High-Energy Mechanical Milling-Driven Reamorphization in Glassy Arsenic Monoselenide: On the Path of Tailoring Special Molecular-Network Glasses

Yaroslav Shpotyuk; Pavlo Demchenko; Oleh Shpotyuk; Valentina Balitska; Catherine Boussard-Pledel; Bruno Bureau; Zdenka Lukáčová Bujňáková; Peter Baláž

doi:10.3390/ma14164478

High-Energy Mechanical Milling-Driven Reamorphization in Glassy Arsenic Monoselenide: On the Path of Tailoring Special Molecular-Network Glasses

Materials (Basel). 2021 Aug 10;14(16):4478. doi: 10.3390/ma14164478.

Authors

Yaroslav Shpotyuk^{1

2}, Pavlo Demchenko², Oleh Shpotyuk^{3

4}, Valentina Balitska⁵, Catherine Boussard-Pledel⁶, Bruno Bureau⁶, Zdenka Lukáčová Bujňáková⁷, Peter Baláž⁷

Affiliations

¹ Institute of Physics, University of Rzeszow, 1, Pigonia Str., 35-959 Rzeszow, Poland.
² Ivan Franko National University of Lviv, 1, Universytetska Str., 79000 Lviv, Ukraine.
³ Faculty of Science and Technology, Jan Dlugosz University in Czestochowa, 13/15, al. Armii Krajowej, 42-200 Czestochowa, Poland.
⁴ Department of Optical Glass and Ceramics, Vlokh Institute of Physical Optics, 23, Dragomanov Str., 79005 Lviv, Ukraine.
⁵ Department of Physics and Chemistry of Combustion, Lviv State University of Life Safety, 35, Kleparivska Str., 79007 Lviv, Ukraine.
⁶ Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35000 Rennes, France.
⁷ Institute of Geotechnics of Slovak Academy of Sciences, 45, Watsonova Str., 04001 Košice, Slovakia.

Abstract

The impact of high-energy milling on glassy arsenic monoselenide g-AsSe is studied with X-ray diffraction applied to diffuse peak-halos proper to intermediate- and extended-range ordering revealed in first and second sharp diffraction peaks (FSDP and SSDP). A straightforward interpretation of this effect is developed within the modified microcrystalline approach, treating "amorphous" halos as a superposition of the broadened Bragg diffraction reflexes from remnants of some inter-planar correlations, supplemented by the Ehrenfest diffraction reflexes from most prominent inter-molecular and inter-atomic correlations belonging to these quasi-crystalline remnants. Under nanomilling, the cage-like As₄Se₄ molecules are merely destroyed in g-AsSe, facilitating a more polymerized chain-like network. The effect of nanomilling-driven molecular-to-network reamorphization results in a fragmentation impact on the correlation length of FSDP-responsible entities (due to an increase in the FSDP width and position). A breakdown in intermediate-range ordering is accompanied by changes in extended-range ordering due to the high-angular shift and broadening of the SSDP. A breakdown in the intermediate-range order is revealed in the destruction of most distant inter-atomic correlations, which belong to remnants of some quasi-crystalline planes, whereas the longer correlations dominate in the extended-range order. The microstructure scenarios of milling-driven reamorphization originated from the As₄Se₄ molecule, and its network derivatives are identified with an ab initio quantum-chemical cluster modeling code (CINCA).

Keywords: X-ray powder diffraction; arsenic monoselenide; extended-range ordering; high-energy mechanical milling; intermediate-range ordering; medium-range structure.