Search results for " solution"

PEO/CHCl3. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena

2003

Vapor pressures were measured for the system CHCl3/PEO 1000 (PEO stands for poly(ethylene oxide) and 1000 for Mw in kg/mol) at 25 °C as a function of the weight fraction w of the polymer by means of a combination of headspace sampling and gas chromatography. The establishment of thermodynamic equilibria was assisted by employing thin polymer films. The degrees of crystallinity α of the pure PEO and of the solid polymer contained in the mixtures were determined via DSC. An analogous degree of polymer insolubility β was calculated from the vapor pressures measured in this composition range. The experiments demonstrate that both quantities and their concentration dependence are markedly affect…

Microstructure analysis of biocompatible phosphoester copolymers

2013

Copolymers with varying compositions of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane (EEP) and 2-ethoxy-4-methyl-2-oxo-1,3,2-dioxaphospholane (EMEP) have been synthesized via 1,5,7-triazabicyclo[4.4.0]dec-5-ene-catalyzed anionic ring-opening polymerization. The molecular weights and comonomer ratios were well controlled and polymers with reasonable molecular weight distributions (<1.5) were obtained in all cases. The copolymers were investigated by 1H and 31P NMR spectroscopies to determine the underlying microstructure via detailed dyad analysis. The copolymers were found to be nontoxic to HeLa cells. Furthermore, the obtained copolymers of EEP and EMEP show thermoresponsive properties, i.e., exh…

Composition-dependent Flory-Huggins parameters: molecular weight influences at high concentrations

1995

Flory-Huggins interaction parameters X were determined by means of equilibrium vapor pressures (measured via a combination of a head-space sampler with a gas chromatograph) and light scattering as a function of composition and temperature for the systems cyclohexanone/polystyrene [CHO/PS] and cyclohexanone/poly(butyl methacrylate) [CHO/PBMA]. The investigation of molecular weight influences on X with the system CHO/PBMA demonstrates that they persist almost up to the pure polymer. In order to rationalize this result, it is postulated (in accord with experimental findings and theoretical predictions) that the dimensions of polymer chains may vary upon the addition of solvent even in highly c…

Dextran-Based Polycations: Thermodynamic Interaction with Water as Compared With Unsubstituted Dextran, 2 - Flory/Huggins Interaction Parameter

2011

Evidence of ternary interaction parameters for polymer solutions in mixed solvents from headspace-gas chromatography

2000

Partial vapor pressures of the volatiles have been measured for four solvent/precipitant/polymer systems at different temperatures. The high molecular weight compounds were polysulfone or polyethersulfone and the mixed solvent was either DMF/acetone or DMF/water. Systems containing the very powerful precipitant water exhibit a special phenomenon: Upon the addition of polymer to a mixed solvent of constant composition the partial vapor pressure of water increases by a factor of more than two before it falls to zero as the volume fraction of the polymer approaches unity. This particular situation cannot be modeled using binary interaction parameters only, in contrast to the results obtained w…

Synthesis and characterization of water-swellable?,?-polyasparthydrazide derivatives

1995

α, β-polyasparthydrazide (PAHy) was crosslinked by glutaraldehyde to form water-swellable materials possessing a three-dimensional molecular network. Different crosslinking degrees were prepared varying glutaraldehyde/PAHy ratio and samples containing 5-fluorouracil were obtained by incorporating the drug into the polymer networks during the crosslinking reaction. All samples were characterized by swelling tests, thermal, x-ray and SEM analysis. Their microstructure was observed through scanning electron microscopy. Furthermore, for samples containing the anticancer drug,in vitro release studies were performed in pH 7.4 buffer solution.

Aqueous Laponite Clay Dispersions in the Presence of Poly(ethylene oxide) or Poly(propylene oxide) Oligomers and their Triblock Copolymers

2008

The effect of polyethylene oxide (PEO) or polypropylene oxide (PPO) oligomers of various molecular weight (Mw) as well as of triblock copolymers, based on PEO and PPO blocks, on aqueous laponite RD suspensions was studied with small-angle neutron scattering (SANS). The radius of gyration (RG) increases for low Mw whereas the opposite occurs for larger Mw. This behavior is explained on the-basis that an effective RG is given by two contributions: (1) the size of the particles coated with the polymer and (2) the interactions between the laponite RD particles which are attractive for small and repulsive for large polymers. The SANS curves in the whole Q-range are well described by a model of n…

The role of potassium and hydrogen ions in the Prussian Blue ⇆ Everitt's Salt process

1998

Cyclic voltammetry experiments have proved very useful in the knowledge and understanding of the role of the potassium and hydrogen ions during the Prussian Blue ⇄ Everitt's Salt process. While potassium ions act as a stoichiometric reactant, the hydrogen ions play a very important role in the kinetics of the electron-hopping process. The entropy change for the reaction PB ⇄ ES has proved to be dependent on the degree of crystallinity of the film, indicating that this entropy change is related to the fixation of inner counterions on the crystal structure of the films.

The correlation between electrochemical impedance spectra and voltammograms of PB films in aqueous NH4Cl and CsCl

1998

Abstract Voltammetric curves of reduction of Prussian Blue Films to the Everitt’s Salt form and oxidation to the Prussian Yellow form show important differences depending on the supporting electrolyte countercation. The rate of the overall electron-hopping depends on the countercation. Apparent diffusion coefficients are evaluated from impedance spectra at different stabilization potentials. The dependence of the apparent diffusion coefficients on the stabilization potential can help understand the dependence of the voltammograms shape on the countercation nature.

The role of inner counterions within PB films during electrochemical processes

1999

Abstract The shape of voltammograms of Prussian Blue films (ferric ferrocyanide, PB) deposited on ITO (indium–tin oxide) electrodes in aqueous KCl, CsCl and NH 4 Cl solutions has been studied. These results proved a double role of countercations during these electrochemical processes. Countercations can either be only retained within the zeolitic pores of the PB structure forming part of their inner solution, or can also form part of the crystalline structure of PB films by replacing some iron sites. The different electrochemical behaviour of PB films in the three studied solutions (KCl, CsCl and NH 4 Cl) is analysed from this point of view.