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.     

Chemical surface composition of the polyethylene implanted by Ag ions studied by phase imaging atomic force microscopy

High density polyethylene (HDPE) has been modified by Ag⁺ ion implantation with the energy of 60 keV. The total amount of implanted silver ions was 1, 5 and 12 × 10¹⁵ ions/cm². The surface topography was observed by atomic force microscopy (AFM), while the surface composition changes were detected using phase imaging AFM. Surface topography changes were studied in detail using 3D surface parameters analyses. The average roughness decreased for the implanted HDPE indicating the flattening of the surface. Phase AFM images indicated the homogenization of the polyethylene during ion implantation, while histogram analyses confirmed the change in surface composition.     

Two component silicone modified epoxy foul release coatings: Effect of modulus, surface energy and surface restructuring on pseudobarnacle and macrofouling behavior

Two component silicone modified epoxy resin based low surface energy and non-toxic foul release coatings were developed. Silicone modified epoxy resin with 15 and 30% silicone content was used as component A and a polyether diamine (Jeffamine-500) was used as the component B. Free standing films were prepared by casting a mixture of components A and B in stoichiometric proportions. The surface composition, surface topography and wetting properties of the coatings were studied by angle resolved X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle goniometry respectively. The mechanical properties of the cured films were evaluated by tensile measurements as well as dynamic mechanical analysis. Pseudobarnacles made of aluminium studs were attached to the coated panels and adhesion tests were carried out by a pseudobarnacle tester. Coated panels were exposed in Mumbai harbor for fouling studies for a period of 90 days. Surface restructuring studies of the coatings upon immersion in seawater were carried out by measuring the changes in advancing and receding contact angles by contact angle goniometry. The effect of surface energy, modulus and surface restructuring of the coatings on the macrofouling and pseudobarnacle adhesion properties has been discussed in detail.     

Surface properties of UV-irradiated poly(vinyl alcohol) films containing small amount of collagen

The surface properties of poly(vinyl alcohol) (PVA) films in the presence of 1%, 3% and 5% of collagen before and after UV-irradiation have been studied by atomic force microscopy (AFM) and by contact angle measurements. PVA films have been obtained by solvent evaporation from water solution of PVA and PVA containing small amount of collagen. After drying, the samples were irradiated with UV light wavelength λ = 254 nm in air. Surface properties before and after UV-irradiation were observed using AFM. Contact angles of two liquids: diiodomethane (D) and glycerol (G) on polymeric films were measured at constant temperature using goniometer.The results have shown that the contact angle and the surface free energy for PVA films were altered by UV-irradiation. These alterations indicate photooxidation and an increase of polarity of the surface. The comparison of surface properties of PVA films and PVA containing collagen points out that collagen is more sensitive to photooxidation than PVA and PVA/collagen blends. PVA films containing collagen easier undergo photooxidation process with formation of new polar groups than pure PVA films.     

Surface free energy of ultra-high molecular weight polyethylene modified by electron and gamma irradiation

Surface free energy of biocompatible polymers is important factor which affects the surface properties such as wetting, adhesion and biocompatibility. In the present work, the change in the surface free energy of ultra-high molecular weight polyethylene (UHMWPE) samples, which is produced by electron beam and gamma ray irradiation were, investigated. Mechanism of the changes in surface free energy induced by irradiations of doses ranging from 25 to 500 kGy was studied. FTIR technique was applied for sample analysis. Contact angle measurements showed that wettability and surface free energy of samples have increased with increasing the irradiation dose, where the values of droplet contact angle of the samples decrease gradually with increasing the radiation dose. The increase in the wettability and surface free energy of the irradiated samples are attributed to formation of hydrophilic groups on the polymer surface by the oxidation, which apparently occurs by exposure of irradiated samples to the air.     

Stability of Phosphonic Self Assembled Monolayers (SAMs) on Cobalt Chromium (Co-Cr) Alloy under Oxidative conditions

Cobalt chromium (Co-Cr) alloys have been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and contact angle measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration.     

Changes in wetting and energetic properties of glass caused by deposition of different lipid layers

An investigation of wetting and energetic properties of different lipid layers deposited on the glass surface was carried out by contact angles measurements and determination of the apparent surface free energy. The topography of the lipid layers was also determined with the help of atomic force microscopy (AFM). Two synthetic phospholipids were chosen for these studies, having the same phosphatidylcholine headgroup bound to the apolar part composed either by two saturated chains (1,2-dipalmitoyl-sn-glycero-3-phospshocholine - DPPC) or two unsaturated chains (1,2-dioleoyl-sn-glycero-3-phosphocholine - DOPC) and one lipid (1,2,3-trihexadecanoyl-sn-glycerol - tripalmitoylglycerol - TPG). The lipid layers, from the 1st to the 5th statistical monolayer, were deposited on the glass surface from chloroform solutions by spreading.The apparent surface free energy of the deposited layers was determined by contact angles measurements (advancing and receding) for three probe liquids (diiodomethane, water, and formamide), and then two concepts of interfacial interactions were applied. In the contact angle hysteresis approach (CAH) the apparent total surface free energy was calculated from the advancing and receding contact angles and surface tension of probe liquids. In the Lifshitz-van der Waals/acid-base approach (LWAB) the total surface free energy was calculated from the determined components of the energy, which were obtained from the advancing contact angles of the probe liquids only. Comparison of the results obtained by two approaches provided more information about the changes in the hydrophobicity/hydrophilicity of the layers depending on the number of monolayers and kind of the lipid deposited on the glass surface.It was found that the most visible changes in the surface free energy took place for the first two statistical monolayers irrespectively of the kind of the lipid used. Additionally, in all cases periodic oscillations from layer-to-layer in the lipid surface free energy were observed. The changes in the surface free energy correlated with those in the topography and roughness of lipid layers.     

Influence of (phospho)lipases on properties of mica supported phospholipid layers

The effect of enzymes: lipase from Candida cylindracea (L_Cc), phospholipase A₂ from hog pancreas (PLA₂) and phospholipase C from Bacillus cereus (PLC) to modulate wetting properties of solid supported phospholipid bilayers was studied via advancing and receding contact angle measurements of water, formamide and diiodomethane, and calculation of the surface free energy and its components from van Oss et al. (LWAB) and contact angle hysteresis (CAH) approaches. Simultaneously, topography of the studied layers was determined by Atomic Force Microscopy (AFM). The investigated lipid bilayers were transferred on mica plates from subphase of pure water by means of Langmuir-Blodgett and Langmuir-Schaefer techniques. The investigated phospolipid layers were: saturated DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), unsaturated DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine), and their mixture DPPC/DOPC. The obtained results revealed that the lipid membrane degradation by the enzymes caused increase in its surface free energy due to the amphiphilic hydrolysis products, which may accumulate in the lipid bilayer. In result activity of the enzymes may increase and then break down the bilayer structure takes place. It is likely that after dissolution of the hydrolysis reaction products in the bulk phase, patches of bare mica surface are accessible, which contribute to the apparent surface free energy changes. Comparison of AFM images and the free energy changes of the layers gives better insight into changes of their properties. The observed gradual increase in the layer surface free energy allows controlling of the hydrolysis process to obtain the surfaces of defined properties.     

Surface modification of TA2 pure titanium by low energy high current pulsed electron beam treatments

Surface integrity changes of TA2 pure titanium including surface topography, microstructure and nanohardness distribution along surface layer were investigated by different techniques of low energy high current pulsed electron beam treatments (LEHCPEBTs). The surface topography was characterized by SEM. Moreover, the TEM observation and X-ray diffraction analysis were performed to reveal the surface modification mechanism of TA2 pure titanium by LEHCPEBTs. The surface roughness was modified by electron beam treatment and the polishing mechanism was analyzed by studying the cross section microstructure of electron beam treated specimens by SEM and TEM. The results show that the surface finish obtains good polishing quality and there is no phase transformation but the dislocations by LEHCPEBT. Furthermore, the nanohardness in the surface modified layer is improved. The remelt and fine-grain microstructure of surface layer caused by LEHCPEBTs are the main polishing mechanism and the reason of modification of surface topography and the increment in nanohardness is mainly due to the dislocations and fine grains in the modified layer induced by LEHCPEBT.     

Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma

The industrial use of polypropylene (PP) films is limited because of undesirable properties such as poor adhesion and printability. In the present study, a DC glow discharge plasma has been used to improve the surface properties of PP films and make it useful for technical applications. The change in hydrophilicity of modified PP film surface was investigated by contact angle (CA) and surface energy measurements as a function of exposure time. In addition, plasma-treated PP films have been subjected to an ageing process to determine the durability of the plasma treatment. Changes in morphological and chemical composition of PP films were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The improvement in adhesion was studied by measuring T-peel and lap shear strength. The results show that the surface hydrophilicity has been improved due to the increase in the roughness and the introduction of oxygen-containing polar groups. The AFM observation on PP film shows that the roughness of the surface increased due to plasma treatment. Analysis of chemical binding states and surface chemical composition by XPS showed an increase in the formation of polar functional groups and the concentration of oxygen content on the plasma-processed PP film surfaces. T-peel and lap shear test for adhesion strength measurement showed that the adhesion strength of the plasma-modified PP films increased compared with untreated films surface.     

Surface investigation of adhesive formulation consisting of UV sensitive triblock poly(styrene–b-butadiene–b-styrene) copolymer

Atomic force microscopy (AFM) analysis in conjunction with macroscopic studies such as peel testing and contact angle measurement have been undertaken to explain the nanomechanical properties of adhesive formulation consisting of triblock poly(styrene–b-butadiene–b-styrene) (SBS) copolymers. The cross-linking of this photosensitive copolymer was investigated by analyzing the mechanical and morphological changes of each phase induced by the UV exposure. Main result is that the adhesive properties are strongly influenced by the cross-linking of the polybutadiene (PB) phase leading to an increase in the surface stiffness without affecting the surface energy. AFM analysis shows that the adhesion force is mostly governed by the contact area between the adhesive and the probe. The surface mobility may explain the increase in adhesion for this pressure sensitive copolymer.     

Effect of different solid matrixes on surface free energy of EGDMA and TRIM polymers

Advancing and receding contact angles of water, formamide, glycerol and diiodometane were measured on the two polymers; EGDMA (dimethacrylate of ethylene glycol) and TRIM (trimethacrylate-1,1,1-trihydroksymethylopropane) which were polymerized next to glass, silanized glass, stainless steel, mica and silicon surfaces as the matrices. Then from the contact angle hystereses (CAH) and van Oss, Good, Chaudhury (LWAB) approaches the apparent surface free energies were evaluated. The measured contact angles not only depend solely on the polymer chemical structure but also, to some extent, on the solid matrix next to whose surface the sample has polymerized. Surface free energy of the polymer samples calculated from the LWAB approach shows that they interact mainly by dispersive forces. The apparent surface free energy of the polymers calculated from the diiodomethane contact angles hysteresis is practically the same irrespective of the kind of the matrix used. Therefore it can be concluded that the observed weak polar interactions in the surface free energy of the samples depend on the polymer surface preparation. The AFM images show that the obtained surfaces are of different roughness. The RMS values of roughness range between 3.7-90.2 nm for EDGMA, and 5.3-124.5 nm for TRIM. However, as reported in literature, rather protrusions bigger than 1 μm may significantly affect the contact angles, especially the receding ones.     

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.     

Surface modification of polypropylene using argon plasma: Statistical optimization of the process variables

Low pressure plasma treatment using radiofrequency (rf) discharge of argon gas was employed to improve the hydrophilicity of polypropylene. The effects of argon plasma on the wettability, surface chemistry and surface morphology of polypropylene were studied using static contact angle measurements, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Increase in surface energy of polypropylene was observed as a result of argon plasma treatment. SEM and AFM images revealed the increased surface roughness. A set of identified process variables (rf power, pressure, argon flow rate and time) were used in this study and were optimized using central composite design (CCD) of response surface methodology (RSM). A statistical model was developed to represent the surface energy in terms of the process variables mentioned above. Accuracy of the model was verified and found to be high.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Study on the surface properties of wood/polyethylene composites treated under plasma

Wood/polyethylene (PE) composites are widely used in many fields for its excellent properties, but they are hard to adhere for the surface lacking of polarity. So low-pressure glow discharge of air plasma was used to improve the adhesion properties of wood/PE composites. The composites were treated by plasma under different discharge power. And the changes on the surface properties of the treated and untreated composites were studied by contact angle, Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS) analysis. The measurement showed that the contact angle decreased after plasma treatment, and the contact angle decreased gradually with the increasing of discharge power. The FTIR analysis results showed that the polar groups such as hydroxyl, carbonyl and carboxyl were formed on the surface of the composites treated under plasma. SEM and AFM results showed that the roughness of plasma treated samples increased. XPS analysis results indicated that the content of carbon element decreased while the content of oxygen element in the composition of wood/PE composites surface element increased and it reached a balance in a higher power, meanwhile a lot of carboxyl groups were formed. The newly formed polar groups are benefit for the adhesion of composites. The shear bonding strength test showed that the adhesion properties of wood/PE composites improved effectively after plasma treatment.     

Air plasma or UV-irradiation applied to surface modification of pectin/poly(vinyl alcohol) blends

Poly(vinyl alcohol), pectin and their blends with different components ratio were exposed to low-temperature air plasma or high energy UV-irradiation (λ = 254 nm) for the purpose of surface modification. The physico-chemical changes in surface properties have been studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and contact angle measurements. Surface free energy of polymeric films, its polar and dispersive components have been calculated by Owens-Wendt method. Moreover, the work of adhesion was estimated and the recovery of hydrophobic properties of modified films after storage have been also studied.The few seconds air-plasma treatment caused more effective surface modification than 5-6 h UV-irradiation. The observed changes were partially reversible, contrary to these caused by photo-modification.It was found that pectin/PVA (50:50) blend was characterised by larger susceptibility to plasma modification compared to pure pectin and pure PVA, whereas the photosensitivity to radiation of 254 nm wavelength was the lowest for this specimen in comparison to other studied samples.     

Preferential surface segregation of homopolymer and copolymer blend films

Surface film properties of the homopolymers polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(butyl methacrylate) (PBMA) and the copolymer poly(methyl methacrylate)-co-poly(butyl methacrylate) (PMMA-co-PBMA) and their blends with PS have been examined by atomic force microscopy (AFM) and contact angle measurements. The total and the Lifshitz-van der Waals, acid and base components of the surface free energy together with the work of adhesion and its components, the cohesive energy density and the solubility parameters of the homopolymer, copolymer and blend films were determined. Films of about 3 μm were considered. The results are discussed in terms of surface migration mechanisms based on surface free energy and solubilities of the polymers in the solvent, toluene in this paper. AFM imaging and contact angles revealed surface enrichment at the air polymer interface of PBMA for both the PS/PBMA blend and the copolymer PMMA-co-PBMA, whereas the PS/PMMA and PS/PMMA-co-PBMA blend film surfaces show island-like phase-separated structure of typical size 27.4-86.5 nm in diameter and 6.9-15.6 nm in height for PS/PMMA, while for PS/ PMMA-co-PBMA film surface the typical size is 49.6-153.3 nm in diameter and 1.6-14.2 nm in height.     

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。     

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.