Probing Sub-atomistic Free-Volume Imperfections in Dry-Milled Nanoarsenicals with PAL Spectroscopy

Structural transformations caused by coarse-grained powdering and fine-grained mechanochemical milling in a dry mode were probed in high-temperature modification of tetra-arsenic tetra-sulfide known as β-As4S4. In respect to X-ray diffraction analysis, the characteristic sizes of β-As4S4 crystallites in these coarse- and fine-grained powdered pellets were 90 and 40 nm, respectively. Positron annihilation lifetime spectroscopy was employed to characterize transformations occurred in free-volume structure of these nanoarsenicals. Experimentally measured positron lifetime spectra were parameterized in respect to three- or two-term fitting procedures and respectively compared with those accumulated for single crystalline realgar α-As4S4 polymorph. The effect of coarse-grained powdering was found to result in generation of large amount of positron and positronium Ps trapping sites inside arsenicals in addition to existing ones. In fine-grained powdered β-As4S4 pellets, the positron trapping sites with characteristic free volumes close to bi- and tri-atomic vacancies were evidently dominated. These defects were supposed to originate from grain boundary regions and interfacial free volumes near aggregated β-As4S4 crystallites. Thus, the cumulative production of different positron traps with lifetimes close to defect-related lifetimes in realgar α-As4S4 polymorph was detected in fine-grained milled samples.