Non-linear dissolution mechanisms of sodium calcium phosphate glasses as a function of pH in various aqueous media

Phosphate glasses for bioresorbable implants display dissolution rates that vary significantly with composition, however currently their mechanisms of dissolution are not well understood. Based on this systematic study we present new insights into these mechanisms. Two-stage dissolution was observed, with time dependence initially parabolic and later linear, and a two-stage model was developed to describe this behaviour. Dissolution was accelerated by lower Ca concentration in the glass, and lower pH in the dissolution medium. A new dissolution mechanism is proposed, involving an initial stage where diffusion-controlled formation of a conversion layer occurs. Once the conversion layer is stabilised, layer dissolution reactions become rate-limiting. Under this mechanism the transition time is sensitive to the nature of the conversion layer and solution conditions. These results reveal the dependence of P₂O₅–CaO–Na₂O glass dissolution on solution pH, and provide new insight into the dissolution mechanisms, particularly regarding the transition between the two dissolution stages.     

Experimental studies and thermodynamic assessment of the Ba-Mo-O system by the CALPHAD method

Thermodynamic measurements on BaMoO₄, BaMoO₃ and BaMo₃O₁₀ are reported, that served as input for the development of a thermodynamic model of the Ba-Mo-O system using the CALPHAD methodology. The valence states of molybdenum in BaMoO₄ and BaMoO₃ were confirmed to be VI and IV, respectively, from X-ray Absorption Near Edge Structure Spectroscopy measurements at the Mo K-edge. The heat capacity at low temperatures of these compounds was obtained from thermal-relaxation calorimetry. Phase equilibrium data in the BaMoO₄-MoO₃ section were also measured, and the transition enthalpy associated with the peritectic decomposition of BaMo₃O₁₀ was determined using Differential Scanning Calorimetry. The developed thermodynamic model used the compound energy formalism for intermediate compounds, and an ionic two-sublattice model for the liquid phase. The optimized Gibbs energies were assessed with respect to the known thermodynamic and phase equilibrium data. A good agreement is generally obtained, but a number of ill-defined data were also identified.     

Optimizing the Optoelectronic Properties of Face-On Oriented Poly(3,4-Ethylenedioxythiophene) via Water-Assisted Oxidative Chemical Vapor Deposition

Engineering the texture and nanostructure to improve the electrical conductivity of semicrystalline conjugated polymers must address the rate-limiting step for charge carrier transport. In highly face-on orientation, the charge transport between chains within a crystallite becomes rate-limiting, which is highly sensitive to the π–π stacking distance and interchain charge transfer integral. Here, face-on oriented semicrystalline poly(3,4-ethylenedioxythiophene) (PEDOT) thin films are grown via water-assisted (W-A) oxidative chemical vapor deposition (oCVD). Combining W-A with the volatile oxidant, antimony pentachloride, yields an optimized electrical conductivity of 7520  ±  240 S cm⁻¹, a record for PEDOT thin films. Systematic control of π–π stacking distance from 3.50 Å down to 3.43 Å yields an electrical conductivity enhancement of ≈ 1140%. The highest electrical conductivity also corresponds to minimum in Urbach energy of 205 meV, indicating superior morphological order. The figure of merit for transparent conductors, σ_dc/σ_op, reaches a maximum value of 94, which is 1.9 × and 6.7 × higher than oCVD PEDOT grown without W-A and utilizing vanadium oxytrichloride and iron chloride oxidizing agents, respectively. The W-A oCVD is single-step all-dry process and provides conformal coverage, allowing direct growth on mechanical flexible, rough, and structured surfaces without the need for complex and costly transfer steps.     

Piezoelectricity of the Transmembrane Protein ba3 Cytochrome c Oxidase

Controlling the electromechanical response of piezoelectric biological structures including tissues, peptides, and amino acids provides new applications for biocompatible, sustainable materials in electronics and medicine. Here, the piezoelectric effect is revealed in another class of biological materials, with robust longitudinal and shear piezoelectricity measured in single crystals of the transmembrane protein ba₃ cytochrome c oxidase from Thermus thermophilus. The experimental findings from piezoresponse force microscopy are substantiated using a range of control measurements and molecular models. The observed longitudinal and shear piezoelectric responses of ≈ 2 and 8 pm V⁻¹, respectively, are comparable to or exceed the performance of commonly used inorganic piezoelectric materials including quartz, aluminum nitride, and zinc oxide. This suggests that transmembrane proteins may provide, in addition to physiological energy transduction, technologically useful piezoelectric material derived entirely from nature. Membrane proteins could extend the range of rationally designed biopiezoelectric materials far beyond the minimalistic peptide motifs currently used in miniaturized energy harvesters, and the finding of robust piezoelectric response in a transmembrane protein also raises fundamental questions regarding the molecular evolution, activation, and role of regulatory proteins in the cellular nanomachinery, indicating that piezoelectricity might be important for fundamental physiological processes.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Schedules with Priorities for Online Resource Management Problems in Aggregated Data Access Systems

Automation and Remote Control - We study the resource management problem in an aggregated data access system on the example of a cloud storage designed to manage data from medium and small...     

QoS-Aware Optical Fog-Assisted Cyber-Physical System in the 5G Ready Heterogeneous Network

Wireless Personal Communications - In recent years, the emergence of Internet of things and cyber-physical system provide a proactive and efficacious solution to enable remote monitoring, machine...     

A Survey on Advanced Multiple Access Techniques for 5G and Beyond Wireless Communications

Wireless Personal Communications - This paper summarizes the ongoing research initiatives based on the advanced multiple access techniques towards the fifth generation (5G) wireless communication...     

Magnetic Properties of Thin Epitaxial SiC Layers Grown by the Atom-Substitution Method on Single-Crystal Silicon Surfaces

Semiconductors - A cycle of experimental investigations is carried out, specifically, the measurements and analysis of field dependences of the static magnetic susceptibility in samples of...     

Hybrid Approach to Modeling the Process of Convective Radiative Heat and Mass Transfer in Closed Differentially Heated Cavities

Journal of Engineering Physics and Thermophysics - A hybrid model has been developed for the analysis of the process of combined mass and heat transfer in closed rectangular cavities under the...