Lattice Boltzmann study of hydrodynamic effects in lamellar ordering process of two-dimensional quenched block copolymers

By incorporating self-consistent field theory with lattice Boltzmann method, a model for polymer melts is proposed. Compared with models based on Ginzburg-Landau free energy, our model does not employ phenomenological free energies to describe systems and can consider the chain topological details of polymers. We use this model to study the effects of hydrodynamic interactions on the dynamics of microphase separation for block copolymers. In the early stage of phase separation, an exponential growth predicted by Cahn-Hilliard treatment is found. Simulation results also show that the effect of hydrodynamic interactions can be neglected in the early stage.

Temperature Dependence of Surface Composition and Morphology in Polymer Blend Film

Thin films of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blend can phase separate upon heating to above its critical temperature. Temperature dependence of the surface composition and morphology in the blend thin film upon thermal treatment was studied using in situ X-ray photoelectron spectroscopy (XPS) and in situ atomic force microscopy (AFM). It was found that in addition to phase separation, the blend component preferentially diffused to and aggregated at the surface of the blend film, leading to the variation of surface composition with temperature. At 185 degrees C, above the critical temperature, the amounts of PMMA and SAN phases were comparable.

Studies on coarsening of microdomains in binary polymer mixtures by Lattice Boltzmann methods

An improved free energy approach Lattice Boltzmann model(LBM) is proposed by introducing a forcing term instead of the pressure tensor. This model can reach the proper thermodynamic equilibrium after enough simulation time. On the basis of this model, the phase separation in binary polymer mixtures is studied by applying a Flory-Huggins-type free energy. The numerical results show good agreement with the analytic coexistence curve. This model can also be used to study the coarsening of microdomains in binary polymer mixtures at the early and intermediate stages.

Morphological transition of dry vesicles into onion-like multilamellar micelles induced through heating at high temperature

In this Letter, we report the morphological transition of dry block copolymer vesicles into onion-like multilamellar micelles induced through heating. When the temperature is higher than the glass transition temperature of block copolymer, the vesicles can collapse, and finally form onion-like multilamellarmicelles via micro phase separation. This phenomenon is observed in both A-B and A-B-A block copolymer vesicles, indicating that the technique used in this study can be an alternative method to synthesize multilamellar micelles.

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.

Defect evolution and hydrodynamic effects in lamellar ordering process of two-dimensional quenched block copolymers

The effects of hydrodynamic interactions on the lamellar ordering process for two-dimensional quenched block copolymers in the presence of extended defects and the topological defect evolutions in lamellar ordering process are numerically investigated by means of a model based on lattice Boltzmann method and self-consistent field theory. By observing the evolution of the average size of domains, it is found that the domain growth is faster with stronger hydrodynamic effects. The morphological patterns formed also appear different. To study the defect evolution, a defect density is defined and is used to explore the defect evolutions in lamellar ordering process. Our simulation results show that the hydrodynamics effects can reduce the density of defects. With our model, the relations between the Flory-Huggins interaction parameter chi, the length of the polymer chains N, and the defect evolutions are studied.

Pore-filling membrane for direct methanol fuel cells based on sulfonated poly(styrene-ran-ethylene) and porous polyimide matrix

We have synthesized a porous co-polyimide film by coagulating a polyimide precursor in the non-solvent and thermal imidization. Factors affecting the morphology, pore size, porosity, and mechanical strength of the film were discussed. The porous polyimide matrix consists of a porous top layer and a spongy sub-structure with micropores. It is used as a porous matrix to construct sulfonated poly(styrene-ran-ethylene) (SPSE) infiltrated composite membrane for direct methanol fuel cell (DMFC) application. Due to the complete inertness to methanol and the very high mechanical strength of the polyimide matrix, the swelling of the composite membrane is greatly suppressed and the methanol crossover is also significantly reduced, while high proton conductivity is still maintained. Because of its higher proton conductivity and less methanol permeability, single fuel cell performance test demonstrated that this composite membrane outperformed Nafion membrane.

Solvent Vapor-Induced Self Assembly and its Influence on Optoelectronic Conversion of Poly(3-hexylthiophene): Methanofullerene Bulk Heterojunction Photovoltaic Cells

Nanoscale-phase separation of electron donor/acceptor blends is crucial for efficient charge generation and collection in Polymer bulk heterojunction photovoltaic cells. We investigated solvent vapor annealing effect of poly(3-hexylthiophene) (P3HT)/methanofullerene (PCBM) blend oil its morphology and optoelectronic properties. The organic solvents of choice for the treatment have a major effect oil the morphology of P3HT/PCBM blend and the device performance. Ultraviolet-visible absorption spectro,;copy shows that specific solvent vapor annealing can induce P3HT self-assembling to form well-ordered structure; and hence, file absorption in the red region and the hole transport are enhanced. The solvent that has a poor Solubility to PCBM Would cause large PCBM Clusters and result in a rough blend film. By combining an appropriate solvent vapor treatment and post-thermal annealing of the devices, the power conversion efficiency is enhanced.

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO2-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et3N) in the presence of CO2 under solventless conditions at 80 degrees C. The catalysts are not soluble in the organic phase in the absence Of CO2 and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the dissolution of the I'd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect Of CO2 pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO2 molecules dissolved. Thus, the maximum conversion appears at a CO2 pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water.

Nanoelectrode ensembles based on semi-interpenetrating network of carbon nanotubes

A method for preparing nanoelectrode ensembles based on semi-interpenetrating network (SIN) of multi-walled carbon nanotubes (MWNTs) on gold electrode through phase-separation method is initially proposed. Individual nanoelectrode owns irregular three-dimensional MWNTs networks, which is denoted as SIN-MWNTs. On the as-prepared SIN-MWNTs nanoelectrode ensembles, the assembled MWNTs clusters in nanoscale serve as individual nanoelectrode and the electroinactive lipid networks located on the top of alkanethiol monolayer are used as a shielding layer. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy (SEM) were used to characterize the as-prepared SIN-MWNT nanoelectrode ensembles. Experimental results indicate that the well-defined nanoelectrode ensembles were prepared through self-assembly technology. Meantime, sigmoid curves in a wide scanning range can be obtained in CV experiments. This study may pave the way for the construction of truly nanoscopic nanoelectrode arrays by bottom-up strategy.

Order-disorder transition in eicosylated polyethyleneimine comblike polymers

Order-disorder transition (ODT) behavior in eicosylated polyethyleneimine (PEI20C) comblike polymer obtained by grafting n-eicosyl group on polyethyleneimine backbone was systematically investigated by the combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy as well as solid-state high resolution nuclear magnetic resonance (NMR) spectroscopy. DSC investigations showed two obvious transitions, assigned to the transitions (1) from orthorhombic to hexagonal and (2) from hexagonal to amorphous phase, respectively. These transitions are induced by the variations of alkyl side chain conformation and packing structure with temperature changing, which consequently lead to the destruction of original phase equilibrium. The ODT behavior can also be confirmed by spectroscopic methods like WAXD, FTIR and NMR. The ordered structure and the transition behavior of the alkyl side chains confined by the PEI backbone are obviously different from those of pristine normal alkanes. The transition mechanism of ODT and the origin of the phase transition behavior in PEI20C comblike polymer were discussed in detail in this paper.

Enhanced electrical conductivity of highly crystalline polythiophene/insulating-polymer composite

Poly(3-butylthiophene) (P3BT)/insulating-polymer composites with high electrical conductivity have been prepared directly from the solution. These composites exhibit much higher conductivity compared to pure P3BT with the same preparation method provided that P3BT content is higher than 10 wt %. Morphological studies on both the pure P3BT and the composites with insulating polymer show that P3BT highly crystallizes and develops into whisker-like crystals. These nanowires are homogeneously distributed within the insulating polymer matrix and form conductive networks, which provide both extremely large interface area between conjugated polymer and insulating polymer matrix and highly efficient conductive channels through out the whole composite. In contrast, the conductivity enhancement of P3HT/PS composite is not so obvious and drops down immediately with increased PS content due mainly to the absence of highly crystalline whisker-like crystals and much larger scale phase separation between the components. The results presented here could further illuminate the origin of conductivity formation in organic semiconducting composites and promote applications of these polymer semiconductor/insulator composites in the fields of organic (opto-)electronics, electromagnetic shielding, and antistatic materials.

Confined intra-molecular clustering in orientated polyethylene after annealing

Deuterated polyethylene tracer molecules with small amount of branches (12 C2H5- branches per 1000 backbone carbon atoms) were blended with a hydrogenated polyethylene matrix to form a homogenous mixture. The conformational evolution of the deuterated chains in a stretched semi-cry stall me film was observed via online small angle neutron scattering measurements during annealing at high temperatures close to the melting point. Because the sample was annealed at a temperature closely below its melting point, the crystalline lamellae were only partially molten and the system could not fully relax. The global chain dimensions were preserved during annealing. Recrystallization of released polymeric chain segments allows for local phase separation thus driving the deuterated chain segments into the confining interlamellar amorphous layers giving rise to an interesting intra-molecular clustering effect of the long deuterated chain. This clustering is deduced from characteristic small angle neutron scattering patterns. The confined phase separation has its origin in primarily the small amount of the branches on the deuterated polymers which impede the crystallization of the deuterated chain segments.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.