Decoupling of Glassy Dynamics from Viscosity in Thin Supported Poly(n-butyl methacrylate) Films.

We utilized fast scanning calorimetry to characterize the glass transition temperature (T g) and intrinsic molecular mobility of low-molecular-weight poly(n-butyl methacrylate) thin films of varying thicknesses. We found that the T g and intrinsic molecular mobility were coupled, showing no film thickness-dependent variation. We further employed a unique noncontact capillary nanoshearing technique to directly probe layer-resolved gradients in the rheological response of these films. We found that layer-resolved shear mobility was enhanced with a reduction in film thickness, whereas the effective viscosity decreased. Our results highlight the importance of polymer-substrate attractive interactions and free surface-promoted enhanced mobility, establishing a competitive nanoconfinement effect in poly(n-butyl methacrylate) thin films. Moreover, the findings indicate a decoupling in the thickness-dependent variation of T g and intrinsic molecular mobility with the mechanical responses (shear mobility and effective viscosity).

Physical Aging Behavior of a Glassy Polyether.

The present work aims to provide insights on recent findings indicating the presence of multiple equilibration mechanisms in physical aging of glasses. To this aim, we have investigated a glass forming polyether, poly(1-4 cyclohexane di-methanol) (PCDM), by following the evolution of the enthalpic state during physical aging by fast scanning calorimetry (FSC). The main results of our study indicate that physical aging persists at temperatures way below the glass transition temperature and, in a narrow temperature range, is characterized by a two steps evolution of the enthalpic state. Altogether, our results indicate that the simple old-standing view of physical aging as triggered by the α relaxation does not hold true when aging is carried out deep in the glassy state.

Reaching the Ideal Glass in Polymer Spheres: Thermodynamics and Vibrational Density of States.

The existence of an ideal glass and the resolution to the Kauzmann paradox is a long-standing open question in materials science. To address this problem, we exploit the ability of glasses with large interfacial area to access low energy states. We submit aggregates of spheres of a polymeric glass former to aging well below their glass transition temperature, T_{g}; and characterize their thermodynamic state by calorimetry, and the vibrational density of state (VDOS) by inelastic neutron scattering (INS). We show that, when aged at appropriate temperatures, glassy spheres attain a thermodynamic state corresponding to an ideal glass in time scales of about one day. In this state, the boson peak, underlying the deviation from the Debye level of the VDOS, is essentially suppressed. Our results are discussed in the framework of the link between the macroscopic thermodynamic state of glasses and their vibrational properties.

Direct observation of desorption of a melt of long polymer chains.

Tuning the thermodynamic state of a material has a tremendous impact on its performance. In the case of polymers placed in proximity of a solid wall, this is possible by annealing above the glass transition temperature, Tg, which induces the formation of an adsorbed layer. Whether heating to higher temperatures would result in desorption, thereby reverting the thermodynamic state of the interface, has so far remained elusive, due to the interference of degradation. Here, we employ fast scanning calorimetry, allowing to investigate the thermodynamics of the interface while heating at 104 K s-1. We show that applying such rate to adsorbed polymer layers permits avoiding degradation and, therefore, we provide clear-cut evidence of desorption of a polymer melt. We found that the enthalpy and temperature of desorption are independent of the annealing temperature, which, in analogy to crystallization/melting, indicates that adsorption/desorption is a first order thermodynamic transition.

Vitrification decoupling from α-relaxation in a metallic glass.

Understanding how glasses form, the so-called vitrification, remains a major challenge in materials science. Here, we study vitrification kinetics, in terms of the limiting fictive temperature, and atomic mobility related to the α-relaxation of an Au-based bulk metallic glass former by fast scanning calorimetry. We show that the time scale of the α-relaxation exhibits super-Arrhenius temperature dependence typical of fragile liquids. In contrast, vitrification kinetics displays milder temperature dependence at moderate undercooling, and thereby, vitrification takes place at temperatures lower than those associated to the α-relaxation. This finding challenges the paradigmatic view based on a one-to-one correlation between vitrification, leading to the glass transition, and the α-relaxation. We provide arguments that at moderate to deep undercooling, other atomic motions, which are not involved in the α-relaxation and that originate from the heterogeneous dynamics in metallic glasses, contribute to vitrification. Implications from the viewpoint of glasses fundamental properties are discussed.

Distinct dynamics of structural relaxation in the amorphous phase of poly(l-lactic acid) revealed by quiescent crystallization.

Fast scanning calorimetry (FSC) experiments were performed to investigate physical aging in amorphous and semi-crystalline poly(l-lactic acid)s (PLLAs) that were thermally crystallized under conditions leading to the α'- or α-crystalline form, and either favouring or inhibiting the development of a rigid amorphous fraction (RAF). The enthalpy of recovery was calculated after two procedures of rescaling to the content of the whole amorphous phase and also to the only content of the mobile amorphous fraction (MAF), which helped in clarifying the contribution of the RAF. From the dependence of the structural relaxation rate on the aging temperature, two regimes were evidenced for all samples. In the aging temperature domain situated close to the glass transition, the structural relaxation occurs significantly faster in the MAF. Its rate is independent of the aging temperature and is not influenced by the microstructure. However, the distance to equilibrium is higher in samples for which the coupling is strong between crystal and amorphous, implying that the time to reach equilibrium is also higher. In contrast, at low aging temperatures, for which the whole amorphous phase can be considered as solid, MAF and RAF exhibit the same structrural relaxation rate. This convergence in the relaxation kinetics by decreasing the temperature of physical aging was interpreted as the evolution of relaxation dynamics in the MAF from segmental to local. This change is highlighted by the comparison between MAF and RAF relaxation kinetics, but it occurs similarly in a pure amorphous system.

Tunable Properties of MAPLE-Deposited Thin Films in the Presence of Suppressed Segmental Dynamics.

Processing polymer thin films by physical vapor deposition has been a major challenge due to material degradation. This challenge has limited our understanding of morphological control by top-down approaches that can be crucial for many applications. Recently, matrix-assisted pulsed laser evaporation (MAPLE) has emerged as an alternative route to fabricate polymer thin films from near-gas phase growth conditions. In this Letter, we investigate how this approach can result in a stable two-phase film structure of semicrystalline polymers via a unique combination of MAPLE and flash calorimetry. In the case of MAPLE-deposited poly(ethylene oxide) (PEO) thin films, we find a 35 °C enhancement in the glass transition temperature relative to melt-crystallized films, which is associated with irreversible chain adsorption in the amorphous region of the film. Remarkably, by varying substrate temperature during deposition, we reveal the ability to significantly tune the crystal orientation, extent of crystallinity, and lamellar thickness of MAPLE-deposited PEO thin films.

Thermodynamic Ultrastability of a Polymer Glass Confined at the Micrometer Length Scale.

We employ fast scanning calorimetry to assess the thermodynamic state attained after a given cooling rate and the molecular mobility of glassy poly(4-tert-butylstyrene) confined at the micrometer length scale. We show that, for such a large confinement length scale, thermodynamic states with a fictive temperature (T_{f}) 80 K below the polymer glass transition temperature (T_{g}) are attained, which allows to bypass the geological timescales required for bulk glasses. Access to such states is promoted by a fast mechanism of equilibration. Importantly, the tremendous T_{f} decrease takes place while the molecular mobility remains bulklike, indicating marked decoupling between vitrification kinetics and molecular mobility.

Vitrification of two active pharmaceutical ingredients by fast scanning calorimetry: From structural relaxation to nucleation phenomena.

Cinchonidine and Theophylline vitrification abilities have been investigated by differential and fast scanning calorimetry. These active pharmaceutical compounds are known in the literature to have a very high tendency to crystallize which has been confirmed by classical differential scanning calorimetry. Due to the growing interest in amorphous pharmaceutical compounds, their possible vitrifications have been investigated by fast scanning calorimetry. This work shows the high potential of this advanced thermal analysis technique to investigate the vitrification of active pharmaceutical compounds by melt-quenching protocol. For the first time, glass transitions of Cinchonidine and Theophylline were measured. From Cinchonidine, it has been shown that complete glassy state can be obtained by cooling from the melt at 2000K/s. Crystallization has also been suppressed by cooling down from the melt at 2K/s. However, such rate does not avoid the formation of nuclei. Theophylline crystallization process has been suppressed by a melt-quenching protocol carried out with a cooling rate of 4000K/s. However, the phenomenon of nuclei formation upon cooling seems unavoidable at this cooling rate. For both active pharmaceutical compounds, physical aging has been observed to play a role on the nuclei formation below the glass transition leading to modify the subsequent crystallization.

Glass transition of anhydrous starch by fast scanning calorimetry.

By means of fast scanning calorimetry, the glass transition of anhydrous amorphous starch has been measured. With a scanning rate of 2000Ks-1, thermal degradation of starch prior to the glass transition has been inhibited. To certify the glass transition measurement, structural relaxation of the glassy state has been investigated through physical aging as well as the concept of limiting fictive temperature. In both cases, characteristic enthalpy recovery peaks related to the structural relaxation of the glass have been observed. Thermal lag corrections based on the comparison of glass transition temperatures measured by means of differential and fast scanning calorimetry have been proposed. The complementary investigations give an anhydrous amorphous starch glass transition temperature of 312±7°C. This estimation correlates with previous extrapolation performed on hydrated starches.

Insights on the Physical State Reached by an Active Pharmaceutical Ingredient upon High-Energy Milling.

We study the physicochemical transformations of crystalline quinidine upon high-energy milling. The investigations have been achieved by classical, high performance, and fast scanning calorimetry combined with broadband dielectric spectroscopy and X-ray powder diffraction. As evolution of crystalline quinidine with time of milling revealed a prominent sub-Tg cold-crystallization phenomenon, independent and complementary analytical techniques were implemented. Fast scanning calorimetry was performed for the first time on a milled pharmaceutical compound to postpone the crystallization event to higher temperatures. These fast thermal analyses allowed one to spotlight a genuine glass transition event. In addition, an aging experiment on the milled powder revealed a clear structural relaxation testifying to the presence of a glassy fraction in the milled sample. Last, dielectric analysis of milled quinidine disclosed the presence of localized and delocalized molecular mobility characteristics of glasses. Results for samples obtained by two distinct amorphization routes, vitrification and high-energy milling, indicate that amorphous fraction in milled quinidine behaves the same way as melt-quenched quinidine. These above-mentioned techniques proved their relevancy and efficiency to characterize milled quinidine, and fast scanning calorimetry in particular appears a promising screening tool for disordered systems.