Identification of phosphorus sites in amorphous LiPON thin film by observing internuclear proximities.

Amorphous lithium phosphorus oxynitrides (LiPON), prepared by reactive magnetron sputtering, have become the electrolytes of choice for all-solid-state thin film microbatteries since its discovery in early 1990s. Nevertheless, there is still a lack of understanding of their atomic-level structure and its influence on ionic conductivity. Solid-state NMR spectroscopy represents a promising technique to determine the atomic-level structure of LiPON glasses but is challenging owing to its low sensitivity in the case of thin film materials. Recently, 31P solid-state NMR spectra of LiPON thin films were acquired under magic-angle spinning (MAS) conditions and assigned with the help of density functional theory (DFT) calculations of NMR parameters. However, the identification of the different P local environments in these materials is still a challenge owing to their amorphous structure and the lack of resolution of the 31P MAS NMR spectra. We show herein how the NMR observation of internuclear proximities helps to establish the nature of P sites in LiPON thin films. The 31P-14N proximities are probed by a transfer of population in double resonance (TRAPDOR) experiment, whereas 31P-31P proximities are observed using one-dimensional (1D) 31P double-quantum (DQ)-filtered and two-dimensional (2D) 31P homonuclear correlation spectra as well as dipolar dephasing experiments using DQ-DRENAR (DQ-based dipolar-recoupling effects nuclear alignment reduction) technique. The obtained NMR data further support the recently proposed assignment of 31P NMR signals of LiPON thin films. With the help of this assignment, the simulation of the quantitative 1D 31P NMR spectrum indicates that PO43- orthophosphate anions prevail in LiPON thin films and N atoms are mainly incorporated in [O3PNPO3]5- dimeric anions. PO3N4- isolated tetrahedra and [O3POPO3]4- anions are also present but in smaller amounts.

The physics of dancing peanuts in beer.

In Argentina, some people add peanuts to their beer. Once immersed, the peanuts initially sink part way down into the beer before bubbles nucleate and grow on the peanut surfaces and remain attached. The peanuts move up and down within the beer glass in many repeating cycles. In this work, we propose a physical description of this dancing peanuts spectacle. We break down the problem into component physical phenomena, providing empirical constraint of each: (i) heterogeneous bubble nucleation occurs on peanut surfaces and this is energetically preferential to nucleation on the beer glass surfaces; (ii) peanuts enshrouded in attached bubbles are positively buoyant in beer above a critical attached gas volume; (iii) at the beer top surface, bubbles detach and pop, facilitated by peanut rotations and rearrangements; (iv) peanuts containing fewer bubbles are then negatively buoyant in beer and sink; and (v) the process repeats so long as the beer remains sufficiently supersaturated in the gas phase for continued nucleation. We used laboratory experiments and calculations to support this description, including constraint of the densities and wetting properties of the beer-gas-peanut system. We draw analogies between this peanut dance cyclicity and industrial and natural processes of wide interest, ultimately concluding that this bar-side phenomenon can be a vehicle for understanding more complex, applied systems of general interest and utility.