Effect of flow on solutions of rod-coil block co-polymers

An elongational flow field is imposed on a solution of block copolymers consisting of semirigid macromolecules with rigid, rodlike sequences of units in combination with random coil (flexible) units. The problem is formulated according to the lattice treatment of Matheson and Flory. In this formulation, the system consists of rigid blocks whose lengths and locations are fixed by the structure within each macromolecule. These blocks are separated by random coiled units. An excess free energy other than the equilibrium Gibbs free energy of the quiescent solution has to be considered due to the flow field that tends to align the rods. This excess free energy is calculated from the potential energy of rods when a steady-state, homogeneous and irrotational flow field is applied to the solution. The effects of composition, polymer-solvent interaction, size of the co-polymer and flow rates are investigated. Depending on the size and number of rods, some of the chains studied exhibit a biphasic region at equilibrium that shifts to lower concentrations with increasing flow. Longer chains with shorter rods that are isotropic at equilibrium, exhibit a biphasic region at finite values of flow. The degree of orientation increases sharply when the system is biphasic. For larger flows, the orientation function is very close to unity which is perfect orientation.     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

Assessing organo-clay dispersion in polymer layered silicate nanocomposites: A SAXS approach

A SAXS method for the quantitative assessment of the morphology of polymer layered silicate nanocomposites is proposed. Fitting the SAXS patterns, the number of clay layers, the periodicity of the layers in the tactoids, the thickness of the regions interposed between the clay platelets and their distributions can be measured. A good agreement with TEM data was obtained, avoiding the inconsistencies with microscopical observations often reported in the literature.     

Synthesis and characterization of a series of star-branched poly(ε-caprolactone)s with the variation in arm numbers and lengths

A series of star-branched poly(ε-caprolactone)s (SPCLs) was synthesized with structural variation of the arm numbers and lengths through ring-opening polymerization under bulk condition. Arm numbers were varied to be 3, 4, and 6 by using multifunctional initiating cores such as trimethylol propane, pentaerythritol, and dipentaerythritol, respectively. The lengths of the poly(ε-caprolactone) arms were varied by controlling the molar ratio of monomer-to-initiating hydroxyl group molar ratio ([CL]₀/[-OH]₀=5, 10, 15). Molecular weights were determined by both ¹H NMR end-group analysis and MALDI-TOF mass spectrometry, which gave reasonably consistent values. On the contrary, the GPC method failed to give accurate values of molecular weight of SPCLs due to the discrepancy with the linear standard. The branching architecture of SPCLs was evaluated by the branching ratio, g, which is the ratio of the mean-square radius of SPCL to that of liner counterpart, linear poly(ε-caprolactone) (LPCL), which is of the same chemistry and having the same molecular weight. The radii of gyration of SPCLs and LPCLs were determined using small-angle X-ray scattering (SAXS) from the initial slopes of Zimm plots, represented as 1/I(q) vs q² with I(q) and q being the scattered intensity and scattering vector, respectively. The g values were observed to decrease with increasing arm numbers, indicating more compact molecular structure for SPCLs with higher arm numbers, while no such effect was observed for arm length variation. Thermal properties as well as the degree of crystallinity of SPCLs were found to be also dependent on structural variations. The melting points and the degradation temperatures were observed to increase with increasing arm lengths but with constant arm number. On the other hand, arm number variation with constant arm length gave no such changes to the thermal transitions of SPCLs. However, for the SPCLs with equivalent molecular weights, the degree of crystallinity was found to decrease with increasing arm numbers.     

Potential tissue implants from the networks based on 1,5-dioxepan-2-one and ε-caprolactone

The synthesis and characterization of degradable polymeric networks for biomedical applications was performed. Cross-linked films of poly(ε-caprolactone) (PCL) and poly(1,5-dioxepan-2-one) (PDXO) having various mole fractions of monomers and different cross-link densities were successfully prepared using 2,2′-bis-(ε-caprolactone-4-yl) propane (BCP) as cross-linking agent. Reaction parameters were carefully examined to optimise the film-forming conditions. Networks obtained were elastomeric materials, easy to cast and remove from the mould. Effect of CL content and cross-link density on the final properties of the polymer network was evaluated. High CL content or degree of cross-linking led to increase in Young's modulus and decrease in elongation at break. An increase in crystalline domains in films having a higher CL content was observed by optical microscopy. A greater thermal stability was observed in films having a high CL content. The hydrophilicity of the materials could be tailored by changing the CL content. The surface of the films became rougher with higher CL content.     

Terminal velocity of non-spherical particles falling through a Carreau model liquid

A procedure has been proposed for the estimation of the terminal falling velocity of non-spherical particles moving in a Carreau model fluid in the transition flow region. The procedure is based on a modification of the relationship formerly developed for the fall of spherical particles including the particle dynamic shape factor. The suitability of the proposed procedure has been confirmed by good agreement between experimental and calculated terminal falling velocity data. In the experiments, the terminal falling velocity of short cylinders and rectangular prisms in polymer solutions of different measure of shear thinning and elasticity has been measured.     

A simple mathematical analysis on the effect of sand in Cr(VI) reduction using zero valent iron

A simple mathematical model was proposed to analyze the enhancement of Cr(VI) reduction when sand materials are added to the zero valent iron (ZVI). Natural decay of Cr(VI) in a control experiment was analyzed by using a zero-order decay reaction. Adsorption kinetics of Cr(VI) to sand was modeled as a first-order reversible process, and the reduction rate by ZVI was treated as a first-order reaction. Natural decay of Cr(VI) was also included in other experiments, i.e., the adsorption to sand, the reduction by ZVI, and both adsorption and reduction when sand and ZVI are present together. The model parameters were estimated by fitting the solution of each model to the corresponding experimental data. To observe the effect of sand addition to ZVI, both adsorption and reduction rate models were considered simultaneously including the natural decay. The solution of the combined model was fitted to the experimental data to determine the first-order adsorption and reduction rate constants when sand as well as ZVI is present. The first-order reduction rate constant in the presence of sand was about 35 times higher than that with ZVI only.     

Bi12TiO20 synthesized directly from bismuth (III) nitrate pentahydrate and titanium glycolate and its activity

Pure phase of sillenite structure, Bi₁₂TiO₂₀, was directly synthesized using stoichiometric bismuth (III) nitrate pentahydrate and titanium glycolate by co-precipitation. The influence of pH on the structure of Bi₁₂TiO₂₀ was studied in the pH range of 3–10. The sillenite structure was characterized using XRD and FTIR. The photo-degradation reaction of 4-nitrophenol (4-NP) was used to study photocatalytic activity of Bi₁₂TiO₂₀ as a function of the preparation pH. The rate of decomposition was followed by UV-vis and TOC. The beginning concentration of 4-NP, 44 ppm, decreased to less than 1 ppm within 30 min for all prepared catalysts. It was found that the decomposition rate constant of Bi₁₂TiO₂₀ is six times higher than those of either TiO₂ or Bi₂O₃ under the same conditions.     

Identification of photoluminescence features of an epoxy resin based on components features and curing effects

Photoluminescence features in a commercial grade cured DGEBA-based epoxy resin have been investigated with as objective to determine which of the material compounds are responsible for cured resin emissions. The origin of the bands has been approached by considering photoluminescence of base resin and hardener taken separately, of their mixture, and in the course of curing. Most of the bands observed in the cured resin could be interpreted based on those found in the components taken separately. Fluorescence of the cured resin appears dominated by two broad bands that are characteristic of the hardener and exhibits a blue shift by up to 30 nm in the course of curing which could be used for cure monitoring purpose of the investigated system. Fluorescence of the base resin is clearly detected in the resin cured with tertiary amine as catalyser. However, it is very weak if the catalyser is not added. Two phosphorescence processes have been isolated in the cured resin, one of them being related to the base resin. Finally, a chemiluminescence spectrum has been recorded in the course of curing, which has been related to either curing-related reactions or to an oxidation process.