Reaction Behavior of Porous TiAl3 Intermetallics Fabricated by Thermal Explosion with Different Particle Sizes

Porous TiAl3 intermetallics were prepared by the thermal explosion (TE) and space holder method with different particle sizes of Ti and Al powders, and their reaction behaviors were investigated. The results showed that with the increase in the particle size of the Ti and Al powders, the interfacial contact between the particles decreased, resulting in low interfacial energy and reaction activity, making the process difficult to initiate. Meanwhile, the heat flow rose from 358.37 J/g to 730.17 J/g and 566.74 J/g due to the extension of the solid–liquid diffusion time. The TiAl3 structures obviously expanded, and the formation of connected pore channels promoted the porosity. Only when the Ti and Al particle sizes were both small did the solid–solid diffusion significantly appear. At the same time, the TE reaction weakened, so the product particles had no time to fully grow. This indicates that the particle size of the raw materials controlled the TE reaction process by changing the solid–liquid diffusion reaction time and the degree of solid-phase diffusion.

Tailoring atomic diffusion for in situ fabrication of different heterostructures

Atomic diffusion has been recognized as a particularly powerful tool in the synthesis of heterostructures. However, controlled atomic diffusion is very difficult to achieve in the fabrication of individual nanostructures. Here, an electrically driven in situ solid-solid diffusion reaction inside a TEM is reported for the controlled fabrication of two different hetero-nanostructures in the Ag-Te system. Remarkably, the morphology and structure of the as-formed heterostructures are strongly dependent on the path of atomic diffusion. Our experiments revealed that the surface diffusion of Te atoms to Ag nanowires leads to a core-shell structure, while the bulk diffusion of Ag atoms give rise to a Ag2Te-Te segmented heterostructure. Heat released by Joule heating caused the surface diffusion process to be replaced by bulk diffusion and thereby determined the structure of the final product. Our experimental results provide an insight into solid-state diffusion reactions under an electric field and also propose a new process for the fabrication of complex nanostructures.

Extended Larché–Cahn framework for reactive Cahn–Hilliard multicomponent systems

At high temperature and pressure, solid diffusion and chemical reactions between rock minerals lead to phase transformations. Chemical transport during uphill diffusion causes phase separation, that is, spinodal decomposition. Thus, to describe the coarsening kinetics of the exsolution microstructure, we derive a thermodynamically consistent continuum theory for the multicomponent Cahn–Hilliard equations while accounting for multiple chemical reactions and neglecting deformations. Our approach considers multiple balances of microforces augmented by multiple component content balance equations within an extended Larché–Cahn framework. As for the Larché–Cahn framework, we incorporate into the theory the Larché–Cahn derivatives with respect to the phase fields and their gradients. We also explain the implications of the resulting constrained gradients of the phase fields in the form of the gradient energy coefficients. Moreover, we derive a configurational balance that includes all the associated configurational fields in agreement with the Larché–Cahn framework. We study phase separation in a three-component system whose microstructural evolution depends upon the reaction–diffusion interactions and to analyze the underlying configurational fields. This simulation portrays the interleaving between the reaction and diffusion processes and how the configurational tractions drive the motion of interfaces.

Non-Covalent Bonding Caught in Action: From Amorphous-to-Cocrystalline Molecular Thin Films

<p>We demonstrate the solvent-free amorphous-to-cocrystalline transformations of nanoscale molecular films. Exposing amorphous films to vapors of a haloarene results in the formation of a cocrystalline coating. This transformation proceeds by gradual strengthening of halogen-bonding interactions as a result of the crystallization process. The gas-solid diffusion mechanism involves formation of an amorphous metastable phase prior to crystallization of the films. <i>In-situ </i>optical microscopy shows mass transport during this process, which is confirmed by cross-section analysis of the final structures using focused ion beam (FIB) milling combined with scanning electron microscopy (SEM). Nanomechanical measurements support the role of rigidity of the amorphous films influences the crystallization process. This surface transformation results in molecular arrangements that are not readily obtained through other means. Whereas cocrystals grown in solution crystallize in a monoclinic centrosymmetric space group, whereas the on-surface halogen-bonded assembly crystallizes into a noncentrosymmetric material with a bulk second-order non-linear optical (NLO) response.<br></p>

Non-Covalent Bonding Caught in Action: From Amorphous-to-Cocrystalline Molecular Thin Films

<p>We demonstrate the solvent-free amorphous-to-cocrystalline transformations of nanoscale molecular films. Exposing amorphous films to vapors of a haloarene results in the formation of a cocrystalline coating. This transformation proceeds by gradual strengthening of halogen-bonding interactions as a result of the crystallization process. The gas-solid diffusion mechanism involves formation of an amorphous metastable phase prior to crystallization of the films. <i>In-situ </i>optical microscopy shows mass transport during this process, which is confirmed by cross-section analysis of the final structures using focused ion beam (FIB) milling combined with scanning electron microscopy (SEM). Nanomechanical measurements support the role of rigidity of the amorphous films influences the crystallization process. This surface transformation results in molecular arrangements that are not readily obtained through other means. Whereas cocrystals grown in solution crystallize in a monoclinic centrosymmetric space group, whereas the on-surface halogen-bonded assembly crystallizes into a noncentrosymmetric material with a bulk second-order non-linear optical (NLO) response.<br></p>