Abstract
Thermochemical events recognized from heat flux DSC measurements involving dynamic and progressive step-cycling are identified in multi-nanophase substances exemplified by melt-quenched and nanomilling-derived AsxS100-x arsenicals enriched in As over As4S3 composition (As60S40, As62S38, As64S36). Thermal-alteration heat transfer in these alloys composed of normal- and plastic-crystalline phases supplemented by dual-nature amorphous substance are complicated by transformations in nanocrystalline dimorphite-type As4S3 and realgar-type As4S4 phases. Primary calorimetric events in the examined nanoarsenicals are shown to be as follows: (i) reduction in onset temperature from normal- (α′-As4S3) to plastic-crystalline (β-As4S3) phase; (ii) depression in pre-melting temperature of β-As4S3 phase; (iii) decrease in decomposition temperature of dimorphite-type phase supplemented by appearance of realgar-type β-As4S4 and amorphous phase, (iv) increase in crystallization temperature of β-As4S3 phase; (v) high-temperature shift in relaxation from liquid to stabilized heterogeneous state. The multiphase occurrence of nanoarsenicals results in unexpected increase in some heat transfer events detected in reheating modes.
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