ABSTRACT
Externally-induced modification activated by high-energy excitation such as γ-irradiation from 60Co source is analyzed in chalcogenide glasses in terms of radiation-structural and glass-relaxation metastability, at the example of sulphides (including stoichiometric arsenic trisulphide, As2S3) and selenides. Unified configuration-enthalpy model evolving conjugated configuration-coordinate (free energy in dependence on configuration coordinate) and thermodynamic enthalpy (temperature deviations in enthalpy, configurational entropy or free volume) diagrams is proposed to describe metastability in these glasses under external influences, such as (1) physical ageing, (2) irradiation, (3) thermal annealing, (4) rejuvenation, and their combinations. The model predicts glass stabilization in the ground state composed of partial sub-states related to (i) irradiation, (ii) rejuvenation, (iii) annealing, as well as (iv) ideal-glass deep states, connected by over-barrier jumping and through-barrier tunneling transitions. This model allows an adequate parameterization of optical responses related to metastability in these glasses defined through blue (bleaching) or red (darkening) shift in their optical transmission spectra.
ABSTRACT
Phase-change materials, demonstrating a rapid switching between two distinct states with a sharp contrast in electrical, optical or magnetic properties, are vital for modern photonic and electronic devices. To date, this effect is observed in chalcogenide compounds based on Se, Te or both, and most recently in stoichiometric Sb2S3 composition. Yet, to achieve best integrability into modern photonics and electronics, the mixed S/Se/Te phase change medium is needed, which would allow a wide tuning range for such important physical properties as vitreous phase stability, radiation and photo-sensitivity, optical gap, electrical and thermal conductivity, non-linear optical effects, as well as the possibility of structural modification at nanoscale. In this work, a thermally-induced high-to-low resistivity switching below 200 °C is demonstrated in Sb-rich equichalcogenides (containing S, Se and Te in equal proportions). The nanoscale mechanism is associated with interchange between tetrahedral and octahedral coordination of Ge and Sb atoms, substitution of Te in the nearest Ge environment by S or Se, and Sb-Ge/Sb bonds formation upon further annealing. The material can be integrated into chalcogenide-based multifunctional platforms, neuromorphic computational systems, photonic devices and sensors.
ABSTRACT
We analyzed the biological performance of spinodally and droplet-type phase-separated 45S5 Bioglass® generated by quenching the melt from different equilibrium temperatures. MC3T3-E1 pre-osteoblast cells attached more efficiently to 45S5 Bioglass® with spinodal than to the one with droplet morphology, providing the first demonstration of the role of micro-/nano-scale on the bioactivity of Bioglass®. Upon exposure to biological solutions, phosphate buffered saline (PBS) and cell culture medium (α-MEM), a layer of hydroxyapatite (HA) formed on both glass morphologies. Although both Bioglass® varieties were incubated under identical conditions, and physico-chemical characteristics of the HA layers were similar, the adsorption magnitude of a model protein, bovine serum albumin (BSA, an abundant blood serum component) and its ß-sheet/ß-turn ratio and α-helix content were significantly higher on spinodal than droplet type Bioglass®. These results indicate that: (i) a protein layer quickly adsorbs on the surface of 45S5 Bioglass® varieties (with or without HA layer), (ii) the amount and the conformation of adsorbed proteins are guided by the glass micro-/nano-structure, and (iii) cell attachment and proliferation are influenced by the concentration and the conformation of attached proteins with a significantly better cell adhesion to spinodal type 45S5 Bioglass® substrate. Taken together, our results indicate that the biological performance of 45S5 Bioglass® can be improved further with a relatively simple, inexpensive fabrication procedure that provides a superior glass micro-/nano-structure. A simple modification to the fabrication procedure of classic 45S5 Bioglass® generates spinodal (A(a)) and droplet (A(b)) varieties and has a significant impact on protein adsorption (B) and cell adhesion (C).
Subject(s)
Ceramics/chemistry , Glass/chemistry , Phase Transition , Tissue Scaffolds/chemistry , Animals , Biocompatible Materials/chemistry , Cell Adhesion/drug effects , Cell Proliferation/drug effects , Cells, Cultured , Ceramics/pharmacology , Culture Media/pharmacology , Durapatite/chemistry , Materials Testing , Mice , Organic Chemicals/pharmacology , Osteoblasts/cytology , Osteoblasts/drug effects , Surface PropertiesABSTRACT
Methodological possibilities of positron annihilation lifetime (PAL) spectroscopy applied to characterize different types of nanomaterials treated within three-term fitting procedure are critically reconsidered. In contrast to conventional three-term analysis based on admixed positron- and positronium-trapping modes, the process of nanostructurization is considered as substitutional positron-positronium trapping within the same host matrix. Developed formalism allows estimate interfacial void volumes responsible for positron trapping and characteristic bulk positron lifetimes in nanoparticle-affected inhomogeneous media. This algorithm was well justified at the example of thermally induced nanostructurization occurring in 80GeSe2-20Ga2Se3 glass.
ABSTRACT
The structural origin of reversible gamma-induced effects in vitreous Ge(23.5)Sb(11.8)S(64.7) has been investigated by high-resolution X-ray photoelectron spectroscopy (XPS). The changes in valence band spectrum from gamma-irradiation suggest a decrease of sulfur lone pair electron concentration accompanied by changes in bonding states of S and Ge. The appearance of additional doublets in the core-level XPS spectra of Ge, Sb, and S atoms for gamma-irradiated sample is described by the formation of over- and under-coordinated charged defect pairs (Ge(3)(-)-S(3)(+)) as a result of radiation treatment. The results verify the switching of Ge-S covalent bonds into S-S bonds as the main microstructural mechanism for gamma-induced optical effects in this glass.