On the continuity of the diffusion behaviour at amorphous polymer–polymer interfaces on both sides of the bulk glass transition temperature

The diffusion behaviour at amorphous polystyrene (PS)–PS interfaces has been investigated over an interval of temperatures (T) from below to above the bulk glass transition temperature (T _g ^bulk) using the Arrhenius and Vogel-Fulcher approaches. No discontinuity in the variation of the logarithm of the diffusion coefficient versus 1/T has been observed when going through the PS T _g ^bulk over a broad interval of T, from T _g ^bulk???50 °C to T _g ^bulk?+?50 °C. The molecular mechanism of interdiffusion has been discussed.     

Study of phase behaviour for the aqueous two-phase polymer–polymer systems using the modified UNIQUAC-NRF model

A modified form of the UNIQUAC-NRF activity coefficient model was used to study the phase behaviour of the aqueous two-phase systems (ATPSs) of polyethylene glycol (PEG) and dextran (DEX) with different molecular weights at various temperatures. In the proposed model, a ternary interaction parameter was added to the expression for the excess Gibbs free energy and, in turn, to the corresponding activity coefficient rendered by the UNIQUAC-NRF model. The combinatorial part of the new model takes the same form as that of the original UNIQUAC model and the residual part considers the nonrandomness and also the binary and the ternary interactions among the molecules in mixtures of PEG, DEX, and water. The results show that the new model can more accurately correlate the experimental data for the systems studied in this work than those obtained from the original UNIQUAC and the UNIQUAC-NRF activity coefficient models. In order to favourably compare the results the same minimisation procedure and the same experimental data were used for the models studied in this work. The results for the Root Mean Square Deviations (RMSD) produced by the three UNIQUAC-based models are also reported.     

Thermodynamic aspects of the heterogeneous structure of “golf-ball-like” polymer particles

Recently, we found that “golf-ball-like” polystyrene (PS)/poly(butyl acrytlate) composite particles could be produced by seeded emulsion polymerization of butyl acrylate with PS seed particles. In this article, the theoretical and experimental thermodynamic instabilities of the golf-ball-like structure are discussed and are compared with core-shell and hemispherical morphologies. Received: 2 February 1999 Accepted in revised form: 3 June 1999     

Synthesis of molecularly imprinted polymer of βcyclodextrin for the efficient recognition of cholesterol

Polymeric receptors for cholesterol were synthesized by crosslinking β-cyclodextrin (β-CyD) with hexamethylene diisocyanate or toluene 2,4-diisocyanate in dimethyl sulfoxide (DMSO) in the presence of cholesterol as the template. Non-imprinted β-CyD polymers were much poorer in the cholesterol adsorption. When β-CyD was cross-linked by epichlorohydrin in aqueous alkaline solutions (even in the presence of cholesterol), the cholesterol adsorbing activity was nil. Use of DMSO as the cross-linking solvent is necessary for the imprinting, since β-CyD molecules form inclusion complexes with cholesterol in this solvent and thus their mutual conformation in the polymer is regulated appropriately for cholesterol binding. The adsorbed cholesterol was completely removed from the polymers by treating the adducts with ethanol, indicating a strong potential for practical applications.     

Inclusion of the regioisomeric nitrobenzene derivatives and ferrocene guests by β-cyclodextrin polymer and their transport through the polymer matrix

Host-guest equilibria have been investigated involving inclusion sites of the microparticulate amorphous β-cyclodextrin polymer, β-CDP-25, and a range of redox guests comprising regioisomeric nitrobenzene derivatives and ferrocene. The equilibria were studied by the batch method. Inclusion-governed, Langmuir-type sorption equilibria occurred in the β-CDP-25/guest systems studied in 1:1 (v/v) aqueous methanolic solutions. A 1:1 (host inclusion site)/guest stoichiometry was found and sorption equilibrium constants were determined. The values of the constants changed by a factor of 20 between the most weakly and strongly included guests. Regioselective discrimination of β-CDP-25 was most pronounced with respect to nitrophenols. Transport phenomena of guest molecules in the β-CDP-25 matrix have also been studied. The apparent diffusion coefficients of guest molecules were determined in the β-CDP-25 matrix by chronamperometry at the (β-CDP-25)-PTFE-carbon composite electrodes. These diffusion coefficients were almost four orders of magnitude lower than the corresponding coefficients of guest molecules in solution in the absence of β-CD. The diffusion mechanism was postulated for the guest molecules in the β-CDP-25 matrix, which invoked hopping of the molecules between inclusion sites.     

Reviewing extrapolation procedures of the electronic properties on the π-conjugated polymer limit

In this article, the extrapolation procedures of π-π* electronic transition energy on π-conjugated oligomers are reexamined. Different models, including the simplest coupled oscillator, the free electron, the Hückel approach, the molecular exciton model, and some specific fitting-functions, are compared using the transition energies derived from theoretical calculations on three thiophene-based oligomer series. Specifically, oligomers of up to 30 repeating units have been considered to include the saturation effects as a function of chain length. The coupled oscillator model of W. Kuhn and the fitting-function of Hirayama are the models that present the better suit on the transition energy interpolation as a function of chain length. Using only the first four oligomers of the series (n = 2 up to 8) yields an estimation of the transition energy on the polymer limit with an average error of ～1.5%. The vertical and adiabatic ionization potential present a better fit with the Hückel model approach. Finally, implications of the environmental polarity on the electronic properties, molecular geometry, charge distribution, and aromaticity are shortly discussed.     

Production of polymer microparticles by “dissolution” of submicron-sized water-insoluble ionized carboxylated polymer particles in the presence of various nonionic emulsifiers

Styrene-butyl acrylate-methacrylic acid terpolymer (50.4/40.9/8.7, molar ratio) particles, 276 nm in diameter, were produced by emulsifier-free emulsion terpolymerization. The emulsifier-free carboxylated terpolymer particles did not dissolve in water even under alkaline condition. However, they dissolved in the presence of nonionic emulsifier under alkaline condition, resulting in polymer microparticles having diameter less than 40 nm. Such a dissolution behavior was examined using five kinds of different polyoxyethylene nonylphenylether nonionic emulsifiers having hydrophilic-lipophilic balance values between 12.2 and 17.5 at various initial pH values, temperatures and times, and its mechanism was discussed.Part CXLIV of the series Studies on Suspension and Emulsion.     

What is the flow activation volume of entangled polymer melts?

We evaluate the flow activation volume in polymer melts of isotactic polypropylene and atactic polystyrene with step-shear experiments at different melt temperatures. The melt is initially sheared with constant shear rate until the attainment of a melt state with nearly constant viscosity. Perturbations to this experiment, involving shear steps in short-time intervals with decreasing rates, are induced next. Measurements of the shear stress value at each shear rate step allow the evaluation of an experimental (apparent) flow activation volume. The true flow activation volume is evaluated by extrapolating the experimental data to infinite shear stress values. The value obtained is larger than the physical volume of the chain and agrees with the volume of a tube confining chains with a molecular weight between M _n and M _w. Besides supporting the validity of tube model, experiments based on this protocol may be used on model polymer samples, in composites with nanoparticles and in polymer blends to access the validity of mechanisms considered by flow models.     

Studies on the synthesis and properties of malachite green imprinted polymer

A new molecularly imprinted polymer was synthesized with malachite green (MG) as molecular template, methacrylic acid (MAA) as functional monomer, ethylene dimethacrylate (EDMA) as crosslinker, and azobisisobutyronitrile (AIBN) as initiator. Recognition properties of the MG imprinted polymer were studied by equilibrium adsorption and HPLC. The results showed that the imprinted polymer had good affinity and marked selectivity for MG, and can separate MG with its analogue commendably. The new polymer can be used for the enrichment of MG in complex sample, and can work as separation media to separate and detect MG by HPLC.     

Evaluation of a molecularly imprinted polymer for the isolation/enrichment of β-estradiol

The selective preconcentration of estradiol was explored using the recognition ability of a molecularly imprinted polymer (MIP) in the solid phase extraction (SPE) format. Polymeric particles were imprinted with 17β-estradiol using methacrylic acid as functional monomer and divinylbenzene as crosslinker. Binding studies of these polymeric particles towards 17β-estradiol showed selectivity over non-imprinted polymers, using acetonitrile as solvent. The imprinted polymer showed a recovery of 88% for β-estradiol in deionized water and 81% in surface water. The selectivity of the MIP over the non-imprinted polymer was relatively low, only 10% higher recovery. The results indicate that the MIP imprinted with 17β-estradiol does not appear to provide a viable approach to be used in a sample clean-up or enrichment step for the determination of estradiol in aqueous systems.     

Influence of polymer structure on the rheological behavior of hydroxypropylmethylcellulose–sodium carboxymethylcellulose dispersions

Aqueous dispersions of mixtures of hydroxypropylmethylcellulose (HPMC) and sodium carboxymethylcellulose (NaCMC) were prepared in accordance with a two-component simplex lattice design, using polymer varieties with different molecular weights and substitution characteristics. The resulting systems were characterized rheologically by capillary viscometry, flow rheometry, and oscillatory shear techniques, for the determination of kinematic viscosity, index of consistency, index of fluidity, elastic modulus, and viscous modulus. The values obtained for these parameters were fitted with appropriate canonical models, which revealed synergistic effects for some polymer proportions. Maximum synergy was observed when polymer proportions were optimal for the establishment of between-polymer interactions. The synergistic effects on viscosity and elasticity are attributable to the establishment of hydrophobic interactions and hydrogen bonds between HPMC and NaCMC chains, as revealed by IR spectroscopy and modifications in the cloud-point temperature. The observed among-mixture differences in the polymer proportions at which maximum synergy occurs, and the degree of this synergy, are explained by differences in molecular weights and substitution characteristics, and indeed the degree of synergy (as measured by interaction parameters from the fitted canonical models) showed strong dependence on these variables. Microviscosity values, derived from theophylline diffusion data for some of the mixtures, show that the crossover and chain expansion of the polymers in the mixtures (i.e. increased viscosity and elasticity) give rise to a three-dimensional network with greater mesh size and a more hydrophilic microenvironment, favoring solute mobility. Received: 17 July 2000 Accepted: 20 November 2000     

The lighter side of darwinism? Photoselection of the species: Applications of luminescence anisotropy measurements to the study of polymer relaxation

The application of luminescence anisotropy techniques to the study of polymer systems is discussed. Investigations of polymer relaxation both in fluid solutions and the solid state are addressed. Particular attention has been paid to considerations of reliable means of information retrieval from experimental time-resolved anisotropy data.     

Fracture of polymer interfaces: what are the relevant length scales?

While it is tempting to relate directly the molecular structure of an interface (between glassy or between semi‐cristalline polymers) with its fracture toughness, these two parameters are simply the two end‐points of a complex network which needs to be understood in order to control the mechanical strength of the interface. The important mechanisms occur at three different length scales: the molecular scale (stress‐transfer across the interface), the microscopic scale (plastic deformation at the crack tip) and the macroscopic scale (loading geometry and elastic constants of the polymers). The couplings existing between these length scales in glassy polymer interfaces are reviewed in this paper in light of the latest experimental studies.     

What is the role of the interfacial interaction in the slow relaxation of nanometer-thick polymer melts on a solid surface?

At the nanoscale and interfaces, the relaxation behavior of polymer melts, which affects the polymer's long-term performance in many important applications, is very different from that in the bulk. The role of polymer-substrate interfacial interaction, which does not have a bulk counterpart, has not been fully understood to date. In this study, the relaxation of nanometer-thick perfluoropolyether melts on a silicon wafer has been investigated by water contact angle measurement. The polymer-substrate interactions have been systematically changed by tailoring the polymer structure to clarify the effect of the interfacial interaction. The experimental results show that (1) when there is attractive interaction at the interface, some polymers are anchored to the substrate and others are free, (2) the attractive interfacial interaction drives the free polymers to relax at the interface, and (3) the relaxation is much slower than in the bulk, which has been attributed to the low mobility of the anchored polymer chains and the motional cooperativity between anchored and free polymer chains in the nanometer-thick films.     

Fire retardancy of polymer clay nanocomposites: Is there an influence of the nanomorphology?

The obvious aspect of nanodispersion and its role when investigating fire retardancy is not often clearly commented upon in the literature. Polymer clay nanocomposites can exhibit different morphologies and these might have consequences for their fire behaviour. Using solid state NMR to quantify the nanodispersion of organoclay in polyamide-6 (PA-6), we have prepared by melt blending PA-6/clay nanocomposite exhibiting different nanomorphologies. NMR results are consistent with transmission electron microscopy (TEM) images but the advantage of NMR is that it is representative of the whole sample and provides a precise quantification. PA-6 nanocomposites exhibit significant reduction of PHRR but the nanomorphology (exfoliation, intercalation and presence of tactoids) does not play any significant role. In other words, we have clearly shown that if nanodispersion is achieved, polymer/clay nanocomposite should exhibit fire retardant properties.     

On the contamination of membrane–electrode assembles of water electrolyzers with solid polymer electrolyte by the elements of titanium alloys

The aspects of contamination of membrane–electrode assemblies of water electrolyzers with solid polymer electrolyte by the elements of titanium alloys (Ti and Fe) are considered. These alloys are used as the material for current collectors/gas-diffusion electrodes, bipolar plates, and other elements of electrolysis system. It is shown that titanium is one of the main impurities that contaminate the membrane and electrocatalytic layers of membrane–electrode assembly in the case that deionized water is used as the reagent. The membrane contamination can lead to the degradation of electrolyzer characteristics and its failure.     

Combinational simulations of free energy of polymer solution

It is conceptually proposed that the total entropy of polymer solution is contributed from two distinct parts: the positional and the oomformational. The former can be represented analytically, while the latter can be simulated with the random self-avoiding walk model on the simple cubic lattice for multichain systems. The obtained results indicated that both the conformational entropy and the mixing heat are consistent with the scaling laws wry well.