Pressure effects on the thermodynamics of trans-decahydronaphthalene/polystyrene polymer solutions: Application of the Sanchez-Lacombe lattice fluid theory

The cloud-point temperatures (T-cl's) of trans-decahydronaphthalene(TD)/polystyrene (PS, (M) over bar (w) = 270 000) solutions were determined by light scattering measurements over a range of temperatures (1-16degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol.-% polymer). The system phase separates upon cooling and T-cl was found to increase with rising pressure for constant composition. In the absence of special effects, this finding indicates positive excess volume for the mixing. Special attention was paid to the demixing temperatures as a function of pressure for different polymer solutions and the plots in the T-phi plane (where phi signifies volume fractions). The cloud-point curves of polymer solutions under different pressures were observed for different compositions, which demonstrated that pressure has a greater effect on the TD/PS solutions when far from the critical point as opposed to near the critical point. The Sanchez-Lacombe lattice fluid theory (SLLFT) was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalpy of mixing, and the volume changes of mixing. The calculated results show that modified PS scaling parameters can describe the thermodynamics of the TD/PS system well. Moreover the SLLFT describes the experimental results well.

What has brought on the effects of number-average molecular weight on the spinodals in polymer mixtures?

On the basis of the thermodynamics of Gibbs, the spinodal for the quasibinary system was derived in the framework of the Sanchez-Lacombe lattice fluid theory. All of the spinodals were calculated based on a model polydisperse polymer mixture, where each polymer contains three different molecular weight subcomponents. According to our calculations, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights, whereas that of the z-average molecular weight is invisible. Moreover, the extreme of the spinodal decreases when the polydispersity index (eta = (M) over bar (w)/(M) over bar (n)) of the polymer increases. The effect of polydispersity on the spinodal decreases when the molecular weight gets larger and can be negligible at a certain large molecular weight. It is well-known that the influence of polydispersity on the phase equilibrium (coexisting curve, cloud point curves) is much more pronounced than on the spinodal. The effect of M, on the spinodal is discussed as it results from the infuluence of composition temperatures, molecular weight, and the latter's distribution on free volume. An approximate expression, which is in the assumptions of v* v(1)* = v(2)* and 1/r --> 0 for both of the polymers, was also derived for simplification. It can be used in high molecular weight, although it failed to make visible the effect of number-average molecular weight on the spinodal.

Preparation of polymer/silica nanoscale hybrids through sol-gel method involving emulsion polymers. II. Poly(ethyl acrylate)/SiO2

Poly(ethyl acrylate) (PEA)/SiO2 hybrids with different compositions were prepared under different casting temperatures and pH values. Their morphology as investigated by transmission electron microscopy (TEM) shows that samples with different compositions have different morphologies. When the SiO2 content is lower, PEA is the continuous phase and SiO2 is the dispersed phase. At higher SiO2 content, the change in phase morphology takes place, nd PEA gradually dispersing in the form of latex particles in SiO2 matrix. Change in phase morphology depends mainly on the time the sol-gel transition occurs. At suitable casting temperature and pH value, PEA/SiO2 in 95/5 and 50/50 hybrids with even dispersion was obtained.

Theoretical estimation of thermodynamic properties of the system PS/PPO on the basis of modified combining rule of Sanchez-Lacombe lattice fluid model

The three scaling parameters described in Sanchez-Lacombe lattice fluid theory (SLLFT), T*, P* and rho* of pure polystyrene (PS), pure poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and their mixtures are obtained by fitting corresponding experimental pressure volume-temperature data with equation-of-state of SLLFT. A modified combining rule in SLLFT used to match the volume per mer, v* of the PS/PPO mixtures was advanced and the enthalpy of mixing and Flory-Huggins (FH) interaction parameter were calculated using the new rule. It is found that the difference between the new rule and the old one presented by Sanchez and Lacombe is quite small in the calculation of the enthalpy of mixing and FH interaction parameter and the effect of volume-combining rule on the calculation of thermodynamic properties is much smaller than that of energy-combining rule. But the relative value of interaction parameter changes much due to the new volume-based combining rule. This effect can affect the position of phase diagram very much, which is reported elsewhere [Macromolecules 34 (2001) 6291]

Surface morphology evolution of thin triblock copolymer films during spin coating

The surface morphology evolution of thin poly(styrene-block-ethylene/butylenes-block-styrene) (SEBS) triblock copolymer films as a function of the copolymer concentration was investigated by means of dynamic mode atomic force microscopy. At a relatively low copolymer concentration (0.025% w/v), the periodically orientated stripes were observed. This kind of surface patterning produced in the spin-coating process has not been reported in the literature before. It has been shown by our experiment that a shearing and stretching field can cause flexible polymer coils or aggregates to orientate during the spin coatings At a copolymer concentration of 0.05% w/v, SEBS molecule aggregates form network structures in the whole film. With further increase of the copolymer concentration, a continuous film with a microphase-separated structure was visualized.

Statistical thermodynamics of polydisperse polymer systems in the framework of lattice fluid model: Effect of molecular weight and its distribution on the spinodal in polymer solution

With the aid of thermodynamics of Gibbs, the expression of the spinodal was derived for the polydisperse polymer-solvent system in the framework of Sanchez-Lacombe Lattice Fluid Theory (SLLFT). For convenience, we considered that a model polydisperse polymer contains three sub-components. According to our calculation, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights of the polydisperse polymer, but the z-average molecular weight ((M) over bar (z)) dependence on the spinodal is invisible. The dependence of free volume on composition, temperature, molecular weight, and its distribution results in the effect of (M) over bar (n) on the spinodal. Moreover, it has been found that the effect of changing (M) over bar (w) on the spinodal is much bigger than that of changing (M) over bar (n) and the extrema of the spinodal increases with the rise of the weight-average molecular weight of the polymer in the solutions with upper critical solution temperature (UCST). However, the effect of polydispersity on the spinodal can be neglected for the polymer with a considerably high weight-average molecular weight. A more simple expression of the spinodal for the polydisperse polymer solution in the framework of SLLFT was also derived under the assumption of upsilon(*)=upsilon(1)(*)=upsilon(2)(*) and (1/r(1)(0))-(1/r(2i)(0))-->(1/r(1)(0)).

Nanostructured hybrid organic-inorganic lanthanide complex films produced in situ via a sol-gel approach

Communication: Nanostructural hybrid organic-inorganic lanthanide complex films were prepared in situ by use of a novel sol-gel precursor containing pendant triethoxy-silyl and carboxyl groups (see Figure). The resulting transparent and crack-free films gave rise to strong red or green emission, even at low lanthanide ion concentration. Phase separation and lanthanide ion aggregation were controlled at the nanoscale.

Thermodynamics of blends of PEO with PVAc: application of the Sanchez-Lacombe lattice-fluid theory

Sanchez-Lacombe (SL) lattice-fluid theory was used to predict the miscibility of the PEO/PVAc blending system. Integral interaction parameters, g of this polymer pair were calculated by using SL theory. And the effect of the temperature, composition of blends and molecular weight of PVAc on the extent of their miscibility has been discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.

Shear induced mixing/demixing: Blends of homopolymers, of homopolymers plus copolymers, and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.

Effects of pressure and molecular weight on the miscibility of polystyrene and cyclohexane

With the aid of Sanchez-Lacombe lattice fluid theory (SLLFT), the phase diagrams were calculated for the system cyclohexane (CH)/polystyrene (PS) with different molecular weights at different pressures. The experimental data is in reasonable agreement with SLLFT calculations. The total Gibbs interaction energy, g*(12) for different molecular weights PS at different pressures was expressed, by means of a universal relationship, as g(12)* =f(12)* + (P - P-0) nu*(12) demixing curves were then calculated at fixed (near critical) compositions of CH and PS systems for different molecular weights. The pressures of optimum miscibility obtained from the Gibbs interaction energy are close to those measured by Wolf and coworkers. Furthermore, a reasonable explanation was given for the earlier observation of Saeki et al., i.e., the phase separation temperatures of the present system increase with the increase of pressure for the low molecular weight of the polymer whereas they decrease for the higher molecular weight polymers. The effects of molecular weight, pressure, temperature and composition on the Flory Huggins interaction parameter can be described by a general equation resulting from fitting the interaction parameters by means of Sanchez-Lacombe lattice fluid theory.

Thermodynamics of PMMA/SAN blends: Application of the Sanchez-Lacombe lattice fluid theory

Polymer blends of poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) with an acrylonitrile content of about 30 wt % were prepared by means of solution-casting and characterized by virtue of pressure-volume-temperature (PVT) dilatometry. The Sanchez-Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalpy of the mixing, the volume change of the mixing, and the combinatorial and vacancy entropies of the mixing for the PMMA/SAN system. A new volume-combining rule was used to evaluate the close-packed volume per mer, upsilon*, of the PMMA/SAN blends. The calculated results showed that the new and the original volume-combining rules had a slight influence on the FH interaction parameter, the enthalpy of the mixing, and the combinatorial entropy of the mixing. Moreover, the spinodals and the binodals calculated with the SL theory by means of the new volume-combining rule could coincide with the measured data for the PMMA/SAN system with a lower critical solution temperature, whereas those obtained by means of the original one could not.

Miscibility and crystallization behavior of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB)/poly(ethylene oxide) (PEO) blends were studied by differential scanning calorimetry(DSC) and polarizing microscopy (POM). It is found that the miscibility is related to the composition of the blends. When the PEO content is over 20 percent, the miscible blends turn into partially miscible and the phase separation can be observed with POM. The addition of the PEO influences not only the morphology of PHB crystals and the radial growth rate of spherulites, but also the cold crystallization temperature.

Application of the Sanchez-Lacombe lattice fluid theory to the system pvme/ps and model calculations

Cloud point curves reported in the literature for five representatives of the system poly(vinyl methyl ether)/polystyrene were evaluated theoretically by means of the Sanchez-Lacombe lattice fluid theory. The measured phase separation behavior can be described within experimental error using only one adjustable parameter (quantifying the interaction between the unlike mers). The Flory-Huggins interaction parameters calculated from this theoretical description depend in good approximation linearly on composition (volume fractions) and on the inverse temperature. An evaluation of these data yields a maximum heat effect which is almost one order of magnitude less (ca. -0.25 J/cm(3)) than obtained via Hess's cycle (dissolution of the components and of the blend) from calorimetric measurements. Model calculations on the basis of the present theory demonstrate that the critical points shift to a different extent upon a certain relative change in the molar mass of the blend components. The sensitivity of the calculated phase diagrams against changes in the scaling parameter decreases in the following order: interaction energies between unlike mers, differences in the scaling temperatures, pressures and densities.

Synthesis and miscibility studies of rodlike flexible polyimide molecular composites via para-para linked aromatic poly(amic ester) precursors

Para-para linked aromatic poly(amic ester) precursors of rodlike polyimide (PI) BPDA-PDA and polyetherimide (PEI) HQDPA-ODA were synthesized. The para-para linked poly(amic ester)s were employed in this work to obtain, in theory, full-imidized polyimides. The two precursors were mixed by dissolving them in N, N'-dimethyl acetamide and subsequently coagulating in methanol. After thermal imidization, the miscibility behaviour of the resulting composites has been studied by means of dynamic mechanical analysis (d.m.a.) and differential scanning calorimetry (d.s.c.). The composites show a single glass transition temperature (T-g) at both d.m.a. and d.s.c. in which the T-g increases with increasing PI content. These Tg values are reproducible in repeated heating cycles, suggesting the true miscibility of the blends. (C) 1997 Elsevier Science Ltd.

Crystallization behavior of blends of high-density polyethylene with novel linear low-density polyethylene

Blends of high-density polyethylene (HDPE) with novel linear low-density polyethylene (LLDPE) samples in the whole range of compositions were investigated by means of differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). The LLDPEs are ethylene/octene-1 copolymers prepared with a single-site catalyst, with a narrower distribution of branches compared to Ziegler-Natta type polymers. It was found that cocrystallization or separate crystallization in the blends profoundly depends on the content of branches in the LLDPE, while the critical branch content of the novel LLDPE for separate crystallization is much lower than that of commercial LLDPE (prepared with Ziegler-Natta catalysts). This implies that the miscibility of linear and branched polyethylene is also affected by the distribution of branches. The marked expansion of the unit cell in cocrystals, which are formed by HDPE with the novel LLDPE, indicates that the branches are included in the crystal lattice during the cocrystallization process. The result is very helpful to understand the phenomenon that the unit cell dimensions of commercial branched polyethylene are larger than those of linear polyethylene.