Thermorheological and glass transition properties of PNIPA/PVP and PNIPA/Carbopol blends

The miscibility of poly(N-isopropylacrylamide) (PNIPA) with poly(vinyl pyrrolidone) (PVP) and a cross-linked poly(acrylic acid) (Carbopol^® 971P) was evaluated from the rheological data of aqueous dispersions and the temperature of glass transitions of films made of binary mixtures. PNIPA has a low critical solubility temperature (LCST) of about 33°C, below which 1% dispersion behaves as a viscous system. At temperatures above LCST, the hydrophobic interactions among the isopropyl groups initially provide transient networks of greater elasticity. The LCST of PNIPA as well as its T _g (144°C, estimated by DSC and MTDSC of films) were not modified by the presence of PVP. The immiscibility of PNIPA and PVP was confirmed by the absence of interaction between both polymers as shown by FTIR analysis of the films. In contrast, PNIPA and carbopol were miscible and the behaviour of their mixtures differed significantly from that of the parent polymers; i.e. a strong synergistic effect on the viscoelasticity of the dispersions was observed below the LCST. As temperature increased, the blends showed a decrease in the loss and storage moduli, especially those with greater PNIPA proportions. The fall was smoother as the PNIPA proportion decreased. This behaviour may be explained as the result of the balance between PNIPA/carbopol hydrogen bonding interactions (as shown in the shift of C=O stretch in FTIR spectra) and PNIPA/PNIPA hydrophobic interactions. The T _g values of the films of the blends showed a positive deviation from the additivity rule; the mixtures containing more than 1:1 amide:carboxylic acid groups have a notably high Tg (up to 181°C). This increase is related to the stiffness induced in the films by the PNIPA/carbopol interactions.     

A simple statistical mechanical theory for the mutual solubility of fluid mixtures of water and organic solvents under high pressure

A simple statistical mechanical theory is presented to explain phase diagrams of fluid mixtures with both a lower critical solution temperature and an upper critical solution temperature under pressure. By postulating a temperature dependence for the interaction free energy parameter of the constituent molecules and a pressure dependence for the excess volume, phase diagrams with both lower critical solution temperature, and upper critical solution temperature and their pressure dependence can be reproduced by quadratic surfaces in temperature-concentration-pressure space. The topological aspects of the observed phase diagrams in this space have been related to our theoretical model, and the thermodynamical meaning of the topologies has been interpreted based on our model. Experimental data for the mutual solubility of water and 2-butanol under pressure and that of water and 3-methylpyridine with added salts have been analyzed quantitatively and theoretical parameters are determined.     

Synergistic mechanical behaviour and improved processability of poly(ether imide) by blending with poly(trimethylene terephthalate)

Fully miscible poly(ether imide) (PEI)/poly(trimethylene terephthalate) (PTT) blends were obtained by melt mixing in an extruder followed by injection moulding. The viscosity of PEI, represented by the pressure at the extruder output, almost halved upon the addition of only 10% PTT, allowing the use of PEI in applications where either complex parts or thin sections must be moulded. The modulus of elasticity showed a synergistic behaviour which was absolute (modulus higher than that of any of the two components) in the blend with 10% PTT. This was attributed mainly to the decrease in specific volume upon blending. The additional absolute synergism in the yield stress of PEI‐rich blends and their ductile nature depict a set of properties that make these new materials attractive in a number of new applications. Copyright ­© 2003 John Wiley & Sons, Ltd.     

Thermal oxidation of blends of poly(ethylene oxide) and poly(methyl methacrylate)

Thermal oxidation of poly(ethylene oxide) (PEO) and its blends with poly(methyl methacrylate) (PMMA) were studied using oxygen uptake measurements. The rates of oxidation and maximum oxygen uptake contents were reduced as the content of PMMA was increased in the blends. The results were indicative of a stabilizing effect by PMMA on the oxidation of PEO. The oxidation reaction at 140°C was stopped at various stages and PMMA was separated from PEO and its molecular weights were measured by gel permeation chromatography (GPC). The decrease in the number-average molecular weight of PMMA was larger as the content of PEO increased in the blends. The visual appearance of the films suggested that phase separation did not occur after thermal oxidation. The activation energy for the rates of oxidation in the blends was slightly increased compared to pure PEO. © 1992 John Wiley & Sons, Inc.     

Miscibility and gas permeability of poly(ethylene-co-5,4 mol% 3,5,5-trimethylhexyl methacrylate)-polydimethyl-siloxane blends

 Blends of poly(ethylene- co-5.4 mol% 3,5,5-trimethylhexyl methacrylate) (PE-TMHM) with poly(dimethylsiloxane) (PDMS) were prepared in the PDMS content range from 0 to 20%. The miscibility was studied for PE-TMHM–PDMS blends by DSC, dynamic mechanical and microscopic spectroscopy, and the gas permeability was measured for O₂, N₂ and CO₂ as function of PDMS content. PE-TMHM and PDMS were partially miscible with each other below 20 wt% of PDMS content. The permeability coefficients (P) for O₂, N₂ and CO₂ were increased by the blending of PDMS to PE-TMHM. The change of P for O₂ with PDMS content well reflected the partially miscible phase separation behavior. Received: 10 June 1996 Accepted: 14 August 1996     

Systematic comparison study on determination of small organics/polymer miscibility

A mixture system of small molecular organics/polymer is widely applied in various industries. A relatively accurate determination of their miscibility is crucial for well understanding and predicting their phase behaviors and material properties. However, miscibility results from different literature could vary much. This study systematically compares various approaches to determine the mixture miscibility, e.g., the interaction parameter (χ), solubility, observations of the phase separation, and a deviation of glass transition temperature (T_g) or melting temperature (T_m), and demonstrates the advantages, disadvantages, general suitability of each method. Four botanical organics, i.e., β-carotene, betulinic acid, astaxanthin, and curcumin, are used as model small molecular compounds. A widely-used, noncrystallizable, hydrophobic polymer of poly (lactic-co-glycolic acid) (PLGA, LA:GA = 55:45) is employed as a model polymer. This systematic comparison is expected to provide a guide to selecting a suitable determination of small organics/polymer miscibility, beneficial for better predicting the phase stability of an amorphous mixture in applications.     

Ferroelectric compounds with chiral (S)-1-methylheptyloxycarbonyl terminal chain – their miscibility and a helical pitch

Compounds with the same chiral terminal chain but different structure of rigid core and non-chiral terminal chain were added to basic highly tilted ferroelectric compound in the aim of establishing whether the miscibility of phases, especially ferroelectric phase, exists in these compounds and what are the helical pitch and tilt angle temperature dependence in bicomponent systems. In certain systems, we obtained a mixture with very short helical pitch at broad temperature range of ferroelectric phase, which open opportunities for the formulation of multicomponent mixtures for fast switching ferroelectric liquid crystals modes.     

Phase equilibrium and charge fractionation in polyelectrolyte solutions

A new type of phase separation in the polyelectrolyte solutions consisting of several types of charged macromolecules differing in their degree of ionization is presented. Via a general thermodynamic consideration we show that even a small difference in the degree of ionization of otherwise equivalent high‐molecular components results in their spatial separation occurring upon decreasing the temperature much earlier than precipitation of any of the pure components from the solution. Some implications of charge fractionation are discussed, including the separation of DNA (or RNA) strands interacting with different proteins and the appearance of heterogeneities in polyelectrolyte solutions of partially charged hydrophobic chains with polydispersed charge distributions such as sodium polystyrene sulfonate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3003–3009, 2007     

Variable reactivity and phase separation in patchy particle systems

ABSTRACT

Using statistical model, we study mechanisms of phase separation in a solution consisting of patchy particles, which are capable to form directed and saturated thermoreversible bonds. We focus on the impact of variable reactivity of patchy particles on the form of miscibility gap. We show that the variation of model parameters determining features of interparticle interaction makes it possible to obtain miscibility gaps of different types within the unified formalism. In particular, we uncover two different mechanisms of the formation of phase separation curves with lower critical solution temperature. The first mechanism is realised in the case of positive bonding energy; the second one can takes place when the energy of formation of two-bonded particles is lower than that for all other m-bonded ones. We conclude that the most interesting and non-trivial phase behavior is observed in the case of patchy particles with variable reactivity. Using rigorous statistical model, we uncover new mechanisms of phase separation in a solution consisting of patchy particles, which are capable to form directed and saturated thermoreversible bonds. This topic corresponds to state of the art in modern chemical physics. The results obtained shed light on interplay between features of non-isotropic interactions and phase behavior in both molecular and nanoparticle systems. We conclude that the most interesting and non-trivial phase behavior is observed in the case of patchy particles with variable reactivity.     

On the morphology of polymer-based photovoltaics

We review the morphologies of polymer-based solar cells and the parameters that govern the evolution of the morphologies and describe different approaches to achieve the optimum morphology for a BHJ OPV. While there are some distinct differences, there are also some commonalities. It is evident that morphology and the control of the morphology are important for device performance and, by controlling the thermodynamics, in particular, the interactions of the components, and by controlling kinetic parameters, like the rate of solvent evaporation, crystallization and phase separation, optimized morphologies for a given system can be achieved. While much research has focused on P3HT, it is evident that a clearer understanding of the morphology and the evolution of the morphology in low bad gap polymer systems will increase the efficiency further. While current OPVs are on the verge of breaking the 10% barrier, manipulating and controlling the morphology will still be key for device optimization and, equally important, for the fabrication of these devices in an industrial setting. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012