Precipitation supramolecular complex for photoinduced anisotropic material with dual mesogenic units

A new family of dual-photoresponsive complexes has been fabricated based on the method of Precipitation Ionic Self-assembly (PISA). Poly (acrylic acid sodium salt) was coupled with two types of ionic mesogenic units containing azobenzene and cinnamate group, respectively, yielding a series of thermotropic liquid crystalline supramolecules. By changing the ratio of the two mesogenic units, different phase behaviors and nanostructures were obtained. Comparable photoinduced orientation of azo groups was observed in all the complex films after being irradiated by linearly polarized laser, while cinnamate groups can be crosslinked under UV light exposure. Furthermore, the influence of crosslinked cinnamate groups on the photoinduced orientation and its thermal stability was investigated in detail. This novel material may be utilized in many fields, such as surface relief gratings, liquid crystal display and nonlinear optics. This green and facial method can provide guidelines for the convenient design of multi-functional supramolecular materials.     

Functionalization of polypropylene film by radiation grafting of acryloyl chloride and subsequent esterification with Disperse Red 1

Polypropylene (PP) films were grafted with acryloyl chloride by γ‐irradiation, and the grafted films were reacted with an azo dye, Disperse Red 1. The films were characterized by X‐ray diffraction, scanning electron microscopy, atomic force microscopy, and differential scanning calorimetry. It was found that the grafting takes place first on the film surface, and with increase in the radiation dose the grafting penetrated inside of the film, decreasing the crystallinity of the PP film. The surface of the films was homogeneous, and a mesophase was observed for the film grafted with the dye through a polarized optical microscope. The dye underwent trans to cis photoreaction, whereby the red films became colorless by the irradiation of UV light at room temperature, although the color was recovered on standing, and more quickly when heated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 172–178, 2004     

Photo-induced change in wettability and binding ability of azoaromatic polymers

Photochromic polymers containing p-phenylazoacrylanilide were synthesized and the photo-induced hydrophobicity change on the surface of the polymer film was studied by measuring water wettability. The wettability increased with UV irradiation and returned to the original value with visible light irradiation. This photo-induced reversible change in wettability was considered to be caused by the large change of dipole moment across the azo bonds due to the isomerization of azo dye from trans to cis form. Furthermore, the photoresponsive polymeric adsorbent prepared from the azo polymer having adsorption behavior of a low molecular weight compound was studied. The binding ability of this polymeric adsorbent was decreased by UV irradiation. These results were attributed to the decreased hydrophobic interaction between the adsorbent and the adsorbate.     

Wetting angles and photocatalytic activities of illuminated TiO2 thin films

TiO₂ thin films have been prepared by physical vapour deposition (PVD) and plasma enhanced chemical vapour deposition (PECVD) to study the UV-induced photo-activity of this material. Wetting angle variations and photo-catalytic activity for the degradation of dyes upon UV illumination have been compared for thin films with different crystalline structure (amorphous, rutile and anatase), microstructure (columnar, compact, etc.) and porosities as estimated from the values of their refraction indices and their direct assessment with a quartz crystal monitor. The surface of the thin films became superhydrophilic upon UV light irradiation and then it recovered its original state by keeping the samples in the dark. Wetting angle decays follow very similar kinetics for amorphous and crystalline films, independently of their actual porosities. By contrast the photo-catalytic activity was very dependent on the crystalline structure of the films (anatase > rutile > amorphous) and on their porosities. The different behaviour depicted by the films with regard to these two properties suggests that they respond to different though related mechanisms and that they cannot be considered as equivalent when trying to prove the photo-activity of TiO₂.     

Optical anisotropy and non-linear optical properties of azobenzene methacrylic polymers

Photoinduced optical anisotropy has been studied in several methacrylic copolymers, either amorphous or liquid crystalline, with cyano azobenzene chromophores in the side chain. Illumination with linearly polarised 488 nm light gives rise to high and stable values of birefringence and dichroism, mainly in liquid crystalline films. Both dichroism and birefringence decrease with the azo content in the copolymer series while some increase can be achieved by the incorporation of biphenyl molecules to the copolymers. Photoinduced anisotropy disappears above the glass transition temperature in amorphous polymers, whereas it increases in liquid crystalline polymers (LCP) due to a thermotropic self-organisation.The non-linear optical (NLO) properties of the films have been studied by second harmonic generation (SHG) measurements. The intensity of the harmonic signal from in situ corona poled polymeric films has been measured. The effect of 488 nm light irradiation on the azo chromophores orientation and consequently on the NLO response of the films was investigated at different temperatures. The intensity and thermal stability of the second harmonic signals obtained after the two different (thermal and photoassisted) corona poling processes have been compared.     

Changes of properties of cured and uncured disiloxane bisbenzocyclobutene thin films under irradiation

The effects induced by α-particles and laser beam irradiation in air atmosphere in uncured and cured bisbenzocyclobutene (BCB) 2 μm thick films, spin-coated on glass/ITO surface have been investigated. α-Particle irradiation was done by means of a thin film ²⁴¹Am source (E_α = 5.486 MeV), up to the total fluence of about 5 × 10¹⁰ particles/cm². Laser irradiation was performed by a Nd³⁺:YAG (λ = 1.06 μm) laser in the free generation and the Q-switch regime, using both focused and unfocused beams. Irradiation induced changes were investigated using Light and Atomic Force Microscopy (AFM), infrared (IR), Ultraviolet/visible (UV/vis) and Raman spectroscopy by inspecting several uncured and cured BCB films before and after irradiation. It has been found that both types of irradiation under investigated conditions have produced a novel phase in the material, which is not present either in the uncured or the cured BCB films. Possible implications of the observed effects on curing and degradation of BCB films have been discussed.     

Graft polymerization of acrylamide onto UV-irradiated films

Graft polymerization of acrylamide was attempted onto the surface of films preirradiated with UV radiation. The films employed are nylon 6, polypropylene, and ethylene–vinyl acetate copolymers. Following UV irradiation in air on films without photosensitizer, they were placed in monomer solution, degassed, and then heated to 50°C to effect the graft polymerization. After rigorous removal of homopolymers, polyacrylamide chains were found to be grafted in the surface region of the films to amounts up to several hundred micrograms per square centimeter of films. An ESCA study revealed the UV-irradiated but not yet grafted surfaces to be oxidized, and formation of peroxides was strongly suggested by the reaction of irradiated films with 1,1-diphenyl-2-picrylhydrazyl. It is likely that the initiator responsible for the graft polymerization is peroxides generated at and near the film surfaces upon UV irradiation. The grafted films became very slippery when contacted with water, in contrast with the films UV-irradiated but not yet grafted.     

Degradation of poly(L‐lactide) films under ultraviolet‐induced photografting and sterilization conditions

The degradation of polymers under ultraviolet (UV) irradiation has been a great concern for biomaterial and agricultural applications. The major objective of this research was to study the effect of UV irradiation on the representative bulk and surface properties of poly (L ‐lactide) (PLA) films. Two UV sources with different spectral outputs and intensities were chosen so that one of them could be used for surface modification and the other could be used for UV sterilization of the PLA films. The results established that the molecular weight of PLA decreased significantly during irradiation from the photografting lamp under atmospheric conditions. Irradiation through a Pyrex container was shown to minimize polymer degradation during UV exposure from the photografting lamp. The PLA films UV‐irradiated under the sterilization lamp for 12 h revealed a similar reduction in the molecular weight and no change in the surface hydrophilicity. However, significantly less photodegradation was observed under the sterilization lamp when the samples were held in a Pyrex container. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Photochromism of polyurethane cationomers with pendent azo groups

A new polyurethane cationomer with pendent azo groups bounds to quaternary nitrogen atoms has been synthesized by polyaddition reaction between poly(tetramethylene oxide) (PTMO), 4,4′-bibenzyldiisocyanate and N-methyldiethanolamine, followed by quaternization of tertiary nitrogen with 4-(3-chloropropionyloxy)azobenzene. E–Z photoisomerization of azo chromophores by UV irradiation with a high pressure mercury lamp and Z–E thermal relaxation were studied both in solution and film. An azo urethane model and a synthetic mixture of polyurethane cationomer with azobenzene were used for comparison.     

Isomerization behavior of aromatic azo chromophores bound to semicrystalline polymer films

The cis–trans isomerization of azo chromophores covalently bound to semicrystalline polymer films was investigated. Various azo chromophores were introduced onto the functionalized semicrystalline polymer films by a chemical transformation reaction and their isomerization behavior was investigated by UV‐visible spectroscopy and a contact‐angle goniometer. The thermal Z → E isomerization rate of the azo moiety covalently bound to low‐density polyethylene (LDPE) and polypropylene (PP) films was determined. The rate of thermal isomerization was also compared between amorphous and semicrystalline polymer films bearing azo chromophores. The effect of the intramolecular steric factor and the nature of chromophores was studied on the thermal isomerization rate of the polymer films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2923–2928, 2001     

Effect of heterojunction on photocatalytic properties of multilayered ZnO-based thin films

In the present study, the effects of the heterojunctions on the optical and structural characteristics and the resulting photocatalytic properties of multilayered ZnO-based thin films were investigated. The junctions were composed of semiconducting ZnO nano-porous films coated on the In₂O₃ and SnO₂ counterpart layers. The multilayered ZnO films based on the triple-layered Ag-doped indium oxide (AIO)/tin oxide (TO)/zinc oxide (ZnO), indium oxide (IO)/Ag-doped tin oxide (ATO)/zinc oxide (ZnO), indium oxide (IO)/tin oxide (TO)/zinc oxide (ZnO) and tin oxide (TO)/indium oxide (IO)/zinc oxide (ZnO) have been fabricated by subsequent sol–gel dip coating. Their structural and optical properties combined with photocatalytic characteristics were examined toward degradation of Solantine Brown BRL (C.I. Direct Brown), an azo dye using in Iran textile industries as organic model under UV light irradiation. Effects of operational parameters such as initial concentration of azo dye, irradiation time, solution pH, absence and presence of Ag doping and consequent of sublayers on the photodegradation efficiencies of ZnO nultilayered thin films were also investigated and optimum conditions were established. It was found that the photocatalytic degradation of azo dye on the composite films followed pseudo-first order kinetics. Photocatalytic activity of AIO/TO/ZnO interface composite film was higher compared with other films and the following order was observed for films activities: AIO/TO/ZnO > IO/TO/ZnO > ATO/IO/ZnO > TO/IO/ZnO. Differences in the film efficiencies can be attributed to differences in crystallinity, interfacial lattice mismatch, and surface morphology. Besides, the presence of Ag doping between layers that may act as trap for electrons generated in the ZnO over layer thus preventing electron–hole recombination.     

Mild and Effective Polymerization of Dopamine on Keratin Films for Innovative Photoactivable and Biocompatible Coated Materials

Mussel‐inspired polydopamine (PD) coating represents a promising route for constructing functional materials and finely tuning or completely changing their surface properties. In this work, a mild and effective method to realize the deposition of PD on keratin‐based films is reported. Reactive oxygen species (ROS), generated by keratin films doped with a photosensitizer, e.g., Azure A (AzA), upon UV–vis and vis‐near IR irradiation, are exploited to obtain the PD coating. Interestingly, the use of vis‐near IR irradiation leads to an increased production of ROS by AzA resulting in a greater PD deposition. Compared to uncoated keratin films, the PD‐keratin coated materials show a granular but homogeneous surface and an increased hydrophilicity, maintaining the ROS generation ability of AzA. This work demonstrates a useful method to effectively and rapidly functionalize with PD materials that are sensitive to temperature, pH and UV light, such as keratin. The proposed strategy allows obtaining new multifunctional biomaterials of potential interest in tissue engineering and drug delivery; in particular, the use of PD‐keratin films for near IR laser bonding of ophthalmic tissue, which is a representative case in wound healing purpose, is shown.     

Photocrosslinked surface relief gratings on azobenzene-containing copolymer films

An amorphous polymer containing Disperse Red 1 (DR1) and crosslinkable acrylic groups as separate side groups was synthesized. Surface relief gratings were optically inscribed onto films of this polymer. Grating depths of 350 nm were obtained after 40 min of irradiation. The first-order diffraction was monitored during the laser irradiation, and an efficiency of about 22% was achieved. The polymer could be photocrosslinked at 80 °C under UV light. Although some photo-degradation due to UV irradiation of the azo chromophores was observed, the surface relief itself was fixed by the photocrosslinking, as observed by the improved thermal stability of the diffraction efficiency. Even after heating above the glass transition temperature (T_g) for 2.0 h, significant diffraction was still present and the grating was still observed. In comparison with the photocrosslinked gratings, a non-crosslinked grating rapidly lost most of its shape when heated above T_g. Thus, photocrosslinking is a useful method to improve the thermal stability of the gratings.     

Surface potential measurements of Langmuir films of azo dye/liquid crystal mixtures

Two-component films of a non-amphiphilic azo dye and a liquid crystal with strongly polar –CN group were studied at an air–water interface on the basis of the surface potential–mean molecular area dependence recorded simultaneously with the surface pressure–mean molecular area isotherm. Additionally, the morphology of the films was monitored with the aid of Brewster angle microscope. A conventional Langmuir technique was used to form dye/liquid crystal films during reduction and expansion of an area occupied by the molecules. From the surface potential value, the effective dipole moment in the first monolayer formed on the water was calculated. Moreover, the number of molecules with dipole moments directed from the water to the air with respect to those directed towards water was estimated. The influence of the two components' miscibilities upon the surface potential after addition of the dye to the liquid crystal was determined.     

XPS and ESR studies of the photodegradation of polyamidoimide and polyimide in O2, O2 + N2, air,N2, and vacuum atmospheres

The photostability of polyamidoimide (PAI) and polyimide (PI) films has been studied. UV irradiation caused a great change in the composition and structure of the film surface. With irradiation in atmospheres such as air, oxygen, and an oxygen—nitrogen mixture, the Cls spectrum had a distinct structure at high binding energy, and the O/C and N/C ratios were considerably increased. On the other hand, in nitrogen and under vacuum, the O/C and N/C ratios remained almost unchanged during an earlier stage of irradiation, but in the latter stage for the nitrogen atmosphere these ratios decreased to a broad minimum and then increased with an increase of irradiation time. UV irradiation also produced free radicals in the polymer films; PAI gave a much stronger ESR signal intensity than PI. The signal intensity vs. irradiation time curve was strongly influenced by irradiation atmospheres. In atmospheres containing oxygen the curve exhibited a broad maximum during an initial stage of irradiation, while under vacuum and in nitrogen the signal intensity increased greatly in the latter stage. The formation of free radicals during an earlier stage of irradiation in atmospheres containing oxygen was promoted by the oxygen incorporated at the film surface, while the radical production under vacuum was considered to be due to rupturing of bonds in the bulk material. The decay of free radicals in the dark after irradiation occurred at a faster speed in oxygen atmospheres than under vacuum.     

Optical parameters and absorption studies of UV‐irradiated azo dye‐doped PMMA films

PMMA and PMMA films doped with different contents of azo dye have been made by using the casting technique. The absorption spectral analysis showed that the doped films have two absorption bands attributed to the π‐π* and n‐π* transition of chromophore groups. These bands disappear upon UV‐irradiation, suggesting that the studied system undergoes a photo degradation process. The absorption coefficient and optical energy gap (E_g) have been obtained from the absorption edge in the 200–900 nm range. It was found that E_g decreases with increasing doping levels, whereas it increases with increasing irradiation time. The width of the tail of localized states in the band gap (ΔE) was evaluated using the Urbach edge method. Some optical parameters were determined from the reflection and transmission spectra in the spectral range of 200–2500 nm. The dependence of the refractive index on irradiation time and doping level have been discussed. It was found that the photo‐induced refractive index changes are very large. These changes suggest the applicability of the studied system in optical devices. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UV polarizers based on oriented poly(vinyl alcohol)–Chrysophenine–Congo red blend films

The availability of efficient low‐cost ultraviolet (UV) film polarizers is of vital importance to a number of applications, which rely on the use of polarized light in the near‐UV regime. We describe here the preparation of such elements based on stretch‐oriented films comprising poly(vinyl alcohol) and a combination of two commercially available azo dyes, Congo Red and Chrysophenine. Films of various dye contents were prepared and oriented by uniaxial tensile deformation. Moderately stretched films (draw ratio l/l₀ = 4–8) exhibit a pronounced optical dichroism, characterized by a polarizing efficiency up to 0.98 at a wavelength of 365 nm. Initial experiments suggest that, even under rather harsh irradiation conditions and without any packaging, these azo‐dye‐based polarizers are surprisingly inert under simulated operating conditions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1235–1239, 2002     

Surface hydrophilic–hydrophobic property on transparent mesoporous silica thin films containing chromium oxide single-site photocatalyst

Using a sol–gel/spin-coating method with organic template, the transparent mesoporous silica thin films containing chromium oxide moieties can be prepared on quartz plate. The spectroscopic characterization has revealed that these thin films contain isolated and tetrahedrally coordinated chromium oxide moieties (single-site photocatalyst) in their frameworks. Even before UV light irradiation these Cr-containing mesoporous silica (CrMS) thin films have demonstrated a hydrophilic surface property more strongly than Cr-containing non-porous silica films and mesoporous silica thin films without chromium oxide. Furthermore, the Cr-containing mesoporous silica thin films showed the super-hydrophilic property not only under UV light irradiation but also even under visible light irradiation from a fluorescent lamp. In the presence of ethylene gas, the polyethylene was successfully formed on the surface of the CrMS thin film under UV light irradiation. After the formation of polyethylene the surface property of the CrMS thin film was converted into hydrophobic while keeping its transparency. The isolated and tetrahedrally coordinated chromium oxide moieties are responsible for these photo-induced surface reactions.     

Simultaneous Laser‐Induced Reduction and Nitrogen Doping of Graphene Oxide in Titanium Oxide/Graphene Oxide Composites

Titanium oxide/graphene oxide nanocomposite thin films were grown by ultraviolet (UV) matrix‐assisted pulsed laser evaporation (MAPLE) technique in controlled oxygen or nitrogen atmospheres. The effect of graphene oxide addition and laser‐induced reduction as well as nitrogen doping on the wetting behavior and photoactive properties of titanium oxide thin films was investigated. Hydrophobic to hydrophilic conversion of titanium oxide films takes place progressively as the relative amount of graphene oxide in the MAPLE composite target increases. Nitrogen doping leads to further decrease of the static contact angle of the composite films. The photoactive properties of the synthesized materials were investigated through the evolution of contact angle under UV light irradiation. Wetting properties of both TiO₂ and TiO₂/GO nanocomposite thin films improved upon exposure to UV light.