Self-confined polymer dynamics in miscible binary blends

Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy was used to measure simultaneously the relaxation rates of polystyrene (PS) molecules at the free surface and in the bulk. The samples were uniaxially stretched and annealed at temperatures below the bulk glass transition temperature of PS. The surface and bulk chain relaxation was monitored by measuring the partial-electron and the fluorescence NEXAFS yields, respectively, both parallel and perpendicular to the stretching direction. The decay of the optical birefringence was also measured to provide an independent measure of the bulk relaxation. Relaxation of PS chains was found to occur faster on the surface relative to the bulk. The magnitude of the surface glass transition temperature suppression over the bulk was estimated based on the information on the temperature dependence of the rates.Received: 1 January 2003, Published online: 14 October 2003PACS: 68.35.Ja Surface and interface dynamics and vibrations - 68.47.Mn Polymer surfaces     

Origin of dynamic heterogeneities in miscible polymer blends: A quasielastic neutron scattering study

In order to investigate the origin of the often invoked nanoheterogeneities in miscible polymer blends, we have performed quasielastic neutron scattering experiments on the component dynamics within the miscible polymer blend polyisoprene/polyvinyl ether including the pure components as a reference. We find that the apparent local heterogeneities observed by spectroscopic techniques originate from the chain specific crossover properties between entropy driven and local chain dynamics and are, thus, a purely dynamical phenomenon.     

Entangledlike chain dynamics in nonentangled polymer blends with large dynamic asymmetry

We discuss simulations of a simple model for polymer blends in the framework of the Rouse model. At odds with standard predictions, large dynamic asymmetry between the two components induces strong nonexponentiality of the Rouse modes for the fast component. Despite chains being much shorter than the entanglement length, it also induces dynamic features resembling a crossover to entangledlike chain dynamics. This unusual behavior is associated with strong memory effects which break down the assumption of time uncorrelation of the external forces acting on the tagged chain.     

Field-theoretical Renormalization-Group approach to critical dynamics of crosslinked polymer blends

We consider a crosslinked polymer blend that may undergo a microphase separation. When the temperature is changed from an initial value towards a final one very close to the spinodal point, the mixture is out equilibrium. The aim is the study of dynamics at a given time t, before the system reaches its final equilibrium state. The dynamics is investigated through the structure factor, S(q, t), which is a function of the wave vector q, temperature T, time t, and reticulation dose D. To determine the phase behavior of this dynamic structure factor, we start from a generalized Langevin equation (model C) solved by the time composition fluctuation. Beside the standard de Gennes Hamiltonian, this equation incorporates a Gaussian local noise, ζ. First, by averaging over ζ, we get an effective Hamiltonian. Second, we renormalize this dynamic field theory and write a Renormalization-Group equation for the dynamic structure factor. Third, solving this equation yields the behavior of S(q, t), in space of relevant parameters. As result, S(q, t) depends on three kinds of lengths, which are the wavelength q ⁻¹, a time length scale R(t) ∼ t ^1/z , and the mesh size ξ ^*. The scale R(t) is interpreted as the size of growing microdomains at time t. When R(t) becomes of the order of ξ ^*, the dynamics is stopped. The final time, t ^*, then scales as t ^* ∼ ξ ^{* z}, with the dynamic exponent z = 6−η. Here, η is the usual Ising critical exponent. Since the final size of microdomains ξ ^* is very small (few nanometers), the dynamics is of short time. Finally, all these results we obtained from renormalization theory are compared to those we stated in some recent work using a scaling argument.     

Glass transition of miscible binary polymer-polymer thin films

The average glass transition temperatures, Tg, of thin homopolymer films exhibit a thickness dependence, Tg(h), associated with a confinement effect and with polymer-segment-interface interactions. The Tg's of completely miscible thin film blends of tetramethyl bisphenol-A polycarbonate (TMPC) and deuterated polystyrene (dPS), supported by SiO(x)/Si, decrease with decreasing h for PS weight fractions phi >0.1. This dependence is similar to that of PS and opposite to that of TMPC thin films. Based on an assessment of Tg(h, phi), we suggest that the Tg(h, phi) of miscible blends should be rationalized, additionally, in terms of the notion of a self-concentration and associated heterogeneous component dynamics.     

Microphase separation in cross-linked polymer blends

We investigate the behaviour of randomly cross-linked (co)polymer blends using a combination of replica theory and large-scale molecular dynamics simulations. In particular, we derive the analogue of the random phase approximation for systems with quenched disorder and show how the required correlation functions can be calculated efficiently. By post-processing simulation data for homopolymer networks we are able to describe neutron scattering measurements in heterogeneous systems without resorting to microscopic detail and otherwise unphysical assumptions. We obtain structure function data which illustrate the expected microphase separation and contain system-specific information relating to the intrinsic length scales of our networks.     

Viscoelastic phase separation in polymer blends

In this paper, the dynamics and morphology of viscoelastic phase separation in polymer blends is investigated based on the two-fluid model in two dimensions. At critical composition, we have carefully checked the role of shear modulus, without taking account of bulk modulus. The results show that the higher shear modulus component tends to form a dispersed phase in the intermediate stage of phase separation, if the difference between the shear moduli of the components is large enough. This is opposite to the role of bulk modulus, that the higher bulk modulus component forms a networklike pattern without taking account of the shear modulus even if it is the minority phase. The morphological formation is determined by the competition of opposite effects of shear modulus and bulk modulus. For polymer blends at critical composition, the bulk modulus difference leads to a networklike pattern formed by the higher modulus component in the intermediate stage of phase separation. But if the difference between the shear moduli of the components is large enough, a co-continuous structure is observed, resulting from the competition between shear and bulk moduli. For off-critical composition, difference in bulk modulus also leads to a networklike pattern of the component with higher bulk modulus in the intermediate stage of phase separation, but phase inversion is observed rapidly. A small difference between the shear moduli of the components can support the networklike pattern to continue for longer time. But the networklike pattern does not occur for large difference between shear moduli.Received: 9 September 2004, Published online: 10 November 2004PACS: 64.75. + g Solubility, segregation, and mixing; phase separation - 83.80.Tc Polymer blends     

Scattering studies from polymer blends

An ultraquenching technique was used to prepare thin (ca. 1000 Å) amorphous films of polypivalolactone and poly(4-methyl-pentene-1). These films were characterized by electron microscopy, electron diffraction, and dynamic mechanical analysis. Other ultraquenched films of these polymers were crystallized by annealing for various times in the vicinity of their glass transition temperatures. Electron microscopy and electron diffraction were used to follow the reorganization of their structures.

Evidence for a double T_g in polypivalolactone (PPVL) was found, with crystallization of annealed, ultraquenched films occurring just above T_g (L) = 270°K. A T_g (U) = 340°K was noted. When the disordered glass was annealed above T_g (L), polypivalolactone crystallized into the a crystal form, which is composed of antiparallel chain segments, suggesting a chain-folded crystallization mechanism.

Poly(4-methyl-pentene-1) (P4MP1) gave evidence for T_g (L) = 220°K and T_g (U) = 325°K by dynamic mechanical analysis. However, morphology and electron diffraction showed that significant crystallization of ultraquenched polymer did not occur until T_g (U) was reached. X-ray data also supported this conclusion, which is explained by the lower density of the crystal phase of P4MP1 (compared to amorphous material) below 320°K. Long-term annealing of films at T_g (U) resulted in the formation of single-crystal structures, again indicative of a mechanism of chain-folded crystallization from the glass.     

Proximity effects in self-organized binary particle-block copolymer blends

Dependent on the surface chemistry of gold nanocrystals of equal metal core size, two morphological types of self-organized block copolymer-particle blends are observed: (1) the segregation of the nanocrystals to the interfacial areas or (2) the preferential uniform distribution within one of the respective polymer domains. The confinement of the nanocrystals to the narrow interfacial regions of the microstructure in type one blends results in high local particle filling fractions and gives rise to electromagnetic coupling upon light irradiation, accompanied by a pronounced increase in absorbance.     

Shear-induced phase transitions in ternary polymer blends

We present a study of flow-induced phase transitions in microemulsion phases of ternary polymer blends. The results match qualitatively with the recent experimental observations on such systems but differ from the behavior expected and observed in the analogous system of surfactants. We rationalize this contrast from a molecular viewpoint suggesting that the interplay between polymer chain conformations and their flow deformations can lead to novel flow effects upon the phase, structural, and rheological behavior of multicomponent polymer systems.     

Morphology of ternary immiscible polymer blends

Ternary blends consisting of thermoplastic and thermotropic immiscible polymers were studied. Both thermodynamic and kinetic considerations were found to affect their multiphase structure. Thermodynamics is expressed by means of spreading coefficients, whereas the kinetic effect is driven by the dispersed phase viscosity ratio. Some morphologies could be predicted, when both effects acted cooperatively. However, in cases where the effects were opposing, kinetics hindered the development of the expected structure; interpenetration between the two minor phases, rather than engulfing or separately dispersed morphology, took place. In cases where two relatively polar phases were dispersed in a nonpolar matrix (e.g., nylon and polycarbonate in polypropylene), the interaction between the two dispersed minor phases always existed due to their low interfacial tension. Spreading of one minor phase over another, rather than penetration, is the dominating mechanism of encapsulation in polymer blends, contrary to low molecular weight liquids where both spreading and penetration play an important role in the structurization.     

Drop deformation in polymer blends during elongational flow

An original method for measuring droplet deformation in polymer melts during uniaxial elongational flow has been developed. It is based on the observation of a limited number of drops, before and after elongation in the melt. The shape of the elongated drops was frozen by fast quenching. Two PS samples for the continuous phase, plus two HDPE, and one PMMA for the drops, allowed a wide range of viscosity ratios (0.0046 < p < 13). Experiments at high capillary number (Ca) values were in good agreement with Taylor's linear newtonian theory up to deformations of about λ = 4: viscous drops (p > 1) deform less than the surrounding matrix, whereas the opposite is observed for low viscosity drops (p < 1) with a limiting ratio of drop vs. matrix deformation of 5/3 at vanishing drop viscosity. Experiments carried out at Ca values of the order of unity showed that the drop deformation increases linearly with their initial radius in agreement with the linear theory. In some cases, the agreement with the data could be improved by using Palierne's theory for viscoelastic systems. Analytical expressions could be obtained for maxwellian fluids and high capillary numbers.     

Dynamic mechanical characterization of relaxations in poly(oxymethylene), miscible blends,and oriented filaments

Multifrequency dynamic mechanical analysis (DMA) data were obtained for molded poly(oxymethylene) (POM) and its blends from-150°C to 150°C. Because of the high crystallinity, the assignment of the glass transition in POM has been controversial in the literature. Low and high glass transition temperature (T _g) phenolated compounds, including poly(vinyl phenol), were found to be miscible with POM. The shift of the β transition in the POM blends favors an assignment of the β transition detected at ?3°C(1 Hz), not the ?80°C γ transition, as the T _g in semicrystalline POM because the latter is invariant with diluent. The peak at the β transition in pure POM is weak and can only be seen clearly by DMA measurements on samples that have not “aged” at ambient temperature. This is further evidence that the β transition arises from a cooperative glass-transition-like motion. The γ transition is not influenced by aging because it is due to a concerted localized main chain motion. The β transition of an oriented POM filament can be seen in the DMA flexural loss spectrum at-18°C (1 Hz), but not in a tensile loss spectrum. The broad a relaxation was detected at about 110°C (1 Hz) in molded POM and its blends, while it was shifted to about 135°C in the higher crystallinity, oriented system. The α peak is also independent of diluent, consistent with a crystalline origin for this transition, as was proposed earlier.     

Mixed crystals in polymer blends: Polypropylene-polybutene-1 system

A method of preparing solid solutions of chemically different polymeric molecules in the crystalline state is reported. The characteristic feature of the method is the high longitudinal flow gradient in which one can achieve very high rates of crystallization as well as supercooling at constant temperature. In the present study, isotactic polypropylene-polybutene-1 blends of different compositions were investigated, and solid solutions were observed up to 20% on each side of the phase diagram. The resultant crystalline blends were investigated by using transmission electron microscopy (TEM) and electron diffraction, wide-angle x-ray diffraction, differential thermal analysis, and mechanical testing. Structural studies reveal the presence of needle-like crystals within the blends. The thermal stability of the blended crystals is unexpectedly high with no major changes in the structure upon annealing. The mechanical properties exhibit only small changes for the different blends.