High‐refractive‐index thin films prepared from aminoalkoxysilane‐capped pyromellitic dianhydride–titania hybrid materials

High‐refractive‐index aminoalkoxysilane‐capped pyromellitic dianhydride (PMDA)–titania hybrid optical thin films (TP0–TP8) were synthesized and characterized in this study. They were prepared with PMDA, aminopropyltrimethoxysilane, and titanium(IV) isopropoxide via a sol–gel process followed by spin coating and multistep baking. Through adjustments in the concentration and reaction time, the inorganic content in the hybrid thin films could be as high as 59.1 wt %. The Fourier transform infrared results indicated successful bonding between the organic and inorganic moieties. However, residues of the chelating ligands were found in the hybrids with high titania contents, affecting their thermal and optical properties. Field emission scanning electron microscopy results suggested a nanosized domain of the titania segment in the hybrid materials TP0–TP8. An atomic force microscopy study suggested that the hybrid thin films had good planarization. The dispersions of the refractive index and extinction coefficient in the wavelength range 190–900 nm were studied. The refractive indices of the prepared hybrid thin films at 633 nm increased linearly from 1.567 to 1.780 with increasing titania content. However, the Abbe numbers of the hybrid thin films showed an opposite trend. Excellent optical transparence was obtained in the visible region for the prepared hybrid thin films. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3419–3427, 2001     

Silica aerogel–poly(ethylene‐co‐vinyl acetate) composite for transparent heat retention films

Poly(ethylene‐co‐vinyl acetate) (EVA) plastic films are widely used for solar coverings including photovoltaic modules and commercial greenhouse films, but are poor at controlling heat flow. In this work, silica aerogel (SA) nanogels were examined for preparing transparent heat retention EVA films that block far infrared spectra radiation to maintain heat, without compromising the optical performance of the films. SA nanogels were melt‐mixed using a mini twin‐screw extruder with EVA pellets to form SA/EVA composite, which were pressed into thin films with controlled thickness. The composite films were characterized in terms of optical properties using a variety of analytical methods including FTIR, UV–Vis spectroscopy, electron, confocal, and atomic force microscopy. Both thermicity and thermal conductivity of commercial and experimental SA/EVA films were measured. The results demonstrated that the SA/EVA films gave improved infrared retention compared to commercial thermal plastic films without compromising visible light transmission, showing the potential for this approach in next generation heat retention films. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 927–935     

Characterization of AlN thin film prepared by reactive sputtering

AlN films with a preferred orientation <002> have been prepared on Si(100) substrates via DC reactive magnetron sputtering. X‐ray diffraction, atomic force microscopy, scanning electron microscopy, ellipsometer, and ultraviolet–visible–near infrared (UV–VIS–NIR) spectrophotometer were used to investigate the structural and optical properties of the AlN thin films. When the sputtering pressure is about 0.4 Pa, the flow ratio between nitrogen and argon is 1 : 3, and the growth temperature is 400 °C, the transmissivity of the AlN film is about 90% in the visible and near‐infrared region, and its optical band gap is ~5.84 eV. The refractive index of the thin films is about 2.05, which is lower than the bulk AlN refractive index. Copyright © 2016 John Wiley & Sons, Ltd.     

Orientation of cellulose triacetate films cast from solution in high magnetic field

Cellulose triacetate solutions with various solvents, including methylene chloride, methyl acetate, and their mixture with ethanol, were cast in high magnetic fields, and the obtained films were subjected to the optical and infrared measurements. The film cast from a solution with a methyl acetate/ethanol mixed solvent exhibited birefringence as well as infrared dichroism, whereas the films cast from the other solutions did not. The aligned structure was discussed by comparison with a mechanically stretched sample. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1942–1947, 2001     

Real‐time orientation and crystallinity measurements during the isotactic polypropylene film‐casting process

A method based on Fourier transform infrared (FTIR) transmission spectra is proposed to measure the crystallinity of isotactic polypropylene (iPP) samples. The method parameters were tuned as compared with wide‐angle X‐ray scattering measurements performed on test samples characterized by different crystallinity values obtained by solidification of thin iPP films under several cooling rates in a homemade device. The FTIR dichroic ratio measurements were adopted to measure crystalline and average Hermans' orientation factors of iPP samples obtained by film casting. The crystalline orientation measurement method was validated as compared with the birefringence measurement. The techniques were successfully used in real time during some film‐casting runs with a suitably modified FTIR system made of a spectrometer equipped with two optical guidelines and an external detector. Real‐time measurements are reported and discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 998–1008, 2003     

Deformation and fracture behavior of poly(vinylidene fluoride‐trifluorethylene) ferroelectric copolymer films under uniaxial tension

The deformation and fracture behavior under uniaxial tension was characterized for P(VDF‐TrFE) 68/32 mol % copolymer films prepared under two different processing conditions. It was found that the copolymer films prepared by solution casting and then annealing show a typical polymeric brittle fracture feature. For the copolymer films prepared by stretching the solution‐cast films and then annealing process, a typical linearly strengthening stage occurs in the stress–strain curve after yielding, and the polymer film samples fracture at a much larger maximum strain and a higher tensile strength than those prepared by the former process. SEM observation and XRD analysis were carried out to examine the morphology and microstructure change during uniaxial tension. The results show that for the stretched film samples, the polymer chains undergo slipping or further reorientation during uniaxial tension, causing the increase of the peak intensity in the X‐ray diffraction pattern. For the directly annealed ones, no yielding phenomenon is observed and there is no apparent X‐ray diffraction intensity change. It was suggested that the highly‐oriented fibril structure of the stretched film samples contributes to the linearly strengthening stage after yielding in the stress–strain curve. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3255–3260, 2005     

Novel biodegradable poly(butylene succinate)/poly(ethylene oxide) blend film with compositional and spherulite‐size gradients

Biodegradable poly(butylene succinate) (PBS)/poly(ethylene oxide) (PEO) polymer blend film with compositional gradient in the film thickness direction was prepared using a method of interdiffusion across the interface between the PBS and PEO layers at a temperature above the melting points of both the component polymers. The miscibility between PBS and PEO was confirmed by observation of the glass transition temperature by differential scanning calorimetry. The compositional gradient structure of PBS/PEO was characterized by microscopic mapping measurement of Fourier transform infrared spectra and dynamic mechanical thermal analysis. Furthermore, a new method for confirming the crystalline/crystalline compositional gradient structure through observing the crystallization behavior by POM (polarized optical microscopy) was put forward. A continuous gradient of the spherulite size along the film thickness direction was succeessfully generated in the PBS/PEO blend film. The compositional gradient blend was found to have significantly improved physical properties that cannot be realized for pure PBS, pure PEO, and even their homogeneous miscible blend system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 368–377, 2005     

Reflection–absorption infrared spectroscopy investigation of the crystallization kinetics of poly(ethylene terephthalate) ultrathin films

Reflection–absorption infrared spectroscopy was used to study the crystallization behavior of poly(ethylene terephthalate) (PET) ultrathin films. The crystallinity of ultrathin films was estimated by the fraction of trans conformers of PET. The isothermal and nonisothermal crystallization kinetics of ultrathin films with different thicknesses were investigated. The thinner PET film showed slower kinetics during isothermal crystallization than the thicker film. Moreover, the final crystallinity of films with various thicknesses were reduced with decreasing thickness. An Avrami equation was used to fit the acquired results. The Avrami exponents decreased with the film thickness. As for the nonisothermal crystallization, the cold‐crystallization starting temperature shifted to a lower temperature as the film thickness increased. The influence of the substrate on the crystallization kinetics of the films was also studied. The half‐crystallization times and final crystallinities of ultrathin films adsorbed onto a self‐assembled‐monolayer‐treated surface and an untreated substrate were clearly different, although their thickness dependence was similar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4440–4447, 2004     

Design and synthesis of optically transparent calcium‐incorporated polymer complexes

Transparent thin films of calcium‐ion‐incorporated polymer composites were synthesized with calcium carbonate (CaCO₃) and polymers such as poly(acrylic acid) (PAA), poly(ethylene glycol) (PEG), and methylcellulose. The homogeneous distribution of Ca²⁺ in the composite films was observed because of the high concentration of COO^? groups along the PAA backbone for the complexation of Ca²⁺ ions. The optical transparency of the composites depends on the weight percentages of the three polymers and the molar concentration of CaCO₃ in the composites. Maximum transparency was obtained for a composite film with a PAA/CaCO₃ ratio of 9:1. The results indicated that methylcellulose improved the film‐forming capabilities and that PEG improved the transparency of the composites. All polymer complexes were characterized with X‐ray diffraction, fourier transfer infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, dynamic mechanical analysis, and optical transparency measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4459–4465, 2004     

Molecular structure and thickness dependence of chain orientation in aromatic polyimide films

Degrees of orientation of main chains and imide rings were quantitatively estimated for spin‐coated films of six kinds of aromatic polyimides (PIs) using polarized attenuated total reflection (ATR)/Fourier transform infrared (FT‐IR) spectroscopy. The degrees of chain orientation parallel to the film planes are significantly larger for the PIs having rigid structures than those having flexible structures, and the introduction of side groups decrease the degrees of chain orientation. In contrast, the rotational orientations of imide rings are almost isotropic for all PI films. Moreover, the film thickness dependences of the degrees of orientation were investigated for two kinds of rigid‐rod PIs having bulky trifluoromethyl ( CF₃) side groups in their diamine moieties. The degrees of chain orientation slightly decrease as the film thickness increases, whereas the rotational orientation of imide rings is independent of the film thickness. The degrees of chain orientation on the substrate sides significantly differ from the atmospheric sides of PI films. This difference was generated during thermal imidization because of tensile stress originated from the mismatch in thermal expansion coefficients between the substrates and the PI films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2109–2120, 2005     

Plasma polymerization of styrene with controlled particle energy

A new type of reactor for plasma polymerization was developed in order to achieve an effective control of styrene polymerization process. Electrons and ions were extracted from the radio frequency (rf) glow discharge region to the downstream region to generate plasma polymerization. The energy of extracted ionized particles was controlled by the bias voltage of a screen grid unit. Deposited polymer thin films were analyzed by X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. The result showed that the polarity and energy of the extracted particles had considerable effect on the deposition rate and structure of the deposited films. At each bias polarity there was a maximum deposition rate vs. voltage magnitude, and the maximum at the positive voltage was higher. In addition, the bulk aromaticity of the film deposited at the negative bias was lower than at the positive bias; the surface aromaticity of the films was much higher than that of the films prepared by usual rf discharge. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1265–1270, 1998     

Fluorescein–formaldehyde oligomeric pH indicator: Facile synthesis,characterization, and potential application

A kind of fluorescent oligomeric pH indicator (fluorescein–formaldehyde product) was synthesized by the reaction of fluorescein with formaldehyde under alkaline conditions by a one‐pot method. The synthesized product was fully characterized with Fourier transform infrared, ¹H NMR, ultraviolet–visible spectra, luminescence spectra, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra. The results indicated that the reaction was a typical phenol–formaldehyde reaction and that the fluorescein–formaldehyde product contained dimer, trimer, tetramer, and even a little octamer. Visible spectra and luminescence spectra showed that the fluorescein–formaldehyde product could still provide pH sensitivity similar to that of fluorescein. In addition, the oligomeric pH indicator immobilized poly(vinyl alcohol) membranes could be easily fabricated and achieved better long‐term stability and fast equilibrium response. Thus, they are promising transparent membranes for optical pH sensors of a wide pH range (0.0–10.0) based on absorption and fluorescence. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3447–3453, 2005     

Facile synthesis,characterization, and potential applications of two kinds of polymeric pH indicators: Phenolphthalein formaldehyde and o‐cresolphthalein formaldehyde

Two kinds of applicable polymeric pH indicators were synthesized by the reaction of phenolphthalein and o‐cresolphthalein with formaldehyde under alkaline conditions by a one‐pot method. The synthesized products were fully characterized with Fourier transform infrared, ¹H NMR, ultraviolet–visible spectroscopy, and gel permeation chromatography. The results indicated that the reaction was a typical phenol formaldehyde reaction. The dosage of formaldehyde and the reaction time were well controlled to obtain soluble polymers, instead of crosslinked products. The polymeric‐pH‐indicator‐immobilized poly(vinyl alcohol) (PVA) membranes were easily fabricated and had good long‐term stability under highly basic conditions and a fast equilibrium response. Moreover, the phenolphthalein formaldehyde immobilized PVA membrane had a linear response from pH 10.0 to 14.0, and so it has promise as a optical transducer for high pH value determinations. The o‐cresolphthalein formaldehyde immobilized PVA membrane had a nonlinear response from pH 9.0 to 13.0. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1019–1027, 2005     

Synthesis and characterization of single‐wall‐carbon‐nanotube‐doped emeraldine salt and base polyaniline nanocomposites

Nanocomposites of polyaniline (PANI) and single‐wall carbon nanotubes (SWNTs) were prepared and characterized via resonance Raman and electronic absorption spectroscopy (ultraviolet–visible/near‐infrared). The chemical synthesis of PANI was performed in the presence of SWNTs in concentrations ranging from 10 to 50 wt % (SWNT/PANI). The obtained materials were hydrophilic, homogeneous composite compounds. The chemical interaction between PANI (in the conducting emeraldine salt form and in the insulating emeraldine base form) and metallic and semiconducting nanotubes was investigated. The emeraldine salt form of the polymer was significantly stabilized in the composite in comparison with plain PANI. A selective electronic interaction process between PANI and metallic SWNTs was found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 815–822, 2005     

Active sol–gel thin film on nanostructured plasmonic surface

Sol–gel hybrid films based on alkyl bridged polysilsesquioxanes and doped with phenol red molecules, were synthesized for sensing purposes. Doped films changes colour from yellow to orange to red when exposed to hydrochloric acid (HCl) both in solution and gas phases. The synthesis was optimized in order to produce porous films after spin coating. The porosity increases reacting surface area and chemical reactivity of the sensing thin film. Porosity, optical and structural characterizations of these films were investigated by transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FT-IR) and Spectroscopic Ellipsometry (SE). Variation of optical characteristics upon immersion of the film in the solution was characterized by UV–visible (UV–vis) spectroscopy. Moreover the same porous sensitive hybrid film was deposited on gold sinusoidal grating in order to detect variations of the dielectric film optical constant after HCl solution dip. This variation was revealed by monitoring surface plasmon polariton excitations.     

Structural and optical properties of TiO2 thin films prepared by spin coating

Transparent semiconducting thin films of titanium oxide (TiO₂) were deposited on glass substrates by the sol–gel method and spin-coating technique. The physical properties of the prepared films were studied as a function of the number of spun-cast layers. The microstructure and surface morphology of the TiO₂ films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), with respect to the film thickness. The XRD analysis reveals that the films are polycrystalline with an anatase crystal structure and a preferred grain orientation in the (101) direction. The morphological properties were investigated by AFM, which shows a porous morphology structure for the films. The optical properties of the films were characterized by UV–Visible spectrophotometry, which shows that the films are highly transparent in the visible region and their transparency is slightly influenced by the film thickness, with an average value above 80 %. The dependence of the refractive index (n), extinction coefficient (k), and absorption coefficient (α) of the films on the wavelength was investigated. A shift in the optical band gap energy of the films from 3.75 to 3.54 eV, as a function of the film thickness, has been observed.     

Optical properties of nanostructure boron doped NiO thin films

Boron doped NiO films were prepared by sol–gel method. The effects of B content on the morphological and optical properties of NiO films were studied with atomic force microscopy, and optical characterization method. The average transmittance at the visible region is reached to 75 % for lower doped films (0.1 and 0.2 % B), whereas, the recorded average value of transmittance was about 62 % for doped film with 1 % B throughout the region. The optical energy gap value for pure NiO film was found to be 3.73 eV. These values were affected by B doping with non-monotonic variation and reached to 3.64 eV for 0.1 % B doped NiO. Also, the refractive index dispersion and dielectric constants of the NiO films were studied throughout the investigated range of wavelengths. The obtained results indicate that the optical parameters of the NiO film are controlled with boron doping.     

In situ sol–gel preparation of high transparent fluorinated polyimide/nano-MgO hybrid films

Hybrid nanocomposite films of magnesium oxide (MgO) in fluorinated polyimide (PI) from 4, 4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4, 4′-Diaminodiphenyl ether (ODA) have been successfully fabricated via an in situ sol–gel polymerization technique. The MgO content in hybrid films was varied from 0 to 5 wt%. The hybrid films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), ultraviolet–visible (UV–Vis) spectroscopy and thermal gravimetric analyses (TGA). The results of FTIR, XRD and FESEM showed that the MgO nanoparticles were well dispersed in the polymer matrix due to the coordination between the carbonyl group of polymers and Mg atom, and the as-prepared hybrid films exhibited excellent optical transparency in the visible region and good UV-shielding properties in the UV region. Although the thermal stability of the hybrid films is slight inferior to pure PI, it is still good for the practical application below the temperature of 300 °C.     

Quantitative characterization of the optical properties of absorbing polymer films: Comparative investigation of the internal reflection intensity analysis method

Nondestructive, three‐dimensional refractive‐index measurements are used for the determination of both the crystallinity and orientation in thin polymer films. The prism wave‐guide coupler is particularly suited for three‐dimensional isotropic and anisotropic thin‐film studies because of the quantitative character of the information obtained and the ease of data acquisition. It has been limited, however, to determining only the refractive index of transparent or weakly absorbing thin‐film samples. On the basis of thin‐film optics, this study develops a new internal reflection intensity analysis (IRIA) method, which uses the intensity information rather than the conventional mode angle values to acquire both the refractive index and the extinction coefficient over a range of transparent to highly absorbing polymer films. Therefore, the IRIA method overcomes the limitations of this prism wave‐guide coupler technique, which can only measure the refractive index of a weakly absorbing sample. With a Metricon PC‐2010 as the skeletal framework, a prototype instrument has been developed to apply and test the IRIA method. A study comparing both the refractive index and extinction coefficient obtained with ellipsometry, ultraviolet–visible/near‐infrared reflectometry, and IRIA for solvent blue 59 dyed polystyrene films confirms that the IRIA method is effective for obtaining the three‐dimensional refractive indices and extinction coefficients of polymer films. In addition, the refractive index and extinction coefficient spectrum (400–800 nm) of solvent blue 59 have been determined with the effective media theory. Furthermore, the three‐dimensional complex refractive indices of highly absorbing black electrical tape, inaccessible to other optical measurement because of its surface character, has been determined by the IRIA method. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 842–855, 2003     

Azobenzene‐containing LC polymethacrylates highly photosensitive in broad spectral range

Two photosensitive chiral liquid crystalline azobenzene‐containing polymethacrylates having different length of flexible spacer connecting chromophores with backbone were synthesized and their phase behavior and photo‐optical properties were studied. Both polymers consist of lateral methyl substituents in ortho‐position of azobenzene chromophores providing high photosensitivity even in red spectral region as well as high thermal stability of photoinduced Z‐form of azobenzene chromophores. It is shown, that smectic phase (SmA*) formation in films of polymer with longer spacer predetermines its quite unusual spectral response to UV and subsequent visible light actions. The SmA* phase promotes spontaneous homeotropic alignment of azobenzene chromophores in polymer films. UV‐irradiation induces not only E‐Z isomerization but also results in disruption of homeotropic alignment, whereas subsequent visible light action enables to obtain films with the low degree of chromophores orientation. The photo‐orientation phenomena under the action of polarized light of different wavelength on polymer films were studied. The possibility of using red polarized light of moderate intensity for optical photorecording on polymer films is demonstrated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2962–2970