Structure and Dynamics of Biobased Polyester Nanocomposites.

The structure and the dynamics of two bio-based polyester polyols are investigated in the bulk and close to surfaces in polymer/layered silicate nanocomposites. The morphology of the neat polymers as well as the structure of the nanohybrids are investigated with X-ray diffraction and their thermal properties are studied by differential scanning calorimetry. One of the investigated polyesters is amorphous, whereas the second one is a semicrystalline polymer with intriguing thermal behavior. Hybrids have been synthesized over a broad range of compositions and intercalated structures are always obtained. The thermal transitions in the nanocomposites are observed only when the polymers are in excess outside the completely filled galleries. The glass transition, whenever it can be resolved, appears insensitive to the presence of the inorganic material, whereas the way the crystallization takes place depends on the composition of the nanohybrid. Dielectric relaxation spectroscopy was utilized to study the polymer dynamics. It revealed multiple relaxation processes for the neat polymers both below and above their glass transition temperatures, whereas in the nanocomposites, similarities and differences are observed depending on the specific mode of the dynamic process.

Dynamics of poly(vinyl butyral) studied using dielectric spectroscopy and 1H NMR relaxometry.

Dielectric Spectroscopy (DS) and 1H Fast Field-Cycling (FFC) NMR relaxometry were applied for understanding the dynamic behavior of the amorphous ter-polymer poly(vinyl butyral) (PVB) across the glass transition temperature (Tg = 70 °C by Differential Scanning Calorimetry). Above Tg, main chain segmental motions (α relaxation) were detected and characterized using both DS and FFC NMR relaxometry. The correlation times extracted by the analysis of DS and FFC NMR relaxometry data agreed within a factor of three and showed a Vogel-Fulcher-Tammann temperature dependence, with an associated Tg of 69 °C and a fragility of 155 for PVB glass. Below Tg, a secondary process (ß relaxation) was revealed by DS, and was ascribed to reorientations of the vinyl alcohol dipoles due to local twisting motions with an associated activation barrier of 11 kcal mol-1. The ß process was also found to contribute to 1H NMR relaxation above Tg.

Dynamics of Hyperbranched Polymers under Confinement: A Dielectric Relaxation Study.

The effect of severe confinement on the dynamics of three different generations of hyperbranched polyesters of the Boltorn family is investigated by dielectric relaxation spectroscopy (DRS). The polymer chains are intercalated within the galleries of natural montmorillonite (Na+-MMT), thus forming 1 nm polymer films confined between solid walls. The structure of the nanocomposites is studied with X-ray diffraction and the thermal behavior of the polymers in bulk and under confinement is determined by differential scanning calorimetry. The glass transition temperatures of the polymers show a clear dependence on the generation whereas the transition is completely suppressed when all the polymer chains are intercalated. The dynamic investigation of the bulk polymers reveals two sub-Tg processes, with similar behavior for the three polymers with the segmental relaxation observed above the Tg of each polymer. For the nanocomposites, where all the polymer chains are severely confined, the dynamics show significant differences compared to that of the bulk polymers. The sub-Tg processes are similar for the three generations but significantly faster and with weaker temperature dependence than those in the bulk. The segmental process appears at temperatures below the bulk polymer Tg, it exhibits an Arrhenius temperature dependence and shows differences for the three generations. A slow process that appears at higher temperatures is due to interfacial polarization.

Temperature dependence of the structural relaxation time in equilibrium below the nominal T(g): results from freestanding polymer films.

When the thickness is reduced to nanometer scale, freestanding high molecular weight polymer thin films undergo large reduction of degree of cooperativity and coupling parameter n in the Coupling Model (CM). The finite-size effect together with the surfaces with high mobility make the α-relaxation time of the polymer in nanoconfinement, τ(α)(nano)(T), much shorter than τ(α)(bulk)(T) in the bulk. The consequence is avoidance of vitrification at and below the bulk glass transition temperature, T(g)(bulk), on cooling, and the freestanding polymer thin film remains at thermodynamic equilibrium at temperatures below T(g)(bulk). Molecular dynamics simulations have shown that the specific volume of the freestanding film is the same as the bulk glass-former at equilibrium at the same temperatures. Extreme nanoconfinement renders total or almost total removal of cooperativity of the α-relaxation, and τ(α)(nano)(T) becomes the same or almost the same as the JG ß-relaxation time τ(ß)(bulk)(T) of the bulk glass-former at equilibrium and at temperatures below T(g)(bulk). Taking advantage of being able to obtain τ(ß)(bulk)(T) at equilibrium density below T(g)(bulk) by extreme nanoconfinement of the freestanding films, and using the CM relation between τ(α)(bulk)(T) and τ(ß)(bulk)(T), we conclude that the Vogel-Fulcher-Tammann-Hesse (VFTH) dependence of τ(α)(bulk)(T) cannot hold for glass-formers in equilibrium at temperatures significantly below T(g)(bulk). In addition, τ(α)(bulk)(T) does not diverge at the Vogel temperature, T0, as suggested by the VFTH-dependence and predicted by some theories of glass transition. Instead, τ(α)(bulk)(T) of the glass-former at equilibrium has a much weaker temperature dependence than the VFTH-dependence at temperature below T(g)(bulk) and even below T0. This conclusion from our analysis is consistent with the temperature dependence of τ(α)(bulk)(T) found experimentally in polymers aged long enough time to attain the equilibrium state at various temperatures below T(g)(bulk).

Origins of the two simultaneous mechanisms causing glass transition temperature reductions in high molecular weight freestanding polymer films.

From ellipsometry measurements, Pye and Roth [Phys. Rev. Lett. 107, 235701 (2011)] presented evidence of the presence of two glass transitions originating from two distinctly different and simultaneous mechanisms to reduce the glass transition temperature within freestanding polystyrene films with thickness less than 70 nm. The upper transition temperature T(u)(g)(h) is higher than the lower transition temperature T(l)(g)(h) in the ultrathin films. After comparing their data with the findings of others, using the same or different techniques, they concluded that new theoretical interpretation is needed to explain the two transitions and the different dependences of T(u)(g)(h) and T(l)(g)(h) on film thickness and molecular weight. We address the problem based on advance in delineating the different viscoelastic mechanisms in the glass-rubber transition zone of polymers. Theoretical considerations as well as experiments have shown in time-scales immediately following the segmental α-relaxation are the sub-Rouse modes with longer length scale but shorter than that of the Rouse modes. The existence of the sub-Rouse modes in various polymers including polystyrene has been repeatedly confirmed by experiments. We show that the sub-Rouse modes can account for the upper transition and the properties observed. The segmental α-relaxation is responsible for the lower transition. This is supported by the fact that the segmental α-relaxation in ultrathin freestanding PS films had been observed by dielectric relaxation measurements and photon correlation spectroscopy. Utilizing the temperature dependence of the segmental relaxation times from these experiments, the glass transition temperature T(α)(g)associated with the segmental relaxation in the ultrathin film is determined. It turns out that T(α)(g) is nearly the same as T(l)(g)(h) of the lower transition, and hence definitely segmental α-relaxation is the mechanism for the lower transition. Since it is unlikely that the segmental α-relaxation can give rise to two very different transitions simultaneously, a new mechanism for the upper transition is needed, and the sub-Rouse modes provide the mechanism.

Temperature and pressure dependence of secondary process in an epoxy system.

Dielectric spectroscopy as a function of temperature and pressure was used to study the secondary relaxation in poly [(phenyl glycidyl ether)-co-formaldehyde] at hydrostatic pressure up to 600 MPa and at different temperatures between 315 and 243 K. From the analysis of the isothermal measurements, we observe that the activation volume of the secondary relaxation has nonmonotonic temperature dependence with a maximum at the temperature of the glass transition at ambient pressure. An interpretation in terms of mean hole volume dispersion is proposed based on literature data. Moreover, from isobaric data, we studied the effect of pressure on activation entropy and enthalpy of the secondary relaxation evidencing its local nature but also the presence of a certain complexity of the motion, which supports the idea that this process reflects the motion of a large part of the molecule.

Relaxation dynamics in tert-butylpyridine/tristyrene mixture investigated by broadband dielectric spectroscopy.

We investigated, by means of dielectric spectroscopy, the relaxation dynamics of glass forming binary mixtures composed by the quite rigid polar molecules tert-butylpyridine dissolved in the apolar solvent tristyrene. By changing the relative concentration of the components we observed a transition from a relaxation scenario with a structural process and an excess wing to that with a structural process and a well resolved secondary process. Another relaxation process, slower than the latter, was observed, well below Tg. Our detailed analysis evidenced that the secondary relaxation with shorter relaxation time can be identified as the Johari-Goldstein relaxation for all the mixtures, whereas the new relaxation process was attributed to a different type of motion of tert-butylpyridine needing a larger amount of free volume for the molecular rotation.

Influence of a reduced mobility layer on the structural relaxation dynamics of aluminum capped ultrathin films of poly(ethylene terephthalate).

The structural dynamics of ultrathin polymer films of poly(ethylene terephthalate) capped between aluminum electrodes have been investigated by dielectric relaxation spectroscopy. A deviation from bulk behavior, appearing as an increase of the relaxation time at a fixed temperature, is observed for films of thickness below 35 nm. The slowing down acts as a constant shift factor independent from the temperature, and the fragility is constant. The interfacial energy between aluminum and poly(ethylene terephthalate) is calculated to be 3 mJ/m2, confirming a strong interaction between polymer and substrate, which leads to the presence of a layer characterized by a reduced mobility at their interfaces. We proposed a mathematical schematization of a multylayer model that allowed qualitative reproduction of the observed thickness dependences of the static and dynamic properties. In terms of such a model, the upper limit for the thickness of the reduced mobility layer was estimated as 20 nm. The conditions to extend the proposed model to different observables are finally suggested.