Thermodynamic behavior of poly(3-alkyl thiophene) blends: Equilibrium cocrystal formation and phase segregation

The equilibrium cocrystal formation of poly(3-alkyl thiophene) (P3AT) blends has been studied by isothermal cocrystallization in a differential scanning calorimeter (DSC-7). The equilibrium melting points (T(m)0) of the cocrystals are measured using the Hoffman-Weeks extrapolation procedure. The equilibrium phase diagrams are of three different types: (a) concave upward, (b) linear, and (c) linear with phase separation at higher content of lower melting component. The phase diagram nature depends on the regioregularity difference and also on the difference in the number of carbon atoms in the pendent alkyl group of the components. The origin of biphasic nature of type "c" phase diagram has been explored from the glass transition temperature (Tg) measurement using a dynamic mechanical analyzer. The biphasic compositions show two glass transition temperatures (Tg) as well as two beta transition temperatures (T beta). The T(g)s of phase-separated regions correspond to almost the component values but the T(beta)s correspond to that of a lower (T beta) component value, and the other is higher than that of the higher (T beta) component value. Possible reasons are discussed from the interchain lamella thickness in the P3AT blends and molecular modeling using molecular mechanics program.     

Phase Behavior of Polymer Blends

The present report deals with some results on phase behavior, miscibility and phase separation for several polymer blends casting from solutions. These blends are grouped as the amorphous polymer blends, blends containing a crystalline polymer or two crystalline polymers. The blends of PMMA/PVAc were miscible and underwent phase separation at elevated temperature, exhibited LCST behavior. The benzoylated PPO has both UCST and LCST nature. For the systems composed of crystalline polymer poly(ethylene oxide) and amorphous polyurethane, of two crystalline polymers poly(-caprolactone) and poly[3,3,-bis-(chloromethyl) oxetane], appear a single T_g, indicating these blends are miscible. The interaction parameter B's were determined to be –14 J cm^–3, –15 J cm^–3 respectively. Phase separation of phenolphthalein poly(ether ether sulfone)/PEO blends were discussed in terms of thermal properties, such as their melting and crystallization behavior.This revised version was published online in November 2005 with corrections to the Cover Date.     

Phase equilibria in ternary polymer blends

The phase states and rheological properties of blends of three polymers??polystyrene, poly(methyl methacrylate), and the styrene-acrylonitrile copolymer??in the common solvent chloroform are studied. The phase diagrams are constructed and the positions of spinodals are determined via the method of turbidity points. The effect of the third polymer on the compatibility of the binary blend obeys Prigogine??s rule; that is, it is determined by the solubility of the added polymer in the first two components. The extremum composition dependence of rheological properties of ternary polymer systems in the vicinity of the separation point (the metastable region) is found. Through the method of convex-shell construction, the phase diagrams are calculated.     

Effect of component interaction on the melting and crystallization characteristics of pe/pib blends

Linear low density polyethylene/polyisobutylene blends were prepared in the entire composition range. Non-isothermal and isothermal crystallization of the samples was carried out and melting behavior was studied as a function of composition and crystallization temperature. The equilibrium melting temperature of the neat PE and the blends was determined by the Hoffman-Weeks extrapolation technique. Flory-Huggins interaction parameters were calculated by the approach of Nishi and Wang. The decrease of melting temperature with increasing PIB content indicated the interaction of the polymers in the melt. Both irregular chain structure of the crystalline polymer and interaction lead to a decrease of the equilibrium melting temperature and maximum lamellar thickness. The results prove that even relatively weak dispersive forces can lead to the miscibility of two polymers.     

Experimental determination of the H2SO4/(NH4)2SO4/H2O phase diagram

We have experimentally investigated the water and sulfuric acid-rich regions of the H2SO4/(NH4)2SO4/H2O ternary liquid/solid phase diagram using differential scanning calorimetry (DSC) and infrared spectroscopy of thin films. We present the liquid/solid ternary phase diagram for temperatures below 373 K and H2SO4 concentrations below 60 wt %. We have determined two ternary eutectics and two tributary reaction points for this system in the regions studied. It is also seen that sulfuric acid tetrahydrate (SAT) forms as a metastable solid over a large concentration range. Two true binary systems have been identified: ice/letovicite and SAT/ammonium bisulfate. Finally, we have compared our results to the predictions of the aerosol inorganics model and have found significant differences both in the final melting points and in the location of some of the phase boundaries including a significant discrepancy in the invariant points predicted versus those observed.     

Thermodynamics of polymer blends

The general principles of thermodynamic equilibrium in binary liquid systems are reviewed briefly, and extended to quasi-binary mixtures of polydisperse polymers. Molecular models allowing actual phase behaviour to be discussed in terms of molecular parameters are exposed to data on the system polystyrene/polyvinylmethylether. Disparity in size and share between the repeating units must be introduced to obtain reasonable agreement between theory and experiment. The neccessary introduction of the molar-mass distribution detracts from this agreement which makes clear that other aspects exist that must be taken into account. For example, cross association between repeating units has a marked effect on phase behaviour. Blends are subject to two kinds of thermodynamic aging which lead either to considerable mutual solubility in supposedly immiscible blends, or to metastable equilibria transforming into states of lower Gibbs energy. In both cases physical proerties of the blend will change with time.     

On the definition of a Monte Carlo model for binary crystal growth

We show that consistency of the transition probabilities in a lattice Monte Carlo (MC) model for binary crystal growth with the thermodynamic properties of a system does not guarantee the MC simulations near equilibrium to be in agreement with the thermodynamic equilibrium phase diagram for that system. The deviations remain small for systems with small bond energies, but they can increase significantly for systems with large melting entropy, typical for molecular systems. These deviations are attributed to the surface kinetics, which is responsible for a metastable zone below the liquidus line where no growth occurs, even in the absence of a 2D nucleation barrier. Here we propose an extension of the MC model that introduces a freedom of choice in the transition probabilities while staying within the thermodynamic constraints. This freedom can be used to eliminate the discrepancy between the MC simulations and the thermodynamic equilibrium phase diagram. Agreement is achieved for that choice of the transition probabilities yielding the fastest decrease of the free energy (i.e., largest growth rate) of the system at a temperature slightly below the equilibrium temperature. An analytical model is developed, which reproduces quite well the MC results, enabling a straightforward determination of the optimal set of transition probabilities. Application of both the MC and analytical model to conditions well away from equilibrium, giving rise to kinetic phase diagrams, shows that the effect of kinetics on segregation is even stronger than that predicted by previous models.     

Na+, K+, Mg2+∥Cl-, SO2-4-H2O五元体系35 ℃介稳相图研究

研究得出（Na+, K+, Mg2+∥Cl-, SO2-4-H2O）五元体系35 ℃时的介稳溶解度数据,绘制了该体系35 ℃的介稳相图,共有9个为氯化钠所饱和的结晶区域：氯化钾、钾芒硝（3K2SO4*Na2SO4）、钾镁矾（K2SO4*MgSO4*4H2O）、钾盐镁矾（KCl*MgSO4*2.75H2O）、光卤石（KCl*MgCl2*6H2O）、白钠镁矾（Na2SO4*MgSO4*4H2O）、硫酸钠、六水硫酸镁（MgSO4*6H2O）和水氯镁石（MgCl2*6H2O）. 所得35 ℃介稳相图与Vant Hoff 25 ℃稳定相图比较有较大区别：软钾镁矾（K2SO4*MgSO4*6H2O）、七水硫酸镁、五水硫酸镁及四水硫酸镁结晶区域消失,钾镁矾和钾盐镁矾结晶区域显著扩大. 所得35 ℃介稳相图与25 ℃介稳相图区别很大：软钾镁矾和七水硫酸镁结晶区域消失,同时出现了钾镁矾和钾盐镁矾的结晶区域. 在该五元体系35 ℃介稳相平衡研究中发现析出的是钾盐镁矾的低水化合物（KCl*MgSO4*2.75H2O）.     

New phase for one-component hard spheres

A completely new phase for one-component hard spheres is reported in an unexpected region of the phase diagram. The new phase is observed at compressibility factors intermediate between the solid and the metastable branches. It can be obtained from either Monte Carlo simulations alone or a combination of Monte Carlo and molecular dynamics calculations. An analysis of the intermediate scattering function data shows that the new phase is in a stable equilibrium. Radial distribution function data, configurational snapshots, bond order parameters, and translational order parameters obtained from molecular simulations indicate that the new phase is significantly different from the isotropic liquid, metastable, or crystalline phases traditionally observed in hard sphere systems. This result significantly changes our previous understanding of the behavior of hard spheres.     

From the two-component system CBrCl3+CBr4 to the high-pressure properties of CBr4

The experimental phase diagram of the CBrCl3+CBr4 system has been determined by means of X-ray powder diffraction and thermal analysis techniques from 200 K to the liquid state. Before melting, the two components have the same orientationally disordered (OD) face-centered cubic phase, and solid-liquid equilibrium is explained by simple isomorphism. The application of multiple crossed isopolymorphism formalism to the low-temperature solid-solid equilibria has enabled the inference of an OD rhombohedral metastable (at normal pressure) phase for CBr4. Experimental determination of the pressure-volume-temperature and construction of the pressure-temperature phase diagrams for CBr4 reveal the existence of a high-pressure phase, the rhombohedral symmetry of which is inferred by means of the thermodynamic assessment of the experimental phase diagram and demonstrated by means of high-pressure neutron diffraction measurements. The procedure used in this work confirms the connection between the appearance of metastable phases at normal pressure and their existence at high-pressure.     

Phase and structural transformations in melts, solutions, and blends of crystallizing polymers under deformation

Experimental results concerning the effect of shear deformation on phase and structural transitions in melts, solutions, and blends of crystallizing polymers are generalized and analyzed. The mechanism responsible for the influence of deformation on the melting (crystallization) temperature, on the structure of the polymers, and on the position of liquidus curves of their solutions and blends depending on the shear rate, molecular mass, and concentration of components is considered.     

Metastable Equilibrium in Quaternary System Li2SO4 ＋ K2SO4＋Li2CO3 ＋ K2CO3 ＋ H2O at 288 K

IntroductionThe Zhabuye salt lake, Tibet in China, is famousfor the high concentrations of lithium, boron, andpotassium in the world. The main components areLi , K , Na , B4O72 -, CO32 -, Cl-, SO42 -, andH2O, including rare elements such as Rb and Cs .The…     

Metastable Phase Equilibrium in the Reciprocal Quaternary System LiCl+MgCl2+Li2SO4+MgSO4+H2O at 348.15 K and 0.1 MPa

The metastable solubilities and the physicochemical properties including density and pH of the reciprocal quaternary system(LiCl+MgCl₂+Li₂SO₄+MgSO₄+H₂O) at 348.15 K and 0.1 MPa were determined using the isothermal evaporation method. The dry-salt diagram and water-phase diagram were plotted based on the experimental data. There are five invariant points, eleven univariant curves, and seven crystallization zones corresponding to hexahydrite, tetrahydrite, kieserite, bischofite, lithium sulfate monohydrate, lithium chloride monohydrate and lithium carnallite. Comparison between the stable and metastable diagrams at 348.15 K indicates that the metastable phenomenon of magnesium sulfate is obvious, and the crystallization regions of hexahydrite and tetrahydrite disappear in the stable phase diagram. A comparison of the metastable dry-salt phase diagrams at 308.15, 323.15 and 348.15 K shows that with the increasing of temperature the epsomite crystallization zone disappears from the dry-salt phase diagram of 303.15 K, and a new kieserite crystallization zone is presented at 348.15 K. The density and pH in the metastable equilibrium solution present regular change with the increasing of Jänecke index J(2Li⁺), and the calculated densities using the empirical equation agree well with the experimental values.     

Phase Relations in Metastable Equilibria of the PbO-GeO2 System

Metastable phase relations in the PbO-GeO₂ system have been studied by DTA and X-ray powder diffraction. Metastable equilibrium was acquired during the solidification of a melt while it was slowly (at 8 K/min) cooled from temperatures slightly exceeding the critical value for a given composition. In the metastable equilibrium acquired in this way, α-PbO-base solid solution and four metastable individual phases were observed in the system at room temperature, with different structures and different thermal stabilities. A metastable equilibrium phase diagram has been mapped.     

Fast FTIR imaging: A new tool for the study of semicrystalline polymer morphology

The distribution of chemical species and the degree of orientation in semicrystalline polymer systems have been studied using fast Fourier transform infrared (FTIR) imaging. A variety of poly(ethylene glycol) systems, including pure polymer, high and low molecular weight blends, and blends with amorphous polymers, were studied. It is shown that fast FTIR imaging can be used to determine the distribution of species with different molecular weights and can be used to determine the degree of segregation of different components in blends with amorphous polymers. Additionally, by employing an infrared polarizer, the degree of orientation was determined in these systems by the generation of spatially‐resolved dichroic ratio images. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2353–2359, 1999     

Solid-liquid Metastable Equilibria in Quaternary System （NaCl＋Na2CO3＋Na2SO4＋H2O） at 273.15 K

The metastable phase equilibria of the quaternary system NaCl+Na2CO3+Na2SO4+H2O were studied at 273.15 K. The salts' solubilities, densities and pH values of the equilibrated solution in this system were determined. According to the experimental data, the metastable equilibrium phase diagram, the diagram of density vs. composition and pH vs. composition diagram were plotted. The phase diagram consists of five univariant curves, four crystallization fields and two invariant points. The four crystallization fields correspond to sodium carbonate decahydrate (Na2CO3·10H2O), sodium sulfate decahydrate(Na2SO4·10H2O), sodium chloride(NaCl) and burkeite(2Na2SO4· Na2CO3), respectively. The crystallization field of sodium sulfate decahydrate(Na2SO4·10H2O) is the largest, which indicates that sodium sulfate is easy to saturate and crystallize from solution at 273.15 K.     

On the phase behavior of blends of polymers and nematic liquid crystals

The phase behavior of mixtures of polymers and nematic liquid crystals (LC) is investigated. Two types of systems are examined. The first one deals with blends in which the polymer is made of linear chains. In this case, a systematic study of the effects of various parameters on the phase diagrams is performed. In particular, it is shown how increasing the polymer size and/or the LC molecule size increases the miscibility gap of the mixture. It also reduces the region where a single nematic phase is observed in the presence of a tiny amount of polymer. Likewise, the relative effects of the isotropic and the nematic interaction parameters on the phase diagrams are examined. The second part of this investigation deals with blends involving crosslinked polymers. Here, substantial differences are observed as compared to the case where the polymer components are made of linear chains. These differences are illustrated by showing the phase diagrams in similar conditions for both blends. Unlike the case of a linear polymer matrix, it is observed that the single nematic phase and the nematic-isotropic spinodal branches are absent from the phase diagram of crosslinked polymers. This results into significant distortions of the phase diagram. In order to highlight all these effects, examples representing hypothetical blends are considered. These examples are chosen for illustration of the results in which the choice of numerical parameters is made consistently with the existing values in the literature which makes comparison with published data possible.     

Metastable Phase Equilibrium in the Aqueous Ternary System K<Subscript>2</Subscript>SO<Subscript>4</Subscript>+MgSO<Subscript>4</Subscript>+H<Subscript>2</Subscript>O at (288.15 and 308.15) K

The metastable solubilities and densities of the aqueous ternary system K₂SO₄+MgSO₄+H₂O at (288.15 and 308.15) K were determined with the isothermal evaporation method. Using the experimental results, the metastable phase diagram and the densities versus composition diagram were plotted. In the metastable phase diagrams of the ternary system at (288.15 and 308.15) K, there are in all two invariant points, three univariant solubility curves, and three metastable crystallization regions corresponding to arcanite (i.e., anhydrous potassium sulfate, K₂SO₄), picromerite (K₂SO₄⋅MgSO₄⋅6H₂O) and epsomite (MgSO₄⋅7H₂O) that are formed in the metastable equilibrium system. A comparison of the stable and metastable phase diagrams at each temperature shows that the metastable regions of magnesium sulfate are obvious, and the crystallizing regions of epsomite and arcanite are much larger than those in the stable phase diagram. The densities of the system changed regularly with the magnesium sulfate content. The resulting information can be used to recover potassium or remove magnesium. The calculated densities using an empirical equation agree well with the experimental results.     

Poly[3,3-bis(azidomethyl)oxetane]–2,4-dinitro-2,4-diazapentane

Constructing phase diagrams for the mixtures of semicrystalline polymers and low molecular mass substances by DSC can meet with difficulties in the case of slow polymer crystallization. A problem of this kind is encountered for high-energy compositions poly[3,3-bis(azidomethyl)oxetane] (PBAMO)–2,4-dinitro-2,4-diazapentane (DNAP). In this study, the experimental phase diagram PBAMO–DNAP is constructed by an optical method, which makes it possible to visualize structural transformations. The kinetic studies by DSC and XRD reveal that 30–50 days of storing a homogenized PBAMO–DNAP mixture at room temperature are needed to attain stationary values of the crystallinity degree and heat of fusion. Even after that, the DSC method cannot deliver a solubility curve of DNAP in PBAMO, which is naturally generated by the optical method. This curve separates a domain of physical gels, effectively crosslinked by polymer crystallites and swollen with the plasticizer molecules, from a two-phase domain, in which the above gel reaches osmotic equilibrium with the pure plasticizer. It is also shown that the melting temperature of DNAP drops with growing the PBAMO content in the mixture, which is consistent with a decrease in the mean size of plasticizer crystals formed in polymer pores during the previous cooling.