Polymer fibers that combine high toughness and heat resistance are hard to achieve, which, however, hold tremendous promise in demanding applications such as aerospace and military. This prohibitive design task exists due to the opposing property dependencies on chain dynamics because traditional heat-resistant materials with rigid molecular structures typically lack the mechanism of energy dissipation. Aramid nanofibers have received great attention as high-performance nanoscale building units due to their intriguing mechanical and thermal properties, but their distinct structural features are yet to be fully captured. We show that aramid nanofibers form nanoscale crimps during the removal of water, which primarily resides at the defect planes of pleated sheets, where the folding can occur. The precise control of such a structural relaxation can be realized by exerting axial loadings on hydrogel fibers, which allows the emergence of aramid fibers with varying angles of crimps. These crimped fibers integrate high toughness with heat resistance, thanks to the extensible nature of nanoscale crimps with rigid molecular structures of poly(p-phenylene terephthalamide), promising as a template for stable stretchable electronics. The tensile strength/modulus (392-944 MPa/11-29 GPa), stretchability (25-163%), and toughness (154-445 MJ/cm3) are achieved according to the degree of crimping. Intriguingly, a toughness of around 430 MJ/m3 can be maintained after calcination below the relaxation temperature (259 °C) for 50 h. Even after calcination at 300 °C for 10 h, a toughness of 310 MJ/m3 is kept, outperforming existing polymer materials. Our multiscale design strategy based on water-bearing aramid nanofibers provides a potent pathway for tackling the challenge for achieving conflicting property combinations.

This article proposes a numerical routine to predict the residual stresses developing in an epoxy component during its curing. The scaling of viscoelastic properties with the temperature and the degree of conversion is modeled, adopting a mathematical formulation that considers the concurrent effects of curing and structural relaxation on the epoxy\'s viscoelastic relaxation time. The procedure comprises two moduli: at first, the thermal-kinetical problem is solved using the thermal module of Ansys and a homemade routine written in APDL, then the results in terms of temperature and the degree of conversion profiles are used to evaluate the viscoelastic functions, and the structural problem is solved in the mechanical module of Ansys, allowing the residual stresses calculation. The results show that the residual stresses mainly arise during cooling and scale with the logarithm of the Biot number.

This paper analyzes the effect of crosslinking reactions on a thermoset polymer\'s viscoelastic properties. In particular, a numerical model to predict the evolution of epoxy\'s mechanical properties during the curing process is proposed and implemented in an Ansys APDL environment. A linear viscoelastic behavior is assumed, and the scaling of viscoelastic properties in terms of the temperature and degree of conversion is modeled using a modified version of the TNM (Tool-Narayanaswamy-Mohynian) model. The effects of the degree of conversion and structural relaxation on epoxy\'s relaxation times are simultaneously examined for the first time. This formulation is based on the thermo-rheological and chemo-rheological simplicities hypothesis and can predict the evolution of epoxy\'s relaxation phenomena. The thermal-kinetic reactions of curing are implemented in a homemade routine written in APDL language, and the structural module of Ansys is used to predict the polymer\'s creep and stress relaxation curves at different temperatures and degrees of conversion.

Although the mesomorphic phase as an intermediate state has been introduced to understand polymer crystallization, the understanding of the mesomorphic phase is far from complete. Here, the effect of chain mobility on the mesophase structuring in melt-quenched poly(ʟ-lactide) (PLLA) treated in low-pressure CO2 at 1.6-2.0 MPa and 0 °C was investigated using infrared (IR) spectroscopy, differential scanning calorimetry (DSC), and atomic force microscopy (AFM). The IR and AFM results demonstrated that the final degree of order and the kinetics of structural evolution during the CO2-induced mesophase formation were critically dependent on the CO2 pressure. This was attributed to the distinct dynamics of conformational evolution (gg to gt conformer transition) due to the different CO2 pressures. The thermal behavior from the DSC results showed that CO2 pressure dominated both the scale and dynamics of the chain motion of PLLA. At a lower CO2 pressure of 1.6 MPa, smaller-scale segmental motion was not replaced by the larger-scale cooperative motion that occurred at a relatively higher CO2 pressure of 2 MPa, which was favorable for faster mesophase formation. Consequently, by inhibiting direct crystallization under limited mobility conditions, it was demonstrated that different chain mobility controlled by CO2 pressure and thus CO2 solubility impacted the dynamics of the mesophase formation of PLLA. The present results have implications for understanding the role of chain mobility in determining the intermediate structural phases in semicrystalline polymers.

The processes of structural relaxation, crystal growth, and thermal decomposition were studied for amorphous griseofulvin (GSF) by means of thermo-analytical, microscopic, spectroscopic, and diffraction techniques. The activation energy of ~395 kJ·mol-1 can be attributed to the structural relaxation motions described in terms of the Tool-Narayanaswamy-Moynihan model. Whereas the bulk amorphous GSF is very stable, the presence of mechanical defects and micro-cracks results in partial crystallization initiated by the transition from the glassy to the under-cooled liquid state (at ~80 °C). A key aspect of this crystal growth mode is the presence of a sufficiently nucleated vicinity of the disrupted amorphous phase; the crystal growth itself is a rate-determining step. The main macroscopic (calorimetrically observed) crystallization process occurs in amorphous GSF at 115-135 °C. In both cases, the common polymorph I is dominantly formed. Whereas the macroscopic crystallization of coarse GSF powder exhibits similar activation energy (~235 kJ·mol-1) as that of microscopically observed growth in bulk material, the activation energy of the fine GSF powder macroscopic crystallization gradually changes (as temperature and/or heating rate increase) from the activation energy of microscopic surface growth (~105 kJ·mol-1) to that observed for the growth in bulk GSF. The macroscopic crystal growth kinetics can be accurately described in terms of the complex mechanism, utilizing two independent autocatalytic Šesták-Berggren processes. Thermal decomposition of GSF proceeds identically in N2 and in air atmospheres with the activation energy of ~105 kJ·mol-1. The coincidence of the GSF melting temperature and the onset of decomposition (both at 200 °C) indicates that evaporation may initiate or compete with the decomposition process.

The influence of partial crystallinity on the structural relaxation behavior of low-molecular organic glasses is, contrary to, e.g., polymeric materials, a largely unexplored territory. In the present study, differential scanning calorimetry was used to prepare a series of amorphous indomethacin powders crystallized to various extents. The preparations stemmed from the two distinct particle size fractions: 50-125 µm and 300-500 µm. The structural relaxation data from the cyclic calorimetric measurements were described in terms of the phenomenological Tool-Narayanaswamy-Moynihan model. For the 300-500 µm powder, the crystalline phase forming dominantly on the surface led to a monotonous decrease in the glass transition by ~6 °C in the 0-70% crystallinity range. The activation energy of the relaxation motions and the degree of heterogeneity within the relaxing matrix were not influenced by the increasing crystallinity, while the interconnectivity slightly increased. This behavior was attributed to the release of the quenched-in stresses and to the consequent slight increase in the structural interconnectivity. For the 50-125 µm powder, distinctly different relaxation dynamics were observed. This leads to a conclusion that the crystalline phase grows throughout the bulk glassy matrix along the internal micro-cracks. At higher crystallinity, a sharp increase in Tg, an increase in interconnectivity, and an increase in the variability of structural units engaged in the relaxation motions were observed.

Glasses frequently reveal structural relaxation that leads to changes in their physical properties including enthalpy, specific volume, and resistivity. Analyzing the short-range order (SRO) obtained from electron diffraction by transmission electron microscopy (TEM) in combination with Reverse-Monte-Carlo (RMC) simulations is shown to provide information on the atomic arrangement. The technique elaborated here features several benefits including reliability, accessibility, and allows for obtaining detailed structural data quickly. This is demonstrated with a detailed view of the structural changes in the as-deposited amorphous phase change material (PCM) GeTe. The data show a significant increase in the average bond angle upon thermal treatment. At the same time the fraction of tetrahedrally coordinated Ge atoms decreases due to an increase in octahedrally distorted and pyramidal motifs. This finding provides further evidence for the atomic processes that govern structural relaxation in amorphous GeTe and other PCMs. A thorough literature review finally unveils possible origins of the large discrepancies reported on the structure of amorphous GeTe.

Block copolymers are a class of materials that are particularly interesting with respect to their capability to self-assemble in ordered structures. In this context, the coupling between environment and dynamics is particularly relevant given that movements at the molecular level influence various properties of macromolecules. Mixing the polymer with a second macromolecule appears to be an easy method for studying these relationships. In this work, we studied blends of poly(methyl methacrylate) (PMMA) and a block copolymer composed of PMMA as the first block and poly(3-methyl-4-[6-(methylacryloyloxy)-hexyloxy]-4\'-pentyloxy azobenzene) as the second block. The relaxational properties of these blends were investigated via electron spin resonance (ESR) spectroscopy, which is sensitive to nanometric length scales. The results of the investigations on the blends were related to the dynamic behavior of the copolymers. At the nanoscale, the study revealed the presence of heterogeneities, with slow and fast dynamics available for molecular reorientation, which are further modulated by the ability of the block copolymers to form supramolecular structures. For blends, the heterogeneities at the nanoscale were still detected. However, it was observed that the presence of the PMMA as a major component of the blends modified their dynamic behavior.

The study of moiré engineering started with the advent of van der Waals heterostructures, in which stacking 2D layers with different lattice constants leads to a moiré pattern controlling their electronic properties. The field entered a new era when it was found that adjusting the twist between two graphene layers led to strongly-correlated-electron physics and topological effects associated with atomic relaxation. A twist is now routinely used to adjust the properties of 2D materials. This study investigates a new type of moiré superlattice in bilayer graphene when one layer is biaxially strained with respect to the other-so-called biaxial heterostrain. Scanning tunneling microscopy measurements uncover spiraling electronic states associated with a novel symmetry-breaking atomic reconstruction at small biaxial heterostrain. Atomistic calculations using experimental parameters as inputs reveal that a giant atomic swirl forms around regions of aligned stacking to reduce the mechanical energy of the bilayer. Tight-binding calculations performed on the relaxed structure show that the observed electronic states decorate spiraling domain wall solitons as required by topology. This study establishes biaxial heterostrain as an important parameter to be harnessed for the next step of moiré engineering in van der Waals multilayers.

Phase-change random-access memory (PCRAM) devices suffer from pronounced resistance drift originating from considerable structural relaxation of phase-change materials (PCMs), which hinders current developments of high-capacity memory and high-parallelism computing that both need reliable multibit programming. This work realizes that compositional simplification and geometrical miniaturization of traditional GeSbTe-like PCMs are feasible routes to suppress relaxation. While to date, the aging mechanisms of the simplest PCM, Sb, at nanoscale, have not yet been unveiled. Here, this work demonstrates that in an optimal thickness of only 4 nm, the thin Sb film can enable a precise multilevel programming with ultralow resistance drift coefficients, in a regime of ≈10-4 -10-3 . This advancement is mainly owed to the slightly changed Peierls distortion in Sb and the less-distorted octahedral-like atomic configurations across the Sb/SiO2 interfaces. This work highlights a new indispensable approach, interfacial regulation of nanoscale PCMs, for pursuing ultimately reliable resistance control in aggressively-miniaturized PCRAM devices, to boost the storage and computing efficiencies substantially.