Phase separation of PS/PVME blend films induced by capillary force

The phase behavior of a miscible PS/PVME (80/20, w/w) blend film in a confined geometry has been investigated at the annealing temperature much lower than the low critical solution temperature (LCST) of the blend. When the annealing temperature (52degreesC) is near the glass transition temperature of the blend (51.2degreesC), PVME-rich phase at the air-film surface under a microchannel forms smaller protrusion. When the annealing temperature is increased to 70degreesC, the protruding stripes, which are almost developed, are mainly composed of the mobile PVME-rich phase. These results reveal that the capillary force lead to the enrichment of PVME-rich phase at the air-polymer interface of a PDMS microchannel, that is, the capillary force lithography (CFL) can induce the phase separation of PS/PVME blend films.

Hole nucleation and growth induced by crystallization and microphase separation of thin semicrystalline diblock copolymer films

We have investigated the hole nucleation and growth induced by crystallization of thin crystalline-coil diblock copolymer films. Semicrystalline rodlike assemblies from neutral/selective binary solvent are used as seeds to nucleate crystallization at temperatures above the glass transition temperature (T-g) but below melting point (T-m). The crystallization of nanorods drives neighboring copolymer chains to diffuse into the growing nanorods. Depletion of copolymer chains yields hole nucleation and growth at the edge of the nanorods. Simultaneously, the polymer chains unassociated into the nanorods were oriented by induction from the free surface and the substrate, leading to limitation of the hole depth to the lamellar spacing, similar to20 nm. The holes, as well as the nanorods, grow as t(alpha), where t is the annealing time and a crossover in the exponent a. is found. The orientation and stretching of the copolymer chains by the surface and interface are believed to accelerate the crystallization, and in turn, the latter accelerates the growth rate of the holes. At T > T-m, the grains melt and the copolymer chains relax and flow into the first layer of the film.

Copolymers derived from bismaleimide oligomer with active solvent

An oligomer from 4, 4'-bis(maleimido)diphenyl methane and methylenedianiline were dissolved in active solvent N,N-dimethyl acrylamide in a solid content up to 50-70%; the solution was poured in a sheet-shaped module and irradiated b y Co-60 with the dose from 20 to 350 kGy at room temperature. The polymerized sheet was postcured at 180degreesC to obtain a transparent red-orange sheet with tensile strength above 100 MPa. The glass transition temperature before and after postcuring was around 100degreesC and 150-180degreesC, respectively. Styrene was used along with DMAA to decrease the water absorption for the copolymers.

Thermal mechanical and dynamic mechanical property of biphenyl polyimide fibers

High-performance polyimide fibers possess man), excellent properties, e.g., outstanding thermal stability and mechanical properties and excellent radiation resistant and electrical properties. However, the preparation of fibers with good mechanical properties is very difficult. In this report, a biphenvl polyimide from 3,3',4,4'-biphenyltetracarboxylic dianhydride and 4,4'-oxydianiline is synthesized in p-chlorophenol by one-step polymerization. The solution is spun into a coagulation bath of water and alcohol via dry-jet wet-spinning technology. Then, the fibers are drawn in two heating tubes. Thermal gravimetric analysis, thermal mechanical analysis, and dynamic mechanical analysis (DMA) are performed to study the properties of the fibers. The results show that the fibers have a good thermal stability at a temperature of more than 400degreesC. The linear coefficient of thermal expansion is negative in the solid state and the glass transition temperature is about 265degreesC. DMA spectra indicate that the tandelta of the fibers has three transition peaks, namely, alpha, beta, and gamma transition. The alpha and gamma transition temperature, corresponding to the end-group motion and glass transition, respectively, extensively depends on the applied frequency, while the beta transition does not.

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone.

Ordered droplet formation by thin polymer film dewetting on a stripe-patterned substrate

The dewetting process of thin polystyrene (PS) film on flat and stripe-patterned substrates is presented. Different dewetting processes were observed when the thin PS films annealed at above the glass transition temperature on these different kinds of substrates. The final dewetting on the flat substrate led to formation of polygonal liquid droplets, while on the stripe-patterned substrate, the droplets were observed to align at the centers of the stripes. A possible explanation for the dewetting process on the stripe-patterned substrate is proposed.

Poly(aryl ether)s containing ter- and pentafluorene pendants for efficient blue light emission

Four novel thermally stable poly(aryl ether)s, e.g., P3F, P5F, P2A3F, and P2A5K containing ter- or pentafluorene units in the side chains for efficient blue light emission have been designed and synthesized. All the polymers show the optical properties identical to the corresponding monomers and are amorphous with higher glass transition temperature (T-g) than their monomeric Counterparts. The polymer light-emitting diodes (PLEDs) were fabricated with the device structure of ITO/(PEDOT:PSS)/polymer/Ca/Al. The incorporation of diphenylamine group to oligofluorene terminals significantly reduces the hole-injection energy barrier in PLEDs. The devices based on P2A3F and P2A5F show the luminous efficiencies of 1.2 and 2.0 cd/A at a brightness of 300 cd/m(2) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.15, 0.13) and (0.19, 0.20), respectively. All these indicate that the high-performance light-emitting polymers can be synthesized with the traditional condensation polymerization through careful design of polymer structures.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Characterization and properties of biodegradable poly(hydroxyalkanoates) and 4,4-dihydroxydiphenylpropane blends: Intermolecular hydrogen bonds, miscibility and crystallization

Intermolecular hydrogen bonds, miscibility, crystallization and thermal stability of the blends of biodegradable poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-3HHx)] with 4,4-dihydroxydiphenylpropane (DOH2) were investigated by FTIR, C-13 Solid state NMR, DSC, WAXD and TGA. Intermolecular hydrogen bonds were found in both blend systems, which resulted from the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of DOH2. The intermolecular interaction between P(3HB-3HHx) and DOH2 is weaker than that between PHB and DOH2 owing to the steric hindrance of longer 3HHx side chains. Because of the effect of the hydrogen bonds, the chain mobility of both PHB and P(3HB-3HHx) components was limited after blending with DOH2 molecules. Single glass transition temperature depending on the composition was observed in all blends, indicating that those blends were miscible in the melt. The addition of DOH2 suppressed the crystallization of PHB and P(3HB-3HHx) components. Moreover, the crystallinity of PHB and P(3HB-3HHx) components also decreased with increasing DOH2 content in the blends.

Preparation and properties of ternary polyimide/SiO2/polydiphenyisiloxane composite films

A series of novel ternary polyimide/SiO2/polydiphenylsiloxane (PI/SiO2/PDPhS) composite films were prepared through co-hydrolysis and condensation between tetramethoxysilane, diphenyldimethoxysilane (DDS) and aminopropyltriethoxysilane-terminated polyamic acid, using an in situ sol-gel method. The composite films exhibited good optical transparency up to 30 wt% of total content of DDS and SiO2. SEM analysis showed that the PDPhS and SiO2 were well dispersed in the PI matrix without macroscopic separation of the composite films. TGA analysis indicated that the introduction of SiO2 could improve the thermal stability of the composite films. Dynamic mechanical thermal analysis showed that the composite films with low DDS content (5 wt%) had a higher glass transition temperature (T-g) than pure PI matrix. When the content of DDS was above 10 wt%, the T-g of the composite decreased slightly due to the plasticizing effect of flexible PDPhS linkages on the rigid PI chains. The composite films with high SiO2 content exhibited higher values of storage modulus. Tensile measurements also showed that the modulus and tensile strength of the composite films increased with increasing SiO2 content, and the composite films still retained a high elongation at break due the introduction of DDS.

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3-butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T-g) and the melting temperature (T-m) of PLA. Moreover, crystallinity of PLA increased with increasing the con-tent of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break.

Preparation and characterization of post-derivatives from functional polystyrene (ATRP) with p-nitroaniline-azomethine phenol and their thermal and optical study

The functional polystyrene, (Cl-PS)(2)-CHCOOCH2CH2OH ( designated as XPSt and coded P2) was prepared by ATRP at 130(0)C using CuCl and bipyridine as catalysts, 2,2-dichloro acetate-ethylene glycol (DCAG) as multifunctional initiator and THF as solvent. 4-Nitoroaniline azomethine-4' phenol (P1) as chromophores were covalently linked to the functional end groups of the polymer by using simple displacement reaction. The functional polystyrenes, namely XPSt (P2) and (PS)(2)-CHCOOCH2CH2OH, designated as X-PSt and coded P3 and their post-derivatives, namely, DXPSt (P4) and DX-PSt (P5) respectively were characterized by IR, NMR and UV spectroscopies, gel permeation chromatography (GPC) and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), polarising optical microscopy (POM) and XRD studies. DSC showed that incorporation of chromophores in the side chains of polymers towards the polystyrene moiety increases the rigidity of the polymer and subsequently, its glass transition temperature; however the incorporation of side chain towards the alcoholic functional group decreases the glass transition temperature. The post derivatives do not play any significant role to increase the thermal stability ( TGA).

Synthesis and characterization of polypropylene/montmorillonite nanocomposites via an in-situ polymerization approach

Polypropylene/montmorillonite (PP/MMT) nanocomposites were prepared by in-situ polymerization using a MMT/MgCl2/TiCl4-EB Ziegler-Natta catalyst activated by trietbylaluminum (TEA). The enlarged layer spacing of MMT was confirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components. X-ray photoelectron spectrometry (XPS) analysis proved that TiCl4 was mainly supported on MgCl2 instead of on the surface of MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXD patterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).

Novel polyimides derived from 2,3,3 ',4 '-benzophenonetetracarboxylic dianhydride

A series of polyimides (PIs) based on 2,3,3',4'-benzophenonetetracarboxylic dianhydride (2,3,3',4'-BTDA) and 3,3',4,4'-BTDA were prepared by the conventional two-step process. The properties of the 2,3,3',4'-BTDA based polyimides were compared with those of polyimides prepared from 3,3',4,4'-BTDA. It was found that PIs from 2,3,3,4'-BTDA have higher glass transition temperature and better solubility without sacrificing their thermal properties. Furthermore the theological properties of PMR-15 type polyimide resins based on 2,3,3',4'-BTDA showed lower melt viscosity and wider melt flow region (flow window) compared with those from 3,3',4,4'-BTDA. The structure-property relations resulted from isomerism were discussed.

Miscibility and hydrogen-bonding interactions in blends of carbon dioxide/epoxy propane copolymer with poly (p-vinylphenol)

The miscibility and hydrogen-bonding interactions of carbon dioxide and epoxy propane copolymer to poly(propylene carbonate) (PPC)/poly(p-vinylphenol) (PVPh) blends were investigated with differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The single glass-transition temperature for each composition showed miscibility over the entire composition range. FTIR indicates the presence of strong hydrogen-bonding interassociation between the hydroxyl groups of PVPh and the oxygen functional groups of PPC as a function of composition and temperature. XPS results testify to intermolecular hydrogen-bonding interactions between the oxygen atoms of carbon-oxygen single bonds and carbon-oxygen double bonds in carbonate groups of PPC and the hydroxyl groups of PVPh by the shift of C-1s peaks and the evolution of three novel O-1s peaks in the blends, which supports the suggestion from FTIR analyses.