Showing papers on "Miscibility published in 2011"

Polymer Crystallization of Partially Miscible Polythiophene/Fullerene Mixtures Controls Morphology

Abstract: Mixtures of polythiophene and fullerene are intensely studied for organic photovoltaic applications. Control of nanoscale morphology of these materials is critical for device performance, but characterization and understanding of this morphology and how it arises is lacking. We use energy-filtered transmission electron microscopy (EFTEM) to obtain high-contrast images of P3HT nanocrystals in organic semiconductor mixtures. Grazing-incidence small-angle X-ray scattering correlates well with the length scales obtained from EFTEM images; we combine the two techniques to follow the morphology evolution under different material processing histories. EFTEM also measures local P3HT concentration in PCBM-rich regions, proving that these components are partially miscible. We determine the P3HT-PCBM χ parameter and Flory–Huggins phase diagram, which predicts miscibility for P3HT volume fractions above 0.42. This miscibility suppresses fullerene crystallization. The nanoscale morphology in these materials, critical ...

Prediction of solubility parameters and miscibility of pharmaceutical compounds by molecular dynamics simulations.

Abstract: The objectives of this study were (i) to develop a computational model based on molecular dynamics technique to predict the miscibility of indomethacin in carriers (polyethylene oxide, glucose, and sucrose) and (ii) to experimentally verify the in silico predictions by characterizing the drug-carrier mixtures using thermoanalytical techniques. Molecular dynamics (MD) simulations were performed using the COMPASS force field, and the cohesive energy density and the solubility parameters were determined for the model compounds. The magnitude of difference in the solubility parameters of drug and carrier is indicative of their miscibility. The MD simulations predicted indomethacin to be miscible with polyethylene oxide and to be borderline miscible with sucrose and immiscible with glucose. The solubility parameter values obtained using the MD simulations values were in reasonable agreement with those calculated using group contribution methods. Differential scanning calorimetry showed melting point depression...

Tailored Media for Homogeneous Cellulose Chemistry: Ionic Liquid/Co-Solvent Mixtures

Abstract: Co-solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non-polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co-solvents in cellulose chemistry could be advanced: Appropriate co-solvents should have values (normalized empirical polarity) > 0.3, very low “acidity” (α < 0.5), and relatively high “basicity” (β ≥ 0.4). Moreover, novel promising co-solvents and binary co-solvent mixtures were identified.

Analysis of the Structure-Properties Relationships of Different Multiphase Systems Based on Plasticized Poly(Lactic Acid)

Abstract: Poly(lactic acid) is one of the most promising biobased and biodegradable polymers for food packaging, an application which requires good mechanical and barrier properties. In order to improve the mechanical properties, in particular the flexibility, PLA plasticization is required. However, plasticization induces generally a decrease in the barrier properties. Acetyl tributyl citrate (ATBC) and poly(ethylene glycol) 300 (PEG), highly recommended as plasticizers for PLA, were added up to 17 wt% in P(D,L)LA. In the case of PEG, a phase separation was observed for plasticizer contents higher than 5 wt%. Contrary to PEG, the Tg decrease due to ATBC addition, modelled with Fox’s law, and the absence of phase separation, up to 17 wt% of plasticizer, confirm the miscibility of PLA and ATBC. Contents equal or higher than 13 wt% of ATBC yielded a substantial improvement of the elongation at break, becoming higher than 300%. The effect of PLA plasticization on the barrier properties was assessed by different molecules, with increasing interaction with the formulated material, such as helium, an inert gas, and oxygen and water vapour. In comparison to the neat sample, barrier properties against helium were maintained when PLA was plasticized with up to 17 wt% of ATBC. The oxygen permeability coefficient and the water vapour transmission rate doubled for mixtures with 17 wt% ATBC in PLA, but increased five-fold in the PEG plasticized samples. This result is most likely caused by increased solubility of oxygen and water in the PEG phase due to their mutual miscibility. To conclude, ATBC increases efficiently the elongation at break of PLA while maintaining the permeability coefficient of helium and keeping the barrier properties against oxygen and water vapour in the same order of magnitude.

Phase behaviour of liquid-crystalline polymer/fullerene organic photovoltaic blends: thermal stability and miscibility

Abstract: The thermal behaviour of an organic photovoltaic (OPV) binary system comprised of a liquidcrystalline fluorene-based polymer and a fullerene derivative is investigated. We employ variabletemperature ellipsometry complemented by photo- and electroluminescence spectroscopy as well as optical microscopy and scanning force nanoscopy to explore phase transitions of blend thin films. The high glass transition temperature correlates with the good thermal stability of solar cells based on these materials. Furthermore, we observe partial miscibility of the donor and acceptor together with the tendency of excess fullerene derivative to segregate into exceedingly large domains. Thus, for charge generation less adequate bulk-heterojunction nanostructures are poised to develop if this mixture is exposed to more elevated temperatures. Gratifyingly, the solubility of the fullerene derivative in the polymer phase is found to decrease if a higher molecular-weight polymer fraction is employed, which offers routes towards improving the photovoltaic performance of non-crystalline OPV blends.

Atomic Force Microscopy-Based Screening of Drug-Excipient Miscibility and Stability of Solid Dispersions

Abstract: Purpose Development of a method to assess the drug/polymer miscibility and stability of solid dispersions using a melt-based mixing method.

Thermal and structural studies of polypropylene blended with esterified industrial waste lignin

Abstract: Microwave-assisted chemical modification of lignin was achieved through esterification using maleic anhydride. Modified lignin (ML) was blended in different proportions up to 25 mass% with polypropylene (PP) using Brabender electronic Plasticorder at 190 °C. The structural and thermal properties of blends were investigated by thermogravometric analysis (TG), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM). TG analysis showed increased thermal stability of blends due to antioxidant property of ML, which opposed oxidative degradation of PP. DSC analysis indicted slight depression in a glass transition temperature and melting temperature of blends due to partial miscible blend behavior between PP and ML. All blends showed higher crystallization temperatures and continuously reducing percentage crystallinity with increasing ML proportion in the blends. WAXD analysis indicated that PP crystallized in β polymeric form in addition to α-form in the presence of ML. However, proportion of β-form did not show linear relation with increase in ML proportion, thus ML acts as β nucleating agent in the PP matrix. SEM analysis showed good dispersion/miscibility in PP matrix indicating modification in lignin is useful.

Switchable Ionic liquids (SILs) based on glycerol and acid gases

Abstract: New types of switchable ionic liquids (SILs), containing 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), glycerol and an acid gas (CO2, SO2), were synthesized and characterized in this study. [DBU][Carbonate] or [sulfonate] were easily synthesized from a non-ionic mixture of molecular organic polyol and amidine base upon bubbling of an acid gas (CO2, SO2). Moreover, they were switched back to the original molecular solvents by flushing out the acid gas (CO2, SO2) by heating and/or bubbling an inert gas such as N2 through it. The structures of the SILs were confirmed by NMR and FTIR. The change from low polarity (molecular solvent) to high polarity (Switchable Ionic Liquid, SIL) was also indicated by the changes in properties, such as viscosity and miscibility with different organic solvents. The decomposition temperatures of the SILs were determined by means of Thermo Gravimetric Analysis (TGA) and gave values in the range of 50 °C and 120 °C for DBU-glycerol-CO2 (SIL1) and DBU-glycerol-SO2 (SIL2), respectively. Due to the reasonable decomposition temperatures, these novel SILs can be employed in multiple applications.

Fullerene-Dependent Miscibility in the Silole-Containing Copolymer PSBTBT-08

Abstract: A high fullerene molecular miscibility of over 40 wt % is found in the copolymer poly((4,4-octyldithieno(3,2-b:2′,3′-d)silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl) (PSBTBT-08)—a member of the PSBTBT low-bandgap polymer family that have produced power conversion efficiencies as high as 5.9% in solar cells. This observation suggests molecular miscibility plays a key role in the photovoltaic effect in this system. The level of miscibility is additionally measured to be highly dependent on the fullerene species with significant differences between C60- and C70-based fullerenes, highlighting a new parameter to be monitored and controlled when considering different fullerene moieties and species in organic solar cells. Surprisingly, a wide-angle X-ray scattering study reveals no significant crystallinity in the PSBTBT with octyl side chains, potentially the cause of low mobilities and in stark contrast to dodecyl and ethylhexyl PSBTBTs, which demonstrates the importance of the side chain in device mo...

Open Cell Microcellular Foams of Polylactic Acid (PLA)-based Blends with Semi- Interpenetrating Polymer Networks

Abstract: Microcellular biodegradable polymer foam with an open porous structure was prepared from amorphous poly-L,D-lactic acid (PL,DLA) blended with polystyrene (PS), or polymethyl methacrylate (PMMA). The blends were prepared by polymerizing either styrene or methyl methacrylate (MMA) in a PL,DLA matrix. The styrene and MMA monomers are good cell-opening agents and constituents for an IPN. Pressure-quench batch foaming was conducted using carbon dioxide as a foaming agent at 80 °C under 10 MPa. The effects of monomers and a cross-linking agent on the foamability and OCC were investigated. Manipulation of the monomer and the cross-linking agent concentrations was able to change the viscoelasticity and partial miscibility of the blend and control the cell size at the micron scale as well as open pore content in the range of 20–90%.

Properties of polymer electrolytes composed of poly(ethylene oxide) and ionic liquids according to hard and soft acids and bases theory

Abstract: We investigated the miscibility of 12 different ionic liquids (ILs) with poly(ethylene oxide) (PEO) under excess salt conditions, using hard and soft, acids and bases (HSAB) theory. The hardness of the component ions of a series of ILs was estimated from the energy calculation of their HOMO and LUMO. ILs composed of relatively hard acids, such as imidazolium cation, and soft bases such as bis(trifluoromethanesulfonyl)imide anion, displayed excellent miscibility with PEO regardless of mixing ratio. Good miscibility implies that the ions strongly interact with PEO chains, and accordingly the ionic conductivity decreased with increasing PEO content. On the other hand, the same ionic conductivity was found regardless of mixing ratio when ILs composed of soft acid and soft base such as N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide was mixed with PEO. These data suggest that high ionic conductivity should be supported by the micro-phase separation of polymers and ionic liquids. Copyright © 2011 John Wiley & Sons, Ltd.

Dispersion Morphology of Poly(methyl acrylate)/Silica Nanocomposites

Abstract: Nearly monodisperse poly(methyl acrylate) (PMA) and spherical SiO2 nanoparticles (NP, d = 14 ± 4 nm) were co-cast from 2-butanone, a mutually good solvent and a displacer of adsorbed PMA from silica. The effects of NP content and post-casting sample history on the dispersion morphology were found by small-angle X-ray scattering supplemented by transmission electron microscopy. Analysis of the X-ray results show that cast and thermally annealed samples exhibited a nearly random particle dispersion. That the same samples, prior to annealing, were not well-dispersed is indicative of thermodynamic miscibility during thermal annealing over the range of NP loadings studied. A simple mean-field thermodynamic model suggests that miscibility results primarily from favorable polymer segment/NP surface interactions. The model also indicates, and experiments confirm, that subsequent exposure of the composites to the likely displacer ethyl acetate results in entropic destabilization and demixing into NP-rich and NP-le...

A study on compatibility of polymer blends of polystyrene/poly(4-vinylpyridine)

Abstract: Blends of polystyrene/poly (4-vinylpyridine) have been prepared by casting from a common solvent. The compatibility of the blends was studied by using dilute solution viscometry (DSV), differential scanning calorimetery (DSC), Fourier transformation-infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The relative viscosity versus composition plots for the blends are not perfect linear. The corresponding intrinsic viscosity values show negative deviation from ideal behavior when plotted against composition. Also, the modified Krigbaum and Wall interaction parameter, Δb, shows small and negative values for all compositions except for the blend PS/P4VP (25 : 75). The results indicate that the polymers are incompatible but small interaction values predict physically miscible blends which eventually show phase separation, as is observed in the present studies. However, the blends as obtained show a single, composition-dependent, glass transition temperature that fits the Fox equation well, indicating the presence of homogeneous phase. The constant, k obtained from Gordon-Taylor equation suggests intermolecular attraction between these polymers. FT-IR and SEM support the results of DSV and DSC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Determination of structural and mechanical properties, diffractometry, and thermal analysis of chitosan and hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol

Abstract: In this work, the structural, mechanical, diffractometric, and thermal parameters of chitosan-hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol were studied. Solutions of HPMC (2% w/v) in water and chitosan (2% w/v) in 2% acetic acid solution were prepared. The concentration of sorbitol used was 10% (w/w) to both polymers. This solutions were mixed at different proportions (100/0; 70/30; 50/50; 30/70, and 0/100) of chitosan and HPMC, respectively, and 20 mL was cast in Petri dishes for further analysis of dried films. The miscibility of polymers was assessed by X-ray diffraction, scanning electronic microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The results obtained indicate that the films are not fully miscible at a dry state despite the weak hydrogen bonding between the polymer functional groups.

Development of a Polarizable Force Field for Molecular Dynamics Simulations of Poly (Ethylene Oxide) in Aqueous Solution

Abstract: We have developed a quantum chemistry-based polarizable potential for poly(ethylene oxide) (PEO) in aqueous solution based on the APPLE&P polarizable ether and the SWM4-DP polarizable water models. Ether–water interactions were parametrized to reproduce the binding energy of water with 1,2-dimethoxyethane (DME) determined from high-level quantum chemistry calculations. Simulations of DME–water and PEO–water solutions at room temperature using the new polarizable potentials yielded thermodynamic properties in good agreement with experimental results. The predicted miscibility of PEO and water as a function of the temperature was found to be strongly correlated with the predicted free energy of solvation of DME. The developed nonbonded force field parameters were found to be transferrable to poly(propylene oxide) (PPO), as confirmed by capturing, at least qualitatively, the miscibility of PPO in water as a function of the molecular weight.

Determination of structural and mechanical properties, diffractometry, and thermal analysis of chitosan and hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol Determinação das propriedades mecânicas e estruturais, difratometria e análises térmicas de filmes de quitosana e hidroxipropilmetilcelulose (hPmC) plastificados com sorbitol

Abstract: In this work, the structural, mechanical, diffractometric, and thermal parameters of chitosan-hydroxypropylmethylcellulose (HPMC) films plasticized with sorbitol were studied. Solutions of HPMC (2% w/v) in water and chitosan (2% w/v) in 2% acetic acid solution were prepared. The concentration of sorbitol used was 10% (w/w) to both polymers. This solutions were mixed at different proportions (100/0; 70/30; 50/50; 30/70, and 0/100) of chitosan and HPMC, respectively, and 20 mL was cast in Petri dishes for further analysis of dried films. The miscibility of polymers was assessed by X-ray diffraction, scanning electronic microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The results obtained indicate that the films are not fully miscible at a dry state despite the weak hydrogen bonding between the polymer functional groups.

Ionic Liquid Extractants in Molecular Diluents: Extraction Behavior of Plutonium (IV) in 1,3-Diketonate Ionic Liquids

Abstract: Room temperature ionic liquids (RTILs) containing β-diketonate anions have been prepared and studied for the extraction of 239Pu(IV), 233U(VI), and 241Am(III) from nitric acid medium. The ionic liquids such as alkylquaternaryammonium thenoyltrifluoroacetonate (R4NTTA), and 1-alkyl-3-methylimidazolium thenoyltrifluoroacetonate (amimTTA), with methyl, butyl, hexyl, heptyl, and octyl moieties have been prepared and characterized by 1H and 13C nmr and IR spectroscopy. The distribution ratio of plutonium(IV) (D Pu(IV)) in a solution of tri-n-octylmethylammonium thenoyltrifluoroacetonate (TOMATTA) present in tri-n-octylmethylammonium bis(trifluoromethylsulfonyl)imide (TOMANTf2) and amimTTA in amimNTf2 was studied as a function of various parameters. The unique property of β-diketonate ionic liquids, namely, the miscibility in molecular diluents, was exploited to elucidate the mechanism of Pu(IV) extraction in these ionic liquids.

Using Hydrogen-Bonding Interactions To Control the Peptide Secondary Structures and Miscibility Behavior of Poly(l-glutamate)s with Phenolic Resin

Abstract: We synthesized three low-molecular-weight poly(glutamate)s—poly(γ-methyl l-glutamate) (PMLG), poly(γ-ethyl l-glutamate) (PELG), and poly(γ-benzyl l-glutamate) (PBLG)—through living ring-opening polymerization of their α-amino acid-N-carboxyanhydride derivatives and then blended them with phenolic resin to control the secondary structures of these polypeptides. Each of the three binary blends exhibited a single glass transition temperature (differential scanning calorimetry) and a single-exponential decay of proton spin–lattice relaxation times in the rotating frame [T1ρH; solid state nuclear magnetic resonance (NMR) spectroscopy], characteristic of a miscible system. The strength of the interassociative interactions depended on the nature of the hydrogen bond acceptor groups, increasing in the order phenolic/PELG > phenolic/PMLG > phenolic/PBLG, as evidenced through analyses using Fourier transform infrared (FTIR) spectroscopy and the Painter–Coleman association model. The fractions of α-helical conformat...

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

Abstract: The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(e-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.

Liquid-liquid domain miscibility driven by composition and domain thickness mismatch in ternary lipid monolayers.

Abstract: This work describes how changes in surface pressure modulate the molecular organization of Langmuir monolayers formed by ternary mixtures of dlPC/pSM/Dchol that exhibit coexistence of liquid-expanded (LE) and liquid-ordered (Lo) phases. It provides a theoretical framework for understanding the pressure-induced critical miscibility point characteristic of monolayer systems with liquid−liquid phase coexistence. From compression isotherms and Brewster angle microscopy of Langmuir monolayers with a composition close to a tie line, we determined experimental values of mean molecular areas, surface potential, and monolayer thickness and could estimate the mean molecular area and composition of each coexisting phase. A surface-pressure-induced enrichment of the PC component in the Lo phase reduces both the compositional miscibility gap and the hydrophobic mismatch between phases. The liquid−liquid miscibility transition point observed at ≈25 mN/m can be explained by a competition between thermal energy and the l...