The influence of UV irradiation on the surface of chitosan films

The surface properties of chitosan films before and after UV-irradiation (λ = 254 nm and 248 nm, respectively) were investigated using the technique of scanning electron microscopy (SEM) and by means of contact angle measurements allowing the calculation of surface free energy. Moreover, in order to determine the film mass changes, quartz crystal microbalance (QCM) measurements were performed. Measurements of the contact angle for diiodomethane (D), formamide (F) and glycerol (G) on the surface of chitosan films were made. The chemical and structural changes during UV irradiation were studied by FTIR-ATR spectroscopy.The contact angle and the surface free energy were altered by UV irradiation of chitosan films. The microscopy images have shown that the KrF excimer laser irradiation caused visible damages on the surface in comparison with the surface exposed to the mercury UV lamp. The surface modification of chitosan films can be achieved using both, the low intensity UV lamp and the excimer laser.     

Surface functionalisation of polypyrrole films using UV light induced radical activation

Electrochemically deposited polypyrrole (PPy) films were functionalised with amine or carboxylic function. The functionalisation was done by grafting allylamine or acrylic acid (AAc) using UV light radical activation. The active groups of the surface were quantified by X-ray photoelectron spectroscopy (XPS) after chemical derivatisation with trifluoroethanol (TFE) or 4-trifluoromethylbenzaldehyde (TFBA), respectively. Grafting with AAc completely covered the PPy film introducing high levels of carboxylic function. In the case of allylamine grafting, a saturation point at low amine carbon level was achieved. Further characterisation of the surfaces was done by time of flight secondary ion mass spectroscopy (TOF-SIMS), atomic force microscope (AFM) and scanning electron microscope (SEM).     

Patterning of nanoparticulate transparent conductive ITO films using UV light irradiation and UV laser beam writing

Indium tin oxide (ITO) thin film is one of the most widely used as transparent conductive electrodes in all forms of flat panel display (FPD) and microelectronic devices. Suspension of already crystalline conductive ITO nanoparticles fully dispersed in alcohol was spun, after modifying with coupling agent, on glass substrates. The low cost, simple and versatile traditional photolithography process without complication of the photoresist layer was used for patterning ITO films. Using of UV light irradiation through mask and direct UV laser beam writing resulted in an accurate linear, sharp edge and very smooth patterns. Irradiated ITO film showed a high transparency (∼85%) in the visible region. The electrical sheet resistance decrease with increasing time of exposure to UV light and UV laser. Only 5 min UV light irradiation is enough to decrease the electrical sheet resistance down to 5 kΩ□.     

Laser induced modification of surface structures

The results on surface modification of materials of different structures; morphology, grain sizes, density and porosity by exposure to nanosecond laser light are given. Laser induced changes in their surface characteristics are presented. Surface layers of Si₃N₄, SiC dense ceramics and BN graphite and turbostratic pressed powders are studied by scanning electron microscopy to reveal the new nanostructures (nanowires or nanotubes) and new morphologies. A pronounced evolution in structure and grain size of BN graphite powders was demonstrated in laser processing layers.     

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).     

Tuning of surface properties of thin polymer films by electron beam treatment

The aim of our work was to understand the impact of electron treatment on polymer thin films, particularly on their surface properties as well as the possibilities and limitations to tune these properties. Two different polymers, polystyrene (PS) and poly-2-vinlypyridine (P2VP), were chosen to form thin polymer films by grafting of end-terminated linear polymer chains to a surface with sufficient grafting density, forming so called “polymer brushes”. We were able to identify the surface properties and specify ongoing physico-chemical changes after electron beam treatment by using zeta potential and contact angle measurements. By varying the absorbed dose it was possible to tune the surface properties over a wide range. The detailed knowledge about the latitude of functionalization of the tested polymers was a prerequisite for the creation of wettability gradients by electron beam treatment by adapting a special mask of known thickness and density. Hence, electron beam treatment opens an easy reproducible way to generate surface gradients in functionality.     

Vacuum ultraviolet-induced surface modification of cyclo-olefin polymer substrates for photochemical activation bonding

The surface of cyclo-olefin polymer (COP) was treated with vacuum ultraviolet (VUV) light at 172 nm wavelength to improve the wettability and adhesion properties. Through VUV treatment in air, the terminal groups of the COP surface were oxidized into oxygen functional groups, containing CO, CO, and COO components, making the COP surface hydrophilic. The extent of oxygenation was evaluated by XPS and FTIR-ATR spectra, and it was shown that the surface properties, hydrophilicity, and functionalization were dependent on both VUV irradiation distance and irradiation time, which have an effect on the concentration of oxygen functional groups. VUV-light treatment with a short irradiation distance was more effective in introducing oxygen functional groups.     

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。     

Characterization of bioactive RGD peptide immobilized onto poly(acrylic acid) thin films by plasma polymerization

Plasma surface modification can be used to improve the surface properties of commercial pure Ti by creating functional groups to produce bioactive materials with different surface topography. In this study, a titanium surface was modified with acrylic acid (AA) using a plasma treatment and immobilized with bioactive arginine-glycine-aspartic acid (RGD) peptide, which may accelerate the tissue integration of bone implants. Both terminals containing the -NH₂ of RGD peptide sequence and -COOH of poly(acrylic acid) (PAA) thin film were combined with a covalent bond in the presence of 1-ethyl-3-3-dimethylaminopropyl carbodiimide (EDC). The chemical structure and morphology of AA film and RGD immobilized surface were investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), atomic force microscopy (AFM), and scanning electron microscopy (SEM). All chemical analysis showed full coverage of the Ti substrate with the PAA thin film containing COOH groups and the RGD peptide. The MC3T3-E1 cells were cultured on each specimen, and the cell alkaline phosphatase (ALP) activity were examined. The surface-immobilized RGD peptide has a significantly increased the ALP activity of MC3T3-E1 cells. These results suggest that the RGD peptide immobilization on the titanium surface has an effect on osteoblastic differentiation of MC3T3-E1 cells and potential use in osteo-conductive bone implants.     

Studies on surface modification of poly(tetrafluoroethylene) film by remote and direct Ar plasma

Poly(tetrafluoroethylene) (PTFE) surfaces are modified with remote and direct Ar plasma, and the effects of the modification on the hydrophilicity of PTFE are investigated. The surface microstructures and compositions of the PTFE film were characterized with the goniometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Results show that the remote and direct plasma treatments modify the PTFE surface in morphology and composition, and both modifications cause surface oxidation of PTFE films, in the forming of some polar functional groups enhancing polymer wettability. When the remote and direct Ar plasma treats PTFE film, the contact angles decrease from the untreated 108-58° and 65.2°, respectively. The effect of the remote Ar plasma is more noticeable. The role of all kinds of active species, e.g. electrons, ions and free radicals involved in plasma surface modification is further evaluated. This shows that remote Ar plasma can restrain the ion and electron etching reaction and enhance radical reaction.     

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.     

Polytetrafluoroethylene surface modification by filamentary and homogeneous dielectric barrier discharges in air

In this paper, polytetrafluoroethylene (PTFE) films are modified using non-equilibrium plasma generated by homogeneous DBD in air at medium pressure, and the results are compared to those treated by using filamentary DBD in air at atmospheric pressure. The surface properties of PTFE films before and after the treatments are studied using contact angle and surface energy measurement, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It is found that the plasma treatments modify the PTFE surface in both morphology and composition. The PTFE films modified in both treatments show a remarkable decrease in water contact and a remarkable increase in surface energy. XPS analysis reveals that oxygen-containing polar groups are introduced onto the PTFE surface, and SEM analysis shows that the surfaces of the films are etched after both the treatments. It is found that homogeneous DBD is more effective in PTFE surface modification than filamentary DBD as it can make the contact angle decline to a lower level by introducing more oxygen-containing groups, and the possible reason for this effect is discussed.     

Synthesis of efficient TiO2-based photocatalysts by phosphate surface modification and the activity-enhanced mechanisms

A simple strategy to greatly increase the thermal stability of nanocrystalline anatase has been put forward to fabricate efficient TiO₂-based photocatalysts under ultraviolet irradiation, via the surface modification with phosphate anions. The results show that the increased anatase thermal stability is attributed to the roles of the phosphate modification effectively inhibiting the contacts among anatase nanocrystals. Compared to un-modified TiO₂, the modified TiO₂ calcined at high temperature (over 700 °C) exhibits much high photocatalytic activity for degrading Rhodamine B (or phenol) solution, even superior to the commercial P25 TiO₂. The activity enhancement is mainly attributed to the increased separation rate of photogenerated charge carriers on the basis of the measurements of steady state- and transient state-surface photovoltage spectroscopy. This work would provide a practical route to reasonably design and synthesize high-performance TiO₂-based nanostructured photocatalysts with high anatase thermal stability.     

Formation of heterostructure of AB semiconductor compounds by surface laser modification

This article refers to our research results concerning creation of the oxide layers produced on the surface of GaSe crystals. These layers are obtained by the exposition of the samples in a pulsed laser beam. Measurements of the received layers were performed by a cathodoluminescence (CL) analysis method as well AES and XES methods. The spectrum was analyzed in the range of 1.2–4.5 eV.     

Influence of slight microstructural gradients on the surface properties of Ti6Al4V irradiated by UV

Ti6Al4V alloy is one of the most widely used materials for biomedical implants. Among its properties, it is remarkable the photoactivity displayed by its passive layer, which is mainly composed by titanium dioxide. However, variations in the processing conditions may yield to differences in the microstructure which can be reflected on the surface properties of the machined product. From contact angle measurements taken on different zones of samples removed from a commercial bar of Ti6Al4V, it has been shown that the modifications of the surface Gibbs energy suffered by the alloy under UV irradiation have a radial dependence. This behaviour is related to slight microstructural changes of the alloy, particularly with an increase in the volume fraction of the β-phase when moving to the interior of the sample, which alters the composition and/or microstructure of the passive layer along its radius. This study shows that gradients in the microstructure and physical properties are sample size dependent and are likely related to thermal gradients during processing.     

Surface modification and adhesion of wood-plastic composite (WPC) treated with UV/ozone

Because of the surfaces of wood-plastic composite (WPC) materials are enriched in polymers of low surface energy, they exhibit low adhesion properties. UV/ozone is proposed as surface treatment for increasing the surface energy and adhesion of WPC materials made with different polymers (polyethylene, polypropylene and polyvinyl chloride). UV lamp-WPC surface distance and time of UV exposure were varied for optimizing UV/ozone treatment of WPC, and UV dose used ranged between 2.02 × 10^?14 and 5.05 × 10^?12 J·s/m². UV/ozone treatment created new carbon-oxygen polar groups in WPC surfaces and increased their surface energy, mainly their polar component. Furthermore, ablation of the outermost WPC surface was produced, more noticeably by reducing the distance between WPC surface and UV lamp and by increasing the duration of the treatment. Noticeable increase in 180° peel adhesion was obtained in the joints made with UV/ozone treated WPC at 10–30 mm distance during 1–5 min (i.e., UV dose between 5.61 × 10^?14 and 2.53 × 10^?12 J·s/m²). Although 180° peel strength of joints made with acrylic adhesive tape and UV/ozone treated WPC for 10 min and 10 mm distance (UV dose: 5.05 × 10^?12 J·s/m²) was not increased because of dominant effect of ablation over creation of polar groups, the cross-hatch adhesion to different coatings was highly improved, irrespective of the polymer used and the wood content of WPC; however, the surface modifications and adhesion of UV/ozone treated WPC were more marked when its wood content was higher and by using UV dose between 0.10 × 10^?12 and 2.53 × 10^?12 J·s/m².     

Effect of nickel doping on the photocatalytic activity of ZnO thin films under UV and visible light

Nanostructured ZnO thin films with different concentrations of Ni²⁺ doping (0, 1, 5, 10 and 15 wt.%) are prepared by the sol-gel method for the first time. The thin films are prepared from zinc acetate, 2-methoxyethanol and monoethanolamine on glass substrates by using dip coating method. The films comprise of ZnO nanocrystallites with hexagonal crystal structure, as revealed by X-ray diffraction. The film surface is with characteristic ganglia-like structure as observed by Scanning Electron Microscopy. Furthermore, the Ni-doped films are tested with respect to the photocatalysis in aqueous solutions of malachite green upon UV-light illumination, visible light and in darkness. The initial concentration of malachite green and the amount of catalyst are varied during the experiments. It is found that increasing of the amount of Ni²⁺ ions with respect to ZnO generally lowers the photocatalytic activity in comparison with the pure ZnO films. Nevertheless, all films exhibit a substantial activity under both, UV and visible light and in darkness as well, which is promising for the development of new ZnO photocatalysts by the sol-gel method.     

Abnormal phenomenon of source-drain current of AlGaN/GaN heterostructure device under UV/visible light irradiation

We report an abnormal phenomenon that the source-drain current (I_D) of AlGaN/GaN heterostructure devices decreases under visible light irradiation. When the incident light wavelength is 390 nm, the photon energy is less than the band gaps of GaN and AlGaN whereas it can causes an increase of I_D. Based on the UV light irradiation, a decrease of I_D can still be observed when turning on the visible light. We speculate that this abnormal phenomenon is related to the surface barrier height, the unionized donor-like surface states below the surface Fermi level and the ionized donor-like surface states above the surface Fermi level. For visible light, its photon energy is less than the surface barrier height of the AlGaN layer. The electrons bound in the donor-like surface states below the Fermi level are excited and trapped by the ionized donor-like surface states between the Fermi level and the conduction band of AlGaN. The electrons trapped in ionized donor-like surface states show a long relaxation time, and the newly ionized donor-like surface states below the surface Fermi level are filled with electrons from the two-dimensional electron gas (2DEG) channel at AlGaN/GaN interface, which causes the decrease of I_D. For the UV light, when its photon energy is larger than the surface barrier height of the AlGaN layer, electrons in the donor-like surface states below the Fermi level are excited to the conduction band and then drift into the 2DEG channel quickly, which cause the increase of I_D.     

Surface modification of diamond-like carbon films with perfluorooctyl functionalities and their surface properties

Photolysis of perfluoroazooctane with diamond-like carbon (DLC) films led to the surface modification to introduce perfluorooctyl functional groups, confirmed by means of FT-IR, XPS, Raman and TOF-SIMS measurements. The DLC films modified with fluorine moieties showed reduction of the surface energy evaluated by contact angle to water, as compared with pristine DLC film. The contact angle of chemically modified DLC film is 105°, comparable to that of polytetrafluoroethylene (PTFE). By monitoring with XPS, we found that the results on the value of fluorine/carbon ratio of fluorinated DLC films depending on irradiation time are consistent with those of contact angle. Chemical modification of DLC films with perfluorooctyl functionalities also led to improvement of their frictional properties. The friction coefficient of the modified film is 0.05 under vacuum condition, whereas that of the pristine film shows very high value (>1).     

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.