Fabrication and Characterization of Two‐Photon Polymerized Features in Colloidal Crystals

The fabrication and characterization of two‐photon polymerized features written within and outside of colloidal crystals is presented. Two‐photon polymerization (TPP) response diagrams are introduced and developed to map the polymerization and damage thresholds for features written via modulated beam rastering. The use of tris[4‐(7‐benzothiazol‐2‐yl‐9,9‐diethylfluoren‐2‐yl)phenyl]amine (AF‐350) as an initiator for TPP is demonstrated for the first time and TPP response diagrams illustrate the polymerization window. These diagrams also demonstrate that the polymerization behavior within and outside of colloidal crystals is similar and electron microscopy reveals nearly identical resolution. Fluorescence confocal microscopy further enables visualization of non‐self‐supporting, three‐dimensional TPP features within self‐assembled photonic crystals. Finally, microspot spectroscopy is collected from a two‐photon feature written within a colloidal crystal and this is compared with simulation.     

Synthesis and Properties of Photoisomerizable Derivatives of Isosorbide and Their Use in Cholesteric Filters

This paper describes the synthesis of photoisomerizable derivatives of isosorbide. These derivatives contain a stilbene or cinnamate moiety and can therefore be used as photoisomerizable chiral compounds in cholesteric liquid‐crystalline mixtures. The reflection wavelength of cholesteric layers made from these mixtures is increased by UV irradiation due to the fact that the Z‐isomers of these derivatives exhibit a lower helical twisting power than the corresponding E‐isomers. The cinnamate derivatives are very suitable for use in cholesteric color filters that find application in liquid‐crystal displays.     

Determination of polymer–polymer interaction parameters using inverse gas chromatography

A modified method is discussed that is based on Farooque and Deshpande's method to obtain polymer–polymer interaction parameters using inverse gas chromatography (IGC) data. In the Farooque and Deshpande method, the ratio of the difference of probe–polymer interaction parameters between two polymers and the probe volume [(χ₁₂ ? χ₁₃)/V₁] is used as the abscissa. In the modified method, the ratio [(?₂χ₁₂ + ?₃χ₁₃)/V₁] is used as the abscissa. Experimental data previously reported for a poly(?‐caprolactone)‐polyepichlorohydrin (PCL/PECH) blend and a poly(ethyl acrylate)‐poly(vinyl propionate) (PEA/PVPr) blend are analyzed. It is found that the slopes obtained by the new method had smaller deviations from the theoretical values than the Farooque and Deshpande method. The standard deviations of both slopes and intercepts obtained from the new method are also smaller. Using the new method, the polymer–polymer interaction parameters obtained from the intercept are negative numbers for the PCL/PECH system and very small positive numbers for PEA/PVPr. Explanations are given for the probe and concentration dependency of the polymer–polymer interaction parameters that are generally observed in IGC studies. A new method for selecting the best probe for calculating the interaction parameter is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 671–680, 2003     

In situ polymerization and characterization of polyester‐based polyurethane/nano‐silica composites

Polyester‐based polyurethane/nano‐silica composites were obtained via in situ polymerization and investigated by Fourier‐transform infrared spectroscopy (FTIR), or FTIR coupled with attenuated total reflectance (FTIR‐ATR), Transmission electron microscopy (TEM), atomic force microscopy (AFM), an Instron testing machine, dynamic mechanical analysis (DMA) and ultraviolet‐visible spectrophotometry (UV‐vis). FTIR analysis showed that in situ polymerization provoked some chemical reactions between polyester molecules and nano‐silica particles. FTIR‐ATR, TEM and AFM analyses showed that both surface and interface contained nano‐silica particles. Instron testing and DMA data showed that introducing nano‐silica particles into polyurethane enhanced the hardness, glass temperature and adhesion strength of polyurethane to the substrate, but also increased the resin viscosity. UV‐vis spectrophotometry showed that nano‐silica obtained by the fumed method did not shield UV radiation in polyurethane films. Copyright © 2003 Society of Chemical Industry     

Towards General Guidelines for Aligned,Nanoscale Assemblies of Hairy‐Rod Polyfluorene

This account highlights recent progress towards understanding the complex hierarchical levels of solid‐state structure in a prototypical helical hairy‐rod polyfluorene, poly[9,9‐bis(2‐ethylhexyl)fluorene‐2,7‐diyl] (or PF2/6). This branched‐side‐chain containing polyfluorene undergoes a systematic intermolecular self‐assembly and liquid‐crystalline phase behavior in combination with uniaxial and biaxial alignment. The latter processes yield full three‐dimensional orientation of the crystallites and polymer chains. Also reviewed are the impact of the molecular structure and phase behavior on surface morphology, anisotropic film formation, and, ultimately, the overall impact of these physical attributes on optical constants. This particular polyfluorene also represents a model system for demonstrating the applicability of mean‐field theory in detailing the self‐organization of aligned hairy‐rod block‐copolymer systems. These results of PF2/6 are compared to those of other archetypical π‐conjugated hairy‐rod polymers. General guidelines of how molecular weight influences nanostructure, phase behavior, alignment, and surface morphology are given.     

Boundary knot method for 2D and 3D Helmholtz and convection–diffusion problems under complicated geometry

The boundary knot method (BKM) of very recent origin is an inherently meshless, integration‐free, boundary‐type, radial basis function collocation technique for the numerical discretization of general partial differential equation systems. Unlike the method of fundamental solutions, the use of non‐singular general solution in the BKM avoids the unnecessary requirement of constructing a controversial artificial boundary outside the physical domain. The purpose of this paper is to extend the BKM to solve 2D Helmholtz and convection–diffusion problems under rather complicated irregular geometry. The method is also first applied to 3D problems. Numerical experiments validate that the BKM can produce highly accurate solutions using a relatively small number of knots. For inhomogeneous cases, some inner knots are found necessary to guarantee accuracy and stability. The stability and convergence of the BKM are numerically illustrated and the completeness issue is also discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

Decreasing miscibility with greater heterogeneity in ternary polymer blend: poly(cyclohexyl methacrylate), poly(α‐methyl styrene) and poly(4‐methyl styrene)

A ternary blend system comprising poly(cyclohexyl methacrylate) (PCHMA), poly(α‐methyl styrene) (PαMS) and poly(4‐methyl styrene) (P4MS) was investigated by thermal analysis, optical and scanning electron microscopy. Ternary phase behaviour was compared with the behaviour for the three constituent binary pairs. This study showed that the ternary blends of PCHMA/PαMS/P4MS in most compositions were miscible, with an apparent glass transition temperature (T_g) and distinct cloud‐point transitions, which were located at lower temperatures than their binary counterparts. However, in a closed‐loop range of compositions roughly near the centre of the triangular phase diagram, some ternary blends displayed phase separation with heterogeneity domains of about 1 µm. Therefore, it is properly concluded that ternary PCHMA/PαMS/P4M is partially miscible with a small closed‐loop immisciblity range, even though all the constituent binary pairs are fully miscible. Thermodynamic backgrounds leading to decreased miscibility and greater heterogeneity in a ternary polymer system in comparison with the binary counterparts are discussed. © 2003 Society of Chemical Industry     

Deep‐UV Photochemistry and Patterning of (Aminoethylaminomethyl)phenethylsiloxane Self‐Assembled Monolayers

The 193 nm photochemistry of (aminoethylaminomethyl)phenethylsiloxane (PEDA) self‐assembled monolayers (SAMs) under ambient conditions is described. The primary photodegradation pathways at low exposure doses (< 100 mJ cm^–2) are benzylic C–N bond cleavage (ca. 68 %), with oxidation of the benzyl C to the aldehyde, and Si–C bond cleavage (ca. 32 %). Amine‐containing photoproducts released from the SAM during exposure remain physisorbed on the surface, where they undergo secondary photolysis leading to their complete degradation and removal after ca. 1200 mJ cm^–2. NaCl(aq) post‐exposure rinsing removes the physisorbed materials, showing that degradation of the original PEDA species (leaving Si–OH) is substantially complete after ca. 450 mJ cm^–2. Consequently, patterned, rinsed PEDA SAMs function as efficient templates for fabrication of high‐resolution, negative‐tone, electroless metal and DNA features with good selectivity at low dose (i.e., ca. 400 mJ cm^–2) via materials grafting to the intact amines remaining in the unirradiated PEDA SAM regions.