Monte Carlo simulation of the aggregation of rod-flexible triblock copolymers in a thin film

The aggregation of rod-flexible ABA and BAB triblock (A was rod block and repulsive with block B) copolymers in a thin film was studied as a function of varying the rigidity (eta) and the length of the rod block by Monte Carlo simulation. The rigidity of block A was defined as eta = R-c/R-max in this study. R-c, was the end-to-end distance below which the conformation of the block was not allowed, whereas R-max, was the longest end-to-end distance that the block could be. If eta = 0 the block was flexible, whereas if eta = 1 the block was a straight rod. The simulation results showed that the ABA triblock copolymer film were likely to form lamella structure with increasing the rigidity (eta) of block A. The lamellas were parallel each other and perpendicular to the film surface. However, the aggregation of BAB triblock copolymers tended to change from lamella to cylinder structure with increasing the rigidity (eta) of block A. Typical lamella and cylinder co-exist structure was obtained at eta = 0.504 for the BAB copolymer film. On the other hand, the simulation results indicated that the film changed from disorder to order, then to disorder structure with increasing the relative length of B block for both ABA and BAB copolymer films.

Fabrication of a metal particle array based on a self-assembled template from a two-armed polymer

A two-armed polymer with a crown ether core self-assembles to produce macroporous films with pores perpendicularly reaching through the film down to the substrate. A possible assembling mechanism is discussed. The pore size can be conveniently adjusted by changing the solution concentration. These through-hole macroporous films provide a template for fabricating an array of Cu nanoparticle aggregates.

Ring-opening polymerization and block copolymerization of L-lactide with divalent samarocene complex

Divalent samarocene complex [(C5H9C5H4)(2)Sm(tetrahydrofuran)(2)] was prepared and characterized and used to catalyze the ring-opening polymerization of L-lactide (L-LA) and copolymerization of L-LA with caprolactone (CL). Several factors affecting monomer conversion and molecular weight of polymer, such as polymerization time, temperature, monomer/catalyst ratio, and solvent, were examined. The results indicated that polymerization was rapid, with monomer conversions reaching 100% within 1 h, and the conformation of L-LA was retained. The structure of the block copolymer of CL/L-LA was characterized by NMR and differential scanning calorimetry. The morphological changes during crystallization of poly(caprolactone) (PCL)-b-P(L-LA) copolymer were monitored with real-time hot-stage atomic force microscopy (AFM). The effect of temperature on the morphological change and crystallization behavior of PCL-b-P(L-LA) copolymer was demonstrated through AFM observation.

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Luminescence properties of lanthanide complexes doped in hybrid material from tetraethoxysilane and 3-glycidyioxyropyl-trimethoxysilane

Hybrid materials, containing in-situ synthesized lanthanide complexes with intense green light, have been prepared via sol-gel process. The luminescence properties and the decay times of as-synthesized samples were investigated. The excitation spectrum of the samples indicates the formation of complexes between terbium (III) and P-Sulfosalicylic acid. The hybrid materials that contain in-situ synthesized terbium complexes exhibit the characteristic emission bands of the rare earth ions. In addition, the effect of concentration of terbium on the luminescence properties as well as the thermal stability were also studied.

Self-assembly of star block copolymers by dynamic density functional theory

The dynamic mean-field density functional method, driven from the generalized time-dependent Ginzburg-Landau equation, was applied to the mesoscopic dynamics of the multi-arms star block copolymer melts in two-dimensional lattice model. The implicit Gaussian density functional expression of a multi-arms star block copolymer chain for the intrinsic chemical potentials was constructed for the first time. Extension of this calculation strategy to more complex systems, such as hyperbranched copolymer or dendrimer, should be straightforward. The original application of this method to 3-arms block copolymer melts in our present works led to some novel ordered microphase patterns, such as hexagonal (HEX) honeycomb lattice, core-shell HEX lattice, knitting pattern, etc. The observed core-shell HEX lattice ordered structure is qualitatively in agreement with the experiment of Thomas [Macromolecules 31, 5272 (1998)].

UV-Vis and surface photovoltage spectra of Fe2O3/polystyrene composite microspheres

Fe2O3 sol with the particle diameter of 3-5 nm was flocculated by the addition of SDS, and the flocculate formed was redispersed by the further addition of that surfactant. Thus the surfactant bilayer was formed on the surface of Fe2O3. The emulsion polymerization of styrene (St) adsolubilized oil the surfactant adsorbed bilayer was carried out by initiator potassium persulfate (KPS). The UV-Vis and surface photovoltage spectra (SPS) indicate that the Fe2O3 particles were encapsulated in polystyrene(PSt) successfully.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

Organic-phase enzyme electrode for phenolic determination based on a functionalized sol-gel composite

An amperometric biosensor for monitoring phenols in the organic phase was constructed by the silica sol-gel immobilization of tyrosinase on a glassy carbon electrode. The organic-inorganic hybrid materials with different sol-gel precursors and polymers were optimized, and the experimental conditions, such as the effect of the solvent, operational potential and enzyme loading were explored for the optimum analytical performance of the enzyme electrode. The biosensor can reach 95% of steady-state current in about 18 s, and the trend in the sensitivity of different phenols is as follows: catechol > phenol >p-cresol. In addition, the apparent Michaelis-Menten constants (K-m(app)) and the stability of the enzyme electrode were discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Confined crystallization behavior of PCL in organic-inorganic hybrid system

poly(epsilon-caprolactone) (PCL) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by sol-gel approach and the crystalline behavior of PCL in the silica networks has been investigated by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). The degree of PCL crystallinity in the PCL/SiO2 hybrid networks reduces with the increase of SiO2 content. PCL is in an amorphous state when the concentration of PCL is lower than 40wt% in the hybrid materials. The melting points of PCL in the networks are lower than that of pure PCL,but they almost have a same value. WAXD results show that when the PCL weight percentage is higher than 40wt% in the hybrid samples,part of PCL can crysatllize and the PCL crystallites are almost in a same size. That means the crystalline movement of PCL molecular chains is strictly confined by the porous gel. The crystalline PCL in the hybrid samples is relatively free from the composition of the materials, because the crystallization temperature and melting point of PCL of the samples are almost equal,and the crystalline PCL of different samples has the same crystalline structure and the same crystallite sizes L-110 and L-200, that means the crystalline part of PCL in the hybrid samples is unperturbed and the porous silica gel gives enough space for PCL to crystallize into the same crystalline structure and the same size crystallites.

Preparation, characterization and luminescent properties of MCM-41 type materials impregnated with rare earth complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.

Surface photovoltage spectra and photoelectrochemical properties of semiconductor-sensitized nanostructured TiO2 electrodes

Three kinds of TiO2 nanostructured thin films and their CdS-sensitized films, consisting of different sizes of TiO2 nanoparticles prepared with different methods, have been investigated. The surface photovoltage spectra (SPS) measurements indicate that the density of surface states on TiO2 is likely dependent upon the details of prepared methods. TiO2 particles prepared from basic sol have more surface states than that prepared from acidic sol. When the TiO2 thin films prepared using the TiO2 sols were sensitized by CdS particles, the SPS responses relative to the surface states on TiO2 from 350 to 800 nm were decreased. The photoelectrochemical properties of nanostructured TiO2 electrodes suggest that the fewer the surface states and the smaller the particle sizes of TiO2, the larger the photocurrent response. For CdS sensitized TiO2 thin film electrode, it is shown that the semiconductor sensitization is an efficient way to decrease the influence of surface states on the charge separation, and can improve the intensity of photocurrent response. (C) 2001 Elsevier Science B.V. All rights reserved.

Crystallization behavior of PCL in hybrid confined environment

Poly(epsilon -caprolactone) (PCL) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by the sol-gel method. The crystallization behavior of PCL in silica networks has been investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The degree of PCL crystallinity in PCL/SiO2 hybrid networks reduces with increase of SiO2. PCL is in an amorphous state when the concentration of PCL is lower than 40wt% in the hybrid system. The melting point of PCL in the networks is lower than, but close to that of pure PCL. WAXD and SEM results show that the crystalline behavior of PCL in PCL/SiO2 hybrid system is strictly confined. (C) 2001 Elsevier Science Ltd. All rights reserved.

Controlled synthesis of L-lactide-b-epsilon-caprolactone block copolymers using a rare earth complex as catalyst

Well-defined block copolymers of L-lactide-b-epsilon-caprolactone were synthesized by sequential polymerization using a rare earth complex, Y(CF3COO)(3)/Al(iso-Bu)(3), as catalyst system. The compositions of the block copolymers could be adjusted by manipulating the feeding ratio of comonomers. The characterizations by GPC, H-1 NMR, C-13 NMR, and DSC displayed that the block copolymer, poly(epsilon-caprolactone-b-L-lactide) [P(CL-b-LLA)], had a narrow molecular weight distribution and well-controlled sequences without random placement.