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.

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 (β 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 β process was also found to contribute to 1H NMR relaxation above Tg.

The presence of sub-Rouse modes in bulk polymers with length scale and relaxation times in between the segmental alpha-relaxation and the Rouse modes had long been justified by theoretical consideration, and found in many experimental studies. The sub-Rouse modes had been seen directly in creep compliance measurements of polymer thin films by McKenna and co-workers. On decreasing film thickness, the sub-Rouse modes shift to shorter times like the segmental alpha-relaxation, but the shift of the former is less than the latter. We had used the sub-Rouse modes and the segmental mode to explain the two transitions found by ellipsometry in freestanding high molecular weight PS films by Pye and Roth ( PR). The upper transition at a higher temperature originates from the sub-Rouse modes, and the lower transition comes from the segmental alpha-relaxation. On the other hand, PR suggested that the upper and the lower transitions both came from the segmental alpha-relaxation, and the upper transition occurs in similar to 90% of the material. In this paper we use dielectric relaxation data of freestanding films to rule out their suggestion. Furthermore, we demonstrate by experimental evidences that the sub-Rouse modes are coupled to density, and respond to physical aging to validate our interpretation.

Most studies of the dynamics at the surface and in thin films of polystyrene (PS) are focused on the change of glass transition temperature from the bulk value. In this perspective, we highlight three new developments in research on the dynamics of PS in high molecular weight (MW) freestanding PS thin films and at the surface of low MW PS. Novel findings from these developments require consideration of viscoelastic mechanisms with length scales longer than the segmental alpha-relaxation. The first development is the creep compliance measurements of high-MW PS thin films, probing not only the segmental alpha-relaxation, but also the polymer chain modes at higher compliance levels, including the sub-Rouse modes and the Rouse modes. The compliance data indicate the relaxation times of the sub-Rouse modes are reduced in thinner films like that of the segmental alpha-relaxation but to a much less extent. The second development is the novel observation of two glass transitions in freestanding polystyrene thin films by ellipsometry. The upper and lower glass transitions occurs, respectively, at temperatures[GRAPHICS]and[GRAPHICS], both are below the bulk glass transition temperature. While the lower transition at[GRAPHICS]is associated with the segmental alpha-relaxation, the only viable explanation of the origin of the upper transition at[GRAPHICS]is from another intrinsic viscoelastic mechanism of PS, and not at different location of the film. Supported by various experiments on PS and other polymers, we show that the sub-Rouse modes are cooperative and coupled to density, and hence giving rise to the upper glass transition in freestanding PS films. The sub-Rouse relaxation times will increase on physical ageing, and bring along an increase in density of the freestanding film due to the coupling. This prediction can be checked by performing ageing experiment. The third development is the reduction of viscosity at the free surface of low MW PS. Since viscous flow of low MW PS is definitely carried out by the sub-Rouse modes and not by the segmental alpha-relaxation, the experimental finding is direct evidence of enhancement of mobility of the sub-Rouse modes by the mitigation of intermolecular coupling at the surface, consistent with the explanations given for the findings in the two other developments. The enhancement of mobility of the sub-Rouse modes occurs simultaneously with the same effect on the segmental alpha-relaxation. Notwithstanding, at the surface, the observed reduction of viscosity from the sub-Rouse modes is significantly smaller than the reduction of the segmental relaxation time, which is explained semiquantitatively. Altogether, the three recent advances in the study of dynamics of polymer thin films and at the free surface have shown not only the change of the glass transition temperature effected by the segmental alpha-relaxation is interesting, but also that of the sub-Rouse modes.

Front Cover: The time evolution of the crystalline, mobile amorphous (MA) and rigid amorphous (RA) fractions of PLLA depends on the crystallization temperature. At high crystallization temperature, RA fraction does not develop, whereas at low crystallization temperature, formation of both a RA fraction and a slightly constrained MA fraction is detected. Further details can be found in the article by Maria Cristina Righetti,* Daniele Prevosto and Elpidio Tombari on page 2013.

A route to extend the measurement bandwidth of local dielectric spectroscopy up to the MHz range has been devised. The method is based on a slow amplitude modulation at a frequency Ω of the excitation field oscillating at a frequency ω and the coherent detection of the modulated average electric force or force gradient at Ω. The cantilever mechanical response does not affect the measurement if Ω is well below its resonant frequency; therefore, limitations on the excitation field frequency are strongly reduced. Demonstration on a thin poly(vinyl acetate) film is provided, showing its structural relaxation spectrum on the local scale up to 45 °C higher than glass temperature, and nanoscale resolution dielectric relaxation imaging near conductive nanowires embedded in the polymer matrix was obtained up to 5 MHz frequency, with no physical reason to hinder further bandwidth extension.

Two transitions were found by ellipsometry in freestanding high molecular weight PS films by Pye and Roth (PR). PR suggested that the upper and the lower transitions both came from the segmental a-relaxation, and the upper transition occurs in 90% of the material. In this paper we use dielectric relaxation data of freestanding films to rule out their suggestion. Furthermore, we demonstrate by experimental evidences that the sub-Rouse modes are coupled to density, and respond to physical aging to validate our interpretation and can explain the upper transition.

The dynamics of polyester polyols in the bulk, under confinement when the polymers are intercalated within the galleries of a hydrophilic clay and close to the inorganic surfaces is investigated utilizing Dielectric Relaxation Spectroscopy (DRS). A series of linear biobased polyesters with hydroxyl end groups were utilized in the bulk and in nanohybrids and the results were compared with the case of hyperbranched polymers of similar chemistry but non-linear architecture. A broad range of temperatures below and above the bulk polymer glass transition temperature, Tg, was investigated covering both the regimes of beta-like local processes and segmental (alpha-process) dynamics. The polymer dynamics observed in all the nanocomposites are quite different compared to the bulk due to the different interactions whereas differences are seen due to the architecture as well. Moreover, non-standard local dielectric spectroscopy has been used to investigate the nanocomposites dynamics at the local scale: polymer relaxation has been investigated in the same material both close and far from the MMT surfaces. The comparison of the results from the two techniques allowed the understanding, in more detail, of the influence of the complex interfacial interactions on the relaxation dynamics.

In semi-crystalline polymers, amorphous segments located in different regions and distance from the crystalline domains can exhibit different dynamics. In poly(L-lactic acid) (PLLA), the existence of (i) two distinct mobile amorphous fractions (a completely mobile amorphous fraction and a slightly constrained mobile amorphous fraction), which vitrify/devitrify in the T-g region, and (ii) a rigid amorphous fraction, which vitrifies/devitrifies at temperatures higher than T-g, has been reported in the literature. The percentage of the three different amorphous fractions, characterized by different segmental mobility, is generally calculated at T-g. In the present study, for the first time, the time and temperature evolution of all the amorphous fractions of PLLA are measured in parallel with the crystalline phase (i) during crystallization at two different temperatures, and (ii) upon the successive cooling step down to room temperature. The kinetics of vitrification/devitrification of the different amorphous fractions in diverse conditions of crystallization and solidification has been determined during the entire thermal history of the material. Rigid amorphous fraction is found to develop not only during crystallization but also upon cooling, after completion of crystallization.

To improve measurements of the dielectric permittivity of nanometric portions by means of Local Dielectric Spectroscopy (LDS), we introduce an extension to current analytical models for the interpretation of the interaction between the probe tip of an electrostatic force microscope (EFM) and a thin dielectric film covering a conducting substrate. Using the proposed models, we show how more accurate values for the dielectric constant can be obtained from single-frequency measurements at various probe/substrate distances, not limited to a few tip radii.

Polymer chains can adsorb onto a solid substrate without the formation of chemical bonds. Because this mechanism of adsorption is driven by the weak dipolar interactions and requires simultaneous pinning of many repeating units of the chain, its kinetics can be extremely slow, especially for polymer melt. As a consequence, polymer chains at the interface with a substrate can reside for very long times in non-equilibrium states, before reaching the equilibrium configuration. Remarkably, recent works verified that the deviations from the bulk behavior in the dynamics of nanoconfined polymers are strongly affected by those non-equilibrium configurations assumed in adsorbed layers. In this Chapter, we report experimental evidences on the existence of an irreversibly adsorbed layer in poly(vinyl acetate) (PVAc) films in contact with different substrates. The presence of such a layer is proved through atomic force microscopy imaging of the residual layer remaining on the substrate after washing the polymer film in a good solvent. Moreover, we demonstrate that the evolution of the irreversibly adsorbed layer is unambiguously related to the change in relaxation dynamics of polymer films under annealing at a high temperature (similar to T-g + 60 K). Finally, we demonstrate the direct effect of this adsorbed layer on the maximum moisture uptake of supported ultrathin PVAc films, hence providing a simple approach for controlling the moisture absorption of the nanosized polymer films.

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.

The segmental dynamics of poly(vinyl acetate) (PVAc) thin films were measured in the presence of an aluminum interface and in contact with an incompatible polymer, poly(4-vinylpyridine). The local dielectric relaxation was found to be faster in thin films than in the bulk; however, no differences were observed for the various interfaces, including a PVAc/air interface. These results show that capping of thin films, even with a rigid material, does not necessarily affect the dynamics, the speeding up herein for capped PVAc was equivalent to that for the air interface. The insensitivity of the dynamics to the nature of the interface affords a means to engineer thin films while maintaining desired mechanical properties. Our findings for PVAc also may explain the discordant results that have been reported in general for the effect of air versus rigid interfaces on the local segmental relaxation of thin films.

In the first two papers separately on the polyalcohols and amorphous polymers of this series, we demonstrated that the fast dynamics observed in the glassy state at high frequencies above circa 1 GHz is the caged dynamics. We showed generally the intensity of the fast caged dynamics changes temperature dependence at a temperature THF nearly coincident with the secondary glass transition temperature Tgβ lower than the nominal glass transition temperature Tgα. The phenomenon is remarkable, since THF is determined from measurements of fast caged dynamics at short time scales typically in the ns to ps range, while Tgβ characterizes the secondary glass transition at which the Johari-Goldstein (JG) β-relaxation time τJG reaches a long time of ∼10(3) s, determined directly either by positronium annihilation lifetime spectroscopy, calorimetry, or low frequency dielectric and mechanical relaxation spectroscopy. The existence of the secondary glass transition originates from the dependence of τJG on density, previously proven by experiments performed at elevated pressure. The fact that THF ≈ Tgβ reflects the density dependence of the caged dynamics and coupling to the JG β-relaxation. The generality of the phenomenon and its theoretical rationalization implies the same should be observable in other classes of glass-formers. In this paper, III, we consider two archetypal small molecular van der Waals glass-formers, ortho-terphenyl and toluene. The experimental data show the same phenomenon. The present paper extends the generality of the phenomenon and explanation from the polyalcohols, a pharmaceutical, and many polymers to the small molecular van der Waals glass-formers.

Secondary relaxations have been classified into two types, depending on whether they are related to the structural α-relaxation in properties or not. Those secondary relaxations that are related to the α-relaxation may have fundamental importance, and are called the Johari–Goldstein (JG) β-relaxations. Two polar molecular glass-formers, one flexible and another rigid, dissolved in apolar host with higher glass transition temperature are studied by broadband dielectric spectroscopy at ambient and elevated pressure. The neat flexible glass-former diethylphthalate (DEP) has a resolved secondary relaxation which, unlike the α-relaxation, is insensitive to pressure and hence is not the JG β-relaxation. In the solution, the JG β-relaxation of DEP shows up in experiment and its relaxation time τβ is pressure and temperature dependent like τα. The result supports the universal presence of the JG β-relaxation in all glass-formers, and the separation between τα and τβ is determined by intermolecular interaction. The rigid glass-former is cyano-benzene (CNBz) and its secondary relaxation involves the entire molecule is necessarily the JG β-relaxation. The dielectric relaxation spectra obtained at a number of combinations of pressure and temperature at constant τα show not only unchanged is the frequency dispersion of the α-relaxation but also τβ. The remarkable results indicate that the JG β-relaxation bears a strong connection to the α-relaxation, and the two relaxations are inseparable when considering the dynamics of glass-forming systems. Experimentally, τα has been found to be a function of the product variables, T/ργ, where ρ is the density and γ is a material constant. From the \invariance of the ratio, τα/τβ, to change of thermodynamic conditions seen in our experiment as well in other systems, it follows that τβ is also a function of T/ργ, with the same γ at least approximately. Since the JG β-relaxation is the precursor of the α-relaxation, causality implies that the T/ργ-dependence originates from the JG β-relaxation and is passed on to the α-relaxation.

The paper (Sibik, J.; Elliott, S. R.; Zeitler, J. A. J. Phys. Chem. Lett. 2014, 5, 1968-1972) used terahertz time-domain spectroscopy (THz-TDS) to study the dynamics of the polyalcohols, glycerol, threitol, xylitol, and sorbitol, at temperatures from below to above the glass transition temperature Tg. On heating the glasses, they observed the dielectric losses, ε″(ν) at ν = 1 THz, increase monotonically with temperature and change dependence at two temperatures, first deep in the glassy state at TTHz = 0.65Tg and second at Tg. The effects at both temperatures are most prominent in sorbitol but become progressively weaker in the order of xylitol and threitol, and the sub-Tg change was not observed in glycerol. They suggested this feature originates from the high-frequency tail of the Johari-Goldstein (JG) β-relaxation, and the temperature region near 0.65Tg is the universal region for the secondary glass transition due to the JG β-relaxation. In this paper, we first use isothermal dielectric relaxation data at frequencies below 10(6) Hz to locate the "second glass transition" temperature Tβ at which the JG β-relaxation time τJG reaches 100 s. The value of Tβ is close to TTHz = 0.65Tg for sorbitol (0.63Tg) and xylitol (0.65Tg), but Tβ is 0.74Tg for threitol and 0.83Tg for glycerol. Notwithstanding, the larger values of Tβ of glycerol are consistent with the THz-TDS data. Next, we identify the dynamic process probed by THz-TDS as the caged molecule dynamics, showing up in susceptibility spectra as nearly constant loss (NCL). The caged molecule dynamics regime is terminated by the onset of the primitive relaxation of the coupling model, which is the precursor of the JG β-relaxation. From this relation, established is the connection of the magnitude and temperature dependence of the NCL and those of τJG. This connection explains the monotonic increase of NCL with temperature and change to a stronger dependence after crossing Tβ giving rise to the sub-Tg behavior of ε″(ν) observed in experiment. Beyond the polyalcohols, we present new dielectric relaxation measurements of flufenamic acid and recall dielectric, NMR, and calorimetric data of indomethacin. The data of these two pharmaceuticals enables us to determine the value of Tβ = 0.67Tg for flufenamic acid and Tβ = 0.58Tg or Tβ = 0.62Tg for indomethacin, which can be compared with experimental values of TTHz from THz-TDS measurements when they become available. We point out that the sub-Tg change of NCL at Tβ found by THz-TDS can be observed by other high frequency spectroscopy including neutron scattering, light scattering, Brillouin scattering, and inelastic X-ray scattering. An example from neutron scattering is cited. All the findings demonstrate the connection of all processes in the evolution of dynamics ending at the structural α-relaxation.

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.

The effects of Strain Induced Crystallization and chain orientation on the cooperativity evolution with temperature are studied on two polymers with similar molecular structure but different crystallization attitude. For this goal, we focus on poly(ethylene terephthalate) (PET) and the copolyester poly(ethylene glycol-co-cyclohexane-1,4-dimethanol terephthalate) (PETg), the last one having very low ability to crystallize. From Temperature Modulated Differential Scanning Calorimetry and Broadband Dielectric Spectroscopy investigations, we show that the crystalline phase appearance in PET implies a large reduction of the Cooperative Rearranging Region size, accompanied with a variation from fragile to strong behavior of the structural relaxation time temperature dependence. Such large variations are not observed in PETg at the same draw ratio. In the case of PETg, a small contribution of chain alignment to the CRR size evolution is evidenced.