Influence of Chemical Composition and Structure on the Cooperative Fluctuation in Supercooled Glass-Forming Liquids.

The kinetics of the glass transition and the characteristic size of the fluctuating spatio-temporal domains in supercooled glass-forming liquids, i.e., the Cooperatively Rearranging Regions (CRR), were measured upon cooling over a broad range of cooling rates using Differential Scanning Calorimetry (DSC) and chip-based Fast Scanning Calorimetry (FSC). The investigations were conducted on a selection of fragile glass formers (fragility indices between 80 and 140), with a large variance in the atomic or molecular structure but comparable thermal glass transition temperatures Tg, with the aim of evaluating the influence of chemical composition and structure on the CRR size and the associated temperature fluctuation. The selected materials are two polymers (poly(vinyl acetate) (PVAc), poly(lactic acid) (PLA)) as well as the simplest chalcogenide glass-former (selenium). It turned out that the CRR size plotted against the reduced temperature T/Tg follows the same trend, irrespective of the considered glass-former.

Highlighting the interdependence between volumetric contribution of fragility and cooperativity for polymeric segmental relaxation.

The blurring around the link between the isobaric fragility and the characteristic size of cooperative rearranging region for glass-forming liquids has been cleared up by considering volumetric and thermal contributions of the structural relaxation. The measurement of these contributions is carried out for three amorphous thermoplastic polymers using broadband dielectric spectroscopy under pressure, providing an understanding of the link between isobaric fragilities, glass transition temperatures, and microstructures. The cooperative rearranging region (CRR) volume is calculated as a function of pressure using the extended Donth's approach, and the values are compared with the activation volume at the glass transition under different isobaric conditions. By combining these different results, a link between the chemical structure and the influence of pressure/temperature on the molecular mobility can be established. Furthermore, this study shows also a strong correlation between the activation volume, leading to the volumetric contribution of the isobaric fragility, and the CRR volume. Finally, this work highlights the influence of inter- and intra-molecular interactions on thermal and volumetric contributions of the isobaric fragility as a function of pressure.

Impact of chirality on the amorphous state of conglomerate forming systems: a case study of N-acetyl-α-methylbenzylamine.

The present work aims at addressing the issue of molecular handedness in glassy and liquid states and its impact on heterogeneous equilibrium. For this purpose, we evaluated the glass forming ability (GFA), crystallization propensity, molecular mobility and hydrogen bonding structure of a chiral conglomerate forming system, N-acetyl-α-methylbenzylamine (Nac-MBA), at various enantiomeric excesses (ees) using experimental and computational techniques. We revealed that the rich relaxational landscape (Debye (D), α, ßJG and ϒ) and the temperature dependence of the time scale of each process were insensitive to chirality. The most remarkable impact of chirality was expressed on the GFA and the recrystallization of heterochiral arrangements. In fact the GFA increases with decreasing ee, while the crystallization propensity increases with increasing ee. The counter enantiomer acted as a disruptor of crystallization and favored the glass formation upon cooling. The molecular dynamics simulation (MDS) results on the architecture of chiral sequences showed that homochiral sequences were more favorable when compared to heterochiral ones in the liquid state. However, this predisposition to form homochiral sequences in the liquid state was not the precursor of the future crystalline structure, since the liquid or the glassy system recrystallizes as heterochiral sequences. As per our understanding the crystallization was mostly controlled by the mean free migration path of an enantiomer to build homochiral or heterochiral sequences. In the present case, it seems that the mean free migration path achieved by an enantiomer for heterochiral sequences is shorter compared to homochiral arrangements in such a way that the crystallization of the metastable racemic compound is kinetically more favorable.

Assessment of Graphene Oxide and Nanoclay Based Hybrid Filler in Chlorobutyl-Natural Rubber Blend for Advanced Gas Barrier Applications.

Nanomaterials have engaged response from the scientific world in recent decades due to their exceptional physical and chemical properties counter to their bulk. They have been widely used in a polymer matrix to improve mechanical, thermal, barrier, electronic and chemical properties. In rubber nanocomposites, nanofillers dispersion and the interfacial adhesion between polymer and fillers influences the composites factual properties. In the present work, a comparison of the hybrid effects of carbon black with two different nanofillers (graphene oxide and nanoclay) was studied. The 70/30 composition of chlorobutyl rubber/natural rubber elastomer blend was taken as per the blend composition optimized from our previous studies. The hybrid effects of graphene oxide and nanoclay in dispersing the nanofillers were studied mainly by analyzing nanocomposite barrier properties. The results confirm that the combined effect of carbon black with graphene oxide and nanoclay could create hybrid effects in decreasing the gas permeability. The prepared nanocomposites which partially replace the expensive chlorobutyl rubber can be used for tyre inner liner application. Additionally, the reduction in the amount of carbon black in the nanocomposite can be an added advantage of considering the environmental and economic factors.

Promoting Interfacial Interactions with the Addition of Lignin in Poly(Lactic Acid) Hybrid Nanocomposites.

In this paper, the calorimetric response of the amorphous phase was examined in hybrid nanocomposites which were prepared thanks to a facile synthetic route, by adding reduced graphene oxide (rGO), Cloisite 30B (C30B), or multiwalled carbon nanotubes (MWCNT) to lignin-filled poly(lactic acid) (PLA). The dispersion of both lignin and nanofillers was successful, according to a field-emission scanning-electron microscopy (FESEM) analysis. Lignin alone essentially acted as a crystallization retardant for PLA, and the nanocomposites shared this feature, except when MWCNT was used as nanofiller. All systems exhibiting a curtailed crystallization also showed better thermal stability than neat PLA, as assessed from thermogravimetric measurements. As a consequence of favorable interactions between the PLA matrix, lignin, and the nanofillers, homogeneous dispersion or exfoliation was assumed in amorphous samples from the increase of the cooperative rearranging region (CRR) size, being even more remarkable when increasing the lignin content. The amorphous nanocomposites showed a signature of successful filler inclusion, since no rigid amorphous fraction (RAF) was reported at the filler/matrix interface. Finally, the nanocomposites were crystallized up to their maximum extent from the glassy state in nonisothermal conditions. Despite similar degrees of crystallinity and RAF, significant variations in the CRR size were observed among samples, revealing different levels of mobility constraining in the amorphous phase, probably linked to a filler-dimension dependence of space filling.

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.

Influence of reduced graphene oxide on flow behaviour, glass transition temperature and secondary crystallinity of plasticized poly(vinyl chloride).

Understanding the rheological behaviour of thermoplastic nanocomposites is important to obtain a concrete knowledge of their processability. The viscoelastic properties of nanocomposites are a reflection of their morphology. The study of flow and deformation of nanocomposites provides essential information related to prevalent interactions in the system as well as contribution from the dispersion of incorporated nanofillers. In the present study, plasticized polyvinyl chloride/reduced graphene oxide nanocomposites (PPVC/RGO) were fabricated using melt mixing technique with different filler concentration. Flow behaviour of the nanocomposites was analyzed using small amplitude oscillatory shear (SAOS) measurements and it indicated an enhancement in the storage modulus (G'), loss modulus (G'') and complex viscosity (η*) with RGO content. This can be attributed to very good dispersion and reinforcing effect of RGO in PPVC matrix as supported by TEM and FTIR results. Weak gel model is used to fit the rheological parameters and is found to be in excellent agreement with the SAOS experiments. Thermal history of the prepared nanocomposites was learned using differential scanning calorimetry. A shift in glass transition temperature (T g) to higher temperature region could be seen, that manifest the effect of RGO in the amorphous portion of PPVC. An interesting property called secondary crystallinity was also found in these materials.