Solid-state amorphization of As 45 S 55 alloy induced by high-energy mechanical milling

Shpotyuk, O.; Kozdraś, A.; Demchenko, P.; Shpotyuk, Ya.; Bujňáková, Zdenka; Baláž, Peter

doi:10.1016/j.tca.2016.09.009

Cited by 16 publications

(11 citation statements)

References 55 publications

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“…Thus, the FSDP can be ascribed to variations in the underlying cage structure of glass‐forming networks composed by interlinked polyhedrons (network‐forming blocks), producing a variety of interlinked circle‐type entities (small rings), keeping some elements of inter‐planar ordering proper to crystalline counterparts of these glasses. This standpoint occurred to be very useful in the interpretation of crystalline‐to‐amorphous transitions in many arsenic compounds (arsenicals) subjected to high‐energy MM …”

Section: Resultsmentioning

confidence: 99%

Effect of high‐energy mechanical milling on the medium‐range ordering in glassy As‐Se

et al. 2019

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Effect of high‐energy mechanical milling on glassy AsxSe100 − x (5 ≤ x ≤ 75) is recognized with X‐ray powder diffraction analysis applied to their diffuse halos ascribed to intermediate—and extended‐range structural ordering, which are revealed respectively in the first sharp diffraction peak (FSDP) and principal diffraction peak (PDP). Straightforward interpretation of the results is developed within modified microcrystalline approach, treating diffuse halos as superposition of broadened Bragg‐diffraction reflexes from remnants of inter‐planar correlations, supplemented by inter‐atomic Ehrenfest‐diffraction reflexes from most prominent inter‐atomic and inter‐molecular correlations between cage‐like molecules (such As4Se4 and/or As4Se3). Milling is shown to be ineffective in glassy arsenoselenides near Se (x < 20), while causing increase in the FSDP width for glasses with 20 ≤ x ≤ 40 due to destroyed inter‐planar ordering. Remnants of cage‐like molecules in over‐stoichiometric As‐rich AsxSe100 − x glasses (40 ≤ x ≤ 75) disappear under milling, promoting formation of higher polymerized structural network. This milling‐driven reamorphization results in a drastic increase in the FSDP position and fragmentation impact on the correlation length of the FSDP‐responsible entities. Breakdown in intermediate‐range ordering in these glasses is accompanied by changes in their extended‐range ordering revealed in high‐angular shift and broadening of the PDP. This effect is concomitant with the disappearance of distant inter‐atomic correlations between quasi‐crystalline planes in the milled arsenoselenide glasses at a cost of prolonged correlations dominating in their extended‐range ordering.

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Section: Resultsmentioning

confidence: 99%

Effect of high‐energy mechanical milling on the medium‐range ordering in glassy As‐Se

et al. 2019

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“…With increase in speed n, the FSDP parameters reach saturation, so that the FSDP is indeed sharp (in a reciprocal space) in REHE-600 due to low width of scattering vector DQ = 0.23 Å -1 centered at Q = 1.14 Å -1 , thus corresponding to R = 5.49 Å in ''quasi-periodicity'' and L = 27.0 Å in correlation length (in a real space). These parameters are well fitted to monotonic compositional dependence in amorphous As-S as going from MQ As 40 S 60 glass [33], MQ As 42 S 58 glass [33] (both being within glass-forming region in binary As-S system [2][3][4]) and completely amorphized As 45 S 55 alloy [7] toward As-rich compositions. Therefore, it can be assumed that under current MM conditions, we deal with continuous generation of compositionally authentic amorphous phase in bAs 4 S 4 arsenical.…”

Section: Amorphization By the Fsdp-related Xrpdmentioning

confidence: 85%

“…The crystal structures of the arsenical pellets were identified by XRPD method, the data being collected in a transmission mode using STOE STADI P diffractometer (STOE & Cie GmbH, Darmstadt, Germany) with linear position-sensitive detector (Cu-Ka 1 radiation, curved Ge(111) monochromator) as was described elsewhere [7,9]. The crystal structure of arsenic sulfide (JCPDS card No.…”

Section: Methodsmentioning

confidence: 99%

“…Within GaskellWright's microscrystalline concept [37,38], the smooth shift in the FSDP position to lower Q (respectively, 2h) with rotational speed n can be treated as domination in the MM products; some structural derivatives arise from cage-type entities of crystalline b-As 4 S 4 . Indeed, the most intensive (11 1) reflex of this b-As 4 S 4 crystal phase (possessing C2/c space group) corresponds just to interplanar distance d ð11 1Þ = 5.76 Å ; that is the highest one within all possible overstoichiometric As-S polymorphs [7]. Simultaneously, the FSDP becomes sharper with increased n, as it is character to longer correlation lengths L of networks built of these cage-type molecular derivatives (Table 1).…”

Section: Amorphization By the Fsdp-related Xrpdmentioning

confidence: 98%

“…Recently [7], some of the current authors reported the first results on observation of complete amorphization in semicrystalline As 45 S 55 alloy subjected to MM in a dry mode under protective Ar atmosphere. The amorphous phase possessing double-T g relaxation originated from intrinsic separation on distinct highand low-temperature glass components was identified as close to alloy of the same nominal chemical composition.…”

Section: Introductionmentioning

confidence: 97%

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Mechanochemically driven amorphization of nanostructurized arsenicals, the case of β-As4S4

et al. 2018

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The amorphization is studied in mechanically activated b-As 4 S 4 using highenergy ball milling in a dry mode with 100-600 min -1 rotational speeds, employing complementary methods of X-ray powder diffraction (XRPD) related to the first sharp diffraction peak, positron annihilation lifetime (PAL) spectroscopy, and ab initio quantum-chemical simulation within cation-interlinking network cluster approach (CINCA). The amorphous substance appeared under milling in addition to nanostructurized b-As 4 S 4 shows character XRPD halos parameterized as extrapolation of the FSDPs, proper to near-stoichiometric amorphous As-S alloys. The structural network of amorphized arsenicals is assumed as built of randomly packed multifold cycle-type entities proper to As 4 S 4 network. The depressing and time-enhancing tendency in the PAL spectrum peak is direct indicative of milling-driven amorphization, associated with free-volume evolution of interrelated positron-and Ps-trapping sites. At lower speeds (200-500 min -1 ), these changes include Ps-to-positron trapping conversion, but they attain an opposite direction at higher speed (600 min -1 ) due to consolidation of b-As 4 S 4 crystallites. In respect of CINCA modeling, the effect of high-energy milling is identified as destruction-polymerization action on monomer cage-type As 4 S 4 molecules and existing amorphous phase, transforming them to amorphous network of triple-broken As 4 S 4 derivatives. These findings testify in a favor of ''shell'' kinetic model of solid-state amorphization, the amorphous phase continuously generated under speed-increased milling being identified as compositionally authentic to arsenic monosulfide, different in medium range ordering from stoichiometric As 2 S 3 .

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DSC TOPEM® study of high-energy mechanical milling-driven amorphization in β-As4S4-based arsenicals

Shpotyuk

Kozdraś

Baláž

et al. 2018

J Therm Anal Calorim

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Solid-state amorphization of As 45 S 55 alloy induced by high-energy mechanical milling

Cited by 16 publications

References 55 publications

Effect of high‐energy mechanical milling on the medium‐range ordering in glassy As‐Se

Effect of high‐energy mechanical milling on the medium‐range ordering in glassy As‐Se

Mechanochemically driven amorphization of nanostructurized arsenicals, the case of β-As4S4

DSC TOPEM® study of high-energy mechanical milling-driven amorphization in β-As4S4-based arsenicals

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