Thermodynamic modeling of gas solubility in aqueous sodium chloride solution

An electrolyte Equation of State is presented by combining the Cubic Plus Association Equation of State,Mean Spherical Approximation and the Born equation.This new model uses experimental relative static permittivity,intend to predict well the activity coefficients of individual ions (ACI) and liquid densities of aqueous solutions.This new model is applied to model water + NaCl binary system and water + gas +NaCl ternary systems.The cation/anion-water interaction parameters of are obtained by fitting the exper-imental data of ACI,mean ionic activity coefficients (MIAC) and liquid densities of water + NaCl binary system.The cation/anion-gas interaction parameters are obtained by fitting the experimental data of gas solubilities in aqueous NaCl solutions.The modeling results show that this new model can correlate well with the phase equilibrium and volumetric properties.Without gas,predictions for ACI,MIAC,and liquid densities present relative average deviations of 1.3％,3.6％ and 1.4％ compared to experimental ref-erence values.For most gas-containing systems,predictions for gas solubilities present relative average deviations lower than 7.0％.Further,the contributions of ACI,and salting effects of NaCl on gases are ana-lyzed and discussed.     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Structural Basis for the Function of the C-Terminal Proton Release Pathway in the Calcium Pump

The calcium pump (sarco/endoplasmic reticulum Ca²⁺-ATPase, SERCA) plays a major role in calcium homeostasis in muscle cells by clearing cytosolic Ca²⁺ during muscle relaxation. Active Ca²⁺ transport by SERCA involves the structural transition from a low-Ca²⁺ affinity E2 state toward a high-Ca²⁺ affinity E1 state of the pump. This structural transition is accompanied by the countertransport of protons to stabilize the negative charge and maintain the structural integrity of the transport sites and partially compensate for the positive charges of the two Ca²⁺ ions passing through the membrane. X-ray crystallography studies have suggested that a hydrated pore located at the C-terminal domain of SERCA serves as a conduit for proton countertransport, but the existence and function of this pathway have not yet been fully characterized. We used atomistic simulations to demonstrate that in the protonated E2 state and the absence of initially bound water molecules, the C-terminal pore becomes hydrated in the nanosecond timescale. Hydration of the C-terminal pore is accompanied by the formation of water wires that connect the transport sites with the cytosol. Water wires are known as ubiquitous proton-transport devices in biological systems, thus supporting the notion that the C-terminal domain serves as a conduit for proton release. Additional simulations showed that the release of a single proton from the transport sites induces bending of transmembrane helix M5 and the interaction between residues Arg762 and Ser915. These structural changes create a physical barrier against full hydration of the pore and prevent the formation of hydrogen-bonded water wires once proton transport has occurred through this pore. Together, these findings support the notion that the C-terminal proton release pathway is a functional element of SERCA and also provide a mechanistic model for its operation in the catalytic cycle of the pump.     

Impact of gypsum on flotation of scheelite and fluorite using sodium oleate as collector

ABSTRACT

In this study, effect of calcium and gypsum on scheelite and fluorite was investigated using sodium oleate as collector. Micro-flotation and contact angle results showed that the adsorption of calcium could inhibit the hydrophobicity of scheelite and fluorite. Moreover, sulfate could enhance the inhibition. FT-IR results showed that calcium could be priori precipitated into calcium oleate and adsorb on mineral surface. The adsorption of calcium could increase the scheelite potential to IEP, while it showed limited effect on fluorite potential. However, the interaction of calcium on scheelite and fluorite in gypsum solution was more complex than that in calcium solution.     

Experimental study of crystal anisotropy based on ultra-precision cylindrical turning of single-crystal calcium fluoride

To realize ultimately efficient signal processing, it is necessary to replace electrical signal processing circuits with optical ones. The optical micro-resonator, which localizes light at a certain spot, is an essential component in optical signal processing. Single-crystal calcium fluoride (CaF₂) is the most suitable material for a highly efficient optical micro-resonator. The CaF₂ resonator can only be manufactured by ultra-precision machining processes, because its crystal anisotropy does not allow the application of chemical etching. However, the optical micro-resonator's performance depends definitely on the surface integrity.This study investigated the relationship between surface quality after ultra-precision machining and crystal anisotropy. Firstly, crack initiation was investigated on the (1 0 0), (1 1 0), and (1 1 1) planes using the micro-Vickers hardness test. Secondly, brittle-ductile transition was investigated by orthogonal cutting tests. Finally, cutting performance of cylindrical turning was evaluated, which could be a suitable method for manufacturing the CaF₂ resonator. The most difficult point in cylindrical turning of CaF₂ is that the crystalline plane and cutting direction vary continuously. In order to manufacture the CaF₂ optical micro-resonator more efficiently, analysis was conducted on crack initiation and surface quality of all crystallographic orientations from the perspective of slip system and cleavage.     

Carbon nanotube filter for heavy metal ion adsorption

This study investigated carbon nanotube filtration technology using catalyst particles supported on silicalite-1–biomorphic carbon materials (BCMs). Aqueous solutions of Mn(II), Cu(II), Cr(III), Cd(II), and Pb(II) were used to test the efficiency of heavy metal ions removal. Carbon nanotubes (CNTs) were synthesized and grown on BCMs by the chemical vapor deposition method catalyzed with the catalyst (Co, Fe, and Ni). The synthesized CNTs with Co– and Fe– nanoparticles were typically multi-walled carbon nanotubes, and they showed good crystallinity (I_D/I_G = 1.05) and yield of (11.10 and 8.86) %. The removal efficiency of Mn(II), Cu(II), Cr(III), Cd(II), and Pb(II) ions using Co-catalyzed CNT filter was 97.57%, 98.01%, 97.89%, 97.42%, and 99.99%, respectively.     

Microstructural and electrical changes in Ca0.9R0.1CeNbMoO8 (R = Y,Sm, Nd,La) ceramics induced by rare-earth ion doping

Rare-earth ions doped Ca_0.9R_0.1CeNbMoO₈ (R = Y, Sm, Nd, La) ceramics have been successfully prepared by solid-state method, and their modifications to the microstructure and electrical properties are also investigated. The rare-earth ions doped ceramics exhibit the scheelite structure. With the increase in the radius of rare-earth ions, the lattice distortion and bond interaction will be enhanced, and the consistency of grain size will be reduced. The ceramics exhibit negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K-1273 K, and the activation energy decreases with the increase of the radius of rare-earth ions. Rare-earth ions doping can increase the content of Ce³⁺ ions and promote the conductivity of ceramics. Except for Sm³⁺-doped ceramics, the high-temperature aging rate of other ceramics is less than 2%. The existence of some metastable Sm²⁺ ions in Sm³⁺-doped ceramics not only increases the activation energy, but also reduces the high-temperature stability of the ceramics.     

Rare-earth free sensitizer in NaLuCrF4:Er upconversion material

Upconversion phosphors are known as a material system that can convert near-infrared light into visible/ultraviolet emissions by sequentially absorbing multiple photons. The studies on upconversion materials often use two rare earth (RE) ions as a sensitizer-activator pair. We investigated the influences on luminescence intensity depending on Cr-doping content (x) of hexagonal NaLu_0.98–xCr_xF₄Er_0.02 (x = 0–0.9) upconversion material by substituting Lu³⁺ ions with Cr³⁺in the absence of Gd³⁺. The change in upconversion luminescence intensity appears with saddle-like shape. We suggest that Cr³⁺ ions play the dual role as a constituent in host lattice and a sensitizer in the upconversion process. Optimal conditions for gaining the strongest upconversion emission correspond to x = 0.3–0.5, where there are effective energy transfers between Cr³⁺ and Er³⁺ ions and CrEr dimers. Apart from these values, the emission intensity decreases rapidly which can be ascribed to the absence of multiple-photon absorption for the case of low Cr³⁺ contents, and to the coupling between Cr³⁺ and/or Er³⁺ ions for the case of high Cr³⁺ contents. Magnetization and electron-spin-resonant measurements were performed to understand the correlation between the optical and magnetic properties.     

Synthesis and characterization of a novel Ca-alginate-biochar composite as efficient zinc (Zn2+) adsorbent: Thermodynamics,process design,mass transfer and isotherm modeling

In this present work, Ca-alginate-biochar adsorbent has been synthesized, characterized and tested its effectiveness in the removal of aqueous phase Zn²⁺ metal. The removal efficiency was studied under various physicochemical process parameters. External mass transfer model, intraparticle diffusion model and pseudo-first-order and pseudo-second-order models were used to fit the experimental Zn²⁺ adoption kinetic results and to identify the mechanism of adsorption. The desorption studies indicate the possibilities of ion-exchange and physical–chemical adsorption of Zn^2+. The adsorption was best described by Langmuir isotherm model. Thermodynamic parameters suggested that the adsorption process becomes spontaneous, endothermic and irreversible in nature.