Pressure dependence of the second virial coefficient of dilute polystyrene solutions

The pressure derivatives of the second virial coefficients [dA₂/dP; 0.1 ≤ P (MPa) ≤ 35.0] for dilute polystyrene (PS) solutions in good, θ, and poor solvents were measured with static light scattering. The solvent quality improved (dA₂/dP > 0) in the good and poor solvents that we investigated (toluene, chloroform; and methylcyclohexane) but deteriorated (dA₂/dP < 0) in θ solvents (cyclohexane and 50‐50 cis,trans‐decalin). The effects of temperature [22 < T (°C) < 45] and molecular weight [25 × 10³ < weight‐average molecular weight (amu mol^?1) < 900 × 10³] on dA₂/dP for PS/cyclohexane solutions were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3070–3076, 2003     

Continuity of solvent quality in polymer solutions. Poor-solvent to Θ-solvent continuity in some polystyrene solutions

Critical temperatures for polystyrene/methyl acetate (PS/MA) and polystyrene/ethyl formate (PS/EF) solutions were measured at positive (PS/MA, PS/EF) and negative (PS/MA) pressure. The results confirm that solvent quality is sensitive to pressure; some solvents, designated Θ, at P_nominal ∼ 0, undergo a Θ-to-poor transition at negative pressure, and others, nominally designated “poor,” show a poor-to-Θ transition at positive pressure. Thus, any dichotomous division into sets of “poor” and “Θ” solvents is inaccurate, unless it accounts for the effects of pressure and other variables on solvent quality. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1251–1259, 1997     

Electrokinetic demixing of aqueous two-phase polymer/salt systems

Electrokinetic demixing of aqueous two-phase polymer/salt systems is demonstrated, resulting in significant enhancement in demixing rates by about 1-4-fold. The effect of field polarity, field strength, volume ratio, and phase composition on phase demixing has been studied. Further the influence of these parameters on phase demixing could be explained based on the hydrodynamic flow-electroosmotic flow (HEF) model.     

Pressure dependence of the demixing behaviour in polymer blends: I. Experimental procedure

The most common way to influence the liquid-liquid phase behaviour in partially miscible (co-)polymer blends is changing the blending temperature. Since most extruders can handle pressures, up to 300 bar, pressure may also be used to influence the miscibility of polymers during blending. We have developed equipment and an experimental procedure to study the pressure dependence of the liquid-liquid demixing behaviour of high-viscous polymer blends under equilibrium conditions. Small amounts (1–4 grams) of specially made polymers are blended in the ‘DSM MINI EXTRUDER’. After a chosen mixing time, a small portion of the blend is injected into a small capillary tube and kept at the blending temperature. The phase behaviour of the blends as a function of temperature and pressure is studied via laser light scattering (at a scattering angle of 90°) in a specially made 400 bar/250°C window autoclave, where the capillary cell is placed in a high temperature grade silicon oil.     

Polymer-solvent demixing under tension. Isotope and pressure effects on liquid-liquid transitions,VII. Propionitrile–polystyrene solutions at negative pressure

Liquid-liquid demixing in propionitrile-polystyrene solutions has been observed (?2 < P/MPa < 4) using a Berthelot tube technique. The experimental isopleths join smoothly to ones gathered at positive pressure by another technique. The equation of state used to describe the transitions thus appears to be valid across the entire liquid range. © 1994 John Wiley & Sons, Inc.     

Organization of nanoscale objects via polymer demixing

We present an extremely versatile method for the lateral organization of nano-scale objects (NOs) based on the phenomenon of polymer demixing. NOs are suspended in a solution of two immiscible polymers, which is used to form a thin polymer film by spin coating. During spin coating the two polymers separate to give a microphase structure, whose length scale depends on the experimental conditions. The NOs spontaneously partition into one or other of the polymer phases resulting in their lateral organization. In this work, the organization of CdSe nanoparticles and fluorescent organic dyes was studied by fluorescence microscopy. The NOs were organized in the polymer film in stochastic patterns or in ordered designs on substrates pre-patterned by soft-lithography techniques. Single-particle measurements, using confocal microscopy, showed that at low concentrations there was little aggregation of the particles.     

Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

Simultaneous measurement of the solubility of nitrogen and carbon dioxide in polystyrene and of the associated polymer swelling

New experimental results for the solubility of nitrogen and carbon dioxide in polystyrene are reported, accompanied by data on the change in volume of the polymer caused by the sorption process. The two phenomena were measured simultaneously with a combined technique, in which the quantity of penetrating fluid introduced into the system was evaluated by pressure‐decay measurements in a calibrated volume, whereas a vibrating‐wire force sensor was employed for weighing the polymer sample during sorption inside of the high‐pressure equilibrium cell. The use of the two techniques was necessary because the effects of swelling and solubility could not be decoupled in a single gravimetric or pressure‐decay measurement. The sorption of nitrogen in polystyrene was studied along three isotherms from 313 to 353 K at pressures up to 70 MPa. The sorption of carbon dioxide was measured along four isotherms from 338 to 402 K up to 45 MPa. The results are compared with values from the literature when possible, although our data extend significantly the pressure ranges of the latter. The uncertainties affecting our measurements with nitrogen are 1 mg of N₂/g of polystyrene in solubility and 0.1% of the volume of the polymer. For carbon dioxide, the uncertainties are 5 mg of N₂/g of polystyrene and 0.5% respectively, carbon dioxide being about 1 order of magnitude more soluble than nitrogen. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2063–2070, 2001     

Demixing in polystyrene/methylcyclohexane solutions

Cloudpoint data for polystyrene/methylcyclohexane solutions extending over moderate ranges of pressure and molecular weight are available in the literature. Those data are supplemented with new results from this laboratory to fill in gaps and extend the MW range (to 761 ≤ MW/amu ≤ 2 × 10⁷). The resulting data net is discussed and reasons to extend studies to higher pressure are presented. © 1996 John Wiley & Sons, Inc.     

Vapor-liquid equilibria of polymer solutions determined by molecular mechanics

A method of calculating interaction parameters used in phase equilibrium calculations was extended for predicting solvent activities of polymer solutions. A pair of interaction parameters are determined by calculating interaction energies between all pairs of molecules in the solution of interest with a molecular mechanics method called the consistent force field (CFF). The conformational space of a pair of molecules is sampled with a Monte Carlo algorithm followed by energy minimizations. The method is used to calculate solvent activities for the diethylketone/polypropylene system, giving results in good agreement with experimental values. In addition, solvent activities are predicted for the diethylketone/polyethylenesystem for which no experimental data are available. The method is fully predictive, as no fitting to experimental phase-equilibrium data is carried out.     

Temperature dependence of the conformational relaxation time of polymer molecules in elongational flow: Invariance of the molecular weight exponent

Using an elongational flow technique, we have investigated the relationship between the molecular conformational relaxation time and the molecular weight for a solvent whose quality was altered thermally from near θ to a good solvent state. The materials used were closely monodisperse samples of atactic polystyrene. The results show that the relaxation time τ varies with the molecular weight M as τ ∝ M^1.5, independent of the solvent quality, a result which apparently is at variance with the observed molecular weight dependence of intrinsic viscosity. Despite this invariance of the molecular weight exponent with solvent quality, our results also show that the coils do expand when the solvent quality was increased in agreement with the mean-field theory of Flory.     

Dynamic viscosity of polymer solutions

The dynamic viscosity of different long chain polymers in Aroclor permits an easy extrapolation to zero concentration only in the limiting cases of Newtonian, i. e., constant viscosity at low and high frequency, respectively. The first intrinsic viscosity []₀ is independent of any concept of the internal viscosity. In the case of polystyrene it is proportional toM ^0,65 which shows that Aroclor is a good solvent for this polymer. The second intrinsic viscosity [] turns out to be independent ofM. It is best reproduced by the model where the internal viscosity resists only the deformation rate of the single link. The displacement rate of more distant beads is affected by the internal viscosity only in the case that it involves the deformation rate of the links. The angles between successive links may be changed at any rate.In the intermediate range of frequencies the extrapolation of the observed dynamic viscosity to the intrinsic value was never made. The experimental data are so much affected by the concentration, i. e., by the interaction of adjacent molecules, that no conclusion may be derived from them about the properties of the isolated macromolecule. A master curve independent ofM andc is obtained by plotting of (G- )K/c over ₁. This means that the deformation mode in the whole molecular weight and concentration range investigated is the same. But this mode is different from that of the independent macromolecule in infinite dilution. The master curve may be described by the excess intrinsic viscosity of the Rouse model with the internal viscosity acting either between the beads on the same link only or between any distinct beads. As a consequence of the concentration effects, however, no conclusions about the properties of the single molecule can be derived from such an agreement.Dedicated to Prof. Dr. F. H. Müller.     

Isotope and pressure effects in polymer solutions. Demixing of polystyrene(h/d) poly-2-chlorostyrene blends

Liquid-liquid demixing, following spinodal quenches of poly-2-chlorostyrene/polystyrene blends, was followed by light scattering at 632.8 nm. The dependences of demixing on H/D substitution and molecular weight of the polystyrene, and on pressure, are reported. In the region of interest, the phase diagram is of the lower critical solution (LCS) type, and demixing is induced by raising the temperature. The transition temperature is lowered by deuterium substitution. At constant quench depth the transition proceeds more rapidly at elevated pressure. © 1995 John Wiley & Sons, Inc.     

Improvement to the lattice-fluid prediction of gas solubilities in polymer liquids

Previously we have shown that the Lattice Fluid (LF) model can quantitatively predict, without adjustable parameters, gas solubilities for hydrocarbon and chlorinated hydrocarbon vapors in nonpolar polymers. For polar polymers, the model can also predict, with reasonable success, the solubilities of polar and aromatic vapors. However, the solubilities in polar/nonpolar combinations of gas and polymer are systematically overestimated. These are cases in which the geometric mean approximation for the interaction parameter is not expected to be valid. This paper demonstrates that with the addition of a simple empirical correlation for the interaction parameter based on Hansen's three-dimensional solubility parameters, the LF model is then able to quantitatively predict solubilities in all types of gas/polymer systems (excluding strongly self-associating systems, such as alcohols). No adjustable parameters are used; only the pure component equation-of-state and solubility parameters are required. © 1993 John Wiley & Sons, Inc.     

Criteria of negative thixotropy for polymer solutions determined from the time dependence of the shear and normal stress

Summary The time dependences of shear and normal stress measured with a Weissenberg rheogoniometer were used in an investigation of the negative thixotropy of poly(methyl methacrylate) solutions in a low-viscosity solvent (mixture of cyclohexanone and isopropanol). A set of criteria was suggested for a complex quantitative evaluation of this phenomenon. The reproducibility of these criteria and their sensitivity towards a change in the velocity gradient were determined.

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Zusammenfassung Es wurde die negative Thixotropie der Lösungen von Polymethylmethacrylat in niedrigviskosem Lösungsmittel (Gemischen von Cyclohexanon und Isopropanol) studiert. Zeitänderungen der Schub- und Normalspannung wurden mit dem Weissenbergschen Rheogoniometer verfolgt und Kriterien zur komplexen quantitativen Beschreibung dieses Effektes wurden entworfen. Die Reproduzierbarkeit und Empfindlichkeit auf die Änderungen des Geschwindigkeitsgefälles wurden ermittelt.

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Dedicated to Prof. Dr.G. Rehage on the occasion of his 60th birthday.

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With 6 figures and 1 table     

Relative molecular weight distributions of cis-polybenzoxazole/polyphosphoric acid rodlike liquid crystalline polymer solutions from dilute solution rheometry

The molecular weight for a dilute solution of cis-polybenzoxazole (PBO) in polyphosphoric acid (PPA) was determined by fitting the rheological data with a semiempirical polydisperse hybrid theory. The hybrid theory models a semiflexible rigid rod as an elastic cylinder. The cylinder has both a rotational relaxation spectrum given by an ideal rigid rod and an internal bending relaxation spectrum spaced in accord with the relaxation time spectra of a flexible coil with fully developed hydrodynamic interactions. The model was fitted to rheological data collected for a 0.05 weight percent solution with intrinsic velocity (one-point determination) of 320 ± 10 cc/g. The model predicts a number-average molecular weight near 12800 ± 400 g/mol with a polydispersity index of 2.5 ± 0.1. By using the Yamakawa-Yoshizaki equation the intrinsic viscosity is calculated for the model molecular weight distribution as 310 cc/g.     

Measurement of activity coefficients in polymer solutions by the reversedflow technique

Summary The reversed-flow, gas-chromatographic method for measuring activities and activity coefficients in binary liquid mixtures is now extended to the determination of activity coefficients of the solvent in polymer-solvent systems over the whole range of polymer concentration, as well as for the calculation of Flory-Huggins interaction parameters. The parameters found by the present method are compared with those determined by other techniques or calculated theoretically.     

Characterization of Pressure Effects on the Cohesive Properties and Structure of Hexane and Polyethylene Using Molecular Dynamics Simulations

Molecular dynamics (MD) simulations using the OPLS‐AA force field are conducted to compute pressure‐ and molecular‐weight‐dependence of Hildebrand's solubility parameters of hexane and high‐density polyethylene (HDPE) at high pressures. The pressure dependence investigation also captures density data computed at high temperature and for external pressures ranging from 100 to 3000 bar. The effect of electrostatic potential energy contribution to cohesive energy and density is investigated and it is shown that the solubility parameter increases monotonically with increasing external pressure for both molecular mechanical models with and without electrostatic terms. Analysis of the pair distribution function is carried out versus pressure together with the influence of electrostatic energy contribution reflecting structural change of the condensed phase.

     

Intermolecular contact interactions and their temperature dependence

A model, based on inverse gas chromatography experiments, has been developed for intermolecular interaction and its temperature dependence. The model ascribes to each substance a four-component solubility parameter; the four components reflect the van der Waals, polar, electron donor, and electron acceptor interactive properties. Their values depend on temperature in the same manner as does the cohesive energy. The latter was found to depend only on the critical temperature, the acentric factor, and the reduced temperature. The model was used for evaluation of the solubility parameters from polymer-solvent interaction coefficients and their temperature dependence with high accuracy. For binary solventsolvent mixtures, the free energy of mixing and its temperature dependence, as well as enthalpy of mixing can be derived from this model with a good accuracy.