Summary: In this study high‐refractive‐index polyimide/titania hybrid optical thin films were successfully prepared using a sol‐gel process combined with spin coating and multistep baking. The hybrid thin films were prepared from a soluble polyimide, a coupling agent, and a titania precursor. Transparent hybrid thin films can be obtained at TiO2 content as high as 40 wt.‐%. The FE‐SEM results suggest that the TiO2 particles in the hybrid thin films have diameters in the nanometer range. The thermal decomposition temperatures of the prepared hybrid materials are above those of the respective polyimide except for the highest TiO2 content hybrids. The refractive indices at 633 nm of the prepared hybrid thin films increase linearly from 1.66 to 1.82 with increasing TiO2 content. The excellent optical transparency, thermal stability, and tunable refractive index provide the potentials of the polyimide/titania hybrid thin films in optical applications.
Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO2/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.
The viscoelasticity of two thermally crosslinked polymer coatings was examined in terms of relaxation of the applied stress after a sudden strain. Two different transient methods were utilized: flat‐ended cylindrical indentation testing of a polymer film on a rigid substrate and tensile testing of a corresponding free‐standing polymer film. The correlation between tensile and indentation tests was studied. The mechanical response of a viscoelastic layer deposited on a rigid substrate was investigated as a function of indentation depth. There was good agreement between the results of the tensile and indentation tests for thick film layers at moderate indentation depths. The findings indicate that the substrate influences the coating performance by reducing the viscous contribution to the stress response and amplifying the magnitude of the equilibrium modulus for large indentation depths. The indentation method utilized here was shown to be a potentially suitable tool for the determination of Poisson's ratio of polymer films.
Coaxial electrospinning using surfactants as sheath fluid for preparing high‐quality polymer nanofibers is studied. PAN nanofibers are fabricated using this process with Triton X‐100 solutions in DMF. FESEM demonstrates that the Triton X‐100 solution has a significant influence on the quality of the nanofibers. The nanofiber diameters can be controlled by adjusting the concentration of Triton X‐100 in the sheath fluids with a scaling law D = 640 C?0.32. The mechanism of the influence of Triton X‐100 solutions on the formation of PAN fibers is discussed and it is demonstrated that coaxial electrospinning with surfactant solution is a facile method for achieving high‐quality polymer nanofibers.
Summary: A novel phosphorus‐containing polymeric retardant, WLA‐3, was synthesized from phenylphosphonic dichloride (PPD) and 2‐(6‐oxido‐6H‐dibenz〈c,e〉〈1,2〉oxaphosphorin‐6‐yl) 1, 4‐benzenediol (ODOPB). The flame‐retardant element, phosphorus, was bonded both in the main chains and in the pendant chains of flame‐retardant polymer molecules, and reached a content of 13.8%. The high phosphorus content and rich aryl group structures of WLA‐3 contribute an excellent flame retardancy to poly(ethylene terephthalate) (PET) without a considerable decrease of mechanical properties. WLA‐3 is also very effective in improving flame retardancy of epoxy resin and unsaturated polyester.
Poly(methyl‐co‐trifluoropropyl)silsesquioxanes (P(M‐co‐TFP)SSQs) were prepared using methyltrimethoxysilane (MTMS) and trifluoropropyltrimethoxysilane (TFPTMS). The molecular weight, microstructure of the copolymers and properties of their thin films have been changed by adjusting reaction parameters such as the molar ratio of water to silane, the molar ratio of catalyst to silane, reaction time, solvent content, and temperature. The refractive index of the copolymer thin film decreased from 1.404 to ca. 1.348 as curing temperature was increased to 420 °C. The dielectric constant of the film decreased with an increase of the molecular weight of the copolymer, and the lowest dielectric constant obtained was ca. 2.2. Hardness and elastic modulus of the thin films were 0.7 and 5 GPa, respectively. Crack velocity was measured to be 10?11 m/s at the film thickness of around 0.9 μm under aqueous environment.
Summary: In this paper, we describe the use of artificial opals from polymer beads as effect pigments in transparent industrial and automotive coatings. For this purpose, we synthesized monodisperse colloids from fluorinated methacrylates by surfactant‐free emulsion polymerization. The fluorinated monomers, in combination with crosslinking, lead to a refractive index contrast, thermal stability, and solvent resistivity necessary for use as effect pigments. After crystallization of the monodisperse polymer beads, crystal flakes with iridescent colors can be obtained. The crystal flakes can act as effect pigments in various transparent industrial and automotive coatings. Due to photonic crystal behavior of effect pigments, color flops up to 100 nm are observed.
Crystal flakes of CS ‐7 as effect pigments in a transparent coating. The diameter of the tube is 5 mm. 相似文献
A microfluidic system was designed, fabricated and implemented to study the behavior of polyelectrolyte capsules flowing in microscale channels. The device contains microchannels that lead into constrictions intended to capture polyelectrolyte microcapsules which were fabricated with the well‐known layer‐by‐layer (LbL) assembly technique. The behavior of hollow capsules at the constrictions was visualized and the properties of the capsules were investigated before and after introduction into the device.
Time series of video frames showing capsules being compressed into a constriction. 相似文献
Electrically conducting films containing AgNws, hydrophilic and hydrophobic resins were prepared. FT‐IR reveals that the interface between the AgNws and epoxy could be successfully modified by APTES. XPS shows that the AgNws were attracted by hydrogen bonds of ? NH2 and ? NH? groups after APTES modification. SEM analysis shows that the AgNws were well dispersed in the resin. The AgNws were also blended with hydrophilic and acrylic resins, and the resulting blends were compared with AgNws/epoxy blends. Results show that AgNw/PVA‐resin films possess the lowest surface electrical resistance. The AgNw/PVA‐resin and silane‐modified AgNw/epoxy resin conductive films possess a similar electrical percolation threshold.
The fabrication and characterization of a hybrid polymer p‐n junction‐type thin film via electropolymerization of NPs and a precursor polymer is described. Blends of TiO2 NPs, CdSe NCs, Cbz‐COOH, and PVK were utilized to enable electrochemical deposition on ITO glass substrates. Spectroscopic, microscopic, and wetting measurements confirmed thin film fabrication. CV yielded a CPN nanocomposite with electropolymerized (i.e., crosslinked) carbazole units embedding CdSe NCs. Absorption and emission measurements confirmed a charge transfer mechanism between the crosslinked carbazole and the NCs resulting in a p‐n junction‐type thin film on ITO; with the observed quenching of CdSe NC emission. Several possible applications of such thin films are also discussed.
Summary: Single‐site coordination polymerization catalysts are considered one of the most important developments on the technology of olefin polymerization during the last two decades. Among the several new capabilities of these catalysts is the ability to produce polymer molecules having narrow molecular weight distribution and long chain branches. These advances in polymer synthesis have stimulated the development of mathematical models to describe and predict several features of their molecular architectures. Many modeling techniques have been used for this purpose, including instantaneous distributions, population balances, the method of moments, and Monte Carlo simulations. This article reviews the mathematical models developed over the last decade to quantify the microstructure of polymers made with single‐site catalysts with special emphasis on the mechanism of long chain branch formation by terminal branching.
Nowadays, nanoporous films are widely employed in biochemical applications or in opto‐photonic devices such as displays, solar cells, or light‐guiding systems. In particular, the technological feasibility of nanoporous layers with low refractive indices has recently enabled the development of high‐efficiency anti‐reflection coatings. In this paper, we report on hybrid polymer nanoporous films that can be fabricated in a single coating step with an industrial aqueous‐based method on very large surfaces. Both high transparency and low refractive index are simultaneously achieved over the entire visible spectrum. We eventually demonstrate the potential of such films for broadband AR applications by combining them in a graded‐index multilayer that reduces the surface reflectivity of a polymer substrate from 10% to few ‰.
The aim of the present contribution is to understand how ionic strength, brought by the addition of salt to laponite/PEO nanocomposite dispersions, influences the texture and adhesion characteristics at nano‐ and microscales in multilayered nanocomposite films prepared from such dispersions. At the nano‐scale, SAXS and XRD measurements indicated that the clay platelets orient parallel to the film plane and that the polymer chains intercalate the clay platelets regardless of salt addition. A gradual transition from an agglomerated structure, containing polymer‐rich and clay‐rich domains, to a fine‐balanced structure with smaller distinct details without excess PEO was observed, via AFM, on the exposed edges of cryo‐microtomed films with increasing ionic strength.
Transparent light‐emitting hybrid materials are produced by UV curing of acrylic resins containing silica precursors and photoluminescent [Cu4I4L4] clusters. Acrylic double‐bond conversion is followed by means of FT‐IR spectroscopy, and optical measurements are performed on cured films showing a high transparency of the films up to a content of 30 wt% TEOS and a bright luminescence with a maximum of emission centered at 565 nm (yellow‐orange). This study shows the possibility to obtain new advanced materials in which functional properties such as photoluminescence and scratch resistance are successfully conjugated in a hybrid film that maintains high transparency.
Summary: The new nanocomposites consisting of metallocene poly(ethylene‐octene) (POE), silicate clay and wood flour (WF) were prepared by means of a melt blending method. In addition, maleic anhydride grafted poly(ethylene‐octene) (POE‐g‐MAH) was studied as an alternative to POE. The samples were characterized by XRD, FT‐IR spectroscopy, DSC, TGA, SEM, and mechanical testing. Based on the consideration of thermal and mechanical properties, it was found that the clay content of 11 wt.‐% was optimal for the preparation of POE‐g‐MAH/clay nanocomposites. The POE‐g‐MAH/clay/WF hybrid could obviously improve the mechanical properties of POE‐g‐MAH/WF hybrid since the former had the smaller WF phase size (being always less than 1.5 µm), the Si? O? C bond and the nanoscale dispersion of silicate layers in the polymer matrix. The biodegradation studies showed that the mass of hybrids reduced by about the content of WF. The new POE‐g‐MAH/clay/WF nanocomposites produced from our laboratory can provide a plateau tensile strength at break when the WF content was up to 50 wt.‐%.
Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).
SEM photograph of silica particles prepared through capillary plate membrane. 相似文献
In this work, a novel method for the preparation of polymer/semiconductor nanocomposites is presented. The nanocomposite is directly prepared from a suspension of nanocrystalline silicon (nc‐Si) in bulk vinyl monomers (acrylates) and focused heating of the nc‐Si by irradiation with a pulsed laser at 532 nm wavelength. The silicon nanocrystals are the inorganic component of the composite and simultaneously act as initiation points of the free radical polymerization forming the hybrid composite. By this method, patterned nanocomposite films with thicknesses up to ≈250 µm can be readily prepared. Furthermore, the polymerization kinetics were investigated for different reaction conditions such as irradiation time, laser intensity, nc‐Si content, and addition of radical initiators.
This article reports on mechanical properties of electron beam cured tripropylene glycol diacrylate (TPGDA) and propoxylated glycerol triacrylate (GPTA) films. This study has been motivated by the need to have direct access to those properties for analyzing the thermo‐mechanical behavior and electro‐optical properties of polymer dispersed liquid crystal systems in general, and systems made either of TPGDA or GPTA and low molecular weight liquid crystals in particular. Representative examples of these systems are considered in this work. The effects of the degree of crosslinking on the mechanical strength of the polymer network are analyzed by considering different doses of the electron beam irradiation. As the radiation dose increases, the mechanical strength of the film is enhanced. Addition of a small amount of liquid crystals leads to remarkable plasticizing effects.
Young modulus and rubbery state modulus as a function of EB dose for cured TPGDA films. The filled symbols represent the Young modulus and the open symbols represent the rubbery state modulus. Circles are for pure TPGDA and squares are for TPGDA/E7 mixture with 15 wt.‐% E7. 相似文献
The effectiveness of electrospinning as a simple approach to disperse POSS into a polymer matrix at a nm‐level has been assessed. Electrospun and cast films were prepared by dissolving CA and epoxycyclohexylisobutyl POSS in the solvent mixture acetone/DMAc. The membranes were characterized by SEM, TEM and WAXD. Whereas films produced by casting showed µm‐sized POSS crystals, thus suggesting a small affinity between the polymer matrix and the POSS molecules, those prepared by electrospinning were characterized by a nanometric POSS distribution. This is explained by considering the peculiar solvent evaporation mechanism, occurring during the electrospinning process, which allows to produce nanofibers characterized by a silsesquioxane dispersion similar to that present in solution.
Summary: A new method to synthesize polyimide (PI)/silica nanohybrids has been presented. It uses silicic acid oligomer as the silica precursor, which was obtained by extracting with tetrahydrofuran (THF) from PH‐adjusted water glass. The films of PI/silica nanohybrids remained transparent even at high silica content due to the formation of nanometer‐scaled SiO2 particles at the addition of γ‐aminopropyltriethoxysilane (APTES). In comparison with pure PI, PI/silica hybrids showed improved thermal stability and mechanical properties, and lower linear coefficients of thermal expansion (CTEs). The glass transition temperatures of the hybrids were increased with increasing content of silica or APTES as a result of the increasing limitation to the movements of the PI backbone.
