Miscibility and morphology of poly(ethylhexylacrylate)/liquid crystal blends prepared under different conditions

A comparative study of the phase diagrams and morphology of blends of poly(2‐ethylhexylacrylate) and low molecular weight liquid crystals (LCs) prepared under different conditions is presented. Two LCs are used; one is the 4‐cyano‐4′‐n‐pentyl‐biphenyl and the other is the eutectic mixture of cyanoparaphenylenes known as E7. Two series of blends are prepared under different conditions. The first series is obtained by the polymerization induced phase separation (PIPS) process under UV‐curing starting from a monomeric mixture, while the second series is prepared by a combination of the solvent induced phase separation and the thermally induced phase separation process starting from a mixture containing a commercial polymer with known molecular weight. Using gel permeation chromatography, it is found that the polymer molecular weight of the UV‐cured systems decreases with the concentration of LC in the precursor mixture. The experimentally obtained phase diagrams of these two series of systems show a miscibility shift at the composition where the molar mass of the polymer in the PIPS/UV blend exceeds that of the commercial polymer. Data are rationalized in terms of the Flory‐Huggins theory of isotropic mixing and the Maier‐Saupe theory of nematic order. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 18–27, 2007     

Phase diagrams of poly(dimethylsiloxane) and 5CB blends

The phase diagrams of poly(dimethylsiloxane) (PDMS) and 4‐cyano‐4′‐n‐pentyl‐biphenyl (5CB) mixtures are studied for two systems of different molecular weights of the polymer. The experimental diagrams are established by polarized optical microscopy (POM), and analyzed using a combination of the Flory–Huggins theory of isotropic mixing and the Maier–Saupe theory of nematic order. The results are compared with those of polystyrene (PS) and 4‐cyano‐4′‐n‐octyl‐biphenyl (8CB) with analogous molecular weight of the polymer. This investigation could be useful for the choice of systems in electro‐optical devices. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 581–588, 2001     

Poly(ethylene oxide)/poly(methyl methacrylate) (semi-)interpenetrating polymer networks: Synthesis and phase diagrams

Interpenetrating polymer networks (IPNs) of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) were prepared by simultaneous network formation. The PEO network was produced by acid-catlayzed self-condensation of α,ω-bis(triethoxysilane)-terminated PEO in the presence of small amounts of water. The PMMA network was formed by free radical polymerization of MAA in the presence of divinylbenzene as crosslinker. The reaction conditions were adjusted to obtain similar crosslinking kinetics for both reactions. An attempt was made to construct a phase diagram of the IPNs by measuring the composition of the IPNs at the moment of the appearance of the phase separation, as indicated by the onset of turbidity. This composition could be determined because the siloxane crosslinks of the PEO network could be hydrolyzed in aqueous NaOH with the formation of linear, soluble PEO chains. The phase diagram was compared with phase diagrams of blends of linear polymers and of semi-IPNs (crosslinked PMMA and linear PEO), obtained under similar conditions, i.e. polymerization of MMA in the presence of varying amounts of PEO. It was observed that the form of the phase diagrams of the linear polymers is similar to that of the IPNs, but is quite different from that of the semi-IPNs. Thus, homogeneous transparent materials containing up to 60% of PEO could be prepared in the blends and the IPNs, but in the semi-IPNs, phase separation occurred with PEO contents as low as 10%.     

Solubility effects of multicomponent liquid crystal blends towards poly (n-butyl-acrylate)

Blends composed of isotropic linear poly (n-butylacrylate) of molecular weight M _w?=?112,000 g mol^?1 and the commercial four-component nematic low molecular weight liquid crystal (LC) mixture E7 exhibit a strong shift of the single nematic–isotropic transition temperature T _NI compared to that of the pure LCs, which was evidenced by using two complementary experimental techniques: differential scanning calorimetry (DSC) and high-performance liquid chromatography. The first one provides direct information about phase behaviour and variation of T _NI of the polymer/LC blends, whereas the second one consists of analysing qualitatively and quantitatively the composition of millimetre-sized segregated LC domains in the two-phase region of the phase diagram.

In order to understand the origin of the unusual phase behaviour, several LC blends were prepared by modifying the concentration of the four single LC components that are present in the eutectic E7 mixture, following the results from the previous chromatographic analysis. These model blends were investigated by DSC measurements, showing that the variation, particularly of the terphenyl LC compound concentration, plays a determining role for the phase behaviour of the LC mixture and the shift of T _NI.     

Coarse‐grained molecular dynamics simulations of stereoregular poly(methyl methacrylate)/poly(vinyl chloride) blends

The stereoregular poly(methyl methacrylate)/poly(vinyl chloride) blends with a wide formulation range are extensively simulated using the coarse‐grained (CG) molecular dynamics (MD) method. To improve the representability, the bonded CG potentials are re‐parameterized against the atomistic simulated melt systems whereas the nonbonded CG potentials are adopted as developed in our previous work. Based on the CG potentials, the MD simulations reproduce all the local distributions of pure systems and the miscibility of mixed systems. Moreover, the global conformational properties are also closer to the target ones than those obtained using the previous CG potentials. The changes in density and volume upon mixing are computed together with the energies of mixing. They are all negative over the entire composition range and indicate stronger intermolecular interactions between distinct components than those between identical components. In particular, it is found that upon mixing the changes in density are insensible to chain tacticity but the changes in volume and the energies of mixing do, which quantitatively confirms that both inter‐molecular interactions and free‐volumes mainly contribute to the observed phase behaviors. Such models and methods reported herein can be used to quickly optimize formulations of polymer blends. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 203–212     

Fibrinolytic poly(dimethyl siloxane) surfaces

PDMS surfaces have been modified to confer both resistance to non-specific protein adsorption and clot lyzing properties. The properties and chemical compositions of the surfaces have been investigated using water contact angle measurements, ATR FT-IR spectroscopy, and XPS. The ability of the PEG component to suppress non-specific protein adsorption was assessed by measurement of radiolabeled fibrinogen uptake from buffer. The adsorption of plasminogen from human plasma to the various surfaces was studied. In vitro experiments demonstrated that lysine-immobilized surfaces with free epsilon-amino groups were able to dissolve fibrin clots, following exposure to plasma and tissue plasminogen activator. [Figure: see text].     

Phase state diagrams of the poly(dimethylsiloxane)—poly(diethylsiloxane) system

Phase equilibria in the poly(dimethylsiloxane)(PDMS)—polydiethylsiloxane (PDES) system in the amorphous and liquid-crystal states were studied by optical interferometry. The findings obtained were compared with the data of calorimetric measurements. The experiments were carried out in a wide range of molecular weights and temperatures, and the phase diagrams were constructed. Thermodynamic analysis of the experimental data was performed in the framework of the Flory—Haggins theory for polymeric solutions. The analytical expressions for calculation of the pair interaction parameter using the binodal and liquidus curves were obtained. The pair interaction parameters of polymers and their dependences on the temperature and molecular weight were determined. The pair interaction parameter was shown to decrease with increasing the molecular weight of the oligomer component, approaching asymptotically a limiting value, which characterizes the interaction of the high molecular-weight PDMS and PDES. It was shown that the phase equilibria in the PDMS—PDES systems can be predicted quantitatively and qualitatively.     

Ternary Chlorides of the Trivalent Early Lanthanides. Phase diagrams,crystal structures and thermodynamic properties

A comprehensive review on phase diagrams, crystal structures and thermodynamics of ternary chlorides formed in systems ACl/LnCl₃ (A=Cs, Rb, K, Na; Ln=La−Gd) is presented. The review summarizes the author’s own studies, published since 1985, and original papers of other scientists. With the larger alkali metal ions compounds such as A₃LnCl₆, A₂LnCl₅ and ALn₂Cl₇were obtained. With sodium additional compounds NaLnCl₄ and Na₃Ln₅Cl₁₈ were obtained. The crystal structures are discussed with the concept of ionic radii, which determine the coordination numbers of Ln³⁺ and A⁺ cations against Cl⁻ anions. The formation enthalpies of the compounds from ACl and LnCl₃ were determined by solution calorimetry. Gibbs’ free energies and entropies for these reactions were obtained by e.m.f. measurements vs. temperature. The stability of a ternary chloride in a systemACl−LnCl₃ is given by the ‘free enthalpy of synproportionation’, that is, the formation of a compound from its neighbour compounds in the system. This ΔG ⁰ _syn must be negative. A surprising result is, that the highest-melting compounds in the systems, A₃LnCl₆, are formed from ACl+A₂LnCl₅ by a loss in lattice energy. They exist as high-temperature compounds due to sufficiently high gain in entropy at temperatures whereTΔS>ΔH. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase equilibria of polymer dispersed liquid crystal systems in the presence of an external electrical field

The effect of an external electrical field on phase behaviors is reported for polymer dispersed liquid crystal films of 4′‐pentyl‐4‐biphenylcarbonitrile/poly(methyl methacrylate) binary mixtures with various polymer molecular weights. The experimental results show that increasing the molecular weight of the polymer or the electrical field intensity can give rise to an increase in the phase‐transition temperature and a widening of the binary phase region. The lattice theory, regarding a binary system consisting of a rigid nematic liquid crystal and a random polymer, has been extended to the case in which an external electrical field is present. A comparison of the theoretical predictions with the experimental results has been carried out, and satisfactory agreement has been found. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1898–1906, 2007     

Phase behavior of polystyrene acrylonitril copolymer and polymethylmethacrylate blends under shear

Polymer blends undergo external stresses such as pressure and shear in course of processing cycles. The knowledge of their phase behavior at each step of these cycles is crucial for understanding their physical properties and eventually improves their performance in practical applications. The effects of shear on the phase diagram of binary polymer blends are considered. A theoretical formulism is used upon which the free energy is the sum of two terms. The first term is modeled with the Flory–Huggins free energy of mixing and describes the thermodynamic behavior of the system in the quiescent state. The second term represents the excess free energy stored during flow. In the presence of shear flow, the excess free energy is expressed in terms of the viscosity and the shear modulus. Both quantities depend on composition and shear rate. The curvature of the variation of viscosity versus composition has a tremendous impact upon the nature of phase separation. Phase diagrams are described by the spinodal curves and show for the case considered here miscibility enhancement with increasing shear rate. A good correlation is found with experimental data of the literature on blends of polystyrene acrylonitril copolymer and polymethylmethacrylate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Phase transition of polycarbonate in blends with liquid crystal

Phase transition temperatures of polycarbonate film consisting of micron-sized liquid crystalline droplets were investigated using differential scanning calorimetry (DSC) and thermo-optical analysis (TOA) methods. Both a decrease in (T _g ) and (T _m ) of the polycarbonate with an increase of liquid crystal (LC) content in the sample were observed. The decrease ofT _g is related to the plastifying effect of a low molecular weight LC substance remaining soluble in the polycarbonate matrix. A fraction of the liquid crystal contained in the droplets was estimated on the basis of theT _g decrease.     

Anomalous melting behavior of cyclohexane and cyclooctane in poly(dimethyl siloxane) precursors and model networks

Building on previous observations of anomalous melting behavior of solvents in polyisoprene, we have expanded our insight into the melting behavior of organic solvents in polymers and polymer networks through a calorimetric investigation of cylcohexane and cyclooctane in poly(dimethyl siloxane) (PDMS) precursors and model networks. The results are contrary to general expectations. Besides deviations between the predictions of the Flory-Huggins model and observed melting point depression of the small molecule organics, it is found that the melting point depression of cyclohexane in model networks is lower than that in the uncrosslinked precursors and unaffected by the molecular weight between crosslinks, which is not consistent with the general observation that higher crosslinking density leads to greater melting point depression. We interpret the observed phenomenon in terms of phase separation. In the case of cyclooctane, it exhibits a double melting peak in the model networks with high molecular weight between crosslinks. Furthermore, the heats of fusion of both cyclohexane and cyclooctane decrease with increasing polymer volume fraction which violates the underlying assumption that the heat of fusion of solvent in the polymer is the same as that in the bulk for both the Flory-Huggins model and the Gibbs-Thomson equation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2779–2791, 2008     

Relationships between the molecular architecture,crystallization capacity,and miscibility in poly(butylene terephthalate)/polycarbonate blends: A comparison with poly(ethylene terephthalate)/polycarbonate blends

Poly(butylene terephthalate) (PBT)/polycarbonate (PC) samples, prepared via reactive blending in the presence of Ti‐ and Sm‐based catalysts, resulted in block copolymers whose block length decreased as the mixing time increased. A single homogeneous amorphous phase occurred when the blocks had monomeric sequences shorter than 10 units. Otherwise, a crystalline phase of PBT developed. Also, in poly(ethylene terephthalate) (PET)/PC blends previously studied, the miscibility was strictly correlated with the crystallizability of the system. Therefore, the miscibility of the PBT/PC and PET/PC blends was compared with respect to the tendency of the PBT and PET blocks to crystallize under isothermal conditions. The crystallization rate of the PBT/PC copolymers was faster than that of the PET/PC copolymers with similar block lengths. Accordingly, the minimum crystallizable sequence length of the PBT blocks was shorter than that of the PET blocks (18 vs 31 monomeric unit sequences). This behavior was interpreted as an effect of the more flexible PBT units, which had a greater tendency to fold and crystallize than the PET units. Therefore, PBT, the blocks of which tended to crystallize even if they were very short and phase‐separated, was characterized by a poorer compatibility with PC than that of PET. As a result, the block size had a fundamental role in determining the crystallizability and, therefore, phase behavior of the semicrystalline block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2821–2832, 2004     

Phase behaviour and morphology of polymer/liquid crystal blends

Abstract

The phase behaviour of blends of poly(ethylene oxide) (PEO) with the liquid crystal p-azoxyanisole (PAA) has been studied by differential scanning calorimetry and optical microscopy. This system exhibits partial miscibility of the components in the molten state (at temperatures above 337 K). The melting temperature and enthalpy of the PAA phase has been found to depend on the blend composition, whereas the melting behaviour of the polymer phase remains quite unaltered. The occurrence of the PAA nematic phase, dispersed within an isotropic liquid phase, has been observed at high concentrations of liquid crystal. The morphology of the blends in the solid state changes largely with the PAA content, depending on the solubility of the components in the liquid phase.     

Phase diagrams of blends of azide-containing polyoxetanes

The mutual solubility of polymers based on the azide-containing oxetane monomers 3,3-bis(azidomethyl)oxetane and 3-azidomethyl-3-methyloxetane is studied. The temperatures of melting, crystallization, glass transition; the upper critical solution temperature; and the compositions of coexisting phases for blends of polymers with different molecular masses are determined via differential scanning calorimetry and multiple-beam microinterferometry. On the basis of these data, the phase diagrams of blends are constructed. The melting regions and the metastable and heterogeneous states are determined. The studied systems are shown to have a complex amorphous-crystalline equilibrium and to differ in the location of boundary curves on the phase diagram, depending on the molecular mass of the components. Amorphous separation below the liquidus line in the metastable region with respect to the crystalline equilibrium is experimentally detected. The motion of the figurative point in different regions of the diagram is thoroughly considered. The specifics of structural and morphological organization of systems are examined via electron microscopy.     

Phase diagrams of binary crystalline-crystalline polymer blends

A thermodynamically self-consistent theory has been developed to establish binary phase diagrams for two-crystalline polymer blends by taking into consideration all interactions including amorphous-amorphous, crystal-amorphous, amorphous-crystal, and crystal-crystal interactions. The present theory basically involves combination of the Flory-Huggins free energy for amorphous-amorphous isotropic mixing and the Landau free energy of polymer solidification (e.g., crystallization) of the crystalline constituents. The self-consistent solution via minimization of the free energy of the mixture affords determination of eutectic, peritectic, and azeotrope phase diagrams involving various coexistence regions such as liquid-liquid, liquid-solid, and solid-solid coexistence regions bound by liquidus and solidus lines. To validate the present theory, the predicted eutectic phase diagrams have been compared with the reported experimental binary phase diagrams of blends such as polyethylene fractions as well as polycaprolactone/trioxane mixtures.     

Immiscibility–miscibility phase transformation in blends of poly(ethylene succinate) with poly(L‐lactic acid)s of different molecular weights

Using differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and Fourier transformed infrared spectroscopy (FTIR), upper critical solution temperature (UCST) phase behavior with immiscibility–miscibility transformation in blends of poly(ethylene succinate) (PESu) with poly(lactic acid)s (PLAs), such as poly(D ,L ‐lactic acid) (PDLLA), poly(L ‐lactic acid) (PLLA), poly(D ‐lactic acid) (PDLA), differing in D/L configurations and molecular weights were investigated. All three binary blends of PDLLA/PESu, PLLA/PESu, and PESu/PDLA exhibit UCST behavior, which means they are immiscible at ambient temperature but can become miscible upon heating to higher temperatures at 240–268 °C depending on molecular weights. The PLLAs/PESu blends at UCST could be reverted back to the original phase‐separated morphology, as proven by solvent redissolution. The blends upon quenching from above UCST could be frozen into a quasi‐miscible state, where the Flory‐Huggins interaction parameter (χ₁₂) was determined to be a negative value (by melting point depression technique). The interaction between PDLLA and PESu in blend resulted in significant reduction in spherulite growth rate of PESu. Furthermore, blends of PESu with lower molecular weight PLLA or PDLA (M_w of PLLA and PDLA are 152,000 and 124,000 g/mol, respectively), instead of the higher M_w of PDLLA (M_w of PDLLA = 157,000 g/mol), are immiscible with UCST phase behavior, which are affected by molecular weights rather than the ratio of L/D monomer in the chemical structure of PLAs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1135–1147, 2010     

Phase diagrams and morphology of polymer-dispersed liquid crystals: An analysis

Thermal and morphological studies of polymer-dispersed liquid crystals (PDLCs) for various compositions of liquid crystalline material 4-undecyloxybenzoic acid (UDBA) in two polymer matrices, polyvinylidenefluoride-co-hexafluoropropylene P(VdF–HFP) or polyethylene oxide (PEO), have been carried out using differential scanning calorimetry (DSC) and polarising optical microscopy (POM). Phase diagrams for different series of PDLCs have been analysed using the Flory–Huggins theory of isotropic mixing and the Maier–Saupe–McMillan theory, to include the anisotropic contributions. Mesogenic transitions of UDBA are observed to be greatly influenced when dispersed in these polymers. The morphologies and miscibility studies of these PDLCs suggest that UDBA is highly miscible in PEO, only partially miscible in poly(methyl methacrylate) (PMMA), but almost immiscible in P(VdF–HFP).     

Morphology of poly(ethylene oxide)/poly(vinyl acetate) blends

The morphology of poly(ethylene oxide)/poly(vinyl acetate) (PEO/PVAc) blends was examined using small angle X-ray scattering (SAXS) and optical microscopy. The morphological and structural parameters of the blends are dependent on both composition and crystallization conditions. Optical microscopy revealed that blend samples prepared by solution casting crystallized with volume-filling crystals up to a composition of 30/70 wt% PEO/PVAc; at higher PVAc content there was no evidence of crystallization in the temperature range studied. Pure PEO always crystallized with a spherulite-hedrite morphology. The formation of spherulites was relatively favoured at lower crystallization temperatures and by addition of PVAc to PEO. Small angle X-ray intensity profiles were analyzed using a recently developed methodology and it was found that, for a given crystallization temperature, the amorphous and interphase thicknesses increased with increasing PVAc content but that the average crystalline thickness was independent of composition. The morphological and structural properties of the PEO/PVAc blends were attributed to the presence of non-crystallizable material in both the interlamellar and interfibrillar regions.