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Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO₃to CaO and CO₂, and the rapid loss of CO₂absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO₃decomposition reaction pathway requires direct observation by time‐resolved (sub‐)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO₃nanoparticles to nanoporous CaO particles comprising high‐surface‐area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X‐ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO₃thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time‐resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO₃defects followed by sweeping reaction front motion across the initial CaCO₃particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub‐)nanoscale dynamics, while also demonstrating calcination of CaCO₃without sintering through rapid heating and precise temperature control.

 

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches. 

Understanding the thermal stability of metallic glasses is critical to determining their safe temperatures of service. In this paper, the crystallization mechanism in spark plasma sintered Fe₄₈Cr₁₅Mo₁₄Y₂C₁₅B₆metallic glass is established by analyzing the crystal size distribution using x-ray diffraction, transmission electron microscopy andin-situsmall angle neutron scattering. Isothermal annealing at 700 °C and 725 °C for 100 min resulted in the formation of (Fe,Cr)₂₃C₆crystals, measured from transmission electron micrographs, to be from 10 to 30 nm. The small angle neutron scattering intensity measuredin-situ, over a Q-range of 0.02 to 0.3 Å⁻¹, during isothermal annealing of the sintered samples, confirmed the presence of (Fe,Cr)₂₃C₆crystals. The measured scattering intensity, fitted by the maximum entropy model, over the Q-range of 0.02 to 0.06 Å⁻¹, revealed that the crystals had radii ranging from 3 to 18 nm. The total volume fraction of crystals were estimated to be 0.13 and 0.22 upon isothermal annealing at 700 °C and 725 °C for 100 min respectively. The mechanism of crystallization in this spark plasma sintered iron based metallic glass was established to be from pre-existing nuclei as confirmed by Avrami exponents of 0.25 ± 0.01 and 0.39 ± 0.01 at the aforesaid temperatures.