How does an oxygen atom in the side chain affect the photophysical properties of alkoxy-substituted organopolysilane homopolymers and copolymers?

Alkoxy-substituted organopolysilane homopolymer (poly[SiMe(OR)]_n) and random copolymers (poly[SiMe(OR)]_m[SiMeR′]_n were synthesized and the solvatochromism and thermochromism for their absorption and fluorescence spectra were examined. The band maxima shifted to longer wavelengths with an increase in the ratio of the alkoxy side chains; however, the influence of the solvent was very small. The thermochromic shifts are dependent on the number of alkoxy side chains. Molecular dynamics calculation showed that the conformation of the polysilanes was determined by the Coulomb interaction between the alkoxy side chains, and the conformations of the polyalkoxysilanes are similar to those of polyalkylsilanes (poly[SiRR′]_n). Molecular orbital (MO) calculations manifested that the interaction between the orbitals of the oxygen atom in the side chain and those of the silicon atom in main chain (σ conjugation system) was larger in LUMO than in HOMO, and the decrease in LUMO energy shifted the absorption maxima to longer wavelength.     

Synthesis of polysilane-acrylamide copolymers by photopolymerization and their application to polysilane-silica hybrid thin films

Various polysilane-acrylamide block copolymers have been prepared from photopolymerization of acrylamide-type monomers using poly(methylphenylsilane) (PMPS) as a macro-photo-radical initiator. The acrylamide block in the copolymers improved the hydrophilic property of PMPS. These PMPS-acrylamide block copolymers have been applied to formation of PMPS-silica hybrid thin films via sol-gel reaction. Homogeneous and transparent PMPS-silica hybrid thin films were obtained from a few PMPS-acrylamide block copolymers. It was found for these hybrid thin films based on hydrogen bonding formation between amide group and silanol group. The surface properties of hybrid thin films were evaluated by water contact angle measurement, scanning electron microscope (SEM), and atomic force microscope (AFM) images.     

Hole structure and its formation in thin films of hydrolyzed poly(styrene maleic anhydride) alternating copolymers

Maleic anhydride moieties on the backbone chains of poly(styrene maleic anhydride) alternating copolymer (SMA) hydrolyzed in a THF solution containing water and hydrochloric acid. Well‐arrayed holes were obtained in spin‐cast thin hydrolyzed SMA films on a single crystal silicon wafer, and the hole diameter and its distribution were measured with AFM data. Results showed that the hole size was almost uniform, and was influenced by water content when spin speed was kept unchanged. The THF solution with a SMA concentration of about 1 g/mL and weight ratio H₂O/SMA of 1/3 produced holes having an average diameter of 0.60 μm and depth of 206.12 nm, when cast at a spin speed of 1400 rpm. It was noted that the formation of the holes in thin hydrolyzed SMA film was different from the dewetting process in thin homopolymer films, but was associated with the intrinsic properties of the copolymer forming the films. The surfactant effect of hydrolyzed SMA was suggested to interpret the formation of the holes. The holes were described to be the traces of water droplets that were emulsified by the hydrolyzed SMA during casting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 267–274, 2000     

Optical and physical properties of zirconium dioxide reinforced poly(methyl methacrylate) nanocomposite films

The objective of this study was to investigate the fundamental aspects of acrylic resin and zirconia nanoparticle interaction to analyze the optical properties and subsequent changes in refractive index with incremental loading of nanoparticles. Poly(methyl methacrylate) (PMMA) reinforced with zirconia nanoparticles were prepared by dip coating, spin coating and solvent casting techniques. An overall understanding of the polymer nanocomposite film has been achieved using the spectroscopic and morphological studies. The vital aspect of this whole study is to derive a simple yet an efficient nanocomposite film capable of imparting extraordinary optical properties. Within the limitations of this research a very crucial property of the material has been revealed. The RI as well as the optical transparency of the nanocomposite film has been steadily maintained with a significant increase of RI by the magnitude of 0.06 and ~100% light transmittance on incorporation of pure zirconia nanoparticles into PMMA matrix has been achieved. The best technique found was spin coating as it could yield thin films and better transparency and higher refractive index.     

Composition fluctuations before dewetting in polystyrene/poly(vinyl methyl ether) blend thin films

We report structural development in blend thin films of deuterated polystyrene (dPS) and poly(vinyl methyl ether) (PVME) below 200 nm in two phase region during the incubation period before dewetting using neutron reflectivity (NR) and atomic force microscopy (AFM). As was predicted by the former optical microscope (OM) and small-angle light scattering (LS) measurements on blend thin films of protonated PS and PVME [Ogawa H, Kanaya T, Nishida K, Matsuba G. Polymer 2008;40:254–62.], the NR results clearly showed that the tri-layer structure consisting of the surface PVME layer, the middle blend layer and the bottom PVME layer was formed in the one phase region. After the temperature jump into the two phase region, it was found that the phase separation of the middle blend layer proceeded in the depth direction during the incubation period before dewetting, suggesting that the dewetting was induced by the composition fluctuations during the incubation period.     

Enhancement in crystallinity of poly(3-hexylthiophene) thin films prepared by low-temperature drop casting

Low-temperature casting of high molecular weight (HMW > 40 kDa) regioregular poly(3-hexylthiophene) (P3HT) is demonstrated to yield highly crystalline P3HT thin films with well defined and preferentially edge-on oriented [(100) contact plane] nanocrystallites on the pure and silanized Si/SiO₂ substrates. Transmission electron microscopy and X-ray diffraction provide evidence for the increase in preferential edge-on orientation of P3HT-conjugated backbone while decreasing the film preparation temperature below room temperature. The optimum growth temperature is about −12°C for the given concentration (2 mg/mL in CHCl₃). The reduced evaporation rate of the solvent results in a better selection of the thermodynamically stable orientation of nanocrystallites onto the substrate. The degree of preferential orientation and size of the crystallites can be further increased on n-octadecyltrichlorosilane-treated SiO₂ substrates as well as by annealing the films at 200°C for 1 h. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

RAFT synthesis of poly(N‐isopropylacrylamide) and poly(methacrylic acid) homopolymers and block copolymers: Kinetics and characterization

Reversible addition‐fragmentation chain transfer (RAFT) polymerization was used successfully to synthesize temperature‐responsive poly(N‐isopropylacrylamide) (PNIPAAm), poly(methacrylic acid) (PMAA), and their temperature‐responsive block copolymers. Detailed RAFT polymerization kinetics of the homopolymers was studied. PNIPAAm and PMAA homopolymerization showed living characteristics that include a linear relationship between M _n and conversion, controlled molecular weights, and relatively narrow molecular weight distribution (PDI < 1.3). Furthermore, the homopolymers can be reactivated to produce block copolymers. The RAFT agent, carboxymethyl dithiobenzoate (CMDB), proved to control molecular weight and PDI. As the RAFT agent concentration increases, molecular weight and PDI decreased. However, CMDB showed evidence of having a relatively low chain transfer constant as well as degradation during polymerization. Solution of the block copolymers in phosphate buffered saline displayed temperature reversible characteristics at a lower critical solution temperature (LCST) transition of 31°C. A 5 wt % solution of the block copolymers form thermoreversible gels by a self‐assembly mechanism above the LCST. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1191–1201, 2006     

均聚物调控的PS-b-P4VP薄膜的微相分离形貌

分别以聚丙烯酸(PAA)和聚氧化乙烯(PEO)与苯乙烯与4-乙烯基吡啶二嵌段共聚物(PS-b-P4VP)进行溶液共混并且旋涂成膜,采用原子力显微镜(AFM)研究了这两种均聚物对PS-b-P4VP薄膜微相分离形貌的调控作用。结果表明,PAA与P4VP链段之间强烈的氢键作用使得P4VP链段对PS链段的热力学排斥作用增强,当PAA质量分数为10%时,PS分散相区以规则的柱体垂直分布于由P4VP/PAA链段相互溶解所形成的连续相基体中。对于PS-b-P4VP/PEO共混体系,共混薄膜形成了PEO/P4VP分散相以柱状形态垂直分布在以PS链段聚集区为薄膜连续相基体中的微相分离形貌,由于PS链段无法在PEO/P4VP柱状微区上方形成覆盖,导致共混薄膜表面出现许多孔洞,孔洞底部伴有PEO链段部分结晶形成的锥状突起。随PEO含量增加,孔洞直径增大,孔洞底部的锥状突起也增大。     

Optoelectronic properties of In-doped SnS thin films

Nanostructured un- and In-doped SnS thin films were deposited on fluorine-doped tin oxide (FTO) substrates via an electrochemical deposition technique. The deposited thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS), photoluminescence (PL) spectroscopy and UV–visible spectroscopy. The XRD patterns demonstrated that all deposited thin films are made of polycrystalline SnS particles. The AFM images illustrated a distinct change in the surface topography of the SnS thin films due to In-doping. The PL spectra showed two blue emission peaks and a green emission peak for all samples. Also, they highlighted a PL peak for the In-doped thin films. The incorporation of In-dopant leads to enhance in the optical absorption of SnS lattice. The optical energy band gap (E_g) of the deposited thin films was estimated using UV–vis spectroscopy, which indicated that In-doping decreases the E_g value of SnS thin films by creating defect levels. The photocurrent results demonstrated a higher photocurrent response and photocurrent amplitude for the In-doped SnS samples relative to the un-doped SnS thin film. The Mott–Schottky analysis revealed p-type conductivity for all samples. In addition, the carrier concentration of SnS was increased after In doping. The EIS spectra declared that In-doping improves the rate of charge transfer for SnS thin films. The charge transfer resistance of In-doped SnS decreased compared to the undoped SnS thin film. Finally, according to the J-V characteristics, the conversion efficiency of the In-doped SnS thin films was higher than that of the un-doped SnS sample. Therefore, the optical and electrical performance of SnS thin films were improved due to In-doping.     

Crystal behavior of semicrystalline polystyrene‐block‐poly(l‐lactide) diblock copolymer in thin films with various structures

The crystal behavior of a semicrystalline polystyrene‐block‐poly(l ‐lactide) diblock copolymer in phase‐separated thin films with various thicknesses at different crystal temperatures has been investigated using atomic force microscopy and transmission electronic microscopy. Parallel and perpendicular lamellae could be obtained by annealing the thin films for different periods of time as reported previously (Chen et al., Macromolecules 40:6631 (2007)). At different temperatures, crystallization in thin films with parallel lamellar structure in the melt state gives dendrite crystals with orthorhombic structure, and the ordered structure in the melt is destroyed after crystallization. When crystallization occurs in thin films with perpendicular lamellar structure, crystal morphology and structure are greatly affected by the crystallization temperature (T_c). When T_c < T_g,ps, where T_g,ps is the glass transition temperature of a polystyrene block, crystallization is hardly confined within the lamellae. The morphology is preserved but the long period of the perpendicular lamellae is increased after crystallization. When T_c > T_g,ps, rod‐like crystals dominate the final morphology, and crystallinity destroys completely the structure in the melt.© 2012 Society of Chemical Industry     

Solution properties of poly(thiocarbonates) containing cyclic side chains

Poly(thiocarbonates) with cyclic side chains have been studied in the theta solvent 1,4-dioxane. The Mark-Houwink-Sakurada (MHS) relationships were established and the unperturbed dimensions determined. The conformational parameters were compared with those of other poly(thiocarbonates) and related polymers. It was found that the polymers containing cyclic groups present a more extended and rigid chain. A marked influence of the nature and structure of the side chain on the conformational parameters was found.     

Synthesis of poly(trioctylammonium p-styrenesulfonate) homopolymers and block copolymers by RAFT polymerization

A method to prepare sulfonated polystyrene-containing block copolymers has been investigated by neutralizing styrene sulfonic acid with trioctylamine to produce the hydrophobic monomer trioctylammonium p-styrenesulfonate (SS-TOA). This monomer was polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization to produce PSS-TOA homopolymers. A PSS-TOA homopolymer was then used as a macro-RAFT agent for the polymerization of styrene to prepare poly(trioctylammonium p-styrenesulfonate)-block-poly(styrene) (PSS-TOA-b-PS). These block copolymers could be ion-exchanged to produce either the hydrophilic sodium salt form of PSS or a hydrophobic quaternary ammonium salt. This approach will be useful for preparing PSS-containing block copolymers with a range of hydrophobic blocks for applications such as ion-exchange membranes.     

Preparation and characterization of thin films of the poly(p‐phenylene vinylene) semiconducting polymer

Conjugated polymers have been the subject of many studies because of their widespread applications in electronic and optoelectronic devices. Poly(p‐phenylene vinylene) is a leading semiconducting polymer in optical applications. This work is focused on the development of thin films of poly(p‐phenylene vinylene) by spin coating and their characterization with Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy to understand their changes. An empirical model has been developed to show the effect of the variables—the spin speed, polymer concentration, and spin time—on the film thickness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The synthesis of hyperbranched poly (amine-ester) and study on the properties of its UV-curing film

Firstly, the monomer of N, N-diethylol-3-amine methylpropionate was obtained via Michael addition of methyl acrylate and diethanolamine. Then the hyperbranched poly (amine-ester) (HBPE) was synthesized through pentaerythritol as core molecules and monomer as AB₂. HBPE was characterized by Fourier transform-infrared spectroscopy, hydrogen nuclear magnetic resonance (¹H-NMR) and elemental analysis. Methyl tetrahydrophthalic anhydride (MTHPA) is grafted to the hydroxyl groups of HBPE and then glycidyl methacrylate (GMA) is introduced to the structure of HBPE, which is obtained by the UV-curable hyperbranched prepolymer (HBPE-MTHPA-GMA). Ultraviolet-differential scanning calorimeter showed that the HBPE-MTHPA-GMA has high photocuring speed under photoinitiator. Furthermore, the films also show good impact strength, outstanding adhesive force and primary thermal stability.     

Orientation microstructure and properties of poly(propylene carbonate)/poly(butylene succinate) blend films

The blends of high molecular weight poly(propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt blended using triphenylmethane triisocyanate (TTI) as a reactive coupling agent. TTI also serves as a compatibilizer for the blends of PPC and PBS. The blend containing 0.36 wt % TTI showed that the optimal mechanical properties were, therefore, calendared into films with different degrees of orientation. The calendering condition, degree of orientation, morphologies, mechanical properties, crystallization, and thermal behaviors of the films were investigated using wide‐angle X‐ray diffraction, scanning electron microscopy, tensile testing, and differential scanning calorimetry (DSC) techniques. The result showed that the as‐made films exhibited obvious orientation in machine direction (MD). Both tensile strength in MD and the tear strength in transverse direction (TD) increased with increasing the degree of orientation. The orientation of the film also increased the crystallinity and improved the thermal properties of the PPC/PBS blend films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optical properties of simultaneous biaxially stretched poly(ethylene terephthalate) films

We offer a detailed study on the anisotropic optical properties in uni and simultaneous biaxially stretched Poly(ethylene terephthalate) (PET) films. Cast amorphous sheets of PET were stretched to a series of extension ratios in two mutually perpendicular directions at 80, 90, and 100°C. Additionally, 0selected films were subsequently “heat-set” by annealing with their width and lengths constrained. The principal refractive indices at sodium D wavelength of these, asstretched and heat-set films were obtained using a modified Abbe refractometer. The changes in the principal refractive indices with the processing history were correlated with the orientation of PET chains and phenyl plane normals, which were determined independently by wide angle X-ray (WAXS) pole figure technique.     

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.     

Optical, dielectric and thermal properties of nanoscaled films of polyalkylsilsesquioxane composites with star-shaped poly(ε-caprolactone) and their derived nanoporous analogues

Nanoscaled films of poly(methylsilsesquioxane-co-ethylenylsilsesquioxane) (PMSSQ-BTMSE) and polymethylsilsesquioxane (PMSSQ) were prepared from the respective soluble prepolymers, and their thermal, optical, and dielectric properties were characterized. The PMSSQ-BTMSE nanofilm containing an ethylenyl bridge comonomer unit BTMSE was found to be thermally more stable than the nanofilm of PMSSQ, a representative polyalkylsilsesquioxane. Further, in comparison to the PMSSQ film the PMSSQ-BTMSE film exhibits a larger refractive index and a larger dielectric constant but a smaller out-of-plane thermal expansion coefficient, when both prepolymers are cured under the same conditions. These characteristics of PMSSQ-BTMSE films are due to the ethylenyl bridge provided by the BTMSE comonomer unit, which promotes the formation of a tighter, more perfect network structure in cured PMSSQ-BTMSE films. Composite films were prepared by solution-blending the pore generator (referred to as the porogen), a star-shaped poly(ε-caprolactone), with the soluble prepolymers then drying the resulting solution, and the nature of their curing reactions and extent of porogen calcination were investigated. It was found that the thermal curing and calcination processes of the composite films successfully produce PMSSQ-BTMSE and PMSSQ films containing pores that are about 400 nm in diameter. It was confirmed that the presence of these generated nanopores significantly reduces the refractive indices and the dielectric constants of the dielectric films but increases their out-of-plane thermal expansivity, depending on the initial porogen loading. The porosities of the nanoporous dielectric films were estimated from the measured refractive indices. The surface topographies of these films were also investigated, giving information about the sizes of the pores generated in the films. It was also found that prior to calcination the presence of the porogen increases the refractive index and dielectric constant of the composite dielectric films because of its inherent high polarizability, and also increases the thermal expansivity of MSSQ-BTMSE composite films but very slightly decreases the thermal expansivity of MSSQ composite films. It is demonstrated that PMSSQ-BTMSE films and the related nanometer scale nanoporous films are candidates for use as low and ultra-low dielectric interlayers in the fabrication of advanced microelectronic devices.