Dimedone and phenylazo dimedone chelates of europium as emitters in polymers

Transparent polymers when incorporated with strongly fluorescent europium chelates were found to be responding to excitation with UV radiation. In this work, two novel europium chelates have been synthesized using the β‐diketones dimedone and phenylazo dimedone along with 1,10‐phenanthroline. These chelates were characterized by elemental analyses, magnetic susceptibility measurements, UV, IR, and ESI mass spectral techniques. The chelates synthesized with metal : β‐diketone : 1,10‐phenanthroline ratio 1 : 3 : 1 were incorporated into polymer matrices. Four polymers, polyethylene vinyl acetate or acetate (EVA), polystyrene (PS), poly methyl methacryalate (PMMA), and polyethylene glycol (PEG) were used for the studies. All these, except the liquid oligomer PEG were cast into thin films. PEG was used as such for the studies. The photoluminescence spectra of the plain polymers were found to be having peaks very close to the absorption peaks of the polymers doped with europium chelate. This observation can be used in optical devices. Thermal analyses like TG/DTG/DTA of the polymer films were conducted to ascertain the thermal stability of the material. The SEM analyses of the films indicated a smooth surface with uniform distribution of the doped chelate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

热老化对PMMA塑料光纤损耗的影响

主要研究了热老化对PMMA塑料光纤损耗的影响及其影响机理.发现热物理老化减少了PMMA聚合物中的局部取向,使其形成少量的半结晶或结晶区,增加了其散射损耗;而热化学老化导致PMMA聚合物的氧化降解,严重增加了其在短波长的电子转移吸收损耗.     

偶氮染料掺夹高分子聚合物PMMA的光信息存储性质研究

本文利用旋涂法(Spin-Coating)在单晶硅片和k9玻璃上分别制备了5-Br-PADAP,DMTAM,TADEB,DMTAA和5-Me-BTAEB五种杂环偶氮染料掺杂高分子聚和物聚甲基丙烯酸甲酯(PMMA)薄膜。测试了薄膜吸收,透过和反射光谱,通过椭圆偏振光谱计算了薄膜的光学常数。结果显示偶氮染料薄膜在450~600nm之间均有强而宽的吸收,5-Br-PADAP,DMTAM,TADEB,DMTAA参杂PMMA薄膜在514nm处具有较大的n值与较低的k值相匹配,有望作为与Ar+激光器相匹配的光盘记录介质;5-Me-BTAEB参杂PMMA薄膜在633nm处具有较大的n值与较低的k值相匹配,有望作为与He-Ne激光器相匹配的光存储记录介质材料。     

Molecular weight studies of the γ‐irradiation degradation of poly(methyl methacrylate) doped with poly(p‐sulfanilamide)

The protection of some poly(methyl methacrylate) (PMMA) samples against γ rays was investigated in the absence and presence of poly(p‐sulfanilamide). Pure PMMA (without additives) and PMMA–poly(p‐sulfanilamide) blend samples were irradiated with γ rays for different exposure doses (5, 15, 25, 35, 50, 75, and 100 kGy). The viscosity‐average molecular weights were determined and thin‐layer chromatography measurements were carried out after each irradiation dose. The maximum protection against γ rays was found when 1% poly(p‐sulfanilamide) was used. The radiation chemical yield for main scission (G_s) was calculated and had lower values in the case of 1% poly(p‐sulfanilamide). The energy absorption per scission was maximum for 1% poly(p‐sulfanilamide), and this confirmed the obtained G_s data. From thin‐layer chromatography studies, it was observed that both the retention factor (R_f) values and polydispersity of the PMMA samples increased with an increasing exposure dose. The effect of γ irradiation on PMMA films doped with 1% poly(p‐sulfanilamide) was investigated with UV spectroscopy after the extraction of the additives. A change in the intensity of the absorption bands with an increasing irradiation dose was recorded. It is suggested that PMMA films doped with this type of polymer can be used as dosimeters. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of antireflective coatings on poly(methyl methacrylate) substrate by different process parameters

The high/low refractive index organic/inorganic antireflective (AR) hybrid polymers were formed using the sol–gel process, in which TiO₂/2‐hydroxyethyl methacrylate (2‐HEMA) (high refractive index hybrid polymer) and SiO₂/2‐HEMA (low refractive index hybrid polymer) two‐layer thin films were formed on a hard coating deposited poly(methyl methacrylate) (HC‐PMMA) substrate by both spin coating and dip coating. The relationship between the process parameters and the optical properties, thickness, porosity, surface morphology, and adhesion was determined. The results show that the reflectance of the two‐layer thin films on HC‐PMMA substrate is less than 0.21% (λ = 550 nm), with good adhesion (5B) and a hardness of up to 4H. In addition, the thickness, porosity, and roughness of the films affect refractive index and the antireflection properties of the AR two‐layered thin film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of a photoinitiator on the photochemical stability of poly(methyl methacrylate) studied with fourier transform infrared spectroscopy

Fourier transform infrared (FTIR) spectroscopy was used to investigate the effect of a commercial photoinitiator [2,2‐dimethoxy‐2‐phenylacetophenone (DMPA); Irgacure 651, Ciba, Basel, Switzerland] incorporated into poly(methyl methacrylate) (PMMA). Pure PMMA and modified PMMA (containing 5% DMPA) films were exposed to a xenon lamp in air. Qualitative and quantitative analyses of the recorded FTIR absorption spectra were done. This allowed us to determine the differences in the course of polymer photooxidative degradation occurring in PMMA and PMMA doped with DMPA. We found that the initiator added to polymer film enhanced the efficiency of the formation of the photooxidized products containing functional groups of different types, which could be distinguished by mathematical treatment of the FTIR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photoinduced reversible refractive index changes in doped poly(methyl methacrylate) lightguides

Planar polymer lightguides of poly(methyl methacrylate)(PMMA) doped with the azo dye, N,N-dihexyl-4-amino-4′-nitro-azobenzene (DHANA) were fabricated on a suitable glass substrate or on one surface of a regular prism. The absorption of this azo dye is strong in the green spectral region. With the red light of a HeNe laser (633 nm) these polymer films may be used as lightguides. However, in this spectral region, the guided light influences the waveguiding properties of the polymer film, making this combination a possible candidate for an all optical device material. The observed refractive index changes are intensity dependent and the response time is of the order of 100ms.     

Synthesis,characterization and nonlinear optical properties of plasma‐prepared poly(4‐biphenylcarbonitrile) thin films

A novel conjugated polymer, poly(4‐biphenylcarbonitrile) (PBPCN), was prepared using a plasma polymerization technique. The effect of the discharge power on the chemical structure and surface compositions of PBPCN thin films was investigated using Fourier transform infrared, UV‐visible absorption and X‐ray photoelectron spectroscopies. A femtosecond time‐resolved optical Kerr effect technique was applied to investigate the third‐order nonlinearity of the obtained plasma PBPCN thin films. For the first time, a non‐resonant optical Kerr effect and ultrafast response for the PBPCN thin films were observed. Copyright © 2006 Society of Chemical Industry     

Preparation and characterization of PS‐PMMA/ZnO nanocomposite films with novel properties of high transparency and UV‐shielding capacity

High transparent and UV‐shielding poly (styrene)‐co‐poly(methyl methacrylate) (PS‐PMMA)/zinc oxide (ZnO) optical nanocomposite films were prepared by solution mixing using methyl ethyl ketone (MEK) as a cosolvent. The films were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) spectra, high‐resolution transmission electron microscopy (HR‐TEM), and atomic force microscope (AFM). Cross‐section HR‐TEM and AFM images showed that the ZnO nanoparticles were uniformly dispersed in the polymer matrix at the nanoscale level. The XRD and FTIR studies indicate that there is no chemical bond or interaction between PS‐PMMA and ZnO nanoparticles in the nanocomposite films. The UV–vis spectra in the wavelength range of 200–800 nm showed that nanocomposite films with ZnO particle contents from 1 to 20 wt % had strong absorption in UV spectrum region and the same transparency as pure PMMA‐PS film in the visible region. The optical properties of polymer are greatly improved by the incorporation of ZnO nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Tunable near‐infrared optical properties based on poly(methyl methacrylate)–oxide waveguide materials

In this study, two classes of low‐loss optical planar waveguides were prepared from trialkoxysilane‐capped poly(methyl methacrylate) (PMMA)–silica and PMMA–titania hybrid materials, respectively. The prepared hybrid films had very uniform structure and surface planarity. The incorporation of the silica or titania segments into the acrylic polymer matrix reduced the intermolecular interaction and thus induced an increase in anharmonicity of the C‐H bond in the acrylic segment. Therefore, the third harmonic stretching vibration absorption of the C‐H bond was red‐shifted and resulted in a tuning of near‐infrared (NIR) optical absorption. The optical loss of the studied waveguides was reduced from 0.65 dB/cm of the PMMA waveguide to 0.26 and 0.28 dB/cm with increasing the silica and titania content in the hybrid materials, respectively. The reduction of the C‐H number density and shifting of the NIR absorption spectra accounted for the relationship between the optical loss and the inorganic oxide content. The increased anharmonicity through the incorporation of the inorganic moiety in the hybrid materials provides another approach for tuning the NIR optical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1224–1228, 2005     

Controlled dispersion of a porphyrin/fullerene donor‐acceptor complex in semiconducting polymer thin films: Intermolecular interactions of polymers with porphyrin and fullerene

Thin films composed of semiconducting polymers [poly(2‐vinyl naphthalene), poly(4‐diphenyl aminostyrene), poly(1‐vinyl pyrene), and poly(3‐hexyl thiophene‐2,5‐diyl)], zinc(II)?5,10,15,20‐tetra‐(2‐naphthyl)porphyrin, and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester blends were prepared to investigate the controlled dispersion of porphyrin molecules in semiconducting polymer thin films. Tailoring the intermolecular interactions between the polymer/fullerene, polymer/porphyrin, and porphyrin/fullerene systems was found to be an effective method of controlling the dispersion. When the polymer/porphyrin interactions were enhanced, intermixed porphyrin/fullerene donor–acceptor complex domains were formed, whereas under conditions where the polymer/porphyrin interactions were weakened, the complex assembled at the borders between the polymer and fullerene phases. This concept could potentially be applied to various combinations of porphyrin/fullerene systems in semiconducting polymer thin films to develop polymer solar cells with excellent performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41629.     

Increase of photoluminescence from fullerene‐doped polymers under laser irradiation

Photoluminescence (PL) from fullerene (C₆₀ and C₇₀)‐doped polymers such as poly(methyl methacrylate) (PMMA), polystyrene (PS), poly(methyl phenyl silane) (PMPS) and poly(phenyl silsesquioxane) (PPSQ) increases gradually under laser irradiation in air (but not in vacuum and in nitrogen) and eventually becomes visible to the naked eye. Concomitantly, the PL peak is broadened and, in most cases, blue‐shifted. No such PL increases are observed for pure C₆₀ films made by vacuum vapor deposition and pure polymer films. Among the polymers used, fullerene‐doped PMMA has the greatest PL increase after several hours of laser irradiation and fullerene‐doped PMPS has the highest rate of PL increase at the initial stage of the laser irradiation. To gain an insight into the mechanism of the PL increase, laser‐irradiated fullerene‐doped PMMA samples were analyzed by UV‐Vis spectrophotometer, FT‐IR, mass spectrometry, GPC and NMR. The results show that the PL increase can be attributed to CH₆₀O_n‐polymer (or C₇₀O_n‐polymer) and oxidized fullerene‐polymer adducts formed by some laser‐induced photochemical reactions among fullerenes, oxygen and polymers.     

Modification of poly(N-vinyl-carbazole) thin films by bromine doping

Poly(N-vinyl-carbazole) (PVK) thin films doped with bromine has been studied by scanning electron microscopy, X-ray diffraction, infrared absorption, X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), optical transmission (visible, near ultra violet) and conductivity measurements. The polymer has been doped at room temperature and at 373 K. It is shown by ESR, XPS and optical measurements that a charge transfer complex (CT-complex) is formed between PVK and Br. However, if some bromine acts as dopant of the polymer there is another bromine contribution, which corresponds to bromine covalently bonded to PVK and some only adsorbed. It is also shown by ESR that there is not only polymer doping by bromine but also some partial polymer degradation. Therefore, it can be said that the optimum doping condition of PVK thin films with bromine has been shown to be room temperature post-doping.     

Experimental and Numerical Evaluation on Optical Properties of Al‐Doped ZnO Film Materials

The aim of this article is to provide a systematic method to perform numerical and experimental evaluation on the optical properties of Al‐doped ZnO nano thin films. Some different doping density samples are deposited for testing the transmittance. The results show that the transmittance of Al‐doped ZnO has a nonlinear relation with the optical constants and Al‐doped quantity. The optical band gap of the Al‐doped ZnO decreases with the Al doping quantity increasing. Meanwhile, the Maxwell‐Garnett (MG) theory is used to investigate the optical properties of Al‐doped ZnO nano thin films in visible range. The comparison can illustrate the validity of both test and design method. It implies a potential design and evaluation method for developing a new type of ceramic nano thin film in engineering.     

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     

Synthesis and properties of PMMA‐ZrO2 organic–inorganic hybrid films

In this work we report the synthesis process and properties of PMMA‐ZrO₂ organic–inorganic hybrid films. The hybrid films were deposited by a modified sol‐gel process using zirconium propoxide (ZP) as the inorganic (zirconia) source, methyl methacrylate (MMA) as the organic source, and 3‐trimetoxy‐silyl‐propyl‐methacrylate (TMSPM) as the coupling agent between organic and inorganic phases. The films were deposited by dip coating on glass slide substrates from a hybrid precursor solution containing the three precursors with molar ratio 1 : 0.25 : 0.25 for ZP, TMSPM, and MMA, respectively. After deposition, the hybrid thin films were heat‐treated at 100°C for 24 h. The macroscopic characteristics of the hybrid films such as high homogeneity and high optical transparence evidenced the formation of a cross‐linked, interpenetrated organic–inorganic network. The deposited PMMA‐ZrO₂ hybrid films were homogeneous, highly transparent and very well adhered to substrates. Fourier Transform Infra‐Red measurements of the hybrid films display absorption bands of chemical groups associated with both PMMA and ZrO₂ phases. The amounts of organic and inorganic phases in the hybrid films were determined from thermogravimetric measurements. The surface morphology and homogeneity of the hybrid films at microscopic level were analyzed by scanning electron microscopy and atomic force microscopy images. From the analysis of optical transmission and reflection spectra, the optical constants (refraction index and extinction coefficient) of the hybrid films were determined, employing a physical model to simulate the hybrid optical layers. The refraction index of the hybrid films at 532 nm was 1.56. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42738.     

Characterization and gamma radiation effects on poly(methyl methacrylate) doped with some benzylidene polymers

Anionic solution polmerization studies of benzylidene malononitrile, benzylidene ethyl cyanoacetate and their para chloro derivtives in dimethyl formamide (DMF) as a reaction medium using pipridene as initiator under nitrogen atmosphere at 100 °C were carried out. Infrared, ¹H NMR and ultraviolet-visible (UV-Vis) spectroscopic studies for the obtained polymers were investigated. The effect of γ-irradiation on PMMA films doped with 1 % of the benzylidene polymers was investigated by uv-vis spectroscopy. A change in the intensity of absorption bands with increasing irradiation dose was recorded. It is suggested that PMMA films doped with this type of benzylidene polymer can be used as dosimeter.     

Conjugated polythiophene/Ni doped ZnO hetero bilayer nanocomposite thin films: Its structural,optical and photoluminescence properties

In this study, synthesis and characterization of plasma polymerized Thiophene/ Nickel doped Zinc Oxide (PTNZO) bilayer nanocomposite films were carried out. Nickel doped zinc oxide (NZO) thin films were obtained by magnetron sputtering technique on glass substrates at 40 W Radio Frequency (RF) power. Plasma polymerized Thiophene (PT) thin films were deposited on the NZO thin films obtained on the glass substrate by Radio Frequency (RF) plasma polymerisation technique. X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), FTIR and Photoluminescence (PL) analyzes were performed for the characterization of PTNZO hetero bilayer nanocomposite films. In the XRD spectra of PTNZO bilayer nanocomposite thin films, (002) planes were determined as the most basic peak, and it was determined that the intensity of this peak, changed depending on the RF power of polymer thin films. Optical properties of nanocomposite thin films such as transmittance, absorbance and optical band gap were determined by UV–Vis spectroscopy. Optical band gap for PTNZO nanocomposites were 2.72?eV, 2.34?eV, and 2.45?eV, respectively, with increasing RF power. For NZO thin films, this value is 3.12?eV. The optical band gaps calculated from the absorption and transmittance spectra obtained using UV–visible spectroscopy had a good compatibility with those of the optical band spectra calculated from the PL spectra. The tetragonal wurtzite structure of the NZO thin films was examined by SEM analysis. The grain size of NZO nanostructure was found to be approximately 59?nm.     

Organic and polymer planar optical waveguides

Single-mode and multi-mode planar optical waveguides with low loss were fabricated by spin-coating thin films of poly(vinyl alcohol) (PVAl) and 4-dihexylamino-4′-nitro-stilbene (DHANS) doped poly(methylmethacrylate) (PMMA) onto glass substrates, and characterised by theoretical analysis and optical guided-mode measurements. The optical constants of the waveguides were determined with good accuracy by measuring the coupling synchronised angles and fitting them, via a recursion method, into the waveguide dispersion equations. The number of the guided modes observed in these thin films can be controlled by tailoring the film thickness.     

Preparation and characterization of binary blends composed of poly(dioctylfluorene‐alt‐hexylsulfonylthiophene) and nonconjugated polymers

The solutions and the thin films of poly[9,9‐dioctyl‐2,7‐fluorene‐alt‐2,5–(3‐hexyl‐sulfonylthiophene)] (PFSO₂T) and its binary blends with other nonconjugated polymers such as poly(methyl methacrylate) (PMMA), polycarbonate (PC), and ethylene vinyl acetate copolymer (EVA) can be prepared by different concentrations from a polymer solution. Binary polymer blends can increase the absorbance and photoluminescence intensities in the solid state due to nonconjugated polymers can act as dispersion agents which can reduce the interchain interaction or the aggregation of the conjugated polymers. Photoluminescence intensity of the thin films of fluorescent polymers blending with ethylene vinyl acetate copolymers exhibited six times higher than that of the neat fluorescent polymers. The PFSO₂T/EVA binary blends reveal the least extent of optical degradation of around 20% compared to those binary blends in both absorption and emission intensities after the irradiation under the UV‐light for 20 h. The cross‐sectional morphology of fluorescent polymers blending with ethylene vinyl acetate copolymers reveals little aggregation and better phase separation among the other binary polymer blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44969.