An unusual demixing behavior in PS-PVME blends in the presence of nanoparticles

The effect of silver nanoparticles (sNP) on the demixing and the evolution of morphology in off-critical blends of 90/10 and 10/90 (wt/wt) PS/PVME polystyrene/poly(vinyl methyl ether)] was probed here using shear rheology and optical microscopy. The faster component (PVME) has a higher molecular weight (80 kDa) than the slower component (PS, 35 kDa), which makes this system quite interesting to study with respect to the evolving morphology, as the blends transit through the binodal and the spinodal envelopes. An unusual demixing behavior was observed in both PVME rich and PS rich blends. Temperature modulated differential scanning calorimetry measurements showed that the T-g value for the blends with sNP was slightly lower than that of the neat blends. A decreased volume of cooperativity at T-g suggests confined segmental dynamics in the presence of sNP. Although, the addition of sNP had no influence on the thermodynamic demixing temperature, it significantly altered the elasticity of the minor component during the transition of the blend from the homogeneous to the heterogeneous state. This is manifested from energetically driven localization of the sNP in the PVME phase during demixing. As a direct consequence of this, the formation of the microstructures upon demixing was observed to be delayed in the presence of sNP. Interestingly, in the intermediate quench depth, the higher viscoelastic phase evolved as an interconnected network, which subsequently coarsened into discrete droplets in the late stages for the 90/10 PS/PVME blends. Similar observations were made for 10/90 PS/PVME blends where threads of PVME appeared at deeper quench depths in the presence of sNP. The interconnected network formation of the minor phase (here PVME), which is also the faster component in the blend, was different from the usual demixing behavior.

Thermally Induced Demixing in an LCST Mixture in the Presence of Densely Grafted Nanoparticles: Tuning the Graft Chain Length To Induce Thermodynamic Miscibility

The demixing in an LCST mixture of PS/PVME (polystyrene/poly(vinyl methyl ether)) was probed here by melt rheology in the presence of gold nanoparticles which were densely coated with varying graft lengths of PS. The graft density for the gold nanoparticles coated with 3 kDa PS was ca. Sigma = 1.7 chains/nm(2), and that for 53 kDa PS was ca. Sigma = 1.2 chains/nm(2). The evolution of morphology, as the blends transit through the metastable and the unstable envelopes of the phase diagram, and the localization of the gold nanoparticles upon demixing were monitored using in situ hot-stage AFM and confocal Raman imaging. Interestingly, gold nanoparticles coated with 3 kDa polystyrene (PS(3 kDa)-g-nAu) were localized in the PVME phase, whereas gold nanoparticles coated with 53 kDa polystyrene (PS(53 kDa)-g-nAu) were localized in the PS phase of the blend. While the localization of PS(3 kDa)-g-nAu in the PVME phase can be expected to be of entropic origin due to expulsion from the PS phase as R-g,R-matrix chains > R-g,R-grafted chains (where R-g is the radius of gyration of the polymer chain), the localization of PS(53 kDa)-g-nAu in the PS phase is believed to be facilitated by favorable melt/graft interactions. The latter nanoparticles also delayed the demixing by 12 degrees C with respect to the neat mixture. The observed changes were addressed in context to enthalpic interactions between the grafted PS and the free PS, the entropic losses (deformational entropic losses on blending, translational entropic loss of the free PS, and the conformational entropic loss of the grafted PS), and the interface of the grafted and the free chains.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

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.

Phase behavior in mixtures of a homopolymer and a block copolymer .4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadienestyrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. (C) 1996 John Wiley & Sons, Inc.

Non-equilibrium segmental dynamics driven by multiwall carbon nanotubes in PS/PVME blends

The present paper discusses the effect of multiwall carbon nanotubes (MWNTs) on the structural relaxation and the intermolecular cooperativity in dynamically asymmetric blends of PS/PVME (polystyrene/poly(vinyl methyl ether)). The temperature regime where chain connectivity effects dominate the thermodynamic concentration fluctuation (T/T-g > 0.75, T-g is the glass transition temperature of the blends) was studied using dielectric spectroscopy (DS). Interestingly, in the blends with MWNTs a bimodal distribution of relaxation was obtained in the loss modulus spectra. This plausibly is due to different environments experienced by the faster component (PVME) in the presence of MWNTs. The segmental dynamics of PVME was observed to be significantly slowed down in the presence of MWNTs and an Arrhenius-type behavior, weakly dependent on temperature, is observed at higher frequencies. This non-equilibrium dynamics of PVME is presumed to be originating from interphase regions near the surface of MWNTs. The length scale of the cooperative rearranging region (xi CRR) at T-g, assessed by calorimetric measurements, was observed to be higher in the case of blends with MWNTs. An enhanced molecular level miscibility driven by MWNTs in the blends corroborates with the larger xi CRR and comparatively more number of segments in CRR (in contrast to neat blends) around T-g. The configurational entropy and length scale of the cooperative volume was mapped as a function of temperature in the temperature regime, Tg < T < T-g + 60 K. The blends phase separated by spinodal decomposition which further led to an interconnected PVME network in PS. This further led to materials with very high electrical conductivity upon demixing.

Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

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]

Theoretical representation of shear and pressure influence on the phase separation behavior of PVME/PS mixture

In the framework of lattice fluid model, the Gibbs energy and equation of state are derived by introducing the energy (E-s) stored during flow for polymer blends under shear. From the calculation of the spinodal of poly(vinyl methyl ether) (PVME) and polystyrene (PS) mixtures, we have found the influence of E., an equation of state in pure component is inappreciable, but it is appreciable in the mixture. However, the effect of E, on phase separation behavior is extremely striking. In the calculation of spinodal for the PVME/PS system, a thin, long and banana miscibility gap generated by shear is seen beside the miscibility gap with lower critical solution temperature. Meanwhile, a binodal coalescence of upper and lower miscibility gaps is occurred. The three points of the three-phase equilibrium are forecasted. The shear rate dependence of cloud point temperature at a certain composition is discussed. The calculated results are acceptable compared with the experiment values obtained by Higgins et at. However, the maximum positive shift and the minimum negative shift of cloud point temperature guessed by Higgins are not obtained, Furthermore, the combining effects of pressure and shear on spinodal shift are predicted.

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.

Theoretical calculation of Flory-Huggins and scattering interaction parameters by means of the lattice fluid theory for PVME/PSD blends

By fitting the spinodals of poly(vinyl methyl ether)/deuterated polystyrene (PVME/PSD) systems, the adjustable parameters epsilon (12)* and delta epsilon* in the Sanchez-Balasz lattice fluid (SBLF) theory could be determined for different molecular weights. According to these parameters, Flory-Huggins and scattering interaction parameters were calculated for PVME/PSD with different molecular weights by means of the SELF theory. From our calculation, Flory-Huggins and scattering interaction parameters are both Linearly dependent on the reciprocal of the temperature, and almost linearly on the concentration of PSD. Compared with the scattering interaction parameters, the Flory-Huggins interaction parameters decreased more slowly with an increase in the concentration for all three series of blends.

Phase-separation behavior of the system PES/phenoxy: An application of the Sanchez-Lacombe lattice fluid theory

Cloud-point curves reported for the system polyethersulfone (PES)/phenoxy were calculated by means of the Sanchez-Lacombe (SL) lattice fluid theory. The one adjustable parameter epsilon(12)*/k (quantifying the interaction energy between mers of the different components) can be evaluated by comparison of the theoretical and experimental phase diagrams. The Flory-Huggins (FH) interaction parameters are computed based on the evaluated epsilon(12)*/k and are approximately a linear function of volume fraction and of inverse temperature. The calculated enthalpies of mixing of PES/phenoxy blends for different compositions are consistent with the experimental values obtained previously by Singh and Walsh [1].

PHASE-BEHAVIOR IN MIXTURES OF A HOMOPOLYMER AND A BLOCK-COPOLYMER .1. FTIR AND DSC STUDIES

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm-1 region due to COCH3 band of PVME and peak position of 698 cm-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. (C) 1995 John Wiley & Sons, Inc.

Étude de l’orientation par déformation de mélanges de polymères à base de polystyrène

La spectroscopie infrarouge à matrice à plan focal (PAIRS) est utilisée pour étudier la déformation et la relaxation des polymères à très haute vitesse, soit de 46 cm/s, grâce à sa résolution temporelle de quelques millisecondes. Des mesures complémentaires de spectroscopie infrarouge d’absorbance structurale par modulation de la polarisation (PM-IRSAS) ont été réalisées pour suivre des déformations plus lentes de 0,16 à 1,6 cm/s avec une résolution temporelle de quelques centaines de millisecondes. Notre étude a permis d’observer, à haute vitesse de déformation, un nouveau temps de relaxation (τ0) de l’ordre d’une dizaine de millisecondes qui n’est pas prédit dans la littérature. Le but de cette étude est de quantifier ce nouveau temps de relaxation ainsi que de déterminer les effets de la température, de la masse molaire et de la composition du mélange sur ce dernier. Des mesures effectuées sur du polystyrène (PS) de deux masses molaires différentes, soit 210 et 900 kg/mol, à diverses températures ont révélé que ce temps est indépendant de la masse molaire mais qu’il varie avec la température. Des mesures effectuées sur des films composés de PS900 et de PS deutéré de 21 kg/mol, ont révélé que ce temps ne dépend pas de la composition du mélange et que la longueur des chaînes de PS n’a aucun impact sur celui-ci. D’autres mesures effectuées sur des films de PS900 mélangé avec le poly(vinyl méthyl éther) (PVME) ont révélé que ce temps est identique pour le PS900 pur et le PS900 dans le mélange, mais qu’il est plus court pour le PVME, de l’ordre de quelques millisecondes.