Sintering theory predicts no long-range mass transport or distortion for uniformly heated particles during particle coalescence. However, in sintering-based manufacturing processes, permanent part distortion is often observed. The driving forces and mechanisms leading to this phenomenon are not understood, and efforts to reduce distortion are largely limited to a trial-and-error approach. In this paper, we demonstrate that distortion during sintering results from mass-transport driven by nonhomogeneous temperature distribution. We then show that hitherto unknown mass transport mechanisms, working in the direction opposite to temperature gradient are the likely cause of distortion. The experimental setup, designed for this purpose, enables the quantification of distortion during sintering. Two possible mass transport mechanisms are defined, and the continuum model applicable to both is formulated. The model accurately predicts the transient and permanent distortion observed during experiments, including their size dependence. Methods to control distortion that can give rise to 4D printing are discussed.
Colloidal nanocrystal (NC) assemblies are promising for optoelectronic, photovoltaic, and thermoelectric applications. However, using these materials can be challenging in actual devices because they have a limited range of thermal conductivity and elastic modulus, which results in heat dissipation and mechanical robustness challenges. Here, we report thermal transport and mechanical measurements on single-domain colloidal PbS nanocrystal superlattices (NCSLs) that have long-range order as well as measurements on nanocrystal films (NCFs) that are comparatively disordered. Over an NC diameter range of 3.0-6.1 nm, we observe that NCSLs have thermal conductivities and Young's moduli that are up to â¼3 times higher than those of the corresponding NCFs. We also find that these properties are more sensitive to NC diameter in NCSLs relative to NCFs. Our measurements and computational modeling indicate that stronger ligand-ligand interactions due to enhanced ligand interdigitation and alignment in NCSLs account for the improved thermal transport and mechanical properties.
Nanoparticles , Ligands , Nanoparticles/chemistry
An emerging class of methylammonium lead iodide (MAPbI3)-based Ruddlesden-Popper (RP) phase perovskites, BA2MAn-1PbnI3n+1 (n = 1-7), exhibit enhanced stability to environmental conditions relative to MAPbI3, yet still degrade at elevated temperatures. We experimentally determine the thermal conductivities of these layered RP phases for n = 1-6, where n defines the number of repeated perovskite octahedra per layer. We measure thermal conductivities of 0.37 ± 0.13/0.12, 0.17 ± 0.08/0.07, 0.21 ± 0.05/0.04, and 0.19 ± 0.04/0.03 W/m·K in thin films of n = 1-4 and 0.08 ± 0.06/0.04, 0.06 ± 0.04/0.03, 0.06 ± 0.03/0.03, and 0.08 ± 0.07/0.04 W/m·K in single crystals of n = 3-6. With the exception of n = 1, these thermal conductivities are lower than the range of 0.34-0.50 W/m·K reported for single-crystal MAPbI3. Reduced-order lattice dynamics modeling suggests that the initially decreasing trend of thermal conductivity in similarly oriented perovskites with increasing n may result from the transport properties of coherent phonons, emergent from the superstructure, that do not scatter at the interfaces of organic butylammonium chains and perovskite octahedra. Reduced group velocity of coherent phonons in n = 3-6, a consequence of band flattening in the phonon dispersion, is primarily responsible for their ultralow thermal conductivities. Similar effects on thermal conductivity have been experimentally demonstrated in deposited superlattices, but never in naturally defined materials such as RP phases. GIWAXS measurements reveal that higher n RP phase thin films are less orientationally controlled and therefore possess apparently elevated thermal conductivities relative to single crystals of the same n.
Atomically precise nanoscale clusters could assemble into crystalline ionic crystals akin to the atomic ionic solids through the strong electrostatic interactions between the constituent clusters. Here we show that, unlike atomic ionic solids, the electrostatic interactions between nanoscale clusters could be frustrated by using large clusters with long and flexible side-chains so that the ionic cluster pairs do not crystallize. As such, we report ionic superatomic materials that can be easily solution-processed into completely amorphous and homogeneous thin-films. These new amorphous superatomic materials show tunable compositions and new properties that are not achievable in crystals, including very high electrical conductivities of up to 300 S per meter, ultra low thermal conductivities of 0.05 W per meter per degree kelvin, and high optical transparency of up to 92%. We also demonstrate thin-film thermoelectrics with unoptimized ZT values of 0.02 based on the superatomic thin-films. Such properties are competitive to state-of-the-art materials and make superatomic materials promising as a new class of electronic and thermoelectric materials for devices.
Structural phase transitions run in families of crystalline solids. Perovskites, for example, feature a remarkable number of structural transformations that produce a wealth of exotic behaviors, including ferroelectricity, magnetoresistance, metal-insulator transitions and superconductivity. In superatomic crystals and other such materials assembled from programmable building blocks, phase transitions offer pathways to new properties that are both tunable and switchable. Here we describe [Co6Te8(PEt3)6][C70]2, a novel superatomic crystal with two separate phase transitions that drastically transform the collective material properties. A coupled structural-electronic phase transition triggers the emergence of a new electronic band in the fullerene sublattice of the crystal, increasing its electrical conductivity by 2 orders of magnitude, while narrowing its optical gap and increasing its spin density. Independently, an order-disorder transition transforms [Co6Te8(PEt3)6][C70]2 from a phonon crystal to a phonon glass. These results introduce a family of materials in which functional phase transformations may be manipulated by varying the constituent building blocks.
