Decreasing Oxygen Partial Pressure Research Articles

Oxygen diffusion in β-Ga2O3 single crystals under different oxygen partial pressures at 1375 °C

Abstract The monoclinic β-polymorph of gallium oxide is a semiconductor with an ultra-wide bandgap. It is becoming increasingly significant for various technological applications. We have investigated the tracer self-diffusion of oxygen in β-Ga2O3 single crystals as a function of the oxygen partial pressure (2, 20 and 200 mbar) at a temperature of 1375 °C. Isotopically enriched 18O2 gas was used as a tracer source and secondary ion mass spectrometry to analyze depth profiles. We observed that, with decreasing oxygen partial pressure, the diffusivities at a given temperature increase significantly. We suggest that this behaviour can be explained by a change in the diffusion mechanism from oxygen interstitials to oxygen vacancies.

Selective oxidation of FeNiCrAl-based alloys under low oxygen pressure and their coking resistance

Selective oxidation of Fe–25Ni–20Cr–xAl-based alloys under low oxygen pressure was studied to improve oxidation and coking resistance. The morphology and oxidation kinetics of the oxide layer were analyzed using multi-scale techniques such as scanning electron microscopy, electron probe micro-analysis, and X-ray photoelectron spectroscopy. The results indicated that when the Al content exceeded 2.5 wt%, a duplex-structure oxide film, mainly consisting of M2O3 (M: Al and Cr) outer and Al2O3 inner layer, was formed on the surface of the alloy after pre-oxidation. When the Al content exceeded 8 wt%, a complete and dense Al2O3 external oxide film was formed through a two-step oxidation process. The decrease in oxygen partial pressure and surface enrichment of aluminum during the pre-oxidation process accelerated the formation of an external Al2O3 oxide film. Therefore, it isolated the catalytic coking reaction of Fe and Ni transition metals in the alloy with the pyrolysis atmosphere, significantly improving the anti-coking performance of the alloy.

Experimental and Numerical Simulation Study of Oxygen Transport in Proton Exchange Membrane Fuel Cells at Intermediate Temperatures (80 °C-120 °C).

Investigating the oxygen transport law within the Membrane Electrode Assembly at intermediate temperatures (80-120 °C) is crucial for enhancing fuel cell efficiency. This study analyzed the resistance to oxygen transport within the Membrane Electrode Assembly at intermediate temperatures using limiting current density and electrochemical impedance spectroscopy. The study findings reveal that, as temperature progressively increases, the Ostwald ripening effect leads to a 34% rise in the local oxygen transport resistance (Rlocal) in relation to the pressure-independent resistance (Rnp) within the cathode catalytic layer. Concurrently, the total transport resistance (Rtotal) decreases from 27.8% to 37.5% due to an increase in the gas diffusion coefficient and molecular reactivity; additionally, there is a decrease in the amount of liquid water inside the membrane electrode. A three-dimensional multiphysics field steady-state model was also established. The model demonstrates that the decrease in oxygen partial pressure can be mitigated effectively by increasing the back pressure at intermediate temperatures to ensure the cell's performance.

Effect of Secondary Oxidants (CO2 and/or H2O) on Oxidation of Fe-20Cr-(Mn, Si)

Ferritic heat resisting alloys are widely used in industry owing to their combination of economy, reasonable strength, and high temperature corrosion resistance. Alloy design centres on forming and maintaining an external, slow growing protective oxide scale by selective oxidation of the desired metal, commonly chromium. Design methods based on diffusion theory succeed when the service environment is oxygen or clean, dry air. However, they can fail badly when secondary oxidants (like CO2 and water vapour) are present, which is commonly the case in energy production etc. This work investigates the effect of CO2 and H2O on corrosion behaviour of Fe-20Cr, in comparison with that in pure O2. The alloying effect of Si and Mn on oxidation behaviour of Fe-20Cr in different gases is also investigated.Model alloys Fe-20Cr, Fe-20Cr-1Si, Fe-20Cr-2Mn (all in wt%) were arc melted and annealed. Sample coupons were cut, ground, mechanically polished to 3mm finish, and further electro-polished to remove subsurface deformation zones. They were then exposed to Ar-2O2, Ar-20H2O-2O2, Ar-20CO2-2O2, Ar-CO2-H2O and Ar-CO2-H2O-O2 (all vol%) gas mixtures, at 650°C for 150h. Corrosion products and cross-sections were examined using optical microscopy, X-ray diffraction, Raman Spectroscopy and scanning electron microscopy equipped with energy dispersive X-ray spectrometry.The alloy behaved protectively in Ar-2O2, forming a very thin Cr2O3 layer on its surface. However, when CO2 or/and H2O was added to oxygen, breakaway oxidation resulted, forming thick multi-layered oxide scales. Detailed analysis revealed that this multi-layered structure contains four layers, where the outer layer was Fe2O3, overlying an Fe3O4 layer and FeCr2O4 spinel innermost layer, and an internal oxidation zone was formed beneath the scale. In the low environment of Ar-20CO2-20H2O, Fe3O4 layer, FeCr2O4 spinel layer and internal oxidation zone formed a three-layered structure. No Fe2O3 was found, which is attributed to the decrease in oxygen partial pressure.Carburisation of Fe-20Cr also resulted from exposure to the three CO2-bearing gases. The deepest and densest internal carburisation zone formed in Ar-20CO2-2O2. In Ar-20CO2-20H2O-2O2 and Ar-20CO2-20H2O, internally precipitated carbides were sparser, but still obvious.Silicon addition dramatically improved the oxidation resistance of Fe-20Cr. Weight gains in all gases were sharply decreased compared with those of Fe-20Cr. As with Fe-20Cr, a very thin Cr2O3 layer on the Si-bearing alloy reacted in Ar-2O2,together with a thin underlying silica layer, indicating that the alloy was fully protected. Unlike Fe-20Cr, the Fe-20Cr-1Si alloy was also protected in Ar-20CO2-2O2. However, when water vapour was present, the alloy started to go into breakaway, forming local Fe-rich oxide nodules. In Ar-20H2O-2O2, some small nodules, consisting of external Fe2O3 and inner spinel were distributed on an otherwise thin, protective chromia scale. In Ar-20H2O-20CO2-2O2 and Ar-20H2O-20CO2, an additional Fe3O4 layer was observed in nodules, between Fe2O3 and inner spinel. Thus, for Fe-20Cr-1Si samples, Fe3O4 can only be observed if 20%CO2 and 20%H2O were both present. Additionally, some small internal oxide particles were observed at breakaway nodule areas in all these three gasses. Internal carbides were found only under the big iron oxides nodules grown in Ar-20CO2-20H2O-2O2.Manganese addition did not much influence the corrosion resistance of Fe-20Cr. In general, oxide morphologies were similar to those of Fe-20Cr. In Ar-2%O2 gas, a thin Mn rich chromium oxide layer was formed over the entire alloy surface, indicating that sample was fully protected. Multi-layered thick oxides developed when CO2 or/and H2O were added. For high gases with the addition of H2O or CO2 (Ar-20H2O-2O2, Ar-20CO2-2O2, and Ar-CO2-H2O-O2), three-layered oxide structures were found to be made up of Fe2O3, Fe3O4, and spinel layers, in sequence from the outer surface to the inner alloy. It is worth noting that the oxide layers were not completely continuous in Ar-20CO2-2O2. About 15% of the cross-section area was protected which indicated that Mn can slightly improve the corrosion resistance in dry CO2 and O2 environments. In lower oxygen partial pressure gas (Ar-CO2-H2O), no Fe2O3 was found, and only Fe3O4 and spinel constituted the oxide scale. The main difference was that the internal oxidation zone became tiny on Fe-20Cr-2Mn samples. Internal carbides were still found under inner oxide in all CO2 bearing gases, most obviously in Ar-20CO2-2O2. However, in all cases the carbide quantities were far less than those in Fe-20Cr, indicating that Mn addition partially inhibited carburisation.After the thermodynamics of the reaction product phase assemblages are considered, this complex pattern of reaction products is discussed in terms of the permeability of different oxides to carbon- and hydrogen-bearing species, along with interactions between secondary oxidants on oxide surfaces and grain boundaries.

Epitaxial growth and characterization of magnesium gallate (MgGa2O4) thin films by pulsed laser deposition

In this work, crystalline MgGa2O4 thin films were grown on c-plane sapphire substrates using the pulsed laser deposition (PLD) technique in a broad range of temperatures and oxygen pressures. The parameters for the crystalline growth were within the temperature range of 300 ℃ to 700 ℃ and the pressure range of 1 × 10-1 to 1 × 10-3 Torr. The acquired XRD patterns confirmed the film growth along the [111] preferential crystal orientation in the lattice and the rocking curve measurement of the prominent (222) plane showed an increasing trend of the crystallinity with growth temperature and pressure. Furthermore, the XRD phi (φ) scan demonstrated the six-fold rotational symmetry of the MgGa2O4 films and the epitaxial relationship of 30° between the film and sapphire substrate. The XPS spectra confirmed the presence of +2 and +3 oxidation state for Mg and Ga respectively, in the films and vacancies that increase with decreasing oxygen partial pressure. The direct bandgap of MgGa2O4 films was obtained to be ∼5.27 ± 0.03 eV by analyzing the UV-Vis absorbance spectra. The film surface exhibited a granular morphology with an increasing trend in grain size as the temperature increased. The refractive index and thickness of these films were in the range of ∼1.90 ± 0.02 and ∼70 ± 2.0 nm, respectively determined from the fitted spectroscopic ellipsometry data. The surface roughness was obtained from AFM images and found to be in good agreement with those obtained from the analysis of the ellipsometry data.

Effect of surface treatment and synergistic effect of O and S elements on hot corrosion behavior of GH738 superalloy

The hot corrosion behavior of GH738 superalloy after solution heat treated (SHT), room temperature machining (RTM) and low temperature burnishing (LTB) coated mixed salt (25% NaCl + 75% Na2SO4) on its surface was investigated at 700 °C. The results showed that the surface grain refinement of the LTB specimens and produced numerous multiple nano-twins, which was conducive to the diffusion of Cr and Al elements from the inside to the outside of the matrix. Dense and continuous Cr2O3 and Al2O3 layers were formed on the surface of the corrosion product layer and between the external corrosion layer and the surface of the matrix, respectively, which improved the hot corrosion resistance. The mechanism of the synergistic effect between O and S elements during corrosion process was found. The sulfide (SO3) reacted with the alloy elements in the matrix to form metal oxides and S, and this process promoted the diffusion of O element into the matrix. The O2 entering the internal corrosion layer and the O2 generated by the decomposition of SO3 together cause the partial pressure of oxygen in the matrix to rise, promoting the reoxidation of the metal sulfide to release S element. The oxygen in the matrix is consumed, resulting in the decrease of oxygen partial pressure. This leads to the reaction between S element and metallic elements with strong affinity to generate metal sulfide (such as TiS). In this process, O element promotes the diffusion of S element to the matrix.

Operando Monitoring of Oxygen Drop in Catalyst Layers Accompanied by a Water Increase in Running Proton Exchange Membrane Fuel Cells.

Accurate understanding of internal phenomena and their feedback is intrinsically important for improving the performance and durability of proton exchange membrane fuel cells. The oxygen partial pressure (p(O2)) at 10 μm from the cathode catalyst layer (CL) in the gas diffusion layer was measured by using an optical fiber with an oxygen-sensitive dye applied to the apex, when the current density was abruptly increased. p(O2) decreased with increasing current density at constant air utilization. This decrease in oxygen partial pressure is attributed to the increased amount of water at the CL at the cathode due to the oxygen reduction reaction and electro-osmotic drag, as previously proposed. A shortage of oxygen in the CL for 1 s was also detected by using this p(O2) monitoring. These results are consistent with the previous results obtained by operando time-resolved measurements of the water distribution in the electrolyte membranes of a running fuel cell.

The Increase in Hemoglobin Concentration With Altitude Differs Between World Regions and Is Less in Children Than in Adults.

To compensate for decreased oxygen partial pressure, high-altitude residents increase hemoglobin concentrations [Hb]. The elevation varies between world regions, posing problems in defining cutoff values for anemia or polycythemia. The currently used altitude adjustments (World Health Organization [WHO]), however, do not account for regional differences. Data from The Demographic and Health Survey (DHS) Program were analyzed from 32 countries harboring >4% of residents at altitudes above 1000 m. [Hb]-increase, (ΔHb/km altitude) was calculated by linear regression analysis. Tables show 95% reference intervals (RIs) for different altitude ranges, world regions, and age groups. The prevalence of anemia and polycythemia was calculated using regressions in comparison to WHO adjustments. The most pronounced Δ[Hb]/km was found in East Africans and South Americans while [Hb] increased least in South/South-East Asia. In African regions and Middle East, [Hb] was decreased in some altitude regions showing inconsistent changes in different age groups. Of note, in all regions, the Δ[Hb]/km was lower in children than in adults, and in the Middle East, it was even negative. Overall, the Δ[Hb]/km from our analysis differed from the region-independent adjustments currently suggested by the WHO resulting in a lower anemia prevalence at very high altitudes. The distinct patterns of Δ[Hb] with altitude in residents from different world regions imply that one single, region-independent correction factor for altitude is not be applicable for diagnosing abnormal [Hb]. Therefore, we provide regression coefficients and reference-tables that are specific for world regions and altitude ranges to improve diagnosing abnormal [Hb].

Electrochemical properties of double molybdate LiSm(MoO4)2 ceramics with ultra-low sintering temperature

A novel double molybdate LiSm(MoO4)2 composition was prepared through a conventional solid-state ceramic route for its potential application as a solid-state Li+-ion conductor for low-loss dielectric ceramics. Ceramic disks were prepared by uniaxial pressing and sintered at the low temperature of 620 °C. Phase formation was confirmed through powder X-ray diffraction (XRD), which was indexed to the tetragonal crystal system with a Scheelite-type structure. Laser Raman spectroscopy showed that the MoO42− tetrahedra in the LiSm(MoO4)2 material are more regular, suggesting high symmetry for the compound. Scanning Electron Microscopy (SEM) revealed the formation of polygonal grains with an average grain size of less than 1 μm. The electrochemical properties of the ceramic system were investigated by Electrochemical Impedance Spectroscopy (EIS) in O2, air, and Ar (250 °C – 500 °C). Data were systematically analyzed using an Equivalent Circuit Model (EQM) combined with a Distribution Function of Relaxation Times (DFRT) analysis. The results revealed the coexistence of both a delocalized (long-range conductivity) and a localized (dipole relaxation) phenomenon, mainly distinguishable at lower temperatures (i.e., for T ≤ 350 °C) and in a pure O2 atmosphere. This localized phenomenon was tentatively attributed to the presence of trapped hole-vacancy pairs with reduced mobility. Conversely, at higher temperatures in O2 (i.e., for T ≥ 350 °C) and in the whole temperature range in less oxidizing conditions (air and Ar), such a localized phenomenon was no longer observed, as a likely result of a decrease in hole concentration with decreasing oxygen partial pressure (pO2). The current work, thus, underscores a different perspective for the development and characterization of ceramic-based solid-state Li+-ion conductors for their application as low-loss dielectric ceramics.

Preliminary screening of biomarkers in HAPE based on quasi-targeted metabolomics.

High altitude pulmonary edema (HAPE) is a serious threat to the physical and mental health of people who quickly enter high plateaus, deserves more attention and in-depth research. In our study, through the detection of various physiological indexes and other phenotypes in a HAPE rat model, the HAPE group showed a significant decrease in oxygen partial pressure and oxygen saturation, and a significant increase in pulmonary artery pressure and lung tissue water content. The lung histomorphology showed characteristics such as pulmonary interstitial thickening and inflammatory cell infiltration. We applied quasi-targeted metabolomics to compare and analyze the components of metabolites in arterial-veinous blood in control rats and HAPE rats. Using kyoto Encyclopedia of Genes Genomes (KEGG) enrichment analysis and two machine algorithms, we speculate that after hypoxic stress and comparing arterial blood and venous blood products in rats, the metabolites were richer, indicating that normal physiological activities, such as metabolism and pulmonary circulationhad a greater impact after hypoxic stress; D-mannoseDOWN, oxidized glutathioneDOWN, glutathione disulfideDOWN, and dehydrocholic acidDOWN in arterial blood play key roles in predicting the occurrence of HAPE; in venous blood, L-leucineDOWN, L-thyroxineDOWN, and cis-4-hydroxy- D-prolineDOWN may have key roles, which can be considered biomarkers of HAPE. This result provides a new perspective for the further diagnosis and treatment of plateau disease and lays a strong foundation for further research.

Comment on "Understanding the Increasing Trend of Sensor Signal with Decreasing Oxygen Partial Pressure by a Sensing-Reaction Model Based on O2-Species".

In the original paper, Zhao and co-workers describe a sensing model to explain the response to a reducing gas as a function of the oxygen partial pressure. In this Comment we specifically analyze the basic gas detection mechanisms proposed in such a work and expressed through surface reactions (eqs 1-5). The consequence of these presented mechanisms lead to inconsistencies that are also regularly found in the literature.

Reply to the Comment on "Understanding the Increasing Trend of Sensor Signal with Decreasing Oxygen Partial Pressure by a Sensing-Reaction Model Based on O2- Species".

In our recent work (ACS Sens.2022, 7, 1095-1104), Mirabella et al. provided comments on our publication, mainly focusing on the controversy between the oxygen vacancy model and the ionosorbed model and the related derivation based on the law of mass action. Herein we explain the correlation between the ionosorption model and the oxygen vacancy model and provide a brief introduction of our view on these two models. Moreover, a more detailed derivation about the law of mass action is provided to explain the relationship between surface electron concentration, oxygen partial pressure, adsorbed oxygen density, and oxygen vacancy density.

HIF-1 ACTIVATION AND INFLAMMATORY RESPONSES TO HYPOXIA

Acute hypoxia is a significant physiological danger during high-altitude flying and military aircraft missions. The human brain requires a constant supply of oxygen to function properly, and is susceptible to settings with low availability of air oxygen. Hypoxia can influence inflammatory signalling, and both central and systemic responses can activate HIF pathway genes. HIFs are critical molecules that regulate inflammation andhypoxia, ensuring appropriate cell function and survival. Hypoxia is the condition in which insufficient oxygen reaches the body's tissues. It can be caused by a decrease in partial oxygen pressure (PO2) in the environment, problems with breathing and/or oxygen transport, or the inability of tissues to utilise oxygen. Different organs are hypoxic due to differences in tissue oxygen tensions, which are determined by differences in aerobic metabolism. Extremely hypoxic individuals have the most dramatic systemic and neurological adaptations to persistent hypoxia. In this review, we provide an overview of central and systemic responses to hypoxia and discuss the activation of HIF-1 pathway.

Oxidation Behavior, Insulation Resistance, and Permeability of FeSiCr Alloys for Multilayer Inductors

FeSiCr alloys are used as soft magnetic materials for power multilayer inductors. The alloys are typically annealed at intermediate temperatures in air during inductor fabrication to form an insulating chromium oxide layer around the alloy particles. The variation of the annealing temperature between 700 °C and 900 °C in air, and, for the first time, the variation of the oxygen partial pressure during annealing at 900 °C are studied, and their effects on the alloy’s oxidation behavior, phase formation, insulation resistance, and permeability are demonstrated. The chromium oxide content increases up to about 12 wt% with annealing temperature in air, whereas it decreases to 8.2 wt% after annealing at 900 °C and 0.001% O2. The observed mass changes during annealing confirm the various tendencies towards oxidation. This oxidation behavior is reflected in an increase in the insulation resistance with annealing temperature or in a resistance reduction with decreasing oxygen partial pressure. The permeability decreases from µ = 22 after annealing at 700 °C to µ = 18.5 at 900 °C in air. The reduction of pO2 during annealing at 900 °C leads to an increase in permeability up to µ = 22.5 at pO2 = 0.001% O2. The results can be used to design cofiring strategies using reduced oxygen partial pressure for new composite multilayer inductive components consisting of FeSiCr- and ferrite layers in combination with silver metallization.

Ferromagnetism enhancement by increasing oxygen vacancies in Co-doped ZnO thin films

In the reported study, thin films of ZnO doped with 10 wt. % Co were fabricated by pulsed laser deposition under different oxygen partial pressures. The results of x-ray photoelectron spectroscopy show that the valence state of the Co ions is 2+ and that the number of oxygen vacancies is increased by lowering the oxygen partial pressure during deposition. The results of UV–visible absorption spectroscopy show that the Co2+ ions substitute for the Zn sites in the ZnO lattice. Ferromagnetism in the Co-doped ZnO thin films is observed up to 300 K. Furthermore, the saturation magnetization increases as the oxygen partial pressure decreases, indicating a strong correlation between the number of oxygen vacancies and the saturation magnetization. This suggests that ferromagnetism in Co-doped ZnO can be enhanced by simply controlling the oxygen partial pressure that causes oxygen vacancies. Furthermore, how the mechanism for the expression of ferromagnetism can be explained by the bound magnetic polaron model is discussed.

Simultaneously Achieving Colossal Permittivity, Ultralow Dielectric Loss Tangent, and High Insulation Resistivity in Er-Doped SrTiO3 Ceramics via Oxygen Vacancy Regulation.

High-performance Sr1-xErxTiO3 (x = 0-0.014) ceramics were sintered in different atmospheres using the conventional solid-state reaction method. The phase structure and micromorphology of ceramics were analyzed using X-ray diffraction and scanning electron microscopy. Meanwhile, the Sr1-xErxTiO3 (when x = 0.012) ceramic sintered in hydrogen attains a colossal permittivity (132 543 @1 kHz, 157 650 @1 MHz) and ultralow tan δ (0.009 @1 kHz, 0.03 @1 MHz) and has good frequency stability (20 Hz to 2 MHz) and temperature stability (-180 to 425 °C). X-ray photoelectron spectroscopy, electron paramagnetic resonance, and impedance analysis show that the colossal permittivity and ultralow dielectric loss are attributed to the defect dipoles and defect clusters [TiTi'-VO••-TiTi'], [ErSr•-TiTi'], [2ErTi'-VO••], and [ErSr•-ErTi']. The insulation resistivity is determined by the grain boundary. The dielectric properties of samples sintered in hydrogen are excellent, and then, the oxidation method is used to backfill the oxygen vacancy (VO••), thus improving the insulation resistivity (2.8 × 1014 Ω cm) of the grain boundary. In addition, the diffusion mechanism of ceramic VO•• from low, medium, and high temperatures was studied by monitoring VO•• behavior in real time. The results reveal that the diffusion coefficient of VO•• in the grain boundary is greater than that in the grain; as a result, as the external oxygen partial pressure rises, the VO•• escapes first from the grain boundary. When the external oxygen partial pressure decreases, oxygen atoms enter the grain boundary region first and backfill oxygen vacancies.

Effects of Fdft 1 gene silencing and VD3 intervention on lung injury in hypoxia-stressed rats.

Hypoxia can induce lung injury such as pulmonary arterial hypertension and pulmonary edema. And in the rat model of hypoxia-induced lung injury, the expression of Farnesyl diphosphate farnesyl transferase 1 (Fdft 1) was highly expressed and the steroid biosynthesis pathway was activated. However, the role of Fdft 1 and steroid biosynthesis pathway in hypoxia-induced lung injury remains unclear. The study aimed to further investigate the relationship between Fdft1 and steroid biosynthesis pathway with hypoxia-induced lung injury. A rat model of lung injury was constructed by hypobaric chamber with hypoxic stress, the adenovirus interference vector was used to silence the expression of Fdft 1, and the exogenous steroid biosynthesis metabolite Vitamin D3 (VD3) was used to treat acute hypoxia-induced lung injury in rats. Sh-Fdft 1 and exogenous VD3 significantly inhibited the expression of Fdft 1 and the activation of the steroid pathway in hypoxia-induced lung injury rats, which showed a synergistic effect on the steroid activation pathway. In addition, sh-Fdft 1 promoted the increase of pulmonary artery pressure and lung water content, the decrease of oxygen partial pressure and oxygen saturation, and leaded to the increase of lung cell apoptosis and the aggravation of mitochondrial damage in hypoxia-stressed rats. And VD3 could significantly improve the lung injury induced by hypoxia and sh-Fdft 1 in rats. Fdft 1 gene silencing can promote hypoxic-induced lung injury, and exogenous supplement of VD3 has an antagonistic effect on lung injury induced by Fdft 1 gene silencing and hypoxic in rats, suggesting that VD3 has a preventive and protective effect on the occurrence and development of hypoxia-induced lung injury.

Thermodynamics of Gallium (Ga) at Black Copper Smelting Conditions Relevant to E-Waste Processing

Electronic waste (E-waste) is considered as a hazardous material, however, it also contains valuable elements, including gallium (Ga). E-waste can be processed through the black copper smelting to recover these valuable elements. However, the detailed thermodynamics behavior of many of the valuable elements during black copper smelting has not been studied comprehensively. This study aims to investigate the thermodynamics of Ga in copper and slag at black copper smelting conditions. High-temperature equilibrium experiments were carried out to measure the distribution ratio of Ga in Fe2O3–CaO–SiO2 slag and copper at temperature range of 1300 °C to 1450 °C (1573 K to 1723 K) and partial pressure of oxygen (pO2) of 10–6 to 10–11 atm. The effect of FeT/SiO2 ratio and basicity (measured as CaO/SiO2) of the slag on the distribution ratio of Ga were also investigated. The partitioning of Ga into the copper phase was found to increase with decreasing oxygen partial pressure, and with increasing temperature, FeT/SiO2 ratio and basicity. The study revealed that a basic slag at higher temperature and at a reducing atmosphere was favorable to increase Ga partitioning to the copper.

Electrical conductivity properties of porous SmBaCo2O5+d and SmBa0.5Sr0.5Co2O5+d layered perovskite oxide systems for solid oxide fuel cell

In this study, the electrical conductivity characteristics of SmBaCo2O5+d (SBCO) and SmBa0.5Sr0.5Co2O5+d (SBSCO) were measured and analyzed by changing the characteristics of the microstructure from dense microstructure to porous microstructure for the cathode application in solid oxide fuel cells. SBCO and SBSCO comprised of the dense microstructure showed metal insulator transition (MIT) and metallic behavior, respectively. In SBCO, when the oxygen partial pressure is reduced, the conductivity value decreases, and the conductivity behavior changes to the behavior of a semiconductor. However, the electrical conductivity behavior of SBSCO did not change even when the oxygen partial pressure was decreased. The electrical conductivities of the porous cathodes were lower than those of the dense cathodes due to the discontinuous electric path, but all porous cathodes showed semiconductor behavior. The conductivity value decreases when the oxygen partial pressure decreases, but the general conductivity behavior of the samples with a porous microstructure does not change under N2 atmosphere. The porous cathode showed the highest electrical conductivity when Pt lines were led to the top of the cathode. In this case, a relatively high electrical conductivity was measured using the method of measuring multiple conductivities at different temperatures while decreasing the measurement temperature starting from a high temperature rather than the method of measuring while raising the temperature starting from a low temperature. In the dense cathode, higher electrical conductivities were measured when a low current was applied, but in the porous cathode, the same electrical conductivity values were measured regardless of the applied current values.

Understanding the Increasing Trend of Sensor Signal with Decreasing Oxygen Partial Pressure by a Sensing-Reaction Model Based on O2- Species.

Although the increasing trend of sensor signal with decreasing oxygen partial pressure was observed quite early, the underlying mechanism is still elusive, which is a hindrance to accurate gas detection under varying oxygen partial pressure. In this work, a sensing model based on previous experimental and theoretical results is proposed, in which the O2- species is determined to be the main oxygen species because O- species has not been observed by direct spectroscopic studies. On this basis, combined with the band bending of SnO2 at different oxygen partial pressures, the functional relationship between the surface electron concentration, oxygen partial pressure, and reducing gas concentration is established, which includes three forms corresponding to the depletion layer, accumulation layer, and flat band. In the depletion layer case, the variation of the sensor resistance to different concentrations of CO and oxygen can be well fitted with our function model. Besides, this model predicts that the response of sensors will no longer maintain the increasing trend in an extremely hypoxic atmosphere but will decrease and approach 1 with the background oxygen content further going down to 0.