Amorphization scenarios in multiparticulate grinding media composed of As4S4/ZnS/Fe3O4 nanocomposites driven by high-energy ball mechanical milling are identified employing the X-ray powder diffraction analysis on intermediate-range ordering in the generated amorphous phase. This amorphous phase is supposed to be nucleated heterogeneously from grain boundaries of beta-As4S4 crystallites followed by penetration deeply into grain interior, stabilizing the crystalline-amorphous core-shell structure of the fine-grained nanoparticles. Coexistence of nanocrystalline nc-beta-As4S4 and amorphous arsenic monosulphide a-AsS phases is crucial feature of these nanocomposites, the amorphous substance being generated continuously due to re-amorphization of disordered phase initially existed in arsenic sulphide prepared by synthesis from elements and direct milling-driven vitrification of nc-beta-As4S4. In monoparticulate beta-As4S4 -based and biparticulate As4S4/Fe3O4 nanocomposites, the amorphizing configurations are composed of single- and triple-broken chain-like network clusters. Under stronger conditions realized in the grinding medium composed by hard nanoparticles biased by their sizes in respect to 20:1 rule, as in triparticulate 1 center dot As4S4-4 center dot ZnS-1 center dot Fe3O4 nanocomposite, the amorphization scenario differs being activated by double-breaking of intramolecular covalent bonds within As4S4 cage-like molecules. This effect is identified as nanocrystalline nc-ZnS-assisted milling-driven arsenic monosulphide amorphization in triparticulate 1 center dot beta-As4S4-4 center dot ZnS-1 center dot Fe3O4 nanocomposite solution. (C) 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.