with basic dyeing agent. A direct linear relationship is shown between the O(1s)/C(1s) ratio and the resulting K/S value or the specific component for this work. Copyright 2001 Academic Press.     

Surface characteristics of low-density polyethylene films modified by oxyfluorination-assisted graft polymerization

In this study, a unique two-step process, i.e., an oxyfluorination-assisted graft polymerization (OAGP), was used to modify the surface properties of low-density polyethylene (LDPE) films. Based on the results of the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method, which was performed to estimate the amount of hydroperoxides generated by oxyfluorination, oxyfluorination conditions that maximize the amount of hydroperoxide groups were selected. Hydroperoxides were generated by oxyfluorination to provide active sites for the OAGP of the different monomers. Depending on the type of monomers used, two different graft polymerization behaviors were observed. Hydrophilic methacrylic acid (MA) monomers were graft polymerized onto the oxyfluorinated LDPE (OFPE) surface in a perpendicular direction, forming a spike-shaped morphology. On the other hand, hydrophobic styrene (ST) monomers were graft polymerized parallel to the OFPE surface, forming a valley-shaped morphology. By changing the type of vinyl monomers, two different surfaces could be prepared using the hydroperoxides generated by oxyfluorination. After OAGP with MA monomers, a hydrophilic surface following the Wenzel model was obtained, whereas after OAGP with ST monomers, a hydrophobic surface following the Cassie–Baxter model was obtained. Therefore, the OAGP process may be an efficient method for preparing two different surfaces by changing the monomer used.     

Surface changes brought about by corona discharge treatment of polyethylene film and the effect on subsequent microbial colonisation

Microbial colonisation of synthetic plastic films is normally slow, which affects the total period of biodegradation. Correlation between the modified surface condition and the ability for microorganisms to colonise low-density polyethylene (LDPE) film was studied. Corona discharge treatment was applied to obtain enriched and activated surface condition of LDPE film. It was found from water contact angle and FTIR spectrum evaluations that surface energy was significantly increased due to production of free radicals. Stabilised oxidised LDPE surface was also obtained by further exposure to the corona which gave more suitable condition for subsequent colonisation. Results were compared with UV irradiated (photo-oxidised) LDPE films. Colonisation of corona discharged and UV treated LDPE films were tested in the laboratory environment using known fungal isolates and in a natural compost environment. More active microbial colonisation was observed in all cases for corona discharged and UV treated LDPE films. Far longer UV exposure was required to have the same physicochemical and biological effect as the corona discharge treatment.     

Electro-responsive transdermal drug delivery behavior of PVA/PAA/MWCNT nanofibers

The electro-responsive transdermal drug delivery system was prepared by electrospinning of poly(vinyl alcohol)/poly(acrylic acid)/multi-walled carbon nanotubes (MWCNTs) nanocomposites. The surface modification of MWCNTs was carried out by oxyfluorination to introduce the functional groups on the hydrophobic MWCNTs. The dispersion of MWCNTs and the compatibility with polymer matrices were improved by oxyfluorination. The MWCNT content and oxyfluorination condition played important roles in the swelling and drug release characteristics of nanofibers. The conductivity of nanofibers increased by increasing the content of MWCNTs and performing oxyfluorination with higher oxygen content. Uniform distribution of the oxyfluorinated MWCNTs in the nanofibers was crucial to the electro-responsive swelling and drug releasing behaviors of nanofibers.     

Mechanisms for surface energy changes observed in plasma immersion ion implanted polyethylene: The roles of free radicals and oxygen-containing groups

Low density polyethylene (LDPE) was modified by plasma immersion ion implantation (PIII) with nitrogen ions of 20 keV. Surface energy and structural transformations were observed during storage of the modified LDPE in air after PIII, by wettability measurements and FTIR-ATR spectra respectively. The appearance of oxygen-containing groups has some kinetic stages with characteristic times from hours to days. The surface energy values attained and comparison with the kinetics of oxidation reveal that the initial changes in the surface energy of LDPE are caused mainly by free radicals and to a lesser extent by oxygen-containing groups. The final surface energies observed after the process known as hydrophobic recovery and the surface energies stabilize are attributable to oxygen-containing groups. The modified surface is “living” and an investigation of the wettability, surface energy, unsaturated and oxygen-containing groups in the surface layer of ion beam modified polymers is incomplete if the kinetics of structural transformations after modification is not taken into account.     

Effect of oxyfluorination on electromagnetic interference shielding of polyaniline-coated multi-walled carbon nanotubes

Highly conducting polyaniline (PANi)-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ polymerization method for electromagnetic interference shielding. The thickness of the PANi coatings was controlled by the oxyfluorination treatment on the multi-walled carbon nanotubes and analyzed with both SEM and TEM. The oxyfluorination with higher oxygen content produced more hydrophilic functional groups on the surface of multi-walled carbon nanotubes. The functional groups led to the well distribution and coating of PANi on the multi-walled carbon nanotubes resulting in the higher interfacial affinity between them. The uniform coating of PANi on MWCNTs by controlling the oxyfluorination conditions also played a crucial role in increasing the electrical conductivity of nanocomposites. The improved interfacial affinity resulted in the higher electromagnetic interference (EMI) SE of 47.03?dB based on the synergistic combination of the conductive components. The EMI shielding mechanism of PANi on MWCNTs suggested that EMI was mainly shielded by adsorption to avoid secondary EMI.     

Surface characteristics of carbon fibers modified by direct oxyfluorination

The effect of oxyfluorinated conditions on the surface characteristics of carbon fibers was investigated. Infrared (IR) spectroscopy results indicated that the oxyfluorinated carbon fibers showed carboxyl/ester groups (CO) at 1632 cm(-1) and hydroxyl groups (OH) at 3450 cm(-1) and had a higher OH peak intensity than that of the fluorinated ones. X-ray photoelectron spectroscopy (XPS) results for the fibers also showed that oxyfluorination introduced a much higher oxygen concentration onto the fiber surfaces than fluorination with F(2) only. Additionally, contact-angle results showed that the surface was better wetted by following oxyfluorination and that the polarity of the surface was increased by increasing the oxyfluorination temperature.     

电火花引发HEMA 接枝LDPE 薄膜及其血液相容性

采用接枝量、ATR－IR、SEM、与水接触角、溶血试验和再钙化时间等测试手段研究了电火花引发甲基丙烯酸β－羟乙酯(HEMA)表面接枝低密度聚乙烯(LAPE)薄膜的接枝聚合反应影响因素、表面结构和血液相容性。结果表明,电火花能有效引发HEMA在LDMA薄膜表面接枝聚合反应,随接枝聚合反应时间延长、单体浓度的增大。接枝量增大。随反应温度升高,接枝量增大到一最大值后,进一步升高反应温度,接枝量下降,最佳接枝聚合温度为60℃当在60℃单体φ=5％水溶液是反应2h时,经空气气氛和1.5kV电火花预处理72s和LDPE薄膜表面接枝量可达169ug/cm^2。接枝改性后LDPE薄膜与水的接触下降,亲水性增加,溶血程度减小,再钙化时间延长,血液相容性得到改善。     

Influence of drawing and heat treatment on surface free energies of polyethylene terephthalate fibers

The surface free energies of polyethylene terepthalate fibers with different draw ratios were experimentally determined by contact angle measurements inn-alkane/water systems. The dispersive component of the surface free energy increased with increasing draw ratio, whereas the nondispersive one remained almost constant. After heat treatment, the dispersive surface free energy increased, but was reduced above 140°C. The nondispersive component increased by heat treatment at 190°C. The increases in the density and birefringence of the fibres due to the drawing and heat treatment suggested that the increase in the dispersive surface free energy was caused by the increase in the atomic density at the fiber surface due to drawing and heat treatment. ESCA results indicated that the increment in the nondispersive surface free energy due to heat treatment was caused by the addition of functional groups to the fiber surface due to heat treatment.     

Effect of atmospheric-pressure plasma on adhesion characteristics of polyimide film

In this work, the effect of atmospheric-pressure plasma treatments on surface properties of polyimide film are investigated in terms of X-ray photoelectron spectroscopy (XPS), contact angles, and atomic force microscopy (AFM). The adhesion characteristics of the film are also studied in the peel strengths of polyimide/copper film. As experimental results, the polyimide surfaces treated by plasma lead to an increase of oxygen-containing functional groups or the polar component of the surface free energy, resulting in improving the adhesion characteristics of the polyimide/copper foil. Also, the roughness of the film surfaces, confirmed by AFM observation, is largely increased. These results can be explained by the fact that the atmospheric-pressure plasma treatment of polyimide surface yields several oxygen complexes in hydrophobic surfaces, which can play an important role in increasing the surface polarity, wettability, and the adhesion characteristics of the polyimide/copper system.     

Photoalignmentability of silsesquioxane-containing citraconimide and its solvent-induced surface enrichment in PMMA matrix

Photo-reactive polymer of silsesquioxane-containing citraconimide (SQ-CI) was synthesised and evaluated as a photoalignment layer for polymerisable liquid crystals (PLC). A generation mechanism of the anisotropy by the linearly polarised ultraviolet light was discussed by comparing optical retardation of SQ-CI with theoretical calculations using density functional theory. In addition, the SQ-CI and poly(methyl methacrylate) were blended for a model of unification of photoalignment layer and protection layer in liquid crystal display. The orientation of PLC on the blend film was dominated by the solvent used for the sample preparation of PMMA/SQ-CI blend. We found that the SQ-CI was enriched at surface of the blend film prepared from the ?-butyrolactone solution, while not in the case of the film prepared from cyclopentanone solution. The surface enrichment in the film prepared from ?-butyrolactone solution does not follow the conventional mechanism which is that the lower surface free energy component segregates to the blend surface, because the surface free energy of SQ-CI is higher than that of PMMA. Based on the result of solvent-annealing effect and photoalignmentability, we concluded that the mechanism of surface enrichment was explained due to the difference of affinity between the polymer and the solvent.     

Surface modification of LDPE film by CO2 pulsed laser irradiation

The influence of the pulsed CO₂ laser irradiation on the surface structure of the LDPE film was investigated. Significant changes were observed on the surface of laser treated films as it was verified by the attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy and contact angle-measurement. Formation of polar functional groups onto the LDPE surfaces exhibited by the ATR-FTIR spectra was shown to be strongly dependent on the number of the CO₂ laser pulses. The intensity of the polar groups increased with increasing the number of pulses up to two and then slightly decreased at three laser pulses. This was also confirmed with the contact angle measurements in which the sample subjected to two laser pulses showed the highest wettability i.e. the lowest water drop contact angle. The concentration of peroxide groups formed on the surface of the laser treated films was determined quantitatively by UV spectroscopic method using iodide procedure. The latter results showed a similar trend with the results obtained using FTIR spectroscopy.     

Surface Energy Characteristics of Polytetrafluoroethylene Bombarded with MeV Protons

Energy characteristics of the irradiated surface of a polytetrafluoroethylene film depend on the energy and fluence of bombarding MeV protons. Irradiation with 2–4 MeV protons leads to an increase in the surface free energy; 4 MeV protons at a fluence of 10¹⁵ proton/cm² increase the polarity of the polymer surface by 40 times due to the appearance of functional groups, the polarity enhancement being manifested in an increase in the acid–base component of the surface energy by more than a factor of 50. There is a correlation between the dispersion component of the surface energy and the degree of crystallinity of the near-surface layer of the polymer a period. They both grow symbatically in the case of bombardment with 1–2 MeV protons and decrease upon irradiation with 4 MeV protons. It has been found that dehydrofluorination results in carbonization of the irradiated surface, a decrease in the fluorine content, and an increase in the proportion of oxygen due to oxidation of the radicals generated by proton bombardment.     

芴酮引发光接枝改性LDPE膜的研究

采用紫外光引发接枝表面改性的方法,以芴酮(FL)为引发剂,在低密度聚乙烯(LDPE)薄膜表面上接枝丙烯酸(AA)、甲基丙烯酸(MAA)、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)、丙烯酰胺(AM)等单体,以赋予薄膜表面新的化学性质.考察了引发剂浓度、紫外光的辐照时间、辐照强度、单体种类对LDPE薄膜接枝程度的影响.结果表明,在一定范围内,增加芴酮浓度,可以提高单体的接枝率,但当芴酮浓度达到5%时,接枝率反而下降.延长辐照时间至4 min和提高紫外光的辐照强度达100 W/m2,均有利于接枝反应的进行.不同单体在LDPE膜上的接枝能力与单体的活性、单体与基材的相容性等因素有关.接枝后,LDPE与水的接触角下降程度不仅与单体在膜上的接枝量有关,还与接枝单体的亲水性能密切相关.     

Application of the chromatographic step profile method for determination of water film pressure and surface free energy of quartz

Summary Investigation of water adsorption by the step profile method (Glueckauf method) was carried out with the help of a modified gas chromatography equipped with thermal-conductivity detector. On the basis of the adsorption isotherm obtained, the water film pressure and the polar component of the surface free energy of quartz were calculated. The calculated value of the polar component of the surface free energy of quartz agrees with analogous values obtained by other methods.     

Characterization of carboxylate sites in surface oxidized polyethylene films by fluorescence techniques

Oxidized reactive sites introduced by controlled chemical reactions in non-crystalline regions of semi-crystalline polyolefin films are located mainly on the film surface or in adjacent subsurface regions. The so-formed reactive sites in low density polyethylene (LDPE) blown films were labelled by fluorescent groups and investigated by various fluorescence techniques. The surface or subsurface location of the labelled site is indicated by a solvatochromic spectral shift and confirmed by the polarity dependent fluorescence lifetime of the labelled LDPE film immersed in a polar liquid. Fluorescence concentration quenching and concentration depolarization demonstrate the high density of oxidized sites near the film surface. The measurement of rotational mobility and orientation during film stretching adds further experimental tools to distinguish reactive oxidized sites in the surface or in the bulk.     

Effects of flame treatment on the interfacial energy of polyethylene assessed by contact mechanics

The effects of flame treatment of low-density polyethylene (LDPE) on the work of adhesion (W) and energy release rate (G) were assessed by a custom-built adhesion testing device (ATD). The contact area and the vertical displacement between planar LDPE films and PDMS lenses (untreated and UV/ozone treated) were varied as a function of the applied load, P. The adhesion and pull-off forces between the extracted PDMS lenses and the LDPE films were studied as a function of the duration of the flame treatment expressed in treatment numbers. A fracture mechanics approach was used to relate the applied load and the radius of the contact area to the energy release rate (G). The difference between the energy release rate and the thermodynamic work of adhesion, defined as the adhesion hysteresis (G - W), increased systematically with increasing treatment numbers for both lens types. In addition, the adhesion hysteresis appeared to be dependent on the contact time. Finally, the origin of the adhesion hysteresis was discussed. It was concluded that bonding by surface functional groups may be the dominating mechanisms for the changes in the observed hysteresis.     

紫外光引发LDPE膜接枝含氟丙烯酸酯的研究

通过紫外光引发表面接枝聚合反应的方法 ,把含氟丙烯酸酯单体R 5 6 1 0引到LDPE薄膜上 .对经丁酮抽提后的接枝膜进行FTIR、ESCA、SEM和DSC等表征 ,证实含氟聚合物以化学键的方式接枝在LDPE基体膜上 .在一定范围内 ,增加紫外光强、引发剂和单体浓度以及反应温度等均有利于提高接枝率 .经计算R 5 6 1 0的紫外光引发接枝聚合反应总活化能为 5 4 2kJ mol.接枝膜的接触角随着接枝率的提高逐步增大 ,直至趋于恒定 .作者提出接枝膜存在一个在接触角测定时影响基体膜与探测水滴相互作用过程的边界层 .当接枝率较低、接枝层厚度小于边界层临界厚度时 ,基体LDPE影响接触角的大小 ,但随着接枝率提高 ,接枝层逐渐变厚 ,氟聚合物层对接触角的贡献逐渐占优势 ,导致接触角随之增大 .当接枝率超过一定值以后 ,接枝层厚度超过边界层临界厚度 ,接枝层对接枝膜的接触角起全部贡献 ,接触角测定值随之稳定     

A study of atmospheric-pressure CHF3/Ar plasma treatment on dielectric characteristics of polyimide films

In this work, the influence of atmospheric-pressure CHF(3)/Ar plasma treatment on surface dielectric properties of polyimide films was investigated using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements. The dielectric characteristics of the films were studied using a dielectric spectrometer. From the results, it was found that the plasma treatment introduced fluorine functional groups onto the polyimide surfaces. F 1s/C 1s ratios of the polyimides were enhanced with the increase of plasma treatment time. Consequently, the fluorine groups led to a decrease of the surface free energy and dielectric constant of the polyimide films, which can largely be attributed to the decrease of the deformation polarizability or London dispersive component of surface free energy of the solid surface studied.     

梯度引发自由基聚合体系(Ⅰ)——基原法合成超高分子量聚合物

90年代在自由基聚合基础研究领域的一个重要成是“长 短终止”理论被进一步确认和接受[1 ,2 ] .按照该模型 ,聚合反应中的终止反应主要发生在长链自由基与短链自由基或初级自由基之间 ,即长链自由基之间很难进行终止反应 ,链终止常数随链长增加而急剧下降 .80年代初 ,Ｓｉｍｉｏｎｅｓｃｕ等[3] 曾报道了用等离子体照射封有单体的玻璃管 ,尔后放入暗处聚合的工作 ,发现不仅可得到分子量上千万的聚丙烯酸或聚丙烯酰胺 ,而且聚合活性可保持几十个小时 ;国内学者[4] 利用该法也得到了分子量接近千万的聚丙烯酰胺 .基于这种终止模型和实验结果 ,…