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Free volume studies on mechanochemically milled β-As4S4 arsenical employing positron annihilation lifetime spectroscopy

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Abstract

Atomic-deficient free-volume transformations in directly synthesized β-As4S4 arsenical subjected to nanostructurization due to high-energy speed-increased (0–200–500–600 rpm) milling are comprehensively studied employing lifetime spectroscopy of annihilating positrons. These data testify that nanocrystalline and amorphous forms coexist among milling products, testifying in favor of milling-driven solid-state amorphization due to “shell” kinetic model. The depressing and time-enhancing trend in the detected positron lifetime spectra serves as a direct indication for continuous generation of amorphous phase, accompanied by free-volume evolution of coupled positron- and positronium (Ps) traps obeying x3-x2-CDA (coupling decomposition algorithm). At the stage of quick accumulation of size-reduced non-interacting nanoparticles characteristic of low speed (200 rpm), triple junctions equivalent to bi-/tri-atomic vacancies appear instead of Ps-traps. At higher rotational speed (500 rpm) exemplified by pelletized arsenicals composed of aggregated nanoparticles due to reversibly enhanced adhesion, these traps grow to characteristic sizes of quadruple vacancies and reduced Ps-to-positron trapping conversion occurs in more amorphous environment. In β-As4S4 subjected to milling at the highest speed (600 rpm), where irreversibly agglomerated nanograins dominate, the positron-to-Ps trapping conversion occurs due to elimination of triple junctions between crystallites and appearance of Ps-traps in more crystalline environment.

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Acknowledgements

This work was supported by the Slovak Research and Development Agency under the contract no. APVV-14-0103 and Slovak Grant Agency VEGA (project 2/0027/14). The publication contains the results of studies conducted by President’s of Ukraine grant for competitive projects (F70/134-2017) of the State Fund for Fundamental Research.

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Authors and Affiliations

  1. Vlokh Institute of Physical Optics, 23, Dragomanov Str, Lviv, 79005, Ukraine

    O. Shpotyuk

  2. Jan Dlugosz University in Czestochowa, 13/15, al. Armii Krajowej, 42200, Czestochowa, Poland

    O. Shpotyuk

  3. Opole University of Technology, 75, Ozimska Str, 45370, Opole, Poland

    A. Ingram

  4. Institute of Geotechnics of SAS, 45, Watsonova Str, 04001, Košice, Slovakia

    P. Baláž & Z. Bujňáková

  5. Ivan Franko National University of Lviv, 1, Universytetska Str, Lviv, 79000, Ukraine

    Ya. Shpotyuk

  6. University of Rzeszow, 1, Pigonia Str, 35-959, Rzeszow, Poland

    Ya. Shpotyuk & J. Cebulski

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  1. O. Shpotyuk
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  2. A. Ingram
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  3. P. Baláž
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  4. Z. Bujňáková
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  5. Ya. Shpotyuk
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Correspondence to O. Shpotyuk.

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Shpotyuk, O., Ingram, A., Baláž, P. et al. Free volume studies on mechanochemically milled β-As4S4 arsenical employing positron annihilation lifetime spectroscopy. Appl Nanosci 9, 647–656 (2019). https://doi.org/10.1007/s13204-018-0645-8

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  • DOI: https://doi.org/10.1007/s13204-018-0645-8

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